Polyolefins 1

Polyolefins
General aspects of polymers, properties and testing, processing, additives, and analysis are discussed in
Plastics, General Survey; Plastics, Properties and Testing; Plastics, Processing; Plastics, Additives; and
Plastics, Analysis, respectively. States of order are treated in Plastics, Properties and Testing. Fundamental
aspects of polymerization reactions are treated in Polymerization Processes.
Kenneth S. Whiteley, formerly ICI Plastics Division, Welwyn Garden City, United Kingdom (Chap. 1)
T. Geoffrey Heggs, current address: The Mill, Great Ayrton, TS9 6PX, United Kingdom , formerly ICI
Chemicals and Polymers Ltd., Wilton, Middlesbrough, United Kingdom (Chaps. 2 and 5)
Hartmut Koch, Shell Chemical International, Shell Center, London, United Kingdom (Chap. 3, based on the
corresponding chapter in Ullmann’s, 4th ed. written by Günther Goldbach)
Ralph L. Mawer, Shell Chemical International, Shell Center, London, United Kingdom (Chap. 3, based on
the corresponding chapter in Ullmann’s, 4th ed. written by Günther Goldbach)
Wolfgang Immel, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 4)

1. Polyethylene . . . . . . . . . . . . . . 2 1.5.3. Gas-Phase Process . . . . . . . . . . . 28

1.1. Introduction . . . . . . . . . . . . . . 2 1.5.4. Solution Process . . . . . . . . . . . . 30
1.2. Properties of Polyethylenes . . . . 3 1.6. Uses . . . . . . . . . . . . . . . . . . . 31
1.2.1. Molecular Structure and Morphol- 1.6.1. Film . . . . . . . . . . . . . . . . . . . . 31
ogy . . . . . . . . . . . . . . . . . . . . 3 1.6.2. Extrusion Coating . . . . . . . . . . . 32
1.2.2. General Properties . . . . . . . . . . . 5 1.6.3. Blow Molding . . . . . . . . . . . . . 32
1.2.3. High Molecular Mass (Bimodal) 1.6.4. Injection Molding . . . . . . . . . . . 33
Polyethylene (HMWPE) . . . . . . . 8 1.6.5. Pipe . . . . . . . . . . . . . . . . . . . . 33
1.2.4. Ultra High Molecular Mass Polyeth- 1.6.6. Wire and Cable Insulation . . . . . . 33
ylene (UHMWPE) . . . . . . . . . . . 8 1.6.7. Ethylene Copolymers . . . . . . . . . 33
1.2.5. Properties of Ethylene Copolymers 8 1.6.8. Ultra High Modulus Polyethylene
1.3. Polymerization Chemistry . . . . . 10 Fibers . . . . . . . . . . . . . . . . . . . 33
1.3.1. Free-Radical Catalysis . . . . . . . . 11 1.6.9. Joining Polyethylene . . . . . . . . . 34
1.3.1.1. Introduction . . . . . . . . . . . . . . . 11 1.7. Chemically Modified Polyethyl-
1.3.1.2. Copolymerization . . . . . . . . . . . 13 enes . . . . . . . . . . . . . . . . . . . . 34
1.3.2. Coordination Catalysis . . . . . . . . 15 1.7.1. Cross-Linked Polyethylene . . . . . 34
1.3.2.1. Phillips Catalysts . . . . . . . . . . . 16 1.7.2. Chlorinated Polyethylene . . . . . . 35
1.3.2.2. Ziegler Catalysts . . . . . . . . . . . . 17 1.7.3. Fluorinated Polyethylene . . . . . . . 35
1.3.2.3. Single-Site Catalysts (Metallocenes) 18 1.8. Environmental Aspects . . . . . . . 35
1.3.2.4. Copolymerization . . . . . . . . . . . 21 1.8.1. Manufacture . . . . . . . . . . . . . . 35
1.4. Raw Materials . . . . . . . . . . . . . 21 1.8.2. Polymer Disposal and Recycling . . 36
1.4.1. Ethylene . . . . . . . . . . . . . . . . . 21 2. Polypropylene . . . . . . . . . . . . . 36
1.4.2. Comonomers . . . . . . . . . . . . . . 22 2.1. Historical Survey . . . . . . . . . . . 36
1.4.3. Other Materials . . . . . . . . . . . . . 22 2.2. Polymer Structure . . . . . . . . . . 37
1.5. Production Processes . . . . . . . . 22 2.2.1. Molecular and Chain Structure . . . 37
1.5.1. High-Pressure Process . . . . . . . . 22 2.2.2. Crystallization and Morphology . . 38
1.5.1.1. Autoclave Reactor . . . . . . . . . . . 24 2.3. Raw Materials . . . . . . . . . . . . . 40
1.5.1.2. Tubular Reactor . . . . . . . . . . . . 25 2.3.1. Propene . . . . . . . . . . . . . . . . . 40
1.5.1.3. High-Pressure Copolymers . . . . . 26 2.3.2. Polymerization Diluents . . . . . . . 41
1.5.1.4. Linear Low-Density Polyethylene 2.3.3. Catalyst Preparation . . . . . . . . . . 41
(LLDPE) . . . . . . . . . . . . . . . . . 26 2.3.3.1. TiCl3 -Based Catalysts . . . . . . . . 41
1.5.2. Suspension (Slurry) Process . . . . . 26 2.3.3.2. Supported Catalysts . . . . . . . . . . 42
1.5.2.1. Autoclave Process . . . . . . . . . . . 27 2.3.3.3. Homogeneous Catalysts . . . . . . . 43
1.5.2.2. Loop Reactor Process . . . . . . . . . 28 2.3.3.4. Aluminum Alkyl Cocatalysts. . . . . 43

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a21 487
2 Polyolefins

2.3.4. Hydrogen . . . . . . . . . . . . . . . . 44 3.4. Applications . . . . . . . . . . . . . . 75

2.4. Polymerization Mechanism . . . . 44 4. Polyisobutylene . . . . . . . . . . . . 77
2.5. Industrial Processes . . . . . . . . . 45 4.1. Introduction . . . . . . . . . . . . . . 77
2.5.1. Suspension Homopolymerization 4.2. Production . . . . . . . . . . . . . . . 78
(Early Diluent Processes) . . . . . . 45 4.2.1. Isobutene as Raw Material . . . . . . 78
2.5.2. Bulk Polymerization in Liquid 4.2.2. Low Molecular Mass Polyisobut-
Propene . . . . . . . . . . . . . . . . . 48 ylenes . . . . . . . . . . . . . . . . . . . 78
2.5.3. Solution Polymerization . . . . . . . 48 4.2.3. Medium Molecular Mass Polyiso-
2.5.4. Spheripol Process . . . . . . . . . . . 48 butylenes . . . . . . . . . . . . . . . . . 79
2.5.5. Hypol Process . . . . . . . . . . . . . 49 4.2.4. High Molecular Mass Polyisobut-
2.5.6. Gas-Phase Processes . . . . . . . . . 49 ylenes . . . . . . . . . . . . . . . . . . . 80
2.5.7. Copolymerization . . . . . . . . . . . 52 4.3. Structure . . . . . . . . . . . . . . . . 81
2.5.7.1. Random Copolymerization . . . . . 52 4.4. Properties . . . . . . . . . . . . . . . . 81
2.5.7.2. Impact (Block) Copolymerization . 52 4.5. Uses and Processing . . . . . . . . . 81
2.5.8. Product Finishing . . . . . . . . . . . 53 4.6. Commercial Products . . . . . . . . 83
2.5.9. Additives . . . . . . . . . . . . . . . . 54 4.7. Copolymers . . . . . . . . . . . . . . 83
2.6. Compounding . . . . . . . . . . . . . 55 5. Poly(4-Methyl-1-Pentene) . . . . . 83
2.7. Properties . . . . . . . . . . . . . . . . 55 5.1. Raw Materials . . . . . . . . . . . . . 83
2.7.1. Homopolymer . . . . . . . . . . . . . 55 5.1.1. Monomers . . . . . . . . . . . . . . . . 83
2.7.2. Copolymers . . . . . . . . . . . . . . . 58 5.1.2. High-Melting Nucleating Polymers 84
2.7.3. Elastomer Blends with Polypropyl- 5.1.3. Catalysts . . . . . . . . . . . . . . . . . 84
ene . . . . . . . . . . . . . . . . . . . . 59
5.2. Industrial Manufacture . . . . . . 85
2.8. Uses . . . . . . . . . . . . . . . . . . . 60
5.3. Polymer Structure . . . . . . . . . . 86
2.8.1. Injection Molding . . . . . . . . . . . 60
5.3.1. Homopolymer . . . . . . . . . . . . . 86
2.8.2. Blow Molding . . . . . . . . . . . . . 61
5.3.2. Copolymers . . . . . . . . . . . . . . . 87
2.8.3. Fibers and Flat Yarns . . . . . . . . . 62
5.4. Properties of PMP Products . . . . 87
2.8.4. Film . . . . . . . . . . . . . . . . . . . . 64
5.4.1. Optical Properties . . . . . . . . . . . 87
2.8.5. Foil and Sheet . . . . . . . . . . . . . 66
2.8.6. Extruded Pipe . . . . . . . . . . . . . . 66 5.4.2. Stability and Chemical Resistance . 88
2.9. Environmental Aspects . . . . . . . 67 5.4.3. Mechanical Properties . . . . . . . . 90
2.9.1. Recycling . . . . . . . . . . . . . . . . 67 5.4.4. Electrical Properties . . . . . . . . . . 92
2.9.2. Pyrolysis . . . . . . . . . . . . . . . . . 68 5.4.5. Surface Properties and Permeability 92
2.9.3. Incineration . . . . . . . . . . . . . . . 68 5.4.6. Rheology . . . . . . . . . . . . . . . . 92
2.9.4. Environmental Interactions . . . . . 69 5.5. Economic Aspects . . . . . . . . . . 93
3. Poly(1-Butene) . . . . . . . . . . . . 70 5.6. Fabrication and Applications . . . 93
3.1. Production . . . . . . . . . . . . . . . 70 5.6.1. Fabrication . . . . . . . . . . . . . . . 93
3.2. Properties . . . . . . . . . . . . . . . . 70 5.6.2. Applications . . . . . . . . . . . . . . 94
3.2.1. Structure and Physical Properties . 70 5.7. Health and Environmental As-
3.2.2. Application Properties . . . . . . . . 74 pects . . . . . . . . . . . . . . . . . . . 94
3.3. Processing . . . . . . . . . . . . . . . 75 6. References . . . . . . . . . . . . . . . 95

1. Polyethylene 1995). In the 1920s research into the polymer-

ization of unsaturated compounds such as vinyl
1.1. Introduction chloride, vinyl acetate, and styrene led to indus-
trial processes being introduced in the 1930s, but
Despite ethylene’s simple structure, the field of the use of the same techniques with ethylene did
polyethylene is a complex one with a very wide not lead to high polymers. The chance observa-
range of types and many different manufactur- tion in 1933 by an ICI research team that traces
ing processes. From a comparatively late start, of a waxy polymer were formed when ethylene
polyethylene production has increased rapidly and benzaldehyde were subjected to a tempera-
to make polyethylene the major tonnage plas- ture of 170 ◦ C and a pressure of 190 MPa, led to
tics material worldwide (45×106 t capacity in the first patent in 1936 and small-scale produc-
 Polyolefins 3

tion in 1939. The polymers made in this way, The three types of polyethylene outlined
by using free radical initiators, were partially above account for the major part of polyethylene
crystalline, and measurement of the density of production (Table 1), but the picture is slightly
the product was quickly established as a means confused since many plants have the capability
of determining the crystallinity. Due to the side of producing more than one type of product (so-
reactions occurring at the high temperatures em- called swing plants). Additionally, copolymers
ployed, the polymer chains were branched, and are made by both types of process. The free-
densities of 915 – 925 kg/m3 were typically ob- radical process is used to produce copolymers of
tained. The densities of completely amorphous vinyl acetate, acrylates, methacrylates, and the
and completely crystalline polyethylene would corresponding acids, but chain transfer prevents
be 880 and 1000 kg/m3 , respectively. the use of higher olefins because of the drastic
During the 1950s three research groups work- reduction in molecular mass of the polymer. The
ing independently discovered three different cat- coordination catalysts are able to copolymerize
alysts which allowed the production of essen- olefins, but are deactivated by more polar ma-
tially linear polyethylene at low pressure and terials. Because of the complex interplay of the
temperature. These polymers had densities in capabilities of modern plants, it is convenient to
the region of 960 kg/m3 , and became known treat separately the products, the catalysts, and
as high-density polyethylenes (HDPE), in con- the processes.
trast to the polymers produced by the exten-
sively commercialized high-pressure process,
which were named low-density polyethylenes
(LDPE). These discoveries laid the basis for
the coordination catalysis of ethylene polymer-
ization, which has continued to diversify. Of
the three discoveries at Standard Oil (Indiana),
Phillips Petroleum, and by Karl Ziegler at the
Max-Planck-Institut für Kohlenforschung, the
latter two have been extensively commercial-
ized. More recently the observation that traces
of water can dramatically increase the polymer-
ization rate of certain Ziegler catalysts has led
to major developments in soluble coordination
catalysts and later their supported variants. Figure 1. Schematic molecular structure
The coordination catalysts allowed for the A) Low-density polyethylene; B) Linear low-density poly-
ethylene; C) High-density polyethylene
first time the copolymerizaton of ethylene with
other olefins such as butene, which by introduc-
ing side branches reduces the crystallinity and
allows a low-density polyethylene to be pro-
duced at comparatively low pressures. Although 1.2. Properties of Polyethylenes
Du Pont of Canada introduced such a process
in 1960, worldwide the products remained a 1.2.1. Molecular Structure and Morphology
small-volume specialty until 1978 when Union
Carbide announced their Unipol process and Figure 1 shows schematic structures for the three
coined the name linear low-density polyethylene polyethylenes, with the main features exagger-
(LLDPE). In addition to developing a cheaper ated for emphasis. LDPE has a random long-
production process, Union Carbide introduced branching structure, with branches on branches.
the concept of exploiting the different molecular The short branches are not uniform in length but
structure of the linear product to make tougher are mainly four or two carbon atoms long. The
film. Following this lead, LLDPE processes have ethyl branches probably occur in pairs [21], and
been introduced by many other manufacturers. there may be some clustering of other branches
The history of these discoveries is covered in [22]. The molecular mass distribution (MMD)
[1–4, 20]. is moderately broad.
4 Polyolefins
Table 1. Polyethylene production capacities in 103 t/a ∗ (1995)

North America Western Europe Eastern Europe Japan Rest of World Total

LDPE 3891 5783 1918 1444 4210 17 246

LLDPE 4422 1848 100 1059 3728 11 157
HDPE 6198 4008 873 1024 4715 16 891
Total PE 14 511 11 639 2891 3527 12 653 45 221

∗ Data from Chem Systems, London.

LLDPE has branching of uniform length from the lamella they may either loop back else-
which is randomly distributed along a given where into the same lamella or crystallize in one
chain, but there is a spread of average concentra- or more adjacent lamellae, thereby forming  tie
tions between chains, the highest concentrations molecules .
of branches being generally in the shorter chains Thermodynamically the side branches are ex-
[23]. The catalysts used to minimize this effect cluded from the crystalline region because their
generally also produce fairly narrow MMDs. geometry is too different from that of the main
chains to enter the crystalline lamellae. There-
fore, the branches initiate chain folding, which
results in thinner lamellae with the branches
mainly situated on the chain folds on the surface
of the lamellae. However, on rapid cooling these
energetically preferred placements may not al-
ways occur, and some branches may become in-
corporated as crystal defects in the crystalline
regions. Detailed measurements by solid-state
NMR and Raman spectroscopy show that the
categorization into crystalline and amorphous
phases is too simplistic and a significant frac-
tion of the polymer is present in the form of an
Figure 2. Folded-chain lamellar crystal of polyethylene “interfacial” fraction which has neither the free-
dom of motion of a liquid, nor the well-defined
HDPE is essentially free of both long and order of a crystal [25, 26]. A further result of a
short branching, although very small amounts side branch is that having been prevented from
may be deliberately incorporated to achieve spe- folding directly into the same lamella, the poly-
cific product targets. The MMD depends on the mer chain may form a tie molecule that links to
catalyst type but is typically of medium width. one or more further lamellae.
Polyethylene crystallizes in the form of Under moderately slow cooling conditions,
platelets (lamellae) with a unit cell similar to that crystallization may be nucleated at a compara-
of low molecular mass paraffin waxes [24]. Due tively small number of sites. Crystallization then
to chain folding, the molecular axes are oriented propagates outwards from these centers until the
perpendicular to the longest dimension of the surfaces of the growing spheres meet. The re-
lamella and not parallel to it as might be expected sulting spherulites show a characteristic banded
(Fig. 2). The thickness of the lamellae is deter- structure under a polarizing optical microscope.
mined by the crystallization conditions and the The typical milkiness of polyethylene is due to
concentration of branches and is typically in the light scattered by spherulites or other, less well
range of 8 – 20 nm. Thicker lamellae are associ- defined aggregates of crystallites, rather than
ated with higher melting points and higher over- by the crystallites themselves, which are much
all crystallinities. Slow cooling from the melt or smaller than the wavelength of light [27]. Ethy-
annealing just below the melting point produces lene copolymers may be transparent, although
thicker lamellae. Where long molecules emerge partially crystalline.
 Polyolefins 5

1.2.2. General Properties melt. This parameter correlates usefully with ex-
trusion processes, where a low value is desirable
LDPE and LLDPE are translucent whitish solids for tubular film, and a high value is necessary for
and are fairly flexible. In the form of films they extrusion coating.
have a limp feel and are transparent with only
a slight milkiness. HDPE on the other hand is a
white opaque solid that is more rigid and forms
films which have a more turbid appearance and
a crisp feel.
Polyethylene does not dissolve in any sol-
vent at room temperature, but dissolves readily
in aromatic and chlorinated hydrocarbons above
its melting point. On cooling, the solutions tend
to form gels which are difficult to filter. Although
LDPE and LLDPE do not dissolve at room tem-
perature, they may swell in certain solvents with
a deterioration in mechanical strength. Manu-
facturers issue data sheets detailing the suitabil-
ity of their products for use in contact with a
wide range of materials. In addition to solvents,
polyethylene is also susceptible to surface ac-
tive agents which encourage the formation of
cracks in stressed areas over prolonged periods
of exposure. This phenomenon, known as en-
vironmental stress cracking (ESC), is believed
to be due to lowering of the crack propagation
energy [28]. In general, HDPE is the preferred
polyethylene for liquid containers.
Some properties of typical LDPE, HDPE,
and LLDPE are listed in Table 2. Polyethylenes
are routinely characterized by their density and
melt flow index (MFI). The MFI test was orig-
inally chosen for LDPE to give a measure of Figure 3. Melt flow index equipment
the melt characteristics under conditions related a) Interchangable piston loading weight; b) Electrically
to its processing. It is carried out by applying heated barrel; c) Piston; d) Die; e) Polyethylene melt
a standard force to a piston and measuring the
rate of extrusion (in g/10 min) of the polyethyl- The behavior of polyethylene under shear is
ene through a standard die (Fig. 3). Other stan- shown in Figure 4, which compares a LDPE and
dard conditions are sometimes used on the same a LLDPE similar to those in Table 2. At suffi-
equipment to extend the range of information ciently low shear rates the viscosity of all poly-
and because higher loads are sometimes con- ethylenes becomes Newtonian, i.e., independent
sidered more appropriate for HDPE. The short of shear rate. Due to its narrow MMD the viscos-
parallel section of the standard die introduces ity of the LLDPE is less shear dependent than
errors which mean that the MFI cannot be ac- that of the LDPE and has a higher viscosity un-
curately related to viscosity (it would be an in- der the higher shear conditions used in process-
verse relationship). For LDPE and HDPE, the ing equipment.
MFI increases disproportionately with the ap- As indicated above, the crystalline proper-
plied load. The ratio of the two MFIs gives a ties are affected by the rate of cooling from the
measure of the ease of flow at high shear and melt and the subsequent thermal history. For the
is sometimes known as the flow ratio. The die purposes of reproducibility it is usual to apply
swell ratio can also be measured in the MFI test a standard annealing treatment to test samples,
and gives a measure of the elastic memory of the such as annealing at 100 ◦ C for 5 min followed
6 Polyolefins
Table 2. Properties of some typical polyethylenes (data from Repsol Quimica)

Property LDPE HDPE LLDPE Method Standard

Polymer grade Repsol PE077/A Hoechst GD-4755 BP LL 0209

Melt flow index (MFI), g/600 s 1.1 1.1 0.85 190 ◦ C/2.16 kg ASTM D1238
High load MFI, g/600 s 57.9 50.3 24.8 190 ◦ C/21.6 kg ASTM D1238
Die swell ratio (SR) 1.43 1.46 1.11
Density, kg/m3 924.3 961.0 922.0 slow annealed ASTM D1505
Crystallinity, % 40 67 40 DSC
Temperature of fusion (max.), ◦ C 110 131 122 DSC
Vicat softening point, ◦ C 93 127 101 5 ◦ C/h ASTM D1525
Short branches ∗∗ 23 1.2 26 IR ASTM D2238
Comonomer butene butene NMR
Molecular mass∗
Mw 200 000 136 300 158 100 SEC
Mn 44 200 18 400 35 800 SEC
Tensile yield strength, MPa 12.4 26.5 10.3 50 mm/min ASTM D638
Tensile rupture strength, MPa 12.0 21.1 25.3
Elongation at rupture, % 653 906 811
Modulus of elasticity, MPa 240 885 199 flexure ASTM D790
Impact energy,
unnotched, kJ/m2 74 187 72 ASTM D256
notched, kJ/m2 61 5 63 ASTM D256
Permittivity at 1 MHz 2.28 ASTM D1531
Loss tangent at 1 MHz 100×10−6 ASTM D1531
Volume resistivity, Ω · m 1016
Dielectric strength, kV/mm 20

∗ Corrected for effects of long branching by on-line viscometry.

∗∗ Number of methyl groups per 1000 carbon atoms.

Figure 4. Dependence of viscosity η on shear rate γ̇ for two

polyethylenes
a) Low-density polyethylene; b) Linear low-density poly- Figure 5. Temperature rise elution fractionation curves (I is
ethylene; c) Apparent shear rate in melt flow index test the cumulative weight fraction)

by slow cooling to room temperature. The crys- used to measure the fusion point, the relative
tallinity correlates with the density, reflecting the heterogeneity of the LLDPEs is demonstrated
average properties of the polymer, but the melt- even more clearly by temperature rise elution
ing point and the softening points for LLDPE fractionation (TREF) [29, 30]. After depositing
are higher than for LDPE due to the presence of the sample by slow cooling from solution onto
some relatively sparsely branched species in the an inert support, elution is carried out over a
former type of polymer. In addition to the dif- programmed temperature range to measure the
ferential scanning calorimetry (DSC) technique concentration of eluted polymer as a function of
 Polyolefins 7

elution temperature. Examples are shown in Fig- have reached almost four times the value mea-
ure 5. LLDPE produced with a single-site cat- sured after 10 s. Thus the effective Young’s mod-
alyst (see Section 1.3.2.3) shows a single sharp ulus after 4 d is only 25 % of the short-term value
peak by this test. and after several years would be lower still. This
The weight-average and number-average mo- creep behavior is particularly marked in the case
lecular masses determined by size exclusion of polyethylenes because the amorphous regions
chromatography (SEC, also known as gel per- are relatively mobile at room temperature [33].
meation chromatography, GPC) are listed in Ta- For design purposes the modulus must be es-
ble 2, and Figure 6 shows their molecular mass timated for the timescale and temperature ex-
distribution curves. pected for the application. A related problem in
designing for long-term use is that a prolonged
high stress may lead to crack formation and fail-
ure at a stress significantly below the conven-
tionally measured yield stress [34].

Figure 6. Molecular mass distribution curves for the poly-

ethylenes of Table 2 (data from Repsol Quimica)
I is the cumulative weight fraction.

In the tensile test the yield strengths and the

elastic moduli are as expected from the respec-
tive crystallinities. The higher rupture strength Figure 7. Tensile creep of HDPE (Rigidex 006-60) [32]
of the LLDPE relative to the LDPE is typical
when the two polymers are chosen to have equal The extremely low loss tangent (power fac-
MFIs, but if the criterion were constant high- tor) makes LDPE ideally suitable as an insula-
shear extrudability (e.g., the high load MFI) the tor for high-frequency cables. Since pure poly-
tensile strengths would be very similar. The ex- ethylene contains no polar groups, a very low
ample chosen for the LLDPE is a butene copoly- power factor is expected, and most of the mea-
mer. For higher performance applications longer sured value is due to traces of oxidation, catalyst
chain olefins are used as comonomers [31]; e.g., residues, antioxidant, etc. Because they contain
octene (Du Pont, Dow), hexene (UCC, Exxon), Ziegler or Phillips catalyst residues, such low
4-methylpentene (BP). These produce higher power factors are not generally achievable with
tensile strengths and impact energies, particu- HDPE or LLDPE.
larly in the form of film. Figure 8 shows the permeability of LDPE and
In common with other polymers, polyethyl- ethylene – vinyl acetate copolymer (EVA) films
ene is viscoelastic in the solid state. This means to oxygen and water vapor. Although LDPE has
that the strain produced by applying a stress is a very useful role as a packaging material, the gas
time dependent, and in defining an elastic mod- and water vapor permeabilities are not particu-
ulus it is important to specify the timescale of larly low compared to other film forming mate-
the measurement. Figure 7 shows the results of rials (see → Films, Chap. 6.2.1.). Since perme-
a measurement of strain versus time for a HDPE ation takes place in the mobile amorphous phase,
specimen at a constant tensile stress of 6.5 MPa the permeability of HDPE is appreciably lower.
[32]. The strain continues to increase approxi- Polyethylene is a high molecular mass hy-
mately linearly with log t and after 4 d would drocarbon which can be considered as toxico-
8 Polyolefins

logically inert, and indeed high-purity forms are A particularly important type of bimodal
used in medical prostheses. The suitability of a polymer is produced by combining a high mo-
polyethylene for use in contact with food or in lecular mass component having a relatively high
medical prostheses depends on its content of cat- concentration of short branches with a low mo-
alyst residues and principally on additives such lecular mass component containing few or no
as antioxidants. Acceptable limits on process branches. In this way the low molecular mass
residues and additives are normally controlled component crystallizes as folded chain lamellae
by national regulatory bodies, but in many cases and the high molecular mass component forms
they are based on the standards defined by the tie molecules which crystallize in several of the
American Food and Drug Administration (FDA) lamellae. This combination of branching and
or the German Bundesgesundheitsamt. molecular mass is the reverse of what is usu-
ally observed in LLDPEs (see Sections 1.2.1 and
1.3.2.3), where the more higly branched compo-
nents have low molecular masses. The desired
bimodal distribution is achieved by careful pro-
cess modifications using multiple reactors. The
optimization of the tie molecules confers excel-
lent resistance to long term crazing and crack
growth [37], making the polymers particularly
suitable for pipe and liquid containers.

1.2.4. Ultra High Molecular Mass

Polyethylene (UHMWPE)
These polyethylenes were commercialized
shortly after HDPE and have extremely high
Figure 8. Permeability P of 0.025 mm films of LDPE and molecular mass (3 – 6×106 according to ASTM
EVA at 23◦ C (data are based on Exxon Escorene Ultra EVA D4020), but do not usually have a broad molec-
copolymers [35])
a) Oxygen; b) Water vapor (50 % R.H.)
ular mass distribution. The viscosity is too high
to be measured by the MFI test, and they are
usually characterized either by the relative so-
lution viscosity in decalin at 135 ◦ C, or by spe-
cially developed melt flow tests. The material
1.2.3. High Molecular Mass (Bimodal)
is processed by techniques similar to those de-
Polyethylene (HMWPE)
veloped for PTFE, which involve fusing by sin-
tering, rather than plastification to a true melt.
This description is usually applied to HDPEs
UHMWPE has a remarkable combination of
with MFIs in the range 0.01 – 0.1 by the nor-
abrasion resistance, chemical inertness, low fric-
mal test, although a higher load is usually
tion, toughness, and acceptability in contact with
used to characterize them. They are processable
foodstuffs. Some properties are listed in Table 3.
with some difficulty on conventional PE pro-
The density is only 940 kg/m3 , even though the
cessing machinery, although some advantages
polymer is unbranched, because the extremely
can be gained by using equipment optimized
high viscosity hinders the crystallization pro-
for these grades. In general, they are not sim-
cess.
ply higher molecular mass versions of normal
HDPE grades, but are specially designed broad-
MMD polymers, often produced by using mul- 1.2.5. Properties of Ethylene Copolymers
tiple reactors or combinations of catalysts [36].
The broad MMD, which may be bimodal, pro- Table 4 lists the principal types of ethylene
duces a highly shear dependent melt viscosity copolymers which are in commercial produc-
combined with good mechanical strength. tion. Of these the vinyl acetate copolymers are
produced in the largest quantities. All the ester
 Polyolefins 9
Table 3. Properties of an ultra high molecular mass polyethylene (Hoechst GUR 412) [38]

Property UHMWPE Method Standard

Molecular mass 4.5×106 viscometric DIN 53 728

Reduced specific viscosity, cm3 /g 2300 0.05 % in decalin
Density, kg/m3 940 DIN 53 479
Crystalline melting range, ◦ C 135 – 138 polarizing microscope
Tensile yield strength, MPa 22 DIN 53 455
Tensile rupture strength, MPa 44
Elongation at rupture, % > 350
Impact energy, notched, kJ/m2 210 double V-notch DIN 53 453
Volume resistivity, Ω · m > 1013 DIN 53 482

and acid copolymers are produced by the high- 10 wt % of (meth)acrylic acid by sodium or zinc
pressure free-radical process, but most of the ions. The ionic salts and the unneutralized acid
plants in the rapidly expanding LLDPE sector groups form strong interchain interactions, pro-
have the capability to produce VLDPE copoly- ducing a form of thermally labile cross-linking
mers with higher content of α-olefin and this is in both the solid and the molten states [43, 44].
an area with a large potential for expansion. The T g of the amorphous material in ionomers is
The principal effect of copolymerization is slightly above room temperature, resulting in a
to reduce the crystallinity. The effect is approx- stiffness similar to that of LDPE at room temper-
imately the same for all comonomers on a mo- ature. However, the stiffness of most ionomers
lar basis, with the exception of propene which decreases rapidly with increasing temperature
can be incorporated into the crystal lattice. At above 40 ◦ C.
room temperature the amorphous regions of the
copolymer (where the comonomer groups are
concentrated) are mobile and the effect of in-
troducing a comonomer is to progressively re-
duce the stiffness (Fig. 9). In addition to the
branches due to the comonomer, the branches
which occur under the high pressure synthe-
sis conditions also contribute to the reduction
in crystallinity. Below room temperature there
are differences between ester copolymers due to
the differences in the glass transition tempera-
ture T g of the amorphous material. This follows
the T g of the ester homopolymer and results in
EEA and EBA copolymers being flexible down
to lower temperatures than EVA, with EMMA Figure 9. Dynamic modulus G (ca. 2 Hz) at 23◦ C as a func-
having the highest T g . The VLDPEs produced tion of total branch points
by the LLDPE processes should have the best
low-temperature properties, particularly in the In polyketone (PK) and cycloolefin (COC)
case of narrow composition distribution poly- copolymers ethylene is present as a 50 mol %
mers. Properties of three typical EVAs and a alternating copolymer [45]. The PK materials
VLDPE [42] are listed in Table 5. are believed to be made with a novel group
The methacrylic and acrylic acid copolymers VIII catalyst [46]. They are targeted at medium-
are produced to provide enhanced adhesion, par- stiffness applications and also have good bar-
ticularly in coextruded films or laminates. Not rier properties for hydrocarbons. The carbonyl
included in Table 4 are terpolymers in which group, however, makes the polymers susceptible
acid monomers are used together with ester to degradation by sunlight. The COC materials
comonomers to improve adhesive properties. from Hoechst make use of the remarkable cata-
The ionomers are produced by the partial lyst activity and copolymerization ability of the
neutralization of acidic copolymers containing new single site catalysts [47] (Section 1.3.2.3)
10 Polyolefins
Table 4. Principal types of ethylene copolymer

Comonomer Abbreviation Feature Catalysis ∗

Vinyl acetate EVA flexibility FR

Methyl acrylate EMA flexibility, thermal stability FR
Ethyl acrylate EEA flexibility at low temperature, thermal stability FR
Butyl acrylate EBA as for EEA FR
Methyl methacrylate EMMA flexibility, thermal stability FR
Butene VLDPE flexibility at low temperature, thermal stability Z, SS
Hexene VLDPE as for butene copolymer Z, SS
Octene VLDPE as for butene copolymer Z, SS
Acrylic acid EAA adhesion FR
Methacrylic acid EMAA adhesion FR
Methacrylic acid + Na+ or Zn2+ (ionomer) adhesion, toughness, stiffness FR
Acrylic acid + Zn2+ (ionomer) adhesion, toughness, stiffness FR
Carbon monoxide PK polyketone, stiffness, high melting ∗∗
Norbornene COC cycloolefin copolymer, transparency SS

∗ FR = free radical, Z = Ziegler catalysis, SS = single-site catalyst. ∗∗ Novel group VIII metal catalyst.

