POLYETHYLENE (Stabilization and Compounding)

POLYETHYLENE (Stabilization and Compounding)
By: Ahmed M. Eltief

Chief Polyethylene process Engineer
July 2001
1
Introduction:
Plastics are used in many fields because they can be processed easily, are relatively
light, and possess excellent chemical and physical properties. However, they also
have undesirable properties from a combination of the material itself and processing.
Therefore, it is important to hide or reduce the defects of plastics while sustaining or
enhancing the merits as much as possible. To attain that aim, many kinds of polymer
additives have been developed.
Additives are agents that sustain material's properties or functions, provide desirable
properties for the bulk of a material, or provide its surface properties. This article
focuses on the most widely used additives in the PE industry.
Compounding is the general term for the operation converting the polyethylene (PE)
produced in a polymerization reactor into a pelletized form suitable for use by a
downstream processor. In the compounding process, the polymer is physically and
chemically modified by incorporating various additives. The selection of additives
and of compounding conditions depends on the end application of the compounded
product.
Compounding is the overall process of incorporating and homogenizing additives into
PE. The equipment needed for the compounding process includes additive feeders,
mixers, extruders, blenders, and pelletizers. Auxilliary equipment is used to control
the process.
In any compounding operation, the first step is stabilizing and incorporating other
additives. Stabilizing the polymer is important to prevent thermal oxidation and
discoloration during melt processing and to impart long-term heat and light stability.
Chief Engineer/ Ahmed M. EltiefPage 1 19/04/2015
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Ahmed M. Eltayef, POLYETHYLENE (Stabilization and Compounding), 2001
Stabilizers are the most widely used additives in the PE industry. Other additives
commonly added to polyethylene are stearates (e.g., calcium and zinc stearates to
neutralize acidic catalyst residues and to impart lubricity), pigments (e.g., carbon
black, cadmium yellow, and titanium dioxide), metal deactivators (e.g., oxalyl
bishydrazide for PE cable insulation), processing aids (e.g., Dynamar, Ucarsil, Viton-
A, to improve flow of the molten polymer), and optical brightners (e.g., Uvitex OB to
enhance appearance). Additives commonly added to polyethylene include
antioxidants (hindered phenolics and phosphites for process stabilization), antiblock
compounds (e.g., silica, talc, and kaolin to reduce sticking of adjacent film layers),
and slip agents (e.g., erucamide and oleamide to reduce friction).
Properties of Polymeric Materials:
It is important to understand the properties of polymers in order to stabilize them. The
processing of polymers also is a key factor for producing desirable properties for
polymers. In processing, temperature, atmosphere, elongation, cooling velocity, as
well as other factors affect the distribution of additives and fillers, the size and
distribution of crystals, and the presence of spheric crystals, which determine whether
the polymer's properties are drawn completely.
The degradation of polymeric materials, therefore, is complicated but generally is
induced by heat, light, mechanical shear, and ozone, which essentially initiates
autoxidation. Autoxidation follows certain fundamental steps after an initiation
reaction. However, reactions that induce crosslinking or gelatin of polymer molecules,
resulting in the material hardening.
The degradation of polymer materials by autoxidation depends on the polymer and
starts wherever bonds have low dissociation energy. A C-H bond, for example,
cleaves more easily in the order of primary, secondary, tertiary, and additionally at the
alpha carbon, adjacent to an olefinic double bond or a carbonyl group. Polymers with
photosensitive functional groups such as carbonyls are likely to degrade when
exposed to light.
Polymers degrade mainly through use, although some degradation occurs in preparing
and processing stages. The primary route for degradation is autoxidation.
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Part I: Additives
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ADDITIVES (Types and Applications):
Plastics have the widest range of mechanical, physical, and other useful properties
combined with easy fabricability and economical costs. However, plastics are seldom
used alone and, to suit end-use requirements such as colorability and fire resistance,
certain additives are almost always mixed with them.
ADDITIVES CLASSIFICATION:
Although additives may be solid, rubbery, liquid, or gaseous, the following nine
classes of materials, the most frequently used, will be discussed here:
· stabilizers,
· fillers,
· plasticizers and softeners,
· lubricants and flow promoters,
· colorants,
· flame retardants,
· blowing agents,
· crosslinking agents, and
· ultra violet degradable additives.
Some of the additive types are used for almost all applications; others are used only
for specific applications.
SYNERGISTIC AND ANTAGONISTIC:
The PE compounder should be aware of the many synergistic and antagonistic
interactions that can arise between additives in PE. In particular, antagonistic
interactions should be avoided as they generally reduce the effectiveness of both
additives. Figure 1 summarizes some of these interactions.
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FIGURE 1: Synergistic and antagonistic interactions that can arise between additives
in polyethylene. AO, antioxidant; UVA, UV absorber; and HALS, hindered-amine
light stabilizer.
Synergistic additive interactions result from a cooperative action between the
additives to produce an effect greater than that resulting from the sum of their
contributions. The most common synergism is that occurring between chain- breaking
antioxidants (such as hindered phenols) and hydroperoxide decomposers (such as
aromatic phosphites). For instance, in PE compounded at 220 °C, approximately 55%
of the Irganox 1076 remains after one extrusion pass when no Irgafos 168 is present.
In contrast, in the presence of Irgafos 168, a much higher content (between 78 and
84%) of the hindered phenolic remains after the first extrusion pass.
Although the mechanism is not fully elucidated, one important role of phosphite
stabilizers is to preserve the hindered phenol. This preservation occurs as the
phosphite reduces the number of radicals formed. The chain-breaking antioxidant,
however, reduces the amount of hydroperoxides produced in the propagation stage,
thus increasing the efficacy of the hydroperoxide composer present.
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A new class of antioxidants known as autosynergists consist of a hindered phenolic
antioxidant and a hydroperoxide decomposer in a single molecule. Irganox 1035 is an
example of such an autosynergist. It is bifunctional, with two hindered phenolic
substituents attached to a central sulfur atom, and is used for special high-temperature
applications in PE pipes and cables.
An additive combination that should be avoided is HALS (such as Chimassorb 944)
and sulfur-containing antioxidants (i.e., thioesters) as they are antagonistic. The
acidity of sulfur antioxidants neutralizes HALS effectiveness. For the same reason,
HALS and acidic carbon black should not be used together. In contrast, alkylated
thiobisphenols, such as Santonox R, exhibit a strong synergism with carbon black,
whereas their methylenebis analogs and many phenolic antioxidants react
antagonistically.
Antagonism has been reported between UV absorbers (i.e.,
hydroxyoctyloxybenzophenone) and calcium stearate. An antagonism between
erucamide and zinc stearate has also been observed. Researchers at Witco Corp. found
that considerable erucamide degradation can occur when the amide is compounded
with zinc stearate to form a masterbatch. For instance, when compounding this
combination at 200 °C, ~20% of the total amide degrades, and of this, 7% converts to
nitriles.
Recently an antagonistic interaction between silica (diatomaceous earth) and
erucamide (e.g., Crodamide ER) was found to degrade the fatty acid amide into
various aldehydic groups (especially nonanal) with low thresholds of odor detection
and consequently an undesirable odor in the polymer. This antagonism is believed to
result from the acid-catalyzed degradation of erucamide by the acidic groups on the
silica surface. In addition, the presence of relatively high levels of iron (i.e., 3000
ppm) in the silica may also contribute to metal-catalyzed redox reactions of
erucamide.
Mineral additives such as silica and talc can reduce antioxidant effectiveness by
adsorbing them on their surface. Compounders sometimes add an epoxy compound
that coats the talc, minimizing the antioxidant's adsorption. Similarly, in
fluoropolymer processing aids, a polyethylene glycol can prevent excessive
adsorption of the fluoropolymer onto the talc. Silica antiblock agents can also reduce
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the lubricating performance of erucamide slip agents because the erucamide becomes
adsorbed and immobilized on the high-surface-area silica.
STABILIZERS:
The properties of polymers deteriorate under the combined effects of high and
ambient temperatures, atmospheric radiation, oxygen, ozone, water, microorganisms,
and other atmospheric agents. The deterioration is attributed to the degradation or
chain scission and crosslinking and to the formation of chromophoric and polar
groups in the polymer. The overall effects on the polymer are loss of strength,
hardening and embrittlement, color formation and/or reduction of optical clarity,
changes in chemical activity, and a decrease in electrical insulation properties. Thus,
for any meaningful use, the polymer needs to be protected from such detrimental
influences.
ANTIOXIDANTS AND UV STABILIZERS:
The degradation of polymers by heat, oxygen, ozone, mechanical shearing, UV
exposure, metal ions, and other agents normally occurs by a free-radical mechanism.
A host of radical species are produced by initiation and propagation mechanisms in
which the hydroperoxide radical is by far the most reactive, decomposing to give rise
to chain scission. Radical species recombine to form extended-chain or crosslinked
polymers in the termination step.
Decomposition and/or crosslinking reactions depend on polymer type and
environmental conditions. Effective antioxidants interrupt the sequence of chain
reactions and are of two types depending on their mode of action: preventive
antioxidants that prevent the formation of radicals Rù and ROOù and chain-breaking
antioxidants that directly intervene in the propagation cycle reaction with Rù and
ROOù radicals and introduce new termination reactions.
Preventive antioxidants prevent the formation of free radicals and are classed as:
peroxide decomposers, metal deactivators, and UV light protectors. Peroxide
decomposers remove peroxide radicals and decompose hydroperoxides, forming
stable products. They include many sulfur and phosphorus compounds such as
sulfides, thioethers, mercaptans, sulfonic acids, tertiary phosphites and phosphates,
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zinc dialkyl dithiophosphates, and zinc dimethyldithiocarbamate. 2,3,6 Peroxides are
deactivated and reduced to alcohols (Equation 1):
1
Variable-valency metal ions (e.g., Mn, Cu, Fe, Co, and Ni) contaminated in the
polymer initiate oxidation by accelerating the rate of decomposition of
hydroperoxides to active radicals. Metal ions can be deactivated by complexing with
chelating agents based on organic phosphites and phosphines and on higher
nitrogenated organic compounds (e.g., melamine, bis-salicylidene diamines, and
oxam-ides).
UV protectors reduce the harmful energy level of radiation (wavelength 290-400 nm)
by absorbing it in preference to the polymer without undergoing decomposition.
Three classes of UV protector are screening agents (or light screens), UV absorbers,
and excited-state quenchers. UV screens absorb the radiation before it reaches the
polymer and are pigments that do not scatter and reflect light. The most effective is
carbon black (particle size 15-25 nm, phr 2-3), which absorbs over the entire UV and
visible range and transforms the radiation into less harmful IR radiation. Carbon black
is a thermal antioxidant and a radical trap. UV absorbers are also light screens that
should not absorb in the visible range. The absorbed energy is disposed of by
radiation, conversion into heat, or chemical changes to harmless stable products.
