Polymer Degradation and Stability 48 (1995) 315-324

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Initiation processes in polymer degradation

Gerald Scott
Aston University, Birmingham 84 7ET, UK

(Received 2 March 1995: accepted 2 April 1995)

Thermal degradation of vinyl polymers often occurs by a free radical

propagation process and thermooxidative degradation almost always does. The
nature of the initiation process, particularly in commercial polymers, is not
well understood and is normally considered to be be due either to homolysis of
the weakest C-C or C-H bond in the molecule or to the direct reaction of
oxygen with the polymer to give free radicals. In practice neither of these is
likely under conditions to which polymers are subjected during manufacture
and use and the evidence suggests that mechanochemical scission of the
polymer chain to macroalkyl radicals is the primary initiating process leading
to the formation of hydroperoxides which are the cause of subsequent
degradation.
It is shown that alkyl radical traps effectively remove macroalkyl radicals
during processing, thus delaying mechanooxidation. The nitroxyl radicals
formed also contribute to subsequent environmental stabilisation of elastomers
and thermoplastic polymers.

1 INITIATION OF POLYMER (3) on thermodynamic grounds:

DEGRADATION

PH:P.+H. (3)
Many papers concerned with the thermal
degradation of polymers by a free radical
However, in saturated polymers neither of
mechanism describe the initiation step by eqn
these reactions normally occur at an appreciable
(1): rate below 300°C and so cannot account for the
PH+X.+P. +XH (1) degradation that is frequently observed during
the processing of polymers.
where PH is a hydrocarbon polymer and X - is a A potential initiating process for oxidative
free radical. degradation is the direct attack of ground-state
The identity and source of X - is rarely oxygen on C-H bonds in the polymer chain;
discussed in detail although it is of crucial
importance in determining whether degradation PH+O,-+P. + .OOH (4)
occurs at all and it is particularly relevant to how
it may be inhibited.
This is known to occur at temperatures above
At a high enough temperature, homblysis of a
500°C and is the basis of oxidative cracking
carbon-carbon bond in the polymer back-bone
processes in the petrochemical industry (e.g.
occurs with the formation of macroradicals,
reaction (5)*).
reaction (2)’
Nevertheless, there is little evidence for this
process at the lower temperatures used in
P-P’>P. +P’* (2) polymer technology even when the molecule
contains allylic methylene groups. More active
This process is normally preferred to reaction forms of oxygen are much more likely candidates
315
316 G. Scott

R. + CH,=CHCH,R’

RCH,CH,CH,R’ + 0, + RCH,tHCH,R’ + .OOH 151

_ -

RCH=CHCH,R’ + H,O,
_ _

for radical generation in unsaturated and Singlet oxygen is very reactive toward olefins
aromatic polymers Thus, singlet oxygen, ‘L&O,, is but unreactive toward alkanes. It may well be
readily formed from ground-state oxygen by involved in the peroxidation of unsaturated
energy transfer from photoexcited states (“Sens*) elastomers under specific conditions (reaction
of many dyestuffs and pigments:” (7))” but is almost certainly unimportant in the
sensitisation of polyolefins:s
Sens* + ‘02 + ‘02 + ‘Sens (6)

/H
v, H2C\ ,OOH
C=CH C-CH
(7)
/ \ / \
-CH, \ CH,- -CH; - CH,.
CH;

Ozone also has the ability to react with olefinic 1.1 The ‘weak-link’ theory
groups at relatively low temperatures but, like
singlet oxygen, it is present in normal atmo-
In-chain peroxides are weak-links in the polymer
spheres to a negligible extent. However, in the
chain and lead to a considerable lowering of the
vicinity of electrical equipment or in industrially
temperature of thermal degradation and this
polluted atmospheres, it may be a major source
accounts for the hardening and cracking of the
of peroxides in polymers (see Scheme 1). A
surface of rubber in an industrial atmosphere. In
variety of peroxidic species are formed in
the stressed state ozone cracking occurs by a
unstressed rubber of which the in-chain ozonides
different mechanism, since the zwitterion and
and polyperoxides are probably the most
associated carbonyl compounds separate with
important.’
much more rapid cracking. In this case,
polyperoxides and hydroperoxides are formed
0 00- ROH OOH
stress I (see Scheme 1). In-chain peroxides are the cause
>czc< + q + _‘r_ l ;+ .t -cm
not only of initial polymer chain scission, but also
1 of susequent chain-initiating alkoxyl radicals.’
I
/ (-c-0-0-)” Another possible source of in-chain peroxides
I
>c /O,C< ALKOXYL
is the co-polymerisation of oxygen during
RADIcALs
\& -
manufacture from monomer. Many monomers
OZONIDE are known to copolymerise with oxygen during
Scheme 1. Reactions of ozone with unsaturated rubbers. vinyl polymerisation’ and in the case of styrene, a
1: 1 copolymer may be formed:

