Oxidative degradation and stabilisation of polymers
S. Al-Malaika
The aim of this review is to present a coherent
treatment of the fundamental aspects of the
science that underpins current technological
practices, and future advances, in the stabilisation
of synthetic organic polymers. Aspects of polymer
oxidation are introduced first before discussing the
role of antioxidants, with numerous examples, to
illustrate their basic mechanisms of action. The
state of the art is discussed with particular
emphasis on recent development and progress.
IMR/386
The author is in the Polymer Processing and Performance
Research Unit, School of Engineering and Applied Science,
Aston University, Aston Triangle, Birmingham B4 ET, UK
(s.al-malaika@aston.ac.uk).
© 2003 IoM Communications Ltd. Published by Maney for
the Institute of Materials, Minerals and Mining and ASM
International.
Introduction
Organic materials are susceptible to attack by at-
mospheric oxygen. In the case of synthetic organic
polymers, molecular oxygen initiates oxidative degra-
dation processes that lead to material failure. Polymer
oxidation is often accelerated by other environmental,
biological and physical factors, e.g. sunlight, ozone,
heat, radiation, mechanical stress, traces of transition
metal ions, water, pollutants and micro-organisms.
Oxidative degradation of commercial organic poly-
mers occurs, to varying degrees, at every stage of
their lifecycle, including manufacture, processing, fab-
rication, storage and in-service, both during their Žrst
and subsequent (i.e. after recycling) lifetimes. Such
oxidative processes lead to the irreversible deterior-
ation of the useful properties (e.g. mechanical prop-
erties: tensile, exural and impact strengths; surface
appearance: gloss, texture, and colour) of polymer
artefacts and are reected in poor performance or
catastrophic failures. The extent of oxidative degra-
dation, however, is not the same in all polymers: it
depends on intrinsic chemical structure (with con-
comitant chemical and physical structural defects)
and susceptibility to external inuences during the
lifetime of the polymer product.
The early searches for ‘antioxidants’ were empiri-
cally based and have led to the production of a
number of inhibitors of oxidation.1–5 Subsequent
development focused on understanding of the under-
lying processes of oxidation and inhibition in poly-
mers.6–9 A further intense period of research ushered
in a new era where an understanding of basic mechan-
isms of action of polymer oxidation and commercial
antioxidants has transformed the trial and error prac-
tices of industry to a mature science based polymer
stabilisation technology.10–12
The terms stabilisers and antioxidants are generally
used in the plastics industry to describe chemical
DOI 10.1179/095066003225010218
agents that combat and inhibit the combined degrad-
ative eVects of oxygen, temperature and light. The
terms primary and secondary antioxidants are also
used sometimes even though the distinction is rather
arbitrary and does not relate to their mechanisms of
action. On the other hand, the rubber industry tends
to use terms such as antidegradants, antifatigue agents
and antiozonants, to refer similarly to chemical agents
that act against the deleterious eVects of temperature,
stress and ozone, respectively. Although antioxidants
and stabilisers are normally used at low concen-
trations (generally <1%) they are key ingredients in
the compounding of polymers. The continuous
growth of polymer markets has ensured a parallel
growth in the demand for antioxidants and stabilisers,
especially in the large tonnage polymers with major
packaging, building, automotive, electrical and elec-
tronics applications.
Autoxidation of polymers
Synthetic organic polymers are susceptible to attack
by molecular oxygen in an autocatalytic reaction;
hence the term autoxidation13–16 is used to describe
an oxidation reaction that starts slowly, possibly with
a short induction period, followed by a gradual
increase in the rate (ascribed to the build up of
hydroperoxides) which eventually subsides giving rise
to a sigmoidal curve. The length of the induction
period is very short or absent when initiators (e.g.
peroxides, azo compounds) are present, but can be
prolonged in the presence of antioxidants and stabil-
isers (Fig. 1). The basic autoxidation theory of hydro-
carbons which involves a complex set of elementary
reaction steps is similarly valid for polymer oxi-
dation.4,17–19 The role of hydroperoxides formed
during autoxidation of polymers cannot be overemph-
asised; they are associated with further initiation,
changes in molar mass and other polymer properties
leading ultimately to loss of properties and cata-
strophic failure (see Fig. 2). Studies of oxidation in
polymers, both in the solid phase (e.g. under service
conditions in the presence of heat or light) and in the
viscous melt during processing, have been shown to
be more complex than in liquid hydrocarbons due to
problems of oxygen diVusion, solubility, and eVects
of polymer crystallinity and morphology.20,21 For
example, oxygen solubility in solid polymers (e.g.
polyoleŽns) is not greatly diVerent (slightly lower)
from that in liquid hydrocarbons, whereas its diVusion
in polymers is two orders of magnitude slower.20
The autoxidation process of polymers involves free
radical initiated chain reactions and proceeds in three
basic steps: initiation, propagation and termination
(Scheme 1).17 Many factors, e.g. heat, mechanical
stress, light and transition metal impurities, contribute
to the initiation step leading to the formation of
the Žrst alkyl macroradicals (Scheme 1, reaction 1).
Bimolecular oxygen–polymer reaction is generally not
International Materials Reviews 2003 Vol. 48 No. 3 165
166 Al–Malaika Oxidative degradation and stabilisation of polymers
1 Generalised scheme for changes in autoxidation
curve caused by presence of initiators and
antioxidants
favoured (very slow at moderate temperatures) on
thermodynamic and kinetic grounds. Such a reaction
may take place only in polymers with very labile
C–H bonds to give relatively stable alkyl radicals
that terminate, rather than propagate, the oxidation
chain reaction.
Propagation reactions involve the very fast reaction
of oxygen diradical, I (oxygen exists in a triplet
ground state) with polymer alkyl radicals leading to
the formation of alkylperoxyl macroradicals
(Scheme 1, reaction 2). This is followed by abstraction
of a hydrogen atom from another macromolecule
resulting in hydroperoxide formation, the Žrst molec-
ular product of the chain oxidation process (Scheme 1,
reaction 3). This reaction involves the breaking of a
C–H bond and, therefore, requires a higher activation
energy than reaction 2. The rate of reaction 3, which
in most polymers at normal oxygen pressures deter-
mines the overall oxidation rate, is a function of both
the C–H bond dissociation energy (allyl<benzyl <
tertiary <secondary <primary, see Table 122) and the
stability of the alkyl macroradical formed.17 The
hydroperoxide macromolecules formed can undergo
2 Generalised scheme relating hydroperoxide
concentration and loss of useful properties
International Materials Reviews 2003 Vol. 48 No. 3
Scheme 1 Basic autoxidation mechanism
homolysis (bond dissociation energy of RO–OH is
about 175 kJ molÕ 1; Ref. 22) under the eVect of heat,
light or metal ions giving rise to alkoxyl and hydroxyl
macroradicals (Scheme 1, reaction 4). Both these rad-
icals can abstract a hydrogen from another polymer
molecule leading to new alkyl macroradicals (reac-
tions 5 and 6a) which continue the chain reaction.
Alkoxyl radicals can undergo further reactions,
e.g. b-scission (see reaction 6b), that would lead to
cleavage of the macromolecular backbone and the
generation of further radicals.
O·–O·
oxygen diradical (biradical), I
Termination of the oxidative process occurs through
combination or disproportionation reactions involv-
ing the various propagating radicals. The exact nature
of the terminating step depends on both the structure
of the polymer substrate and the oxygen concen-
tration. Since reaction 3 (Scheme 1) is rate determin-
ing, alkylperoxyl radicals are the predominant
reactive species under normal oxygen pressure
(oxygen saturation), i.e. [POO· ]>[P· ], and termin-
ation occurs primarily through reaction 7 leading to
diperoxides, carbonyl compounds and alcohols.23–25
In the presence of a limited amount of oxygen (oxygen
deŽciency), however, alkyl radicals predominate, i.e.
[P· ]>[POO· ], and bimolecular termination reac-
tions 8–10 (Scheme 1) assume greater signiŽcance
leading to polymer cross-linking (and higher molar
mass, reaction 9) and/or disproportionation (reaction
10; without changes in molar mass). Both ‘limiting
conditions’ occur in polymers in the course of their
Table 1 Dissociation energies of carbon–
hydrogen bonds22
R–H DR–H , kJ molÕ 1* Bond type
CH2 CHCH2–H 343 Allylic
C6 H5 CH2 –H 347 Benzyl
(CH3 )3 C–H 380 Tertiary
(CH3 )2 CH–H 393 Secondary
CH3 –CH2 –H 414 Primary
* To convert to kcal molÕ 1 , multiply by 4·184.
 Al–Malaika
Scheme 2 Schematic presentation of cyclical
oxidation process and some of main
reactions/products formed from
propagating radicals
lifecycle, with oxygen saturation dominating in the
course of end-product use, and oxygen deŽciency (i.e.
diVusion limited oxidation) occurring mainly during
polymer processing (e.g. extrusion) as well as in thick
cross-sections, when oxidation rate is controlled by
oxygen diVusion. Other radical–polymer reactions,
including fragmentation and addition to double
bonds to give rise to further free radicals, can also
take place depending on the reaction conditions.26–29
These molecular changes lead ultimately to loss of
mechanical properties (e.g. impact strength, tensile
strength, elongation), modiŽcation of surface appear-
ance (e.g. crack formation, loss of gloss, ‘chalking’),
yellowing and premature failure. Scheme 2 highlights
the cyclical oxidation pathways and the nature and
eVects of oxidation products arising from the diVerent
propagating species.
Thermal oxidation during processing
and in-service
Hydrocarbon polymers are normally processed (e.g.
by extrusion and injection moulding) at high temper-
atures in the presence of mechanical shearing forces
to produce the Žnal fabricated article. Under these
conditions, the polymer is subjected to a process of
thermal degradation which is accelerated by atmos-
pheric oxygen (ambient, dissolved or trapped in the
polymer). Although thermal oxidation of plastics and
rubbers can occur at all stages of their lifecycle, it is
most pronounced at the high melt processing temper-
atures (e.g. 180 to 330°C) needed for conversion
Table 2 Characteristics of Ziegler (Z) and metallocene (m) octane based linear low density polyethylene
(LLDPE) polymers 30
Density, MFI*,
Polymer g cmÕ 3 g/10 min MFR† 1-octene, wt-%
Z-LLDPE 0·92 1·0 36 10·5
m-LLDPE PL1840 0·91 1·0 38 13·5
*MFI is melt flow index.
†MFR is defined as the ratio of high load melt index to low load melt index.
Oxidative degradation and stabilisation of polymers 167
processes. As a consequence, various oxygen contain-
ing groups are introduced into the oxidised polymer
substrate leading to changes in the molecular struc-
ture and the formation of low molecular mass prod-
ucts that would adversely aVect the performance (e.g.
mechanical and electrical properties) of the Žnal poly-
mer product. Clearly, therefore, the thermal history
of a polymer can play a major role on its subsequent
in-service performance.
A typical polymer melt extrusion process consti-
tutes a closed system whereby dissolved oxygen in
the polymer melt is consumed rapidly and the
environment inside a closed extruder becomes oxygen
deŽcient. Under these conditions, therefore, the oxi-
dation becomes oxygen diVusion limited and the
concentration of [R· ] exceeds that of [ROO· ] in the
polymer system. Termination of the chain reaction is
expected to proceed predominantly through reactions
of the alkyl macroradicals, including:
d recombination ( leading to cross-linking and
increase in molar mass of the polymer matrix)
d fragmentation (chain scission resulting in lowering
of molar mass)
d disproportionation (oleŽn formation, with reten-
tion of molar mass)
d addition to double bonds
d oxidation (b-scission leading to lowering of molar
mass).
The nature of the polymer matrix exerts a profound
eVect on the mechanothermal oxidation chemistry of
the system. Examples of the chemical and physical
changes that occur during melt processing of some of
the important commercial polymers are highlighted
below.
Polyethylenes
Polyethylenes ( high density, HDPE; low density,
LDPE; and linear low density, LLDPE) diVer in their
densities, type and extent of branching, and type and
amount of double bonds (depending on the polymeris-
ation process used commercially). Some of the charac-
teristics of two diVerently polymerised LLDPE
polymers, Ziegler (Z) and metallocene (m), are given
in Table 2.30 The structural diVerences, as well as the
processing conditions, play a signiŽcant role in
determining the type of oxidative degradation reac-
tions that take place during the melt extrusion of
polyethylenes. Ziegler-type polyethylene polymers
generally undergo predominantly cross-linking reac-
tions and enlargement of molar mass, particularly at
lower extrusion temperatures. However, the import-
ance of chain scission reactions (and reduction in
molar mass) becomes more pronounced at higher
temperatures (see Fig. 3), though varying the
Unsaturation, mol LÕ 1
Vinyl t-vinylene Vinylidene Total double bond
0·25 0·06 0·08 0·39
0·03 0·27 0·22 0·52
International Materials Reviews 2003 Vol. 48 No. 3
168 Al–Malaika Oxidative degradation and stabilisation of polymers
3 Effect of extrusion temperature on molecular
weight changes of Ziegler-type linear low
density polyethylene (Z-LLDPE) 31
extrusion conditions, e.g. screw speed, can alter the
relative importance of these two reactions.31
Controlling changes in molar mass is crucial, since
the Žnal properties of fabricated products are greatly
dependent on the molar mass of the base polymer.
The high mechanical shearing forces in an extruder
lead to chain scission of the C–C backbone and the
formation of alkyl macroradicals. Both alkyl and
alkoxyl macroradicals are important intermediates
that are ultimately responsible for the formation of
chemical impurities and structural defects, e.g. hydro-
peroxide macromolecules (a potential source of oxi-
dative instability in the fabricated product ), carbonyl
groups, double bonds, that adversely aVect the molar
mass of the base polymer, and, consequently, its
rheological characteristics and performance (see
Scheme 3). The presence of unsaturated groups
(e.g. vinyl; CH CH–, vinylidene; CH C <, trans-
2 2
PP =polypropylene; PE=polyethylene
Scheme 3 Reactions of alkyl macroradicals during
high temperature processing of poly-
olefins
International Materials Reviews 2003 Vol. 48 No. 3
Scheme 4 Intramolecular hydrogen abstraction
and formation of vicinal hydro-
peroxides in PP
vinylene; –CH CH–) as impurities in polyethylene