Table 5. Properties of ethylene copolymers

Property EVA EVA EVA VLDPE Condition Standard

(Repsol PA-501) (Repsol PA-538) (Repsol PA-440) (DSM TMX 1000) a

Vinyl acetate 7.5 18 28

content, wt %
Melt flow index, 2 2 6 3 190 ◦ C/2.16 kg ASTM D1238
g/600 s
Density, kg/m3 926 937 950 902 rapid annealed ASTM D1505
Vicat softening 83 64 66
point, ◦ C
Tensile strength, 16 16 11 11.5 50 mm/min ASTM D638
MPa
Elongation at 700 700 800 TMX 1000:
rupture, % 0.4 m/s
Modulus of 156 b 47 b
24 b
95 c

elasticity, MPa
Permittivity at 2.46 2.70 ASTM D1531
1 MHz
Loss tangent at 0.014 0.035 ASTM D1531
1 MHz
Volume resistivity, 2.0×1015 2.5×1014
Ω·m
Dielectric strength, 19 20
kV/mm
a
Octene copolymer.
b
0.2 % strain, 100 s.
c
ASTM D790.

and the high transparency and low birefringence moval is thus a key factor in a commercial poly-
will allow its use in compact discs and transpar- merization process. Some processes (e.g., ICI
ent packaging. autoclave, Unipol fluidized bed) employ only a
limited conversion per pass, and the heat of re-
action is absorbed by the cool reactants. The un-
1.3. Polymerization Chemistry reacted monomer is then cooled in the recycle
stage. In other cases (e.g., UCC or BASF tubular
Heat of Reaction. The heat of polymeriza- and various slurry processes) more surface area
tion of ethylene is 93.6 kJ/mol (3.34 kJ/g). Since or more residence time is provided, and heat is
the specific heat of ethylene is 2.08 J ◦ C−1 g−1 , removed through the reactor walls.
the temperature rise in the gas phase is ca. 16 ◦ C
for each 1 % conversion to polymer. Heat re-
 Polyolefins 11

1.3.1. Free-Radical Catalysis 1) In addition to the effect of concentrating the

gaseous monomer, the pressure also influ-
1.3.1.1. Introduction ences the reaction rate constants, as is also
the case for liquid systems subjected to high
Free-radical catalysis is used exclusively in the pressures [50]. This is generally considered
high-pressure process, that is at pressures above in terms of a volume of activation, analogous
100 MPa. The reason for the use of such high to the energy of activation. High pressure af-
pressures is a combination of historic, economic, fects the configuration change necessary for
and technical factors [39]. Because ethylene is the reactants to reach the transition state. The
gaseous above its critical temperature of 9 ◦ C, overall contribution of the effect of pressure
a pressure of ca. 20 MPa would be necessary in on the rate constants over the pressure range
any case to achieve a reasonable concentration of 0 to 200 MPa is to increase the polymeriza-
monomer. Employing pressures of ca. 200 MPa tion rate by a factor of ca. 12 [51].
and temperatures above 160 ◦ C enables the poly- 2) The reaction temperatures employed are also
ethylene produced to dissolve in the unreacted high, an average of ca. 220 ◦ C being typical.
ethylene, and the high reaction rate makes the In parts of the reactor the temperature may
best use of the very expensive high-pressure be as low as 140 ◦ C but in other parts may
equipment. 20 % conversion of the monomer is reach over 300 ◦ C. These high temperatures
typically achieved in 40 s. A schematic phase di- also contribute to the high reaction rates, the
agram for an ethylene – polyethylene system is activation energy being 32 kJ/mol.
shown in Figure 10 [48]. For a more detailed ac- 3) The growing polymer chains are linear alkyl
count of the effect of molecular mass and MMD radicals and as such are very reactive not
on the phase equilibria, see [49]. merely in the addition to double bonds, but
also in abstracting hydrogen atoms from
other molecules, thereby forming saturated
alkyl chains and new radicals. The process is
called chain transfer. Since these hydrogen
atom abstraction reactions have higher acti-
vation energies than polymerization, they be-
come increasingly important as the polymer-
ization temperature rises. On the one hand
they put stringent demands on the monomer
purity to avoid traces of compounds which
could give rise to chain transfer and thereby
reduce the molecular mass, and on the other
hand it is possible to use low concentrations
of suitable materials (so-called chain-trans-
fer agents or modifiers) to control the poly-
mer molecular mass. Chain-transfer agents
which have been used commercially include
hydrogen, propane, propene, acetone, and
methyl ethyl ketone. Chain transfer to some
compounds with very active hydrogen atoms
Figure 10. Schematic cloud point surface for ethylene – such as propene, and particularly the higher
polyethylene [48] alkenes, can lead to radicals which are insuf-
ficiently reactive towards ethylene to reiniti-
The single-phase ethylene – polyethylene ate new chains rapidly, and reduced reaction
mixture allows the reaction to take place as a rates result.
classical free-radical-initiated solution polymer- 4) Chain transfer can also occur with the
ization (→ Polymerization Processes). Some as- polyethylene chains themselves, either to
pects which are particularly important for ethyl- the same growing chain (intramolecular) or
ene systems are as follows:
12 Polyolefins

to other polyethylene chains (intermolec- bone. Since the long-branching reaction is a

ular transfer). These reactions create the chain-transfer mechanism, the average chain
characteristic structural features of LDPE length of an unbranched molecule or a branch
which distinguish it from HDPE. As can be is shorter than it would be in the absence
demonstrated with models, the most prob- of the long-branching reaction. The effects
able intramolecular chain-transfer reaction of temperature and pressure are similar to
is to the carbon atom four carbons back those for short branching, but additionally
down the chain, which produces butyl groups the amount of long branching is propor-
(Fig. 11 A). This so-called back-biting mech- tional to the concentration of dissolved poly-
anism was first published by M. J. Roedel mer. In principle, this leads to a clear differ-
of Du Pont [52]. If, after the addition of ence between plug flow (tubular) and con-
one ethylene molecule to the newly formed tinuous stirred-tank reactors (CSTRs, auto-
secondary radical, a further back-bite occurs claves). Theoretical analyses have been pre-
(Fig. 11 B), a pair of ethyl branches or a 2- sented for autoclave [55–57] and tubular [58]
ethylhexyl group is formed. A further possi- reactors.
bility, shown in Figure 11 C, is that a back- 6) Initiation is very similar to that in many other
bite occurs to a branch point, and the ter- free-radical polymerizations, but there are
tiary radical then decomposes into a new some limitations. Initiators are commonly re-
short radical, leaving a vinylidene group at ferred to as “catalysts”. In the sense that one
the end of the polyethylene chain. This pro- mole of initiator will achieve the polymer-
cess is the principal chain-termination mech- ization of several thousand moles of ethyl-
anism in LDPE, and concentrations of vinyli- ene this is so, but the initiator is destroyed in
dene groups approach one per number aver- the process and so the term is, strictly speak-
age molecule for LDPEs produced at high ing, incorrect. Oxygen was used as initiator
temperature. These three reactions account in the early commercial processes because
for the principal features observed in the in- of the ease of introducing it into the pro-
frared spectrum of LDPE, but to a lesser ex- cess. With the development of high-pressure
tent other intramolecular transfers also occur pumps and new initiators, modern plants are
[9]. Since the activation energy for transfer able to maintain more precise control of tem-
is higher than for the polymerization reaction perature profiles by the injection of solutions
and the activation volume is smaller, branch- of liquid catalysts. The mechanism by which
ing and unsaturation increase with increas- oxygen forms free radicals is rather compli-
ing polymerization temperature and decrease cated, and at lower temperatures oxygen can
with increasing reaction pressure [53, 54]. act as an inhibitor [59]. In the autoclave pro-
5) Intermolecular transfer leads to long branch- cess the use of oxygen has been largely su-
ing and broadening of the molecular mass perseded, but in the tubular reactor process
distribution. Since they have more hydrogen it is still widely used, sometimes in combi-
atoms available for chain transfer, the long nation with liquid initiators. The two overall
chains tend to be the most highly branched, limitations on initiators are that they should
and there may be branches on the branches. be readily soluble in alkanes and they should
Statistically each new radical produced by produce reactive radicals, ideally alkyl or
initiation or chain-transfer reactions has a alkoxy radicals. On the former count, all the
range of probabilities of growing to vari- aqueous systems and most azo compounds
ous lengths before being terminated by one are excluded, and on the second count diben-
of these same chain-transfer or radical com- zoyl peroxide is unsuitable. The initiators are
bination reactions. The probable length is selected for use on the basis of their half-lifes
the same whether the chain grows from a at the reaction temperature. Since the resi-
new initiating radical or a branch point. Thus dence time in the reactor zone may be of the
branches are statistically the same length as order of 20 s or less, to obtain good control of
the backbone itself and, taking into account the reaction rate, an initiator half-life of about
statistical variations, the branches may in 1 s is required. For a tubular reactor the same
some cases be longer than the initial back- initiator is active over a wider range of tem-
 Polyolefins 13
−R•1 + M2 −→ −R•2 υ 12 = k 12 [R1 ] [M2 ]
peratures, but its selection is equally critical.
Typical initiators are listed in Table 6 [60]. −R•2 + M1 −→ −R•1 υ 21 = k 21 [R2 ] [M1 ]
7) The mechanism of kinetic chain termination
is by combination of radicals. This further −R•2 + M2 −→ −R•2 υ 22 = k 22 [R2 ] [M2 ]
widens the MMD in long-branched systems
when the rate of inititation-combination is r 1 = k 11 /k 12 r 2 = k 22 /k 21
high [57].
8) Although the conversion of ethylene to poly- −R•1 represents a growing radical where the last
ethylene is thermodynamically favorable, the unit added is monomer 1 (ethylene for the pur-
decomposition into carbon and a mixture of pose of this discussion).
methane and hydrogen is also highly exother- Table 7. Copolymerization reactivity ratios and chain transfer a
mic:
Comonomer r 1 (rel. to r 1 (rel. to VA) b Chain transfer c
C2 H4 −→ C + CH4 ∆H = 127 kJ/mol M2 ethylene)

Vinyl acetate 1.05 0.7

(VA)
Methyl acrylate 0.13 0.1 0.4
C2 H4 −→ 2 C + 2 H2 ∆H = 53 kJ/mol. Ethyl acrylate 0.08 3.3
Methyl 0.06 0.015 2.2
For kinetic reasons these reactions are only im- methacrylate
portant at the high temperature and pressures Methacrylic 0.015 0.01
acid
of the high-pressure process. In a confined sys- Styrene 0.01 0.01
tem the large amount of heat released can raise Vinyl chloride 0.18 0.23 > 10
the temperature, and hence the pressure, of the Propene 1.3 1.1
Butene 2.0 2.0 20
methane and hydrogen to potentially danger- Isobutene 1.0 2.1
ous levels. The theoretical final temperature and Hexene 1.4 > 20
pressure for a contained decomposition start- a
ing at 250 ◦ C and 200 MPa are 1400 ◦ C and
Reactivity ratios and chain transfer measured in a continuous
reactor at 190 ◦ C and 157 MPa, except for the olefins where
620 MPa. In practice much of the heat would be the data are from a batch reactor at 140 ◦ C and 196 MPa.
b
Literature values from [40, 41]. c d[log(MFI)]/d[M2 ] in
absorbed by the walls of the vessel or pipework. decades of MFI change per mol % in reaction mixture.
High-pressure plants are designed with relief
valves or bursting disks to protect the equipment For low concentrations of monomer 2 it fol-
from overpressurization due to decomposition. lows from the well-known copolymerization
Decompositions usually start as a runaway poly- equation that:
merization reaction, but then they can propagate
concentration of monomer 2 in copolymer
as a slow flame front even into cold gas. Experi- 1/r1 =
concentration of monomer 2 in reactor
mental decompositions usually show low propa-
gation velocities of ca. 0.2 m/s [61], but under the The value of r 1 can thus give guidance on the ef-
more turbulent conditions of commercial plant fectiveness of incorporation of comonomer rel-
operation, propagation can be more rapid. ative to the feed concentration. Some measured
values are shown in Table 7. A more compre-
hensive compilation is given in [9]. Vinyl ac-
1.3.1.2. Copolymerization etate has a reactivity ratio of almost exactly
1.0 which means that the copolymer has the
High-pressure ethylene copolymerization fol- same composition as the reactor feed. Acrylates
lows the classical free-radical copolymeriza- on the other hand have r 1 much lower than 1
tion mechanism (→ Polymerization Processes, which means that the copolymer is much richer
Chap. 2.2.1.). One of the most important charac- in acrylate than the reactant mixture. This has
teristics are the reactivity ratios r 1 and r 2 . The implications for the type of reactor. A continu-
rates υ of the four growth reactions are ous stirred-tank reactor (CSTR) operates with
the comonomer concentrations in a dynamic
−R•1 + M1 −→ −R•1 υ 11 = k 11 [R1 ] [M1 ] equilibrium. To make a copolymer containing
20 wt % ethyl acrylate, the feed composition
14 Polyolefins
Table 6. Peroxide initiators for the high-pressure process [60]

Figure 11. Principal intramolecular chain-transfer reactions

would contain typically 4 % of ethyl acrylate, progressively along the reactor. A useful feature
but the reactor and the stream leaving the reactor of r 1 for vinyl acetate being 1.0 (and r 2 is also
would contain only 1.6 %. In the case of a contin- 1.0) is that values of reactivity ratios reported in
uous plug flow reactor (CPFR), corresponding to the literature for other monomers copolymeriz-
a tubular reactor or a laboratory batch reactor, the ing with vinyl acetate can be used to estimate
corresponding figures would be 3.1 and 0.7 %. the reactivity ratios for ethylene at high pressure
The copolymer would in this case be a contin- [39]. This is illustrated in Table 7.
uous blend of compositions ranging from 38 % Comonomers also act as chain-transfer
to 9 % produced as the comonomer was used up agents. Table 7 shows some practical measure-
 Polyolefins 15

ments of these effects on the MFI under stan- The direct insertion of ethylene into σ-
dard conditions. Reference [9] tabulates the bonded aluminum alkyls was discovered by
chain-transfer effects in terms of molecular Ziegler in 1950, but the reaction was slow and
mass reduction. Clearly a moderate chain-trans- did not lead to high polymers. The prior coor-
fer activity can be tolerated more readily for a dination of ethylene is clearly crucial. The ac-
comonomer with a low r 1 since the concentra- tive species in commercial catalysts is complex,
tion in the reactor will be lower. The chain-trans- but there is a very large worldwide activity in
fer activity of the higher α-olefins such as butene investigating coordination catalysts, usually by
is very high, precluding their use in the free- way of model compounds [16, 17]. Commercial
radical process. The radicals produced by chain catalysts are virtually all heterogeneous solids
transfer are relatively stable and retard the reac- (at least on a microscopic scale) and require
tion. Propene is less extreme in these effects and careful attention to the particle shape and size
is sometimes used in the high-pressure process. in the development of the manufacturing pro-
Copolymerization theory shows that if r 2 cess. A feature of modern coordination cata-
is greater than 1 (it usually approximates to lysts (except those used in solution processes)
1/r 1 ), then the overall reaction rate is reduced. is that the catalyst particles grow by a process
In a continuous process this translates to an of replication [13]. This means that the over-
increased initiator demand which in extreme all shape of each particle is maintained as it
cases makes the process inoperable. As indi- grows by polymerization, and thus the distri-
cated above for homopolymers, a high initia- bution of polymer particle sizes is related to
tion rate broadens the MMD. Thus acrylate and the distribution of catalyst particle sizes. For
methacrylate copolymers require higher initia- this type of growth to occur, the polymeriza-
tor injection rates and produce hazier films due tion process must break down the catalyst par-
to the wider MMD. ticles into much smaller entities which remain
held together by the polymer formed, some-
times in the form of fibrils (Fig. 12). Electron
1.3.2. Coordination Catalysis microscopy has shown, for one type of sup-
ported catalyst at least, that the growth occurs
The three independent discoveries of low-pres- in the form of cylinders, in the growing end of
sure routes to linear polyethylene had one thing which a catalyst fragment is embedded[62]. This
in common: they used catalysts containing tran- type of growth explains why polymerization rate
sition metals. Despite their very different meth- does not decrease as the overall particle size in-
ods of preparation, there is general agreement creases, since the monomer diffusion path re-
that the basic mechanism of polymerization by mains short. The active catalyst fragments range
these catalysts is the same. At some stage a σ- in size from about 4 nm for TiCl3 to 100 nm for
bonded alkyl group is formed. Ethylene is co- oxide-supported catalysts.
ordinated to the transition metal by a π-bond. By suitable technology, catalysts can be pre-
This then facilitates the insertion of the ethylene pared so that replication leads to polymer parti-
molecule into the metal – alkyl bond producing cles with a spherical shape and a diameter of ca.
a longer chain alkyl and a vacant coordination 1 mm, suitable for direct use without a pelletiza-
site. tion step. Examples of this are the Phillips Par-
ticle Form and UCC’s Unipol processes based
on silica-supported catalysts, and the Montedi-
son Group’s Spheripol catalyst based on MgCl2 .
Outside the United States there is considerable
resistance by fabricators to the direct use of poly-
mer powder, and much of the product is pel-
letized.
Not being simple isolated molecules, the ac-
tive catalyst sites are not all identical and their
activities and the average chain lengths which
they produce vary. Instead of a simple statisti-
16 Polyolefins

Figure 12. Catalyst particle growth by replication [13]

cal distribution of molecular mass, which would initial reaction with ethylene the catalyst’s color
lead to a ratio of weight-average to number- changes from orange to blue. This is believed to
average molecular mass of 2.0, appreciably be due to the reduction to Cr2+ . The reduction
broader MMDs are obtained (Fig. 13). can also be brought about by treatment with car-
bon monoxide, and in this case the catalyst reacts
immediately with ethylene without an induction
period.

The selection and treatment of the support

is fundamental to the process, and a plant may
use catalysts made from a variety of supports
to produce the whole range of products. The
Figure 13. MMD curve of a Ziegler HDPE compared with
simple statistical theory optimum silica is claimed to have a high per-
a) Most probable distribution; b) Hostalen GD-4755 centage of pores with a pore diameter of 20 –
50 nm. A frequently used grade, Grace Davi-
son 952, combines the required pore character-
istics with a microspheroidal form. Where the
1.3.2.1. Phillips Catalysts spherical form is not necessary, other silicas are
also used, made from crushed and graded silica
A typical Phillips catalyst is produced by im- gel with the required pore structure. The sup-
pregnating silica particles with a solution of ports are normally supplied with the chromium
CrO3 to give a chromium content of ca. 1 %. already impregnated, leaving only the activation
The powder is then calcined in a current of air stage to be carried out at the polyethylene plant.
with increasing temperature to a final value of ca. As a means of increasing the catalyst produc-
800 ◦ C. At this temperature all of the physically tivity and facilitating the production of lower
absorbed water and most of the surface hydroxyl molecular mass (higher MFI) polymers, treat-
groups are driven off [63] and the chromium is ment with titanium compounds is frequently
present as surface chromate. The formation of a used [64]. The resulting polymers have MFIs
surface silyl chromate is significant, because at more suitable for many applications and also
the calcining temperature CrO3 would decom- have somewhat broader MMDs. Molecular mass
pose to lower valent oxides. This catalyst, which control is a problem with the Phillips process,
is now moisture sensitive, will polymerize eth- since it is not possible to use a chain-transfer
ylene, but with an induction period. During the
 Polyolefins 17

agent such as hydrogen, which is oxidized to hydroxyl groups on silica [16, 17, 71, 72]. Par-
water by the chromate groups and acts as a cata- icularly favored is dicyclopentadienyl chromi-
lyst poison. Molecular mass control is therefore um (chromacene). Unlike the Phillips catalyst
effected mainly by the choice and treatment of it is believed that the chromium is attached to
the support. The use of titanium compounds is the support by only one bond, with one bond
believed to result in the chromium atoms be- remaining to a cyclopentadienyl group. A very
ing bound to the support via titanate bonds [65]. useful feature of these catalysts is their sensi-
A further parameter available for modifying the tivity to hydrogen, which allows a wide range
surface characteristics is treatment with fluo- of molecular masses to be produced. The MMD
rine compounds which convert surface hydroxyl produced is fairly narrow, but not as narrow as
groups to fluoride and reduce the surface area. that from some of UCC’s Ziegler catalysts.
To some extent the effect is similar to high tem- Somewhat similar to the Phillips catalyst is
perature calcination [65, 66]. the Standard Oil (Indiana) catalyst which was
Catalyst productivities are of the order of 5 the first of the coordination catalysts to be disco-
kg PE per gram of catalyst [63] or higher, with vered [73]. It typically consists of MoO3 sup-
a corresponding chromium content of 2 ppm or ported on alumina or silica and calcined in air at
less. The percentage of chromium atoms which high temperature. Unlike the Phillips catalyst it
form active polymerization centers has been es- is necessary to reduce the precursor with hydro-
timated as 12 % [67]. With a number-average gen at elevated temperature before using in the
chain length of the order of 1000 monomer units, polymerization reactor. Despite extensive devel-
each chromium atom thus produces about 1000 opment it has not been widely commercialized.
molecules. The chains are terminated by a β-hy-
drogen shift reaction:
1.3.2.2. Ziegler Catalysts

The range of catalysts which function by the

Ziegler mechanism is extremely broad and it
would be impossible to cover all the variants
here. However, those catalysts which meet the
requirements of modern polyethylene processes
are more restricted in number and tend to follow
a common pattern. Some of the developments
forming an unsaturated molecule and an ethyl in Ziegler catalysts for polyethylene have arisen
ligand attached to the chromium atom [66]. out of developments for polypropylene (see Sec-
The primary form of molecular mass (and tion 2.1), but since ethylene has a higher reac-
hence MFI) control is by selection of a catalyst tivity and the extra parameter of stereoregular-
which favors the hydrogen shift reaction, but fine ity does not have to be dealt with, the require-
adjustments can be made by varying the reaction ments of the polyethylene catalysts have gener-
temperature, since a higher temperature favors ally been met more easily.
the shift reaction. Early Ziegler catalysts for ethylene were
There have been two developments of chro- based on β-TiCl3 , produced by reducing TiCl4
mium catalysts by UCC which fall conceptu- with AlEt2 Cl or Al2 Et3 Cl3 at low temperature.
ally in the field of Phillips catalysts. Carrick As cocatalyst, AlEt3 was used. The TiCl3 pro-
et al. reported that bis(triphenylsilyl) chromate, duced in this way contains 13 mole of cocrys-
which is closely related to the proposed active tallized AlCl3 . Although the catalyst productiv-
site of a Phillips catalyst, polymerizes ethylene ities were much higher than for propene, it was
at high pressure [69]. When supported on sil- necessary to extract the catalyst residues in or-
ica it forms a very active catalyst for low-pres- der to reduce the quantities of Ti and Cl in the
sure polymerization [70]. The second type of product to acceptable levels. Later, by the use
catalyst is formed by the reaction of chromium of longer chain aluminum alkyls as cocatalyst
compounds having π-bonded ligands with the and alkoxytitanium chlorides as transition metal
compound [74, 75], the catalyst productivity was
18 Polyolefins

improved sufficiently to allow the costly residue alyst preparation [78] or by prepolymerization
removal stages to be eliminated. treatment with a higher olefin [79].
Kinetic studies have shown [17, 67] that only The molecular mass of polyethylene is nor-
a small proportion of the titanium atoms in TiCl3 mally controlled by the use of hydrogen. With
catalysts form active centers (typically < 1 %). Ziegler catalysts at 70 – 100 ◦ C this can require
This is believed to be due to the fact that, even 20 mol % hydrogen in the gaseous phase of a
with the small polymerizing particles, only a slurry process or a gas-phase process. When
small fraction of the titanium atoms are at the other olefins are copolymerized with ethylene
crystallite surface. In order to make a higher pro- the concentration of hydrogen required is lower,
portion of the titanium atoms available to form due to chain transfer to the comonomer. At
active centers, various developments were made the high temperatures employed in the high-
to support the transition metal compound on a pressure process, the hydrogen concentrations
carrier. Early attempts to support TiCl4 directly used are much lower due to a relative acceler-
onto silica, alumina, or magnesia did not lead to a ation of the rate of chain transfer to hydrogen
sufficient increase in productivity [74]. The first and also a greater proportion of chain trans-
useful high-yield catalyst used Mg(OH)Cl as fer by the β-shift reaction. Chain transfer to
support [76]. Since then a variety of magnesium monomer or comonomer by the β-shift reaction
compounds have been used successfully as sup- results in unsaturation, primarily in the form of
ports [17, 74], but preeminent amongst these is vinyl groups, but hydrogen chain transfer forms
MgCl2 or reaction mixtures which can produce methyl-terminated chains.
this compound, at least on the support surface.
Most modern Ziegler processes seem to use cat-
alysts which fall into this category. The massive 1.3.2.3. Single-Site Catalysts (Metallocenes)
increase in activity of MgCl2 supported cata-
lysts has been claimed to be due to an increase in Typical Phillips or Ziegler catalysts do not fol-
the percentage of titanium atoms forming active low classical polymerization kinetics and the re-
centers (approaching 100 %) and not to a signif- sulting MMDs are substantially broader than the
icant increase in reaction rate at the active center simple statistical case (see Section 1.3.2). For
[16,67]. The MgCl2 supported catalysts produce homopolymers this is probably an advantage and
polyethylenes with narrower MMDs than unsup- gives rise to the good processing characteristics
ported catalysts [16] and a narrower distribution of HDPE. In the case of copolymers this type
of composition in the case of LLDPEs. As with of kinetic behavior leads to a broad distribu-
polypropylene, electron donors such as esters or tion of composition, in which some chains have
THF may be employed to modify the character- low comonomer concentrations and others high
istics of the MgCl2 based catalysts [16], but are concentrations. For LLDPE there are advantages
not invariably used in the case of polyethylene. such as higher stiffness than LDPE of the same
For some processes, particularly the density, but disadvantages of higher extractable
fluidized-bed and loop reactors, the catalyst fractions and stickiness in the lower density ver-
shape and size is very important, and proce- sions. A catalyst which could produce a narrow
dures such as ball-milling and chemical reaction composition distribution would overcome these
used to produce the basic catalysts do not lead disadvantages, and at the same time less of the
to particle sizes and shapes suitable for direct expensive comonomer would be required for a
use. Further processing is required to produce a given density reduction.
defined particle size range. Spray-drying can be Catalysts which behave in a uniform man-
used to produce spherical paricles. UCC have ner to produce simple statistical distributions
filed patents on the use of the microspheroidal of molecular mass and composition have been
silicas used in the Phillips process for support- known for many years, but they are low-yield
ing MgCl2 – TiCl4 systems for their gas-phase systems and have not been commercialized for
process [77]. For solution processes, as small polyethylene [80]. Such catalysts, made from
a particle size as possible is desirable, and this vanadium oxide trichloride [80] and bis(cy-
may be achieved either by the method of cat- clopentadienyl)titanium dichloride [81], remain
soluble in the presence of the cocatalyst.
 Polyolefins 19

In 1983 Kaminsky described a catalyst a transition metal cation associated with an alu-
which combined ideal MMD and composition minoxane counteranion [19, 20]. Some investi-
distribution with high yield [82, 83]. A basic gators believe that the function of the MAO is
form of the catalyst was bis(cyclopentadienyl)- to act as a source of free trimethylaluminum and
dimethylzirconium with a massive excess of also to act as a receptor of the anion produced by
methyl aluminoxane (CH3 – Al – O)n as cocata- the reaction between the catalyst and cocatalyst
lyst. Al/Zr ratios as high as 10 000 or more are [86, 87]. Polymerization proceeds more rapidly
typically employed. Since then there has been in aromatic solvents and even more rapidly in
intensive development in academia and indus- chlorinated aromatic solvents, and this supports
try with the objectives of improving the thermal the view that a higher dielectric constant aids
stability of such catalysts, reducing the concen- the formation of an optimal ion pair [87] (see
tration of cocatalyst, and, above all, making sup- bottom of page).
ported versions. Both metallocene dichlorides and dimethyl
Because the original catalysts were bis(cy- forms of the catalysts are frequently described,
clopentadienyl) transition metal compounds, but MAO transforms the former into methyl-
known as metallocenes, there is a tendency to substituted species. Chemical changes have
refer to these as “metallocene catalysts”, but been generally directed to modifying the stereo-
a more general term is “single-site catalysts”. chemical environment of the active center and
Given that metallocenes had previously been in- include changes such as replacing the cyclo-
vestigated as catalysts with conventional alky- pentadienyl groups with indenyl or fluorenyl,
laluminum compounds as cocatalysts [84], it alkyl substitution of the cyclopentadienyl rings,
could be said that the key discovery was the use and linking two indenyl units to form a more
of methyl aluminoxane (MAO) as cocatalyst. rigid cage. Alkyl substituents can have a major
The latter is made by controlled hydrolysis of effect on the catalyst activity [88]. Single-site
trimethylaluminum and has a rather ill-defined catalysts have also been made which have only
structure. To avoid too rapid a reaction leading one cyclopentadienyl ligand [89]. Some general
to aluminum hydroxide and unreacted trimethyl, forms of single-site catalysts include:
Sinn et al. initially used the water of crystalliza-
tion of materials such as copper(II) sulfate pen-
tahydrate as the source of water [85]. Later de-
velopments have led to physical methods for the
controlled hydrolysis and the material is com-
mercially available.
Since the transition metal components of the
catalysts are stable entities with well-defined
structures, investigators have been able to make
systematic changes to the structure and achieve
the sort of control over the polymerization pro- The active sites are tetrahedrally coordinated,
cess which had been hoped for in the early days in contrast to heterogeneous Ziegler catalysts
of Ziegler catalysis. Principal achievements in- which are octahedrally coordinated in a TiCl3
clude stereospecific polymerization (see Chap- or MgCl2 crystal lattice. In principle the greater
ter 2), higher reactivity towards other olefins and openness of the tetrahedral configuration allows
also towards other monomers not industrially more ready access to bulkier monomers than
polymerizable by Ziegler catalysis. It is gener- the octahedral structure, but the ligands them-
ally accepted that the active catalytic species is selves are generally rather large. The improved
20 Polyolefins

incorporation of monomers larger than ethylene locene catalysts tend to be thermally labile and
is generally only achieved by bridged systems, decompose to inactive species [87].
in which the opening angle can be greater than Industrially, the fact that the original met-
the 109◦ of a regular tetrahedron. Dow refer to allocene catalysts were soluble meant that the
their catalysts as “constrained geometry” cata- immediate applications were in solution pro-
lysts and specify that they reduce the bond angles cesses. Exxon took the view that the catalysts
of the coordinated ligands to less than 109◦ , so were short-lived and expensive and developed
that a greater solid angle is available for the entry a high-pressure process to give a high catalyst
of monomers to the free coordination site [90]. yield [94, 95]. Product targets were VLDPEs
Developments in cocatalysts have been di- with a lower content of extractables and less
rected to reducing the ratio of cocatalyst to tran- tackiness. Dow, which operates a solution pro-
sition metal and developing better defined chem- cess for HDPE and LLDPE, has developed high-
ical entities as cocatalysts. Montell have shown temperature catalysts for producing a range of
that highly active aluminoxanes can be formed homopolymers and copolymers. They claim im-
from trialkylaluminum compounds other than proved processability for these products due to
the methyl derivative, and that in some cases incorporation of long branches by copolymer-
they are even more active than MAO [91]. ization of vinyl end groups of polymer chains
When made from higher molar mass aluminum formed by β-scission [90]. The solution pro-
alkyls, well-defined cocatalyst compounds such cess favors end-group polymerization because
as tetraalkyldialuminoxanes can be isolated. the high temperature leads to formation of a
high proportion of chain ends by β-scission; the
polymer to monomer concentration ratio is high;
and the catalyst is chosen to readily incorporate
higher molecular mass olefin monomers. Other
routes to improve the processability of the prod-
uct include the use of mixed catalysts with dif-
The large excess of MAO found to be neces- ferent molar mass dependence on hydrogen con-
sary to obtain optimum activity in many studies centration or temperature [96, 97].
on metallocene catalysts may be due in part to For use in fluidized bed or slurry phase reac-
moderately high molar concentration of the co- tors, a supported catalyst is required. This has
catalyst needed to generate the active centers. been achieved by many companies by treating a
When catalyst and cocatalyst are precontacted silica having the required particle size with MAO
at high concentrations and then diluted for poly- and then with the metallocene catalyst. The char-
merization, Al/Zr ratios as low as 20 can be ef- acteristics of narrow MMD etc. are maintained.
fective [92]. Apart from aluminum-based cocat- In 1996 most major manufacturers are devel-
alysts, boron compounds have been used and al- oping single-site catalyzed PEs, but the amount
low much lower cocatalyst/catalyst molar ratios actually being sold is a very small fraction of PE
to be achieved [93] (see top of page). sales. However, the catalysts can be used in all
The general aspects of ethylene polymeriza- the major PE processes now using Phillips and
tion with metallocene catalysts are similar to Ziegler catalysts, and a changeover to single-site
those of Ziegler catalysis: molecular mass con- catalysts could occur comparatively quickly, de-
trol can be effected by chain transfer to hydro- pending on the advantages and disadvantages the
gen; at higher temperatures chain transfer by the new products present to plastics fabricators and
β-shift reaction produces vinyl groups; metal- end-users.
 Polyolefins 21

1.3.2.4. Copolymerization America was originally ethane, with naphtha be-

ing used more commonly in Europe. The ten-
Copolymerization of ethylene and α-olefins is dency now is for crackers to be designed to ac-
the basis of the large and expanding LLDPE mar- cept a wider range of feedstocks, so as to match
ket. As with the free radical case the important the range of coproducts such as propene to the
factors in addition to those of homopolymeriza- market requirements.
tion are the relative reactivities and chain trans- Modern plants produce ethylene with a qual-
fer. Both Phillips and Ziegler catalysts copoly- ity which in many cases is suitable for polymer-
merize olefins, but the latter are more widely ization with little or no further purification. In
used because they can be more readily tailored North America and Europe, producers supply
to produce narrow distributions of composition ethylene to an agreed specification via a com-
and molecular mass. As has been noted in Sec- mon ethylene grid, and polymerization plants
tion 1.3.2, polymerizations with typical coordi- take their supplies from these pipelines. In the
nation catalysts do not follow classical polymer- case of sensitive catalyst systems such as the
ization kinetics and hence the reactivity ratio Phillips catalyst some further purification may
concept is not strictly applicable. For completely be necessary to ensure that maximum impurity
soluble polymerization systems r 1 is very high levels are not exceeded. Table 8 lists specifica-
and increases with the comonomer chain length tions for a polymerization-grade ethylene suit-
(e.g., 29 for butene and 73 for octene, calculated able for most processes. There are overall lim-
from data in [41]). However, in the case of het- its on inert materials such as ethane or nitrogen
erogeneous catalysts and heterogeneous poly- which, because of the efficient recycle system,
merization systems, in particular, the apparent could build up and dilute the process stream.
reactivity ratios are lower and may even decrease The main impurities of importance to the free-
with increasing olefin chain length. This is pre- radical process are oxygen and water. The for-
sumably due to mass transfer and solubility ef- mer could cause inhibition of low-temperature
fects in the growing particles. Chain transfer is initiators, or uncontrolled initiation of reaction
enhanced in the presence of olefin comonomer, at higher temperatures. At moderate concentra-
but this can be compensated by lowering the hy- tions (after concentration by the recycle) water
drogen concentration. can form ethylene hydrate [98] in the cooler parts
Literature articles have appeared on the co- of the high-pressure process, completely block-
polymerization of ethylene with monomers such ing the pipework. Some of the other specified
as styrene, butadiene, vinyl chloride, esters, and compounds can produce problems of molecu-
others but these have involved Ziegler catalyst lar mass control or inhibition in the free-radical
variants with poor yields. For practical pur- process, but only at very much higher concen-
poses the range of comonomers polymerizable trations.
by Ziegler catalysis is at present limited to Table 8. Specifications for polymerization-grade ethylene ∗
olefins and nonconjugated diolefins. The advent
of single-site catalysts with high intrinsic activ- C2 H 4 > 99.9 vol %
ity is removing some of these limitations. CH4 , C2 H6 , N2 < 1000 vol ppm
Olefins + diolefins < 10 vol ppm
Acetylene < 2 vol ppm
H2 < 5 vol ppm
1.4. Raw Materials CO < 1 vol ppm
CO2 < 1 vol ppm
O2 < 5 vol ppm
1.4.1. Ethylene Alcohols (as MeOH) < 1 vol ppm
H2 O < 2.5 vol ppm
Sulfur < 1 vol ppm
The first polyethylene plant built by ICI used Carbonyl sulfide < 1 vol ppm
ethylene produced by dehydration of ethanol.
Modern ethylene production plants are based on ∗ Data obtained from Repsol.

the thermal cracking of hydrocarbon feedstocks In the case of the Phillips and Ziegler pro-
at ca. 850 ◦ C. Due to the availability of raw mate- cesses, the materials included in the specifica-
rials, the feedstock used predominantly in North
22 Polyolefins

tion act as catalyst poisons. Hydrogen is a poison products. High-pressure processes can produce
only for the Phillips catalyst. LLDPE in addition to the normal range of LD-
PEs and ester copolymers. As well as HDPE
some low-pressure plants can also produce
1.4.2. Comonomers LLDPE and VLDPE, and in many cases these
The vinyl acetate and acrylate esters used as compete for the same market as LDPE and the
comonomers in the free-radical process are nor- ester copolymers. A guide to the applicability of
mal commercial quality materials containing the various types of processes is given in Table 9.
sufficient stabilizer to prevent homopolymeriza- Table 10 compares the capital and operating
tion in storage or during pumping, but not so costs for various types of polyethylene plant.
much as to affect the copolymerization reaction. The comparison is on the basis of construction
They must be freed of dissolved oxygen by ni- on a United States Gulf Coast site using the
trogen sparging. largest stream size currently (1996) available for
The butene used in LLDPE is normally a pu- licensing. The costings assume the production of
rified refinery product, although in the United pellets and this results in higher costs for the gas-
States material is available from the oligomer- phase and slurry plants than would be the case
ization of ethylene. As an alternative to buying if 100 % sales of ex-reactor granules could be
butene with its associated transport problems, assumed. Some differences due to the economy
IFP have developed the Alphabutol process [99, of scale occur as a result of the available stream
100] for dimerizing ethylene as a compact ad- size. The production costs are dominated by the
junct to a polymerization plant. There is also cost of ethylene, although some differences such
the possibility of using a polymerization catalyst as the extra cost of electrical energy can be noted.
capable of simultaneously dimerizing ethylene In the case of LLDPE these costings assume a
[101, 102]. unit cost for the butene equal to 1.05 times that
The higher α-olefins such as hexene and of ethylene. In many other parts of the world the
octene used in LLDPE processes are ethylene price of butene, including transport, is consider-
oligomerization products. They must be freed of ably higher. The unit price of higher olefins is
oxygen and water before use in the polymeriza- generally appreciably higher than that of ethyl-
tion process. The 4-methylpentene used by BP ene, from which they are derived by oligomer-
is a propylene dimer made by an alkali metal ization.
catalyzed process.
1.5.1. High-Pressure Process
1.4.3. Other Materials
A flowsheet of the high-pressure polyethylene
The initiators and catalysts are described in Sec- process is shown in Figure 14. The reactor may
tion 1.3.1. All the free radical initiators and many take one of two forms: a high-pressure auto-
of the Ziegler and Phillips catalysts are manufac- clave or a jacketted tube, but otherwise the pro-
tured by specialist suppliers. Some of the sim- cesses are similar. The reaction pressure is typ-
pler Ziegler catalysts may be made on-site from ically in the range 150 – 200 MPa for the auto-
basic chemicals such as TiCl4 , MgCl2 , etc. The clave process and 200 – 350 MPa for a tubular
aluminum alkyls are made by a very few inter- reactor. Such high pressures call for very spe-
national suppliers. cialized technology and many key features have
Initiator solvents and compressor lubricants remained proprietary information. The design of
for the free-radical process are carefully selected thick-walled cylinders requires a different type
to be free of aromatic compounds, since much of analysis [103, 104] from that for lower pres-
of the product may be used for food packaging. sure vessels, and fatigue is a major design con-
sideration for pumps and compressors. A draw-
1.5. Production Processes ing of the second stage cylinder of a high-pres-
sure ethylene compressor is shown in Figure 15,
Modern polyethylene production processes of-
fer the possibility of a versatile range of
 Polyolefins 23
Table 9. The technical applicability of processes for polyethylene manufacture ∗

High-pressure High-pressure tubular Gas-phase fluidized Slurry phase Solution

autoclave bed autoclave/loop autoclave

Installed capacity ∗∗ 8.8 8.3 12.8 12.5 3.2

worldwide, 106 t/a
LDPE + + − − −
EVA copolymers + + − − −
Acrylate copolymers + + − − −
HDPE − + + +
0
HMW HDPE − − + + −
UHMPE − − + −
0
LLDPE + + +
0 0
VLDPE + + − +
0

∗ + = suitable; 0 = technically feasible with some limitations; − = unsuitable or not possible. ∗∗ Capacity data (1995) obtained from
Chem Systems, London.

