Impact polypropylene copolymers:

fractionation and structural characterization

Francis M. M i r a b e l l a Jr
Quantum Chemical Corporation, Process Research Center, Morris, IL 60450, USA
(Received 30 January 1992; revised 16 July 1992)

Impact polypropylene copolymers may be produced in a two-reactor system to yield a blend of homopolymer
with an ethylene-propylene rubber (EPR). The polypropylene homopolymer, which is itself brittle and has
low impact strength, is markedly toughened by the presence of the EPR. The rubber-like EPR exists as a
phase-segregated discrete particle in a continuous matrix of the hard phase. The molecular structure analysis
of the resulting complex mixture is a formidable task.
The purpose of this paper is to describe a preparative and an analytical temperature-rising elution
fractionation (t.r.e.f.) technique as the primary tools to separate and characterize a commercial impact
copolymer. These techniques permit the isolation and subsequent characterization of the components of
the impact copolymer by ancillary techniques, primarily 13C nuclear magnetic resonance and differential
scanning calorimetry. These techniques were applied to the structural analysis of a commercial impact-grade
polypropylene with a melt flow rate of 6. It was found that this impact copolymer was composed of about
75wt% of isotactic polypropylene, about 17wt% of a highly non-crystalline EPR and about
8 wt% of semicrystalline ethylene-propylene copolymers. A major component of the semicrystalline
ethylene-propylene copolymers was an ethylene-rich copolymer containing between 0 and 8 wt% of
propylene comonomer.
The separate characterization of the components of the impact copolymer gives insight into the chemical
synthesis process used to produce these copolymers. Further, it permits one to gain a better understanding
of the location and function of each of the components in the complex mixture.

(Keywords: impact polypropylene; copolymers; fractionatie,~; characterization; temperature-rising elution fractionation)

INTRODUCTION markedly. The EPR is known to exist as very small,

Commercial isotactic polypropylene homopolymer is discrete particles in the polypropylene matrix 2. These
limited in its applications by its relatively low impact particles toughen the matrix against crack propagation
strength and high brittleness temperature. The properties by dissipating large amounts of energy in the matrix
of polypropylene can be greatly extended by blending material around the particle, thereby blunting the crack
with a minor fraction of a rubber-like material. This is and inhibiting crack propagation.
routinely done commercially by synthesizing reactor Impact polypropylene copolymers may be made either
blends of isotactic polypropylene and ethylene-propylene by blending rubbers into polypropylene homopolymer
rubbers (EPR) in situ. These blends of isotactic poly- or in situ in a two-reactor system 3. The in situ method
propylene and EPR are widely known as impact of producing impact polypropylene is considered to be
polypropylene and dominate a large fraction of the more advantageous than post-reactor blending, as judged
polypropylene market. The EPR acts as a toughener for by the superior properties of the resins produced and the
the brittle, low-impact-strength isotactic polypropylene commercial success of this method 3. Polypropylene
matrix. It is well known that the addition of a low-Tg, homopolymer is made in the first reactor and the EPR
rubber-like material to a high-Tg, hard polymer material is made in a second reactor. The polypropylene is blended
may result in dramatic improvement in the toughness of with the EPR in a sequential process in which the
the hard polymer 1. The rubber-like phase is known to polypropylene is added into the second reactor while the
exist as a phase-segregated discrete particle in a EPR is being polymerized.
continuous matrix of the hard phase 2. The rubber-like This product made in this sequential reactor system,
particles are typically added at low concentration and, impact polypropylene, is a complex mixture of poly-
thus, form a discrete phase in the continuous matrix of propylene homopolymer and ethylene-propylene co-
the hard phase. An example of a toughened polymer is polymers. The complete molecular structure analysis of
impact polypropylene 2. Polypropylene itself has poor such a polymer system is a formidable task. The purpose
impact resistance and is very brittle at low temperatures. of this paper is to describe the molecular structure
However, when about 10 20% of an ethylene-propylene analysis of a commercial impact polypropylene using
copolymer rubber (EPR) containing about 50% ethylene temperature-rising elution fractionation (t.r.e.f.) as the
is added to polypropylene, the impact strength increases primary technique. The t.r.e.f, technique is primarily
dramatically and the brittleness temperature is decreased employed to separate the complex mixture into discrete