Ph Ph Ph
) CH,=CHPh 1 I Repeat
XCHiHPh + 0: - XCH,CHOO, -_) XCH,CHOOCH,CH. W Copolymer (8)

Only a minute proportion of oxygen is normally stable at temperatures below 100°Cx to give
necessary to destabilise the polymer to further alkoxyl radicals and the subsequent degradation
degradation since many polyperoxides are un- is normally a chain reaction.
 Initiationprocesses in polymer degradation 317

However, peroxides do not need to be in the

polymer back-bone to initiate degradation. They
are formed particularly readily under ambient
conditions in polymers that contain a small
amount of unsaturation or branching such as
polypropylene. Polymers are subjected to stress
and strain during their histories from the
53 /
-3
II O-

\’
Q
h -m2, I
fabrication process through to their ultimate ,-cB2
-a12L 'ctI2OOEi -al; a2 '
disposal. All thermoplastic polymers when
processed in a batch mixer or in a screw extruder h
at elevated temperatures are subject to high Scheme 2. Mechanodegradation of natural rubber.
shear stresses which are related to the polymer
viscosity in the polymer melt.’ This leads to molecule (Scheme 2). The latter process is
random scission of the polymer chains and the accelerated by thiols and disulphides, called
formation of macroalkyl radicals which form ‘peptisers’ by rubber technologists. They appear
alkylperoxyl and hydroperoxides in the presence to act in a redox mode with hydroperoxides;
of even the small amounts of oxygen present in a
POOH+RSH+PO. +H,O+RS. (9)
screw extruder and even more readily in a batch
mixer. Peroxidation causes a very rapid decrease Perhaps not surprisingly in view of the
in molecular weight in many polymers under revolutionary nature of Watson’s proposals, they
normal processing conditions and a proportion of were contested by some polymer scientists who
the peroxides persist in the fabricated product, questioned the reality of the scission of polymer
thus affecting environmental stability.’ Accumu- molecules to give free radicals under these
lating evidence emphasising the importance of conditions. Thus, Aberghini & Sukarnek,” have
mechanical chain scission in polymer degradation argued that the ‘inverse Arrhenius effect’ that is
will be reviewed in the following sections. observed during the mechanooxidation of rub-
bers is due to normal thermooxidative reactions
whose rates have been increased as a result of
2 MECHANODEGRADA~ION OF viscous interactions between the polymer chains
ELASTOMERS leading to localised increase in temperature.
However, subsequent studies by Sohma’” in
2.1 During thermal processing which polyethylene was milled in the solid state
at 77 K showed the initial formation of a primary
The importance of mechanodegradation was macroalkyl radical by ESR even at this
recognised by W.F. Watson in the early 1950~‘~~” temperature. This isomerised to a secondary
during a fundamental study of the technological alkyl radical at 143 K but the initial radical could
process known as ‘mastication’, whose purpose is be trapped by nitroso compounds to give a
to transform the tough resilient material that nitroxyl radical whose hyperfine structure iden-
comes from the rubber tree to a viscous liquid tified the initial alkyl radical. At 200 K peroxyl
product by ‘open milling’ in the presence of radicals are formed which themselves decay at
oxygen or on the industrial scale by shearing in a 313 K with the formation of hydroperoxides
large scale internal mixer. In the absence of (Scheme 3).
oxygen little change in viscosity occurs, but in air, Watson and co-workers’“~‘1,‘4,15were also able
the viscosity drops rapidly due to addition of to demonstrate that macroalkyl radicals formed
oxygen to the macroalkyl radicals (Scheme 2). during mechanodegradation of rubber at higher
Other alkyl radical trapping agents such as rmltion 127K
benzoquinones also stabilise the macroradicals -cB2cB2~2~2- - -af2aQaI2* + -ctr*2-
17x
almost as efficiently as oxygen, but in so doing,
02 ZOOK
they are converted to hydroquinones and
I
subsequently stabilise the polymer to further
oxidative degradation. Oxygen by contrast leads -52=2-
to the formation of hydroperoxides which initiate
the further chain scission of the polymer Scheme 3. Mechanodegradation of polyethylene at 77 K.
318 c. Scott