Table 10. Production costs for polyethylene processes in $/t (1996 U.S. Gulf Coast prices) ∗

Product LDPE LLDPE HDPE

Process Autoclave Tubular Fluid bed Solution Fluid bed Ziegler Phillips

Capacity, 103 t/a 117 200 225 200 200 200 200
Capital cost, 106 $ 85 116 98 138 90 135 105
Monomer costs 447 443 450 ∗∗ 452 ∗∗ 449 456 445
Catalysts, chemicals 20 18 29 31 26 22 20
Electricity 31 33 15 9 15 16 16
Other utilities 5 2 5 17 5 10 11
Manpower 10 6 6 6 6 6 6
Maintenance 15 13 9 15 9 15 13
Overheads 35 29 22 31 22 26 29
Production costs 565 544 534 561 553 553 539
Depreciation 71 59 44 69 45 68 53
Total costs 636 603 578 630 577 620 592

∗ Data from Chem Systems, London. ∗∗ Includes cost of butene monomer at a unit price equal to1.05 times that of ethylene; other
locations or the use of other olefin comonomers could lead to a higher monomer cost.

which illustrates the massive construction nec- duce the polymer temperature to a value suit-
essary and the avoidance of cross-bores to im- able for feeding the pelletizing extruder. The
prove fatigue resistance at the very highest pres- polyethylene is separated from the majority of
sures. Specialized forms of sealing joints in ves- the unreacted monomer in the intermediate sep-
sels and pipework have been developed which arator at ca. 27 MPa. This pressure is chosen
make use of the pressure itself to increase the to give a compromise between separation effi-
sealing forces [105]. ciency and compression energy savings. The re-
Referring to Figure 14, the fresh ethylene en- maining monomer is removed in the low-pres-
ters from the refinery at ca. 5 MPa, mixes with sure separator that feeds the pelletizing extruder.
the low-pressure recycle and is compressed to The extrudate is pelletized underwater by a die-
25 MPa. After mixing with the intermediate- face cutter, and the pellets are then dried and
pressure recycle, the pressure is raised in the sec- conveyed to temporary storage hoppers to await
ondary (or hyper) compressor to 150 – 350 MPa quality control clearance. Finally the pellets are
for feeding to the reactor. The pressure in the transferred to silos for blending and storage, be-
reactor is controlled automatically by a flow fore off-loading to tankers or sacks.
control valve at the reactor outlet. The reac-
tion mixture then passes through a cooler to re-
24 Polyolefins

Figure 14. High-pressure autoclave process

a) Ethylene stock tank (5 MPa); b) Primary compressor; c) Secondary compressor (200 MPa); d) Autoclave reactor; e) Ini-
tiator pumps; f) Product cooler; g) Separator (25 MPa); h) Recycle cooler; i) Low-pressure separator and melt extruder;
j) Low-pressure stock tank (0.2 MPa); k) Booster compressor

Figure 15. Second stage cylinder of a Nuovo Pignone compressor with 350 MPa maximum output pressure
a) Piston; b) Packings; c) Lubricant injection to packings; d) Valves

1.5.1.1. Autoclave Reactor mounted directly into the reactor walls to pro-
vide unrestricted passage for the reactor contents
A typical autoclave design is shown in Figure 16. in the event of a pressure rise due to a decompo-
The autoclave volume is chosen to give an over- sition.
all residence time of ca. 30 – 60 s, with corre- The autoclave functions as an adiabatic con-
sponding volumes in larger plants of ≥ 1 m3 . A tinuous stirred-tank reactor (CSTR), with the
novel feature is the internal stirrer motor. The heat of reaction being removed by the fresh
Du Pont process uses an external motor. The ethylene entering the reactor. The conversion
elongated cylindrical form arises partly from of monomer to polymer is thus related to the
the fabrication constraints of making a thick- difference in temperature between the feed gas
walled forging, and partly from the requirements and the final reaction temperature. For practical
of the process for multiple zones. Cross-bores purposes percentage conversion = 0.075×∆T .
are provided along the length of the reactor for Most modern reactors have two or more zones
thermocouples, and monomer and initiator en- with increasing temperatures. The reaction tem-
tries. Bursting disks or other relief devices are
 Polyolefins 25

peratures are maintained constant by controlling ing arranged as a series of straight sections con-
the speeds of the pumps feeding initiators into nected by 180◦ bends. Inner diameters of 25 –
the respective zones. The first zone is typically 75 mm have been quoted, but 60 mm or some-
180 ◦ C and the final zone 290 ◦ C. For adequate what larger is probably typical of modern tubu-
control the initiators must have decomposition lar reactors. A ratio of outer to inner diame-
half-lifes of ca. 1 s under the reaction conditions ters of about 2.5 is used to provide the neces-
in the zone. Table 6 lists a range of commercial sary strength for the high pressures involved. At
initiators used in both the autoclave and tubular many of the pipe junctions thermocouples are in-
processes. troduced to follow the course of the reaction, and
initiator and gas inlets or pressure relief devices
may also be incorporated. Unlike the autoclave
process, no after-cooler is required for the sec-
ondary compressor, but the first section of the
tubular reactor must function as a preheater to
raise the ethylene to a sufficiently high temper-
ature for the reaction to start. This temperature
depends on the initiator employed, ranging from
190 ◦ C for oxygen to 140 ◦ C for a peroxydicar-
bonate. The latter part of the reactor functions as
a product cooler similar to that of the autoclave
process.
A tubular reactor works in the plug flow
regime with heat transfer to the jacket. Plug flow
is achieved by the correct choice of pipe diam-
eter relative to the flow rate [106] so as to give
sufficient turbulence and good axial mixing. Al-
though heat is transferred through the reactor
wall, it is not generally possible to maintain
isothermal conditions, and temperature peaks
occur. Because of the temperature peaks, which
may not occur at exactly constant position in
the tube, automatic temperature control must be
more sophisticated than in the autoclave process;
i.e., it must be possible to calculate average tem-
peratures for appropriate regions of the reactor.
When oxygen is used as initiator, the tempera-
ture control acts on the rate of addition of oxygen
in the lower pressure part of the system. When
peroxide initiators are used, the speeds of the
high-pressure pumps are controlled. Oxygen is
still widely used in the tubular reactor process,
either alone or in conjunction with peroxides.
Because of its complex initiation mechanism,
Figure 16. High-pressure autoclave reactor oxygen tends to give more gentle temperature
a) Stirrer motor; b) Stirrer shaft; c) Bursting disk ports peaks with less tendency for decomposition. In
the case of reactors with multiple initiator in-
jection, liquid initiators offer more flexibility,
since they can be injected at points where there
1.5.1.2. Tubular Reactor is no fresh ethylene injection (which would be
required to carry in oxygen as initiator). Injec-
A tubular reactor typically consists of several tion of initiator at various positions along the
hundred meters of jacketted high-pressure tub- tube produces new temperature peaks, increas-
26 Polyolefins

ing the overall conversion. By using these tech- 1.5.1.4. Linear Low-Density Polyethylene
niques higher conversions than in the autoclave (LLDPE)
reactor can be achieved, but at a higher cost in
compression energy. Although conversions of CdF Chimie converted high-pressure pro-
up to 35 % (compared with 20 % for the auto- cess equipment to use Ziegler catalysts to
clave) have been claimed, the maximum useful make HDPE. These plants were later used to
conversion depends on the product quality re- copolymerize ethylene with butene and other
quired, since quality deteriorates markedly with comonomers to make LLDPE. The catalysts
increasing conversion. used are generally of the Ziegler type but have
been specially developed for the high temper-
atures of the high-pressure process [107]. Sev-
1.5.1.3. High-Pressure Copolymers eral other manufacturers have modified existing
high-pressure plants to enable them to make a
The high-pressure processes described are also rapid, but limited entry into the LLDPE mar-
suitable for the copolymerization of monomers ket, but this route is not seen as suitable for a
such as vinyl acetate or acrylic esters. The auto- large new investment. The required modifica-
clave process is generally preferred for its well- tions (generally similar to those for free-radical
defined operating conditions and its ability to co-polymers together with some additional ones
produce a useful conversion at a low maximum associated with the different type of catalyst) are
temperature. In the case of vinyl acetate the reac- as follows:
tivities of the two monomers are virtually iden-
tical and so they are consumed at the same rate. 1) Purification columns to remove polar impuri-
This means that the reacting monomer mixture ties from the ethylene and olefin comonomer.
and the copolymer produced maintain a constant 2) Hydrogen injection for MFI control.
composition even in multizoned reactors, but the 3) Compressor modifications to take account of
recycle system must handle high concentrations the lower compressibility and poorer lubri-
of vinyl acetate. The converse is the case for the cating properties of the monomer mixture
acrylate esters. If a multizoned or a tubular reac- [108]. The concentrations of butene or other
tor is used the composition varies in the different olefin of ca. 50 % are much higher than in the
zones, but the recycle is nearly pure ethylene. free-radical copolymer case.
The principal modifications to a high-pressure 4) Catalyst handling equipment to produce
polyethylene plant to enable it to manufacture pumpable dispersions, and to maintain the
copolymers are: catalyst under a nitrogen atmosphere.
5) A system for injecting a catalyst deactiva-
1) Installation of liquid pumps, which usually tor such as a suspension of calcium stearate
pump the comonomer into the suction of the [109], after the reactor and before the sepa-
secondary compressor rator.
2) In the case of vinyl acetate, it is necessary 6) Usually some modifications to the pelletizing
to collect the monomer which condenses in extruder to take account of the higher torque
the low-pressure recycle system and purify it generated by LLDPE.
before returning it to the liquid pump
3) The system for removing final traces of
monomer must be improved, because the
comonomers are more soluble than ethylene 1.5.2. Suspension (Slurry) Process
and they have more offensive odors
The formation of polyethylene suspended in a
Technically a copolymer plant could also hydrocarbon diluent was envisaged as a conve-
copolymerize acrylic or methacrylic acid, but nient form of production process from the ear-
there are long-term corrosion problems. Major liest patenting by Ziegler [110]. This was re-
producers of these copolymers have constructed inforced by the fact that, for a given pressure,
plants especially for their manufacture, using most Ziegler catalysts give their highest yields
corrosion-resistant steels.
 Polyolefins 27

at temperatures at which polyethylene is insolu- ported single-site catalysts, the limit is reduced
ble. The Phillips process on the other hand origi- to around 920 kg/m3 .
nated in the laboratory as a solution process that
uses a fixed bed of catalyst [111] and was com-
mercialized in 1956 as a solution process using 1.5.2.1. Autoclave Process
a powdered catalyst which had to be removed
by filtration. Laboratory developments led to the Figure 17 shows a flowsheet for a suspension
discovery of high-activity catalysts which frag- (slurry) process based on various descriptions of
ment at temperatures below 105 ◦ C to enable the Hoechst process [8, 74, 112, 113]. The pres-
the low concentration of finely divided catalyst sure employed is between 0.5 and 1.0 MPa, al-
residues to be left in the product. Since 1961 all lowing the use of large reactors (ca. 100 m3 ). The
Phillips plants have been of this type using novel reaction temperature is 80 – 90 ◦ C. The diluent
process technology to implement their Particle is a low-boiling hydrocarbon such as hexane.
Form suspension process. The catalyst compounds and aluminum alkyl
Many companies have built plants to make are slurried with diluent in the catalyst mixing
polyethylene by using Ziegler catalysts, but be- vessel before being fed to the reactor at a rate
cause the license was only for the use of the cat- sufficient to maintain the required polymeriza-
alyst, there has been a diversity of process de- tion rate. Only one main reactor is shown but, at
signs, even amongst the suspension processes. least in the case of bimodal MMD high molec-
The Phillips process was licensed as a package ular mass polymers [114], two or more reactors
and the plants themselves tended to be very simi- in cascade may be used. The reaction mixture is
lar. More recently the picture has become blurred then passed to a run-down reactor where the dis-
as chromium-based catalysts have been used in solved ethylene is consumed almost completely,
fluidized-bed reactors and Ziegler catalysts are avoiding the need for an ethylene recycle. The
being employed in loop reactors. Early Ziegler slurry concentration is an important parameter in
plants included a catalyst residue removal stage the process. A high concentration allows higher
which added considerably to the complexity and outputs from a given reactor volume, but the
cost. Since the late 1960s it has been possible to heat transfer to the cooling jacket is worse and
eliminate this step. Other variations arise from stirring becomes more difficult. The maximum
the selection of the diluent. A high-boiling dilu- usable slurry concentration depends on a num-
ent generally requires more energy to remove ber of factors, including solvent type, particle
the final traces from the polymer, and stripping size and shape, but principally on the bulk den-
with steam is frequently employed. Because of sity of the polymer particles. Slurry concentra-
the low flash point, the use of a low-boiling dilu- tions vary from 15 to 45 wt % [115], with many
ent such as hexane requires more care in the de- patents reporting values in the range 30 –35 %
sign and operation of the plant, but this seems to in a heavy diluent.
be the preferred route for modern plants. The slurry from the run-down reactor then
The suspension process has been used ex- passes to a centrifuge to remove the bulk of the
tensively for the production of HDPE, and in diluent, which is recycled directly to the reac-
many cases these polymers incorporate a small tor. This diluent contains aluminum alkyl and
amount of comonomer to increase the tough- comonomer, if used, and the injection rates of
ness or resistance to stress cracking. The use these raw materials are adjusted to take into ac-
of higher concentrations of comonomer to pro- count the amounts reintroduced by the diluent
duce LLDPE presents problems however, as a recycle. The polymer is dried in a continuous
significant fraction of the product dissolves in fluidized-bed drier in a stream of hot nitrogen
the diluent. Because of the poorer solvent prop- to remove residual diluent. Further quantities
erties of isobutane, the Phillips process is best of diluent are condensed from the circulating
suited to making lower density materials. With nitrogen stream and recycled. Before extrusion
the original Phillips catalysts the lower density into pellets, stabilizers are added to neutralize
limit was considered to be about 930 kg/m3 , the catalyst residues, and other additives such as
but with more recent catalysts, particularly sup- antioxidants may be added at this point.
28 Polyolefins

Figure 17. Hoechst suspension polymerization process

a) Catalyst preparation vessel; b) Polymerization reactor; c) Run-down reactor; d) Centrifuge; e) Fluidized-bed drier; f) Diluent
condenser; g) Nitrogen circulator; h) Powder-fed extruder

The powder-fed extruder has a longer bar- the reactor with diluent from the metering device
rel than is the case for the high-pressure pro- at the base of the catalyst slurry tank. The poly-
cess because in addition to generating sufficient mer is taken off from a sedimentation leg which
pressure for the pelletizing head, it must also enables the slurry to be passed to the flash tank at
melt the polymer powder. Although a single long a concentration of 55 – 65 % instead of the 30 –
barreled extruder is shown, new installations in- 35 % circulating in the loop reactor [111]. The
creasingly make use of a combination of a short isobutane diluent evaporates in the flash tank and
extruder to melt the polymer followed by a gear is then condensed and recycled. Residual isobu-
pump to generate the pelletizing pressure. This tane is removed in a nitrogen-flushed conveyor.
combination has a lower energy requirement. Pelletization is carried out in a powder-fed ex-
truder in a similar way to the Hoechst process.

1.5.2.2. Loop Reactor Process

A simplified flowsheet for the Phillips Particle 1.5.3. Gas-Phase Process

Form process is shown in Figure 18. The novel
double loop reactor constructed from wide-bore Fluidized-bed processes for the production of
jacketted pipe was developed by Phillips engi- HDPE were developed in the late 1960s by
neers to avoid deposits, which had been trou- Union Carbide and somewhat later by Nafta-
blesome in a stirred autoclave [111, 116]. It also chemie (now BP). Although an innovative tech-
has a high surface-to-volume ratio, facilitating nology, the process did not offer clear economic
heat removal and allowing short residence times. advantages over the established slurry processes
The impeller forces the reaction mixture through (see Table 10). A rapid increase in the build-
the pipework in a turbulent regime with a ve- ing of fluidized-bed plants followed Union Car-
locity of 5 – 10 m/s. The reaction conditions of bide’s announcement of their Unipol process for
100 ◦ C and 3 – 4 MPa correspond to the needs LLDPE in 1977. In this case the fluidized-bed
of the chromium-based Phillips catalyst and the process is competing with solution and high-
required productivity. The diluent used is isobu- pressure processes compared to which it has
tane which facilitates the subsequent flash sep- lower capital and operating costs, particularly if
aration and, being a poor solvent for polyethyl- it can be assumed that customers are able to use
ene, permits higher operating temperatures than ex-reactor granules directly (not assumed in Ta-
the higher alkanes. The catalyst is flushed into ble 10). Many fluidized-bed units have been built
 Polyolefins 29

Figure 18. Flowsheet of the Phillips Particle Form process

a) Catalyst hopper and feed valve; b) Double loop reactor; c) Flash tank; d) Purge drier; e) Powder-fed extruder; f) Impeller;
g) Sedimentation leg

as dual-purpose plants (“swing plants”) with the density of the product being made, and the pres-
ability to produce either LLDPE or HDPE ac- sure is in the range of 0.7 – 2.0 MPa. Originally,
cording to demand. The fluidized-bed process lower pressures were used for butene and hexene
can produce a very wide range of MFIs and to avoid condensation in the recycle cooler, but
densities since it is free of the viscosity con- it is now claimed that condensation can be used
straints of the solution process and the solubil- to increase the output since the heat of vaporiza-
ity constraints of the slurry process. Ranges of tion of the liquid olefin absorbs more heat from
< 0.01 to > 100 in MFI and densities from 890 to the polymerizing particles [120]. The conversion
970 kg/m3 have been claimed [117, 118]. Origi- per pass is ca. 2 % for HDPE, but higher when
nally the process used butene as the comonomer using an olefin comonomer in the condensing
for LLDPEs, but later hexene was introduced mode. The positioning of the catalyst feed point
for high-performance copolymers. BP uses 4- and the polymer offtake is important to minimize
methylpentene for its high-performance LLD- the loss of catalyst particles, which results in low
PEs. conversion. A cyclone and/or filter prevent fine
Figure 19 shows a flowsheet for the Union particles reaching the recycle cooler and com-
Carbide fluidized-bed process [119]. The reactor pressor. The polymer is removed via a sequenced
has a characteristic shape with a cylindrical reac- valve to a powder cyclone, from which residual
tion section, and an expanded section in which monomers are recovered and recompressed. The
the gas velocity is reduced to allow entrained main recycle compressor circulates gas at a high
particles to fall back into the bed. The bed di- flow rate, but with a small pressure rise. Since
ameter is ca. 4 m with a working height of 10 m the process operates close to the melting point
and an overall height of the reaction unit of ca. of the polymer, accurate temperature control is
30 m. The gas enters the reactor through a dis- necessary by regulating the rate of catalyst ad-
tributor plate which provides an even distribu- dition. If a runaway reaction is detected, a gas
tion of gas and must also prevent powder falling such as carbon dioxide can be injected to poison
through when the gas flow is stopped. The flu- the catalyst.
idized bed functions more or less as a continuous The selection of the catalyst is critical for
stirred-tank reactor in which mass transfer pro- the success of the process. The catalyst particle
vides back mixing of material and heat through- grows by a process of replication to about 15 –
out the reactor. There is a predominant upflow at 20 times its initial size. Not only does this af-
the center and downflow at the walls. Reaction fect the fluidization characteristics, but the poly-
temperature is 80 – 100 ◦ C, depending on the merization rate and heat transfer must be con-
30 Polyolefins

Figure 19. Fluidized-bed process

a) Catalyst hopper and feed valve; b) Fluidized-bed reactor; c) Cyclone; d) Filter; e) Polymer take-off system; f) Product
recovery cyclone; g) Monomer recovery compressor; h) Purge hopper; i) Recycle compressor; j) Recycle gas cooler

trolled to prevent fusion of the particles or a Pont process has a catalyst residue removal stage
thermal runaway reaction. Catalysts based on and for this reason is probably not the most eco-
microspheroidal silica or MgCl2 with a mean nomic solution process.
particle size of about 50 µm are claimed to be Figure 20 shows a flowsheet of the Sclairtech
particularly suitable [77]. process of Du Pont of Canada [121]. The ethyl-
ene is dissolved in a diluent such as cyclohexane
and pumped to the reactor at ca. 10 MPa. The
1.5.4. Solution Process reaction step is adiabatic and the reaction tem-
perature is in the range 200 – 300 ◦ C. The feed
Solution processes have been developed by var- contains ca. 25 wt % ethylene, of which 95 % is
ious companies including Du Pont, Dow, DSM, converted to poylethylene in the reactor. The res-
and Mitsui for the manufacture of LLDPE or idence time is ca. 2 min. The catalyst most fre-
HDPE/LLDPE on a swing basis. The advan- quently quoted in patents is a mixture of VOCl3
tages are that they readily handle a wide range of and TiCl4 activated by an aluminum alkyl. Al-
comonomer types and product densities and, de- though the catalyst components may be initially
pending on catalyst type, tend to produce narrow soluble, the active catalyst species appears to be
MMD products more readily. Like the high-pres- heterogeneous [80]. The polyethylene solution
sure process (which is also a solution process) leaving the reactor is treated with a deactivat-
they are unable to handle high-viscosity prod- ing agent and the mixture then passes through
ucts. The Du Pont and DSM processes are simi- a bed of alumina where the deactivated cata-
lar to the high-pressure process in that they func- lyst residues are adsorbed. Two depressurization
tion adiabatically with short residence times, stages follow, similar to the high-pressure pro-
whereas the Dow and Mitsui processes remove cess, in which solvent and unreacted monomers
heat from the reaction mixture. Since the Du are volatilized. After extrusion into pellets, fur-
Pont process is available under license and more ther removal of solvent residues is achieved by
plants of this type have been constructed, this is passing a heated stream of gas through the bed
the process included in the table of cost esti- of pellets.
mates (Table 10) and described below. The Du
 Polyolefins 31

Figure 20. Solution polymerization process

a) Reactor feed pump; b) Temperature control; c) Reactor; d) Catalyst adsorber; e) First separator; f) Low-pressure separator
and melt-fed extruder; g) Purged product hopper; h) Recycle cooler; i) Diluent and monomer purification unit

Table 11. Consumption by application∗, %

techniques of plastics fabrication are treated in
Market HDPE LDPE and → Plastics, Processing and so only the aspects
LLDPE particular to polyethylene are discussed here.
Film 24 71
Blow molding 36 1
Injection molding 21 6 1.6.1. Film
Extrusion coating 9
Pipe 10 2
Wire and cable insulation 1 4 LDPE retains its position as a preferred pack-
Others 8 6 aging material because of its limp feel, trans-
∗ Percentages based on data for Western Europe, Japan, and parency, toughness, and the ability to rapidly
North America 1996 [122]. take up the shape of the contents of the bag.
Other materials such as thinner HDPE film or
paper may in some cases be more economical,
1.6. Uses but are less acceptable to the customer. Most
LDPE film is produced by the film blowing
Table 11 shows an analysis by end-use of ap- process (→ Films) but flat film extruded onto
proximately half of the world market for poly- chilled rolls (→ Films) is also made, particularly
ethylenes. The pattern is very different for the in the United States. An LDPE for high-clarity
two classes. LDPE (together with LLDPE which film typically has a MFI of 2 and a density of
is sold into the same market) is used predomi- 920 kg/m3 and is extruded at 160 – 180 ◦ C. The
nantly for films, not all of which is for packaging. cast film process is usually used with higher den-
Because of its greater rigidity and better creep sity polyethylenes (930 – 935 kg/m3 ), where the
properties, HDPE is used in more structural ap- quenching on the chilled rolls enables good op-
plications, and also has important applications tical properties to be achieved with a higher film
in the packaging of aggressive liquids such as stiffness. The bubble diameter in the tubular film
bleach, detergent, and hydrocarbons. The basic process may be up to 2 m for general purpose
32 Polyolefins

packaging, and larger for heavy gauge indus- uct advantage of LLDPE, since high stresses
trial film. Originally, bags were made directly do not occur when the melt is drawn down
from tubular film by welding one end, but the to thin film. LLDPE can be drawn down to
tendency now is to make wide film on large ma- much thinner film without the bubble tearing
chines and fabricate the bags by welding and cut- than can a LDPE with equivalent mechanical
ting. Apart from packaging film and heavy duty properties.
sacks, increasing quantities of polyethylene are HDPE film is generally made on units specif-
used for impermeable or stabilizing membranes ically optimized for the high molecular mass
in civil engineering construction. grades normally used. To produce tough films
Additives play a particularly important role in a balanced orientation of the film is necessary,
the production of LDPE film by the film blowing and a high ratio of die diameter to bubble di-
process. Without additives, the pressure of the ameter (“blow ratio”) is used so as to balance
windup rollers on the warm film forces the sur- the machine direction draw with a high trans-
faces into such close contact that subsequently verse draw. A characteristic stalk-shaped bubble
it may be virtually impossible to separate them. is used in which substantial machine-direction
High-gloss films are the worst affected. This is draw takes place before a rapid expansion oc-
overcome by adding an antiblocking agent such curs some distance above the die. Mechanical
as very fine silica, which roughens the surface guides are needed to stabilize the bubble. HDPE
on a submicroscopic scale without significantly film is opaque and is usually used in much thin-
affecting the optical properties. To reduce the ner gauges than LDPE. It competes with LDPE
friction between the surfaces a slip agent such in areas such as carrier bags and supermarket
as oleamide or erucamide is added. Other ad- convenience bags.
ditives may be added to achieve effects in the
final product such as oxidation resistance, UV
resistance, or antistatic properties. 1.6.2. Extrusion Coating
A film extruder designed for LDPE requires
LDPE is used extensively for coating cardboard,
extensive modifications to allow it to extrude
paper, and aluminum for milk cartons etc., for
LLDPE at comparable rates [123–125]. To avoid
which a very low level of impurities is required.
this investment and the lack of flexibility, many
Extrusion is carried out at ca. 300 ◦ C through a
film manufacturers (particularly in Europe) use
blends of LDPE and LLDPE. The equipment wide-slit die. Polymers with a high die swell due
modifications required are: to long branching perform best, since the ten-
dency to expand on leaving the die opposes the
1) The screw must have greater clearance bet- “neck-in” tendency when the melt is drawn onto
ween the flights and the barrel to avoid tem- the substrate. A typical LDPE used for this appli-
perature buildup due to the higher shear vis- cation has a MFI of 4 and a density of 920 kg/m3 .
cosity. Ideally the screw should be shorter.
2) The die gap must be widened to reduce the
1.6.3. Blow Molding
shear rate and so avoid a type of surface de-
fect, known as shark skin, to which narrow HDPE is now the preferred material for blow-
MMD polymers are prone. To some extent molded containers for liquids, combining ade-
this problem can be avoided by incorporat- quate environmental stress crack resistance with
ing additives based on fluoroelastomers (Du higher rigidity than LDPE, and hence permitting
Pont, 3M) or silicones (UCC) [126–128]. lower bottle weights for a given duty. The major
3) The cooling ring must give more rapid uses are in the domestic market for bleach, de-
quenching of the melt to avoid the develop- tergents, and milk. For this application a HDPE
ment of excessive crystalline haze, and also with a MFI of 0.2 and a density of 950 g/m3 is
to give more support to the bubble because suitable. Other uses include a variety of indus-
of the lower tensile viscosity under the infla- trial containers and gasoline tanks. There is a
tion conditions. Apart from this lack of in- trend to higher molecular mass and to broader
herent stability of the bubble, the low tensile MMD polymers, with bimodal MMDs achieved
viscosity is responsible for the major prod- by using catalyst or reactor developments [129].
 Polyolefins 33

1.6.4. Injection Molding 1.6.7. Ethylene Copolymers

Injection molding is used for a variety of prod- The processing techniques used for copolymers
ucts. Some, such as caps and lids are used in are generally the same as used for polyethylene
the packaging field. Other applications such as homopolymers, but the range of applications is
housewares, toys, and industrial containers are generally more diverse [12]. The property most
more durable. According to whether high flex- generally exploited is the decreased rigidity to
ibility is required or not, LDPE or HDPE may give more flexible film, moldings, and tubing
be used. Some LLDPEs with a narrow MMD than is possible with LDPE. Copolymers with
are particularly well suited for this method of high comonomer content are generally compet-
fabrication. MFIs range from 2 to > 40. A nar- itive with plasticized PVC and rubbers, with a
row MMD gives the best compromise between low extractable additive content as an advan-
toughness, flow into the mold, and freedom from tage. For flexibility down to the lowest temper-
warpage in the finished product. atures acrylate copolymers are preferred over
EVA copolymers. VLDPE copolymers, partic-
ularly those made by single-site catalysts, are
1.6.5. Pipe increasingly being used in applications requir-
ing flexibility combined with thermal stability
The use of polyethylene for pipes is one of the and good low-temperature flexibility.
few engineering applications, where the applied Ethylene copolymers are also used in blends,
stresses are carefully assessed and a lifetime of in the same way as rubbers, to confer in-
at least 50 years is required. Polyethylene is used creased toughness. Particular applications in-
for water and natural gas local distribution sys- clude blends with wax and with bitumen for
tems and, unlike many other uses, there is a paper coating and road surfacing, respectively.
substantial stress applied continuously. The po- Copolymers are also used as constituents of hot
tential problem is thus long-term stress rupture, melt adhesives.
and this must be carefully assessed by extrapo-
lation and accelerated testing. Large quantities
of pipe made of a medium-density polyethylene 1.6.8. Ultra High Modulus Polyethylene
designed to withstand a stress in the PE of 8 MPa Fibers
have been laid, but advances in bimodal HDPE
polymers now enable a 50-year lifetime at a de- Because of their low softening point polyeth-
sign stress of 10 MPa to be met. The first poly- ylene fibers have not been of interest for gen-
mers which met this specification (PE 100) were eral purpose textile use, although substantial
introduced by Solvay in their TUB 120 range, amounts are used for producing monofilament.
but now all major producers have similar poly- In 1973 Capaccio and Ward showed that solid
mers in their ranges [130, 36]. HDPE could be drawn at elevated tempera-
tures to very high draw ratios to produce fibers
with a tensile modulus of 70 GPa and a ten-
1.6.6. Wire and Cable Insulation sile strength of 1 GPa (Kevlar 149: 172 GPa and
3.4 GPa, respectively). Theoretical values for a
Because of its outstanding dielectric properties, perfect extended-chain crystal are 300 GPa and
the first application of polyethylene was the in- ca. 25 GPa, and thus these early results achieved
sulation of very high frequency and submarine a significant fraction of the maximum modu-
telephone cables. These have continued to be lus possible. Further developments have been on
made from LDPE, but uses have expanded into parallel fronts: melt spinning followed by solid-
telephone and power cables. In the latter case state drawing, and gel spinning.
cross-linking is increasingly used to enhance the Melt spinning has been adopted commer-
properties and allow a higher current rating for cially by Celanese, SNIA, and Mitsui. Gel spin-
a given size of cable. ning consists of forming a dilute solution in a
heavy solvent and then extruding it so that gelled
PE fibers are formed on cooling and can then be
34 Polyolefins

drawn on conventional fiber-making equipment. The automated machine then removes the heater
The solvent has to be removed by evaporation or and presses the ends together at a predetermined
solvent extraction. The gel-spinning process is force. The procedure produces a bead of PE on
operated by Allied Signal and DSM. The melt- the inside and outside surfaces, and the external
spinning process is limited to moderate molecu- bead is machined flush with the pipe surface.
lar masses because of the polymer viscosity, but Because of its low surface energy PE can-
the gel-spinning process can use higher molec- not be joined in its natural state by any of the
ular mass PEs and achieves higher modulus and strong adhesives such as epoxy resins. Rubbery
tensile strength (172 GPa and 3.0 GPa). Further adhesives such as pressure-sensitive and hot-
advances may be expected on using PEs made melt adhesives function satisfactorily, but the
with single-site catalysts. Since the production mechanical strength of the bonding material is
costs of the gel-spinning process are higher there not very high. By treatment of the surface it is
seems to be a market for both types of product. possible to form a bond with epoxies. A rec-
Limitations on the uses include the low soft- ommended method is oxidation with chromic
ening temperature and creep. Creep can be acid, after which the surfaces can be glued with
reduced considerably by cross-linking [131]. epoxy resin [135]. A more recent development
For use in composites the fibers must exhibit for bonding polyolefins is the use of an aliphatic
good adhesion to epoxy resins, and this can amine primer that penetrates into the surface of
be achieved by various methods, principally by the PE. When a cyanoacrylate adhesive is then
plasma treatment [132]. PE fibers have poor applied, polymerization to form a bond occurs
compressive strength and so for composites they in the usual way [136].
are usually used in combination with other rein-
forcing fibers such as glass or carbon. The prin-
cipal market is probably in energy-absorption 1.7. Chemically Modified Polyethylenes
applications such as personal armour where the
characteristics which are responsible for creep 1.7.1. Cross-Linked Polyethylene
give rise to energy absorption superior to ex-
isting materials. Other applications which make As noted in Section 1.3.1, polyethylene free rad-
use if its high modulus are in leading-edge sport- icals combine to form larger molecules, unlike
ing goods where it competes with carbon fiber, materials such as polypropylene, which tends
aramid etc. [132–134]. to degrade. This cross-linking reaction has been
made use of in a number of ways to effectively
increase the molecular mass with corresponding
1.6.9. Joining Polyethylene improvements in some properties. The principal
commercial methods of cross-linking [137] are:
The most satisfactory method of joining PE is
by welding but considerable experience is re- 1) Free radicals can be generated by mixing in
quired to achieve satisfactory results. A widely a peroxide such as dicumyl peroxide or di-
used method uses a stream of hot gas (usually tert-butyl peroxide in an extruder at as low a
nitrogen to avoid oxidation) in a similar manner temperature as possible and then curing the
to gas welding of metals. The edges to be joined extruded cable in an external heated zone
are chamfered to allow a bead of PE to be melted [138]. This process uses ca. 2 % peroxide
into the join. The heating causes changes in the and the curing process must be carried out
annealed state of the PE adjacent to the join and under pressure to avoid excessive formation
it may become weaker than the original material, of voids. Peroxide together with a blowing
but this can be overcome by welding a reinforc- agent is used for making foamed sheeting or
ing strip over the joint line [135]. molded articles, particularly of EVA.
Welding is used by the gas and water indus- 2) Polyethylene can be cross-linked by radia-
tries to join pipe in their distribution networks. tion either above or below the melting point,
The most satisfactory method is butt welding, but commercially, products are cross-linked
in which the ends are machined true and then in the solid state after the basic fabrication
heated by a PTFE-insulated electrical heater.
 Polyolefins 35

step. There are some differences in proper- Du Pont manufacture a chlorosulfonated

ties between peroxide and radiation cross- polyethylene (Hypalon) in which the sulfonyl
linked polyethylene due to the fact that in groups are used in a propietary vulcanizing pro-
the solid state the cross-links occur in the ex- cess. The materials are used as rubbers with good
isting amorphous regions, and the existing weathering properties.
crystallinity is largely retained. Electron ac-
celerators are used to provide the radiation
in a readily controlled process [139]. Prod- 1.7.3. Fluorinated Polyethylene
ucts include shrink tubing and sheeting, wire
insulation, and water pipes. Fluorinated polyethylene is not produced as a
3) Dow has developed a process (Sioplas-E) in bulk material, but surface treatment of articles
which a peroxide is used to graft a vinylsilane with fluorine gas is used to produce a highly
to the polyethylene. The silane groups can fluorinated surface layer. In this way the perme-
then react together in the presence of mois- ability of containers to a wide range of solvents
ture to form cross-links. A catalyst such as can be reduced drastically. The treatment can be
dibutyltin dilaurate is added to accelerate the applied to finished articles, or fluorination can be
cross-linking reaction. The process has the carried out in-line by employing a dilute mixture
advantage that only a tenth of the amount of of fluorine gas in nitrogen as the blow gas in the
peroxide is required and the curing stage is blow molding process [143]. Gasoline tanks are
simpler. However, since water must diffuse a major application, but the process is also used
in from the surface, curing times become ex- for containers for materials such as solvents and
cessive for thick sections. The original pro- pesticides.
cess produced the graft polymer as a sepa-
rate stage from the cable extrusion, but the
Monosil process achieves the grafting in the 1.8. Environmental Aspects
cable extruder [140].
4) A further variant of silane cross-linking is the 1.8.1. Manufacture
production of a silane copolymer by direct
copolymerization of a vinylsilane in a high- Under normal operating conditions the impact
pressure polyethylene reactor. This process on the environment of polyethylene production
developed by Mitsubishi for their Linklon-X plants is minimal. There are some hydrocarbon
polymers has been licensed to A. T. Plastics emissions, particularly from those plants using
for their Aqualink process [141]. solvents, but these are regulated by local legis-
lation. In some cases hazardous materials such
as the Phillips catalyst or aluminum alkyls are
1.7.2. Chlorinated Polyethylene handled safely by attention to detail in the plant
design and operation. The preparation of both
Both LDPE and HDPE can be chlorinated to peroxide initiators and Ziegler catalysts involves
form what are in effect ethylene/vinyl chlo- some extensive chemical operations with the at-
ride copolymers which are not accessible by di- tendant problems of waste disposal. All peroxide
rect polymerization. Chlorine contents of 34 – initiators are now made by specialist producers
44 wt % are reported [142]. By selection of the and there is also a tendency for this to be the case
polyethylene and the chlorination conditions, for Ziegler and Phillips catalysts.
products can be made with a range of process- The high-pressure autoclave process is pro-
ing viscosities and with the chlorination either tected against over-pressurization by bursting
randomly distributed or concentrated in seg- disks. When a disk bursts, the vessel contents, in-
ments, leaving some polyethylene crystallinity. cluding carbonized polyethylene, are discharged
The principal application is as a toughening quite safely to the atmosphere, but with the im-
agent for PVC, but there are other uses in the pression of an explosion. Thus, it is not feasible
same general area as flexible materials such as to site this type of plant as close to residential
EVA, but with the emphasis on outdoor weather areas as would otherwise be possible.
resistance.
36 Polyolefins