0032-3861/93/081729~)7
© 1993 Butterworth-HeinemannLtd. POLYMER, 1993, Volume 34, Number 8 1729
Impact polypropylene copolymers: F. M. Mirabella Jr

fractions, which can then be individually characterized,

thereby yielding the identification of the individual 15
components of the complex mixture 4. This knowledge
permits one to gain a better understanding of the location
and function of each component in the complex mixture. t ,2

EXPERIMENTAL 14
Analytical temperature-rising elution fractionation
Fractionation of the resins was done by temperature-
rising elution fractionation (t.r.e.f.) 4. This technique
consists of dissolving the sample in trichlorobenzene
(TCB) at a concentration of 0.007 g cm -3 at 140°C. This
solution is deposited on a steel column (250 m m x 10 m m
i.d.) packed with an inert support, Chromosorb P. The
column is then capped and cooled to room temperature

'L
at 1.5°Ch -1 over about 3 days. The column is then 2
connected into a system through which TCB is pumped

/
at 2.0 ml m i n - 1 while the temperature is increased at
8
2 0 ° C h - L The species eluting from the column are
detected with an i.r. detector set at a detection wavelength 5-
of 3.41 #m (C H stretch). The eluting species can be
trapped independently in fractions as a function ofelution
temperature. Only a very small mass in each fraction can
[6
be obtained in this primarily analytical technique.

Preparative temperature-rising elution fractionation

17
In order to collect large fractions of the fractionated
resins, a preparative t.r.e.f, apparatus was constructed.
The construction and operation of a similar version of
this apparatus has been described in detail, previously s.
It is shown in Figure 1. The polymer is dissolved in TCB
and cooled slowly as in the analytical t.r.e.f, procedure.
The cooled polymer and solvent are then introduced into
the chamber of the apparatus in Figure 1 and heated Figure 1 Schematicdiagram of the increasing-temperaturesequential
slowly in incremental steps of temperature. Fractions are extraction or preparative t.r.e.f, apparatus. The parts of the apparatus
are as follows: (1) distillation chamber consisting of a boiler (la) and
removed from a valve at the bottom of the apparatus. a refluxing column (lb); (2) sample fractionation chamber; (3) hot plate
The polymer is recovered by evaporating the TCB solvent to boil solvent; (4) tap-water-cooled condenser; (5) nickel-chromium
and drying thoroughly in a vacuum oven. wire gauze baskets; (6) hot plate to heat solvent to within 10°C of
In order to facilitate the preparative-scale fractionation, desired temperature;(7) heat tape to raise temperature to within _+0.2°C
the soluble polymer, which was primarily the EPR, was of set point; (8) extension tube; (11) PTFE stopcock for aliquot removal;
(12) addition funnel for replenishing stock antioxidant solution; (13)
removed as a room-temperature-soluble prefraction nitrogen gas entrance tube; (14) 10°C cooled condenser; (15) nitrogen
in a preliminary fractionation step. The preliminary gas exit fitting to glycerin trap; (16) addition chamber; (17) nitrogen
fractionation step was done as follows: The impact pressure valve; and (18) pressure relief valve
copolymer (PP/E-1) was dissolved at a concentration
of 5.10g in 2 5 0 m l of spectroscopic-grade 1,2,4-
trichlorobenzene (TCB). Dissolution was attained at
approximately 160°C with gentle stirring. The solution in aluminium sample pans. The temperature was
was allowed to cool to r o o m temperature and the programmed at 10°C m i n - 1. Other parameters used were
precipitated polymer was recovered by centrifugation and according to the typical D u P o n t 990 operating procedure.
filtration. The soluble polymer remained in TCB solution
at room temperature. This procedure was repeated two 13C nuclear magnetic resonance
additional times on the TCB-insoluble polymer to remove 13C nuclear magnetic resonance was done on a J E O L
exhaustively all soluble polymer. The soluble polymer
FX-90Q n.m.r, spectrometer. Typical conditions were:
was recovered by evaporative stripping of the TCB
300 scans, 90 ° pulse angle, 10 s pulse delay (ca. 1 h scan
solvent and drying in a vacuum oven. The soluble accumulation) and 10 m m tubes were used for relatively
polymer was 15.3 w t % of the original impact copolymer. small sample mass (ca. 25-50 mg). Samples were swelled
Only the insoluble polymer fraction was introduced into
with a minimum volume (ca. 1 ml) of TCB. D a t a were
the preparative fractionation apparatus in Figure 1.
handled according to standard techniques 6.