Examples are 2-hydroxy benzophenones, O-hydroxyphenyl benzotriazoles, resorcinol
monobenzoate, phenyl salicylate and derivatives, and phenol/resorcinol esters of tereor
isophthalic acids. Excited-state quenchers react with photoexcited polymer
molecules and dissipate the excess energy as irradiation (e.g., nickel(II) chelates and
the newer hindered amines).
Chain-breaking antioxidants are nonstaining hindered phenols and aromatic amines
(phr 0.02-1). Used in excess oxidation may be facilitated by these antioxidants.
Stabilizer Synergism, Autosynergism, and Antagonism:
Some stabilizer combinations are more powerful than the sum of the individual
members; in some the effect of each component is doubled. This phenomenon is
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known as synergism. In polyolefins a chain-breaking antioxidant (e.g., 4-methyl-2,6-
di-t-butyl phenol) and a peroxide decomposer (e.g., dilauryl thiodipropionate) give
synergistic stabilization. Cd/Ba and Cd/Ba/Zn stearates and laurates make synergistic
combinations in PVC. The most powerful combinations for polyolefins can be
achieved using a chain-breaking antioxidant, a regenerating agent, a peroxide
decomposer, a metal deactivator, and a UV stabilizer.
Some antioxidants functioning via more than one mechanism are autosynergistic. An
antioxidant that is synergistic with one member may be antagonistic to another
antioxidant. Carbon black is synergistic with some phenolic sulfides but is
antagonistic to many phenols and amines, for example.
Antioxidants and Processing Stabilizers:
Oxidation of polymers i.e. plastics is invariably manifested by loss of physical
properties and ultimate failure of polymer artifacts. Polymer stabilization deals
primarily with the inhibition of oxidative processes throughout the lifetime of the
polymeric material. The underlying mechanisms of polymer oxidation (and
degradation) are well known, and the selection and design of stabilizers (and
antioxidants) for polymers are made in the light of current understanding of their
mode of action.
Environmental and physical factors, for example, high temperatures, stress, UV light,
ozone, and high-energy radiation, exert detrimental effects on polymer performance.
These effects, however, can be mitigated by the incorporation of low levels of
stabilizers during the fabrication process; the more demanding the application, the
greater the need for more efficient stabilizers to achieve economic optimum properties
of polymer products. Antioxidants and stabilizers, therefore, occupy a key position in
the market of compounding ingredients for polymers, in particular, commodity
polymers, such as polypropylene, polyethylene, and polyvinyl chloride.
The terms “stabilizers” and “antioxidants” are generally used in the plastics industry
to describe chemical agents that inhibit degradative effects of oxygen, light, heat, and
high temperatures. The terms “antidegradants,” “antifatigue agents,” and
“antiozonants,” are widely employed by rubber technologists to refer to similar
chemical agents, as well as to inhibitors, that combat the effects of stress and ozone.
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“Antioxidant” is used herein to comprehensively describe all chemical agents that act
to inhibit oxidation of a polymer matrix arising from the adverse effects of
mechanical, thermal, photochemical, and environmental factors during the
manufacture of the polymeric material and throughout the service life of the end-use
product.
EFFECTS OF PROCESSING AND ENVIRONMENTAL FACTORS ON
OXIDATIVE DETERIORATION OF POLYMERS:
Thermooxidative degradation of polymers can occur at all stages of their life cycle
(polymerization, storage, fabrication, weathering), but its effect is most pronounced
during conversion processes of the polymer to finished products. Polymer fabrication
and conversions are normally achieved through the use of high shear mixing
machinery (e.g., in extrusion, injection moulding, internal mixing, milling, and
calendering). Oxidative degradation of polymer articles in the outdoor environment is
often exacerbated by combined factors in the environment, such as sunlight, rain,
ozone, temperature, humidity, atmospheric pollutants, and microorganisms.
Polymer oxidation is best described by a cyclical free-radical chain reaction ( Scheme
I ). Free radicals are initially generated (reaction Ia) and are involved in propagation
reactions that lead to the formation of hydroperoxides (reactions Ib and Ic), followed
by termination reactions in which free radicals are eliminated from the oxidizing
system (reactions Ig, Ih, Ii). Hydroperoxides are inherently unstable to heat, light, and
metal ions and would therefore give rise to further radicals (reaction Id) that continue
to initiate the chain reaction. This autooxidation process normally starts slowly but
autoaccelerates, leading in most cases to catastrophic failure of the polymer product.
It is generally accepted that this radical chain reaction, which involves both alkyl and
alkylperoxyl radicals as propagating species, is similarly involved in both thermaland
photooxidation of polymers, albeit at faster rates of initiation for the latter.
Hydroperoxides are the main initiators in both thermal- and photooxidation. The prior
thermal-oxidative history of polymers determines, to a large extent, their
photooxidative behavior in service. Hydroperoxides formed during processing (and to
a lesser extent during manufacturing and storage) are the primary initiators during the
early stages of photooxidation, whereas the derived carbonyl-containing products
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(e.g., those formed via chain scission through hydrogen abstraction (reaction If), or
via Norrish type I and II reactions), ( Scheme II ), exert deleterious effects during later
stages of photooxidation. The initiating species, hydroperoxides and their
decomposition products, for example, are responsible for the changes in molecular
structure and overall molar mass of the polymer that are manifested in practice by the
loss of mechanical properties (e.g., impact, flexural, tensile strengths, and elongation)
and by changes in the physical properties of the polymer surface (e.g., loss of gloss,
reduced transparency, cracking, chalking, and yellowing).
The extent of oxidative degradation of the macromolecular chain during melt
processing and in service depends ultimately on the nature and structure of the base
polymer. Polyolefins exhibit widely different oxidative stabilities as a result of both
chemical and physical effects. Morphological differences, for example, are implicated
in the greater susceptibility of polypropylene (PP) and high-density polyethylene
(HDPE) toward photodegradation than of low-density polyethylene (LDPE). See
scheme III
SCHEME I: Oxidative degradation processes and antioxidant mechanisms.
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SCHEME II: Polymer hydroperoxidation during processing and further photolysis of
derived carbonyl compound.
SCHEME III: Oxidative degradation of PE and PP.
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ANTIOXIDANTS (Overview):
Everyone is familiar with the oxidation of iron; the oxidation reaction product is the
reddish, dusty material called rust. With polymers, the oxidation reaction product is
not as easily identified or recognized. Polymers have more subtle changes such as
indirect changes in color, loss of initial gloss or clarity, crazing, chalking, or
brittleness. With iron, rust spreads and penetrates deeper into the body of the material.
Eventually, the iron becomes brittle, small pieces and flakes start to break off, and the
article begins to lose its original strength and physical properties. A less obvious
process occurs with polymers; nevertheless, the end result is still an overall loss of
physical properties.
Slowing down this process of oxidation is what many scientists strive to do. Trace
amounts of transition metals and carbon are used to turn iron into stainless steel. For
polymers, trace amounts of antioxidants are used. These antioxidants do not transform
polymers into “stainless” polymers; however, they do significantly inhibit the
oxidation process, thereby increasing the useful lifetime of the polymer. Antioxidants
have been well reviewed.
Since the invention of plastics, there has been a need for antioxidants. At first, these
antioxidants were only somewhat effective. The colloquialism “cheap plastic” is often
used to describe plastic articles that fail at their intended use. Important strides have
been made in the improvement and utility of plastic articles, primarily because of
better chemistries for preventing oxidation. This does not mean that cheap plastic has
completely disappeared. It only means that producers of cheap plastic have thriftily
chosen to avoid the proper stabilization for their products. Often, plastics have
become high quality materials, primarily through polymer structure but also through
the use of antioxidants to preserve that structure.
Polymer Autoxidation:
Often, free radicals are generated at the onset of high temperatures and high shear
associated with melt compounding the polymer. Still, the melt compounding of the
polymer is virtually unavoidable if the polymer powder, granules, or beads are to be
transformed into a useful article. Lower temperatures could be used, but melt
viscosity will increase, thereby further straining the processing equipment so that
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throughput rates would diminish. Similarly, lower shear extrusion equipment could be
used, but insufficient melting or mixing might occur. Consequently, there are tradeoffs
to consider.
Because it is generally accepted that oxidation is the key process by which a polymer
loses its original properties, it is important to discuss the chemistry of oxidation.
Actually, the most appropriate term is autoxidation as the process is automatic once
polymers are exposed to oxygen. Autoxidation then feeds upon itself because of the
by-products of the process, giving it a catalytic aspect. In addition, impurities in the
polymer also tend to accelerate the process. There are four general steps as shown in
Scheme I (Equations 1-13), where R is a macromolecule.
Reactions 1-13, via free-radical chemistry, eventually lead to polymer chain scission,
polymer crosslinking, and sometimes a combination of both. Changes in molecular
weight and molecular weight distribution occur. This alteration of the polymer is the
mechanism by which the original properties of the polymer are significantly
transformed. These types of changes in molecular weight and molecular weight
distribution not only affect polymer processing characteristics but also significantly
affect physical properties. Ultimately, without interrupting the free-radical chemistry,
the polymer is oxidized to the point where discoloration, brittleness, crazing,
cracking, and chalking are eventually observed.
Polymer Stabilization:
To prevent this undesirable chain of events, various chemistries can be used to
interrupt the free-radical process of oxidation. One class of chemistries is based on
chain breaking or primary antioxidants. Another class is based on preventive or
secondary antioxidants, which decompose hydroperoxides before they are
transformed into free radicals.
Chain-Breaking or Primary Antioxidants:
This general class of antioxidants is capable of interrupting free-radical processes by
donating labile hydrogen atoms that neutralize or quench the free radical. These
hydrogen-donating antioxidants, AH, slow down oxidation by effectively competing
15
with the polymer for free radicals, thereby abbreviating the chain length of the
propagation reactions (Equations 17 and 18).
16
The formation of ROOA is not necessarily the only product nor the end result. Heat,
shear, and light can affect this type of molecule so that it initiates free-radical
chemistry. However, certain antioxidants are less likely to undergo damaging
transformation chemistries because of the nature of their molecular structure. They
will be discussed below.
Phenolics:
The chemistry of phenolic antioxidants will not be discussed in detail here other than
to describe how they can be used in practice. The point of incorporating them into the
polymer is to stop the chemistry associated with free radicals by first donating
hydrogen atoms, not a proton or a hydride, to interrupt the autoxidation process.
Phenolics typically react with oxygen-centered free radicals, and consequently, can
interrupt the autoxidation cycle depicted in Scheme 1 in the equations with oxygencentered
free radicals at either side. In general, phenolic antioxidants quench free
radicals by donating hydrogen atoms. Thermodynamically, this occurs because the
resulting phenoxy radical is more stable than the oxygen-centered free radical it
quenches, primarily through resonance structures in the phenyl ring, Figure 2 .