play an important role in the overall oxidation and
cross-linking of the polymer. For example, the rela-
tively high concentration of vinyl groups (with respect
to other types of unsaturation) in the Zeigler polymers
(see Table 2), suggest that cross-linking reactions may
occur, at least in part, through addition of alkyl
macroradicals to the vinylic double bonds (see
Scheme 3).29,31 Degradation by chain scission at
higher temperatures, on the other hand, proceeds to
a large extent by b-scission of alkoxyl radicals
(Scheme 3).
Polypropylene
Polypropylene (PP) undergoes predominantly chain
scission under all processing conditions26–29,33,34
giving rise to pronounced reduction in the molar
mass and melt viscosity of the polymer (see Scheme 3).
The propagation reaction (reaction 3, Scheme 1) at
the tertiary carbon atom of PP is 20% faster than a
corresponding reaction at a secondary carbon atom
(e.g. in PE). Furthermore, this reaction is particularly
facilitated in PP by intramolecular hydrogen abstrac-
tion leading to the formation of adjacent hydroper-
oxides ( less stable than isolated hydroperoxides) along
the polymer chain resulting in an increased rate of
initiation (see Scheme 4). Consequently, the kinetic
chain length (i.e. the average number of oxidation
cycles, reactions 3 and 4, before termination occurs)
for PP autoxidation is quite high, approximately 100
(compared to only about 10 for the more oxidatively
stable PE).
Polystyrene
Polystyrene (PS) behaves similarly to PP under pro-
cessing conditions (see Scheme 5) where decompos-
ition of tertiary hydroperoxides results in b-scission
(and formation of acetophenone groups on the PS
chain35,36) causing a sharp drop in melt viscosity (due
to a sharp reduction in molar mass37). Thermal
oxidative degradation of copolymers or terpolymers
Scheme 5 Chain scission of polystyrene (PS)
hydroperoxides formed during melt
processing
 Al–Malaika
Scheme 6 Reactions of alkyl macroradical during
high temperature processing of poly-
vinyl chloride (PVC)
of PS, such as styrene–acrylonitrile (SAN) and acry-
lonitrile–butadiene–styrene (ABS), is a more complex
process. For example, the presence of the rubber
component (butadiene rubber, BR) in ABS makes the
polymer much more thermo-oxidatively sensitive due
to the rapid oxidation of the rubber phase; oxidation
of BR results in cross-linking and loss of rubber
properties, e.g. impact.38
Polyvinyl chloride
Unlike polyoleŽns and polystyrene, melt processing
of polyvinyl chloride (PVC) results mainly in elimin-
ation reaction rather than changes in molar mass.
The initial macroradicals formed in PVC melt give
rise to two competing reactions: elimination of HCl
leading to the formation of conjugated double bonds
(with visible discolouration observed with at least
seven double bonds) (Scheme 6, reaction c). The
damage was found to be greatest during the Žrst few
minutes of processing when viscosity is highest.39–42
Although the small amount of impurities or struc-
tural defects found in commercial grades of PVC,
such as vinyl [CH CH–CH(Cl)–] and vinylene
2 on their photoxidative stability under the combined
[–CH –CH CH–CH(Cl)] double bonds, have been
2
thought responsible for the high susceptibility of PVC
to HCl elimination, evidence from melt processing
work based on unstabilised polymer has shown that
their overall eVect is far less than the damaging
role of functional groups (e.g. hydroperoxides, un-
saturation) formed during the early stage of melt
processing.39
Engineering polymers
Aliphatic polyamides (PA) and polyesters are more
stable under processing conditions than polyoleŽns.
However, after the initial formation of mechano rad-
icals, they undergo free radical attack by hydrogen
abstraction at methylene groups in position a to the
nitrogen (polyamides) or oxygen (polyesters) atoms
Oxidative degradation and stabilisation of polymers 169
Scheme 7 Reactions of polyamides (PA) during
high temperature processing
resulting in peroxidation and reduction in molar
mass39,43–45 (see e.g. Scheme 7). These polymers, along
with other heteroatom containing polymers, such as
polycarbonates (PC) and polyethylene terephthalate
(PET), are also highly susceptible to hydrolytic degra-
dation (Scheme 8), giving rise to chain scission,
reduction in molar mass and deterioration of mechan-
ical properties.12 These polymers must be thoroughly
dried before melt processing which is normally per-
formed at temperatures of up to 300°C.
Polymers may be further subjected to long term
thermal oxidation during their in-service life, for
example, in automotive (e.g. under-the-bonnet) and
electronics applications and domestic appliances. In
addition to temperature, both polymer morphology
and sample thickness inuence signiŽcantly the long
term thermal oxidative behaviour of polymers. In
contrast to melt processing, under conditions of long
term thermal oxidation (usually conducted at much
lower temperatures than processing ) under ambient
conditions, the concentration of alkylperoxyl radicals
[ROO· ] exceeds that of [R· ] in the polymer system.
Under these conditions, for thin polymer samples
(<30 mm), oxygen diVusion is not rate determining
and the main termination process (in the absence of
antioxidants) is a bimolecular reaction of alkylperoxyl
radicals (e.g. Scheme 1, reaction 7). For thick polymer
sections, and particularly at service high temperatures,
oxygen may become deŽcient inside the sample during
long term thermal exposure, hence increasing the role
of alkyl radicals in polymer oxidation, and require
diVerent strategies for its inhibition.
Photoxidation and effect of outdoor
environment
The outdoor performance of polymers depends largely
Scheme 8 Hydrolytic degradation of poly-
carbonate (a) and polyethylene tere-
phthalate (b)
International Materials Reviews 2003 Vol. 48 No. 3
170 Al–Malaika Oxidative degradation and stabilisation of polymers
Scheme 9 Photolysis of PE (Norrish reactions)
action of light and oxygen. The ultraviolet (UV ) part
of the sun’s radiation reaching earth, in the region
290–400 nm, is mainly responsible for the light
induced polymer oxidation (photoxidation). Pure
saturated hydrocarbon polymers are intrinsically
transparent to solar radiation greater than 290 nm.
However, commercial hydrocarbon polymers (e.g. PE,
PP) absorb weakly at wavelengths above 285 nm
because of the presence of light absorbing impurities,
particularly oxygen containing species, and trace
levels of metals and adventitious species introduced,
inadvertently, during the various manufacturing and
conversion processes. Hydroperoxides formed during
melt processing (and to a lesser extent during manu-
facturing and storage) are potent photoinitiators of
polymer photoxidation46 (see Scheme 1, reaction 4b).
The later stages of photoxidation are predominated
by the derived carbonyl-containing impurities, leading
to backbone scission according to Norrish types I
and II photocleavage processes (Scheme 9).47–50
Apart from the direct eVect of UV light and oxygen,
outdoor weathering of polymer articles involves other
environmental factors such as heat, pollutants, water
(particularly in the case of polymers containing
heteroatoms), ozone (especially for unsaturated
elastomers). These factors catalyse the formation of
free radicals and light sensitive chromophoric groups
and initiate photoxidation.51–53 Under photoxidative
conditions, the alkyl/peroxyl radical ratio is high, i.e.
[R· ]À [ROO· ], due to a higher rate of initiation
(compared to oxidation under thermal conditions)
and low rate of oxygen diVusion in the solid
polymer.21,54
The photoxidative behaviour of commercial poly-
mers is widely diVerent. The most photoxidisable
polymers are the unsaturated rubbers with labile P–H
bond, hence they are heavily loaded with carbon
black (an eVective sun screen) for outdoor appli-
cations. Similarly, rubber modiŽed plastics, e.g. high
impact polystyrene (HIPS), are more susceptible to
photoxidation than polyoleŽns due to rapid peroxi-
dation of the rubber component that will sensitise the
polymer to further photoxidation (see Scheme 10),
causing detrimental changes to colour and impact
properties.38
Scheme 10 Photoxidation of polybutadiene–
polystyrene graft copolymer (high
impact PS)
International Materials Reviews 2003 Vol. 48 No. 3
Scheme 11 Oxidation cycles, antioxidant
mechanisms and some examples
representing different antioxidant
(AO) classes
In the case of polyoleŽns, the photostability of
diVerent members of the family varies signiŽcantly
depending on their chemical and morphological struc-
tures. Generally, PP and HDPE are more susceptible
to photoxidation than LDPE;32,55 PVC and PS
should be relatively stable to photoxidation, but their
thermal history exerts signiŽcant eVects on their sub-
sequent photoxidative behaviour.40,56,57 Engineering
polymers, e.g. aliphatic polyesters and polyamides,
are generally more stable than polyoleŽns, albeit
similar photoxidative processes are involved; i.e. per-
oxidation, photo-induced reactions and chain scis-
sion.58–63 Other engineering polymers, such as
polycarbonates (PC), polysulphones (PSO), poly-
phenylene oxide (PPO), are also more stable to UV
light than, for example, polyoleŽns and PVC.
Prolonged outdoor exposure of these polymers leads
to changes in their molar mass, and deterioration of
mechanical (e.g. impact strength) and optical (e.g.
yellowing) properties, the latter can be particularly
important in certain applications, e.g. outdoor use of
PC instead of glass.50,63 The outdoor performance of
all polymers can, however, be markedly improved by
photoantioxidants and UV stabilisers.
Antioxidants
Antioxidants and stabilisers are a group of com-
pounds that are known to inhibit or retard oxidative
degradation of polymers. Low concentrations of anti-
oxidants (0·03–0·25 wt-% for thermal antioxidants,
and up to 1 wt-% for photoantioxidants) are generally
incorporated during melt processing of polymers.
Antioxidants are usually classiŽed according to the
way they interrupt the overall oxidation process:
chain breaking and preventive antioxidants (see
Scheme 11). Examples of commercial antioxidants
and their main mode of action are given in Table 3.
Antioxidant mechanisms
Chain breaking (CB) antioxidants (sometimes referred
to as primary antioxidants) interrupt the primary
oxidation cycle by removing the polymer propagating
radicals, POO· and P· (Ref. 10). Chain breaking
donor antioxidants (CB-D), such as hindered phenols
and aromatic amines, AH, (see Table 3, AO1–AO12),
are hydrogen atom donors which are capable of
 Al–Malaika
Scheme 12 Main reactions and competing
pathways involved in chain breaking
antioxidant activity
reducing POO· to POOH (see Scheme 12, reaction
a). EVective CB-D antioxidants must compete
eYciently with POO· for the polymer, i.e. prevent
hydrogen abstraction from the polymer (chain propa-
gating step, reaction 12b), and the antioxidant radical
(A· ) produced from reaction 12a must lead to stable
molecular products, i.e. A· does not continue the
kinetic chain either by hydrogen abstraction (reaction
12ci) or reaction with oxygen (reaction 12cii).
Enhancing the steric hindrance of the antioxidant
(e.g. hindered phenols) in addition to any other factor
that increases the stability of the derived antioxidant
radical (A· ) would contribute to reducing the rate of
the chain transfer reaction (reaction 12ci) and increas-
ing the inherent eVectiveness of the antioxidant.
Chain breaking acceptor antioxidants (CB-A) act
by oxidising alkyl macroradicals (reaction 12d) in a
stoichiometric reaction (P· are removed from the
autoxidising system) in competition with the chain
propagating reaction (reaction 12e) and hence are
only eVective under conditions of low oxygen concen-
tration. Quinones, stable free radicals, and the recently
developed antioxidants based on benzofuranone
derivatives (lactones) and hydroxylamines are good
examples of CB-A antioxidants.64–68 Hindered amine
derivatives (often referred to as hindered amine stabil-
isers (HAS), e.g. Table 3, AO25–AO27) function also
by a chain breaking mechanism and, through their
transformation products, are able to trap both P· and
POO· in a cyclical regenerative mechanism.46,50,69–73
Preventive antioxidants (sometimes referred to as
secondary antioxidants) interrupt the second oxidat-
ive cycle by preventing or inhibiting the generation
of free radicals (see Scheme 11, cycle B). The most
important preventive mechanism is the non-radical
hydroperoxide decomposition (PD).11,74 Phosphite
esters and sulphur containing compounds (e.g.
AO15–AO24, Table 3) are the most important classes
of peroxide decomposers. Phosphites reduce hydro-
peroxides to alcohols and are themselves oxidised to
the corresponding phosphates with a 1 : 1 stoichi-
ometry and are referred to as stoichiometric peroxide
decomposers (PD-S) (see Scheme 13, reaction a).
Some phosphite esters behave additionally as catalytic
peroxidolytic agents (PD-C) and others (e.g. hindered
Oxidative degradation and stabilisation of polymers 171
Scheme 13 Peroxidolytic (PD) and chain breaking
(CB) activity of phosphorous anti-
oxidants
aryl phosphites, see AO15–AO18, Table 3) are also
capable of functioning by a chain breaking mechanism
(Scheme 13, reactions b and c). The contribution of
each of these modes of action to the overall mech-
anism depends on the structure of the phosphite,
oxidisability of the substrate and the reaction con-
ditions.75,76 Sulphur compounds, e.g. thioethers, esters
of thiodipropionic acid and metal dithiolates (see
AO19–AO24, Table 3), decompose hydroperoxides
catalytically (PD-C) whereby one antioxidant mol-
ecule destroys several hydroperoxides through the
intermediacy of sulphur acids (see Scheme 14, reac-
tions a, b, c).11,74,77,78
Metal ion deactivators (MD) act, primarily, by
retarding metal-catalysed oxidation of polymers (see
Scheme 1, reaction 4b), and are used in polymers in
contact with metals, e.g. copper in wires and power
cables. These are normally polyfunctional metal chel-
ating compounds (e.g. AO33, AO34, Table 3) that
form stable metal complexes with reduced catalytic
activity of the metal.79,80 The UV absorbers (UVA)
act by absorbing UV light thereby retarding the
formation and photolysis of hydroperoxides. Typical
examples that are based on 2-hydroxybenzophenone
and 2-hydroxybenzotriazole structures are given in
Table 3, AO28–AO32. These compounds are photost-
able with high absorptivity in the spectral region
300–360 nm. Their activity is based essentially on
absorption of the harmful UV radiation and its
harmless dissipation as heat. For example, UV light
induces intramolecular hydrogen transfer in
2-hydroxybenzophenones to give an enol which is
converted, radiationlessly, back to the original ketone
in a tautomeric interconversion process.22,81
Factors affecting practical use of antioxidants
The eVectiveness and use of stabilisers and antioxi-
dants in real polymer applications depends on several
Scheme 14 Peroxidolytic activity of simple alkyl
sulphides
International Materials Reviews 2003 Vol. 48 No. 3
172 Al–Malaika Oxidative degradation and stabilisation of polymers