Thermal analysis Materials

The thermal behaviour of the materials studied in this The impact copolymer characterized in this work was
work was determined on a D u P o n t 990 differential a commercial impact polypropylene copolymer with a
scanning calorimeter. Samples of 5-10 mg were sealed melt flow rate MFR = 6 and designated PP/E-1.

1730 POLYMER, 1993, Volume 34, Number 8

 Impact polypropylene copolymers. F. M. Mirabella Jr
28!

-~ ZONE 1

2c
O
e-
t~

o
¢/1

<
"0 12

ZONE 3

•~ 1 I ~ i ~ - ' - - '-- ' I - t

24 36 48 60 72 84 96 108 120

Temperature Deg C
Figure 2 Analytical t.r.e.f, of the whole commercial impact grade polypropylene copolymer (PP/E-1). Elution temperature range designations are
defined later in the text and in Figure9

RESULTS 2a
The molecular structure of commercial impact poly- 24
propylenes, which are typically produced in multi-
reactor systems, has been rarely reported in the 820
literature. The primary reason for this scarcity of
microstructural data on commercial impact polypropylene "
resins is the difficulty of separating the many different
components of these complex mixtures. Identification and < -
"o12
characterization of the components in the unfractionated ~,
whole polymer is presently not possible, if a definitive _~ a L
analysis is required. One of the few studies in the literature
reported on the fractionation of impact polypropylene
copolymers into two fractions, a xylene-soluble fraction and
a xylene-insoluble fraction 7. The xylene-soluble fraction 0 I I ] \.
was found to contain ethylene-propylene copolymer. The 60 72 84 96 108 120
Temperature Deg C
xylene-insoluble fraction was found to contain isotactic
polypropylene homopolymer and a small amount of Figure 3 Analytical t.r.e.f, of the TCB fraction, insoluble at room
polyethylene. N o evidence was seen for ethylene-to- temperature, of the impact-grade polypropylene copolymer
propylene linkages due to block or graft ethylene-to-
propylene sequences. Analysis was done by d.s.c, and 13C
n.m.r.
The analytical t.r.e.f, elution pattern for the impact 2a
polypropylene copolymer studied in this work is shown
in Figure 2. This impact copolymer (PP/E-1) was 24
fractionated in a preliminary step to remove the E P R
component. The remainder of the polymer was analysed ~ 2o
by analytical t.r.e.f, and this is shown in Figure 3. It can
be seen that Figure 3 is similar to Figure 2, except that ~ is
the low-temperature-eluting E P R component is absent <
from Figure 3. The polymer in Figure 3 was fractionated x~ 12 1
by preparative t.r.e.f, and separated into 12 fractions. The i

analytical t.r.e.f, chromatograms of each of these 12 ~ a

fractions are shown in Figures 4-7. It can be observed
in Figures 4 7 that the approximate peak elution
temperatures increase as fraction number increases. The 4
increase in peak elution temperature indicates an increase i I I I I
in the level of crystallinity. However, the analytical t.r.e.f. °0 12 24 36 48 60 72 84 96 108 120
curves are rather broad and complex, and display Temperature Deg C
significant overlap between fractions. This is indicative
of the complexity of the mixture of components in the Figure 4 Analytical t.r.e.f.s of preparative t.r.e.f, fractions 1-3