temperatures were effective initiators for vinyl cis-polyisoprene with methylmethacrylate (reac-
polymerisation forming block copolymers and the tion (10)) was one of the first block copolymers
product formed by high-shear mixing of natural to be marketed as ‘Hevea-plus’.

cn, cu, cn,

I I
P.+CH,=CCOOCH, -WP[-CH?-C- ],CH,C.
-BLOCKCOPOLYMER (10)
I -1
COOCH, COCH,

This same process has also been used to initiate

the addition of thiols to double bonds in
elastomers (see Scheme 4) and results in the I (‘4 II

covalent bonding of antioxidant groups to the P.

polymer through sulphur.” This reaction does /

not occur in the absence of shear.

Ass = Q-NE~NnaJcn,sn IUOA

Numbers in parentbmii M .NO.eoncentmtiona
(Id m0U1oOg)

OH
Scheme 5. Spin trapping of macroalkyl radicals in EPDM at
teu tsu 120°C.
0
:I
cn$?lI
SlimI

amine (NDPA, I). However, it is known that the

corresponding alkyl hydroxylamine (reaction (b)
of Scheme 5) and free hydroxylamine (reaction
(c) of Scheme 5) are co-products of the reactions
of nitroxyls with macroalkyl radicals during the
Scheme 4. Modification of unsaturated polymers by mecha- processing of themoplastic polymers (see below).
nochemically initiated thiol addition.
Moreover, the hydroxylamines III and IV are
quantitatively oxidized to the bis-nitroxyl (V) by
Spin trapping by nitroso compounds and m-chorperbenzoic acid (mCPBA) This provides
nitrones is widely used in biological oxidation a convenient method of assessing the extent of
studies to identify and quantify alkyl radical total trapping of spin traps by the polymer It was
intermediates that are too reactive to identify found that approximately 90% of the NDPA that
directly by ESR. This procedure is equally reacts with the polymer is unextractable by an
applicable to radicals produced in polymer effective solventt and, of this, 67% is in the form
oxidation although, because of the multiplicity of of nitroxyl and 33% as hydroxylamines.
the products formed under these conditions, it is The temperature at which the processing
not normally possible to identify the radical operation is carried out makes little difference to
species involved. We have recently applied this the trapping process or the products formed.
technique to the spin trapping of macroalkyl Other aromatic nitroso compounds behave
radicals during the processing of EPDM at similarly. Thus PMNB (VI) gives -80% of
temperatures between 80 and 140X” Nitroxyl,
II (Scheme 5), was found to be the primary t Acetone (110 cm’)/methanol (42 cm’)/trichloroethane (60
product of the reaction of 4-nitrosodiphenyl- cm’) azeotrope.
 Initiation processes in polymer degradation 319

polymer-bound adduct of which ~25% is nitroxyl and the remainder hydroxylamines.”