Depending on the structure of the phenolic, several different reaction schemes
resulting in the rearrangement or deactivation of the phenoxy radical are possible (
Figures 2 and 3 ). The main point is that the phenolic, on the basis of its molecular
structure, is capable of donating hydrogen atoms, undergoing rearrangement
reactions, and further reacting with free radicals until it is fully consumed. This total
consumption of the phenolic is typically undesirable because it generates color bodies.
Because discoloration should be avoided, many practical techniques that prevent the
total consumption of the antioxidant have been developed. These techniques typically
involve using co-additives with the phenolic, such as trivalent phosphorous
compounds and scavengers for acidic catalyst residues.
17
Fig. (2): Oxidation chemistry of a representative hindered phenol, butylated hydroxy
toluene (BHT), followed by resonance stabilization of the phenoxyl free radical.
Fig. (3): Oxidation chemistry of the phenoxyl radical producing different end
products.
18
For many phenolic antioxidants, the complete exhaustion of the molecule results in a
conjugated system that typically appears yellow. As an example, the overoxidation of
butylated hydroxytoluene (BHT) is shown in Figure 4 .
The structure of the original phenolic and the resulting conjugated system will dictate
the nature of the discoloration, lmax, and the strength of the discoloration through the
absorption coefficient, e. Many commercial antioxidants are designed to avoid a rapid
transformation into highly colored species. A review of this phenomenon, including
transformation products and their associated color and intensity, has been discussed in
detail.
Fig. (4): Stepwise oxidation chemistry of a representative hindered phenol, butylated
hydroxytoluene (BHT), producing a discoloring transformation product.
Phenolic antioxidants are radical scavengers combined with aromatic amine
antioxidants. The latter antioxidant is used almost entirely in rubber because it colors
the materials during use. A phenolic antioxidant, however, is used in many fields and
is an indispensable component for stabilizing plastics. A phenolic antioxidant is
effective for scavenging oxygen-containing radicals such as ROù and RO2ù. The
steps can be illustrated, using phenol as an example, as follows:
19
14
15
16
The step of Equation 14 proceeds 103 to 104 times faster than the steps shown in
Equations 4 and 5 because of the stabilization from the resonance of an intermediate
phenoxy radical (see Equation 15). Accordingly, adding 1% of a phenolic antioxidant
to polymers can stop the competing steps in Equations 4 and 5 effectively, breaking
the cycle of autoxication (Equation 16).
Structure and Action:
Phenolic antioxidants used today contain the following moieties: (Structure 1) as
fundamental skeleton. The effect of substituents of phenolic moieties has been studied
by Howard and Ingold and is explained by the mechanism that substituents influence
an electrophilic reaction of peroxy radical as shown in Equation 17
Structure 1
In addition, the role of substituents are also explained from the standpoint of steric
hindrance. As shown in Table 3 , less hindered phenols (e and f) exhibit higher rate
constants than hindered phenols (a through d). The latter phenols, however, have
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higher values of n, which the number of many phenoxy radicals trapped by an
equivalent of a phenol. Although a phenol can generally trap twice as many moles of
peroxy radicals per mole of a phenolic moiety, a less hindered phenol or a phenol
having small substituent at para-position, such as 2,6-di-tert-butyl-4-methyl-phenol
(BHT), can enter into the coupling reaction between phenoxy radicals, resulting in a
lower n value (Equations 18-20):
18
19,20
21
Characteristics:
A phenolic antioxidant shows synergistic effects when it is used with one or more
additives. A phenol, for example, can contribute to heat stabilization with a sulfur- or
phosphorus-containing compound. However, phenols color polymer materials such as
fabrics, which have frequent contact with NOx gases. The mechanism is shown in
Equations 21-23.
21-23
Fabrics and carpets are inclined to lose antioxidants by extracting during dry cleaning,
followed by much easier degradation. Extracting an antioxidant from plastics depends
on the molecular weight of a phenol. A phenol having a molecular weight greater than
2000 can resist extraction remarkably well. However, a phenol with a molecular
weight of 2500 decreases the effect because of a bad affinity with plastics and
difficult mobility. A phenol with a molecular weight of about 100,000 exhibits little
effect, if any. Thus, the preferred molecular weight for a phenol used for extraction
resistance will range from a few hundred to 3000, depending on use.
22
Aromatic Amines:
Certain classes of antioxidants, such as aromatic amines, are effective at scavenging
free radicals as are the phenolic antioxidants. Aromatic amines are even more
powerful in easily oxidized polymers like unsaturated elastomers. The chemistry,
however, is not as well understood because of the nature of the products and their
reactions. Although potent, aromatic amines tend to stain or discolor. This
discoloration is not necessarily caused by the original antioxidant structure, but rather,
by the chemical transformations that occur when aromatic amines interact with free
radicals. Aromatic amines are typically used in elastomeric systems that are
pigmented or loaded with carbon black to mask staining.
Hindered Amines:
This class of chemistry is typically associated with light stabilizers because they are
extremely effective at protecting certain classes of polymers from the damaging
effects of ultraviolet radiation. However, hindered amines also belong to the family of
chain-breaking antioxidants because they are also capable of scavenging free radicals.
The most common hindered amine is based on 2,2,6,6-tetramethylpiperidine. The four
methyl groups create steric hindrance and block elimination reactions at the carbon
atoms adjacent to the amine group. The N-H group also exists as N-R and N-OR,
where R is a hydrocarbon. Their antioxidant behavior based on the N-H group is
shown below (Equations 19-20).
Some researchers suggest that hindered amines are capable of decomposing
hydroperoxides (Equation 22).
23
These are only representative mechanisms, and they have been the subject of much
discussion. Nevertheless, the point is that hindered amines in one way or another
efficiently interrupt the autoxidation chain reaction. The mechanism may involve
reacting with carbon and oxygen-centered radicals, as well as decomposing peracids
or hydroperoxides. Although in practice, hindered amines are eventually exhausted,
the processes described above clearly show that hindered amines are capable of
regenerating. This multiple turnover performance may include either free-radical
scavenging, hydroperoxide, or peracid decomposition. Regardless, hindered amines
perform well as long-term thermal stabilizers at lower temperatures, in addition to
their recognized capability as light stabilizers.
The antioxidant capability of hindered amines proceeds most efficiently at
temperatures below 135 °C and preferably below 120 °C. Consequently, hindered
amines should not be considered as melt-processing stabilizers. In practice, after melt
compounding, most polymers are not typically exposed to such high temperatures.
Metal Deactivators:
Polymers that come into contact with metals that have low oxidation potentials, such
as copper, are susceptible to oxidation from the metal catalyzed decomposition of
hydroperoxides, as shown in reactions in Scheme I. One way to avoid these types of
free radical activators is by using metal deactivators. Metal deactivators are designed
to contain hydrazide or amine functional groups, which can complex to the metal.
Most commercial materials also include a phenolic antioxidant as part of the
molecular structure. Metal deactivators are usually melt compounded into the
polymer, which then interacts with the metal by migrating to the polymer/metal
interface. This chemistry is particularly important for wire and cable applications.
Preventive or Secondary Antioxidants:
One of the most damaging species in the autoxidation process is the hydroperoxide,
ROOH. Under elevated temperatures, hydroperoxides decompose via a homolytic
cleavage to yield two free radicals. This step demonstrates the catalytic nature of
autoxidation. The destruction of the hydroperoxides, which continually build up in the
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polymer, is essential in protecting the polymer. Most commercially available peroxide
decomposers are based on trivalent phosphorus compounds and divalent sulfur
compounds.
Trivalent Phosphorus Compounds:
The chemistry of phosphites and phosphonites has been studied. In essence, a P(III)
compound reacts with a hydroperoxide converting it to alcohol, ROH, with the
subsequent oxidation of P(III) to P(V), as shown in Reaction 23. This chemistry takes
place during melt compounding of the polymer in processing equipment. At ambient
temperatures, the reaction is very slow. This slower reaction rate increases the
importance of the hindered amines mentioned above, which are capable of
decomposing hydroperoxides at temperatures below 120 °C to 135 °C (Equation 23).
Phosphorus III compounds are also capable of reacting with free radicals; however,
the contribution of this chemistry is secondary in comparison to hydroperoxide
decomposition (Equations 24 and 25). 28
The groups attached to phosphorus play a key role in the reactivity and the hydrolytic
stability of the compound. In a very general sense, with less steric hindrance, the
reactivity with hydroperoxides increases and the hydrolytic stability decreases.
Sometimes co-additives are used to increase the hydrolytic stability, such as triisopropanol
amine, alkaline acid scavengers, or both. In addition, material with small
particle size can be compacted so that there are larger particles with less surface area.
These techniques will improve handling of the material in the open atmosphere.
Nevertheless, when the additives are melt compounded into the polymer, the
hydrolysis inhibitors are diluted into the polymer in the same way that the phosphorus
compound is dispersed. This process leaves hydrolytically unstable phosphites at the
25
mercy of residual water in the polymer whenever it has contact with water for
prolonged periods. Hydrolysis of phosphites, which is a stepwise reaction for each of
the RO- groups attached to the phosphorus atom, is summarized as follows (Equation
26).
The phosphorous acid corrodes processing and compounding equipment, leading to a
phenomenon known as black specks. In addition, the liberated alcohols, or phenols,
usually have low molecular weight and can be oxidized.
However, increasing the steric hindrance can improve the compound's hydrolytic
stability which allows for easier handling in the open atmosphere; yet, the reactivity
with hydroperoxides decreases. Typically, one must decide which is more important:
fast reactivity or safe handling of the material and stability in the postproduction
polymer. Some commercial phosphites offer a balance between these two extremes.
Recent efforts have focused on designing phosphorus-based compounds with
improved hydrolytic stability to provide excellent performance as a melt processing
stabilizer.
Divalent Sulfur Compounds:
The chemistry of S(II) compounds has been discussed and reviewed. They react
similarly to phosphorus compounds in that hydroperoxides are transformed into
alcohols with concomitant oxidation of S(II) to S(IV) as shown below (Equations 27
and 28).
26
The chemistry does not stop with the sulfone or sulfoxide. Elimination reactions result
in the formation of sulfenic and sulfonic acids, which can further decompose to sulfur
dioxide and sulfur trioxide. The good news is that these sulfur transformation
products are also very effective at decomposing hydroperoxides. On a per-weight
basis, the sulfur compounds, after the first two oxidation steps, provide multiple
equivalents of stabilization via the sulfur transformation chemistry. The concern is
that organoleptics can form, which becomes an issue when polymers are used in
products that have contact with food.