Table 3 Some examples of commercial antioxidants representing major antioxidant mechanisms

Antioxidant Code* Tradename Molecular mass
CHAIN BREAKING ANTIOXIDANTS
Hindered phenols
AO1 BHT 220

AO2 Irganox 1330 775

AO3 Irganox 3114 784

AO4 Irganox 1076 531

AO5 Irganox 1010 1178

AO6 Irganox 1098 637

AO7 Irganox 259 639

AO8 Irganox 3052 385

AO9 Irganox 1081 359

AO10 Irganox E 201 431

Aromatic amines
AO11 Nonex OD 393
AO12a Nonex DPPD 260
AO12b … 252

Lactones

AO13 HP136 351

Hydroxylamines
AO14 Irgastab FS 042 537

* AO=antioxidant.

International Materials Reviews 2003 Vol. 48 No. 3

 Al–Malaika Oxidative degradation and stabilisation of polymers 173

Table 3 Some examples of commercial antioxidants representing major antioxidant mechanisms (cont.)
Antioxidant Code* Tradename Molecular mass
PREVENTIVE AND PHOTOANTIOXIDANTS
Peroxide decomposers
AO15a Ultranox TLP 586 Q
N
N
AO15b Irgafos TNPP 689
N
AO16 Irgafos 168 647
N
R Phosphite
N esters
AO17 Irgafos P-EPQ 991 N
N
N
AO18 Ultranox U626 … S

Q
AO19 Irganox PS802 683 N
AO20 Irganox PS800 515 N
R Sulphur
N compounds
AO21 Robec Z bud …
N
AO22 Iron dithiocarbamate …
N
AO23 Nickel dithiophosphate …
S
AO24 Nickel xanthate …

Photoantioxidants, hindered amine stablilisers

AO25 Tinuvin 770 481 Q

AO26a Tinuvin 765 509
N
N
3100–4000 N
N
AO26b Tinuvin 626

N
R HAS
N
N
2000–3100 N
N
AO27 Chimassorb 944

N
S

UV absorbers

Q
N
N
AO28 Chimassorb 81 326

R UVA
AO29 Tinuvin 320 323
AO30 Tinuvin 571 394 N
AO31 Tinuvin P 225 N
AO32 Tinuvin 326 316 S

Metal deactivators
Q
AO33 Irganox MD1024 553 N
N
R MD
N
N
S
AO34 Eastman OABH 294

Hydrogen chloride scavengers

Q
N
N HCl
AO35 Dibutyl tin maleate 347
R
N scavengers
N
AO36 Dioctyltin thioglycolate 750 S

* AO=antioxidant.