POLYMER, 1993, Volume 34, Number 8 1731

Impact polypropylene copolymers." F. M. Mirabella Jr
28 polymer, and also the limited separation efficiency of the
preparative t.r.e.f.
24 The elution temperature ranges of the room-
temperature prefraction and the succeeding 12 preparative
¢ 2O
o
C
t.r.e.f, fractions are presented in Table 1. These fractions
were characterized by differential scanning calorimetry
o
¢/} 16 (d.s.c.) and 13C nuclear magnetic resonance spectroscopy
..Q
< (n.m.r.). Copolymer compositions, monomer sequence
distributions and stereoregularity of propylene units were
determined by a3C n.m.r, by established techniques 6.
Melting endotherms from d.s.c, analysis were used to
determine copolymer compositions by comparison with
d.s.c, data of copolymers with known composition. These
d.s.c, and ~3C n.m.r, data were used to determine the
0 I i I chemical composition and stereoregularity of the com-
0 12 24 36 48 60 72 84 96 108 120 ponents of each fraction. Table 1 shows the major and
Temperature Deg C minor chemical components and stereoregularity of these
Figure 5 Analytical tr.e.f.s of preparative t.r.e.f, fractions 4-6 13 fractions.

28

24 24

8 20 2O
g ¢-
t~

0 16 o
u~ 16
.0 .Q ~i0
< <
"10 7 -9
12 12

¢-
8

0 0
0 12 24 36 48 60 72 84 96 108 120 0 12 24 36 48 60 72 84 96 108 120
Temperature Deg C Temperature Deg C
Figure 6 Analytical t.r.e.f.s of preparative t.r.e.f, fractions 7 9 Figure 7 Analytical tr.e.f.s of preparative t.r.e.f, fractions 1(~12

Table 1 Components of fractions from PP/E-1

Elution Component
temperature Fraction Fraction
range (°C) number wt% Major Minor Trace

RT prefraction 15.3 EPR Atactic

50/50 C2/C3 polypropylene
RT 1 0.4 E/P copolymers (negligible crystallinity)
R T~40 2 1.4 E/P copolymers (negligible crystallinity) ppb
40-60 3 2.2 E/P copolymers (low crystallinity) ppb
60-85 4 3.5 L L D P E c + ppb (crystalline) ppb
89-90 5 2.1 L L D P E c + ppb (crystalline) ppb
9(395 6 1.4 PP" + L L D P E c ppb
95 100 7 1.6 pp. PE (linear) d ppb
100 105 8 6.1 pp" PE (linear) a
105-110 9 10.8 pp. PE (linear) d
110-115 10 23.1 pp. PE (linear) a
115-120 11 13.2 pp. PE (linear) a
120-140 12 18.9 ppa PE (linear) d

a Highly isotactic P P ) The observation of high- and low-

stereoregularity P P m a y be in
b LOW stereoregularity P P ) different or the same molecular chain(s)
" L L D P E refers to PE with a minor a m o u n t of propylene comonomer (~< 8%)
d PE (linear) refers to PE without observable c o m o n o m e r