N=O N=O

CH,
VI. PMNB
\
h‘I
’
VII. HMNB

CH3
Y OH

2.2 During use effective against fatigue whereas bezoquinone

Rubber products have to withstand a wide range
of conditions during service. For example, the
automotive tyre has to be resistant to thermal
degradation under high speed running conditions
where tyre temperatures can rise to 100°C or
higher. It is also subjected to the effects of
dynamic mechanical stress, particularly during
braking and cornering, and to continuous static
stress for long periods in the presence of
significant concentrations of ozone.
The effects of high temperature and stress has
a much more severe effect on the mechanical
performance of a tyre than the effects of heat
alone and the development of ‘stress cracks’ or
‘fatigue cracks’ in the tyre tread grooves and the
more rapid abrasion of rubber in the presence of
oxygen than in its absence suggested to oxidation
chemists that mechanical stress must play a
significant part in the initiation of oxidation.”
This is supported by the fact that conventional
chain-breaking antioxidants are very effective
‘heat-ageing’ antioxidants but are much less
which is not a thermal antioxidant has antifatigue
activity.” However, the most widely used
‘antidegradants’ in tyres are the secondary
alkylaminodiphenylamines (e.g. IPPD, VIII,
Y=H, Table 1). These have the unique ability to
inhibit thermal oxidation, ozone degradation and
fatigue. It has been shown that ‘activated’
diphenylamines of which IPPD is typical are
converted rapidly to nitroxyl radicals during
fatiguing of rubber”,*” (Scheme 6) and the
nitroxyls themselves are even more effective
antifatigue agents than the parent amines (see
Table 1)).2”~21~22However, under these conditions
diary1 nitroxyls are also partially reduced back to
the parent amine, probably primarily by sulphur
compounds present in the rubber (see Scheme
6).” Although the same oxidation chemistry
occurs with a related piperidinoxyl, XI, this
nitroxyl is a much less effective antifatigue agent,
since the parent hindered amine is not an
effective antioxidant and the nitroxyl is reduced
to the inactive amine by the chemistry described
above.23

Table 1. Antifatigue activity of diarylamines and derived oxidation products”

Antioxidant Code Time to sample break (h)

Y=H Y=O . Y=OH

R,=H, R,=NHiPr VIII 274 337

R,=R,=MeO IX 207 411 56”
R,=R,=rOct X 83 88 107

W-&COO XI 25 30 39

“Insoluble in rubber.
320 G. Scott

chemically attached to the polymer (see Table 2).

The apparent disadvantage of macroradical
formation has in this case been turned to

>n-H _
POO.
,N-0.
h >N-OP
advantage in producing more substantive anti-
oxidants in the fabricated product.
It is important to note that although
intermediate macroalkylamine (NOP, Scheme 6)
may be formed in polyunsaturated rubbers
during fatiguing, it is not the end product of the
[S- 1 reaction. Nitroxyl is regenerated even at ambient
temperatures, at least in part by formation of the
N-W is a substituted diphanylamine c.g.IPPD (see Table 1) NOH, since conjugated unsaturation is formed in
the rubber. Abstraction of a hydrogen /? to a
Scheme 6. Catalytic antifatigue mechanism of diphenylam-
ines. (N-H is a substituted diphenylamine: see Table 1.)
carbon radical is thus facilitated by the presence
of a conjugated double bond in the product:
The essential difference between thermal >NO . + -CH=CHCHCH, - + > NOH
oxidation and fatigue then lies in the nature of
the initiation step. The more rapid formation of + -CH=CHCH=CH- (11)
macroalkyl radicals when the rubber is mechani- However, regeneration of nitroxyl by hydrope-
cally stressed at ambient temperatures predicates roxide and particularly by peracid oxidation is a
the need for a macroalkyl trap (i.e. a CB-A facile reaction and these species are always
antioxidant) in addition to a CB-D antioxidant. present as products of the peroxidation of
In practice the NO - /NOH,NOP combination is elastomers under stress.
a highly effective catalytic antioxidant system
with the ability to deactivate both alkyl and
alkylperoxyl radicals.
3 MECHANODEGRADATION OF
It was noted above that 4-
THERMOPLASTIC POLYMERS
nitrosodiphenylamine (NDPA, I) was partially
converted to macroalkyl nitroxyl and hydroxyla-
3.1 Polyolefins
mine during processing in EPDM. The NDPA
adduct in EPDM made by this procedure was
found to be as effective as IPPD as an antifatigue The polyolefins are much less stable during
agent when used at the same concentration in processing than their formal structures would
natural rubber (see Table 2) and it was suggest. When unstabilised, they begin to
considerably more effective after solvent extrac- degrade in a screw extruder with molar mass
tion. Even 2,3,4,5,6_pentamethyl nitrosobenzene reduction below 200°C with the concomitant
(PMNB, VI) which contains no recognised formation of oxidation products in the polymer.
antioxidant function is moderately effective A convenient way of measuring molar mass
before extraction and as effective as IPPD after changes is by following viscosity change or, more
extraction. The extraction results reflect the fact usually, melt flow index (MFI_F) which is
that both of the nitroso compounds are partially inversely related to it, during processing in an
internal mixer.’
Polypropylene and polyethylene respond quite
Table 2. Antifatigue activity of NR vulcanisates (CSS/S) differently to processing. At 2OO”C,PP shows an
containing polymer-bound spin wlducts”(coot. in each case
1 g/l~ g)
increase in MFI with time (i.e. M, reduction),
whereas, PE shows the opposite behaviour. Gpc
Cycles to break ( x IO-‘) examination of the products similarly shows a
Unextracted Extracted
downward shift of molar mass in the case of PP
and molecular enlargement in the case of
Control 400 345 LDPE.y,24 However, as in the case of cis-PI
NDPA adduct 1150 500
PMNB adduct 860 380
IPPD additive 2200 31.5 1-MFI = the amount of polymer extruded through a
standard orifice in a given time.
 Initiationprocesses in polymer degradation 321