International Materials Reviews 2003 Vol. 48 No. 3

174 Al–Malaika Oxidative degradation and stabilisation of polymers
factors: chemical, physical, toxicological, and econ-
omic. Under aggressive service conditions their per-
formance can be dominated by their physical
characteristics, e.g. physical loss from polymers
through volatilisation during processing and fabri-
cation, or by exudation and solvent extraction during
end-use. Physical loss is more serious in semicrystal-
line polymers and with polymer artefacts having high
surface/volume ratio, e.g. coatings, Žbres, Žlms.20,82
Chemical factors include structure, hydrolytic-,
thermal- and photochemical stability of both the
parent antioxidant molecule and its transformation
products. The intrinsic chemical activity of stabilisers
and antioxidants is a function of their molecular
structure which can be determined from studies in
model substrates. Some stabilisers, notably aromatic
amines and some hindered phenols, impart discolour-
ation or yellowing to the polymer substrate during
processing and fabrication or during long term use.
This is highly undesirable in plastics and is largely
due to the formation of quinonoid-type transform-
ation products of the parent antioxidant molecule.83,84
Aromatic amines cause extensive discolouration,
hence they are generally restricted to the stabilisation
of rubbers. Some stabilisers are also sensitive towards
hydrolysis, especially phosphites, and to a lesser
extent, phosphonites (see Scheme 13, reaction d). This
results not only in the loss of their antioxidant activity,
but also in the formation of acidic species that can
initiate corrosion in processing machines,76 hence
special attention is needed for storing and handling
hydrolytically sensitive antioxidants and stabilisers.
Physical factors such as solubility, diVusivity, vola-
tility, leachability of antioxidants are further inu-
enced by the chemistry and morphology of the
polymer substrate. Physical loss of antioxidants into
the contact media can have severe toxicological conse-
quences in addition to risks associated with premature
failure of the polymer product. Most countries have
stringent regulations regarding the use of these addi-
tives in applications involving the human environ-
ment, e.g. food packaging and medical applications.
Although stabilisers and antioxidants destined for
such applications have to undergo strict toxicity
testing regimes, their approval, however, does not
necessarily mean that their transformation products
(derived from the parent molecule during processing,
or as by-products of their protective action) are also
non-toxic.
The use of a highly chemically eYcient antioxidants
does not in itself guarantee successful long term
protection of polymers under aggressive environment
where the problem of physical loss is most severe.
For example, the hindered phenol BHT (AO1,
Table 3) has a very high intrinsic antioxidant activity
but is ineVective in protecting thermoplastic polymers
because of its rapid physical loss and depletion
through volatilisation from the polymer.85 Indeed the
physical behaviour of stabilisers is a major factor
aVecting their permanency, eYciency and accept-
ability, especially in polymer applications destined for
use under aggressive service environments, typical
examples being organic solvents, e.g. dry cleaning
solvents, hot water and detergents, hot oils, acids,
fatty food, hot air and intense solar radiation. The
International Materials Reviews 2003 Vol. 48 No. 3
problem of physical loss was partly solved by the
advent of ‘new’ high molecular mass antioxidants
based on the same hindered phenol function which
were synthesised by increasing the length of the
aliphatic chain and/or increasing the equivalent
weight of the active moiety, i.e. di-, tri-, and poly-
phenolic antioxidants, e.g. Irganox 1010, Irganox 1330
(AO5, AO2, Table 3), and which have outperformed
BHT.12
Stabilisation of polymers
Stabilisation of polymers against the eVects of temper-
ature, shear, and UV light and other oxidising agents
is required both to prevent mechanothermal oxidation
at the processing stage (processing antioxidants) and
to aVord protection during in-service ( long term
thermal stabilisers and photostabilisers). In addition,
the thermal stability of reprocessed polymers
(recycled) must be preserved and reinforced by
additional stabilisation (recycling stabilisers) for
further reprocessing and end-use. Both thermal- and
photostabilisers must satisfy the basic chemical
and physical requirements outlined previously (see
‘Factors aVecting practical use of antioxidants’ above).
In addition, photostabilisers must be photostable, i.e.
stable to UV light, to withstand continuous periods
of UV exposure without being prematurely destroyed
or transformed into sensitising products.
Stabilisation during processing
The choice of antioxidants for the stabilisation of
polymer melts, during processing, is made after exam-
ination of several factors: structure and oxidisability
of the base polymer, temperature of conversion pro-
cesses, rate of application of mechanical stress, type
and amount of structural defects and impurities, and
performance targets of the end-use applications. Thus,
structural diVerences in polyoleŽns, for example, give
rise to macromolecular structures with diVerent levels
of oxidisability, as discussed above in ‘Thermal
oxidation during processing and in-service’.
Polypropylene, for example, is very sensitive towards
oxidation and may not be processed without adequate
stabilisation. High density PE is less sensitive to
oxidation than PP and lower antioxidant concen-
trations are normally needed, whereas LDPE (pro-
cessed around 200°C) is more oxidatively stable and
may even be used (for certain applications) without
the addition of an antioxidant. DiVerent classes of
antioxidants are used, and their stabilising action in
polymer melts is discussed below.
Aromatic amines, hindered phenols, lactones and
hydroxylamines
Antioxidants based on p-phenylenediamine (e.g.
AO11, AO12, Table 3 ) are highly eVective peroxyl
radical scavengers (more eVective than hindered phe-
nols). Their use is limited, however, to elastomers
because of their extreme staining power. Sterically
hindered phenols (also eYcient CB-D antioxidants),
on the other hand, have been used extensively as melt
processing stabilisers in plastics. The primary step in
their stabilising action involves the scavenging of
alkylperoxyl (ROO· ) radicals giving rise to harmful
 Al–Malaika
Scheme 15 Key reactions that take place during
antioxidant action of 4-propionate
hindered phenols
hydroperoxides (see Scheme 12, reaction a). In prac-
tice, therefore, hindered phenols are generally used in
combination with a peroxide decomposer, typically a
hydrolysis resistant phosphite.12,39,86 The eYciency of
hindered phenols depends on the degree of steric
hindrance and the nature of the para-substituents
present. Generally, decreasing steric hindrance in the
2- and 6- positions results in increasing the rate of
hydrogen abstraction from the phenol. Similarly, the
nature of para-substituents aVects the extent of dis-
colouration as it determines the nature of transform-
ation products obtained from the parent phenol.87
Discolouration is typically caused by the formation
of coloured conjugated quinonoid-type transform-
ation products with visible absorption wavelengths,
extending to more than 400 nm.88 Propionate esters,
e.g. AO4 and AO5, are good stabilisers for polyoleŽns
and styrenics, the propionamide AO6 is used in
aliphatic polyamides, and the ester AO7 is suitable
for polyesters. Scheme 15 shows some key reactions
of propionate based hindered phenols used for poly-
mer stabilisation in order to illustrate their antioxi-
dant action and the formation of discolouring
products. It is clear that the major transformations
of phenolic antioxidants during melt processing con-
sist of quinone-type products, C–C and C–O coupling
products. Transformation products of antioxidants
can further inuence the overall stabilisation imparted
to the polymer by exerting anti- or pro-oxidant eVects,
and hence synergise or antagonise the action of the
parent antioxidant.
Antioxidants which act by a CB-A mechanism are
particularly suitable for melt stabilisation. The bifunc-
tional hindered phenol semiacrylate antioxidant (AO8
in Table 3) which acts primarily by deactivating alkyl
radicals, is an eVective processing stabiliser for styr-
ene–butadiene–styrene copolymers.89 The new lactone
stabilisers (see AO13, Table 3), which are used com-
mercially in phenol-free blends (e.g. with phosphites)
or in blends containing combinations of hindered
phenols and phosphites, have been shown65,66 to be
highly eYcient in oxygen deŽcient environments par-
ticularly during melt processing. Lactone stabilisers
Oxidative degradation and stabilisation of polymers 175
Scheme 16 Chain breaking reactions involved in
antioxidant action of benzofuranes
(lactone stabilisers)
act by trapping alkyl macroradicals, as well as peroxyl
radicals, through the intermediacy of the resonance
stabilised lactone ( benzfuranyl ) radical (see
Scheme 16). Similarly, the hydroxylamines (see AO14,
Table 3), which can also scavenge the alkyl macrorad-
icals via the intermediacy of nitrones have been
shown64 to be highly eYcient processing stabilisers
(Scheme 17, a, b). Hydroxylamines have also been
shown (see Scheme 17, c) to be able to reduce hydro-
peroxides to alcohols and form the corresponding
nitrones (peroxide decomposer).
Phosphites and sulphur compounds
Alkyl and aryl phosphite esters are eVective melt
stabilisers (see Scheme 13). They are often used in
combination with hindered phenols to give highly
eYcient melt stabilising systems (see Table 4), and to
reduce discolouration of the polymer due to the
oxidation products of the phenols present. Phosphites
(particularly those derived from aliphatic alcohols
and unhindered phenols) are, however, generally sus-
ceptible to hydrolysis. For example, hydrolysis of
phenyl phosphites gives rise to low molecular mass
phenol and hydrogen phosphite which is further
hydrolysed to phosphorous acid (Scheme 13, reaction
d).75,76 Consequently, moisture sensitive phosphites
adversely aVect the handling characteristics (i.e. ow
properties) of the additive package and are a source
of other problems: corrosion of metal surfaces, forma-
tion of dark coloured spots and gel formation. In
practice, hydrolysis resistant phosphites based on
sterically hindered phenols are used, e.g. AO17,
AO18, Table 3.
Sulphur containing compounds are highly eVective
PD antioxidants but they are more complex in their
behaviour than the phosphites. They react with
hydroperoxides in a catalytic process which leads to
the formation of sulphur acids that are responsible
for the catalytic non-radical destruction of hydroper-
oxides. The ‘simple’ dialkyl sulphides, e.g. thiodipro-
pionate esters such as Irganox PS800 and PS802
(AO20, AO19, Table 3) function as weak melt stabil-
Scheme 17 Chain breaking (a, b) and per-
oxidolytic (c) reactions of hydroxyl-
amine antioxidants
International Materials Reviews 2003 Vol. 48 No. 3
176 Al–Malaika Oxidative degradation and stabilisation of polymers
Scheme 18 Elimination of labile chlorine from PVC
by an organotin stabiliser
isers (Table 4, sample S1). They give rise to a pro-
oxidant eVect in the polymer due to the generation
of free radicals (see Scheme 14, reaction (d) by an
initial redox reaction with hydroperoxides.67 The
sulphoxide transformation products formed from thi-
odipropionate esters have been shown to be more
eVective melt stabilisers as they give rise to sulphenic
acid, an eYcient chain breaking antioxidant39 (see
Scheme 14, reaction e). In view of the prodegradant
eVects of thiodipropionate esters, these sulphide anti-
oxidants are always used in combination with CB-D
antioxidants, such as Irganox 1010 (AO5; see Table 4,
sample HS1 ), in order to deactivate the free radicals
formed.
Metal carboxylates as hydrogen chloride
scavengers and use of co-stabilisers
The aim of melt stabilisation of PVC is to reduce the
formation of both HCl, which results in conjugated
double bonds and colour, and hydroper-
oxides.39,40,90,91 In general, plasticised PVC is pro-
cessed at lower temperatures than rigid PVC, and
less damage is therefore expected during its melt
processing. The removal of labile chlorine atoms from
the polymer backbone, instead of elimination of HCl
(Scheme 6, b), is the most important stabilisation
mechanism for PVC. This can be achieved through
substitution reactions with carboxylate and mercap-
tide salts of certain metals such as zinc, calcium,
barium, cadmium and tin. Such compounds can
attack the labile chlorines and substitute them by
more thermally stable C–O or C–S (than C–Cl in
PVC) bound ligands (e.g. AO35, AO36, Table 3).
Scheme 18 shows the substitution reaction by a tetra-
valent derivative of tin, that removes the labile chlor-
ine and reduces the risk of further initiation from
allylic chlorine sites ( by relocation of the double bond
away from the ‘adjacent’ allylic chlorine). Generally,
dialkyl tin carboxylates are more eVective as chlorine
trapping reagents than the metal group II (e.g. Zn,
Cd, Ca, Ba) carboxylates.91
Table 4 Melt stabilising efficiency of phosphites in polypropylene (processed in internal mixer at 190°C):
melt flow index (MFI) measured at 230°C and 2·16 kg
Sample
code Antioxidant (AO)
C1 Control 1 (virgin, not processed)
C2 Control 2 (processed with no AO)
H1 Irganox 1010 (AO5)
P1 Irgafos 168 (AO16)
S1 Irganox PS800 (AO20)
HP1 Irganox 1010+Irgafos 168
HS1 Irganox 1010+Irganox PS800
International Materials Reviews 2003 Vol. 48 No. 3
Scheme 19 Antioxidant action of Cd/Ba
carboxylates system in PVC
However, neither the zinc nor the cadmium carb-
oxylates can be used alone for the thermal stabilis-
ation of PVC because of the ease of formation of
their chloride salts during the polymer processing.
Both zinc- and cadmium-chlorides are strong Lewis
acids and would therefore destabilise PVC by catalys-
ing the dehydrochlorination reaction.92 Two diVerent
metal II carboxylates are, therefore, generally used in
combination (e.g. Ca/Zn or Ba/Zn and Ba/Cd stabil-
iser systems) to eVect synergistic stabilisation of PVC.
In the case of barium and cadmium compounds, the
cadmium carboxylate is able to substitute labile chlor-
ine atoms in the PVC giving rise to cadmium chloride,
CdCl (Scheme 19, reaction a), which reacts readily
2
with barium carboxylate to give BaCl and cadmium
carboxylate (Scheme 19, reaction b); 2cadmium carb-
oxylate substitutes a further labile chlorine atom in
the polymer (repeat reaction a). This reaction (reac-
tion b) can also hinder partially the destabilising eVect
of the CdCl (a Lewis acid). The barium carboxylate
2
can react directly with HCl as shown in reaction c.
Combinations of Ba/Zn and Ca/Zn carboxylates sta-
bilising systems act also synergistically in a similar
way to that described for the Cd/Ba system,90,92,93
where the zinc carboxylates substitute the labile chlor-
ine atoms by the more stable carboxylate groups
(Scheme 20, reaction a). However, the destabilising
eVect of zinc chloride formed in the reaction is much
more pronounced than that of cadmium chloride due
to the stronger Lewis acidity of the former. Calcium
or barium carboxylates used in zinc soap containing
systems can suppress, at least partially, the detrimen-
tal eVect of any ZnCl formed via an ester exchange
2
AO, wt-% MFI, g/10 min
0 2·0
0 11·7
0·05 5·9
0·05 7·7
0·1 8·4
0·05+0·05 4·3
0·05+0·10 4·9
 Al–Malaika
Scheme 20 Antioxidant action of Zn/Ca
carboxylates system in PVC
reaction similar to that shown for the Cd/Ba system
(see Scheme 20, reaction b) and both CaCl and BaCl
2 2
are neutral.
The performance of stabilising systems containing
zinc or cadmium salts can be further improved by
the addition of other co-stabilisers (secondary antioxi-
dants), such as polyols, epoxidised fatty acid esters,
and phosphites that prevent or delay the formation
of the respective Lewis acid metal chlorides. These
co-stabilisers have been shown to be capable of
reacting with labile allylic chlorines (see e.g.
Scheme 21, reactions a and c), as well as their direct
reaction with HCl (Scheme 20, reaction b).92 They
have also been shown to have the ability to chelate
the active metal centres which alters the Lewis acidity
of the chloride salts. b-diketone compounds (e.g.
dibenzoyl methane) that have been used as
co-stabilisers, e.g. with Zn/Ca antioxidant systems to
delay early colour formation, are thought to act also
through a ZnCl catalysed substitution reaction,
2
C-alkylation (Scheme 21, reaction e). Since this reac-
tion also results in the production of HCl, b-diketones
must be used in the presence of an eVective HCl
acceptor. Overall, therefore, the synergistic eVects
related to the strong catalytic action of, for example,
ZnCl , in HCl elimination from PVC have been
2
shown to be either due to limiting the accumulation
of ZnCl (or CdCl ) through the exchange reaction
2 2
Scheme 21 Mechanism of organic phosphites,
epoxidised soya bean oil, and b-
diketones as PVC antioxidants
Oxidative degradation and stabilisation of polymers 177
with Ca (or Ba) carboxylate, through direct consump-
tion by co-stabilisers (e.g. epoxy or phosphites), or by
moderation of the catalytic power by complexation
with various co-synergists.92
Both dialkyl tin maleates and thioglycollates (e.g.
AO36, Table 3) also function by eliminating HCl in
an exchange reaction similar to that of the metal
carboxylates; it diVers only in that the tin alkyl
chlorides formed do not exert a destabilising
eVect.40,90,91 In addition, the maleates function
by removing the unsaturation and limiting colour
development, whereas the thioglycollates have an
additional peroxidolytic function (see Scheme 22
below). Lead based stabilisers are among the oldest
group of thermal stabilisers for PVC. However, due
to toxicological and eco-toxicological problems, the
level of their use in PVC stabilisation will be drasti-
cally curtailed, and may be phased out altogether,
with future trends centred more on the use of
improved metal soap combinations (e.g. Ca/Zn) and
metal-free organic based stabiliser systems.
Stabilisation in-service: long term thermal
stability
Hindered phenols and aromatic amines (CB-D) are
highly eVective inhibitors of peroxyl (ROO· ) radicals,
the predominant propagating species under long term
thermal conditions, and are used as antioxidants for
long term thermal stability of polymers. In practice,
however, these CB-D antioxidants are used in combi-
nation with peroxide decomposers, such as phosphite
esters (see Table 5), to ensure eVective long term
stability at high service temperatures ( below the
softening point of the polymer).12
Many sulphur containing peroxidolytic (PD) anti-
oxidants, especially the metal dithiolates, are very
eVective long term thermal stabilisers, as well as melt
and photoantioxidants74,77,78 (see below). The eVec-
tiveness of dithiolate antioxidants, within any one
series depends strongly on their solubility in the
polymer. For example, in the case of nickel dialkyl
dithiophosphate (NiDRP, AO23, Table 3) series, the
lower molecular mass members of the series are less
soluble and less eVective than the higher members
(see Fig. 4 for PP);94 the zinc dialkyl dithiocarbamate
(ZnDRC, AO21) series too show similar behaviour.
Long term thermal stabilisation of PVC is normally
achieved by the same antioxidants used for melt
stabilisation. Thiotin stabilisers (e.g. AO36) were
shown to be more eVective thermal antioxidants than
the more traditional dialkyl tin maleates (e.g. AO35,
Table 3), and result in the drastic reduction, even
disappearance, of both the unsaturation and per-
oxides from the polymer which is generally attributed
to the peroxidolytic activity of sulphur.40 The acidic
species (peroxidolytic antioxidants) are formed by
reaction of thiotin with hydroperoxide (see Scheme 22,
reactions a–c) in a similar manner to the formation
of sulphur acids from thiodipropionate ester (see
Scheme 14). Moreover, reaction with HCl, liberated
in PVC, results in the formation of thioglycolic ester
(Scheme 22, reaction d ), which adds ( by Kharash
addition) to the developing monomeric unsaturation
International Materials Reviews 2003 Vol. 48 No. 3
178 Al–Malaika Oxidative degradation and stabilisation of polymers