1732 POLYMER, 1993, Volume 34, Number 8

 Impact polypropylene copolymers: F. M. Mirabella Jr

In Table 1, PP = polypropylene, PE = polyethylene and with homogeneous catalyst systems 8. In the case of
LLDPE=polyethylene with a small concentration of copolymers made with heterogeneous catalysts, it is
propylene. The complex structure of impact propylene known that these systems often produce heterogeneous
copolymers can be rationalized on the basis of the copolymers, i.e. copolymers with very broad compositional
sequential polymerization process used to produce these distributions 9, ~o
polymers. The weight percentage of each fraction is This behaviour has also been observed in fractionation
given in Table 1. The polypropylene accounted for studies on linear low-density polyethylenes ~1. These
about 75 wt%, the EPR about 17 wt% and the other LLDPE copolymers are made on similar titanium-based
copolymers about 8 wt% of the total. catalyst systems as used in the production of impact
The results of the characterization of this impact copolymers. In these studies, it was shown that the
copolymer show that impact copolymers are typically copolymers of ethylene and butene gave not only
blends of polypropylene homopolymer, EPR (with broad composition distributions, but also multimodal
negligible crystallinity), a high-density-like polyethylene composition distributions. No theory exists for the
component and crystallizable copolymers of ethylene and calculation of the copolymer composition distributions of
propylene. The presence of polypropylene homopolymer copolymers made over heterogeneous catalysts. However,
is obviously explained by the production of such the calculation of the theoretical composition distribution
homopolymer in the first reactor where only catalyst, function for copolymers made with homogeneous catalyst
propylene monomer and hydrogen are present. The systems is helpful in understanding the composition of
ethylen~propylene rubber (EPR) is present because of copolymers produced in the secondary reactor in the
its deliberate production in the second reactor where production of impact copolymers. This copolymer
ethylene, propylene, catalyst and hydrogen are all present composition distribution function isS:
in order to form this copolymer.
3(2/2aobok) 1/2
However, it is unexpected that crystallizable copolymers
of ethylene and propylene are also present besides the W(y) dy = 4(1 + 2y2/2aobok) 5/2 dy (1)
non-crystallizable EPR. The reason that the presence of
these crystallizable ethylene-propylene copolymers is where 2=number-average DP of growing chains, ao,
unexpected is because the monomer ratio of ethylene to b o = average molar copolymer composition, A, B = molar
propylene in the second reactor is such that a copolymer composition of monomer feed,
rich in both ethylene and propylene should be produced. k = aor2A/B + borlA/B
This copolymer is expected to be non-crystallizable and
rubber-like, which is the copolymer that is desired. The r 1, r 2 reactivity ratios, y = a - a o = bo - b is the compo-
=

majority of the copolymer produced in the second reactor, sition deviation parameter, and a, b=variable molar
i.e. the EPR, fulfils these requirements. copolymer composition.
However, it was initially surprising to find, in addition This function is the composition distribution for all chain
to the EPR, an apparent spectrum of crystallizable lengths and is calculated from some basic polymerization
copolymers of ethylene and propylene, which contain parameters such as feed composition, reactivity ratios,
small quantities of propylene in an ethylene-rich number-average chain length and average copolymer
copolymer and small quantities of ethylene in a composition. The calculated composition distribution
propylene-rich copolymer. The purpose of the next functions for several typical copolymers formed as second
section is to give a theoretical basis for the presence of reactor products are presented in Figure 8. These
these crystallizable ethylene-propylene copolymers, as composition distributions are relatively narrow, but they
well as the EPR. do exhibit the type of distribution of copolymer species
expected for second reactor products. It is anticipated
THEORETICAL DISCUSSION that the actual composition distributions of the second
reactor product are much broader than those presented
The theory that describes the expected composition in Figure 8. This is because heterogeneous catalysts may
of copolymers is well developed for copolymers made contain a spectrum of sites and processes in contrast to

(a) (b)

wOO w(Y)

0.585 0.685 0.785 0.40 0.50 0.60

Mole Fraction C2 Mole Fraction C 2

Figure 8 Composition distribution functions (equation (1)) for ethylene-propylene copolymers containing an average mole percentage of ethylene
(C2) of (a) 68.5% and (b) 50%

POLYMER, 1993, Volume 34, Number 8 1733

Impact polypropylene copolymers: F. M. Mirabella Jr

homogeneous catalysts I°. However, the distributions

presented in Figure 8 are useful for qualitatively
demonstrating the effect of these distributions on the
structure of the copolymers produced.