Peroxide Decomposers:
Sulfur-Containing Antioxidants:
A sulfur-containing antioxidant is known as an effective hydroperoxide decomposer
and is added to various polymers with a phenol because it is ineffective when used
alone. A sulfur-containing antioxidant decomposes hydroperoxides ionically to inhibit
initiation reactions, which would otherwise be induced by homolytic cleavage. Of all
such antioxidants only a thiopropionic acid derivative is very effective, and this may
be because of the action mechanism of a sulfur compound. One action mechanism
that has been proposed is shown in Equation 24
24
Table 4 shows the heat resistance of polypropylene when various sulfur-containing
antioxidants are mixed with phenolic antioxidants.
27
A sulfur compound does not provide good stabilization at a higher temperature
because of the formation of an intermediate, which forms during decomposition of
hydroperoxides and works as a pro-oxidant as shown in Equation 25
A sulfur compound acts on hindered amine light stabilizers with antagonism, resulting
in the decreased weather resistance of plastics.
However, it exhibits remarkable synergism with a phenolic antioxidant.
Phosphorus-Containing Antioxidants:
A phosphorus-containing antioxidant functions similarly to one containing sulfur.
Thus, it also is used advantageously as a processing stabilizer.
A phosphorus compound can decompose hydroperoxides ionically by the overlapping
of the d-orbital of a trivalent phosphorus over a hydroperoxide formed in oxidative
28
degradation of polymers. Thus, it controls the cleavage of polymer chains during
processing (see Equations 26 and 27)
26,27
A phosphorus compound also acts as a radical scavenger as shown in Equations 28
and 29
28,29
In the oxidation of cumene, however, phosphorus compound does not show any
eminent inhibition. Its radical-scavenging ability is inferior to that of BHT. The
inhibitive action radical-trapping, therefore, may be neglected in a practical use.
Phosphorus compounds are used to stabilize plastics by ionic decomposition of
hydroperoxides, the rate of which depends on the molecular structure of a phosphorus
compound. An alkyl phosphite, in general, decomposes hydroperoxides faster than an
aryl phosphite. The former, however, is sensitive to hydrolysis and heat degradation
during processing and on the shelf and consequently does not show firm effect. The
stabilization of phosphorus compounds against hydrolyses is considerably important
and is achieved in the compounds shown in Structures 2-5
2-5
29
A phosphorus compound behaves like a sulfur compound in terms of the
hydroperoxide decomposition, but the former compound shows remarkably higher
effects, especially in processing at a temperature above 200 °C. A phosphorus
compound is also characterized by no formation of any pro-oxidant like a sulfur
compound after the hydroperoxide decomposition.
Although the synergism with a phenol is not so remarkable as that of a sulfur
compound, a phosphorus compound often can inhibit coloration in plastics stabilized
by a phenol.
Synergist Mixtures of Antioxidants:
When used alone, neither trivalent phosphorus compounds nor divalent sulfur
compounds are capable of providing complete melt processing and thermal stability
of the polymer. However, combined with a phenolic antioxidant, the results are better
than the sum of the performance levels of each additive type. This is known as
synergism. What represents a synergistic mixture of additives in one polymer does not
necessarily translate into an optimum mixture in another polymer system.
For example, blends of a phenolic antioxidant and a phosphite are very useful for melt
compounding of polyolefins and for engineering polymers. Together, they work well
to maintain the polymer's molecular weight while simultaneously affording low color.
The phosphite shares the work load with the phenolic so that neither one becomes
exhausted or overoxidized. Even if the phosphite is entirely consumed, it has done its
share of work by preserving more of the phenolic antioxidant for long-term thermal
stability. For example, blends of a phenolic antioxidant and a divalent sulfur
compound provide an excellent combination for improving a polymer's long-term
thermal stability. Although the sulfur compound produces no activity during melt
processing, it does perform well as a hydroperoxide decomposer during long-term
thermal aging. This contribution, along with the free radical scavenging capability of
the phenolic, offers a good mix (provided that taste or odor are not key measurements
of performance). Typically, blend titration experiments are performed at a set loading
of additives, starting with 100% of component A and 0% of component B. A series of
formulations are designed to shift to the other extreme with 0% component A and
100% component B.
30
The optimum ratio of A to B can be determined by measuring a series of performance
parameters. Although time consuming, this procedure eventually can identify the
optimum ratio with real data. If three or more components are assessed at the same
time, statistically designed experiments often can sort out the data set.
Antagonistic Mixtures of Antioxidants:
Mixtures of antioxidants can work together synergistically, as described above; they
can also work against each other. Chemistries that interfere with each other may not
necessarily be obvious until the evidence is presented. For example, a phenolic
antioxidant combined with a divalent sulfur compound for thermal stability and a
hindered amine for light stability ensures long-term thermal and good light stability.
Regrettably, the oxidation products of the sulfur compound can be quite acidic. These
acidic species from the sulfur compound can complex the hindered amine as a salt,
preventing the hindered amine from entering into its free-radical scavenging cycle.
This antagonism has been known for quite a while and recently was discussed. Other
types of antagonistic chemistry often involve relatively strong acids or bases, either
Bronstead or Lewis, that can interact with the antioxidants in such a way as to divert
them into transformation chemistries that have nothing to do with polymer
stabilization. These types of interactions are sometimes difficult to elucidate, typically
time consuming, and always a waste of a perfectly good antioxidant.
Ancillary Properties:
In reality, there is more to antioxidants than providing stability to the polymer by
quenching free radicals and decomposing hydroperoxides. Other key issues besides
rates of reactivity and efficiency include performance parameters such as volatility,
compatibility, color stability, physical form, propensity to form transformation
products with taste or odor, regulatory issues associated with products used in food
packaging, and in-polymer performance versus cost.
Volatility:
Most additives are melt compounded into the polymer after the polymer exits the
polymerization reactor. The exiting polymer, as either a molten mass or a free-flowing
31
powder, is converted to pellets that are stored in containers and then shipped to
customers. The customer then transforms these pellets into shaped articles, which are
stored and then shipped to the next customer. The two melt-compounding steps
represent significant heat histories. In some climates, the product is stored in warm
temperatures. It is important that the stabilizer and its transformation products, which
may also provide stability, not volatilize from the polymer. Many commercial
antioxidants have been designed with higher molecular weights with climatic
conditions in mind. For those antioxidants with lower molecular weights, volatility
may actually be desired.
Compatibility:
Antioxidants should be soluble in the polymeric matrix. If they are not, they should at
least migrate or diffuse slowly. A slower diffusion rate is important because if the
antioxidant exceeds its solubility limit in the polymer, there is a driving force for
additives to be exuded. Exudation or blooming involves the migration of the additive
out of the polymer matrix and onto the surface as a very thin film. At the surface, the
additive becomes susceptible to extraction, oxidation, volatilization, or being washed
away. Blooming of the antioxidant also can diminish surface gloss, create stickiness,
or eliminate blocking (cling) of film surfaces to one another. Antioxidants can be
modified to improve compatibility.
Color Stability:
Antioxidants need to perform well as stabilizers for the polymer, but they must also
not produce unwanted color from the transformation chemistries associated with
preventing oxidation. As mentioned earlier, some antioxidants produce color by their
very nature, while other antioxidants discolor only when they have been overoxidized.
If masks are used, color is not a key issue.
Physical Form:
Antioxidants often are free-flowing white powders; however, health and safety
hazards associated with fine powders or dust are becoming more of a concern. Many
antioxidants now are offered commercially in dust-free forms. Liquid or molten
32
antioxidants are another interesting alternative, provided that they are compatible in
the polymer matrix. Some manufacturers require fine powders to mix well with their
reactor product.
Taste and Odor:
Taste and odor become key issues when applications are for home or personal use or
involve contact with food. Interestingly enough, the human nose often detects these
odors better than many powerful analytical instruments.
Regulatory Issues:
Antioxidants used in polymers that come into contact with food require clearance
from various regulatory agencies. Chronic and subchronic toxicological testing is
performed in different species. Extractability using different food simulants is also
evaluated. Accordingly, concentrations of the material expected in the diet can be
assessed. A product typically should have minimal health hazards associated with its
use or handling. Safety is usually assessed by studying the toxic effects in tests where
anitoxidants are tasted, inhaled, or come into contact with eyes and skin. Mutagenicity
tests are also carried out.
Performance Versus Cost:
Antioxidants are not free, but they are affordable. Essentially, the appropriate type
and level of antioxidants must be selected in order to stabilize the polymer adequately
for a particular use. Some articles are used once, such as bags and food wrap, and
others are expected to last, such as geomembranes, an insulation for electric cables or
for gas and water transmission pipes.
For example, if the material is a nondurable good, an article used only once or twice
before disposal, then the type and concentration of antioxidant are chosen to minimize
unnecessary costs associated with stabilizing the polymer. The antioxidants should
provide stabilization for the initial melt compounding of polymerization reactor
granules into pellets and from pellets into a finished article, be it tape, film, fiber,
sheet, cups, or eating utensils. Stabilizing the polymer to last 10 years when the
product is going to be used only once or twice does not make sense. However,
33
maintaining quality becomes important when scrap from the melt compounding is
recycled. Minimizing costs by reducing antioxidants can sometimes result in inferior
products. In addition, a cushion usually is built into the system to avoid unexpected
shut-downs and start-ups or prolonged storage in hot places.
However, if the material is a durable good, a product with a long period of use, the
type and concentration of the phenolic antioxidant is chosen to meet the performance
criteria. The costs associated with this type of antioxidant is worth the additional
value for such products as pipes, insulation bumpers, gears, rotors, covers, housings,
membranes, hose, tubing, carpet, furniture, toys, and so on. The value-added feature
of the product pays for the additional stabilizers needed to ensure high quality and
durability.
Performance Testing:
Testing is needed to validate the use of a particular antioxidant system before a
product is commercialized. Initial testing frequently involves melt compounding of
the polymer with various formulations composed of different additive systems or
mixtures. Color, appearance, and retention of molecular weight are common
measures. Long-term thermal stability is carried out usually in ovens set at elevated
temperatures to accelerate the aging process. Color development and retention of
physical properties are measured as a function of time at that test temperature.
Varying extrusion temperatures and changing shear rates afforded by the processing
equipment are also useful measurements. Testing the ancillary properties mentioned
above is also important.
INHIBITION OF OXIDATIVE DEGRADATION: CLASSIFICATION OF
ANTIOXIDANTS AND THE BASIS OF THEIR MECHANISMS OF ACTION:
The terms “antioxidants” and “stabilizers” cover a number of chemical classes of
compounds that can interfere with the oxidative cycles (see Scheme I ) to inhibit or
retard oxidative degradation of polymers. Two major classes have been identified
according to the way they interrupt the overall oxidation process: chain-breaking and
preventive antioxidants. Tables 1a and 1b show some typical examples of different
classes of commercial thermal- and photo-antioxidants.