1.8.2. Polymer Disposal and Recycling transport is also eased in that the cracked feed-
stock could be produced in relatively small local
At the time of writing (1997), much of the poly- units and transported in tankers to the refineries.
ethylene produced is dumped into landfill within Another approach is to burn the polyethylene
a few months of manufacture. This represents to recover electrical or thermal energy, thereby
the fraction used in packaging. However, the use saving on fossil fuel which in most economies
of disposable packaging is being increasingly is still being used for this purpose.
called into question. In the 1970s and 1980s the
concern was with the unsightliness of a mate-
rial which was littering the environment, and did 2. Polypropylene
not degrade. Various schemes were developed to
promote more rapid degradation based either on 2.1. Historical Survey
photosensitized oxidation [144] or biodegrada-
tion of blends with starch [145]. Some of these In the 1950s Karl Ziegler discovered new cat-
developments have reached commercialization, alysts which were to revolutionize the plastics
but now public opinion is moving towards the industry. Before then, propene could not be poly-
need to conserve plastics. Table 12 shows some merized to high molecular mass products with
of the options available to deal with the problem the catalysts then available, namely, free-radical,
of disposable packaging. anionic and cationic systems. Even the most fa-
Much emphasis centers on recycling, that is vorable of these yielded only liquids consisting
converting the polyethylene back into granules of many isomers and greaselike materials un-
and then using it to produce more film etc. There suitable for making hard plastic products.
is some oxidation during use and recovery, lead- In 1953 Karl Ziegler, Professor at the Max-
ing to some cross-linking and a slight deteriora- Planck-Institut für Kohlenforschung, demon-
tion in extrusion properties. It will be difficult strated that ethylene could be polymerized to
therefore to match the original manufacturer’s a high molecular mass crystalline polymer at
tightly controlled specification, particularly if moderate pressure and temperature. His group
the recovered material is of a variety of grades had for some years been using aluminum alkyls
from different producers. There will also be a to convert ethylene into a range of oligomers
problem of suitability for use in contact with having an even number of carbon atoms. Unex-
food, since the recovered material may contain pectedly, almost total conversion to butenes oc-
a range of unknown organic and inorganic impu- curred in one experiment. The cause was even-
rities. At present the intentions are to use recy- tually traced to nickel-ion contamination in the
cled material in uncritical nonfood uses. How- autoclave. Tests with many other metallic com-
ever, a successful recycling program could out- pounds revealed that a combination of zirco-
strip such uses. Ideally recycling should be at nium ion with aluminum alkyl converted eth-
the monomer level, but polyethylene does not ylene to high molecular mass polymer. Fur-
readily decompose to form ethylene. ther searching revealed that titanium ion was
Processes have been developed which crack even more active in producing polyethylene
the plastics waste to a liquid hydrocarbon suit- (November 1953). Such combinations of transi-
able for use as the feedstock to a conventional tion metal compounds with an aluminum alkyl
cracker, which effectively allows recycling via later became known as Ziegler – Natta Catalysts,
the monomer [146]. In the BP process plastics thereby acknowledging the immense contribu-
waste is fed to a fluidized bed reactor main- tion of Giulio Natta to discovering and char-
tained at about 500 ◦ C, and the liquid feedstock acterizing polypropylene (PP) and other α-olefin
is recovered from the recirculating gas stream. polymers in 1954.
Gaseous byproducts are used as fuel to maintain Natta, Professor and Director of the Milan
the temperature of the fluidized bed. This pro- Institute of Industrial Chemistry, was a consul-
cess has advantages over the hypothetical pro- tant to Montecatini, to whom Natta assigned
cess of cracking PE to ethylene in that it toler- his patents. The close collaboration between
ates the presence of other plastics materials, even Ziegler and Natta was acknowledged in 1963
PVC. The ever present problem of collection and by the joint award of a Nobel prize in Chemistry
 Polyolefins 37
Table 12. Polyethylene packaging disposal strategy

Disposal method Advantages Disadvantages

Incineration avoids landfill generates CO2 without benefits

Incineration with energy recovery displaces existing fossil fuel use loss of fabrication costs
Biodegradation removes unsightly refuse doubts about completeness of degradation; generates
CO2 without benefits
Promoted degradation removes unsightly refuse; lower labor degradation slow away from sunlight; generates CO2
costs for agricultural uses without benefits
Recycling via melt makes use of scarce resource some deterioration in quality
Recycling via monomer top-quality product; processes mixed fairly large scale processing plant
plastics
Reuse saves on fabrication costs PE may not be the best material

for their outstanding contributions to polymer tion of PP started at Ferrara, Italy, in 1957
science. A fascinating account of Ziegler and with a 6×103 t/a plant. By the end of 1994
Natta’s personal approach to these discoveries global capacity had risen to 20.5×103 t/a (Ta-
is provided by McMillan [147]. ble 13), spread over 35 countries [150]; to-
day, new plants are expected to be capable of
producing 200×103 t/a to achieve reasonable
Table 13. Global PP capacity (103 t/a) and its distribution
economies of scale.
Country/region End 1990 End 1994 Growth ∗ There are several reasons for this phenom-
1990 – 1994, % enal growth, which exceeds that of other bulk
Western Europe 4530 5705 26 plastics [151] (Table 14). At first propene was
North America 4400 5440 24 readily available, almost at byproduct prices,
Japan 1870 2656 42 from petrochemical cracker plants making eth-
Other Far 2734 4090 50
East/Australia ylene. The polymer itself was suitable for a wide
Middle 280 655 34 range of existing and new applications such as
East/Africa films, various fibers, large and small moldings
South America 450 1035 30
Eastern Europe 790 930 18
from boat hulls to instrument parts. In addi-
Total/average 15 054 20 511 36 tion, new manufacturing technologies based on
∗ 7 % per annum growth for four years is 31 % total growth.
MgCl2 supported catalyst systems yielded both
cost savings and improved products by eliminat-
In the the United States, patents on crys- ing atactic PP removal steps and then the deash-
talline polypropylene were awarded originally to ing stage. Some 40 years on there are expecta-
Natta et al. (on behalf of Montecatini), but were tions that the new metallocene catalyts will ex-
overturned later in favor of Phillips Petroleum tend these uses, even to the extent of challenging
Company. The immense legal procedings to es- products such as polyamide, ABS, and flexible
tablish inventor rights to crystalline polypropyl- PVC for part of their market [152].
ene in the United States are outlined by Hogan
and Banks [148], with more recent comments
2.2. Polymer Structure
by Pino and Moretti on this costly litigation
[149]. Phillip’s polymerization catalyst, consist- 2.2.1. Molecular and Chain Structure
ing of chromium-ion promoted silica – alumina,
has not been used in any commercial plant to Polypropylene is a synthetic, high molecular
manufacture crystalline polypropylene. mass linear addition polymer of propene. In
Notwithstanding the complexities and haz- 1954/5, Natta et al. prepared sufficiently large
ardous nature of these new coordinated cat- amounts of PP to isolate and characterize var-
alysts, industrialists and academe alike were ious stereoisomers. This led to a new descrip-
stimulated by Ziegler and Natta’s prompt tive nomenclature still used today. Commercial
and prolific disclosures concerning this new, interest lies primarily in highly crystalline PP,
high-melting polymer. Industrial-scale produc- together with its further modifications through
copolymerization.
38 Polyolefins

In perfectly isotactic PP, each monomer unit the emergence of high molecular mass ver-
in the chain is arranged in a regular head-to-tail sions deliberately made with a metallocene-
assembly without any branching or 1,3 additions based catalyst, [(Me2 SiFlu2 )ZrCl2 ] (Flu = flu-
(Fig. 21 A). This is the result of template-type orenyl) [153].
constraints by the heterogeneous stereospecific All Ziegler – Natta commercial polymers
catalyst. In practice such perfection is hard to have broad molecular mass distributions within
achieve. An occasional error (Fig. 21 B), aver- the range M w /M n = 5 – 10 for ex-reactor ma-
aging about 0.3 – 1.5 per hundred chain links, terial. Any reduction is achieved by peroxide-
occurs in some, but not equally in all chains. induced chain clipping in an extruder. Met-
The multisite nature of solid catalysts is thought allocene polymers have narrower distributions
to be responsible for this behavior. (M w /M n = 2 – 4) as a consequence of their
single-site mechanism. This avoids the need for
Table 14. Major polymer usage in Western Europe
peroxide additives, which produce objectionable
odor and volatile byproducts.
Polymer Consumption, 103 t/a Growth rate, %

1974 1984 1994 ’74/’84 ’84/’94

2.2.2. Crystallization and Morphology
LLDPE +LDPE 3080 4089 6015 33 47
HDPE 1035 1704 3570 65 110
PS 1118 1290 1908 15 48 Polypropylene’s strength and versatility stem
PVC 3360 3825 5480 14 43 from a matrix of interlocking crystallites that
PP 680 1895 5178 179 173 allow formation of rigid and tough articles.
Highly isotactic polymer, with its regular struc-
ture, forms a helical coil having three monomer
Solvay and MgCl2 supported systems reduce units per turn. These coils stack together into
the extent of these errors, and with them the thin lamellar crystallites which force the chains
amount of noncrystalline (atactic) polymer. Still to fold several times as they emerge and reenter
at the development stage, metallocene-based lamellae. Polyethylene behaves similarly (see
single-site catalysts (SSCs) also produce stere- Fig. 2)
oregularity errors, but these seem to be dis- While the equilibrium (i.e., thermodynamic)
tributed more uniformly along the chains, re- melting point is 188 ◦ C, at normal analysis heat-
gardless of their length (Fig. 21 E). This con- ing rates the final melting point is ca. 160 –
trasts with multisite catalysts (MSCs), for which 170 ◦ C. Three crystalline forms are known (Ta-
misplacements vary in frequency and in num- ble 15), of which the α-form is the most stable.
ber. The tendency here is for the high molecular Rapid quenching yields the β-form with a lower
mass fraction to contain fewer faults, while the density and melting point of 150 ◦ C. Polymers of
short chains suffer from excessive dispruptions, lower stereoregularity and random copolymers
which lead to reduced crystallinity. usually contain γ- crystallites in addition to the
Until recently, syndiotactic PP (Fig. 21 C) α-form.
was not commercially important because of Crystallization is complicated further by as-
unacceptable polymerization difficulties at low sembly of these lamellar crystals into larger
temperatures. Some metallocene catalysts over- structures, called spherulites. These have radial
come this problem to produce a regular sequence symmetry and can adopt five different forms (Ta-
of racemic (r) propene placements yielding a ble 16). While the size of the crystallites is in the
crystalline polymer melting at 130 ◦ C. Mitsui region of 10 – 50 nm, too small to scatter visi-
Toatsu and Fina have entered into a joint venture ble light (400 – 600 nm), spherulites are much
to assess costs and customer reaction to syndio- larger (103 – 105 nm). The latter are responsible
tactic PP. for the translucency of slowly cooled PP mold-
Complete loss of steric regulation generates ings. Rapid crystallization from the melt by fast
atactic polymer chains (Fig. 21 D), incapable of cooling, adding nucleating agents, and reducing
crystallizing. Hitherto this low molecular mass spherulite sizes by stretching a partially solidi-
byproduct had only a few commercial outlets fied melt all improve transparency.
for adhesives. The position could change with
 Polyolefins 39

Figure 21. PP chain structures

Table 15. Crystal habits of PP [154–156]

Crystal form System Crystal density (20 ◦ C), g/cm3 Chains per unit cell mp, ◦
C∗

Iso α monoclinic 0.932 – 0.943 4 171

Iso β pseudo hexagonal 0.922 9 150
Iso γ triclinic 0.939 1 131
Smectic 0.916
Amorphous 0.85
Syndio orthorhombic 0.93 2 138
(4/1 helix)

∗ The enthalpy of melting for 100 % crystalline isotactic PP is variously reported, due to different techniques. Wunderlich [154] gives
165 ± 18 J/g, Brandrup and Immergut report 209 J/g [155], the ICI DSC standard is 185 J/g, and the Shell DSC standard is 188 J/g
[157, p. 590].

Crystallization from a viscous melt is hin- ence would be masked in blends and in ethyl-
dered by chain entanglements and by the need ene copolymers. Using the melting curve over-
for helices to fold as they close-pack into lamel- comes this analytical difficulty. Another aspect
lae. This, and the formation of nuclei might con- of tardy crystallization is the low level of crys-
tribute to the low degree of crystallization even in tallinity in fabricated items, even when highly
highly stereoregular polymers. Typically, the on- stereoregular polymers are used. Commercial
set of crystallization occurs at ca. 110 – 120 ◦ C articles vary from 30 % crystallinity in rapidly
in DSC instruments. This point coincides with quenched films to 50 – 60 % in moldings. Even
the cooling peak for polyethylene, whose pres- purified and annealed samples of highly stereo-
40 Polyolefins

regular PP rarely achieve more than 70 % crys- quate for most plants, but certain sensitive sup-
tallinity. Polypropylene is properly regarded as ported catalysts require the lower levels listed for
a semicrystalline polymer for these reasons. carbonyl sulfide, carbon monoxide, and oxygen
(this quality is said to be suitable for metallocene
Table 16. Spherulitic structures
catalysts) [160]:
Spherulite type Crystal type Features

I α positive birefringence, lost at Propene 99.5 wt % min.

160 – 170◦ C; epitaxial branching; Propadiene 5 vol ppm max.
always associated with type II Propyne 5 vol ppm max.
II α negative birefringence, lost at Butadienes 10 vol ppm max.
160 – 170 ◦ C; fibrillar crystals
Oxygen 5–2 vol ppm max.
radiating from nucleus; most
stable of all spherulites Carbon monoxide 3 – 0.3 vol ppm max.
III β strongly negative birefringence; Carbon dioxide 5 vol ppm max.
associated with β-crystals and Carbonyl sulfide 0.5 – 0.03 vol ppm max.
high shear in cooling; melts and Total sulfur 1 wt ppm max.
reverts to type II at 145 –150 ◦ C Water 5 wt ppm max.
IV β special case of Type III, Methanol 5 vol ppm max.
characterized by banded Ammonia 1 vol ppm max.
concentric rings Ethane 500 vol ppm
V γ rare variant formed under high Propane 0.5 wt %
pressure with γ-crystals Butane 500 vol ppm
N2 + CH4 300 vol ppm
Isobutene 50 vol ppm (estimated)
Hydrogen 10 vol ppm max.
Ethylene 50 vol ppm max.
2.3. Raw Materials 1-Butene 50 vol ppm max.

2.3.1. Propene
Ethylene and 1-butene copolymerize with
Sensitive Ziegler – Natta catalysts require pure propene to marginally reduce the polymer soft-
propene to ensure high polymerization rates ening point. Hydrogen is a powerful chain-trans-
and good yields of isotactic polymer, without fer agent whose concentration must be accu-
wasteful byproducts. Harmful impurities can be rately controlled in the reactor.
grouped into two main categories which have Propene is normally manufactured outside
different effects on the process. The most de- the PP plant. An important source of both eth-
structive contaminants are polar and highly un- ylene and propene, in the approximate weight
saturated compounds which react directly with ratio of 2: 1, is from steam cracking naphtha or
the catalyst systems, retarding polymerization gas oil at 700 – 950 ◦ C, followed by fractiona-
and impairing stereospecificity. Examples in- tion. Refinery catalytic cracking of petroleum
clude acetylenes, dienes, carbon monoxide and products yields 2 – 5 % of propene, which is iso-
dioxide, carbonyl sulfide, water, alcohols, and lated as a chemical grade containing 90 – 95 %
ammonia. The second group contains materi- of the monomer with much propane. This can
als which adversely influence the process, but be purified further to polymer-grade specifica-
not the chemistry, by raising the pressure during tion, but some PP plants which are able to handle
reaction due to an accumulation of inert sub- the extra propane may bypass further refining or
stances. These further complicate the monomer add a simplified hydrogenation unit to reduce di-
recovery section and recycle streams. This group enes [161]. These possibilities arise at the milder
contains materials such as methane, ethane, pro- end of the cracking range of 400 – 500 ◦ C, which
pane, butane, and nitrogen. then generates lower amounts of harmful highly
Most manufacturers use polymer-grade unsaturated products. There has been some inter-
propene as feedstock, which can be further re- est in building propane dehydrogenation plants
fined by passing it through local guard columns as a third source of pure propene [161, 162].
containing alkali, molecular sieve, alumina, sup- Some properties of propene relevant to
ported copper, etc. to guarantee consistently polypropylene production are as follows:
high purity [158, 159]. Typically, monomer con-
forming to the following specification, is ade-
 Polyolefins 41

Heat of polymerization 2514 kJ/kg

An overview of the four development phases is
bp − 47.7 ◦ C given in Table 17.
Critical temperature 92 ◦ C
Critical pressure 4.6 MPa
Vapor pressure at 20 ◦ C 0.98 MPa
2.3.3.1. TiCl3 -Based Catalysts

Of the four known crystalline forms of TiCl3 ,

2.3.2. Polymerization Diluents three are purple (α, γ, δ) while the fourth is
brown (β). The latter is not used in PP manu-
Most early processes and some current plants facture because of its poor stereospecificity. All
use an inert hydrocarbon diluent in the reactor to the purple forms have a layer lattice consisting
help transfer propene to the solid catalyst and to of closely packed chlorine atoms (Fig. 22) either
convey reaction heat to the water- cooled jacket. hexagonal (α), cubic (γ), or intermediate bet-
Typically there is twice as much diluent in the ween the two (δ). Preparative methods are crit-
reactor as polymer; thus, the purity demands on ical to achieve good stereoregulation and high
the diluent are as important as for the monomer. activity with these catalyst components.
Refined petroleum fractions and synthetic hy-
drocarbons in the C6 – C8 range perform well,
while solvents ranging from butane to dode-
cane are also used commercially. Polar impuri-
ties, such as alcohols, carbonyl compounds, wa-
ter, and sulfur- containing compounds must be
kept below 1 – 5 ppm. The content of aromatics
should be below 0.1 – 0.5 vol %, depending on
the catalyst employed. Here UV spectroscopy,
supplemented with IR spectroscopy and refrac-
tive index measurement, is used to monitor qual-
ity. Regular checks must be made on recycled-
diluent quality to prevent oxidized species and
catalyst fragments accumulating unnoticed.
Polypropylene articles, such as films and con-
tainers, are widely used for food packaging and
handling. In these cases the diluents and other
additives must conform with the appropriate
health regulations.
Since polymerizations carried out in the gas
phase or in liquid propene only use small
amounts of diluent as catalyst carriers, their pu- Figure 22. Layer lattice of α-TiCl3 [165] (printed with per-
rity requirements are less stringent. mission of Harwood Academic Publishers)

Early work by the Natta school used pure

2.3.3. Catalyst Preparation [163] TiCl3 made by hydrogen reduction of TiCl4 , fol-
lowed by ball milling to give a high surface area.
All current commercial manufacturing pro-
cesses for highly isotactic PP use heteroge- TiCl4 + 1/2 H2 −→ TiCl3 + HCl
neous Ziegler – Natta catalyst systems. These
two-component initiators consist of a solid A more active form is made by reduction with
transition-metal halide, usually TiCl3 , and an aluminum powder, followed by ball milling.
organoaluminum alkylating agent such as di- 3 TiCl4 + Al −→ 3 TiCl3 · AlCl3
ethylaluminum chloride (DEAC). This system
was the basis of PP plants until about 1980 Much of the aluminum chloride is present as a
when supported catalysts were commercialized. true solid solution in crystalline δ-TiCl3 . This
42 Polyolefins
Table 17. Catalyst development

System Catalyst performance Plant

Activity, kg PP/g catalyst I.I. ∗, wt % process

1st Generation
1957 – 1970 0.8 – 1.2 88 – 93 deash and remove
TiCl3 · AlEt2 Cl atactic
2nd Generation
1970 – 1980 3–5 92 – 97 deash/deactivate,
TiCl3 · AlEt2 Cl + atactic usually remains
Lewis base (Solvay)
3rd Generation
1980 – 1990 5 – 20 ≥ 98 no deash and
MgCl2 -supported TiCl4 · AlEt3 no atactic removal
4th Generation
1995 ca. 20 ? no deash and
Metallocene/MAO systems no atactic removal
MMD ca. 2 – 4

∗ Isotactic index ( % insoluble in boiling heptane).

catalyst has a larger surface area of 10 – 40 m2 /g where x = 0.15, z = 0.20

and is commercially available from several com- 2) The brown β-TiCl3 solid is treated with di-
panies. Nowadays, a Lewis base, such as an ester isoamyl ether to dissolve out most of the alu-
or ketone, may be introduced at the milling stage minum compounds
to increase stereospecificity. 3) The extracted solid is reacted with neat tita-
Another important route dispenses with ball nium tetrachloride at 65 ◦ C to transform the
milling by reducing a hydrocarbon solution β crystallites to the violet δ-form
of TiCl4 with an organoaluminum compound
The novelty lies in removing much of the
below room temperature. Di- and trialkylalu-
aluminum residues at the β stage, without col-
minum compounds are suitable. In this process
lapsing the particle, and then transforming to
the titanium trichloride precipitates in the brown,
the stereoregulating δ-form while retaining a
β form. Heating to 80 – 120 ◦ C completes the re-
spongelike structure with a surface area of
duction and transforms this solid to the required
150 m2 /g [164]. Analogous commercial prod-
purple variety. Several hydrocarbon washes re-
ucts are available in Japan and the United States.
move some of the aluminum compounds to leave
an active, stereospecific catalyst. A useful as-
pect of this technique is that conditions can be 2.3.3.2. Supported Catalysts
selected to precipitate spherical catalyst parti-
cles. Subsequent propene polymerization then The third-generation, supported titanium cata-
yields spherical polymer particles that exhibit lysts, are based on research by Montedison (now
good flow characteristics. This ability to repli- Montell) in Italy and Mitsui Petrochemical In-
cate the shape of catalyst particles is quite gen- dustries (now Mitsui Sekka) in Japan. Collabora-
eral in Ziegler – Natta polymerization. Polymer tion and cross-licensing between these two com-
forms throughout the agglomerate of small cat- panies avoided incipient interference claims.
alyst clusters, expanding the particle uniformly Starting around 1968 with finely milled magne-
in all dimensions as polymerization continues. sium chloride, which has a similar layer structure
Major refinements in alkyl-reduced TiCl3 to violet TiCl3 , ways were discovered of deposit-
systems were made by Solvay [164–166] in their ing stereoregulating titanium compounds on the
three-stage process, which gives a 4 – 5-fold in- surface.
crease in activity: A particle-form supported catalyst may be
prepared as follows [167]:
1) Titanium tetrachloride solution is reduced
with diethylaluminum chloride at 0 ◦ C 1) A spheroidal support is prepared by making
a fine dispersion of molten (125 ◦ C) mag-
TiCl4 + AlEt2 Cl −→ TiCl3 · x AlCl3 · z AlEtCl2 nesium chloride ethanolate complex in hot
 Polyolefins 43

kerosene containing sorbitan distearate as placing triethylaluminum with methyaluminox-

surfactant. The dispersion is quenched by ane (MAO) enormously increased the polymer-
pumping into kerosene at − 15 ◦ C to give ization rate of ethylene when combined with a
particles with a diameter of 5 – 30 µm. substituted zirconocene dichloride. There were
2) A slurry of the particles is added to neat TiCl4 several other major hurdles to overcome before
at 20 ◦ C. a suitable candidate was available for use in
3) Diisobutyl phthalate (17 % v/w) is added and PP plant. Low stereospecificity succumbed to
the mixture heated to 120 ◦ C. a more stereorigid metallocene, and the poor re-
4) Decant, and heat with further TiCl4 to activity and polymerization temperature restric-
130 ◦ C. Isolate by hot filtration and washing. tions were solved by further molecular tailoring.
The product contains 2.3 wt % Ti, 63 wt % Trials were conducted in 1996 on commercial-
Cl, 20 wt % Mg, and 9.9 wt % diisobutyl scale streams.
phthalate. Metallocences suitable for isotactic PP manu-
facture generally seem to be based on zir-
For the polymerization of propene, trieth- conocenes supported on inert solids to preserve
ylaluminum is used as a cocatalyst, and phenyl- particle size and shape. This makes them more
triethoxysilane as an additional external Lewis compatible with the advanced process technolo-
base stereoregulator. Potential corrosion prob- gies of the major operators who refer to them
lems have been substantially reduced by using as “drop-in catalysts”. Sophisticated chemistry
the chlorine-free triethylaluminum. (Figure 23) is needed to prepare the base metal-
By ca.1980, commercial plants were achiev- locenes, many of which have been made only in
ing 20 – 30 kg polymer per gram catalyst, and laboratory-scale equipment. An additional con-
the isotactic index progressively improved from straint is the heavy patenting, already amounting
88 to 99 %. to some 900 applications since 1984. Hoechst,
These catalysts form the basis of advanced Exxon, Fina, Mitsui, and BASF together hold
technology plants in which deashing (removal half of these.
of catalyst residues) and atactic polymer sep- The great versatility of single-site metal-
aration can be eliminated entirely [168]. It is locenes has been demonstrated in trials that
estimated that by 1998 70 % of global plants yielded improved and novel polymers. It re-
will be operated with such “high mileage” tech- mains to be seen how many of these desirable
nology. Coupled with this is the possibility of features can be incorporated in a single catalyst
exploiting the good handling characteristics of and how easily appropriate changes can be in-
the Spheripol coarse particle-form powders, thus troduced at plant level. Some of these polymer
dispensing with the need for expensive pelletiz- properties are mentioned in Section 2.7.1 [169].
ing plant. The segregation of added powdered
stabilizers during storage and the problems of
handling such mixtures are addressed, to some 2.3.3.4. Aluminum Alkyl Cocatalysts.
degree, by Montell’s Valtec products, in which
the additives are treated to provide a hard coat- Nowadays, aluminum alkyls are purchased from
ing on the polymer. Some customers still prefer outside manufacturers. In the case of DEAC sys-
to handle traditional granules from an extruder. tems it is necessary to tailor the chlorine content
to the type of TiCl3 used. As the various alkyls
interact rapidly, it is simple to adjust the compo-
2.3.3.3. Homogeneous Catalysts [163, 169, sition by adding AlEt3 or AlEtCl2 :
170],
2 AlEt2 Cl
AlEtCl2 + AlEt3
Metallocenes have been used for 30 years as Triethylaluminum is made commercially from
model compounds for Ziegler – Natta reactions. aluminum, ethylene, and hydrogen. Care should
They were quite unsuitable for commercial reac- be taken to avoid the high levels of the hy-
tors because of their extremely low activity and dride that are sometimes present. Trimethylalu-
poor stereocontrol. In the early 1980s, Sinn and minum is available from outside maufacturers,
Kaminsky serendipitously discovered that re- as is methyl aluminoxane (MAO). The latter is
44 Polyolefins

Figure 23. Hoechst (left) and BASF metallocenes

made by the controlled addition of water to the active site (Fig. 24. B), whose immediate crystal
trialkyl with various techniques to moderate the geometry controls both the initial coordination
potentially violent reaction. One method uses and the configuration as the monomer inserts
a salt hydrate, such as such as hydrated potas- into the titanium – alkyl σ-bond (Fig. 24 C). Ac-
sium aluminum sulfate (potassium alum). Vari- cordingly, this is a template type [171] polymer-
ous grades of MAO are available, possibly due ization controlled by the surface shape, and not
to the different manufacturing methods and the by the previously inserted monomer unit. Atac-
polymeric nature of the product, which contains tic polymer is formed at more open surface sites
linear and cyclic short chains. having two vacancies or two weakly bonded
chlorine atoms. While there are a number of
alternative proposals [163, 172, 173] the essen-
2.3.4. Hydrogen tials of the Cossee – Arlman model are widely
accepted.
Pure hydrogen is used at concentrations of 0.05 – Since each active site on the crystal is unlikely
1 vol % based on propene to control molecu- to be unique, a distribution of imperfections is
lar mass. Polar and highly unsaturated contam- to be expected. Sometimes Ziegler – Natta cat-
inants should be excluded, as usual. alysts are referred to now as multisite catalysts
to emphasize this wide distribution of polymer
chain lengths and stereoregularities.
In MgCl2 supported titanium chloride sys-
tems, 10 – 20 % of the titanium is thought to be in
the form of active sites, substantially more than
in Solvay’s improved catalyst, which contains
ca. 0.8 – 2.7 % of the titanium in active form.
2.4. Polymerization Mechanism Surface geometry still controls stereoregularity,
but Lewis bases are much involved in this regu-
Many kinetic and theoretical models have been lation [174].
applied to Ziegler catalysts. Only a very small In 1996 metallocene single-site catalysts
proportion (< 1 %) of the titanium atoms in vi- have unique structures which secure precise
olet TiCl3 are active for stereospecific polymer- control and definition of the active site. Con-
ization. Cossee proposed that an active site is sequently, a narrow molecular mass distribu-
generated at those surface titanium atoms which tion and better control of chain irregulari-
have one chloride vacancy and one exposed and ties, now including new types of chain de-
weakly bound chloride anion, the remaining four fects, may be obtained with selected metal-
chlorine atoms being firmly held in the lattice. locenes/aluminoxanes. These catalysts can be
These sites are located on the lateral faces of used in solution, but manufacturers usually pre-
violet TiCl3 crystals where the protruding chlo- fer them supported to secure better control of
rine is alkylated by aluminum alkyl (Fig. 24 A). particle size and shape, together with freedom
An incoming propene molecule approaches this from reactor build-up [170]. Apparently certain
 Polyolefins 45

Figure 24. Cossee – Arlman model for polymerization site

A) Alkylation of lateral surface chlorine; B) Propene complex; C) Insertion into Ti – C2 H5 σ-bond

supports can be used without spoiling catalyst their higher cost base means that they are be-
or plant performance. Hence the name drop-in coming increasingly uncompetitive, except in
catalysts to emphasize the ease with which they some highly specialized and low-tonnage appli-
can be introduced into existing plant. Their con- cations. Some 70 % of global PP plants have in-
siderable potential and performance are being stalled new ”High Mileage” processes .
tested at the pilot-plant stage [175]. The following sections describe one older
slurry type of plant and four state-of-the-art ad-
vanced processes. From these it will be possi-
2.5. Industrial Processes ble to visualize a number of hybrid alternatives
to suit particular catalyst characteristics [178].
In the laboratory, it is a fairly simple matter to Copolymerization is dealt with separately for
make a sample of PP from a given catalyst. All each system in Section 2.5.7, though for con-
that is necessary is to suspend the solid transi- venience the process flow sheets illustrating ho-
tion metal compound in dry, inert-gas-blanketed, mopolymerization (Figs. 26, 27 and 29) include
pure heptane containing aluminum alkyl cocat- the bolt-on copolymer plant.
alyst and then bubble in propene gas at about
60 ◦ C and atmospheric pressure. Polymer forms
as a white solid permeating the catalyst particles 2.5.1. Suspension Homopolymerization
which give an overall red-pink hue (with TiCl3 ). (Early Diluent Processes)
Elevated pressures increase reaction rates ac-
cording to a first order law. Details of the individual steps shown in Fig-
Industrial manufacturing plants must incor- ure 25 vary between manufacturers as regards
porate many other stages to secure salable prod- process conditions and type of equipment.
uct: some of these complications are eliminated
in modern high-technology plants by using ad- Polymerization. For continuous systems,
vanced catalysts. Here the residual catalyst and which have largely superseded batch polymer-
atactic levels can be sufficiently low not to dis- ization, the mean residence time of catalyst in
color polymer nor to generate odor and smok- the reactor(s) is usually 1.3 – 3 h. Individual au-
ing. Although older plants still using the tra- toclaves started out as 10 – 30 m3 vessels, but as
ditional process make high quality products, stream capacities increased sizes up to 100 m3
46 Polyolefins

Figure 25. Schematic of early PP manufacturing process

have been installed. Another common practice centration be allowed to exceed 42 wt % unless
involves linking reactors together in series or a very low density diluent is used.
in parallel configurations. The maximum out- As a rule, polymerization temperatures lie
put rate of a reactor is determined by the heat between 50 and 75 ◦ C; the desirability of us-
removal system, which no longer relies simply ing a higher temperature being countered by
on water- cooled polymerizer jackets. Internal decreased catalyst stereospecificity causing in-
and external cooling circuits provide the neces- creased solubles and poorer properties. While
sary extra cooling at these high rates (> 0.3 t h−1 reactor pressures of 0.5 – 1.0 MPa typified ear-
m−3 ). lier plants, intensified processes expand this to
It is only necessary to meter catalyst into the 2 MPa.
first reactor of a cascade system, both because
the activity decay is fairly small, and because it Propene Flashing and Recovery. Two ways
is not desirable on quality grounds to generate a of removing and recovering unreacted propene,
second family of particles downstream. Propy- stages b and k in Figure 25, are practiced com-
lene and hydrogen feeds to each reactor maintain mercially. Most commonly, slurry from the last
the required pressure and gas compositions to reactor discharges into a heated vessel at lower
secure the correct polymerization rate and mo- pressure to flash off propene vapor and other
lecular mass. Most of the reaction diluent is me- volatiles. After cooling and condensation, frac-
tered into the first vessel in the train, but some tional distillation recovers pure propene as an
can be added further downstream to minimize overhead stream with a bottom discharge of pro-
fouling as the polymer concentration increases. pane and some diluent. In certain cases it is
Slurry viscosity increases rapidly during the lat- more economical to return the flashed propene to
ter stages of polymerization as the swollen poly- an adjacent plant for use there. The alternative
mer particles approach close packing. This point scheme simply allows polymerization to con-
is strongly dependent on the size and shape of tinue without feeding any fresh propene to the
the catalyst particles. Seldom will the slurry con- latter part of the reaction train. Propene in solu-
tion is gradually converted into polymer as the
 Polyolefins 47

polymerization rate falls exponentionally in the Drying. Drying the wet cake sometimes re-
first-order reaction. This simple scheme entirely quires more than one stage, particularly in pro-
eliminates the recovery stage, but it does call for cesses using high-boiling solvents. Steam distil-
additional reactors working at low rates. lation removes most of the diluent to leave an
aqueous slurry from which the polymer is read-
Catalyst Removal (Deashing). Catalyst re- ily isolated by filtration. A conventional drier
moval, steps c and d in Figure 25, involves the removes the small amount of water still adher-
extraction of highly polar particulate TiCl3 from ing to the hydrophobic particles. More elabo-
a hydrophobic polymer particle. Procedures dif- rate driers, operating under a nitrogen atmo-
fer appreciably, but the first step always converts sphere, remove diluent directly in flash drying,
titanium and aluminum residues into complexes fluidized beds, or hot surface contact type sys-
or alkoxides that are soluble in the diluent, usu- tems. Before the advent of high-technology sys-
ally by heating to 60 ◦ C with 2 – 20 % of an al- tems (Section 2.5.4), some manufacturers had
cohol, though acetylacetone has also been used. already improved catalyst stereospecifity such
The choice of ethanol, propanol, or butanol is that the low level of atactic polymer in the dilu-
influenced by the diluent boiling point and sub- ent could be left in the product. In this case, the
sequent recovery schemes. total slurry can be dried without previous cen-
Step d, Figure 25, shows a widely practised trifugation. This avoids all atactic polymer han-
arrangement whereby water washing is used dling problems. All these drying stages must use
to transfer all these catalyst complexes into an nitrogen blankets throughout to minimize haz-
aqueous phase, leaving behind a purified poly- ards with flammable hydrocarbons, as well as to
mer slurry. protect the polymer.