Scheme 22 Stabilisation mechanism of thiotin

stabilisers for long term thermal
stability of PVC

including nickel complexes, and sterically hindered

4 Effect of length of R-group in NiDRP [0·4%] on
thermoxidative stability of polypropylene (PP)
at 140°C
(formed by HCl elimination) thus removing sensitising
allylic methylene groups (see Scheme 22, reaction e);
the monosulphides formed are themselves eVective
thermal antioxidants.
Stabilisation during outdoor exposure to
sunlight
As with thermal stabilisers, photostabilisers must
satisfy basic chemical and physical requirements (see
‘Factors aVecting practical use of antioxidants’ above).
In addition, they must be photostable, i.e. stable to
UV light, to withstand continuous periods of UV
exposure without being prematurely destroyed or
eVectively transformed into sensitising products.
There are essentially three classes of compounds that
are categorised as photostabilisers/photoantioxidants:
UV absorbers and pigments, peroxide decomposers
amine light stabilisers.
UV absorbers and pigments
Most of the UV absorbers (UVA) used commercially
fall into two main classes of compounds, the
2-hydroxybenzophenones (e.g. AO28, Table 3), and
the 2-hydroxybenzotriazoles (e.g. AO29–AO32,
Table 3), with the 2-hydroxy group being essential for
their activity.95 These UVAs operate by additional
mechanisms too, for example, by removing initiating
radicals (e.g. alkoxyl radicals) in a weak chain break-
ing donor (CB-D) mechanism (see Scheme 23).96 UV
absorbers, such as AO28, also synergise eVectively
with peroxide decomposers, e.g. metal dithiolates (see
Table 9 below).
UV screening pigments have been used extensively
to protect polymers against the harmful eVect of UV
radiation. Carbon black gives extraordinary stabilis-
ation because it is a highly eYcient UVA. However,
like other UVAs, carbon black has additional photo-
antioxidant activities associated with its chemical
structure.97 Carbon black has a highly condensed
aromatic ring structure with small amounts of phe-
nolic, ketonic, carboxyl functions, and a relatively
high concentration of ‘oxyl’ radicals which are stabil-

Table 5 Long term thermal stabilisation of different polymers* in draft air oven†12
EMT, EBt50 , TS t50 , EBt50 , EB t50 ,
days at days at days at days at days at
Formulation 120°C 100°C 120°C 120°C 160°C
PP (tape; 30 mm thick)
Control 1 … … … …
AO5, 0·05% 22 … … … …
AO5, 0·1% 30 … … … …
LLDPE (octene comonomer film; 100 mm thick)
Control … 21 … … …
AO4, 0·03% … 225 … … …
AO5, 0·03% … 400 … … …
PA6.6 (injection moulded at 285°C; 1 mm thick)
Control … … 13 4 …
AO6, 0·5% … … >80 15 …
AO6+AO16, 0·25%+0·25% … … 89 16 …
PBT (injection moulded at 255°C; 1 mm thick)
Control … … … … 3
AO5, 0·25% … … … … 12
AO6+AO16, 0·13%+0·13% … … … … 14
AO2, 0·25% … … … … 15
AO7, 0·25% … … … … 11
AO7+AO16, 0·13%+0·13% … … … … 20
* PP=polypropylene; LLDPE=linear low density polyethylene; PA =polyamide; PBT=polybutylene terephthalate.
† EMT=time to embrittlement; EBt50 =time to 50% retained elongation; TSt50 =time to 50% retained tensile strength.

International Materials Reviews 2003 Vol. 48 No. 3

 Al–Malaika Oxidative degradation and stabilisation of polymers 179

Scheme 24 Simplified mechanism of stabilisation

of nickel dithiophosphate and
thiophosphoryl disulphide
Scheme 23 Chain breaking stabilising activity of
UV absorbers

ised in the conjugated system. These structural fea- MRX, respectively; see AO21–AO24, Table 3), which
tures give carbon black its radical scavenging ability are highly eVective catalytic peroxide decomposers
and CB function. Additionally, carbon black has a (PD-C) and excellent melt stabilisers, are generally
peroxidolytic activity (PD) because of its acidic eVective photoantioxidants.11,74,77,98 Their eVective-
nature. ness is attributed mainly to the much higher UV
stability of dithiolates compared to simple sulphides.
Peroxide decomposers and nickel complexes Both the nature of the metal ion in the dithiolate
The photostability of these antioxidants varies greatly complexes and their concentration play a crucial part
depending on the stability of their transformation in their overall eVectiveness as UV stabilisers.
products to UV light. Simple sulphides, such as the Transition metal complexes containing nickel, cobalt
thiodipropionate esters (e.g. AO19 or AO20, Table 3), and copper are more photostable than zinc- and iron-
which are good melt stabilisers (see ‘Phosphites and containing complexes, and hence are more eVective
sulphur compounds’ above) are unstable to light (see Table 6). Furthermore, the photoantioxidant
because of the facile dissociation of their primary activity of nickel dithiolates is greatly eVected by their
oxidation products to photo-initiating radicals (see solubility in the polymer99 as was shown earlier in
Scheme 14, reaction f ), and are not useful as photosta- their use as thermal stabilisers (see section on
bilisers. Similarly, conventional chain breaking anti- ‘Stabilisation in-service’ above). These peroxide
oxidants, such as hindered phenols which are excellent decomposers also synergise eVectively when used in
melt and long term stabilisers, have only very limited combination with UV absorbers (see Table 6 and also
photostabilising activity due to the photo-pro-oxidant ‘Synergism and antagonism’ below). The primary
eVects of some of their transformation products. oxidation product of metal thiolates, e.g. nickel dialkyl
Metal complexes of dithioic acids, e.g. dithiocarba- dithiophosphate, NiDRP (AO23, Table 3) is the
mates, dithiophosphates, xanthates (MDRC, MDRP, corresponding thiophosphoryl disulphide (DRDS)
which undergoes further oxidation to give diVerent
Table 6 Effect of different metal dithiolates on sulphur acids, the real catalysts for peroxide decom-
photostability (UV EMT*) of PP processed position74,99,100 (Scheme 24).
at 190°C (see Table 3 for structures) Processing history can have a profound eVect on
the photoantioxidant activity of sulphur compounds.
Concentration,
For example, the melt stabiliser, DRDS, formed as
Antioxidant ×10Õ 4 mol/100 g UV EMT, h
the primary oxidation product of NiDRP, is further
Unstabilised PP 0 90 converted to a more eVective photoantioxidant by
ZnDEC 2·5 175 oxidative processing101 (see Scheme 24 and Table 7).
NiDEC 0·25 140 Similar oxidative processing (in the presence of excess
NiDEC 2·5 740
oxygen or added hydroperoxide and with increasing
NiDEC 3 790
NiDEC 10 840
time) results in enhanced photoantioxidant activity
FeDMC 0·25 85 of other sulphur peroxidolytic antioxidants such as
FeDMC 2·5 150 the mercaptothiazolines, RMTZ102 (see Table 7),
FeDMC 5 336 through the intermediacy of the disulphide, DMTZ.
NiOctX 3 700 Further oxidation depletes DMTZ of its sulphur
CoOctX 3 1600 content through the loss of low molecular mass
Chimassorb 81 3 245 sulphur acids. The Žnal photoproducts absorb UV
NiDBP+Chimassorb 81 6 2650 light above 290 nm which, together with the slow
* UV EMT =ultraviolet embrittlement time. liberation of sulphur acids, is the reason for their