34
Chain-breaking (CB) antioxidants (sometimes referred to as primary antioxidants)
interrupt the primary oxidation cycle by removing the propagating radicals, ROOù
and Rù. Chain-breaking donor (CB-D) antioxidants are electron or hydrogen atom
donors that are capable of reducing ROOù to ROOH, ( Scheme IV , reaction IV b). To
perform their function, CB-D antioxidants must compete effectively with the chainpropagating
step (reaction IV f) and the antioxidant radical (Aù) produced from
reaction IV b must lead to stable molecular products, that is, Aù must not continue the
kinetic chain either by hydrogen abstraction (reaction IV g) or reaction with oxygen
(reaction IV h). Hindered phenols and aromatic amines ( Table 1a , AO1-AO12) are
significant examples of commercial CB-D antioxidants. Chain-breaking acceptor
(CB-A) antioxidants act by oxidizing alkyl radicals (reaction IV d) in a stoichiometric
reaction (Rù are removed from the autoxidizing system) in competition with the
chain-propagating reaction (reaction IV a) and hence are effective only under
conditions of low oxygen concentration. Quinones and stable free radicals that can act
as alkyl radical trapping agents are good examples of CB-A antioxidants.
Preventive antioxidants (sometimes referred to as secondary antioxidants), however,
interrupt the second oxidative cycle by preventing or inhibiting the generation of free
radicals. The most important preventive mechanism is the nonradical hydroperoxide
decomposition, PD. Phosphite esters and sulfur-containing compounds, for example,
AO13-AO18 ( Table 1 ), are the most important classes of peroxide decomposers. The
simple trialkyl phosphites (e.g., Table 1 , AO13) decompose hydroperoxides
stoichiometrically (PD-S) to yield phosphates and alcohols ( Scheme V , reaction V
a). Sterically hindered aryl phosphites have an additional chain-breaking activity: they
react with peroxyl and alkoxyl radicals during their function as antioxidants (reactions
V b, V c).
Sulfur compounds, e.g., thiopropionate esters and metal dithiolates ( Table 1 , AO16-
AO18), decompose hydroperoxides catalytically whereby one antioxidant molecule
destroys several hydroperoxides through the intermediacy of sulfur acids. Metal
deactivators (MDs) primarily act by retarding metal-catalyzed oxidation of polymers;
they are, therefore, important under conditions in which polymers are in contact with
metals, e.g., wires and power cables. Metal deactivators are normally polyfunctional
35
metal-chelating compounds (e.g., Table 1 , AO19-AO22) that can chelate with metals
and decrease their catalytic activity.
UV absorbers (UVAs) act by absorbing UV light, hence retarding the photolysis of
hydroperoxides. Typical examples are based on 2-hydroxybenzophenones (AO 16)
and 2-hydroxybenztriazoles (e.g., Table 1 , AO23-AO27); both are relatively stable
to light between 300 and 360 nm and have high molar absorptions in this region.
Their activity is also associated with hydrogen bonding between the 2-hydroxy group
and the chromophore.
PROCESSING ANTIOXIDANTS:
Stabilization against mechano-oxidative degradation during high-temperature
processing is essential in order to stabilize the polymer melt and to minimize the
formation of adverse molecular impurities and defects that may contribute to early
mechanical failure of finished articles during service. The choice of antioxidants for
melt stabilization varies depending on the level of oxidizability of the base polymer,
the extrusion temperature, and the performance target of the end-use application.
The effectiveness of melt-processing antioxidants is normally measured by their
ability to minimize changes in the melt flow index (MFI) of the polymer that occur in
their absence. Chain-breaking antioxidants are generally used to stabilize the melt in
most hydrocarbon polymers. Hindered phenols (CB-D, e.g., Table 1 , AO1-AO4) are
very effective processing antioxidants for polyolefins, ( Table 2 ). Aromatic amines,
however, have limited use because they give rise to highly colored conjugated
quinonoid structures during their antioxidant function. Although hindered phenols do
not suffer as much from the problem of discoloring polymers during melt processing,
yellowing can occur as a result of intensely colored oxidation products, such as
stilbene quinone (SQ) from BHT ( Scheme VI ). Transformation products of
stabilizers formed during melt processing may exert anti- and/or prooxidant effects.
For example, in BHT, peroxydienones (PxDs) (reactions VI b, VI bà) lead to
prooxidant effects, because of the presence of the labile peroxide bonds, whereas
quinonoid oxidation products BQ, SQ, and Gù (reactions VI, VI b, VI c, VI d) are
antioxidants and are more effective than BHT as melt stabilizers for PP. The quinones
are effective CB-A antioxidants, and those that are stable in their oxidized and
36
reduced forms (e.g., galvinoxyl, Gù, and its reduced form, hydrogalvinoxyl, H G)
may deactivate both alkyl (CB-A mechanism) and alkylperoxyl (CB-D mechanism)
radicals in a redox reaction (reactions VI, VI e, VI f). Alkyl sulphides (e.g., Table 1 ,
AO-16, AO-17), which are catalytic peroxide decomposers (PD-Cs) acting through
further oxidation to sulfur acids, are also used as antioxidants during processing of
polyolefins. However, a major disadvantage of these simple sulfides is that their
conversion to sulfur acids ( Scheme VII ) involves a parallel series of prooxidant
reactions involving the formation of propagating radicals (e.g., reaction VII e).
Therefore, such antioxidants (e.g., AO-17) are always used in combination with
effective chain-breaking donor antioxidants. Similarly, in the case of phosphites (e.g.,
AO-14), free-radical-forming reactions (reactions V a, V aà) are believed to occur
simultaneously with the stoichiometric peroxide decomposition reaction, hence the
normal practice of using phosphites in combination with CB-D antioxidants (e.g.,
Irganox 1010) for stabilizing polyolefin melts. Table 2 shows the improvement in
melt stabilization of PP achieved when the sulfide (AO-17) and phosphite (AO-14)
antioxidants are used in combination with Irganox 1010 (AO-4).
Aromatic amines (e.g., Table 1 , AO-6 and AO-7) are more effective than hindered
phenols (e.g., Table 1 , AO-1 and AO-4) for melt stabilization of polyamides.
Copper salts (e.g., copper acetate) in combination with small amounts of a halide
(e.g., potassium iodide) are also used to stabilize polyamides, although this system
gives rise to polymer discoloration and suffers from the ease of loss by water
extraction.
THERMOOXIDATIVE ANTIOXIDANTS:
Stabilizers with high molar masses (e.g., antioxidants 4 and 5 in Table 1 ) have lower
volatility and are potentially more effective than those with lower molar masses
containing the same antioxidant function, e.g., BHT (antioxidant 1 in Table 1 ) for
thermooxidative stabilization in service. Furthermore, peroxide decomposers, such as
sulfur-containing compounds enhance the performance of high-molar-mass phenols
under high-temperature conditions in service. For example, in polyolefins, dialkyl
37
sulfides such as antioxidants 16 and 17 (see Table 1 ) are often used as peroxide
decomposer synergists.
38
39
SCHEME IV: Chain-breaking mechanism and competing chain reactions. AH is an
antioxidant and RH is a polymer substrate.
40
SCHEME V: Peroxide decomposition by phosphites.
SCHEME VI: Oxidate transformation products formed during the antioxidant action
of BHT.
41
SCHEME VII: Simplified reaction scheme for the antioxidant mechanism of simple
alkyl sulfides.
UV STABILIZERS:
There are two classes of UV stabilizers used in PEs: UV absorbers and hinderedamine
light stabilizers (HALS). A common UV absorber is Chimassorb٨١ (or
Cyasorb٥٣١ ), which is chemically known as 2-hydroxy-4-n-octyloxybenzophenone.
These additives absorb UV radiation in the range of 300-360 nm, the spectral region
of sunlight most damaging to polymers. The damaging radiation that is absorbed
usually dissipates harmlessly as heat. In benzophenones, a six-membered ring can
form through hydrogen bonding between the hydrogen atom of the hydroxyl group
and the oxygen atom of the carbonyl group. The absorbed UV energy is dissipated by
a keto-enol tautomerism of this hydrogen-bonded molecule. Ultraviolet absorbers of
the benzophenone class are often used in formulations that contain sulfur-containing
antioxidants because there is no antagonism between these additives.
Hindered-amine light stabilizers have become increasingly important in the UV
stabilization of PE and have generally displaced UV absorbers. The first widely used
HALS was Tinuvin٧٧٠ chemically known as bis(2,2,6,6- tetramethyl-4-
piperidinyl)sebacate. Newer oligomeric HALS such as Chimassorb 944 LD have
greater retention in the polymer and have largely replaced the older monomeric-type
HALS. HALS inhibit photooxidation in PE extremely well. For instance, at
concentrations as low as 0.5 wt %, they can provide the same protection as 1 wt % of
a typical UV absorber. The mechanism by which HALS function involves their
oxidation to a nitroxyl radical that scavenges alkyl radicals. This reaction then
produces hydroxylamines that can react with peroxyl radicals and, in turn, regenerate
42
nitroxyl radicals. This cycling of nitroxyl radicals accounts, in part, for the high
effectiveness of HALS, even at low concentrations.
UV Absorbers:
There are many kinds of photostabilizers that protect plastics from degradation by
light, especially harmful UV light. A UV absorber is added to various plastics to keep
the bulk and surface of plastic materials protected from light. It can absorb light with
a wavelength of about 290 to 310 nm by transferring a hydrogen atom and then
releasing the energy as heat according to Equation 30.
30
This additive contains both a functional group absorbing UV light and a labile
hydrogen closely positioned to the group. UV absorbers having the following
fundamental skeletons are mentioned as examples (Structures 6-8).
These three absorbers can absorb wide ranges of UV and visible light as shown in
Figure 5
43
Fig. (5): UV spectra of representative UV absorbers.
A benzxotriazole absorber has a wider absorption range compared with a
benzophenone absorber and absorbs a little visible light. It offers no initial coloration
and stabilizes color shade for long periods. Commercial products of benzotriazoles are
illustrated as shown in Structures 9-12.
9-12
44
A benzotriazole absorber shows high synergism with hindered amine light stabilizers
(HALS) and is used in various plastics such as polyolefins, polycarbonates, and
polyesters, because it inhibits fading of pigments and dyes.
UV absorbers often evaporate during processing if they have low molecular weights.
In addition, benzophenone and benzotriazole absorbers also lose their functions
through oxidation because they belong to kinds of phenols and consequently are
sensitive to oxygen and peroxy radicals (RO2ù).
PIGMENTS:
Carbon black is probably the most common pigment and UV screener used in PE.