Extrusion and Pelletizing. Powder leaving

the driers at about 100 – 120 ◦ C can be fed di-
rectly to a pelletizing extruder, in which it is
It is vital to work with either a strongly acidic stabilized and converted into dense granules.
or strongly alkaline complexing medium to re- As intermediate powder storage is often nec-
press hydrolysis and polycondensation, which essary, common practice introduces a cooling
impair the extraction efficiency. This technique stage to 70 – 80 ◦ C to prevent adventitious oxi-
normally yields polymer containing 10 – 30 ppm dation when antioxidants are absent.
of Ti, 10 – 40 ppm of Al, and 20 – 40 ppm of Cl
residues. Very pure polymer can be made in Diluent and Alcohol Recovery. An essential
an alternative form of step d. Here, the poly- part of the schematic plant shown in Figure 25 is
mer is isolated by filtration, and is repeatedly solvent and alcohol recovery, and atactic poly-
washed by reslurrying in diluent/alcohol mix- mer separation (stages h – j). Diluent from the
tures to remove all solubilized catalyst without centrifuge contains soluble polymer and traces
introducing water. This process adds to the load of alcohol. This mixture, together with liquid
on diluent and alcohol recovery, but PP quality from the driers, is separated by multistage distil-
improves. lation. Pure diluent is then recycled to the poly-
merizers, while viscous atactic polymer sepa-
Centrifuging. Centrifuging the deashed rates out as a heavy end. Wiped film evaporators
slurry (step e, Figure 25) removes most of the can be used to strip the last traces of diluent from
free diluent, but the wet cake can still hold up highly viscous solutions.
to 50 wt % (dry basis) of diluent containing dis- Most of the alcohol is recovered from the
solved atactic polymer. Depending on the grade first few water washes by fractional distillation
of polymer being produced, it is sometimes ben- (step h) followed by azeotrope splitting.
eficial to introduce a washing stage with diluent
while centrifuging to reduce the amount of sol-
uble polymer in the final product. Centrifuges
can be of the filtering (basket) or decanting type
according to the powder characteristics.
48 Polyolefins

2.5.2. Bulk Polymerization in Liquid extraction, nor removal of atactic polymer be-
Propene cause of the high stereospecificity. Homopoly-
merization takes place at ca. 70 ◦ C and 4 MPa
A special case of the slurry is to use liquid in liquid propene circulating round one or more
propene, with its poorer solvent power, instead loop reactors. A single axial flow agitator in each
of an inert diluent. Polymerization rates in- loop maintains high flow rates to ensure good
crease considerably with pressures around 3 – heat transfer to the water-cooled jackets, whilst
4 MPa. Stirred autoclaves incorporating evapo- also preventing any polymer particles settling
rative cooling, and loop reactors provide good from the slurry [181]. Typically the PP concen-
heat-transfer rates. The chemistry parallels that tration is ca. 40 wt %.
described in Section 2.5.1, but the engineering Continuously metered catalyst, trieth-
demands are greater [178]. After polymeriza- ylaluminum, and a Lewis base stereoregulator
tion, the catalyst is solubilized with polar com- such as a dialkyldimethoxysilane are fed into the
plexing agents to permit extraction from the reactor to maintain polymerization and stereo-
polymer by countercurrent washing with liquid control. The initial few seconds of polymeriza-
propene. Hybrid plants are known which use tion with a new high-activity catalyst particle
liquid propene for polymerization, followed by are quite critical to secure good performance.
flashing and resuspension in heptane for poly- For this reason, some processes have a prepoly-
mer deashing. merization stage in which the catalyst compo-
nents react at lower temperature and monomer
concentration. This can be either a batch or con-
2.5.3. Solution Polymerization tinuous pretreatment which produces only small
amounts of polymer (< 100 g/g) in the catalyst.
In contradistinction to polyethylene manufac- This prepolymerized catalyst is then fed into the
ture, solution polymerization at high tempera- loop reactor as usual. Mean residence time in a
ture is rarely practiced for isotactic PP. Special single polymerizer is 1 – 2 h. Two loop reactors
catalysts are necessary to minimize the custom- can be operated in series to narrow residence
ary reduction in stereospecificity above 100 ◦ C, time distributions, modify the polymer, and in-
but the activity and stereoregularity still remains crease output.
too low to dispense with catalyst extraction and A continuous stream of polymer slurry dis-
removal of atactic PP. The original Eastman – charges through a heated zone for the first stage
Kodak process makes grades for some special of pressure let down in cyclone (b). For ho-
markets, but there are no plans for further new mopolymers, this connects directly to the sec-
plants along these lines. While polymerization at ondary cyclone (d), bypassing the copolymeri-
ca. 150 – 200 ◦ C should permit some useful re- zation unit (Section 2.5.7.2). Unreacted propene
covery of polymerization heat, overall costs are flashes off from the first cyclone and is con-
high for isotactic PP. It is reported [179] that the densed with cooling water and recycled to the
solution process is being used to make atactic reactor. A compressor is required for gas from
PP, for which it seems more suited. Commercial cyclone (d). Polymer powder from the cyclone
plants dedicated to make only atactic PP have is fed into vessel (e) for deactivation with small
been announced by Himont (Canada), El Paso amounts of steam and undisclosed additives.
(Texas), and Huls (Germany). Residual moisture and volatiles are removed by a
hot nitrogen purge in vessel (f) before conveying
polymer to storage silos for conventional finish-
2.5.4. Spheripol Process [180] ing as stabilized powder or extruded pellets.
Provided the expensive extrusion stage can
Figure 26 depicts a modern state-of-the-art plant be dispensed with by selling powder, then it
based on Himont technology [180] for mak- is claimed that the capital cost of Himonts
ing homopolymer and impact copolymers (Sec- Spheripol process is only 50 % of the suspen-
tion 2.5.7.2) with supported catalysts. The latter sion process described in Section 2.5.1 [180].
are sufficiently active not to require any catalyst
 Polyolefins 49

Figure 26. Spheripol process

a) Loop reactors; b) Primary cyclone; c) Copolymer fluidized bed; d) Secondary and copolymer cyclone; e) Deactivation;
f) Purging

2.5.5. Hypol Process homopolymers, impact copolymers, and random

propylene – ethylene copolymers using high-
Mitsui Petrochemical, co-inventor with Himont activity, highly stereospecific catalysts. The re-
of the supported catalyst system, has developed actor vessels, of 25, 50, or 75 m3 capacity,
an analogous cheap process using bulk polymer- are equipped with proprietary helical agitators,
ization with their own supported catalysts. It dif- which give excellent agitation. Homopolymer-
fers from the Spheripol system in that batch pre- ization needs only the primary reactor, into
polymerization is used with washing. Two con- which the catalyst components are fed. These
ventional stirred polymerizers are used in series, must be very well dispersed in the powder bed to
with heat removal by evaporative cooling of liq- avoid build-up. The reaction conditions of 70 –
uid propene in the reactors. Slurry is then dis- 80 ◦ C and 3 – 4 MPa ensure that the monomer
charged into a stirred, heated flash vessel, where phase is gaseous in the reactor. Low concentra-
propene is recovered from polymer, as in the Hi- tions of hydrogen are used to control molecu-
mont system. lar mass over wide ranges. The temperature is
controlled by removing gaseous propene from
the reactor head space, condensing it with cool-
2.5.6. Gas-Phase Processes ing water, and then recirculating it back into the
reactor, where its evaporation provides the re-
In gas-phase processes, gaseous propene is con- quired cooling, as well as further aeration of the
tacted with solid catalyst intimately dispersed stirred powder bed. Each tonne of polymer made
in dry polymer powder. Industry uses two dif- requires ca. 6 t of liquid propene to be evaporated
ferent methods of carrying out this reaction de- as coolant.
pending on the chosen method of heat removal. Powder and associated gas discharge contin-
The Union Carbide/Shell process uses an adap- uously from the primary reactor dip tube directly
tation of the Unipol polyethylene fluidized-bed into a low-pressure cyclone (g). Propene carrier
system. BASF and Amoco use mechanically ag- gas from this cyclone is recycled to the reactor
itated dry powder beds with evaporative cool- after compression, liquifaction, and, sometimes,
ing in vertical and horizontal autoclaves, respec- distillation. The powder then passes to a purge
tively. vessel where a deactivator quenches all residual
catalyst activity, and nitrogen strips out traces of
BASF Novolen Process [182]. Figure 27 propene from the hot powder. From here pow-
shows the BASF continuous process for making der is conveyed into silos for stabilization and
50 Polyolefins

Figure 27. BASF gas-phase Novolen process

a) Primary reactor; b) Copolymerizer; c) Compressors; d) Condensers; e) Liquid pump; f) Filters; g) Primary cyclone; h) De-
activation/purge

extrusion into granules. BASF also offers a post- provides cooling, while uncondensed monomer
granulation steam-stripping package to remove and hydrogen injected into the base main-
any oligomers and oxidized residues from the tain the gas composition. Figure 28 also in-
granules for demanding applications. cludes a fluidized-bed deactivation system for
BASF pioneered their gas-phase process with use with second-generation, chlorine-rich cat-
commercial production in 1969. The products alysts. Amoco – Chisso claim that their reac-
made, Novolen 1300 series, were based on high tor achieves some degree of plug flow, roughly
molecular mass total work up polymers (i.e., equivalent to that of 2 – 3 fully back mixed reac-
containing atactic PP and catalyst residues) hav- tors in series [183].
ing reduced stereoregularity. Today, such grades
still find niche markets, although they are vulner- Unipol – Shell Fluidized-Bed Process
able to competition from random copolymers. [184]. The Unipol – Shell plants, commissioned
Production is to be phased out shortly. in 1986, combine technologies from Union Car-
BASF also uses their process with a cheaper bide and Shell. Most conspicuous in this process,
second-generation catalyst TiCl3 /AlEt2 Cl, Figure 29, is the tall fluidized-bed reactor with
which then requires an additional dry-powder its expanded upper section to reduce gas velocity
dechlorination stage. and powder entrainment. Continuous feeds of
catalyst components, comonomer, if any, hydro-
Amoco – Chisso Stirred-Bed Process. Col- gen, and propene are thoroughly mixed in the
laboration between Amoco and Chisso resulted dense-phase fluidized bed of powder. A large
in joint licensing arrangements from 1985. This cooler in the gas recirculation loop removes all
process uses a horizontally stirred reactor, Fig- the reaction heat from the considerable gas flow.
ure 28, instead of the vertical helical agita- In this system the fluidized bed is said to behave
tor of the BASF process. Condensed recycled as a fully back mixed reactor, without undue
monomer sprayed into the top of the reactor separation of coarse particles. No mechanical
 Polyolefins 51

Figure 28. Amoco – Chisso gas-phase process

a) Horizontal reactor; b) Fluidized-bed deactivation; c) Compressor; d) Condenser; e) Hold/separator tank

Figure 29. UCC/Shell – Unipol fluidized-bed process

a) Primary fluidized bed; b) Copolymer fluidized bed; c) Compressors; d) Coolers; e), f) Discharge cyclones; g) Purge

agitation is needed. Reaction conditions are re- directly to a purge vessel (g) to remove residual
ported as < 88 ◦ C and < 4 MPa. monomer. Neither catalyst removal nor atactic
Product powder and associated gas are dis- polymer extraction is necessary with the mod-
charged from just above the distributor plate by ern Shell catalysts used in the Unipol process.
timed valves into a cyclone separator (e) and then
52 Polyolefins

2.5.7. Copolymerization 2.5.7.2. Impact (Block) Copolymerization

[188, 189]
Copolymers of propene with other α-olefins ac-
count for ca. 30 % of all PP sales. There are Impact copolymerization is regarded as the low-
two distinct classes of copolymer having differ- est cost process for making toughened PP. It
ent application areas. Random copolymers, ob- can be visualized as a method for producing
tained by copolymerizing mixtures of propene an intimate blend of PP homopolymer with a
and other α-olefins have lower melting points toughening ethylene – propene elastomer. Ap-
and improved clarity. Impact (block) copoly- proximately 10 – 20 wt % of this elastomer suf-
mers, made in a two-stage polymerization pro- fices for most applications, though the availabil-
cess, are high-impact-strength grades that con- ity of products containing 30 – 40 wt % will ex-
tain dispersed propene – ethylene elastomers. pand their use.
The minimum requirement for block copoly-
2.5.7.1. Random Copolymerization merization is a two-stage process. In one stage
homopolymer is prepared by any of the meth-
Random copolymers are made in the same way ods described in Sections 2.5.1, 2.5.2, 2.5.3,
as homopolymers, but a mixture of propene and 2.5.4, 2.5.5, 2.5.6. The other stage uses a mixed
the comonomer is used in place of pure propene. monomer feed of ethylene and propene to pro-
Usually, polymers containing 2 – 6 wt % of com- duce a largely amorphous, elastomeric phase
bined ethylene cover most applications. Some- within the polymer particles. Many other more
times the resulting copolymers are referred to complex configurations have claimed to be ad-
as “statistical” because heterogeneous Ziegler vantageous for certain products, but two stages
catalysts rarely yield truly random copolymers are generally adequate [188, 189].
[157] with mixed feeds of monomers. 1-Butene Homopolymer, or a very low ethylene
can also be used, especially as a termonomer copolymer, is always made in the first reactor be-
along with ethylene. The higher α-olefins are cause the elastomer fragments catalyst particles
more expensive and less reactive than propene in diluent systems and produces sticky products
and can complicate the monomer recycle stage. in gas-phase reactors. This first stage of reac-
However, attractive product properties are stim- tion, using propene and hydrogen as molecular
ulating manufacture [185, 186]. mass controller, is indistinguishable from con-
In the case of suspension polymerization, ei- ventional homopolymerization. In batch slurry
ther in hydrocarbon diluent or in bulk, significant systems, propene is metered into a reactor until
amounts of soluble byproducts add to handling the amount of polymer formed is 80 – 90 % of the
difficulties due to viscosity increases at higher intended final make. The remaining 10 – 20 % is
comonomer contents. Drying temperatures must made in the second stage as follows. Normally
be reduced because of the lower softening point the propene concentration is allowed to fall, by
and more cohesive nature of the particles. continued polymerization, to a predetermined
Gas-phase systems, especially those having value before introducing ethylene, propene, and
some degree of mechanical agitation, are less possibly hydrogen. No further catalyst is needed
adversely affected, though maximum tempera- for the second stage, and the reaction tempera-
tures still need careful control. ture might be lowered to reduce the amount of
Random copolymers often find use in food soluble polymer diffusing out of the particles.
packaging (see Section 2.7.2), where the poly- The high reactivity of ethylene promotes rapid
mer must not contain high proportions of ex- copolymerization in a more exothermic reaction.
tractable material. Clarity improves and melting Venting and polymer isolation follow the proce-
points fall as comonomer and solubles increase. dure already described in Section 2.5.1, but fil-
A compromise is reached at about 3 wt % of eth- tration and atactic polymer separation are more
ylene. Changes to catalyst and polymerization difficult because of additional amounts of vis-
techniques can raise this by securing a more cous soluble copolymer.
uniform disruption of the isotactic sequences,
which in turn encourages formation of the lower
melting γ- crystallites [187].
 Polyolefins 53

Gas-phase systems using modern catalysts 2.5.8. Product Finishing

avoid much of this difficulty. Figure 27 shows
a typical BASF continuous process using two Considerable capital is involved in the finishing
stirred reactors for making impact copolymers areas of all plants after the dry powder stage. The
[182]. Active polymer and gas from the first great majority of this powder is extruded with a
reactor discharge directly into the copolymer- variety of additives, pelletized, tested, and then
izer, operated at 1 – 2 MPa lower pressure and stored in various packages for sale. Direct sale of
lower temperature. Normally, the propene/eth- suitably stabilized reactor powder circumvents
ylene/hydrogen ratio is adjusted such that the some, but not all, of these costs.
rubbery copolymer made in this reactor contains
40 – 60 wt % ethylene, depending on the partic- Extrusion and Pelletization. Proprietary
ular grade. This gas composition is not readily equipment from specialist manufacturers will al-
condensed with cooling water alone, so a com- ways be used for high-throughput plants oper-
pression stage is added to liquify some of the re- ating at 5 – 20 t/h and 250 ◦ C. In selecting ex-
cycled gas returned to the reactor base. Copoly- truders the following factors are relevant (in
mer powder, with its associated carrier gas, dis- addition to costs): powder morphology, prod-
charges into the low-pressure cyclone separator uct MFI range, melt filtration needs, devolatal-
(g), which passes this carrier gas to recompres- ization, turn down ability (i.e., efficient oper-
sion for return to the copolymerizer. Residual ation at low rates), temperature control, mix-
monomer in the copolymer is removed in a com- ing needs, and additive feeds. The types of ex-
bined purging and deactivation vessel (h) before truder available include long, single-screw ma-
conveying powder into silos for extrusion. chines and two-stage systems in which pow-
Analogous gas-phase techniques are used der is melted in a continuous high-speed mixer
by other manufacturers. Amoco – Chisso (see which discharges the melt into a short, pressure-
Fig. 28) add a second horizontal stirred reactor generating extruder. Twin-screw machines with
when making impact copolymers, and El Paso corotating and segmented screws are increas-
also add a similar polymerizer after their bulk ingly used for additional flexibility. Versatility
first stage. Unipol – Shell introduce a second, but and output can also be increased by installing
smaller, fluidized bed (Fig. 29), operating at ca. a gear pump between the die plate and the dis-
1.5 MPa, for their impact copolymers, thus tak- charge end of the screw in any of these systems.
ing advantage of enhanced copolymerization ac- Pelletization takes two forms. Extruded laces
tivity. Sumitomo’s new process also uses two flu- from the die plate are quenched in water to give
idized beds. Himont (Fig. 26) and Mitsui Petro- rigid strands. High-speed cutters then chop the
chemical retain their normal bulk polymeriza- continuous strands into 2 – 5 mm lengths to pro-
tion for the first, homopolymerization step, but duce so-called lace-cut pellets. In the other sys-
use gas-phase copolymerization in a fluidized tem, high-speed knives rotate against the ex-
bed for producing impact copolymers. Such dry truder die plate to cut off short lengths of the
powder reactions overcome the problems aris- molten extrudate. Either the insulated die plate
ing from extraction of soluble copolymer species is immersed in water, or the molten pellets are
in liquid-based processes. At the same time, instantly solidified by being flung into a water
copolymer diffusion to the surface should be re- ring quench zone to prevent cohesion. These die
duced by the lower degree of swelling in dry face cut granules are increasingly common in
powder systems. large plants.
While copolymers containing 40 %, or more,
of elastomer can be handled satisfactorily in Salable Powder. Densification is avoided
plant processes, their cohesiveness calls for entirely for those outlets willing to use suit-
more care than with homopolymers. Himont ably stabilized powder. Spherical particles, up
patents suggest that their fluidized-bed technol- to ca. 0.3 mm diameter, have been available for
ogy recognizes this aspect. Overall, there is com- many years, but in most applications pellets are
plete unanimity that a gas-phase copolymeriza- preferred because of their better housekeeping
tion stage is preferred for this class of copolymer
in modern plant.
54 Polyolefins

(spillages, dust, etc.), easier handling in stan- the amount of each of these additives is 0.05 –
dard systems, and absence of concern about pos- 0.2 wt %, but in more aggressive environments
sible dust explosions due to powder attrition. the levels might rise to 0.5 %, with thiodipro-
Emergence of coarse Spheripol powders from pionate esters as peroxide decomposers. The
Himont, 1 – 5 mm diameter, should dispel some choice of stabilizer is influenced by the applica-
of these concerns provided adequate and non- tion, for example, interaction with spin finishes
separating stabilization systems are established [191], resistance to extraction by hot water, and
with mechanically robust coarse particles. This regulatory constraints.
will entail some additional manufacturing costs, Traces of copper or cobalt powerfully ac-
and perhaps more product constraints, but this celerate thermal oxidation, especially at sus-
expenditure should be less than that for capital tained temperatures above 60 ◦ C. In these cases
and energy intensive extrusion and pelletization a chelating agent such as a bishydrazone is added
operations. Himont is constructing a PP plant [192].
in Brazil, due for completion in 1991, which is Continuous outdoor exposure also requires
claimed to have no extrusion facilities. However, protection from the damaging effects of UV
these have subsequently been installed. radiation. The severity of embrittlement in-
creases at high temperature and with rainfall
Additive Incorporation. Extrusion pro- in some polypropylenes. Atmospheric pollu-
vides an efficient and convenient way of in- tion can deposit protective layers on the sur-
corporating antioxidants and other modifiers face. Ultraviolet-absorbing compounds, such
into polymers. Metered amounts are mixed with as alkoxybenzophenones and hydroxybenzotri-
the main powder feed to the extruder and ho- azoles for thick sections, and hindered amine
mogenized in the molten polymer. Good mixing light stabilizers (HALS) for films, provide
is essential to prevent extrusion of unstabilized protection at contents of 0.1 – 1.0 wt % [193].
product at high temperature. Nitrogen blanket- Screening with some fine pigments or carbon
ing is common practice. Highly specialized and black is effective, but restrictive on appearance.
low-tonnage formulations are either made on a Gamma radiation, used for packaged food
separate plant having appropriately sized equip- and sterilization of medical equipment, degrades
ment, or the customer himself adds concentrates PP, causing embrittlement. The effects can be
in the form of stabilizer master batches. mitigated by the careful choice of stabilizer.
Liquid additives, such as some antistats, can
be metered directly into the melt, given good Antistats. The familiar static charges and re-
subsequent homogenization in the extruder. sulting dust deposits on many plastics can be
overcome in PP by incorporating 0.2 – 1.0 wt %
of polar additives. Suitable materials, such as
2.5.9. Additives polyether fatty amide and fatty amine conden-
sates and glyceryl monostearate reduce the sur-
Stabilizers [190]. Like most hydrocarbons, face resistivity from > 1013 to ca. 107 Ω. The
PP must be protected against oxidation, partic- mechanism involves slow diffusion of the addi-
ularly above 100 ◦ C. The dominant reaction is tive to the surface where it picks up atmospheric
chain scission by free-radical attack at the ter- moisture. Hence, time and humidity are impor-
tiary carbon atoms of the backbone. This gen- tant. At 50 % RH most of the recommended ad-
erates hydroxyl and carbonyl groups, accompa- ditives are satisfactory, but at 30 % RH the fatty
nied by yellow discoloration and brittleness. In- amine derivatives are advantageous. A few days
corporating radical scavengers considerably de- storage at room temperature is sufficient to de-
lays the onset of embrittlement and increase of velop the conducting surface layer.
the MFI. Antioxidants are always incorporated Compositions containing moderate amounts
into PP before or during extrusion at manufac- of conductive carbon black are also effective, as
turing plants. Usually a peroxide decomposer, are small amounts of polyacetylenes. The latter,
such as a phosphite, is introduced to improve and the incorporation of small amounts of fine
melt stability, together with hindered phenols metallic wire, are too expensive for PP applica-
to confer long-term aging resistance. Typically, tions.
 Polyolefins 55

Antacids. Most of the earlier PP formu- run lengths in specified compounding extrud-
lations contained 0.05 – 0.2 wt % of calcium ers or mixers. For this reason, and for con-
stearate to prevent traces of acidic catalyst cern about cross contaminating unmodified PP
residues from corroding customers’ equipment. grades, compounding plants usually operate sep-
It behaves as a mild slip agent and suppresses arately from main PP production plants.
attack of HCl on certain antioxidants. Zinc, Substantial property enhancements enable
magnesium, and sodium stearates have also polypropylene-based products to compete in
been used, and more recently synthetic hydro- quite demanding areas where unmodified PP
talcite (a hydrated magnesium aluminum hy- would be inadequate (see Table 18). Examples
droxycarbonate). Lower levels of such additives include tough front and rear bumpers for cars,
are still widely used. rigid coupled glass compositions for washing
machine tubs, dense grades for outdoor gar-
Slip and antiblock agents are mainly used in den furniture, and temperature-resistant compo-
film production where high-speed handling re- sitions for car under hood applications. Long-
quires a controlled reduction in frictional forces. fiber-reinforced PP secures further increases
0.1 – 0.5 wt % of oleamide, erucamide, glyceryl in toughness and stiffness over short-glass-
monostearate, etc., usually suffices. Fine, spher- fiber compounds [196]. Fibers with a minimum
ical particles of silica incorporated at the pel- length of between 0.8 and 3 mm, depending on
letization stage prevent layers of film adhering the coupling between matrix and fiber, are likely
to each other during storage. to be satisfactory. These form an interlocking
skeletal structure which dissipates the impact en-
Crystallization Nucleants. Although pure ergy over a large area of the molding.
PP has a final melting point of 176 ◦ C, the The combination of lower production rates,
melt supercools by 50 – 60 ◦ C before crystal- specialized equipment, and dense additives
lization sets in at ca. 115 ◦ C. Small amounts mean that PP compounds are always more ex-
of certain additives [194] nucleate the melt, pensive than natural grades.
raising the crystallization temperature by 10 –
15 ◦ C. Smaller spherulites result, sometimes
having different structures. Advantages of nu- 2.7. Properties
cleated grades include shorter injection mold- 2.7.1. Homopolymer
ing cycles, higher moduli, greater transparency,
and higher heat distortion temperatures. Suitable Basic mechanical properties are largely influ-
additives include dibenzylidene sorbitol and enced by molecular mass and molecular mass
substituted variants, di-tert-butylbenzoate salts, distribution (MMD), chain stereoregularity, and
sodium benzoate, finely divided talc, sodium di- processing conditions, which introduce orienta-
aryl phosphates, and some pthalocyanine pig- tion, strain, etc. Various additive packages must
ments. These materials are somewhat selective be tailored to the application to achieve good and
in their effects, i.e., some are particularly good durable performance.
for transparency improvement, but less effective
for modulus enhancement. Careful balancing of Molecular Mass. At low shear rates melt vis-
the overall additives recipe is also essential be- cosities are proportional to the 3.4 power of the
cause both adverse and beneficial interactions weight-average molecular mass. At the higher
occur between some of the components [195]. shear rates found with most processing equip-
ment, the dependence is still greater than a power
of 2 because much chain entanglement still ex-
2.6. Compounding ists. As a result of this sensitivity, and the di-
rect relevance to processing, the melt flow index
Compounding includes incorporating mineral (MFI) is always used to describe the viscosity
fillers, glass fibers, elastomers, flame retar- characteristics of each polymer grade. The de-
dants, pigments, and carbon black. It is a spe- pendence of melt viscosity on shear rate is also
cialized operation dealing with relatively short related to MMD as a result of the strong influ-
ence of very long chains. Hence MFI is often
56 Polyolefins
Table 18. PP compounds – property enhancement

Property Homopolymer Impact copolymer Compound Composition

Toughness, kJ/m2 (N Izod, 0 ◦ C) 3.0 10.0 > 50 rubber + filler (car spoilers)
Modulus, GPa 1.5 1.0 7.6 coupled glass
1.5 1.0 2.7 chalk loaded
Heat distortion temperature 105 90 160 coupled glass
(0.45 MPa), ◦ C 105 90 130 talc filled (heater casings)

measured at two different shear rates to give further melting point reductions by copolymer-
some idea of MMD. Increasing importance is ization without significantly increasing the low
being attached to a more comprehensive rheo- level of xylene-soluble material.
logical characterization [197, 198].
A typical, medium-flow polymer has an MFI Other Properties. Table 19 lists the proper-
(230 ◦ C/2.16 kg) value of 3 dg/min, correspond- ties of several polymers measured by standard
ing to a M w of 460 000 and M n of 54 000. The procedures, with some copolymer data included
practical grade range of 0.3 – 50 MFI covers ap- for comparison. Care must be taken in translat-
plications from sheet and pipe extrusion to high- ing these exact values to fabricated products be-
speed fiber spinning. cause properties are dependent on built in stress
Heterogeneous Ziegler – Natta catalysts yield and orientation. Increasing the molecular mass,
broad MMD polymers having M w /M n of 5 – i.e., lowering MFI, raises toughness somewhat,
10, the lower values being associated with the but the modulus and hardness decrease with the
more recent Solvay and supported catalysts. lower crystallinity.
Very narrow MMDs are still made by preferen- Some general and electrical properties of
tially cleaving long chains in an extruder, usu- polypropylene are as follows:
ally with the assistance of organic peroxides.
Density, kg/m3
Such grades, commonly referred to as controlled
20 ◦ C 905
rheology (CR) polymers, reduce extrusion and 200 ◦ C 770
molding orientation caused by high molecular 220 ◦ C 760
mass species with their long relaxation times 240 ◦ C 740
260 ◦ C 710
[199]. Note that reworked polymer is likely to
have a higher MFI and a correspondingly nar-
rower MMD than the starting material. Coefficient of linear expansion, K−1
20 ◦ C 1.1×10−4
80 ◦ C 1.7×10−4
Stereoregularity. Very high stereoregularity
is now achievable with modern catalysts, even
Specific heat, kJ kg−1 C−1
without removing any soluble byproduct. In 20 ◦ C 1.93
some applications processing is helped by a 50 ◦ C 2.04
small lowering (detuning) of the isotactic index. 100 ◦ C 2.37
150 ◦ C 4.0
This is readily achieved by minor changes to the
polymerization recipe, and by introducing small
amounts of copolymerized ethylene. Glass transition temperature T g ,
◦
C
isotactic −13 to 0
Metallocene-Based PP. An expanded range atactic −18 to −5
of products is iminent following the encouraging
metallocene developments. Further pilot trials Flammability
and customer assessment of processing, product, UL 94, 3 mm thick UL 94 HB
and economics is needed before precise defini- ASTM D635, 3 mm 23 mm/min
FMVSS 302
tion is possible. The advantages already seen in- 1 mm 43 mm/min
clude higher extrusion rates for films and fibers, 2 mm 38 mm/min
enhanced clarity, absence of oligomers, supe- 3 mm 20 mm/min
rior property balances, and the ability to control
Table 19. Mechanical and thermal properties of PP Origin “Propathene” (with permission of ICI Chemicals & Polymers)

Property Method Temperature Homopolymer Impact copolymer Random copolymer

GSE 16 GWM 22 LYM42 LZM 55/52 GWM 101 GWM 213 LXF 301

Melt flow index (230 ◦ C/2.16 kg), ISO 1133 1.00 4.00 12.00 33.00 6.00 2.00 7.50
g/10 min (dg/min)
Tensile yield stress, MPa ISO 527 33.50 34.50 34.50 34.00 27.00 23.50 25.00
Flex. modulus, GPa ISO 178 (10 mm/min) 1.45 1.50 1.50 1.55 1.15 1.00 0.85
Izod impact strength, kJ/m2 ISO 180 (0.25 mm notch 23 ◦ C 4.50 4.50 4.00 3.00 9.50 no break 5.00
radius)
0 ◦C 3.00 3.00 2.50 2.00 5.50 10.00 2.50
−20 ◦ C 2.00 2.00 2.00 3.50 7.50
−40 ◦ C 5.00
Instrumented drop weight impact ICI method 23 ◦ C 7.00 10.00 10.00
strength, J
0 ◦C 6.00 11.00 2.00
−20 ◦ C 6.00 11.00
−40 ◦ C 9.50
◦
Embrittlement temperature, C ICI method > 23 > 23 > 23 > 23 −20.00 −45.00
Rockwell hardness ISO 2039/2, 93.00 95.00 95.00 95.00 90.00 75.00
ASTM D785 R scale
Vicat softening temperature (10N ISO 306A, BS 2782: 154.00 154.00 154.00 154.00 147.00 143.00 135.00
force), ◦ C 120A
Heat distortion temperature, ◦ C ISO 75/A & /B
A – 1.8 MPa 65.00 65.00 65.00 68.00 60.00 50.00 46.00
B – 0.45 MPa 100.00 100.00 100.00 102.00 95.00 90.00 71.00
Polyolefins
57
58 Polyolefins

Thermal conductivity, W m−1 ◦ C−1 0.209

comonomer and its distribution along the chain.
Combustion heat, kJ/g 44.0 Table 19 shows how the modulus decreases for
Autoignition temperature, ◦ C 360 a random copolymer containing ca. 3 wt % of
O2 index (ASTM D28) at 600 ◦ C 3.5 combined ethylene.
Relative permittivity at 1 kHz 2.25
(IEC 250)
Volume resistivity, 1 min, Ω · m > 1015
(IEC 93)
Electrical strength
(20 – 80 ◦ C, 10 – 20 s, 3.2 mm, > 12 kV/mm
IEC 243)

Dissipation factor tan δ (IEC 250)

50 Hz 0.00015
1 kHz 0.0002
1 MHz 0.00015

The final melting point of commercial PP lies

in the range 160 – 170 ◦ C, with purified polymer
reaching 176 ◦ C. However the safe upper work-
ing temperature limit should be 100 – 120 ◦ C,
depending on the stress, with short excursions up
to 140 ◦ C being permissible. This comfortably
extends the upper operating range available with
high-density polyethylene by ca. 20 ◦ C, which
has a similar room temperature modulus.
Favorable long-term creep characteristics un- Figure 30. A) DSC heating endotherm; B) DSC cooling
der load permit useful increases in the stacking exotherm
height of PP crates or other pelletized contain- Courtesy of the “Propathene” Business, ICI Chemicals &
ers. The repose angle of PP moldings on wood Polymers
or canvas, unpredictably 30 % higher than for
HD polyethylene, is allegedly a useful stabiliz- Several applications take advantage of the
ing feature in mechanical conveyors. lower melting point to make thermoweldable
The crystalline and nonpolar nature of PP film. Ideally, it would be useful to have a low
confers good resistance to a wide range of aque- melting range without undue increases in the
ous and polar media, including emulsifier solu- proportion of xylene-soluble residues. This is
tions with their strong stress cracking abilities. claimed to be possible with butene copolymers,
Powerful oxidizing agents and highly aromatic perhaps because the solubles are produced at
or chlorinated solvents are too aggressive for semi-exposed catalyst sites more easily acce-
safe storage in PP containers. sible to ethylene [186]. Some advantages are
The ease with which homopolymers can be also claimed for propene – ethylene – butene ter-
drawn into high strength structures has been polymers [180, 185]. Butene helps the devel-
heavily exploited in the fiber and film industries opment of low-melting γ-triclinic crystallites.
(see Section 2.8.3). Random copolymers are somewhat tougher than
homopolymers, and do not exhibit the familiar
stress-whitening behavior of the tougher copoly-
2.7.2. Copolymers mer impact grades.

Random Copolymers. Incorporating 2 – Impact Copolymers. Section 2.5.7.2 de-

7 wt % of ethylene into the main chain lowers the scribes block copolymerization systems for
overall crystallinity, gives a broader softening making high impact strength grades of PP. These
range with reduced melting points (Figs. 30 A, are often referred to as block copolymers, tough-
30 B), increases the fraction of soluble polymer, ened polypropylene, or more pedantically het-
and improves transparency and surface gloss. erophasic copolymers [180].
These changes are dependent on the amount of
 Polyolefins 59

Essentially, these products are best viewed as mopolymer, and this second phase reduces the
an intimate dispersion of elastomer in a PP ma- translucency. Severe deformation causes some
trix. The particulate rubber phase confers good whitening or blushing [200] in the stressed re-
toughness, while the homopolymer matrix is re- gions, particularly in very high impact grades. In
sponsible for retaining good high-temperature other respects the rules relating processing and
performance and adequate stiffness. In this re- properties to MFI, nucleation, controlled rheol-
spect they are far superior to random copoly- ogy, stabilization, etc., are the same as for ho-
mers, and become the first choice when impact mopolymer.
strength and rigidity are called for. In extruded
pellets or molded articles the rubbery copolymer
phase is well distributed in the form of droplets 2.7.3. Elastomer Blends with Polypropylene
1 – 5 µm in diameter. Such a structure (Fig. 31)
is produced during melting and recrystallization. Originally, PP was toughened by blending with
Powder direct from the reactor has elastomer ca. 10 wt % of polyisobutylene (PIB) elastomer.
permeating throughout the particle in a more In some situations the same technique is used
continuous form. Many of the complex inter- today, with ethylene – propene rubber (EPR) or
actions which control the stability of this phase ethylene – propene – diene rubber (EPDM) re-
structure and the resulting toughness, await fur- placing PIB.
ther study [189]. As rubbers are incompatible with PP, con-
siderable mechanical work is necessary to se-
cure the vital fine dispersion of elastomer. Good
blending also requires a reasonable viscosity
match between the two components. Common
practice is to use a two-stage process in which
the elastomer is first compounded with PP to
give a 50 – 70 wt % masterbatch of the rubber as
free flowing granules. Such masterbatches can
be purchased at extra cost. Good mixing devices
are essential for the final compounding step with
PP. Twin-screw extruders or high-speed mixing
devices perform satisfactorily.
Well-prepared blends have physical property
combinations only just short of those of directly
polymerized impact copolymers. However, the
latter are generally preferred on account of con-
sistency and grade versatility. Elastomer blend-
ing is also part of the broad spectrum of com-
pounds referred to in Section 2.6. Here they are
used to uprate the toughness of homopolymer
and impact copolymers in these complex for-
Figure 31. Electron micrograph of high impact copolymer mulations. Some manufacturers also introduce
molding after hexane surface wash HD polyethylene, in addition to rubber, to se-
cure further toughness improvements. In these
Toughness, stiffness, and softening points are cases, electron microscopy reveals that in well-
given in Table 19 for two impact copolymers dispersed systems the polyethylene is always lo-
containing ca. 10 and 20 % of elastomer. Gas- cated inside and towards the center of these rub-
phase polymerization systems are able to in- ber droplets. This encapsulation of PE makes
crease the rubber content to 40 %, but the prod- it behave more like rubber towards the matrix,
ucts are not available in large commercial quan- thereby increasing toughness at the expense of
tities at present. These impact copolymers nat- modulus in such ternary blends.
urally contain more soluble polymer than ho-
60 Polyolefins

2.8. Uses ings having high flow ratio geometries (flow ra-
tio is the ratio of longest path to the section thick-
Polypropylene is readily processed in conven- ness). The inevitable fall in impact strength at
tional equipment used for other thermoplastics. high MFI can be recouped, in some cases, by
Injection molding, commonly using screw-type moving from homopolymer to impact copoly-
reciprocating machines, accounts for 40 – 50 % mer grades.
of all applications. Extrusion processes account While molding conditions vary with the size
for the remainder with domination by fiber and and complexity of the article, the following ma-
film. chine settings will cover most products [199]:
A more detailed picture is obtained by
Melt temperature: 230 – 275 ◦ C
analysing the North American 1996 sales data Injection pressure: 55 – 100 MPa
(in 103 t/a) listed in the following [202] : Mold temperature: 40 – 80 ◦ C, lower still for thin walled
items
Blow molding
Containers 74 The low moisture absorption of PP largely
Others 5 dispenses with any need to dry granular feed-
Total blow molding 79
Extrusion
stock. Neither do gaseous or carbonaceous
Coatings 5 decomposition products form in extruder dead
Fibers and filaments 1463 spots. Instead, polymer remaining there be-
Film (up to 0.25 mm) comes progressively more fluid through chain
Oriented 503
Unoriented 111
scission. Machine shot weight capacities nor-
Pipe and conduit mally refer to performance with polystyrene,
Sheet (over 0.25 mm) 110 i.e., the polystyrene yardstick figure. The lower
Wire and cable 5 melt density of PP (0.75 g/cm3 ) lowers the ma-
Others 43
Total extrusion 2240 chine’s weight capacity by ca. 25 % when mold-
Injection molding ing PP. Plasticizing capacity is slightly greater
Appliances 139 than for polyethylene, but is lower than for
Consumer products 565
Rigid packaging 523
amorphous polystyrene. Machine outputs with
Transportation 186 PP benefit from the ability to eject moldings at
Others 131 higher temperatures than with their lower soft-
Total injection molding 1544 ening counterparts.
Export 503
All others 1177
Linear post-molding shrinkage of PP is 1 –
Total 5543 2 %, of which 85 % occurs within the first 24 h.
Distortion in molded products reflects internal
stress caused by nonuniform cooling and poly-
mer orientation. The latter is especially pro-
2.8.1. Injection Molding
nounced in surface skins where the viscous melt
stretches as it is pulled along by the advanc-
An exceptionally wide range of injection-
ing melt front adjacent to cool walls. Controlled
molded products stems from the rigidity, tough-
rheology (CR) polymer, containing fewer of the
ness, and chemical and temperature resistance of
orientation-prone long chains, reduces this type
PP. Examples include automotive trim and venti-
of warping [199].
lation components, bottle crates, industrial con-
An important practical aspect of PP concerns
tainers, washing machine tops and tubs, kitchen-
its ability to form strong integral hinges, such
ware, tool handles, domestic waste systems, and
as in a lidded box, where the lid is permanently
small boat hulls. Such a variety of articles re-
attached to the base by a thin web of polymer
quires careful grade selection according to the
along the whole of one edge (Fig. 32). This web,
required impact strength of the product and the
about 0.25 – 0.6 mm thick, can be produced di-
melt flow constraints of the processing equip-
rectly in the molding process or by post form-
ment. An MFI (230 ◦ C/2.16 kg) range of 2 –
ing operations. An initial flexing of the hinge
20 dg/min meets most needs. Increasing the MFI
while slightly warm induces the correct molec-
not only assists mold filling and reduces cycle
ular orientation to permit repeated opening, even
times, but it helps manufacture of complex mold-
 Polyolefins 61

at subzero temperatures. In the laboratory, such (i.e., an injection of polymer insufficient to

hinges have withstood 23×106 flexes without fill the mold).
failure [203]. 3) In the counterpressure method the mold is
pressurized prior to filling to prevent de-
gassing at the melt front.
4) In hollow section molding (e.g., CINPRES)
nitrogen is injected in a continuous stream
into the mold at the same time as the polymer
melt. Under appropriate conditions, hollow
or ribbed moldings are produced when gas
flows preferentially down thick, hot sections
of the molding. This technique is of increas-
ing interest.