Table 7 Effect of oxidative processing on photoantioxidant activity of dibutyl thiophosphoryl disulphide

(DBDS) in PP101,102
UV embrittlement time, h
Processing conditions
in internal mixer, DBDS RMTZ Unstabilised
time at 190°C DBDS +TBH* (R=Eth) PP
Closed mixer, 5 min … 700 … …
Closed mixer, 10 min 250 … 670 90
Open mixer, 10 min 280 … 750 55
Open mixer, 15 min … … 850 …
* Oxidative conditions; TBH is tertiary butyl hydroperoxide.

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180 Al–Malaika Oxidative degradation and stabilisation of polymers

Scheme 25 Regenerative chain breaking

mechanism of hindered amine
stabilisers

improved photostabilising activity with increasing

processing severity.
Hindered amine
SigniŽcant commercial development has been based
on hindered piperidines, known as hindered amine
stabilisers, HAS (see AO25 and AO26, Table 3), which
have been used extensively as photostabilisers in
commercial polymers. The hindered amine stabilisers
are a unique class of photostabilisers that do not
function as UV screens, singlet oxygen or triplet
carbonyl quenchers, or peroxide decomposers. Their
eVectiveness is attributed to their primary transform-
ation product, the corresponding nitroxyl radicals
(>NO· ), which is capable of scavenging alkyl radicals
in competition with oxygen, i.e. an eVective CB-A
antioxidant. Its photostabilising mechanism involves
also the regeneration of the nitroxyl radical from both
the corresponding hydroxylamine (>NOH an eVec-
tive CB-D) and alkylhydroxylamine32,68,72,73,81 (see
Scheme 25). Overall, the photoantioxidant activity of
HAS can be ascribed to a regenerative donor-acceptor
(CB-A/CB-D) antioxidant mechanism involving
>NO · and >NOH (see Table 8 for AO28 and its
derivatives).
Synergism and antagonism
The cooperative interaction between two or more
antioxidants (or antioxidant functions) that enhances
the stabilisation of a polymer by more than the sum
of their individual eVects is referred to as synergism.
Synergism can result from the combined action of
two chemically similar antioxidants ( homosynergism),
Table 8 UV stabilising effect of HAS* based
antioxidants in PP, concentration of each
6× 10Õ 4 mol/100 g
Antioxidant UV EMT, h
AO28, >N–H 750
920
1040
Control, no HAS 90
* HAS =hindered amine stabiliser.
International Materials Reviews 2003 Vol. 48
HAS=hindered amine stabiliser (Tinuvin 770, AO25/
Tinuvin 765, AO26a); PD =peroxide decomposer (Irgafos
168, AO16)
5 Effect of molar composition of mixture of
HAS and PD (total [AO]= 7× 10Õ 3 mol kgÕ 1 ,
in each case) on a extent of synergism and
antagonism during photoxidation of PP104 and
b thermoxidative stability of PP in air oven 106
e.g. two hindered phenols, or from two diVerent
antioxidant functions present in the same stabiliser
molecule (autosynergism), e.g. Irganox 1081 (AO9,
Table 3), or when separate stabiliser molecules that
carry diVerent antioxidant functions are physically
blended in a stabiliser formulation (heterosynergism).
In contrast, two antioxidants may interact antagon-
istically to cause a decrease in the sum of their
individual contributions.85,39
Highly eVective UV stabilising systems can be
achieved by the use of synergistic mixtures of com-
pounds acting by diVerent mechanisms. Table 9 illus-
trates the synergism obtained from combinations of
diVerent metal dithiolates with the UV absorber
Chimassorb 81 (AO28, Table 3) in LDPE. Hindered
phenol antioxidants combined with sulphur contain-
ing compounds exhibit synergism during thermal
stabilisation of polyoleŽns. In contrast, similar combi-
nations of Irganox 1076 (AO4, Table 3) with diVerent
metal dithiolates lead to antagonism during photosta-
bilisation (see Table 9).77,103 This antagonistic behav-
iour has been attributed to sensitisation leading to
photolytic destruction of the dithiolates by oxidation
products of phenols, particularly stilbenequinones.
No. 3
 Al–Malaika Oxidative degradation and stabilisation of polymers 181

Stabilisers that contain two diVerent antioxidant func-
tions (e.g. PD and CB activities) in the same molecule,
such as phenolic sulphides, show much higher molar
intrinsic activity as thermal antioxidants (due to auto-
synergism) than conventional hindered phenols with
only CB activity.85
Hindered amine stabilisers exhibit a complex
behaviour when present in combination with other
antioxidants and stabilisers. As discussed above (see
‘Hindered amines’) these have to be oxidised Žrst to
the corresponding nitroxyl radical before becoming
eVective. Consequently, both CB-D and PD-C anti-
oxidants that remove alkyl peroxyl radicals and
hydroperoxides, respectively, antagonise the UV
stabilising action of this class of compounds, (see
Fig. 5a).104,105 However, since the hindered piperi-
dines themselves are neither melt nor thermal stabil-
isers for polymers, they have to be used with
conventional antioxidants and stabilisers. EVective
synergism in both melt and thermal stabilisation has
been achieved when secondary and tertiary HAS were
used in combination with both aromatic and aliphatic
phosphites; the synergistic optimum depends on the
structure of the phosphite (see Fig. 5b).106 Hindered
amine stabilisers also synergise the action of UV
absorbers, e.g. benzotriazoles, in diVerent polymers
such as PP, PS and ABS.48
Other developments in polymer
stabilisation
The problems of antioxidant loss from polymers in
contact media, especially in human contact appli-
cations, have generally been associated with the use
of traditional low molecular mass antioxidants.
Alternative types of antioxidants have been developed
to address both questions of safety and eYciency.
One of the earliest approaches to address the problem
of physical loss of antioxidants was to develop oligom-
eric and macromolecular antioxidants (both thermal-
and photoantioxidants, e.g. AO5, AO26, Table 3)
which have been shown to oVer superior retention in
polymers, and hence excellent performance under
demanding service conditions, e.g. at elevated temper-
atures in the presence of oils and other solvents.107
Another approach aimed at reducing migration of
antioxidants into hostile contact media is based on
grafting reactive antioxidants onto preformed com-
mercial polymers via any one of various routes: during
vulcanisation, by decomposition of free radical
initiators (peroxides, hydroperoxides, AIBN), by UV-
or c-irradiation of polymer surfaces, by mechanical
scission and during melt processing in the presence
of added initiators. A reactive antioxidant contains
one or more antioxidant functions (the antioxidant
component ) and one or more chemical functions
capable of reacting with polymers (the reactive com-
ponent). The antioxidant moiety can be based on any
of the conventional antioxidant functions discussed
above, while the reactive group can be chosen from
a variety of polymerisable or non-polymerisable func-
tions, e.g. vinyl, allyl, a–b unsaturated acyl or amide
groups (e.g. acryloyl, acrylamide, methacryloyl or
methacrylamide), styrene, isopropenyl, epoxy and
mercaptan.108 The main prerequisite here is that the
reaction leading to chemical attachment of the anti-
oxidant should be achieved without detriment to the
overall polymer properties or the basic processes
involved, e.g. vulcanisation in case of rubbers or melt
processing/fabrication in plastics.
The use of reactive antioxidants during melt pro-
cessing of polymers can give rise to high levels of

Table 9 Synertistic and antagonistic effects on photostability of LDPE processed at 150°C

Photoembrittlement time, h
Concentration, Calculated Ref.
Stabiliser system ×10Õ 4 mol/100 g Observed effect*† no.
Control PP (no AO) … 1000 … 77
ZnDEC 3 1400 … 77
NiDEC 3 1800 … 77
Tinuvin 770 3 2400 … 77
Irganox 1076 3 1750 … 77
NiDBP 2·5 2800 … 103
NiBX 2·5 2500 … 103
CuDIP 2·5 2300 … 103
Chimassorb 81 3 1650 …
Synergistic systems
NiDEC +Chimassorb 81 3+3 … … 77
ZnDEC +Chimassorb 81 3+3 4000 3000 77
NiDBP+Chimassorb 81 2·5+2·5 5500 4500 103
NiBX+Chimassorb 81 2·5+2·5 4900 4200 103
CuDIP+Chimassorb 81 2·5+2·5 5350 4000 103
Antagonistic systems
NiDEC +Irganox 1076 3+3 1580 3550 77
ZnDEC +Irganox 1076 3+3 1250 3150 77
NiDEC +Tinuvin 770 3+3 1850 4200 77
NiDBP+Irganox 1076 2·5+5 … … 103
* Concentration of HOBP in this case was 5×10Õ 4 mol/100 g.
† Per cent synergism ={[(Es ­Ec )­(E1 ­Ec )+(E2 ­Ec )]/(E1 ­Ec +E2 ­Ec )}×100, where Es , Ec , E1 , and E2 are embrittlement time
of synergist, control, antioxidant 1, and antioxidant 2 respectively.