Usually added in concentrations between 2 and 3 wt %, carbon black protects against
UV light. When compounded into LDPE, carbon black can inhibit thermal oxidation
for ~30 h at 140 °C. Its effectiveness as an antioxidant increases with the amount of
chemically bound oxygen. Unpaired electrons have been detected in carbon black
particles suggesting that they act as a radical trap. Furthermore, carbon black can be
an effective hydroperoxide decomposer. Because of its acidic nature, carbon black
decomposes hydroperoxides into non-radical products. The pigments used in HDPE
bottles and bags are often based on inexpensive metal oxides. For instance, the most
common pigments (brown, grey, and orange) are based on various iron oxides and
hydrates that act as prooxidants or prodegradants at high temperatures (200 °C)
encountered during processing. Inorganic green pigments are usually based on
chromium(III) oxide, which readily catalyzes the thermooxidative degradation of
HDPE even in trace quantities.
Common Additives Used in polyethylene:
Silica is commonly used as an antiblocking agent for LDPE film-grade resins. The
silica is usually diatomaceous earth (e.g., Celite) that creates little mounds (asperites)
on the surface of the LDPE film and reduces sticking or blocking between adjacent
film surfaces. Erucamide, chemically known as cis -13-docosenamide, is a fatty acid
amide CH3-(CH2)7-CH=CH-(CH2)11-CO-NH2 commonly used in LDPE film to
provide “slip.” Erucamide, which is incompatible with PE, migrates to the surface of
the LDPE film over ~24 h. It is essentially a surface-active molecular lubricant used
45
to lower the film's coefficient of friction (COF), allowing adjacent surfaces to slide
smoothly over one another and bags to slide smoothly in automatic operations such as
form, fill, and seal.
Erucamide is an unsaturated compound highly susceptible to oxidation. The oxidation
of erucamide can occur before it is incorporated into the polymer during storage at
ambient temperatures. This degradation leads to yellowing of the erucamide because
nitrile compounds form. Moreover, erucamide can degrade significantly during
compounding at processing temperatures that exceed 200 °C. The consequences of
erucamide degradation are a rancid odor from the film, lower slip performance
because the amide degradation products are not effective slip agents, and printing
problems with PE film.
CONCLUSIONS
It is important to evaluate additives for the purpose intended. A degrading polymer
does not always result in limited use. The evaluation of polymer degradation is carried
out by observing chemical and physical changes of a material's properties (see Table
6 ). Degradation occurs during processing or use with the corresponding estimation
procedures established. Processing degradation can be evaluated by measuring the
melt flow index under actual processing conditions. Degradation during use, however,
is generally evaluated according to accelerated methods by means of a weather-ometer
for weather resistance and an oven for heat. There is no absolutely reliable
evaluation method. The data obtained should be interpreted by understanding the
merits and defects of the method and instrument used. The evaluation results also
depend on the atmosphere or environment of the experiment as well as the shape and
thickness of the materials tested.
46
Additives are used to preserve the properties of polymers that were designed to meet
certain specifications. Antioxidants are comprised of various chemistries that perform
by different mechanisms. Understanding the chemistry combined with the judicious
selection of the appropriate additives for a product's use is the key to success.
47
Part II: Compounding

48
COMPOUNDING PRINCIPLES & PRODUCT PROBLEMS RELATED TO
COMPOUNDING:
Additive Feeding
Additives must be precisely weighed for the compounding extruder with a continuous
feeder.
Slip and lubricants such as calcium stearate are low-melting-point additives that melt
before the polymer is fully plasticized. Thus, they lubricate the screw and
consequently reduce dispersive mixing. To overcome this effect, these additives can
be injected downstream of the main extruder with a side-stream extruder after
plasticizing the polymer.
The additive's physical form is important to consider when compounding PE. Fine
powders can create nuisance dust and also pose a dust explosion hazard. Major
additive suppliers are now marketing low-dusting additives in a compacted or “prill”
form. These compacted versions also improve feeding and metering consistency. For
small amounts of different additives, a preblended additive package may improve
accuracy and reduce cost. The major advantage of such preblends is that the
compounder need only control the feed rate of one additive rather than many. The
preblended package consists of two or more additives in fixed ratios. The most
commonly used preblend in the PE industry is produced by CIBA Corp. and is known
as Irganox B900 (a 4:1 blend of Irgafos ١٦٨ and Irganox 1076). Another phenolic
and phosophite preblend that is frequently used is Irganox B911 (a 1:1 blend of
Irganox 1076 and Irgafos 168). Enichem recently commercialized preblends of
Irganox 1076 with zinc stearate.
Dispersion:
Additives, such as antioxidants, should be distributed uniformly throughout the
polymer, particularly as some downstream converting operations such as injection
molding and rotomolding involve little mixing. Often, however, the distribution of
additives in PE pellets is non-homogeneous with some pellets rich in additive and
others having no detectable amounts. The reasons for this non-uniformity of additive
dispersion include feeding problems in the additive extruders because of hopper
“bridging” or barrel “plate-out,” surging of the polymer melt from the main extruder,
49
inadequate mixing of the melt, and inadequate post-blending. Indeed, some PE
manufacturers do not add any antioxidants during extrusion (to allow controlled
degradation to occur); instead, they add an antioxidant concentrate in pellet form to
pelletized polymer.
Poor additive dispersion in pelletized PE can be readily checked by a simple test:
exposure to iodine vapor. In this test, pellets rich in antioxidant are stained dark violet
and pellets low in antioxidant are a light pink color. In this way, variations in
antioxidant concentrations are easily discerned. This test relies on the affinity of
iodine vapor with polar compounds such as phenolic antioxidants.
Carbon black is always introduced to the polymer from a concentrate (i.e.,
masterbatch). It is essential that a proper dispersion is obtained during compounding
and that the average particle size is between 15 and 25 microns. In a good dispersion
of carbon black in PE, a uniform, dark background with only some isolated
agglomerates can be seen under 100X magnification on thin microtomed PE samples.
A poor dispersion, however, has an almost clear background with numerous clusters
visible.
Dispersion agents, based on silicon oil, are sometimes used with titanium dioxide
pigments for a better dispersion in PE. These agents should be avoided, however, as
they cause sealing and printing problems. Because silicon oil migrates to the PE film
surface, a laboratory check can confirm its presence. The test involves swabbing the
suspected area with cotton wool that is then extracted by a Soxhlet extractor. The
extract is concentrated by rotary evaporation and the presence of silicon checked by
atomic absorption spectrometry.
Interaction
Polymer Blending:
The term compounding also embraces the physical mixing of two or more polymers.
For instance, a common blend is LDPE with linear low-density PE (LLDPE). Adding
LLDPE can improve the toughness and elongation of LDPE, making it possible to
produce a significantly thinner film (downgauging) with strength and impact
properties equal to or better than a thicker LDPE film. LDPE also improves the
processability of LLDPE. Blends of LDPE with 10, 20, 30, and 60% LLDPE include
50
pallet shrink wrap, briquette bags, horticulture bags, and microirrigation pipes,
respectively. Other blends manufactured by PE producers are LDPE and butyl rubber,
which imparts environmental stress-crack resistance to the former.
COMPOUNDING PRINCIPLES:
Compounding primarily involves the melt plasticization of a PE reactor product,
generally accompanied by additives. The equipment and the compounding parameters
employed depend on the operation’s size and the desired end product properties. An
intensive mixing device is often used with a plasticating extruder, followed by melt
filtration, pelletization, and blending. Two types of processes are necessary for
compounding PE and additives: distributive mixing and dispersive mixing.
Distributive mixing is essential for homogenizing the polymer and for distributing the
additive properly. Dispersive mixing is essential for carbon black, which tends to
form agglomerates. Recirculating vortices in the melt produce distributive mixing,
while high shear planes between the screw's channels give good dispersive mixing.
Continuous Mixers
For high production rates (e.g., 6-15 tonne/h), a combination of a continuous mixer
and hot-melt extruder is recommended. Farrel Corp. in the United States is the largest
manufacturer of continuous mixers for the PE industry. The Farrel continuous mixer
(FCM) uses specially designed rotors, similar to those used in a Banbury, to convert
the powder resin feed (i.e., fluff) into a molten polymer mass in the form of a ribbon
(that feeds) into a hot-melt extruder. New continuous mixers made by Farrel are the
9UM and the larger 18UM, which can process up to 9 and 18 tonne/h, respectively. A
scheme outlines the basic principle in Figure 6. These units consist of two stages, with
a single screw pumping the polymer to the mixing elements that are housed in a
clamshell-shaped barrel. The high throughput of large intensive mixers is achieved
with short residence times at high temperatures. For a single-screw extruder, a
temperature profile of 200-240 °C is generally used for PE. However, in large
finishing equipment, temperatures from 260 °C upwards are used. Finishing line
equipment is energy intensive as much of the heat required to raise PE's temperature
51
to 260 °C is generated through the mechanical work input to the polymer which is
powered by large electric motors (~ 0.2-0.3 kW/kg).
Fig.(6): Schematic showing how a continuous mixer operates. Note transition region
where black specks can form.
Twin-Screw Extruders:
Twin-screw extruders, in contrast to single-screw units, have two screws mounted
parallel in a single barrel with a figure-of-eight cross-section. These extruders provide
intensive shearing and are well-suited for incorporating pigments. Twin-screw
extruders fall into two catagories: co-rotating and counter-rotating screws. The extent
to which the screws intermesh further defines their classification. The screws can be
non-intermeshing, partially intermeshing, or fully intermeshing. The most common
high capacity twin-screw finishing extruders for PE are those produced by Werner-
Pfleider Corp. and known as ZSK extruders. They have intermeshing, co-rotating,
segmented screws that are self-cleaning. Because the segments are removable and
interchangable, they can be assembled in various ways to provide the desired
combination of fluff feeding, melting, shearing, and metering zones.
Twin-screw vented extruders are used for phase separation between polymer and
solvents or monomers. Stripping extruders are used in the Hoechst and Phillips HDPE
52
processes to remove the solvent of polymerization. These intermeshing twin-screw
extruders enable precise control of the polymer melt’s temperature as only a small
amount of polymer has contact with the barrel surface. Because the melt is spread out
thinly over the barrel wall, the diffusion of volatiles from the polymer is facilitated. A
volatile-rich layer is generated in the intermesh region. This partially filled region is
vented to an atmospheric or vacuum con-denser. The screws are specifically designed
to provide melt sealing and allow only a low degree of fill for each venting stage.
Because vented extruders are expensive and have low throughput, pellet driers are
often used instead. In the pellet driers, volatiles are removed by passing dessicated air
or nitrogen (to avoid polymer oxidation) through a bed of pellets.