2.8.2. Blow Molding

The extrusion blow molding process for PP

copies that already well established for low-
Figure 32. Integral hinge
Courtesy of the “Propathene” Business, ICI Chemicals &
and high-density polyethylene. However, appli-
Polymers cation to PP has been slow while suitably vis-
cous and tough polymers were developed at at-
Various types of structural foamed moldings tractive prices. At present, the important areas
can be produced having a cellular core sand- are smaller packaging containers which take ad-
wiched between solid integral skins giving an vantage of good transparency, good form stabil-
overall density in the range 600 – 800 kg/m3 ity up to 140 ◦ C for hot filling or sterilization,
[204]. These lightweight, but rigid parts can vary and greater freedom from environmental stress
in size from a paint brush handle to a sack pal- cracking with aggressive products. Brake fluid
let or car body panel. Foaming results from us- reservoirs exemplify this. Very large containers
ing a tumble-blended feedstock of granules and are dominated by high-density polyethylene.
a chemical blowing agent. Alternatively, high- Extrusion blow molding employs two linked
pressure nitrogen can be injected into the melt. processes [205] in which an extruded molten
Molding techniques are altered to achieve ex- parison is transferred to a mold for inflation with
tremely rapid polymer injection rates into the low-pressure air at 0.4 – 1.0 MPa. High molec-
mold. This prevents premature foaming before ular mass polymer, MFI (230 ◦ C/2.16 kg) 0.4 –
the solid skin forms. Foaming in the core arises 2.0 dg/min, combined with low melt tempera-
by allowing the melt pressure to fall rather than tures at the die of 200 – 210 ◦ C, provide a suit-
maintain the customary pressure hold to keep ably stiff melt. If the melt stress in a heavy PP
the mold full. parison exceeds ca. 20 kPa, then the resulting
Four alternative foam processes exist: tension thinning will be troublesome as regards
parison stability and uniform wall thickness.
1) In the ICI sandwich molding process, differ- Injection blow molding replaces the ex-
ent polymers are used for the skin and core truded parison with an injection-molded pre-
by using two separate injection barrels. As form. Blowing takes place in a second mold
the skin is unfoamed, high-quality surfaces which maintains the high-definition neck of
result. the preform. This process eliminates scrap and
2) In the Varitherm Process (BASF, Krauss makes it easier to produce wide mouth contain-
Maffei), improved surface finish is achieved ers having improved dimensional accuracy and
by using a hot mold (100 – 120 ◦ C) followed appearance.
by rapid cooling after a short shot of the melt Injection stretch blow molding is a further re-
finement which introduces a plunger stretching
62 Polyolefins

stage to elongate a conditioned parison or pre- is needed between the die plate and the wind-
form just before the final blow (see → Plastics, up roll. Line speeds up to 1000 m/min at the
Processing). Better mechanical properties and spinning stage, increasing to 3000 m/min dur-
enhanced transparency stem from partial orien- ing solid drawing over hot rolls, call for com-
tation. This technique is sometimes referred to plex and expensive haul off, drawing, and wind-
as the melt phase process. up sections. Product may be packed off as con-
In stretch blow molding, the extruded or tinuous yarn, tow, or staple. Suitable polymers
molded preform is carefully conditioned to just have MFI (230 ◦ C/2.16 kg) in the range 12 –
below the polymer melting point before stretch- 25 dg/min, with narrower molecular mass dis-
ing. Axial stretching of the preform with si- tribution grades offering some advantage with
multaneous or almost immediate blowing in the such high rates of melt draw. These are high-
mold produces a very high quality container. throughput plants, best suited to long runs of a
Correctly carried out, this process secures in- single grade of product.
creased rigidity and toughness, high transparan-
cies, and reduced permeabilities as a direct result Table 20. Polypropylene fiber processes
of significant amounts of orientation. The more
Process Filament count, Product
complex technique increases capital and operat- tex ∗
ing costs, but it is of growing interest [206] and
is already being applied extensively to biaxially Long spin 0.2 – 3.0 high-tenacity
monofilament; drawing
oriented PETP bottles. integral or separate; high
Coextruded parisons can be used as pre- output
BCF yarn 0.2 – 2.0 special case of long spin
cursers for blow molding when special bar- making only bulked
rier properties are required [207]. In particu- continuous fiber
lar, a central layer of ethylene vinyl alcohol Spunbonded 0.2 – 2.0 venturi haul off; no 2nd
stage draw. bonded mat
copolymer (EVOH) to reduce oxygen diffusion, output
combined with moisture protective outer layers Shortspin 0.2 – 40 compact unit; tow
of propene – ethylene random copolymer, give stretched and cut in line
for staple
containers suitable for storing oxygen-sensitive Melt blown 0.002 – 0.02 low orientation, very
food products. fine fiber; only bonded
mat output
Fibrillated yarn 110 – 500 oriented slit film;
fibrillated for baler
2.8.3. Fibers and Flat Yarns twine, rope, etc.
Weaving tape ca. 110 nonfibrillated slit film
for carpet backing,
Very large amounts of polypropylene homopoly- sacks, etc.
mers are used for fiber manufacture in Europe Strapping tape 500 – 1000 thick, oriented tape as a
and the United States. These applications ex- steel alternative

ploit the wide range of physical forms, includ- ∗ tex = weight in grams of 1000 m of yarn;
√ equivalent
ing increasing amounts of versatile nonwoven cylindrical fiber diameter inµm = 37 tex.
fabrics [208–210]. Monoaxial orientation can
be applied to conventional spinneret yarns, as In a variation of this technique [212], the
with polyamides and polyesters, and to flat tapes integrated spunbonded process (see → Fibers,
made from extruded film. These differ in the fol- 3. General Production Technology, Chap. 6.),
lowing respects (Table 20). yields a continuous bonded mat of partially ori-
ented yarn as a consequence of some draw in
Spinneret Type Yarns. Here melt is ex- the venturi type haul off operating at up to
truded through a die plate perforated by many 5000 m/min. There is no further drawing as the
small holes to generate individual thread lines. fiber is collected as a mat on the take-off belt
In the long spin process [211] (see → Fibers, 4. for conversion into nonwoven fabrics. These are
Synthetic Organic, Chap. 4.1.2.2.), which has in- used, for example, in geotextiles, furnishings,
tegral spinning and finishing stages as well as out carpet backing, etc. The balance of drawdown
of line drawing options, there may be 50 – 250 rate and orientation in this process is influenced
holes per spinneret. An air cooling gap of 2 – 5 m by the polymer molecular mass distribution.
 Polyolefins 63

Figure 33 depicts a compact shortspin pro- are bonded together and wound onto a roll. This
cess for staple production using a die containing process produces nonwoven fabrics which are of
ca. 40 000 holes. Cooling air jets freeze the melt increasing importance for industrial wipes and
within about 20 mm so that Godet haul off rolls surgical wrap, and for a variety of filtration appli-
can be placed only 1 m away from the die. Ori- cations, such as face masks made from bonded
entation is achieved by the in-line stretching of mats of very fine fibers.
this tow in an air oven, followed by chopping
in line to produce staple [207]. Broad molecular
mass distribution polymers give the necessary
melt strength, while MFI (230 ◦ C/2.16 kg) re-
quirements increase from 7 to 20 dg/min as the
filaments become finer. These find use in geo-
textiles, carpet face fiber, and diaper cover stock
applications. A useful feature of PP fabrics made
Figure 34. Melt blowing process
from fine fibers is the ability of underwear gar- a) Extruder; b) Gear pump; c) Heated die; d) Hot air mani-
ments to reduce claminess by transferring mois- fold; e) Collector; f) Take-off roll
ture away from the skin to an outer absorbent
layer. Polypropylene based fabrics are also used
for sports clothing and socks, but the low melt- Flat Yarns [214] (see also → Fibers, 4.
ing point of PP calls for special attention to the Synthetic Organic, Chap. 4.2.). In this process
heat setting of the average domestic iron. (Fig. 35), extruded film is the basis of a cheap
and different type of product to that achiev-
able with filament-based yarns. Melt from a
conventional slot die is rapidly quenched with
cold water or water- cooled steel rolls to give
low- crystallinity film, 50 – 250 µm thick. Razor
blade type knives then slit this broad film into
strips 5 – 20 mm wide, which are oriented in a
hot air oven at 120 – 180 ◦ C by drawing between
Godet rolls at ratios in the range 5 : 1 to 10 : 1.
Both film thickness and width diminish in this
operation by approximately the square root of
the draw ratio.

Fibrillated Tape (see also → Fibers, 4. Syn-

thetic Organic, Chap. 4.2.). While flat yarns are
quite strong in the direction of draw, they are
very weak in the transverse direction. With nor-
mal homopolymer, simply twisting high-draw-
Figure 33. Shortspin process ratio tape induces spontaneous fibrillation. A
a) Spinneret; b) Quenched fibers; c) Air-jet cooling Courtesy
of the “Propathene” Business, ICI Chemicals & Polymers web of irregular fine fibers is formed as the film
splits down its length. The resulting product re-
sembles a coarse sisal twine, for which it is a
In the third production process (Fig. 34), air is
good substitute. Such fibrillated yarns can be
blown through a very fluid polymer melt main-
tailored to specific applications by controlling
tained at high temperature to assist chain scis-
draw ratios, thickness, and polymer. Nowadays,
sion in the spinning process itself [212, 213].
pin fibrillation, in which a corotating spiked roll
Polymer MFI (230 ◦ C/2.16 kg) at the nozzle can
contacts the film just after slitting, offers more
range from 35 to 300 dg/min or higher. The spe-
precise control over this step. The products are
cially designed die, having a row of nozzles
familiar as baler twine, string, and some ropes.
along its width, sprays a stream of short, low-
orientation fibers onto a moving belt where they
64 Polyolefins

Figure 35. Flat tape/yarn production unit

a) Wind up frame; b) 3rd Godet stand; c) Hot air annealing oven; d) 2nd Godet stand; e) Hot air orientation oven; f) 1st Godet
stand; g) Simple film costing unit; h) Extruder; i) Film die; j) Water- cooled chromium-plated rolls or water bath; k) Slitting
unit; l) Starting drum; m) Individual precision flangeless bobbin wind up
Courtesy of the “Propathene” Business, ICI Chemicals & Polymers

Weaving Tapes. High strength tapes, with- 2.8.4. Film

out fibrillation, are made by controlling extru-
sion, orientation, and polymer type. Introduc- Packaging film is an important outlet for PP, ac-
tion of finely divided chalk, together with some counting for about one sixth of polymer sales
polyethylene, usually as the chalk masterbatch, in Europe, and rather more in Japan (see Sec-
is particularly effective in reducing splitting. tion 2.6). By far the major proportion of this
Impact copolymers are a more expensive, and is biaxially oriented PP (BOPP), an established
rarely used, alternative to homopolymer for this replacement for regenerated cellulose. Although
application. the equipment needed for orientation is complex
Both tapes and fibers contain residual stress and expensive, it secures superior physical prop-
from the extrusion and orientation processes. erties.
This results in linear shrinkages of up to 8 % Good clarity in unoriented film is depen-
immediately after manufacture, but after stor- dent on very rapid quenching of the melt to
age for a few days at room temperature the value reduce spherulite size. The chill roll extrusion
falls to about 2.5 %. For those applications, such process (see → Films, Chap. 2.2.2.) for making
as weaving tapes for carpet backing, where zero 30 – 250 µm film extrudes a mobile, hot melt
shrinkage is often needed, a heat setting stage from a slot die onto water-cooled, highly pol-
is essential. Out-of-line storage of the tapes on ished steel rolls. Extrusion temperatures of 240 –
bobbins at 130 – 135 ◦ C for several hours often 270 ◦ C combined with an MFI (230 ◦ C/2.16 kg)
suffices. of about 7 dg/min minimize surface irregulari-
Thick, 0.3 – 0.9 mm, oriented tapes are es- ties in the melt. Random copolymers containing
tablished alternatives to steel bands in many 2 – 3 wt % of combined ethylene enhance tough-
strapping applications. They are generally made ness, clarity, and gloss, with some loss of modu-
by the water quench process operating at draw lus. These soft-feel transparent films are used as
ratios of 9 – 10. Thicker tapes are made from textile packages, bakery wraps, and document
foil or individually extruded film tapes. High sleaves at thicker gauges.
molecular mass, MFI (230 ◦ C/2.16 kg) 0.4 – Tubular quenched (TQ) film made in a down-
2.0 dg/min, homopolymers and block copoly- wardly extruded bubble (Fig. 36) uses some ex-
mers with added chalk and polyethylene largely ternal water cooling which achieves reasonable
suppress fibrillation. A further precaution here clarity in film for packaging. In contrast, the less
is to emboss the finished tape with a diamond common tubular film from the air- cooled up-
pattern. A useful aspect of PP strapping tapes wardly extruded bubble is more hazy, but finds
is their higher elongation and elastic recovery use in the production of weaving tapes (Sec-
which helps them to remain tight on packages tion 2.8.3). For most film applications, slip and
prone to shrink or settle. antiblock additives are needed.
 Polyolefins 65

Figure 36. Tubular quenching process

a) Melt from extruder; b) Die; c) Air ring; d) Air flow;
e) Film; f) Water quench weir; g) Cooling skirt; h) Nip rolls;
i) Dewatering, slitting, wind up etc.

Biaxially oriented polypropylene (BOPP)

film [215, 216], typically 12 – 40 µm thick, has
excellent transparency, toughness, and stiffness,
and is widely used in cigarette and biscuit pack-
ages, potato chip bags, and carton overwrap.
Film modulus is three times that of the unori-
ented cast product. These complex film manu- Figure 37. BOPP bubble process
a) Cast tube; b), c) Stretching heaters; d) Bubble guides;
facturing plants are usually proprietary systems f) Air ring; g) Wind up, slitting, etc.
based either on a bubble process, or on a flat die
(stenter) process. In the bubble process (Fig. 37),
thick cast tube is reheated and then blown into a It is impossible to heat seal such highly
bubble with simultaneous stretching in the trans- oriented material because unacceptable shrink-
verse and machine directions to produce a bal- age then occurs. Low-melting surface coatings
anced film. The stenter process (see → Films, overcome the problem by reducing the seal-
Chap. 2.3.2.) uses thick cast sheet which is re- ing temperature to a level which the films
heated and conditioned for drawing. Longitudi- can safely withstand. Suitable materials are
nal and lateral stretching are performed sepa- vinylidene chloride copolymers, polyethylene,
rately and can be adjusted to secure the required poly(1-butene), as well as butene, propene, and
orientation balance. The typical area draw in ethylene co- and terpolymers. Some of these
these processes is 30 : 1 to 50 : 1. may be applied as aqueous emulsions, but com-
mon practice is to coextrude the low-melting
polymer as an outer layer of the cast tube or
66 Polyolefins

sheet. After orientation, this layer can be less ening using traditional glass fiber lamination
than 1 µm in thickness. These more compati- techniques. Punched sheets can be biaxially ori-
ble polyolefin coextruded coatings also simplify ented to generate heavy duty meshlike structures
scrap recovery and recycling without fear of the for geotextiles [217].
coating instability inherent in halogenated poly- Thick sheet, as made, has a nonuniform struc-
mers. ture across its thickness as a result of consider-
Polypropylene film, however made, is not able differences in cooling rate.
receptive to printing inks and adhesives be-
cause of the low polarity. Mild surface oxidation
by corona discharge treatment overcomes these 2.8.6. Extruded Pipe
problems.
Compared with polyethylene, tubing applica-
tions for PP are quite small. However there are
2.8.5. Foil and Sheet several areas where PP’s increased resistance to
aggressive media and its better performance at
Slow heat transfer rates in sheet and thick foil elevated temperatures are advantageous.
call for extended cooling times at the extru- Extrusion at ca. 225 ◦ C is straightforward;
sion stage. Foil, up to about 0.7 mm thick, a central torpedo is used to make the hollow
can be made by the cast tube process (Sec- pipe [218]. Homogeneous melts require an ex-
tion 2.8.4), but the more versatile three roll stack truder having a length-to-diameter ratio of 25 : 1
system (Fig. 38) is able to produce sheet with and a compression ratio of 4 : 1 to reduce the
thicknesses of 0.3 – 15 mm. Use of additional risk of trapping air in the extrudate. Pipe up to
and larger diameter rolls extends this range to 300 mm outside diameter is generally vacuum
40 mm. Thicker sheets are made by compres- sized in a water bath: semi-molten pipe passes
sion molding of granules or large molded slabs, through a finely perforated steel tube having vac-
and by injection – compression molding. This uum applied to its external surface. Larger pipes
can make 2 m square slabs with thicknesses are made by pressure sizing where nitrogen or
up to 240 mm. High molecular mass homo- air is injected via a small capillary into the tor-
and copolymer, MFI (230 ◦ C/2.16 kg) ca. 0.3 – pedo to expand the pipe to the sizing die form.
1.0 dg/min, provide higher dimensional stabil- Both homopolymers and impact copolymers are
ity in slow- cooling, thick-section melts whose used in the MFI (230 ◦ C/2.16 kg) range 0.3 to
temperature at the die exit is ca. 210 ◦ C. Higher 2.0 dg/min, increasing to 4.0 for drinking straws
flow grades with MFI (230 ◦ C/2.16 kg) of up to and ballpoint pen tubing.
5 dg/min may be used for thin foil, depending Copolymers, providing superior impact
on the available equipment. strength with some flexibility, find use in domes-
tic waste systems. Homopolymers have higher
resistance to stress. It is essential to have a heavy
duty stabilization system which will withstand
extraction for applications involving aggressive
and hot environments, such as chemical plants
Figure 38. Three roll stack extrusion and effluent pipes. Manufacturers offer guid-
a) Extruder; b) Slot die; c) Polishing stack; d) Nip rolls; ance [218] on polymer selection and pipe de-
e) Wind up sign conforming to the various pressure classes
in BS 4991, and to BS 52 254 and BS 5255 for
Commercial sheets, normally up to 2 m wide domestic waste pipes and fittings. Creep data
provide stock for fabricating into welded tanks are available [218] for pressure pipes predicting
for storing corrosive liquids. They are also used performance for up to 50 years.
as linings for steel and concrete containers, for Pipe jointing uses all the common techniques,
ducting construction, and as an inert construc- with the exception of solvent welding. Ring seals
tion stock for chemical plant. It is possible to with rubber inserts allow some movement in do-
bond woven glass or polyester fabric to the mestic waste pipes. Also used are flanged joints,
heated surface for subsequent further strength-
 Polyolefins 67

hot plate butt welding, and socket fusion weld- surprisingly useful materials by blending and re-
ing, the latter being optionally supplemented compounding. To them, the availability of essen-
with hot-gas bead welding. Compression joints tially pure PP is the prime requirement.
involving copper alloys should not be used at
temperatures exceeding 60 ◦ C because of re- Plastics Converters. Turning PP into mold-
duced life expectancy. ings, pipe, film, etc., invariably involves some
scrap production. Apart from substandard arti-
cles, there are sprues from moldings, edge trim
2.9. Environmental Aspects from film and sheet, parison waste, and stamped
sheet from thermoforming. These are recovered
2.9.1. Recycling for recycling by the converter himself if the ap-
plication allows, or more often by an outside
The structure and properties of PP make it compounder. In favorable situations involving
well suited to recycling operations. There is long runs of a standard product, the converter
no fear about cross-linking, nor of complica- segregates waste, grinds it, and then recycles it
tions with plasticizers or chlorine-rich species. by blending small amounts with virgin feedstock
Re-extruding PP usually lowers its molecular when specifications permit. Occasionally there
mass and narrows the molecular mass distri- is an undemanding application which can ac-
bution, particularly in aged feedstock. This can cept large proportions of such regrind without
be helpful in some applications that require en- difficulty. Storage and segregation problems are
hanced flow. Adverse factors which must be reduced when the converter simply collects his
assessed include some loss of strength from scrap together in the form of regrind for sale to
reprocessing/ageing, oxidation stability, discol- a compounder.
oration, and contamination. The British Plastics Federation (BPF) esti-
mates [219] that there are about 60 reprocessing
PP Manufacturers. Manufacturers usually companies in the United Kingdom handling at
produce small proportions of PP which do not least 150 000 t/a of polymer. Forty three of these
meet their full quality requirements. Examples process an estimated 25 000 t/a of PP [220]. Only
include deviations in MFI/MMD, antioxidant a few of these also process recovered scrap into
levels, copolymer characteristics, and gels. Pro- molded products such as horticultural, highway,
vided these faults are within predetermined lim- safety, and street furniture, which do not make
its in the quality protocol, the material may be excessive demands on polymer behavior. In-
recycled in small proportions, sometimes with cluded in the estimated figure are 15 000 t of
further corrective adjustments to the composi- recovered used battery cases and crates which
tion. This operation calls for additional work, can be converted into quite respectable com-
and can reduce plant output by having to pro- pounds. Most reprocessors only handle sin-
cess the polymer twice. For this reason, and in gle polymers, not mixtures. Their main supply
those cases where recycle is not permitted or the sources are plastics converters and industrial or
deviations are too large, manufacturers either re- commercial establishments as suppliers of fairly
classify the product to a lower grade, or sell to well defined PP scrap [221].
an outside compounder for further reprocessing.
This minimizes disturbances to continuous man- Recycling PP After a Full Service Life.
ufacturing processes. Nearly half the thermoplastics used in Europe
A second source of much lower grade mate- are converted into packaging [222]. In the United
rial, arises when manufacturing conditions are Kingdom 13 % of this is based on PP, involving
severely disturbed. This can be due to instru- an estimated 142 000 t of polymer in 1988.
mental and human error, blockages, equipment Polymers used in United Kingdom for pack-
failure, or extrusion disturbances. In these cases aging in 1988 (in 103 t) broke down as follows
scrap can vary from substandard reactor pow- [222]:
der to blocks of polymer from extruder dumps.
External reprocessors convert such products into
68 Polyolefins

Low-density polyethylene (LLDPE and LDPE) 510

polymers, which are essentially incompatible
High-density polyethylene 255 and contaminated. Generally, they will be chan-
Polypropylene 142 neled into some massive products, such as posts,
Polystyrene 78 construction boards, and other bulky structures
Poly(vinyl chloride) 68
Poly(ethylene terepthalate) 53
where resistance to water and decay is more im-
Expanded Polystyrene 21 portant than high inherent strength. Some 20
Total 1127 different European schemes aim to make re-
Inevitably, much of this has only a short life cycled plastic components as wood and con-
before it ends up as waste in some form. Domes- crete replacements for agricultural applications
tic waste contains 5 – 7 wt % (up to 20 % by vol- [223, 230]. Comingled scrap can be upgraded by
ume) of such products [220], very little of which blending with other recycled polymers to assist
is currently recovered. Public concern about the processing.
environment naturally includes highly visible
plastic litter, which is made unduly prominent 2.9.2. Pyrolysis
by its low density and durability. This is an addi-
tional factor accelerating legislation for recovery PP can be cracked to liquid hydrocarbons by
of all types of packaging, including glass, metal, thermal pyrolysis at 400 – 550 ◦ C. In a pro-
paper, as well as plastic [223–225]. cess developed in Japan [231], zeolite cata-
In the case of PP, notable success rests with lysts enable this temperature to be reduced to
recycling old plastic bottle crates and battery 200 – 420 ◦ C by using a two-stage heating pro-
boxes in Western Europe and the United States. cess. Other polyolefins, such as polyethylene
This is mainly attributable to the ease with which and polystyrene, and some chlorinated plastics
large amounts of a clean single polymer can can also be pyrolized to liquid products. Process
be collected without cross contamination from cost estimates are $ 235 per ton of plastic, which
other plastics. Cooksons Plastics [226] and oth- yields 0.5 m3 of gasoline, 0.5 m3 of kerosene,
ers [227, 228] have expanded on lead recovery and diesel products. Plants are expected to be
to retrieve PP battery cases themselves. A mech- built in Taiwan and Korea in 1991.
anised sorting system has to separate stones,
metal, wood, string, ebonite paper, and residual
acid. The Cookson process involves crushing, 2.9.3. Incineration
several stages of washing, flotation, and screen-
Municipal waste is normally disposed of in land-
ing followed by drying and extrusion. The fi-
fill sites, with incineration being the next most
nal products include good-quality PP capable of
important method [232]. As suitable landfill
being used in automotive products and for cer-
sites become rarer and more expensive, pressure
tain types of battery cases. Success here rests
is exerted to reduce waste volume either by in-
in quality upgrading by adding elastomer to en-
cineration or by scrap recovery.
hance toughness, stabilizers, and antacid incor-
Modern incineration technology, with energy
poration to recoup oxidative stability, and mo-
recovery in the form of electricity generation,
lecular mass tailoring with peroxides for specific
can take advantage of the high calorific value of
applications. Hoechst [229] plan to collect plas-
thermoplastics. Municipal waste calorific values
tic waste from scrap cars, household appliance
average 10 kJ/g, compared with 30 – 35 kJ/g for
industries, and presorted packaging waste. The
coal. At 44 kJ/g, PP and other polyolefins have
5000 t/a plant near Cologne should be in opera-
the same calorific value as fuel oil. Moreover, PP
tion by mid-1992. ICI studies on scrap recycling
has an exceptionally low sulfur content, mak-
from used PP crates stress the need to incor-
ing it a very clean fuel with no apprehensions
porate additional stabilizer in weathered prod-
about toxic flue-gas emissions. These incinera-
ucts, and to allow for some reduction in impact
tion plants are costly to build. Even after allow-
strength for seven-year-old crates.
ing for the sale of electricity, the net disposal cost
Recovery and reuse of mixed plastics is more
in the United States is estimated at 40 – 70 $/t
difficult. The real need is to develop applications
of processed waste [224]. Special burners have
and fabrication processes for such comingled
been developed to handle atactic and isotactic
 Polyolefins 69

waste PP feedstock, but more profitable outlets Propene and ethylene monomers themselves
are now available. are nontoxic asphyxiant gases whose flammable
nature calls for the usual extensive precautions.
Ignition by static electricity is possible with
2.9.4. Environmental Interactions high-pressure leaks and accidental discharges.
Autoxidation of hot, unstabilised PP powder
Overall PP manufacture, like any other product, in storage silos containing air is another known
involves some interaction with the environment. cause of fire.
Various essential inputs, such as raw materials
and services need to be considered along with Effluents. Although catalyst components
all the plant output streams. constitute only a very small proportion of plant
materials, both their manufacture and disposal
Inputs. The principal input for PP is pure involve noxious substances. Titanium tetrachlo-
propene, with lesser amounts of ethylene for ride is used for all catalysts, sometimes in
copolymer grades. Energy is required to manu- considerable excess for high-activity systems.
facture these monomers from petroleum feed- Whereas expensive recycle and recovery stages
stocks, and still more is needed for conversion may be installed as capacities increase, some
into polymer. At present, most of this power remaining complexed residues will require dis-
comes from burning fossil fuel which then dis- posal. Often, this involves hydrolysis with wa-
charges carbon dioxide and water vapor to the ter to generate corrosive HCl and titanium diox-
atmosphere. Table 21 compares the overall en- ide suspensions. After neutralization with alkali,
ergy input needed to make various raw materi- these slurries are either discharged as aqueous
als. This can be expressed either as the weight of effluent or settled out and used in landfill. Some
oil to produce this energy, or in terms of joules incineration is planned. Disposal facilities also
per unit volume. Both values include energy for need to be capable of receiving occasional faulty
monomer production, but exclude the hydrocar- catalyst batches. Older plants still using catalyst
bon content of the monomer, which is trans- extraction processes simply use aqueous slurry
formed into polymer without combustion. On a discharges, or dump concentrated residues from
weight basis, polyolefin energy requirements are the base of stills.
broadly similar to those of most alternative raw Lower aluminum alkyls are pyrophoric, react
materials. On a more realistic volume basis, the violently with water, and are intensely aggres-
strength and lightness of plastics gives energy sive towards exposed skin. Safe handling usually
savings. Usually this is enhanced further in the calls for full protective clothing. Disposal can be
final article where, for example, thin and strong by burning to generate alumina, or quite often,
plastic bottles show savings over their thicker by controlled hydrolysis with water after deacti-
glass counterparts. vation with alcohols. Some alkyl manufacturing
plants will accept returned waste alkyls for dis-
Table 21. U.K. energy requirements for the manufacture of natural posal in their own dedicated facilities.
and synthetic materials [232]

Material Energy requirements Atactic PP. Older plants needed to dispose

TOE ∗, overall kJ/cm3 up to 5 % of their output as low molecular
conversion mass atactic residues from solvent recovery
Aluminum 5.6 661 streams. Landfill was a common outlet, with
Tinplate 1.3 427 some incineration. Useful low- cost applications
Copper billet 1.2 469 appeared in adhesives and roofing felt composi-
Glass bottles 0.5 46
Paper and board 1.4 50 tions, which now consume nearly all of the in-
Cellulose film 4.4 293 creasingly rare atactic PP byproduct.
Low-density polyethylene 1.2 51
PP, old process, with extrusion 1.5 61
Gaseous Effluent. Traditional flare stacks
PP, new process, with extrusion 1.3 52
receive most of the voluntary and involuntary
∗ TOE = tonnes of oil equivalent to the energy requirement for process gaseous discharges. Normally, these
overall conversion.
comprise small flows from distillation column
70 Polyolefins

purges which can be dealt with by screened low the catalyst- containing aqueous phase are then
level flares. These reduce the visual impact of separated.
flares which some people find objectionable, es- During the polymer/monomer separation
pecially at night. Some nitrogen purges con- step, unreacted 1-butene is separated from the
taining traces of hydrocarbons are discharged to poly(1-butene) for recycle to the reactor. Sep-
the atmosphere. Scrubbing systems and carbon aration is carried out by heating the polymer
adsorption beds reduce hydrocarbon emissions, solution under pressure then flashing off the
but only a few manufacturers use them because monomer by rapidly reducing the pressure. The
of the cost. remaining molten polymer feeds the extrusion
step, while the vaporized monomer flows to the
monomer purification section of the process.
3. Poly(1-Butene) The monomer purification step accomplishes
separation of impurities both heavier and lighter
3.1. Production than 1-butene. Water is removed by azeotropic
distillation. Fresh 1-butene is added to the pro-
Introduction. Poly(1-butene) is a thermo- cess at this stage.
plastic polymer produced by solution polymer- In the extrusion step further volatile hydro-
ization of 1-butene with a Ziegler – Natta cata- carbons are removed, additives for color, prod-
lyst system. Hüls developed a process during the uct performance, processing, and stabilization
1960s and produced the polymer in a 12 000 t/a are added, and the polymer is pelletized.
plant in the Federal Republic of Germany. Mobil The pellets are pneumatically conveyed to the
started to develop a process in 1968 and, together batch blending stage and then transferred to the
with Witco, built a plant in Taft, Louisiana with packaging area. Pellets are typically sold in 450-
a capacity of 30 000 t/a. Shell (USA) bought the kg boxes.
plant in 1977 and is at present the only commer-
cial producer. 3.2. Properties
The feedstock of pure 1-butene is supplied
from the Shell Higher Olefins Plant in Geismar, 3.2.1. Structure and Physical Properties
Louisiana.
The poly(1-butene) plant produces grades The properties of a high-molecular material are
specifically developed for pipe and speciality essentially determined by the dimensions and
film applications. structure of the molecular chain (fine structure)
and by the thermomechanical history [233].
Process. The commercial poly(1-butene) Since the fine structure of poly(1-butene) can
production process consists of seven pri- be varied across a broad range by means of the
mary unit operations: (1) polymerization, (2) polymerization process, a knowledge of this is
deashing, (3) polymer/monomer separation, (4) essential for the spectrum of properties.
monomer purification, (5) extrusion, (6) pellet Molecular Structure. Polymerization with
blending, and (7) packaging (Fig. 39). Ziegler – Natta catalysts produces both atactic
In the polymerization step the catalyst system and isotactic polymer. Atactic poly(1-butene)
is fed into the reactor with the purified 1-butene is virtually impossible to crystallize, while iso-
recycle stream. Hydrogen is added as a chain tactic poly(1-butene) has a crystallinity of 40 –
terminator to control the melt flow index of the 55 % at normal cooling speeds.
polymer. Ethylene is fed to the reactor when pro- The molecular chains in the crystal form he-
ducing random 1-butene – ethylene copolymers. lices. Depending on the crystallization condi-
Polymerization catalyst residues must be re- tions, poly(1-butene) forms 113 , 31 , or 103 he-
moved from the product to preserve its long- lices, which differ in their helical dimensions
term properties. In the deashing step, the poly [234–236] and give rise to different crystalline
(1-butene) is mixed with dilute caustic soda to modifications (see below).
dissolve and extract the catalyst components. The isotactic content of poly(1-butene) is
The cleaned hydrocarbon – polymer phase and generally determined by the solubility in boiling
 Polyolefins 71

Figure 39. Flow sheet for the production of poly(1-butene)

a) Monomer purification; b) Polymerization; c) Deashing; d) Monomer/polymer separation; e) Extrusion and pelletizing;
f) Blending and storage; g) Packaging

diethyl ether (“ether extract”), whereby it is as- These equations also apply to atactic poly(1-
sumed that only the atactic components are sol- butene).
uble. However, infrared spectroscopy and X-ray The molecular mass distribution can be de-
crystallography have shown that the atactic ex- termined easily by gel permeation chromato-
tract contains crystallizable components, mostly graphy in 1- chloronaphthalene as solvent. In-
of low molecular mass. A quicker and more re- dustrial products have molecular nonunifor-
liable method of determining the atactic content mities U = (M w /M n ) – 1 between 5 and 12
is by evaluating the infrared band in the region (M w = weight-average value, M n = number-
of 920 cm−1 [237]. This leads to the following average value).
definition of the atactic content Y a :
v − 918 cm−1
Crystal Structure and Superstructure.
Ya = Like most polymers isotactic poly(1-butene) can
30 cm−1
crystallize in various modifications. However,
where v is the band position of the unknown
the polymorphism is more marked and of greater
sample in cm−1 .
industrial significance in poly(1-butene) than in
The advantage of this method is that it is in-
any other polymer. Four crystal forms of poly(1-
dependent of the molecular mass and of the mor-
butene) are known at present and are designated
phology of the sample.
modification I, I , II, and III [234, 240]. Charac-
teristic physical data of these modifications are
Molecular Mass. The average molecular
listed in Table 22.
mass may be determined either by direct meth-
Modifications I and III are formed on crys-
ods such as light scattering or osmometry, or
tallization from solution. They are of no indus-
by indirect methods such as determination of
trial importance. However, modifications II and
the intrinsic viscosity [238, 239]. The molecular
I, which are obtained by crystallization from the
mass is calculated from the viscosity number us-
melt, are industrially significant. All the crys-
ing the Mark – Houwink equation [239]. Mark –
tal forms can be obtained from modification III
Houwink equations for isotactic poly(1-butene),
in a single step [246], as shown in Figure 40.
which give virtually identical molecular masses
The transitions from one crystal form to an-
are as follows:
other are monotropic. Modification I crystal-
[η]n−nonane = 5.9 × 10−5 ×M 0.80 lizes preferentially from solution at lower tem-
[η]dekalin,135◦ C = 6.2 × 10−5 ×M 0.79
peratures [240], while at high temperature the
72 Polyolefins
Table 22. Characteristic data for crystal modifications of poly(1-butene)

Modification II Modification I Modification III Modification I Amorphous Reference

(tetragonal) (hexagonal) (orthorhombic) (hexagonal) phase

Helix type 113 /4011 31 103 31 [235, 240,

242]
Helix length per monomer unit, nm 0.187 0.217 0.217
Helix cross section, nm2 0.055 0.044
Specific volume at 25 ◦ C, cm3 /g 1.1364 1.0453 1.1579 [243]
1.16 for mod. II
1.14 for mod. I [243]
Specific coefficient of volume 3.05 × 10−4 3.13 × 10−4 8.12 × 10−4 [243]
expansion, cm3 g−1 K−1
Melting point, ◦ C ca. 125 ca. 140 93 – 98 100 [241,
244–246]
Heat of fusion, kJ/mol ca. 3.1 ca. 6.7 [247–249]

Figure 40. Monotropic interconversion of the four modifications of poly(1-butene)

orthorhombic modification III is produced [250, depending on the temperature and thermal his-
251]. Modification III is also formed by precipi- tory [234]. The transformation from II to I is as-
tation, e.g., by addition of methanol to a benzene sociated with a change in various physical prop-
solution of poly(1-butene) [252]. Modifications erties, e.g., an increase in melting point, density,
I and III are also formed in solution or suspen- [243] and modulus (Fig. 41).
sion polymerization [253].