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182 Al–Malaika Oxidative degradation and stabilisation of polymers

grafting of the functional antioxidants on the polymer
backbone by manipulating chemical factors and pro-
cessing parameters.108–113 Table 10, for example, illus-
trates the advantages, especially under extractive
conditions, of using reactive photoantioxidants which
are highly grafted on PP, compared to traditional
non-reactive (non-graftable) analogues.111,114–117 The
grafted HAS photoantioxidant AOTP, for example,
shows superior performance under extractive con-
ditions compared to the commercial HAS, Tinuvin
770 (AO25, Table 3), as it is less readily lost from the
polymer during processing and service. Furthermore,
both grafted HAS antioxidants, e.g. AOTP (mono-
functional ) and AATP (bifunctional ) structures in
Table 10, synergise eVectively when used in combi-
nation with other classes of photostabilisers, e.g. UVA
such as Chimassorb 81 (AO28, Table 3). A graftable
UVA based on a hydroxybenzophenone structure,
HAEB, is also shown to give eVective synergism in
combination with a highly grafted hindered phenol,
DBBA, when the grafting of the latter was conducted
in the presence of a reactive non-antioxidant
comonomer, Tris (see Table 10 for structure). The
cografting of this polyfunctional comonomer (Tris)
with monovinyl antioxidants (and other monofunc-
tional additives) in extruders or internal mixers has
been shown109 to lead to the production of highly
grafted antioxidants in non-cross-linked polymer
products without detriment to the physical and mor-
phological characteristics (e.g. crystallinity) of the
polymer. Highly grafted and ‘permanently Žxed’ anti-
oxidant concentrates (masterbatches) can be produced
for blending with, and dilution in, polymers in the
same way as conventional antioxidants.
A more recent development to address safety issues,
has been based on a stabilisation strategy that exploits
the use of a fat soluble biological antioxidant (vitamin
E). The most bioactive form of vitamin E, a-tocoph-
erol (AO10, Table 3), is a highly eYcient biological
chain breaking antioxidant which is known to be
involved in the natural defence mechanisms of living
organisms.118 Studies on vitamin E in polymers have
demonstrated its high antioxidancy in diVerent poly-
mers, especially as a melt processing stabiliser in
polyoleŽns.86,119–125 Figure 6 shows the superior per-
formance of vitamin E when compared to Irganox
1010 during melt extrusion of PP, in particular at
very low concentrations. Vitamin E can, therefore, be
employed cost eVectively to stabilise polyoleŽns using
only a small fraction of the concentration needed of
typical synthetic hindered phenols. Its eVectiveness is
attributed to its eYcient deactivation of macroradicals
and to its oxidative transformation products which
are themselves highly eVective melt stabilisers.86
In general, sterically hindered phenols contribute
to some discolouration (yellowing) of polyoleŽns
mainly through the formation of coloured oxidation
products, e.g. quinonoid structures, and interactions
with catalyst residues.126 The use of a small concen-
tration of the phosphite Ultranox U626 (AO18,
Table 3) with vitamin E results in drastic reduction
in discolouration, as well as an increase in the level
of retention of the parent vitamin (see Fig. 7).86 The
reduction in consumption of other synthetic hindered

Table 10 UV embrittlement times (UV EMT) of PP films containing different grafted (g) reactive
antioxidants when used alone and in combination with other stabilisers: extraction in
dichloromethane
UV EMT, h
Composition without and Conc. in Before After
Antioxidant structure with grafted AO PPfilm,% extraction extraction

AOTP-g 0.4 … 1200

AOTP-g+Chimassorb 81 (AO28) 0.4+0.2 3000 …

AATP-g 0.4 1850 …

AOTP-g+Chimassorb 81 (AO28) 0.4+0.1 2050 …

HAEB 0.3 330 70

DBBA 0.2 205 80

(HAEB-g+DBBA-g)Tris 0.2+0.2 1160 1130

BPM-g 0.1 2850 1400

Irganox 1010+Chimassorb 81 AO5+AO28 0.2+0.2 1750 70

Chimassorb 81 AO28 0.4 330 110
Tinuvin 770 AO25 0.4 1500 130
(CH2 CHCOOCH2 )3 CCH2 CH3 Tris … … …