Melt Filtration and Pelletization:
Polymer melts must be filtered to remove particulate contaminants. This is usually
achieved with a breaker plate and wire-mesh screen. The breaker plate consists of a
steel plate with numerous holes, and the screens are installed on the plate's upstream
face. Usually, several progressively finer screens are used (e.g., a 40-mesh supporting
an 80-mesh supporting a 200-mesh screen). When the pressure drop across the filter
gets too high, the screen-pack assembly must be removed and cleaned. Automatic
screens (e.g., HiTech) enable new screens to be inserted without interrupting the
extrusion process. Other automatic systems have screens incorporated in a spur gear.
This gear is periodically rotated to introduce clean screens into the melt stream as the
preceding screens become plugged. The dirty screens can be replaced as they exit the
melt stream.
Pelletization generally involves the extrusion of the polymer melt through a die plate,
solidification (usually underwater), and the cutting of the polymer strands into pellets.
The pellets are drained on a shaking screen and dried with hot air. Shaking and
vibrating screens (e.g., Rotex ‫ د‬screens) are also used to remove irregular pellets, long
strands, and fines.
Pellet Handling and Post Blending:
The usual mode of pellet transport in PE manufacturing plants is by high-velocity
pneumatic conveying. Transfer lines can damage pellets from the high-speed
53
interactions between the pellets and the pipeline. The result is fines, streamers, and
other defects. Damage to pellets can be minimized by using large radius elbows (e.g.,
Hammertek ‫ د‬elbows), pipes with smooth joints, and moderate conveying velocities.
Pellets are transferred from the compounding extruder to large bins where they
undergo a mixing process known as post blending. The post-blending bins contain
intricate internal structures to thoroughly mix the pelletized polymer. Excessive
blending, however, can also lead to fines and streamers, especially for high Melt
Index resins. To remove the fines, elutriators and aspirators are sometimes used. In
some instances, the final blending stage plays a key role in end-product homogeneity
(consistent product properties across a blend).
PRODUCT PROBLEMS RELATED TO COMPOUNDING:
Figure 7 shows the most common customer complaints received by PE producers,
and all of these complaints can be related in some way to the compounding and
stabilization process.
Fig. (7): Common customer complaints for low-density and high-density
polyethylene. All are related to the stabilization and compounding process. COF,
coefficient of friction
54
Gel Contamination:
Gels are the most common problem in compounding PE and the number one source of
complaints for LDPE. Gels are small regions of loosely crosslinked polymer that
generally form in an extruder during compounding. These gel particles are usually
generated in dead-spots (i.e., stagnant regions where there is poor flow) in the
extruder. Polymer that hangs-up in such areas experiences longer residence times,
thereby depleting the antioxidant supply and promoting crosslinking. Gels are
particularly undesirable in thin PE films where they can act as lenses and appear much
larger than their actual size because of their distortion from the surrounding film. Gels
causing imperfections in PE film are known descriptively in the industry as fisheyes
and arrowheads depending on their appearance. Their occurrence in PE film may
appear as isolated gel particles or as a cluster of gel particles. The latter is attributed to
small pockets of degraded material that have “hung-up” in the extruder. These regions
are periodically swept back into the mainstream and then become fragmented while
passing through the extruder's narrow die gap. Gels can also act as stress
concentrators and may cause “blow-outs” in bottles made from HDPE. Their rubbery
nature allows them to elongate and squeeze through screenpacks, making them
difficult to eradicate once formed.
Various anti-gel additives for PE have been claimed in the patent literature based on
radical trappers, metal phenolates, and polyethylene glycol. One compound, in
particular, appears to be quite effective at preventing gel formation in LLDPE films.
Kemamine AS990, although primarily intended as an antistatic agent, can passivate
acidic residues and control gel formation through a poorly understood mechanism.
Black Speck Contamination:
Common sources of contamination in HDPE are black specks, local burnt regions
within pellets. These are small areas of highly degraded polymer or degraded additive
that have been carbonized because of excessive residence time, excessive shearing, or
the presence of hot spots (localized high-temperature regions) in an extruder. As with
gels, these black specks typically occur in low flow or stagnant regions in the
extruder. In large hybrid processing equipment such as a 9UM mixer, the transition
point between the melt pump screw and the mixing heads is usually a site where black
55
specks are generated (see Figure 6 ). Black specks cause a major problem in the blow
molding of natural or white bottles where they are aesthetically undesirable.
Black specks may also be caused by the charring of the additives present in PE
(ironically, such additives as hindered phenols and hindered phosphites stabilizers).
Antioxidant suppliers have addressed this problem with new additive systems.
American Cyanimid developed Cyanox٢٧٧٧ , a blend of Cyanox 1790 hindered
phenolic antioxidant and tris(2,4-di-t-butylphenyl)phosphite, which is claimed to be
ideal for high-temperature processing conditions as it purportedly resists black speck
formation. Ethyl Corp. released a new fluorophosphonite antioxidant system known
as Ethanox 398, which exhibits high thermal stability (up to 287 °C) and outstanding
resistance to charring. These features help prevent the black specks often encountered
during high-temperature extrusion.
Extraneous Contamination:
Typical contaminants in commercial PE are degraded polymer, metal, sand, paper,
and fiber. Degraded polymer contamination (known in the industry as burnt resin) is
usually a translucent brown color and shatters under pressure. Often, such
contamination may appear yellow or amber depending on the extent of degradation.
In fact, under microscopic examination, a color gradient may be evident, indicating
that the darkest side has been in direct contact with the extruder barrel wall. Paper and
fiber often originate from bags and cardboard octobins used for packaging the resin or
its additives. Metal contamination in HDPE (usually referred to as tramp metal) arises
from the wearing of processing equipment such as extruder gates, granulators,
aluminum adapters, frayed screenpack wire, welding slag, and attrition of pelletconveying
pipeline. Occasionally, metal shot contamination may be found after plant
transfer lines are cleaned. Small fragments of metal can cause major problems in
injection molding applications because they can plug precision injection nozzles. In
addition, ferrous and ferric ions because of their multivalent nature act as oxidation
catalysts in redox reactions and promote PE degradation.
56
Odor:
Odor in PE is generally associated with the polymer's oxidation, the additives, or
both. Common causes of odor in HDPE are thermal oxidation of the fluff (or polymer
powder) during storage before stabilization. In the Unipol process, in particular, the
HDPE fluff is stored for some time (frequently at elevated temperatures) before
compounding. The polymerization is generally performed at 90-100 °C, and the fluff
leaves the reactor at ~80 °C. Because of its low thermal conductivity, fluff can remain
at 60-70 °C for many days. 35 During this time, hydroperoxide groups can form in
PE, which when compounded, can decompose to give odorous, oxygenated species
such as alcohols, acids, aldehydes, and ketones. HDPE made with Ziegler catalysts
employ triethylaluminium (TEAL) as cocatalysts. After polymerization, these resins
are purged with steam to strip and deactivate the TEAL. Incomplete deactivation,
however, can contribute to odor forming in the polymer after compounding. A further
source of odor in HDPE can originate from calcium or zinc stearate additives
degrading. These metallic stearates can deposit on the extruder screw during
compounding. The stearates undergo thermal decomposition to yield stearic acid that,
after further oxidation, produces odorous aldehydic products. This phenomenon is
also encountered by the PE processor, where degraded stearic acid can foul nip rollers
and build-up on internal bubble cooling systems used to produce high molecular
weight HDPE film.
In LDPE, compounding can liberate some bound chain-transfer agents. The chaintransfer
agent is used to regulate the polymer's MW during polymerization and in the
process is incorporated onto the chain. These transfer agents are usually based on
ketones such as methyl ethyl ketone (MEK); thus, LDPE made using an MEK transfer
agent may have some ketonic odor. Because LDPE is branched, it is more susceptible
to oxidation during compounding than HDPE. This is because hydrogens at tertiary
carbons have a lower bond dissociation energy than other hydrogens in PE's structure
and, thus, are likely to be the first extracted by propagating radicals. Such oxidation
can be associated with long residence time and high-temperature compounding
conditions. Often, odor in LDPE is attributed to the oxidation of the fatty acid amide
slip agent. Various workers have reported that fatty acid amide slip additives can
cause film odor, usually when these additives are stored for too long or extruded
57
under conditions where the compounds can oxidize. This oxidation produces
aldehydic and nitrile species that are rancid-smelling compounds.
Specialty additives are available for binding PE odors that could otherwise taint
delicate matrices such as spring water. The best known odor-absorbing additive for
PE is Abscents by UOP Corp., which is based on an aluminosilicate zeolite. These
compounds are effective at concentrations as low as 500 ppm and can be incorporated
by standard melt-compounding.
Pellet Geometry:
Poor pellet geometry is the term that describes any deviation in pellet shape from that
which is standard or desired. Polymer pellets are usually 3-4 mm i.d. and cylindrical,
cubical, or spherical shaped. The shape of pellets can influence their behavior in
extruders and injection molding machines. There are many variations of poor pellet
geometry, including match-sticks, jackstraws, bullet-heads, shorts, tails, streamers,
fines, and angel hair (see Figure 8 ).
FIGURE 8: Diagram illustrating some variations of poor pellet geometry of
compounded polyethylene.
58
Uniform pellet size is important for uniform feeding and melting in the downstream
conversion steps. In film-grade resins, non-uniform pellet size may cause surging of
the melt, leading to bubble instability. Excessive fines tend to accumulate in the
hopper and feed throat of extruders as a result of static and, periodically, such deposits
fall into the hopper causing bridging problems and non-uniform melting.
In commercial PE production, the melt is generally extruded through a die plate
containing scores of bored holes and then cut into pellets underwater by rotating
knives. If the pellets stick to the cold face of the die plate then pellet freeze-off can
occur, resulting in plastic deformation of the solid pellet at one end to produce bulletheads;
pellets that are flat at one end. Matchsticks are extra long pellets, up to 3 cm
long. Jack-straws are even longer, generally more than 3 cm. Poor cutter alignment
produces under-sized pellets known as shorts. Streamers and angel hair generally
form in the pneumatic conveying pipelines. Because of their high transfer velocities,
the pellets in contact with the pipe wall begin to melt from the high frictional forces.
Elbows, in particular, are regions where these streamers tend to form. Shotblasting of
transfer lines (to roughen the internal surface) and rounding off sharp corners can
reduce streamer formation.
Poor pellet geometry generally results from knives misaligned with the die plate,
blunt cutting edges, poor heat distribution in the die plate (leading to pellet freezeoff),
the cooling water too warm, insufficient or excessive melt back-pressure, poor
die plate geometry, a dirty die plate, or pellet conveying problems.
A new heated die plate designed for pelletizing PE underwater was recently
developed by Werner & Pfleiderer and reportedly prevents pellet freeze-off. The die
plate features a series of slots, each feeding up to 20 or 30 holes and having its own
heat channel, either steam or hot oil. The heat channels run parallel to the melt
channel, reportedly providing better heat distribution and, consequently, more
uniform pellet sizes.