02
/
(P- 1 -fcE2- -&CR- (PE (C=C))

\ t

P' P/ \P
R-N=0 - >Ib
-0. AoR I

PA-O-
XII
CN-A
ANTIoxIDANT
(SEE samm 9)
POOE
PROOXIDANT
(gEBsamlR8)
POON
)+-%k Poo-

RN=@ = PUNS, Etms. NNP, etc.

Scheme 7. Inhibition of thermal degradation of PP by
Where R-N=0 = PRNB, RRNR. RNP, etc.
radical traps.
Scheme 9. Catalytic mechanism of nitroso spin traps in vinyl
polymers during processing.
already discussed, hydroperoxides are also
formed (Scheme 7). converted to the corresponding hydroxylamine
Nitroso compounds are able to compete with (Scheme 9).
oxygen for the initially formed macroalkyl Nitrones, and in particular diphenyl aldonit-
radicals during the processing of polypropylene rone (DPN, XIVa, Scheme 10) and a-phenyl-l\‘-
and thus retard the formation of hydroperoxides tert-butyl aldonitrone (PBN, XIVb, Scheme 10)
and the subsequent polymer degradation reac- have been found, like the nitroso spin traps, to
tions summarised in Schemes 7 and 8. PMNB inhibit MFI change in PP (see Fig. 1) with the
(VI) and HNB (VII) inhibit MFI change almost associated formation of nitroxyl (Scheme 10)
completely over a period of 30 min at 180°C (see
Awn I I
Fig. 1) whereas unstabilised PP becomes
unusable (65% increase in MFI) within 5 min
under the same conditions.25

A.hv
INITIA?ION
73 -
73
-cRzQlo. + .m
-azcaooR
(swscmm67)
_ PO.

-3 p3 PO-/-OR Tg3 p3
-a+!E2cFI- + -Q124y2(9-
PE 008 10 20 30
PN
TINE, qin

I
A,hv
Fig. 1. Change in MFI (AMFI) of polypropylene during
73 y3 processing at 180°C in the presence of nitroso compounds
-cR2lpi2cn- + ali (PMNB, HNB and MNP) and nitrones (PBN and DPN) all
O- at lo-’ mol g-‘.

02
\
P / f
$3
-cR2=0 +
-3
-ct&-
(P- 1 4!cR2~ -c&R- (PN (C=C)l

Scheme 8. Oxidation of polypropylene during processing.