International Materials Reviews 2003 Vol. 48 No. 3

 Al–Malaika
6 Melt stabilising performance of vitamin E
(a-tocopherol) and Irganox 1010 (AO5) in PP
phenol antioxidants by phosphite co-stabilisers has
been reported though the mechanism is not fully
understood.127,128 In the case of the hindered aryl
phosphite Ultranox U626 used in combination with
tocopherol, the evidence86 points to the regeneration
of the parent tocopherol through a redox reaction
between products of the two stabilisers. Scheme 26
illustrates this and shows that the phenoxyl radical
produced through the CB activity of Ultranox U626
undergoes a C–C coupling reaction to produce a
hindered phenol dimer (A) which can react further
with the tocopheroxyl radical in a redox process that
regenerates the parent hindered phenol.86
Conclusion
Stabilisers and antioxidants are essential ingredients
in almost all plastics formulations. Hydroperoxides
are key initiators of oxidative degradation resulting
in free radical formation in polymers. Antioxidants
are used to prevent the formation of hydroperoxides
and/or to convert them into harmless chemicals (per-
oxidolytic antioxidants), or to deactivate the free
7 Effect of phosphite concentration [Ultranox
U626] in combinations containing 300 ppm
tocopherol on colour stability of PP and extent
of tocopherol retention: PP extruded at 260°C86
Oxidative degradation and stabilisation of polymers 183
Scheme 26 Cooperative interactions between
aromatic phosphite and tocopherol
(vitamin E) resulting in regeneration
of vitamin
radicals, e.g. alkyl and alkylperoxyl, formed (chain
breaking antioxidants).
Stabilisers are chosen for target applications on the
basis of chemical, physical and toxicological, as well
as economic factors. Stabilisation of polymers during
melt processing, heat aging and outdoor exposure is
normally achieved through the use of synergistic
combinations of well known commercial stabilisers
with complementary antioxidant mechanisms. The
use of chain breaking hindered phenols in combi-
nation with peroxidolytic phosphite antioxidants is
commonly used for melt stabilisation of polymers.
Hindered amine stabilisers, in the presence or absence
of UV absorbers, oVer a general approach to photo-
stabilisation. The Žnal selection of an antioxidant
package must take into consideration the per-
formance requirements of the end-use polymer article
including appearance, colour, and toxicity. Issues of
eYciency and safety (including migration) of stabi-
lisers has been at the forefront of recent progress
made in the areas of macromolecular, reactive and
biological antioxidants. Further progress will almost
certainly involve optimisation and Žne tuning of the
physical and chemical performance of the wide range
of commercially available antioxidants and stabilisers.
References
1. c. moureu and c. dufraisse: Bull. Soc. Chim., 1922, 31,
(4), 1152.
2. c. dufraisse: Rubber Chem. T echnol., 1933, 6, 157.
3. c. moureu and c. dufraisse: Chem. Rev., 1926–1927, 3, 113.
4. g. scott: ‘Atmospheric oxidation and antioxidants’; 1965,
London, Elsevier.
International Materials Reviews 2003 Vol. 48 No. 3
184 Al–Malaika Oxidative degradation and stabilisation of polymers
5. s. al-malaika: in ‘History of polymer composites’, (ed.
R. Seymour and R. D. Deanin), 223; 1987, Utrecht, VNU
Science Press.
6. w. l. hawkins: ‘Polymer stabilisation’; 1972, New York, Wiley.
7. j. pospisil and p. klemchuk (eds.): ‘Oxidation inhibition of
organic materials’, Vol. 1; 1990, Boca Raton, CRC Press.
8. n. c. billingham and d. m. wiles (eds.): ‘Polymer stabilisation,
mechanisms and applications’; 1991, London, Elsevier
Applied Science.
9. r. gachter and h. muller (eds.): ‘Plastics additives hand-
book’; 1987, Munich, Hanser.
10. g. scott: in ‘Atmospheric oxidation and antioxidants’,
(ed. G. Scott), Vol. 1, 121; 1993, London/New York, Elsevier
Applied Science.
11. s. al-malaika: in ‘Atmospheric oxidation and antioxidants’,
(ed. G. Scott), Vol. 1, 161; 1993, London/New York, Elsevier
Applied Science.
12. f. gugumus: in ‘Oxidation inhibition of organic materials’,
(ed. J. Pospisil and P. Klemchuk), Vol. 1, 61; 1990, Boca
Raton, CRC Press.
13. j. l. bolland: Q. Rev., 1949, 3, 1.
14. j. l. bolland and g. gee: T rans. Faraday Soc., 1946, 42, 236.
15. l. bateman, Q. Rev., 1954, 8, 147.
16. l. bateman and a. l. morris: T rans. Farad. Soc., 1953, 49, 1026.
17. s. al-malaika: in ‘Atmospheric oxidation and antioxidants’,
(ed. G. Scott), Vol. 1, 45; 1993, London/New York, Elsevier
Applied Science.
18. d. barnard, l. bateman and j. f. smith: in ‘Chemistry and
physics of rubber-like substances’, (ed. L. Bateman), 593; 1963,
London, McClaren.
19. l. reich and r. s. stivala: ‘Autoxidation of hydrocarbons
and polyoleŽns’, Vol. 1; 1969, New York, Marcel Dekker.
20. n. c. billingham: in ‘Oxidation inhibition of organic mater-
ials’, (ed. J. Pospisil and P. Klemchuk), Vol. 2, 249; 1990, Boca
Raton, CRC Press.
21. n. c. billingham: in ‘Atmospheric oxidation and anti-
oxidants’, (ed. G. Scott), Vol. 2, 219; 1993, London/New York,
Elsevier Applied Science.
22. j. g. calvert and n. j. pitt: ‘Photochemistry’; 1966, New
York, Wiley.
23. j. a. howard: Adv. Free Radical Chem., 1972, 4, 49.
24. j. a. howard and k. u. ingold: Can. J. Chem., 1967, 45,
783, 789.
25. j. a. howard, k. adamic and k. u. ingold: Can. J. Chem.,
1969, 47, 3793, 3803.
26. m. iring and f. tudos: Prog. Polym. Sci., 1990, 15, 217.
27. h. hinsken, s. moss, j.-r. pauquet and h. zweifel: Polym.
Degradation Stab., 1991, 34, 279.
28. s. s. stivala, j. kimura and s. m. gabbay: in ‘Degradation and
stabilisation of polyoleŽns’, (ed. N. S. Allen), 63; 1983, London,
Applied Science.
29. r. t. johnston and e. j. morrison: in ‘Polymer durability:
degradation, stabilisation and lifetime prediction’, Advances
in Chemistry Series 249, (ed. R. L. Clough et al.), 651; 1996,
Washington, DC, ACS/OUP-USA.
30. s. al-malaika and x. peng: unpublished work.
31. s. al-malaika and s. issenhuth: unpublished work.
32. s. al-malaika and g. scott: in ‘Degradation and stabilisation
of polyoleŽns’, (ed. N. S. Allen), 283; 1983, London, Applied
Science.
33. s. moss and h. zweifel: Polym. Degradation Stab., 1989, 25, 217.
34. w. o. drake, j. r. pauquet, r. v. todesco and h. zweifel:
Angew. Makromol. Chem., 1990, 176/177, 215.
35. l. dulog and k. h. david: Makromol. Chem., 1971, 145, 67.
36. h. c. beachell and l. h. smiley: J. Polym. Sci., 1967, 5,
(A-1), 1635.
37. g. geuskens, p. bastin, q. lu vinh and m. rens: Polym.
Degradation Stab., 1980–1981, 3, 295.
38. g. scott: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 1, 309; 1979, London, Applied Science.
39. g. scott: in ‘Atmospheric oxidation and antioxidants’, (ed.
G. Scott), Vol. 2, 141; 1993, London/New York, Elsevier
Applied Science.
40. b. b. cooray and g. scott: in ‘Developments in polymer
stabilisation’, (ed. G. Scott), Vol. 2, 53; 1980, London,
Applied Science.
41. a. guyot: J. V inyl T echnol., 1985, 7, 92.
42. a. michel: J. V inyl T echnol., 1985, 7, 77.
43. b. f. sagar: J. Chem. Soc. B, 1967, 428, 1047.
International Materials Reviews 2003 Vol. 48 No. 3
44. a. casale and r. s. porter: ‘Polymer stress reactions’, Vol. 1,
69; 1979, London/NewYork, Academic Press.
45. a. casale and r. s. porter: ‘Polymer stress reactions’, Vol. 2,
370; 1979, London/NewYork, Academic Press.
46. g. scott: in ‘Atmospheric oxidation and antioxidants’, (ed.
G. Scott), Vol. 2, 385; 1993, London/New York, Elsevier
Applied Science.
47. s. al-malaika and g. scott: Polym. Degradation Stab., 1983,
5, 415.
48. f. gugumus: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 1, 261; 1979, London, Applied Science.
49. d. j. carlsson and d. m. wiles: J. Macromol. Sci. Rev.
Macromol. Chem., 1976, C14, (1 ), 65.
50. f. gugumus: in ‘Oxidation inhibition of organic materials’,
(ed. J. Pospisil and P. Klemchuk), Vol. 2, 29; 1990, Boca
Raton, CRC Press.
51. a. davis and d. sims: ‘Weathering of polymers’, 137; 1983,
London, Applied Science.
52. h. h. g. jellinek (ed.): ‘Photochemistry of air pollution; 1961,
New York, Academic Press.
53. d. j. carlsson and d. m. wiles: Macromolecules, 1976, 9, 695.
54. g. scott: Pure Appl. Chem., 1980, 52, 365.
55. w. l. hawkins: in ‘Polymer stabilisation’, (ed. W. L. Hawkins),
9; 1972, New York, Wiley.
56. g. ayrey, b. c. head and r. c. poller: J. Polym. Sci., Macromol
Rev., 1974, 8, 1.
57. h. o. wirth and h. andreas: Pure Appl. Chem., 1977, 49, 627.
58. l. tang, d. sallet and j. lemair: Macromolecules, 1985,
18, 1771.
59. l. tang, d. sallet and j. lemair: Macromolecules, 1986,
19, 579.
60. j. lemair, j. l. gardette, a. rivaton and a. roger: Polym.
Degradation Stab., 1986, 15, 1.
61. a. rivaton: Polym. Degradation Stab., 1993, 41, 283.
62. m. day and d. m. wiles: J. Appl. Polym. Sci., 1972, 16, 175.
63. a. factor, w. v. ligon and r. j. may: Macromolecules, 1987,
20, 2462.
64. d. horsey: Proc. Int. Conf. on ‘Additives 96’, Houston, TX,
Feb. 1996, Executive Conference Management.
65. p. nesvadba: Proc. Int. Conf. on ‘Additives 97’, New Orleans,
LA, Feb. 1997, Executive Conference Management.
66. h. zweifel: ‘Stabilisation of polymeric materials’, 53; 1998,
Berlin, Springer.
67. t. j. henman: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 1, 39; 1979, London, Applied Science.
68. g. scott: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 7, 65; 1984, London, Elsevier Applied Science.
69. e. t. denisov: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 3, 1; 1980, London, Applied Science.
70. v. ya shlyapintokh and v. b. ivanov: in ‘Developments in
polymer stabilisation’, (ed. G. Scott), Vol. 5, 41; 1982, London,
Applied Science.
71. h. berger, t. a. b. m. bolsman and d. m. brouwer: in
‘Developments in polymer stabilisation’, (ed. G. Scott), Vol. 6,
1; 1983, London, Applied Science.
72. s. al-malaika, e. o. omikorede and g. scott: J. Appl. Polym.
Sci., 1987, 33, 703.
73. d. j. carlsson, a. graton and d. m. wiles: in ‘Developments
in polymer stabilisation’, (ed. G. Scott), Vol. 1, 219; 1979,
London, Applied Science.
74. s. al-malaika: in Mechanisms of polymer degradation and
stabilisation’, (ed. G. Scott), 61; 1990, New York, Elsevier
Science.
75. k. schwetlick: in Mechanisms of polymer degradation and
stabilisation’, (ed. G. Scott), 23; 1990, New York, Elsevier
Science.
76. k schwetlick and w. d. habicher: in ‘Polymer durability:
degradation, stabilisation and lifetime prediction’, Advances
in Chemistry Series 249, (R. L. Clough et al.), 349; 1996,
Washington, DC, ACS/OUP-USA.
77. s. al-malaika, k. b. chakraborty and g. scott: in
‘Developments in polymer stabilisation’, (ed. G. Scott), Vol. 6,
73; 1983, London, Applied Science.
78. j. r. shelton: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 4, 23; 1981, London, Applied Science.
79. z. osawa: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 7, 193; 1984, London, Elsevier Applied Science.
80. m. g. chan: in ‘Oxidation inhibition of organic materials’, (ed.
J. Pospisil and P. Klemchuk), Vol. 1, 225; 1990, Boca Raton,
CRC Press.
 Al–Malaika
81. f. gugumus: in ‘Plastics additives handbook’, 2nd edn, (ed.
R. Gachter and H. Muller), 128; 1987, Munich, Hanser.
82. n. c. billingham and p. d. calvert: in ‘Developments in
polymer degradation’, (ed. N. Grassie), Vol. 3, 139; 1980,
London, Applied Science.
83. j. pospisil: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 1, 1; 1979, London, Applied Science.
84. j. pospisil: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 7, 1; 1984, London, Elsevier Applied Science.
85. s. al-malaika and g. scott: in ‘Degradation and stabilisation
of polyoleŽns’, (ed. N. S. Allen), 247; 1983, London, Applied
Science.
86. s. al-malaika, c. goodwin, s. issenhuth and d. burdick:
Polym. Degradation Stab., 1999, 64, 145.
87. a. f. bickel and e. c. kooyman: J. Chem. Soc., 1956, 2218.
88. p. p. klemchuk and p. l. horng: Polym. Degradation Stab.,
1991, 34, 333.
89. s. yachigo, k. ida, m. saski, k. inoue and s. tanaka: Polym.
Degradation Stab., 1993, 39, 317.
90. h. andreas: in ‘Plastics additives handbook’, 2nd edn, (ed.
R. Gachter and H. Muller), 193; 1987, Munich, Hanser.
91. g. ayrey and r. c. poller: in ‘Developments in polymer
stabilisation’, (ed. G. Scott), Vol. 2, 1; 1980, London, Applied
Science.
92. a. guyot and a. michel: in ‘Developments in polymer stabilis-
ation’, (ed. G. Scott), Vol. 2, 89; 1980, London, Applied
Science..
93. d. balkose, h. i. gokcel and s. e. goktepe: Eur. Polym. J.,
2001, 37, 1191.
94. s. al-malaika, m. coker and g. scott: unpublished work.
95. j. f. rabek: in ‘Mechanisms of photophysical processes and
photochemical reactions’, 594; 1987, New York, Wiley.
96. p. vink: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 3, 117; 1980, London, Applied Science.
97. w. l. hawkins: in ‘Encyclopedia of polymer science and
technology’, 2nd edn, (ed. H. F. Mark and J. I. Kroschwitz),
539; 1989, New York, Wiley.
98. t. colclough and j. i. cunneen: J. Chem. Soc., 1964, 4790.
99. s. al-malaika, p. desai and g. scott: Plastic. Rubber Process.
Appl., 1985, 5, 15; s. al-malaika and g. scott: Eur. Polym.
J., 1980, 16, 503 and 1983, 19, 241.
100. s. al-malaika and g. scott: Polymer, 1982, 23, 1711.
101. s. al-malaika, m. coker and g. scott: Polym. Degradation
Stab., 1985, 10, 173.
102. s. al-malaika, k. b. chakraborty, g. scott and z. b. tao:
Polym. Degradation Stab., 1985, 10, 55.
103. s. al-malaika: in ‘Comprehensive polymer science’, (ed. G. C.
Eastmond et al.), Vol. 6, 539; 1989, New York, Pergamon.
104. i. bauer, w. d. habicher, s. korner and s. al-malaika:
Polym. Degradation Stab., 1997, 55, 217.
105. f. tudos, g. balint and t. kelen: in ‘Developments in polymer
stabilisation’, (ed. G. Scott), Vol. 6, 121; 1983, London,
Applied Science.
Oxidative degradation and stabilisation of polymers 185
106. i. bauer, w. d. habicher, c. rauteneberg and s. al-malaika:
Polym. Degradation Stab., 1995, 48, 427.
107. j. sedlar: in ‘Oxidation inhibition of organic materials’, (ed.
J. Pospisil and P. Klemchuk), Vol. 2, 1; 1990, Boca Raton,
CRC Press.
108. s. al-malaika: in ‘Reactive modiŽers in polymers’, (ed.
S. Al-Malaika), 266; 1997, London, Blackie Academic
Professional.
109. s. al-malaika: in ‘Chemistry and technology of polymer
additives’, (ed. S. Al-Malaika et al.), 1; 1999, Oxford,
Blackwell Science.
110. d. munteanu: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 8, 179; 1987, London, Applied Science.
111. g. scott and s. al-malaika: ‘ModiŽed polymers’, US Patent
5,382,633, Jan. 1995.
112. g. scott, s. al-malaika and a. ibrahim: ‘Bound antioxidant
masterbatches’, US Patent 4,959,410, Sept. 1990.
113. g. scott: in ‘Developments in polymer stabilisation’, (ed.
G. Scott), Vol. 8, 209; 1987, London, Applied Science.
114. s. al-malaika, g. scott and b. wirjosentono: Polym.
Degradation Stab., 1993, 40, 233.
115. s. al-malaika and n. suharty: Polym. Degradation Stab.,
1995, 49, 77.
116. s. al-malaika, a. q. ibrahim, j. rao and g. scott: J. Appl.
Polym. Sci., 1992, 44, 1287.
117. s. al-malaika, a. q. ibrahim and g. scott: Polym. Degradation
Stab., 1988, 22, 233.
118. g. w. burton, a. joyce and k. u. ingold: L ancet, 1982,
(ii), 327.
119. s. al-malaika, h. ashley and s. issenhuth: J. Polym. Sci.,
Part A: Polym. Chem., 1994, 32, 3099.
120. s. al-malaika and s. issenhuth: in ‘Polymer durability:
degradation, stabilisation and lifetime prediction’, Advances
in Chemistry Series 249, (ed. R. L. Clough et al.), 425; 1996,
Washington, DC, ACS/OUP-USA.
121. s. al-malaika and s. issenhuth: Polym. Degradation Stab.,
1999, 65, 143.
122. s. al-malaika and s. issenhuth: Polymer, 2001, 42, 2915.
123. s. al-malaika: Polym. Polym. Compos., 2000, 8, 537.
124. j. ghosh: Proc. Conf. Additives ‘99, San Francisco, CA, Mar.
1999, Executive Conference Management, paper 2.
125. s. f. laermer and f. nabhulz: Plast. Rubber Process. Appl.,
1990, 14, 235.
126. j. e. kresta and j. majer: J. Appl. Polym. Sci., 1969, 13, 1859.
127. w. o. drake, j. r. pauquet, r. v. tedesco, and h. zweifel:
Angew. Makromol. Chem., 1990, 176, 215.
128. j. schiers, j. pospisil, m. j. o’connor and s. w. bigger: in
‘Polymer durability: degradation, stabilisation and lifetime
prediction’, Advances in Chemistry Series 249, (ed. R. L.
Clough et al.), chap. 24; 1996, Washington, DC, ACS/OUP-
USA.
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