Recent advances in hardening steel blades with carbide coatings means that die plate
cutters have a long life and improved pellet geometry. For instance, granulator knives
that resolve chipping and fracturing problems found with traditional carbide materials
have been reported based on ferro-titanium carbide composites consisting of an
impact-resistant, hard layer of silicon carbide diffusion bonded to a tool steel body.
59
Color:
During PE compounding, the natural pellets are frequently discolored, usually
yellowing, although pink and grey hues can also develop. In nearly all cases, the
discoloration is related to the additives present.
The most well-known origin of discoloration in PE is the yellowing imparted by
stilbene quinone compounds that are the rearrangement products (usually dimers) of
hindered phenolic antioxidants. These compounds are highly conjugated and can
yellow PE at low concentrations by virtue of their high extinction coefficients. The
most notorious antioxidant that forms stilbene quinone compounds is BHT, which is
no longer used prevalently in the PE industry. Irganox 1076 also forms yellow
transformation products but to a lesser extent. Figure 9 shows the common conversion
products of Irganox 1076, which can cause yellowing. Biscinnamate and the
conjugated and unconjugated bisquinonemethide of Irganox 1076 are the primary
dimers responsible for yellowing PE. Quinone-related yellowing can be confirmed by
exposing the PE sample to strong UV light causing the quinones to break down and
the yellowing to disappear.
Fig.(9): The common conversion products of Irganox 1076 causing polyethylene to
yellow.
60
Another common route by which yellowing or pinking occurs is by the interaction
between bridged phenolic antioxidants such as Isonox 129 and catalyst residues such
as titianium and vanadium ions. In this reaction, intensely colored metal phenolates
form. Although these species appear bright orange or red when produced in solution,
they are reduced to subtle hues of yellow and pink when diluted in the polymer. This
interaction has been widely studied by Pospisil. Pink discoloration can also occur in
HDPE containing high levels (e.g., greater than 2%) of the antioxidant Permanax ‫د‬
WSP because of this additive's intrinsic pink color.
Yellowing also occurs during storage of PE pellets in rail cars before delivery to the
processor. In this case, the yellowing is from a complex interaction between the
hindered phenolic antioxidants, iron compounds from the container walls, and
condensation of moisture.
Generally, discoloration is more pronounced in thick sections or in bulk rolls of film
because of the greater optical path length and the contrast that is apparent on the butt
end of a roll of film. In many cases, discoloration, although developed during
compounding, becomes evident only when the pelletized material is converted to a
product. For instance, in thick-wall sections, such as large-part blow molding (LPBM)
of containers for dangerous liquids, yellowing is often apparent. This yellowing
usually results from the stearates that are present as processing lubricants in the high
molecular weight HDPE formulation.
Compounding with high levels of silica antiblock (e.g., 1%) in LDPE can result in
grey discoloration. Yellowing in LDPE can arise as a result of excessively high
compounding temperatures. A grey discoloration has also been observed in HDPE
containing Irganox 1010 and DHT 4A (an acid scavenger based on synthetic
hydrotalcite), although the mechanism of this interaction is unclear.
Strategies for combating discoloration in PE are prevention, neutralization, and
masking. Prevention relies on careful formulation, control of extrusion parameters,
and an inert atmosphere during compounding to prevent chromophores from forming
at the onset. Novacor Corp. produces a high molecular weight HDPE blow molding
grade resin with good color by compounding under a nitrogen blanket.
Neutralization methods rely on compounds such as phosphites and phosphonites that
render colored species colorless.
61
Fig.(10): Reactions of phosphite stabilizers with highly colored dimeric oxidation
products of phenolic antioxidants to yield colorless products
Figure (10), shows the reaction of Irgafos 168 with highly colored quinoidal
conversion products of phenolic antioxidants to yield colorless products. Sandostab
PEPQ chemically known as tetrakis (2,4-ditertbutylphenyl) 4, 4à-biphenylene
diphosphonite is a diphosphonite used to maintain PE color during processing. A
newer class of additives for neutralizing color in PE is based on calcium lactate and
calcium stearoyl 2-lactylate. These lactate-based compounds were recently
commercialized by the Patco Additives Division of the American Ingredients Co.
They reportedly preserve polymer color by acting as acid neutralizers and chelating
with pro-degradant metal ions. Strong reducing agents such as sodium sulfite have
also shown neutralizing behavior in PE.
PE discoloration can be masked with optical brightners such as Uvitex OB, which
mask yellowing by emitting into the blue spectrum. An optical brightener can be used
to mask the stearate-induced yellowing in high molecular weight HDPE for LPBM by
using concentrations as low as 50 ppm (see Figure 11). This level offsets the
additive's high cost.
62
Fig.(11): Typical formulations of commercial grades of polyethylene. MFI, melt flow
index; D, density; HMW, high molecular weight; and ESCR,
63
Rheology:
PE from the reactor generally undergoes changes in its rheological properties during
compounding. HDPE can undergo chain scission and crosslinking reactions during
melt processing. These reactions are competitive, and the net change in the melt flow
index is dictated mainly by the extruder's oxygen content and the polymer’s degree of
unsaturation. In the presence of oxygen, macroalkyl radicals rapidly convert to
peroxyl radicals and, thus, macroalkyl recombination reactions (which lead to
crosslinking) are negligible. However, the oxygen level should be fairly low in an
extruder, and the high consumption rate means that the oxygen concentration
decreases rapidly as the polymer melt moves through the extruder. With Phillips-type
HDPE, crosslinking is generally favored, whereas Ziegler-type HDPE mainly
undergoes chain scission during melt processing. Phillips HDPE has a terminal vinyl
group on each polymer chain. This vinyl group concentration decreases during melt
processing. The predominance of crosslinking reactions in Phillips HDPE can be
explained by alkyl radicals added to the carbon-carbon double bonds. A melt flow
drift across compounding can also indicate poor oxidative stability. For instance, if
significant oxidation occurred before compounding (during fluff storage, for
example), an appreciable increase in MFI may be observed across compounding.
The molecular weight distribution (MWD) of PE (especially the high MW
component) can greatly affect its swell characteristics. Thus, certain grades of
polyethylene, such as those used in the blow molding of consumer bottles, have
constant swell from one batch to the next. High swell is undesirable because it leads
to parison problems (i.e., instability). Similarly, if the swell is too low, it can cause
poorly formed bottle handles. High variation of swell from batch to batch and within a
batch are most undesirable because then the tooling (e.g., die-gap) of the blow
molding machines and processing conditions (e.g., temperature profile) must be
adjusted constantly to compensate for the varying swell. Swell variation can be
decreased by either running the extruder at high throughput (and hence high shear
rates) or by extruding the polymer in the absence of antioxidant and in the presence of
air (known as tailoring). Both these techniques lead to controlled scissioning of the
polymer chains, in which the longer chains are statistically more likely to undergo
64
cleavage. As a result, the polymer's MWD is narrowed, the swell is lowered, and the
swell variation is reduced.
PROCESS CONTROL IN COMPOUNDING:
Polyethylene compounding facilities usually depend on regular process control
measurements of the compounded product to operate efficiently. One common
requirement for process control is to determine if the correct levels of additives are
present in the polymer. These tests must yield a quick, reliable result so that feedback
can be given to the compounder, allowing process corrections to be made mid-stream.
To this end, many sophisticated techniques are employed. The level of antioxidant in
the final polymer can be determined by testing the oxidative induction time (OIT), as
measured by differential scanning calorimetry. A low OIT value indicates additive
feeding problems, additive degradation, or the antioxidant's lack of uniformity. The
level of nitrogen-containing additives such as HALS and erucamide can be
determined by nitrogen pyrochemiluminescence (e.g., using an Antek Nitrogen
Analyzer). The carbon black content of the compounded PE can be determined by
dynamic thermogravimetry, for which a small quantity of polymer is heated in
nitrogen until 650 °C in a thermal balance followed by admission of oxygen until 800
°C. Similarly, the antiblock content of compounded LDPE is determined by
gravimetry after furnace ashing in air.
Another critical parameter for control during compounding is PE's rheological
characteristics. The MWD and swell behavior can be determined by capillary
rheometry, which forces the molten polymer through an orifice under varying
pressure (e.g., Zwick on-line melt indexer). Another technique based on rheometry
(e.g., Rheometrics RMS800 rotational rheometer instrument) uses a parallel plate
geometry and measures PE's dynamic shear modulus. This value can be related to the
melt elasticity and the amount of warpage the HDPE will undergo on cooling from the
melt.
The gels generated during compounding can be assessed by blowing film from a
composite production sample acquired by diverting a trickle feed stream from the
main production stream. This film can then be inspected by a real-time gel counter
(e.g., Intec ‫ د‬automatic gel detector) that classifies and quantifies the gel particles by
65
their size and abundance. Gel particles can also be detected in PE before pelletizing
occurs. The Advisor ‫ د‬defect monitor by Flow Vision Inc. can simultaneously classify
up to four different gel defects as small as 50 microns in PE melt at commercial
production rates.
To classify and quantify contamination in PE, a representative quantity of resin (e.g.,
100 kg) is usually run through an extruder fitted with a 100-mesh screenpack, acting
as a filter and collecting and concentrating any particulate contamination in the resin.
Subsequently, the contents of the screenpack can be analyzed by various methods
(e.g., microscopy after xylene vapor exposure) to facilitate identifying the
contamination source.
Release checks on pelletized PE product are also undertaken to determine if the resin
has any objectionable odor. These tests are generally performed by a group of people
who sniff the resin. However, this method can be quite unreliable because of the
subjectivity involved and the problems with olefactory fatigue. There are also
questions about the health risks of this test. Recently developed, faster, more accurate
methods use a semiconductor-based odor meter (e.g., Cosmos Odor Meter) for
detecting and quantifying odor from LDPE pellets. The response of this instrument
correlates well with PE odor intensity as assessed by human subjects. By fitting a
hypodermic needle to this hand-held device, the headspace of bagged PE product
stored in warehouses can be sampled to assure quality.
Commercial color sorters, employing electro-optic sensors that can discriminate
between natural and colored pellets, are increasingly used in the PE industry. These
machines can highlight the presence of discolored pellets and other contaminants
arising from compounding disruptions. They can also be used to upgrade batches
containing occasional colored pellet contamination, thereby increasing the prime
stock and decreasing the amount of off-specification resin produced. For instance,
transfer lines are not always properly purged and cleaned and natural resin can be
contaminated by a small quantity of black pellets. Similarly, natural pellets that have
yellowed can be sorted at high production rates (e.g., 10 tonne/h) to upgrade the offspecification
material.

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POLYETHYLENE (Stabilization and Compounding)

By: Ahmed M. Eltief

Part II: Compounding

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