Figure 41. Time dependence of the shear modulus G of mod-

ification II of poly(1-butene) Figure 42. Time dependence of specific volume during
Thermal history: 1 mm thick test bar cooled from the melt transformation (II → I) of poly(1-butene) at 20 ◦ C
(160 ◦ C) in air to the test temperature of 20 ◦ C a) Quenched; b) Crystallized for 200 min at 92 ◦ C; c) Crys-
tallized for 5700 min at 102 ◦ C; d) Crystallized for 5600 min
at 102 ◦ C; e) Crystallized for 7500 min at 106 ◦ C; f) Crys-
The tetragonal modification II and the hexag- tallized for 7200 min at 108 ◦ C
onal form I are industrially important. As a
melt cools, i.e., after most processing operations, These changes in properties are primarily due
form II crystallizes out first. This is thermody- to the change in crystal modification. The de-
namically unstable and in the absence of external gree of crystallization and the mean spherulite
mechanical stresses it changes monotropically size remain virtually constant during the transi-
into the stable hexagonal modification I after a tion from II to I [243]. The crystallite size also
period ranging from a few hours to several days, remains unchanged [244]. This is a purely crys-
 Polyolefins 73

tal – crystal transformation without experimen- [256]. The conversion rate can also be increased
tally detectable melting of modification II crys- by certain additives, such as polypropylene or
tals. plasticizers (see Fig. 43) [240, 257, 258].
The rate of conversion, as indicated for exam-
ple by the half-value time t 1/2 depends on the
thermal history (Fig. 42) and on the temperature
(Fig. 43).

Figure 44. Poly(1-butene) conversion curves for modifica-

tion II → I for various constant tensile stresses
R is the ratio of the IR extinction of modification I at
920 cm−1 to the extinction of modification II at 920 cm−1 .
The half-value time t 1/2 (II → I) is reached when R has a
value of ca. 1.5
a) 0 MPa; b) 0.12 MPa; c) 1.48 MPa; d) 1.91 MPa;
e) 2.55 MPa; f) 2.95 MPa; g) 4.23 MPa

Figure 45. Crystallization time t c of poly(1-butene) at 78 ◦ C

Figure 43. Temperature dependence of half-value time t 1/2
as a function of the viscosity-average molecular mass M̄ v
for the transition II → I
Curve: measurements on fractions,  unfractionated prod-
a) Pure poly(1-butene); b) Melt mixture of poly(1-butene)
uct
and polypropylene in the ratio of 1: 1; c) Poly(1-butene) with
30 % butyl stearate
The molecular mass and the molecular mass
Mechanical stresses may significantly in- distribution have virtually no effect on the con-
crease the conversion rate [254, 255]. Figure 44 version rate. However, the molecular mass does
shows the influence of constant tensile stress have significant influence on the rate of crystal-
on the conversion rate, monitored by IR spec- lization of modification II (Fig. 45). The crys-
troscopy. Whereas these measurements show a tallite and spherulite sizes of all crystal modi-
stress-free sample to have a half-value time of fications can be varied over a broad range by
5500 min, the half value for a sample under a modifying the cooling and crystallization con-
tensile load of 4.4 MPa is only ca. 10 min. In- ditions of the melt [248, 259, 260]. Surprisingly,
ternal stresses and orientations have a similar the mean crystallite size and size distribution
effect to external stresses. The conversion of II are not increased by subsequent tempering [259,
to I is also accelerated by hydrostatic pressure 260]. This may be a reason for the low time de-
74 Polyolefins

pendence of certain mechanical properties (see ylene, but at lower temperature they are in-
page 74). ferior [265]. Nevertheless the low-temperature
The four modifications are distinguished an- strength, as characterized by the brittle point, is
alytically and characterized quantitatively by a relatively good [254, 265].
combination of X-ray, infrared, and differential The stress – strain behavior of modification I
thermal analysis [245–247, 261]. differs noticeably from that of other polyolefins.
The differences are not only in the shape of the
stress – strain curve, which for industrial mate-
3.2.2. Application Properties rial has virtually no maximum [265, 266], but
also in the dependence on time and tempera-
In normal processing operations, isotactic ture [267]. Figure 46 shows the yield strength
poly(1-butene) is heated to above its melting σ ys , measured in an uniaxial tensile test as a
point. Therefore it is the unstable modification function of the stretching time t s . Whereas the
II which forms immediately after cooling, and is yield strength of polyethylene and polypropyl-
converted to the stable form I during storage or ene declines sharply with increasing stretching
on application of mechanical stress. Since only time, the values for poly(1-butene) remain virtu-
the properties of form I are of interest from the ally constant above 0.1 s. The good creep resis-
point of view of applications, the statements be- tance and resistance to stress cracking of poly (1-
low refer only to this modification. butene) pipes subject to internal pressure [262]
In terms of density, melting point, and glass is due to the low time dependence of the mechan-
transition temperature, poly(1-butene) resem- ical properties.
bles polyethylene rather than polypropylene
[262]. This similarity extends to cross-linked
polyethylenes, although some of their properties
naturally vary, depending on their cross-linking
density [263]. Commercial material is around
40 % to 55 % crystalline. Since the crystalliza-
tion rate is slow by comparison with polyeth-
ylene and polypropylene, superstructures which
are of interest for applications can be obtained
by the choice of cooling conditions [264]. Nucle-
ators increase the rate of crystallization, leading
in some conditions to a material that is somewhat
more brittle at low temperature [264].

Mechanical Properties. Table 23 lists some

mechanical properties of poly(1-butene), poly-
ethylene, and polypropylene. According to the
VDE hardness, poly(1-butene) is softer than
polyethylene and polypropylene. However, the
Shore hardness is virtually the same as for poly-
ethylene. The surface gloss of components made Figure 46. Yield strength σ ys , measured in a tensile test at
from poly(1-butene) is similar to those made 22 ◦ C, as a function of the stretching time t s [266]
from polypropylene [265]. a) Polyethylene; b) Polypropylene; c) Poly(1-butene)
The rigidity of poly(1-butene) is relatively
low. The flexural stress at conventional deflec- Since this low time dependence of the
tion and modulus of elasticity are lower than for mechanical characteristics is maintained at
polyethylene (Table 23). higher temperatures, poly(1-butene) is particu-
The impact strength and notched impact larly suitable for hot-water pressure pipes [263,
strength are significantly higher than those of 268]. Figure 47 shows the burst hoop stress per-
polypropylene. Above 0 ◦ C the values are sim- formance of poly(1-butene) pipe under inter-
ilar to those for high molecular mass polyeth-
 Polyolefins 75
Table 23. Hardness, rigidity and strength of low-pressure polyolefins [265]

Property Test method Polyethylene Polypropylene Poly(1-butene)

VDE hardness (60 s), MPa VDE 0302 44 – 64 61 – 80 25 – 45

Shore D hardness DIN 53 505 62 – 69 70 – 75 60 – 68
Flexural stress at conventional
deflection, MPa DIN 53 542 26 – 43 34 – 50 15 – 25
a
Modulus of elasticity, MPa 900 – 1200 1000 – 1500 500 – 900
Impact strength DIN 53 453 no break no break no break
Notched impact strength, kJ/m2 DIN 53 453 5 to no break 3 – 15 20 to no break
Brittle point, ◦ C ASTM D 746-57T below − 70 + 20 to − 5 − 10 to − 30
a
Measured in Hooke range by bending tests.

nal pressure according to ISO-SEM (DIS 9080) Resistance to Chemicals and Gas Per-
[269]. meability. Because of its paraffinic structure,
poly(1-butene) is resistant to most common
chemicals such as acids, alkalies, salts, alcohols,
and ketones. However, it swells or dissolves in
hot aromatic and chlorinated hydrocarbons. It is
less inert to aliphatic hydrocarbons than poly-
ethylene and polypropylene and more prone to
permeation [265, 271, 272]. A detailed table on
the resistance of poly(1-butene) to chemicals is
given in [270].
Permeability to gases and vapors, in particu-
lar water and oxygen, is comparable to that of
polyethylene of similar crystallinity. Permeabil-
ity to carbon dioxide, however, is higher [264].
Figure 47. Burst hoop stress performance of poly(1-butene)
pipes
3.3. Processing
As well as the outstanding resistance to stress
Processing poly(1-butene) on conventional ma-
cracking, the unusually good creep behavior is
chines presents no problems. Because of its
significant. The tendency to creep, i.e., to un-
low crystallite melting point and particularly be-
dergo plastic deformation below the yield point,
cause of the rapid decrease in melt viscosity with
is significantly lower than for other polyolefins,
increasing temperature, poly(1-butene) can be
even at temperatures up to 100 ◦ C [263, 265,
processed by extrusion (pipes, profiles, sheets),
270]. This is also an essential requirement for
extrusion blow molding (hollow bodies), and in-
the use of poly(1-butene) as a film material, par-
jection molding (engineering products, sheath-
ticularly for the packaging sector [270].
ing for metals) [265]. Sheets made by extrusion
or compression molding can be shaped hot or
Electrical Properties. The electrical behav- cold. A special feature is cold shaping of the rel-
ior of poly(1-butene) does not differ significantly atively soft modification II. Articles shaped from
from that of polyethylene and polypropylene this modification then become increasingly rigid
[265]. Apart from the usual quantities of sta- as the conversion to modification I progresses.
bilizers, it only contains residues of polymer-
ization catalysts. Because of its good resistance
to chemicals, outstanding resistance to stress 3.4. Applications
cracking, and flexibility, poly(1-butene) is an im-
portant material for special applications in the Pipe. The major outlet for poly(1-butene) is
cable and electrical industry. in high-performance pipes, which exploit its
creep resistance and long lifetime at elevated
service temperatures, flexibility, light weight,
76 Polyolefins

corrosion resistance, and its ability to be heat bility of poly(1-butene) with polypropylene. The
welded [263]. It competes in plumbing and ra- incompatibility of poly(1-butene) in blends with
diator heating applications with copper, where various polyethylenes and ethylene copolymers,
progress is mainly limited by resistance to re- such as low-density polyethylene, linear low-
placing traditional working practises. In the un- density polyethylene, high-density polyethylene
derfloor heating pipe market it competes with and ethylene – vinyl acetate copolymers, forms
other plastics such as cross-linked polyethylene the basis of peelable seals (see Fig. 48).
and polypropylene. Peel-seal technology provides a robust pack,
The advantage of poly(1-butene) over other yet allows the consumer to open it easily without
polymers in both these applications is its bet- ripping or tearing. The key attributes of systems
ter ability to retain its mechanical and perfor- based on poly(1-butene) are the broad heat seal-
mance properties at elevated temperature. For ing range and the cohesive failure mechanism,
instance a comparison of tangent modulus, yield which results in an aesthetically attractive pack-
stress, ultimate stress, and elongation at break age after opening. This is because cohesive fail-
within and transverse to the extrusion direction ure propagates through the peel-seal layer itself
of the pipes shows a more balanced performance due to the weaker intermolecular forces between
for pipes made of poly(1-butene) [273]. In the the dissimilar materials, and results in clean uni-
last decade the long-term properties of poly(1- form separation. Additional advantages are good
butene) pipes and their lifetime at temperatures clarity and a clean peel with no stringing [279,
up to 120 ◦ C have been studied [274] and the 280]. The more conventional system relies on
methodology for such long-term tests has been delamination between layers as a result of adhe-
developed for various plastics [275–277]. sive failure and is also more difficult to control.
Extrapolation methods give estimated life- A correlation of peel-seal strength with blend
times of 50 years at 70 ◦ C [273]. An evalua- composition and temperature is shown in Fig-
tion of pipes based on polymers as well as tradi- ure 49.
tional materials, such as copper, favored poly(1-
butene) [278].
The problem of oxygen diffusion in plastic
piping systems, which was given as one expla-
nation of corrosion in metal radiators, tanks, and
boilers in the past, has been resolved by the use
of multilayer pipes containing an oxygen-barrier
layer and the addition of inhibitors to the circu-
lating hot water [278].

Figure 49. Dependence of peal-seal strength on blend com-

position

Manufacture of packaging film or sheet in-

Figure 48. Cross section of a coextruded peel-seal layer on
an LDPE substrate
corporating a poly(1-butene) peel-seal blend is
a) LDPE substrate; b) Peel-seal blend LDPE in which in- possible by all the conventional processes such
compatible poly(1-butene) particles are dispersed as film blowing or casting, sheet extrusion or co-
extrusion, extrusion or coextrusion coating, and
lamination.
Packaging. In the packaging sector, poly (1- Poly(1-butene) peel seals are used in flexi-
butene) has become established in speciality film ble packaging such as box liners for cereals,
applications which require resistance to cooking cake mixtures, and biscuits. In combination with
temperatures, and in heat-seal layers for oriented more sophisticated barrier films, they are used
polypropylene, which exploit the high compati-
 Polyolefins 77

for processed meat and vegetable packs. They High molecular mass polyisobutylenes were
are also used for packaging medical products. first prepared by Otto and Müller-Cunradi
An important growth area for peelable seals by polymerizing isobutene below − 10 ◦ C in
is in lids for rigid or semirigid containers. These presence of volatile inorganic halides [284].
range from the relatively simple yogurt, milk,
and cream pots to individual-portion containers Polymerization Mechanism. Even in the
for microwave meals. early studies, two important aspects of the poly-
Two features of poly(1-butene) peel seals are merization of isobutene were recognized: (1)
considered to be of particular importance to the catalysis with initiators of the Friedel – Crafts
development of the next generation of high- type, and (2) the inverse dependence of the mo-
performance packages. The first is their resis- lecular mass on the temperature. Subsequent
tance to high-temperature cooking or steriliza- studies led to the first formulations of a reaction
tion. Often referred to as “retortability”, this is an mechanism [285].
increasingly important feature both in the food According to these ideas, which essentially
and nonfood sectors. Poly(1-butene) peel seals remain valid today, the reaction consists of the
can be made heat resistant by formulation with following steps:
higher-temperature-resistant materials such as
polypropylene or high-density polyethylene.
The second important feature is a distinct
whitening effect when the seals are opened
because of the characteristic cohesive failure
mechanism. This gives a clear indication that
the package has been opened or tampered with.

4. Polyisobutylene
4.1. Introduction

Industrially important polyisobutylenes can be

divided into five groups:
1) Di-, tri-, and tetraisobutenes
2) Low molecular mass polyisobutylenes with
M̄ n = 330 – 1600
3) Medium molecular mass polyisobutylenes
with M̄ n = 20 000 – 45 000
4) High molecular mass polyisobutylenes with
M̄ n = 75 000 – 600 000
5) Ultra high molecular mass polyisobutylenes
with M̄ n > 760 000

History. In 1925 Lebedew was the first to

prepare polyisobutylene [281, 282]. He obtained
products of varying chain length: liquids of oily The initiator is a Lewis acid (BF3 , AlCl3 )
to honey-like consistency; sticky, doughy mate- in combination with a proton source, which is
rials; or solid, rubber-like materials. usually present as a trace impurity, e.g., water,
Relatively uniform low molecular mass hydrogen, fluoride, or hydrogen chloride.
polyisobutylenes were first obtained by the The competition between the growth reac-
company de Bataafse [283] by polymerizing tion and chain termination determines the chain
isobutene at + 10 to − 10 ◦ C in the presence of length (i.e., the molecular mass). Since the ac-
metal halides. tivation energy of chain termination is higher,
78 Polyolefins

increasing the polymerization temperature low- column, washed in a wash tower with ca. 20 %
ers the polymer chain length (ln M ∼1/T ). caustic soda solution to remove sulfur, cooled
Meanwhile [286], a series of studies have ap- in a heat exchanger, dewatered in a water sep-
peared which have revealed a considerably re- arator, dried in silica gel towers and, after fur-
fined view of the course of the reaction; yet a ther low-temperature cooling in a second heat
comprehensive mechanism which is consistent exchanger, introduced into the lower part of the
with all experimental findings is still lacking. reaction vessel. The polymerization takes place
Other studies deal with new initiators (aluminum here at temperatures between − 43 and +16 ◦ C
alkyls; inorganic initiators such as acid clays and and pressures of 0.1 – 0.35 MPa, so that the liq-
molecular sieves; Ziegler catalysts; high-energy uid phase is maintained. The catalyst used is
radiation as an initiator). However, none of these a mushy suspension of finely divided (50 – 100
new catalyst systems are used industrially. In- mesh) aluminum chloride in dry, liquid polyiso-
dustrial processes for polyisobutylene produc- butylene, which is prepared in a mixing tank and
tion still use the conventional Friedel – Crafts supplied to the reaction vessel by a gear pump.
catalysts, boron trifluoride and aluminum chlo- The quantity of aluminum chloride is about
ride. 10 – 20 % of the total hydrocarbons in the reac-
tion mixture. The activity of the aluminum chlo-
ride is increased by adding 0.08 – 0.12 % hydro-
4.2. Production gen chloride (relative to aluminum chloride) as
activator and accelerator. Water or chloroform
4.2.1. Isobutene as Raw Material have the same effect. The diameter of the reac-
The production of isobutene is described in tion zone (A) and the feed rate of the catalyst
→ Butenes, Chap. 4., → Butenes, Chap. 5. slurry are so matched to each other that the alu-
The purity requirements for the isobutene dif- minum chloride particles do not settle. Zone (B)
fer according to the type of polyisobutylene pro- of the reaction vessel, with a diameter two to
duced. six times that of zone (A), reduces the flow rate
For the production of low molecular mass by a factor of about three to four, and functions
polyisobutylenes, butadiene-free C4 fractions as a calming zone. It merges into the settling
can be used, which apart from isobutene con- zone (C), in which the aluminum chloride par-
tain n-butane, isobutane, and n-butenes; stricter ticles settle and are pumped off as a suspension
requirements are set for the isobutene for high through the offtake pipe which extends into zone
molecular mass and solid polyisobutylenes. (B). This catalyst slurry returns via a cooler into
During isolation of isobutene from C4 frac- the reaction zone (A). Spent, aggregated catalyst
tions, an isobutene must be obtained which is is discharged at the bottom of the reaction zone.
as free from n-butene as possible. Primarily the A variant of the process uses separate vessels
content of cis- and trans-2-butene must be min- for polymerization and for catalyst settling.
imized. Both are powerful polymerization poi- From the settling zone flows a clear, light
sons and chain terminators. On the other hand, solution of liquid polyisobutylene in unreacted
1-butene can be used as a regulator in the produc- starting material. To improve the yield, the reac-
tion of high molecular mass and solid polyiso- tion mixture is pumped at least four times, but
butylenes. usually more than eight times, through the reac-
tion zone (A). The clear polymer solution flows
through the heat exchangers (g) and (d) to cool
4.2.2. Low Molecular Mass Polyisobutylenes the isobutene and, after a water wash to remove
acidic constituents, into a stripping column in
Figure 50 shows the layout of the Cosden which about one to two thirds of the inert, un-
Petroleum continuous process, which can be re- reacted starting material is distilled off. After
garded as a kind of fluidized-bed process. post-treatment of the concentrated polymer so-
A liquefied refinery-gas mixture with C1 – C5 lution in a clay-filled tower, which may precede
hydrocarbons and an isobutene content of 3 – the stripping column, all volatile constituents of
50 % is freed from pentenes in a preliminary dis- the starting material, especially unpolymerized
tillation, enriched in isobutene in an absorption
 Polyolefins 79

Figure 50. Cosden Petroleum process for producing low molecular mass polyisobutylene
a) Preliminary distillation; b) Absorption column; c) Caustic soda solution wash tower; d) Heat exchanger; e) Water separator;
f) Silica gel towers; g) Heat exchanger; h) Reaction vessel; i) Mixing tank; j) Refrigeration unit; k) Gear pump; l) Pump;
m) Offtake pipe; n) Cooler; o) Stripping column; p) Clay-filled tower; q) Distillation column; r) Water cooler; s) Pressure
column; (For A to D, see text)

isobutene, are vaporized in a distillation column reaction vessel. Simultaneously, a slurry of 5 %

and returned via a water cooler into the absorp- finely divided aluminum chloride in hexane at
tion column. In a further column, the last traces a temperature of below − 23 ◦ C flows into the
of volatile constituents are distilled from the liq- reaction vessel.
uid polyisobutylene at atmospheric pressure. The polymerization takes place with power-
Aside from this process of the Cosden ful stirring so that the aluminum chloride does
Petroleum Corp., others have been developed. not settle, and external cooling. The through-
For a description of the BASF and Exxon pro- put is 378.5 L/h isobutene – hexane mixture and
cesses, see [287, pp. 94 – 97], [288]. 0.454 kg/h AlCl3 . The resulting solution of
polyisobutylene in hexane with suspended alu-
minum chloride is drawn off, and after it has
4.2.3. Medium Molecular Mass passed through a heat exchanger an excess of
Polyisobutylenes dilute caustic soda solution is added to destroy
the catalyst. After thorough mixing in a noz-
The basic principle of the Exxon process for zle mixer, the mixture of polymer solution and
producing medium molecular mass polyisobut- dilute caustic soda solution runs into a settling
ylenes (Fig. 51) [289] resembles the process for tank, where it forms two layers. The lower layer,
low molecular mass polyisobutylenes. However, consisting of dilute caustic soda solution, alu-
a purer isobutene is used as starting material and minum hydroxide, and salts, is discarded. The
pentane or hexane is added as solvent. The poly- upper layer, consisting of a solution of poly-
merization temperature must be lower to obtain a mer in hexane and unreacted starting material,
higher molecular mass. A mixture prepared from is fed into a degassing vessel, in which the
fresh isobutene, recycled isobutene, and hexane lower boiling components, principally unreacted
with 30 % isobutene and 70 % hexane is brought isobutene, are stripped off at 99 ◦ C and 0.35 bar.
via a heat exchanger and a cooler to the polymer- n-Butenes if present are removed from the sys-
ization temperature of − 40 ◦ C and fed into the tem to avoid poisoning the reaction. In a sec-
80 Polyolefins

Figure 51. Exxon process for producing medium molecular mass polyisobutylenes
a) Mixing vessel; b) Reaction vessel; c) Heat exchanger; d) Nozzle mixer; e) Cooler; f) Settling tank; g) Degasser; h) Degassing
vessel; i) Water separator

ond degasser, the last traces of volatile con- molecular mass of the polyisobutylene. A suffi-
stituents are removed. The unreacted isobutene cient quantity of gaseous boron trifluoride for the
is condensed, dewatered in a water separator, polymerization is then carefully introduced into
and added as recycle isobutene to the starting the mixture. The mixture starts to boil, and the
mixture. evaporating ethylene removes the heat of poly-
In its batch process for producing medium merization. The polyisobutylene remains behind
molecular mass polyisobutylenes, BASF makes in the reaction vessel in the form of a white foam.
use of the chain-terminating effect of di- It is removed from the vessel and freed from all
isobutene [287, pp. 88 – 91], [290]. volatile constituents in a degassing machine.

4.2.4. High Molecular Mass

Polyisobutylenes
BASF and Exxon have developed continuous
processes for producing high molecular mass
solid polyisobutylenes [287, pp. 97 – 104 ].

BASF Belt Process. In the belt process, the

conical polymerization vessel of the BASF batch
process described above is replaced by a contin-
Figure 52. BASF belt process for high molecular mass
polyisobutylenes uous polymerization belt (Fig. 52) [291].
a) Steel belt; b) Twin-screw machine; c) Cooling and com- A gently inclined trough-shaped continuous
pounding; d) Purification steel belt, 16 – 18 m long and 50 cm wide, runs
in a gastight housing over a drive roller and
In a conical reaction vessel with good thermal a tension roller. A mixture of pure, dry liquid
insulation, pure, dry liquid isobutene and pure, ethylene and isobutene in the ratio 1 : 1 flows
dry liquid ethylene as internal coolant are mixed through a pipe onto one end of the steel belt.
in the ratio 1 : 2. The quantity of diisobutene From a second pipe a solution of boron tri-
added to the isobutene depends on the desired fluoride in the same quantity of ethylene as is
 Polyolefins 81

mixed with the isobutene is added. The quan- chemical resistance. The good solubility in hy-
tities of cocatalyst and chain-length regulator drocarbons and chlorohydrocarbons and the in-
[287, pp. 82 – 91] depend on the desired molec- solubility in alcohols, esters, and ketones also
ular mass. The polymerization starts instantly. It result from the paraffinic nature of the polyiso-
continues at the boiling point of the liquid ethyl- butylenes.
ene (−103.7 ◦ C) and in a short time is ended. The At room temperature, polyisobutylenes are
heat of polymerization is absorbed by the evap- resistant to dilute and concentrated hydrochloric
oration of ethylene. The vaporized ethylene is acid, sulfuric acid, phosphoric acid, chlorosul-
recycled via a purification and liquefaction sys- fonic acid, phenolsulfonic acid, naphthalenesul-
tem. The polyisobutylene is stripped from the fonic acid, formic acid, acetic acid, ammonia,
steel belt with a scraper and degassed and ho- potassium hydroxide solution, caustic soda so-
mogenized in a twin-screw machine. lution, as well as aqueous calcium hydroxide,
aqueous hydrogensulfite, copper sulfate solu-
Exxon Process. Polyisobutylene is also pro- tion, potassium permanganate solution, hydro-
duced by the process used for butyl rubber (see gen peroxide, chromic acid, and dichromate so-
→ Rubber, 3. Synthetic) [292]. lution. Above 80 ◦ C, concentrated sulfuric acid
causes carbonization and concentrated nitric
acid causes decomposition.
4.3. Structure Some properties of polyisobutylene that are
independent of the degree of polymerization are
The polymer obtained by cationic polymeriza- as follows:
tion has the following structure: Density, g/cm3 0.92
Volume coefficient of thermal
expansion at 20 ◦ C, K−1 6.3×10−4
Specific heat, kJ kg−1 K−1 2.0
Glass transition temperature (DSC), ◦ C − 60
Thermal conductivity, W K−1 m−1 0.19
Refractive index nD20 1.51
Dielectric constant εr (50 Hz, 20 ◦ C)
DIN 53 483
2.2
Dielectric loss factor tan δ (50 Hz,
In the stretched state polyisobutylene gives a
20 ◦ C) DIN 53 483 ≤ 5×10−4
well-developed X-ray diffraction pattern which Water vapor permeability,
shows that 8 monomers with their 16 methyl g m−1 h−1 mbar−1 2.5×10−7
groups are arranged in an almost regular helix
around the principal axis, forming one transla-
tion period of the chain after 3 rotations [293]. Further properties are listed in Tables 24 and
It has been shown by IR spectroscopy that 25.
the principal end group is the methylene group
[294].
4.5. Uses and Processing

4.4. Properties The low molecular mass polyisobutylenes are

used as plasticizing components for modifying
The rubber-like polyisobutylenes, like all other sealants. In addition, they are used for producing
polyisobutylenes, owe their physical and chem- insulating oils.
ical properties to their paraffinic character. This After further functionalization with polar
results in a low glass transition temperature, low groups, the low molecular mass polyisobut-
specific thermal conductivity, very low water va- ylenes are used as dispersants in fuel and lu-
por permeability, high dielectric strength, high bricant additives.
resistivity, low dielectric constant, low dielec- The medium molecular mass polyisobut-
tric loss factor, high ageing resistance, and rot ylenes are chiefly used as raw materials for
resistance as well as an unusually wide-ranging adhesives and sealants. Due to their very low
82 Polyolefins
Table 24. Properties of polyisobutylenes dependent on degree of polymerization, exemplified by Oppanol B (BASF)

Oppanol Viscosity, Pa · s Intrinsic viscosity Number-average molecular

at 20 ◦ C at 100 ◦ C [η], cm3 /g mass M̄ n ∗

Low molecular mass

B3 25 0.2 ± 0.02 820
Medium molecular mass
B 10 5.0×104 2.2×102 27.5 – 31.2 24 000
B 12 34.0 – 39.1 30 000
5 3
B 15 5.0×10 3.0×10 45.9 – 51.6 40 000
High molecular mass
B 50 1.5×108 8.0×105 113 – 143 120 000
B 80 178 – 236 180 000
B 100 3.6×108 6.7×107 241 – 294 250 000
B 120 295 – 361 300 000
B 150 416 – 479 425 000
B 200 1.5×1011 1.0×109 551 – 661 600 000
Ultra high molecular mass
B 246 > 770 > 760 000


[η] · 103
M̄n =0.94 2.27 .

Table 25. Behavior of Oppanol B100 and B200 towards solvents

water-vapor permeability, permanently flexi- (weight increase by swelling in wt % at room temperature)
ble sealants based on polyisobutylene – carbon
Storage time 3 1/2 days 30 days
black are important in the production of sealed
double glazing units. Combinations of polyiso- Oppanol type 100 200 100 200
butylene with paraffin or wax are used for im- Acetone 1.7 1.5 3.9 3.6
pregnating paper and board. Alcohol 0.1 < 0.1 0.35 0.2
The breaking point of bitumen is lowered and Benzene 400 400 500 500
Butyl acetate 34 24 34 37
its flexibility improved by addition of medium
Carbon tetrachloride soluble
molecular mass polyisobutylene. Chlorobenzene soluble
High molecular mass polyisobutylenes are Chloroform soluble
used as blends with medium molecular mass Cyclohexane soluble
Cyclohexanone 9 7.4 24 18
grades for producing self-adhesive compounds, Dimethylformamide 0.6 0.6 2.1 1.7
e.g., for adhesive plasters. Ether 200 100
Because of their good tolerance by the skin, Ethyl acetate 18 12 21 20
filled polyisobutylenes are used to produce seal- Ethylene glycol 0.6 1.4 0.9 2.0
Gasoline soluble
ing rings for colostomy bags. Glycerol 0.6 0.6 1.0 1.6
Unstabilized polyisobutylenes are used in Hydrogen sulfide soluble
chewing gum bases. Isobutanol 1 0.3 2.4 0.7
Isooctane soluble
Blending polyisobutylenes with paraffin oil Methanol < 0.1 < 0.1 0.1 0.1
and inorganic fillers gives permanently elastic Methyl acetate 8 5 7.8 10
sealants, which are usually marketed in extruded Methylene chloride 200 200 200 200
form as strip or round-profile string. Mineral oil soluble
Nitrobenzene 3 2 5.4 4.5
High molecular mass polyisobutylenes with Olive oil 4 1.5 4.2 3.1
high filler contents are used to produce sheets Paraffin soluble
that are used for sealing buildings against Paraffin oil soluble
Tetrahydrofuran soluble
groundwater and seeping water as well as for
Toluene soluble
protection against corrosion and radiation. Con- Water < 0.1 < 0.1 0.1 0.1
ductive and magnetic polyisobutylene sheetings Xylene soluble
are also available.
The cold impact resistance of polypropylene
is improved by blending with polyisobutylene.
The sensitivity of polyethylene to environmental
 Polyolefins 83

stress cracking is reduced by adding polyisobut- on C5 – C18 olefins centers on polymerization

ylene. mechanisms and the interesting crystallization
Polyisobutylenes are compatible with natural behavior of homopolymers and copolymers,
and synthetic rubber and with reclaimed rubber. but only poly(4-methyl-1-pentene), PMP, based
Solutions of ultra high molecular mass resins have reached commercial production sta-
polyisobutylenes (M̄ n > 760 000) in organic sol- tus. Their excellent optical clarity combined
vents even in low concentrations ( 1 %), have with a high melting point, reasonable toughness,
pronounced viscoelastic properties and dis- and general inertness has led to use in demanding
tinctly increased extensional viscosity. applications where the much higher raw mate-
Polyisobutylene can be compounded on a roll rial cost is a secondary consideration. Operating
mill or in an internal mixer. Compounding is temperatures for PMP in service can be as high
carried out at 140 – 170 ◦ C to minimize thermal as 200 ◦ C for short times, after which thermal
degradation of the polyisobutylene. oxidation is likely to start. For this reason and be-
cause of impact strength limitations, the poten-
tial advan-tages of even higher melting poly(α-
4.6. Commercial Products olefins) cannot be realized in practice. Engineer-
ing resins such as polyimides, polysulfones, and
polysulfides must be used for sustained high-
BASF, Germany: Oppanol B 3 (liquid); Oppanol B 10,
B 12, B 15 (flexible resin-like, tacky); temperature operations and extra toughness.
Oppanol B 50, B 80, B 100, B 120, 4-Methyl-1-pentene monomer can be poly-
B 150, B 200, B 246 (solid,
rubber-like)
merized with cationic and Ziegler – Natta cata-
Exxon, United States: Vistanex LM-MS, LM-MH (flexible lysts. The former cause some isomerization and
resin-like, tacky); Vistanex MM L-80, yield irregular chains, giving amorphous vis-
MM L-100, MM L-120, MM L-140
(solid, rubber-like) cous liquids or rubber-like solid products of little
commercial interest [299, 300].
In addition, a range of low molecular mass In 1965 ICI made several grades of PMP, un-
polyisobutylenes are marketed. der the trade name TPX, in its semitechnical
plant at Welwyn Garden City for distribution and
in-depth evaluation [301]. Manufacture on its
4.7. Copolymers [295] Wilton production site started in June 1968 on a
2000 t/a plant producing transparent and opaque
Isobutene – isoprene – divinylbenzene terpoly- grades. In 1973 the process was sold to Mit-
mers are produced under conditions similar to sui Petrochemical Industries, which became the
those used for butyl rubber, with the addition sole manufacturer on its plant at Iwakuni-Ohtake
of divinylbenzene. Unlike butyl rubber, they ex- works in Japan. Capacity was increased from
hibit no cold flow. 2000 t/a to 3000 t/a in 1982, and then to 6000 t/a
Isobutene – styrene copolymers behave simi- in 1983. In 1989, Phillips 66 in Bartlesville,
larly to polyisobutylenes or butyl rubber. United States, started supplying development
The copolymers have no economic signifi- quantities from a 250 t/a pilot plant in the United
cance. States under the trade name Crystalor.