DISCUSSION
Figure 9 shows a qualitative representation of the broad
composition distribution that was observed for the second
reactor in the production of impact copolymers. The
important point to illustrate in Figure 9 is that the central
portion highlighted with cross-hatching represents
copolymers that contain a large fraction of ethylene and
propylene and, therefore, are expected to be rubber-like io 8'0 16o 12o
and exhibit negligible crystallinity. The extremities of the TEMPERATURE°C
curve, on the other hand, represent copolymers that are
rich in one of the monomers with only a small fraction Figure 10 Analytical t.r.e.f, of an EPR made separately under second
reactor conditions, i.e. no polypropylene homopolymer present
of the other monomer. These copolymers would be
expected to be semicrystalline. Figure 2 shows the
temperature ranges in Figure 9 in which the various Table 2 Elution temperature (TE) ranges for components of impact
polymers elute in the t.r.e.f, chromatogram of the impact polypropylene copolymers
copolymer. It has been observed in these t.r.e.f, chromato-
grams that the copolymers of ethylene and propylene TE (°C)
elute from the chromatograph in two distinct regions. Ethylene-propylene rubber (~3(~70% ethylene) 25-60
The EPR elutes immediately at room temperature. On High-density polyethylene 93-95
the other hand, the crystallizable ethylene-propylene Isotactic polypropylene 107-109
copolymers elute just before the elution of the propylene Atactic polypropylene 25-60
homopolymer. The order of the elution of these
copolymers from the t.r.e.f, is governed by the melting
point of the crystals as described by the Flory equation12. observed. This small hump, at higher temperature, would
Previously, it was unclear why there should be appear as a shoulder on a large polypropylene peak in
effectively two regimes of copolymers structure observed the t.r.e.f. This can be observed by consulting Figure 2
in the t.r.e.f, fractionation process. However, now where the shoulder is identified as zone 3. The copolymers
it is clear, by consulting Figure 9, that this is to that elute around 85-105°C are much richer in ethylene
be expected because in the central region of the than the EPR or much richer in propylene than the EPR,
copolymer distribution are rubber-like copolymers that so that these copolymers are semicrystalline.
elute at room temperature in the t.r.e.f. The copolymers The identity of the major peaks in the t.r.e.f, of the
represented by the extremities of the curve in Figure 9 impact copolymer can be determined qualitatively
are semicrystalline and, therefore, are expected to elute according to the elution temperature of each major
at a much higher temperature from the t.r.e.f., as observed species. Table 2 presents the elution temperatures for
in Figure 2. species present in impact polypropylene copolymers. The
This behaviour was substantiated by fractionating an polymers eluting around 93°C were shown by a3C n.m.r.
EPR synthesized under conditions typical of the second and d.s.c, data to be due to polyethylene containing
reactor but without any propylene homopolymer present. between 0 and 8 wt% of propylene comonomer. This
Figure 10 shows the t.r.e.f, chromatogram for this EPR. polymer is due to the ethylene-rich extremity of the
It can be seen that both an EPR eluting at room broad copolymer distribution shown in Figure 9. It is
temperature and a small peak around 85-105°C are close to the large polypropylene peak, which elutes later,
and the mixing of these two species is shown in Table 1.
As shown in Figure 2, copolymers rich in propylene and
containing small concentrations of ethylene would elute
towards the higher-temperature side of the 85-105°C
range. However, a copolymer of propylene with a minor
wOO amount of ethylene was not observed, as shown in Table
1. A t.r.e.f, of such a copolymer containing 96.1 wt%
propylene and 3.9wt% ethylene was analysed by
analytical t.r.e.f, and this is shown in Figure 11. It, in fact,
does elute at a peak temperature of about 100°C, as
predicted. However, copolymers richer in propylene than
the EPR were not observed in fraction numbers 2-7 (Table
1). These copolymers are represented on the left
0% 50% 100% (low-ethylene) side of the curve in Figure 9.
Weight % Ethylene The polypropylene homopolymer, itself, exhibits a
distribution of elution temperatures over the temperature-
Figure 9 Qualitative representation of the composition distribution rising elution fractogram. In fact, the polypropylene
function (weight percentage of ethylene) of the second reactor polymer
in an impact-grade polypropylene copolymer. Zone designations refer elutes over the entire fractogram. This is due to
to those indicated in Figure 2 the tacticity distribution of this polymer. The tacticity

1734 POLYMER, 1993, Volume 34, Number 8

 Impact polypropylene copolymers. F. M. Mirabella Jr

linked together as blocky copolymers. This was in

99,3
i00,5 agreement with the results of the study of Vernon 7.