5. Poly(4-Methyl-1-Pentene) 5.1. Raw Materials

As described for polypropylene in Chapter 2, 5.1.1. Monomers
Ziegler – Natta stereospecific catalysts disco-
vered in 1954/1955 polymerize α-olefins to Several monomers are used in TPX produc-
crystalline products. Foremost of these are tion to overcome the deficiencies of haze and
polypropylene and, to a lesser extent, poly(1- brittleness in pure homopolymers of 4-methyl-
butene), but higher α-olefins also yield crys- 1-pentene. The restricted availability of these
talline products having helical chains in the monomers in commercial quantities in the early
crystallites [296–298]. Much laboratory work
84 Polyolefins

1960s proved troublesome for ICI’s develop- Commercial quantities of these pure olefins up
ment program. to C18 are priced at about £1/kg. Table 27 lists
Polar and highly unsaturated contaminants some of their physical properties, together with
retard polymerizations with Ziegler – Natta cat- those of useful branched comonomers.
alysts. Handling precautions must recognize
flammability hazards and facile peroxidation of
these liquid monomers on exposure to air. At 5.1.2. High-Melting Nucleating Polymers
high concentrations they exert a narcotic effect.
It is reported [308, 309] that < 1 % of well dis-
4-Methyl-1-pentene (4MP) is prepared by persed high-melting polymers from branched
selectively dimerizing propene at ca. 150 ◦ C and α-olefins nucleate PMP crystallization to en-
10 MPa with supported alkali metals, particu- hance transparency. Isotactic polymers of
larly potassium. British Petroleum first estab- 3-methyl-1-butene, 3-methyl-1-pentene, and
lished a commercial process in 1967, followed 4,4-dimethyl-1-pentene are preferred. These
by further patents to Chevron and Idemitsu (Ta- branched monomers are much more expensive
ble 26). All these processes yield a liquid frac- than linear α-olefins because they arise only as
tion containing ca. 80 % of 4MP. Separation of minor byproducts from refining and cracking
pure 4MP from the C6 fraction requires super- operations, or by special synthesis. For exam-
fractionation with a 100-plate column. ple, 3-methyl-1-butene can be prepared by de-
Apart from being the main feedstock for PMP hydrating isoamyl alcohol. The same isospecific
manufacture, 4MP is now used as comonomer catalysts used to polymerize 4MP are also suit-
in certain grades of linear low-density polyethyl- able for making these branched olefin polymers
ene. However, 4MP is not traded commercially, (see Section 5.2). Preferably these high-melting
and there is no quoted price. The name plate ca- polymers are prepared as a stage of the PMP
pacity of Mitsui Petrochemical Industries plant polymerization process, rather than as separate
for 4MP is 13 000 t/a. additives.
A typical analysis (wt %) of 4MP monomer
used by ICI to make TPX is as follows:
5.1.3. Catalysts
4-Methyl-1-pentene 97.4
Lighter than C6 0.1
cis-4-Methyl-2-pentene 0.9 Most Ziegler – Natta catalysts suitable for
trans-4-Methyl-2-pentene 1.5 polypropylene polymerize and copolymerize
1-Hexene 0.1 4MP to give linear head-to-tail polymers. The
Some physical properties of 4MP [306, 307], reactivity of the higher α-olefins is apprecia-
relevant to its polymerization are: bly lower than that of propene under compara-
ble conditions. Copolymerization data compiled
bp, ◦ C 53.86 by Kissin [310, 311] illustrate how branching
mp, ◦ C − 153.64
Density at 20 ◦ C, g/cm3 0.6637
and chain length impede reaction with titanium-
Vapor pressure at 20 ◦ C, kPa 29.47 based catalysts (Table 28). Steric hindrance by
◦
Vapor pressure at 50 C, kPa 89.34 bulky groups in the 3-position, adjacent to the
Refractive index n20
D 1.38267 double bond, is particularly pronounced (3-
Heat capacity of liquid at 25 ◦ C, 2.191
J g−1 K−1 methyl-1-butene and 3-methyl-1-pentene). 4-
Heat of vaporization at bp, J/g 0.3221 Methyl-1-pentene is several times less active
Flash point, ◦ C − 7.0 than propene, as are all the higher linear α-
Autoignition temperature, ◦ C 300
olefins. Low overall reaction rates arise when
some of the active sites on certain catalysts are
Linear C6 – C12 α-Olefins. Most commer- inaccessible to bulky monomers [311].
cial grades of PMP contain small amounts of It is necessary to use highly isospecific cat-
higher α-olefins as comonomer to modify the alysts to achieve good yields of crystalline
main chain. Usually, the even carbon number polymer without much atactic byproduct. Pre-
olefins are made by oligomerizing ethylene with ferred systems use combinations of TiCl3 with
triethylaluminum or soluble nickel complexes. Al(C2 H5 )2 Cl as activator [312], or possibly
 Polyolefins 85
Table 26. Dimerization of propene to 4-methyl-1-pentene [298]

Company Process Catalyst Temperature, ◦ C Pressure, MPa Yield ∗, % 4MP Patent

priority

British Petroleum [302] rocking bed K on graphite 160 11 85 12.12.62

British Petroleum [303] fixed bed Na on K2 CO3 160 12 75 8.8.63
Chevron [304] slurry K on MgSiO3 150 5 80 17.5.66
Idemitsu [305] slurry K/Cu/tert-amine 180 7 90 13.4.76

∗ In liquid fraction.

Table 27. Physical properties of some comonomers ∗ [306]

Comonomer bp, ◦ C mp, ◦ C Density at 20 ◦ C, g/cm3 mp of isotactic

homopolymer, ◦ C

1-Pentene 29.96 − 165.22 0.6405 75 – 80

3-Methyl-1-butene 20.05 − 168.49 0.6272 310
1-Hexene 63.48 − 139.83 0.6732 amorphous at 20 ◦ C
3-Methyl-1-pentene 54.17 − 153.0 0.6674 > 350
4-Methyl-1-pentene 53.86 − 153.64 0.6637 235 – 250
4,4-Dimethyl-1- 72 0.6827 > 380
pentene
1-Octene 121.29 − 101.72 0.7149 34
1-Decene 170.60 − 66.28 0.7408 45
1-Dodecene 213.30 − 33.60 0.7583 60

∗ Data for 4-methyl-1-pentene included for comparison.

the newer supported catalyst systems such as 5.2. Industrial Manufacture

TiCl4 – MgCl2 – Al(C2 H5 )3 with an appropri-
ate Lewis base [313]. Catalysts made directly Published information on the production of TPX
from TiCl4 and organoaluminum compounds is very limited apart from the disclosures of
only yield 60 % of crystalline polymer, and ICI. Details which follow relate to their early
even violet TiCl3 activated with aluminum tri- slurry process, but some improvements have
alkyls produces some 20 % of solubles. These been introduced by Mitsui Petrochemical Indus-
trialkylaluminum – titanium halide systems also tries as their manufacturing capacity expanded
cause some isomerization of 4MP, but this is from 2000 to 6000 t/a.
completely avoided with TiCl3 – AlEt2 Cl. The Semibatch polymerizations used a conven-
original ICI process used a coarse, preformed tional water-jacketed stirred reactor containing
spherical TiCl3 made by controlled reduction of inert aliphatic hydrocarbon diluent, AlEt2 Cl,
TiCl4 with alkyl aluminum chlorides. Experi- and particle-form purple TiCl3 catalyst. A nu-
ments showed that it was important to secure a cleating polymer of a high-melting polyolefin
very mobile slurry to permit thorough catalyst can be formed on this catalyst either prior to
extraction for the highest polymer transparency. its introduction into the reactor, or at the end
of the main polymerization stage [301]. Over-
Table 28. Relative copolymerization activities r 2 of higher
α-olefins relative to propene [310] all reaction cycles are shortened when the cata-
lyst is first subjected to prepolymerization as a
Monomer r2 ∗
concentrated slurry in a separate reactor to gen-
Ethylene 8 – 20 erate the high-melting polymer. This procedure
Propene 1 yields a supply of treated catalyst ready for use
1-Pentene 0.2 – 0.5
1-Hexene 0.2 – 0.4 in the main reactor without delays caused by
1-Decene 0.1 – 0.3 the low-activity monomer. Sometimes this sim-
1-Octadecene 0.1 – 0.15 ple technique yields prepolymer which is poorly
3-Methyl-1-butene 0.02 – 0.06
3-Methyl-1-pentene 0.05
dispersed. The problem is reportedly overcome
4-Methyl-1-pentene 0.15 [309] by first polymerizing a small amount of
4MP on the catalyst before adding monomer
∗ Ratio of propagation rates, r 2 = k 22 /k 12 .
86 Polyolefins

to generate nucleating polymer. An even sim- United States, making 4MP monomer to con-
pler procedure apparently works: If a mixture of vert into PMP for evaluation and sale. This plant
4MP and the preferred monomer for nucleation operates a slurry process using a conventional
is used for prepolymerization, 4MP is consumed semibatch stirred reactor.
first because of its higher reactivity, leaving the Patents to BASF [315, 316] describe bulk
virtually pure second monomer free to polymer- polymerization of 4MP at 90 – 150 ◦ C under in-
ize on the expanded catalyst particles. Less than ert gas pressures up to 2 MPa to increase the
1 % of this additive is needed. yield. Catalysts used were TiCl3 · AlCl3 /tributyl
Following the addition of (prepolymerized) phosphine/AlEt2 Cl. Hot-heptane solubles of ca.
catalyst to the main reactor, an initial charge of 30 % were, however, high, and no process has
4MP and comonomer establishes both the re- yet been announced.
quired composition and the polymerization rate, Institut Français du Petrole’s intriguing
which is first order with respect to catalyst and isomerization – polymerization of potentially
monomer. As polymerization proceeds at ca. cheap 4-methyl-2-pentene to PMP, using TiCl3 ,
60 ◦ C, continuous injection of monomers main- nickel acetylacetonate, and AlEt2 Cl, has not
tains the reaction conditions until the prescribed been commercialized [317, 318].
amount of polymer has formed. This reaction
lasts a few hours, during which small injec-
tions of hydrogen control molecular mass, as 5.3. Polymer Structure
in polypropylene manufacture. Termination of
monomer feeds, followed by a short run-down 5.3.1. Homopolymer
period ensures that most of the monomer is con-
sumed before deashing starts. PMP polymer, made with highly isospecific cat-
All catalyst components are solubilized by alysts, has the following regular head-to-tail
adding a C3 – C6 alcohol to the slurry in a sec- structure in which all isobutyl groups lie on one
ond heated vessel. Centrifuging, followed by side of the chain in a two dimensional Fischer
several stages of washing with alcohol – diluent projection.
mixtures extracts catalyst residues and soluble
polymer. Importantly, addition of water, used in
some polypropylene deashing processes, results
in lower transparency of molded articles. Ash
levels below 0.01 %, and < 10 ppm of Al and
Ti are readily achieved. All filtrates are recycled
after separation by fractional distillation.
Conventional hot-nitrogen driers remove NMR spectroscopy, so useful in polypropyl-
diluent from the centrifuged cake. After addition ene and ethylene – propene copolymer charac-
of stabilizers, the dry powder is densified at 270 – terization, is of limited use for higher poly (α-
300 ◦ C in an extruder with a length/diameter olefins) where overlapping resonances of the
ratio of about 30/1. Various grades differ in main- chain atoms and pendant groups severely
comonomer content, molecular mass, and addi- impair resolution and interpretation [319]. De-
tive formulation (e.g., reinforcement with glass ductions concerning polymer stereoregularity
fibers, mica, and mineral fillers). largely rely on crystallinity related phenomena,
A Mitsui patent [314] describes techniques such as X-ray and IR spectra, melting behav-
for making broad MMD (co)polymers from ior, solvent fractionation, and various physical
4MP using MgCl2 supported catalysts in a two- properties.
stage polymerization system. This can be ei- Stereoregular poly(α-olefin) chains pack to-
ther conventional diluent-based slurry for each gether to form high-melting crystallites, which
stage, or slurry for the first stage followed by then assemble into a superstructure of radi-
a fluidized-bed reactor operating at 100 ◦ C and ally symmetric spherulites during crystalliza-
0.2 MPa absolute pressure. tion from a melt phase. In unbranched poly-
In 1989, Phillips Petroleum commissioned ethylene, the chains adopt a zig-zag arrange-
a 250 t/a integrated pilot plant at Bartlesville, ment in the crystal. The methyl side group
 Polyolefins 87

in polypropylene forces the chain to adopt a single copolymer preparation yielding chains
helical configuration involving three monomer with a wide range of compositions and degree of
units per turn (3/1 helix). With still larger block structure. The more active comonomers,
branches the helix unwinds to 4/1. In the case such as ethylene and propene, produce a dis-
of PMP, the bulky isobutyl group is accommo- persed phase of slightly modified PE or PP,
dated in a 7/2 helix with 3.5 monomer units even when only 5 mol % of the comonomer is
in each turn, and four chains per unit cell of fed [325]. The amount of this phase increases
28 monomer units. Unit cell parameters are as more comonomer is used, thereby further
a = b = 1.86 nm and c (chain axis) = 1.38 nm reducing transparency through light scattering.
[320]. This gives an exceptionally low calculated 1-Hexene and a few other comonomers be-
crystal density of 0.822 ± 0.006 g/cm3 , largely have differently in that they are able to sub-
because of the loose space packing of helices. stitute for 4MP units in the crystal without
At room temperature, the amorphous phase in significantly distorting or altering the crystal
this semicrystalline polymer has the higher den- structure of PMP; nor do they generate a sec-
sity of 0.838 g/cm3 [320, 321]. In a typical mold- ond dispersed phase [326]. In these cases, the
ing, the average polymer density of PMP is ca. physical properties still resemble those of PMP
0.83 g/cm3 . Such a unique reversal of crystalline at low comonomer contents. Small decreases
and amorphous polymer densities has some in- in crystallinity and melting point are measur-
teresting implications for molding operations. able but they are less severe than with non-
At 60 ◦ C, a common mold temperature, the den- cocrystallizing monomers. 1-Pentene copoly-
sities of the two phases are judged to be equal, mers also readily cocrystallize, causing some
i.e., there would be no volume change for crys- slight lattice contraction. Only small proportions
tallization at this temperature. of 1-butene can be accommodated within the lat-
Crystalline PMP finally melts at about tice.
250 ± 5 ◦ C (slow heating) and has a glass tran- Increasing the monomer chain length to
sition temperature T g of 50 – 60 ◦ C at 100 Hz octene, decene, and above makes cocrystal-
[312] (18 – 30 ◦ C by dilatometry [321]). Other lization increasingly difficult. However, small
transitions have been reported [322]: 130 ◦ C amounts of 1-octene and 1-decene are accom-
(start of crystal disordering) and at − 120 ◦ C to modated within the lattice by expansion, but oc-
− 150 ◦ C (relaxation of short chain segments). tadecene is far too large. The latter monomer
Crystallization from the melt does not require severely reduces crystallinity and forces the
massive supercooling. Isothermal crystalliza- copolymer into amorphous regions. The mag-
tion half time at 220 ◦ C is 0.5 min, increasing to nitude of these crystal changes is detailed in
480 min at 236 ◦ C. As with polypropylene, PMP [326]. α-Axis spacing in cocrystallized copoly-
is properly viewed as a semicrystalline polymer, mers can expand from 1.86 to 1.91 nm with
achieving a crystallinity of ca. 75 % in fully an- octene, and shrink to 1.81 nm with 1-pentene
nealed samples, 40 % in quenched moldings, and copolymers.
55 – 65 % in normally fabricated articles [323]. Glass transition temperature is favorably
The only stable crystallite formed from polymer reduced by 15 – 20 ◦ C in 5 mol % 1-decene
melts is tetragonal, but up to five polymorphs copolymers. This in itself is only sufficient to
can be obtained by crystallization from solution give a small toughness improvement because of
[324]. the high T g of PMP homopolymer. Copolymer-
ization usually lowers the modulus.

5.3.2. Copolymers
5.4. Properties of PMP Products
Random copolymers of 4MP, with ca. 2 – 8 wt %
of C6 – C12 linear α-olefins, are important com- 5.4.1. Optical Properties
mercially because of their good transparency
and robust processing behavior. Crystalline PMP polymers exhibit unusually
All linear α-olefins copolymerize with 4MP high optical transparency, both in terms of clar-
to some degree. Products are complex, with a ity (narrow-angle scatter) and haze (high-angle
88 Polyolefins

scatter). Optical transmittancies of commercial copolymers to reduce the size of spherulites

resins are in the region of 90 – 95 %, compared from 50 µm to < 5 µm. In quenched, nucleated
with 88 – 92 % for polystyrene and 90 – 92 % for homopolymers optical transmission reaches
acrylics. Other, more familiar crystalline poly- 96 %, which only falls to about 88 % with slower
olefins, such as polyethylene and polypropylene, cooling (Tables 29 and 30). Copolymers, al-
are at best translucent in thin sections. In these ready quite transparent when quenched, now
cases light is scattered from spherulitic assem- achieve transmittancies around 96 % in slow-
blies of crystalline and amorphous regions that cooled moldings after nucleation (Table 30).
have different optical refractivities. Addition- The combination of nucleation, rapid cooling,
ally, the crystallites themselves are anisotropic. and copolymerization virtually eliminates mi-
With spherulitic PMP, high transparency is crovoiding in most moldings.
favored by the similar densities of the crys-
Table 29. Optical transmission of PMP homopolymer with
talline and amorphous regions, and by the poly(4,4-dimethyl-1-pentene) nucleant [309]
low optical anisotropy of helical chains in the
Spherulite size, µm Transmission of
spherulites. Providing polymers have been thor-
oughly deashed, homopolymer optical transmit- Max. Mean Min. quenched moldings, %
tances of 80 – 85 % can be realized in quenched, 100 50 <1 69
3 mm thick moldings, and > 90 % in 1.5 mm 15 10 <1 86
thick samples. Plaques cooled more slowly de- <1 <1 <1 96
velop considerable haze and lower transparency
(20 %) as a result of increased interspherulitic Excellent light transmission in the near UV
voiding. These voids, about 1 µm in diameter, region makes PMP superior to glass and other
cluster round the boundaries of spherulites in transparent plastics in this respect, and inferior
the form of “shells” which are responsible for only to quartz (Figure 53).
haze [327]. Quenched moldings have fewer mi-
crovoids because crystallization takes place at
lower temperatures. This lowers the volume re-
duction on crystallization as the densities of
amorphous and crystalline phases become more
similar. At this lower temperature, the stronger
melt is more able to resist shrinkage stresses
without forming voids.
Copolymers of the type described in Sec-
tion 5.3.2 have improved transparencies be-
cause of such reduced voiding. With these prod-
ucts the crystallization temperature is reduced
by 10 – 30 ◦ C, depending on composition, giv-
ing improved transparency in both quenched Figure 53. Light transmission [329]
a) Quartz; b) Poly(4-methyl-1-pentene); c) Glass
and slowly cooled moldings. With 11 wt % 1-
octene copolymer, the transmittance increases
to 91 % and 85 % in 3 mm thick quenched and
slowly cooled moldings, respectively. This im- 5.4.2. Stability and Chemical Resistance
provement with copolymers is useful, even with
5 wt % comonomer, because high transparency The semicrystalline and saturated hydrocarbon
then becomes less dependent on maintaining nature of PMP confer excellent resistance to
very precise molding conditions. It is interesting polar solvents and inorganic substances, and
to note that spherulite size is largely unaffected to strong aqueous solutions of most mineral
by copolymerization, or by quenching a molding acids, alkalies, and salts. Vulnerable tertiary C –
[328], except in the thin surface skin. H bonds make PMP unsuitable for use in highly
The final, but major improvement to opti- oxidizing environments, such as chromic acid,
cal transparency comes from introducing prop- concentrated nitric acid, and chlorine. It is per-
erly dispersed nucleating agents into homo- or meable to some light hydrocarbons, aromatic
 Polyolefins 89
Table 30. Copolymer nucleation a with poly(3-methyl-1-pentene) [309]

Comonomer Optical transmission, %

Quenched moldings Slow-cooled moldings

No nucleant Nucleated No nucleant Nucleated

b
1-Pentene , 2 wt % 84 97 40 94
1-Hexene b , 2 wt % 84 97 40 94
1-Octene b , 2 wt % 84 97 40 94
1-Decene b , 2 wt % 84 97 40 94
None 84 95 20 88
1-Hexene, 2 wt % 84 97 40 94
1-Hexene, 5 wt % 87 98 72 96
a
Nucleated samples all had mean spherulite diameters < 2 µm, while unnucleated samples had mean spherulite diameters > 25 µm.
b
Optical transmission similar for all four comonomers.

liquids, and halogenated solvents, which cause ers incorporated by manufacturers severely re-
swelling and some loss of strength. Repeated tard much, but not all degradation.
sterilization with superheated steam at 135 ◦ C
over 60 cycles causes only minor reductions in Thermo-oxidation. Oxygen greatly acceler-
mechanical properties [330]. Accordingly, PMP ates the rate of chain scission over heat alone
is especially suited to medical uses. None of the [334–336]. Precautions must be taken not only
alternative transparent polymers (polystyrene, at high melt processing temperatures, but also
acrylics, polycarbonate, and polyester) can of- in the solid state. Oxidation is accompanied by
fer PMP’s broad range of resistance at room and molecular mass reduction along with hydroxyl
elevated (60 ◦ C) temperature. Resistance to de- and carbonyl formation in the polymer, leading
tergent stress cracking, while better than other to yellow discoloration, brittleness, and odor at
transparent polymers, is not quite up to the stan- long exposures. Low molecular mass volatiles
dard of the best bottle-blowing grades of poly- such as aldehydes, ketones, acids, water, and car-
ethylene. bon dioxide form in chain reactions involving
Above 100 ◦ C, several aromatic and aliphatic peroxidation of tertiary C–H bonds and radical-
solvents will effect complete dissolution. Stable induced chain cleavage. The well-established
gels containing 0.5 – 2 mm diameter spherulites faster oxidation of PMP compared to PP is at-
form on rapidly quenching cyclohexane solu- tributed to the more rapid diffusion of oxygen in
tions containing 150 g/L of PMP [331]. Decalin the open PMP structure. Studies indicate [335]
at 135 ◦ C is suitable for conventional molecu- that oxygen also attacks PMP crystallites, and
lar mass measurements by viscometry accord- not just the amorphous phase, as in PP.
ing to the Mark – Houwink equation [332] [η] = Stabilizers derived from bulky hindered phe-
1.94×10−4 M 0.81
v . nols and polyphenols, phosphites, and thioesters
provide reasonable protection against deteriora-
Thermal Degradation. Processing temper- tion during processing and in service at elevated
atures of ca. 300 ◦ C are necessary for the ma- temperature. The useful life with ca. 0.2 – 0.5 %
jority of PMP grades. Even under high vac- of these additives increases from around one day
uum these severe conditions promote degrada- at 200 ◦ C to seven years at 100 ◦ C [337]. Man-
tion as evidenced by a marked decrease in mo- ufacturers advise on the most suitable polymer
lecular mass and gas evolution [333], principally grade and further appropriate antioxidants for
isobutene (55 %) and propane (35 %). Carbon- demanding applications.
carbon bond cleavage occurs in chain reactions
in which hydrogen is abstracted from tertiary C– Photo-oxidation. Photodegradation of PMP
H bonds. The initial high rate seems to stem from is basically similar to thermal oxidation, but UV
a few weak links, possibly resulting from ad- light of wavelength < 400 nm seriously acceler-
ventitious oxidation. Degradation subsequently ates decomposition because chromophores, per-
continues at a lower rate. Suitable melt stabiliz- haps from impurities or oxygen charge-transfer
complexes, assist oxidation by peroxide inter-
90 Polyolefins

mediates. Chain decomposition then yields an modulus, heat deflection temperature, and sur-
array of oxidized products and lowers the mo- face hardness. A presumed lowering of the glass
lecular mass [338–340]. These reactions can be transition temperature accounts for the increased
minimized by incorporating into the polymer unnotched impact strength of MX004, although
specific stabilizers to deactivate excited chro- this is still inade-quate to raise notched impact
mophores, scavenge radicals, and reduce perox- strengths at room temperature.
ides. Hindered amine light stabilizers (HALS),
which behave as UV-stable antioxidants, and
metal chelates are quite effective [340]. How-
ever, the latter can cause mild blue-green dis-
coloration.
Enhanced oxygen diffusion in PMP is cited
as a principal reason for its greater suscept-
ability to photodecomposition than PP. Appli-
cations involving extended outdoor weathering
need careful appraisal, even with UV-stabilized
grades, unless there is heavy protection by pig-
ment screening with carbon black, ferric oxide,
rutile, etc. Light reaching earth is screened of
wavelengths < 290 nm by the atmosphere.
Suitably formulated PMP is also able to with-
stand up to 50 kGy of high energy β- and γ-
radiation, used for sterilization, without discol- Figure 54. DSC traces for TPX, RT 8XB [343]
oration or embrittlement [341]. Irradiation at a) Melting endotherm; b) Crystallization exotherm
higher doses (3 MGy) causes cross-linking and
generation of volatiles [342], whereas chain scis-
sion is the dominant reaction with PP except at
high doses.

5.4.3. Mechanical Properties

PMP has mechanical properties reasonably sim-

ilar to those of PP at 0 – 100 ◦ C. This applies to
flexural modulus, yield strength, and hardness,
though the precise comparison is dependent on
the chosen grade (Table 31). Copolymers are
more flexible with lower yield strengths and soft-
ening points. Melting and crystallization curves
of two commercial copolymer grades, provided
by Mitsui Petrochemical Industries (Figs. 54
and 55) illustrate some differences. Figure 54
shows DSC (differential scanning calorimetry)
Figure 55. DSC traces for TPX, MX004 (food grade) [343]
exotherms and endotherms for a lightly copoly- a) Melting endotherm; b) Crystallization exotherm
merized PMP. While the final melting is at
242 ◦ C, with a peak melting rate at 233 ◦ C, the
Carefully molded PMP articles are less brittle
onset of melting is clearly visible at 200 ◦ C. The
than transparent polystyrene and acrylics, and
second copolymer (Figure 55) is much less crys-
they are nearly as tough as polypropylene ho-
talline (melting peak areas 28.2 and 37.2 J/g re-
mopolymer. The latter usually fails with some
spectively), with a slightly lower final melting
yielding in unnotched Izod tests at room tem-
point of 231 ◦ C and a peak at 226 ◦ C. This reduc-
perature, thereby giving high failure energies.
tion in crystallinity is responsible for lowering
Table 31. Mechanical properties of PMP a

Property Method Poly(4-methyl-1-pentene) Polypropylene

Crystalor TPX Crystalor, TPX Propathene

HBC-020 (ho- CBN-020 RT18 (copolymer) MX004 30 % glass fiber filled GWM 22 (homopolymer) GWM 101
mopolymer) (copolymer) (copolymer) (copoly-
mer)

Density (20 ◦ C), g/cm3 ASTM D 1505 0.835 0.835 0.833 0.834 1.04 0.905 0.905
Melt flow index (MFI) at 260 ◦ C, ASTM D 1238 20 20 26 26 4.0 b 6.0 b
5 kg, g/10 min
Melting point, ◦ C Manufacturers 240 235 240 240 230 – 240 170 165 – 170
Vicat softening point, ◦ C ASTM D 1525 188 175 173 160 154 147
Heat deflection temperature, ◦ C ASTM D 648
0.46 MPa load 90 85 90 85 227 100 95
1.80 MPa load 54 49 40 189 65 60
Tensile yield strength, MPa ASTM D 638 32.4 27.6 23.0 19.6 59 – 67 34.5 27
5 mm/min
Flexural modulus, GPa ASTM D 790 1.92 1.24 1.27 0.74 5.5 – 5.9 1.5 1.15
Izod unnotched impact strength, ASTM D 256 12 19 15 49 22 60 tough
kJ/m2
Charpy notched impact strength, ASTM D 256 5 5 5 4 8 4.5 9.5
kJ/m2
Hardness (Rockwell) ASTM D 785 85 60 107 95 90
a
Taken from manufacturer’s literature of Phillips 66, Mitsui Petrochemical Industries, and ICI.
b
Measured at 230 ◦ C, 2.16 kg.
Polyolefins
91
92 Polyolefins

PMP’s higher T g causes failure in a brittle mode ture and frequency ranges. A combination of low
unless it is sufficiently modified by copolymeri- dielectric loss factor and good form stability at
zation. Above 150 ◦ C, PMP has greater strength high temperature makes it very suitable for mi-
and form stability than PP and polycarbonate crowave oven applications. Due to its negligible
as a result of its high melting point. At 20 ◦ C moisture absorption, PMP preserves these elec-
PMP creeps less in long-term tests than either trical characteristics under adverse conditions.
polypropylene or high-density polyethylene.
Polymers filled with glass fiber and mineral
additives are available from Mitsui, Phillips, and 5.4.5. Surface Properties and Permeability
Schulman in Belgium. Composites with 30 %
glass fiber are particularly useful due to their PMP’s surface tension of only 24 mN/m is the
enhanced modulus and greater form stability at second lowest to PTFE (20 mN/m) [345]. This
200 – 250 ◦ C. With 30 wt % glass fiber, room confers good stain resistance and excellent re-
temperature modulus is triple that of PMP ho- lease properties towards other materials.
mopolymer, while the heat deflection tempera- Confirmation of PMP’s loose space packing
ture increases from 90 ◦ C to 227 ◦ C (Table 31). is to be found in its high permeability towards
gases (Table 33). Oxygen, nitrogen, and car-
bon dioxide diffuse some 25 times more rapidly
Table 32. General properties of PMP products
through PMP film than through cast PP or HDPE
films. Moisture vapor transmission is substan-
tial, despite the low absorption of only 0.01 %,
even after total immersion in water.

Table 33. Gas and water vapor permeability of 50 µm PMP film

[346]

Permeability to PMP HDPE PP

−2 −1 −1
Oxygen, L m d atm 40 1.1 1.6
Nitrogen, L m−2 d−1 atm−1 9.5 0.3 0.36
Carbon dioxide, L m−2 d−1 atm−1 120 4.6 6.5
Water vapor, g m−2 d−1 atm−1 65 4.0 7.0

5.4.6. Rheology

PMP melts are strongly non-Newtonian. Their

viscosity decreases rapidly at high shear rates
and with increasing temperature (Fig. 56). These
a
For 100 % crystalline polymer. b Mitsui value; for other
two effects produce particularly fluid melts un-
measurements see [320,323,344]. der optimum processing conditions, and they
call for some alteration to processing techniques
compared to PP. In most cases friction heating
alone in the extruder barrel is insufficient for
5.4.4. Electrical Properties
uniform melting, and pressure generation also
needs improving. Allowance should be made for
The excellent electrical insulation properties of
low melt strength. There is a suggestion [323] of
PMP (Table 32) are similar to those of PTFE
some melt order in view of the low entropy of
and the best cable-grade polyethylene, whilst in
fusion, 10.3 J K−1 mol−1 . The particularly rapid
the frequency range of 10 kHz to 20 MHz PMP
decline in viscosity with increasing temperature,
is superior. Its permittivity (dielectric constant)
around 280 ◦ C, also has been linked with helical
is the smallest of all synthetic plastics, and it
association in the melt [344, 347, 348].
remains essentially constant over wide tempera-
 Polyolefins 93

5.5. Economic Aspects the ideal type employs a slow- compression

screw with an L/D ratio of 20 – 24. The cylinder
The following list prices (in £/t) for polymer- must be capable of being heated to 350 ◦ C, with
ization grade materials and polymers prevailed precise temperature control over the preferred
in the fourth quarter of 1991: operating range of 280 – 320 ◦ C. Friction heat-
ing is inadequate, and can cause local decompo-
Propene (Western Europe) 210
4-Methyl-1-pentene Not traded sition. An alternative is to feed the machine with
1-Hexene 1010 granules preheated to 130 ◦ C. A valved nozzle
1-Octene 920 prevents die drool between shots with very fluid
1-Decene 900
Polypropylene (Western Europe and
melts. Injection pressures only need to be 50 and
United States) 360 – 450 25 MPa for the primary and secondary stages,
PMP (grade and volume dependent) 2500 – 4300 with a relatively slow injection speed (< 50 % of
The higher cost of PMP over PP re- the machine capacity) into a mold at 20 – 60 ◦ C.
flects higher raw material prices without the Gas venting of molds is imperative to avoid burn-
economies of scale now realized for PP, as well ing from any volatile decomposition products
as 10 years difference in experience. formed at high melt temperatures.

Extrusion Blow Molding. The attraction of

making high-quality transparent containers by
blow molding PMP is tempered by poor melt
strength and additional heating requirements.
Some simple adjustments to secure accurate
melt temperature control in the range 220 –
250 ◦ C, the use of a parison controller and accu-
mulator, and pressure generation with a barrier
type torpedo are satisfactory for certain appli-
cations. Still higher quality and better produc-
tion rates call for a number of additional alter-
ations. These include continuous parison extru-
sion, modification of the pinch-off blades, a long
L/D extruder, and mold vents. Manufacturers ad-
vise on the best conditions for their resins.
Figure 56. Viscosity curves [347]
a) Polypropylene (Propathene) MFI 4.0 (230 ◦ C/2.16 kg);
b) – d) Poly(4-methyl-1-pentene), TPX, grade DX810, Injection stretch blow molding is the ideal
MFI 70 (260 ◦ C/5.0 kg) method for making high- clarity containers hav-
ing excellent physical properties due to biax-
ial orientation (see Section 2.8.2). A standard
low- compression screw normally suffices, but
5.6. Fabrication and Applications improved heating to 200 ◦ C is called for in the
conditioning station before transfering to the fi-
5.6.1. Fabrication nal mold. Here, the blowing air must have a sup-
ply pressure of 3 MPa. Standard machines are
In principle, most of the normal fabrication tech- easily modified to process PMP.
niques used for polyolefins can be used to make
PMP articles, provided due recognition is given Extrusion. PMP can be used in most plas-
to its high melting point and low melt viscosity. tic extrusion processes for making film, fiber,
Further changes to processing techniques have sheet, pipe, and coatings for wire and paper. In
been introduced over the past five years to im- all cases the extrusion stage should have am-
prove output rates and quality. ple barrel heating arrangements. Twin and single
conventional full-flighted or three-stage screws
Injection Molding. While both piston and used for PE or PP are suitable, provided that
screw injection molding machines can be used, those generating excessive shear are avoided.
94 Polyolefins

However, the throughput is reduced with PMP, curing of rubber with heat or by UHF vulcaniza-
and surging tends to occur when the screw speed tion. Inert mandrels made from flexible grades
is increased. A more suitable single screw has a of PMP are used as supports during the manu-
double flight in the compression zone to separate facture and curing of reinforced high-pressure
melt and solid polymer before it is plasticized rubber hoses.
(Fig. 57). This secures stable operation without Good electrical properties and heat resistance
any throughput penalties. meet specifications for use as covering for heat
The downstream equipment used for making resistant wire, power, oil well, and communica-
sheet, film, tubes, and coatings is similar to that tion cables. Glass-fiber-filled grades have suf-
used for PP, but with appropriate temperature ad- ficient shape retention after a few minutes at
justments. Fine fibers can be made by the blown 260 ◦ C to be used in dip soldering applications.
melt method or by the long spin process (see Other industrial uses include replacement of
Section 2.8.3). stainless steel chemical treatment trays, sight
glasses and floats, and a multitude of electrical
Difficult and Impractical Processes. Ther- insulators.
moforming, either by vacuum, pressure, or Labware and medical products were the first
matched-mold processes is difficult, but possi- to take advantage of PMP. Transparency, con-
ble, with PMP thin sheet. The need to use high venience of sterilization with either γ-rays, eth-
temperatures, followed by a long cooling pe- ylene oxide, dry heat, or steam autoclaves, and
riod gives a cycle time of approximately 1.5 min. resistance to soiling are all relevant. Examples
However, attractive food trays for microwave include blood test cells, medical instruments,
ovens are being made from thin sheet by using tubing connectors, centrifuge cups, syringes and
low draw down ratios. Rotational molding and other measuring devices, urine collection tubes,
mechanical forming are unsuited to PMP. Small and blood transfusion equipment. In the labo-
amounts of foamed moldings are marketed. ratory, PMP cages for small animals are easily
cleaned and sterilized. Shatterproof transparent
replacements for glass embrace most of the fa-
5.6.2. Applications miliar items such as beakers, measuring cylin-
ders and jugs, funnels, bottles, and Petri dishes.
The sales pattern of PMP worldwide in 1991 Important outlets exist in food preparation
is reported by Mitsui Petrochemical Industries where resistance to heat, oil, and steam is
(MPC) as follows [350]: needed. Baking trays for bread, and thermo-
formed PMP- coated paper cartons for cook-
Release film and paper 22 %
Industrial 20 %
ing foods, either in microwave or sometimes
Medical and laboratory 13 % in gas-heated ovens, have superior releasability
Cookware 11 % to aluminum foil containers. Application extend
Electric 7% to coffee maker parts, popcorn popper covers,
Packaging 6%
Others 21 %
packages suitable for food retorting, microwave
oven cookware, and service trays.
PMP film, manufactured by MPC under the New areas under investigation include out-
trade name Opulent, is available in different lets for PMP fibers, such as nonwoven fabric,
thicknesses (25 – 500 µm), with different flex- gas separation systems, and optical fibers.
ibilities (modulus 0.7 – 1.6 MPa), and with al-
ternative surface finishes. Three-layer laminates
with Kraft paper or low-softening polyolefins 5.7. Health and Environmental Aspects
extend the range. These products find extensive
use in applications requiring good release char- PMP itself is regarded as inert and nontoxic, like
acteristics combined with high temperature re- polyethylene and polypropylene. Formulation
sistance and chemical inertness. Important ex- systems for various grades are available to con-
amples include release films in manufacturing form with food regulations in Japan, Germany,
electronic circuit boards, in curing advanced the United States, and the United Kingdom. Be-
composites for aircraft parts, and in continuous ing a saturated hydrocarbon, PMP presents no
 Polyolefins 95

Figure 57. Screw for PMP [349]

L/D ≥ 28; CR = H f /H m = 2.5 – 3.0; H f = Depth of feed zone; H m = Depth of metering zone

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