CONCLUSIONS
It was shown that the impact polypropylene copolymer
PP/E-1 was composed of about 7 5 w t % of a highly
isotactic polypropylene, which forms the continuous
matrix. An ethylene-propylene rubber (EPR) comprised
about 17 wt%, which has been shown to exist primarily
as a discrete phase-segregated particle dispersed in the
polypropylene matrix in similar systems 2. The balance
of about 8 wt% was comprised of partially crystalline
TEMPERATURE °C ethylene-propylene copolymers. A major component of
the partially crystalline ethylene-propylene copolymers
Figure 11 Analytical t.r.e.f, of an ethylene-propylene copolymer was an ethylene-rich copolymer containing no observable
containing 3.9 wt% ethylene
propylene up to 8 wt% of propylene comonomer.
The t.r.e.f, technique provides a powerful tool to
separate complex mixtures of polymers of dissimilar
physical (stereoregularity) and chemical structure. The
separated components may then be conveniently charac-
,'q terized, thereby providing an understanding of the
,'q
detailed structure of the complex mixture. Such an
-,q understanding is extremely difficult to deduce from the
,'q unfractionated mixture.
:=
,'q This study provides a detailed structural characterization
,'q of an impact polypropylene copolymer. The function of
,'q the components of the mixture may be deduced from this
\'4

a priori structural analysis. The detailed structure of the

impact copolymer would be difficult to anticipate based
on synthesis conditions alone.
~ N N N N N ~ . . . . . . . .
i00
PERCENT ISOTACTICITY
ACKNOWLEDGEMENTS
Figure 12 Weightpercentageversus percentageisotacticityas determined The author would like to acknowledge the expert
by ~3C n.m.r, for polypropylene homopolymer in the impact-grade
polypropylenecopolymer assistance of Mr Stanley P. Westphal for the d.s.c.
measurements, Dr Fred Swiecinski for the 13C n.m.r.
measurements and the expert assistance of Mary Cantwell
distribution of the polypropylene homopolymer component for the preparation of the t.r.e.f, fractions.
is given in Figure 12. The tacticity of the polypropylene
was determined according to the well known 13C REFERENCES
n.m.r, technique 6'~3. The tacticity distribution for a
polypropylene homopolymer made independently of an I Bucknall, C. B. 'Toughened Plastics', International Ideas,
impact copolymer is essentially identical to that shown Philadelphia, 1977
2 Prentice,P., Papapostolou,E. and Williams,J. G. Polym. Mater.
in Figure 12. Sci. En 9. 1984,51, 635
The elution temperatures from the t.r.e.f, of the various 3 Rift, M. R., Ficker, H. K. and Walker, D. A. S.P.E. A N T E C
components of a P P impact copolymer are related to the 1986, 316
chemical structure of these components in a rather 4 Wild,L, Ryle, T., Knobeloch, D. and Peat, I. J. Polym. Sei.,
Polym. Phys. Edn. 1982, 20, 441
complex manner. The superposition of the elution 5 Kusy,R. P. and Whitley,J. Q. J. Biomed. Mater. Res. 1986,20,
temperature ranges for the EPR, the semicrystalline E/P 1373
copolymers and the tacticity-variable polypropylene 6 Randall, J. C. 'Polymer Sequence Determination: Carbon-13
homopolymer (atactic to highly isotactic) yields the NMR Method', AcademicPress, New York, 1977
complex temperature-rising elution fractogram shown in 7 Vernon,W. D. S.P.E. A N T E C 1987, 1423
8 Stockmayer,W. H. J. Chem. Phys. 1945, 13, 199
Figure 2. The identification of the various components 9 Ham,G. E. 'Copolymerization',lnterscience,New York, 1964
was made possible by the previous preparative fractionation 10 Boor,J. 'Ziegler Natta Catalystsand Polymerizations',Academic
followed by fraction characterization. These fractionations Press, New York, 1979
further showed that the major species, viz. the EPR, the 11 Mirabella,F. M. and Ford, E. A. J. Polym. Sci., Polym. Phys.
Edn. 1987, 25, 777
highly ethylene-rich polymer and the highly isotactic 12 Flory,P. J. Trans. Faraday Soc. 1955,51, 848
polypropylene copolymer, could be separated into 13 Bovey,F. A. 'High Resolution NMR of Macromolecules',
discrete fractions. This proved that these species were not Academic Press, New York, 1972

POLYMER, 1993, Volume34, Number8 1735