P' 8
+* +*

PMNB completely inhibits the formation of

..Po~,
hydroperoxide over 20 min under the above Foml. etc
_H
conditions whereas in its absence, hydroperoxide Poe* -
increases from zero to 5 x lop5 mol/lOOg in the
same period. It is also a thermal antioxidant in an
air oven at 140°C; its effectiveness reaching a XIV(a), R = R'= Ph DPN
XIV(b), R = Ph. R' = tBu PRN
maximum at longer (15 min) processing times. XXV(c), R = Ph. R' I Ila PRN
This corresponds to the time when the initially Scbeme 10. Catalytic mechanism of nitrone spin traps in
formed nitroxyl reaches a maximum and is then vinyl polymers during processing.
322 G. Scott

structure, have been largely unsuccessful and

even the most likely ‘in-chain’ impurity, XVI,
does not appear to be sufficiently unstable to
account for the very great instability of PVC
during processing.“-“’

Cl
I
CH,CHCH,CHCH,CHCH, -CHCH=CHCH,
5 10 15 20
XV XVI
PROCESSING TIME, min

Fig. 2. Formation
of nitroxyl from spin traps PMNB. DPN Ceresa & Watson” demonstrated in 1959 that
and MNP during processing in polypropylene at 180°C. PVC undergoes macroalkyl radical formation
during milling and that the radicals produced are
which, as in the case of nitroxyls from nitroso capable of initiating vinyl polymerisation.”
compounds, rises to a maximum and then decays Maleic anhydride and maleic esters are able to
slowly (see Fig. 2). DPN is somewhat more react with mechanoradicals to inhibit their
effective than PBN, possibly reflecting the greater subsequent reactions so that no further degrada-
volatility of the latter at processing temperatures. tion occurs.” The products of PVC mechanodeg-
Spin trapped nitroso alkanes (e.g. MNP) are radation during processing all arise from
particularly effective light stabilisers for pol- subsequent reactions of end-chain macroradicals
yolefins and behave in a manner entirely (Scheme 11). Both the thermal elimination of
analogous to that of the hindered HCl and the concomitant formation of hydrope-
piperidinoxyls.*‘-‘” roxides are of crucial importance to subsequent
It is clear from the above that macroalkyl thermal and environmental degradation of
radicals are the primary initiators in the PVC,“’ since the combination of hydrogen
mechanooxidative degradation of PP during high chloride and macromolecular hydroperoxides
shear mixing but that the hydroperoxides formed constitutes a potent radical generating system
from them are the subsequent cause of during processing (see Scheme 11, reaction (8)).
chain-scission under these relatively low tem- The subsequent photostability of PVC has been
perature conditions (see Scheme 8) and during shown to be directly related to the amount of
environmental exposure. Not only do the nitroso hydroperoxide formed at this stage.z’
compounds and nitrones trap the initially formed
macroalkyl radicals but the resulting nitroxyls
also further oxidise macroalkyl radicals in the
polymer (see Schemes 9 and 10) with the
formation of in-chain double bonds. The
hydroxylamine forms, with the cognate nitroxyl.
a catalytic chain-breaking antioxidant system
analogous to that of the hindered piperidinoxyls
previously observed under similar conditions25.‘h
and the mechanism both during processing and
under environmental conditions is entirely 1
(d)
-CH=CHCH=CH2 + Cl. etc
analogous.‘s-2y
(9) F’
HCI + HoocHzcHz- + CI- + H$ + .WHCH2-
3.2 Polyvinylchloride
Scheme 11. Mechanodegradation of PVC.

Many papers have been published on the thermal

degradation of PVC with the object of explaining
the formation of colour (polyconjugated un-
saturation) in the polymer during processing.
Attempts to relate the thermal stability to that of
model compounds (e.g. XV), with similar
Both nitroso and nitrone spin traps effectively
scavenge macsoalkyl radicals in PVC during
processing”4 by the mechanisms already outlined
in Schemes 9 and 10. Figure 3 shows that the
maximum nitroxyl concentration is formed from
 Initiationprocesses in polymer degradation 323

free radicals. However, it is not possible to

6 12 18
Procersing Time , min
Fin. 3. Formation and decav of nitroxvl in PVC containine
M-b during processing at’ 180°C. Ail samples contained
2 X lo-’ mol g- ’ MNP + 7.2 X lo-” mol g-’ DBTM. (From
J. App. Polym. Sci.. 34 (1987) 2673, with permission.)
2-methyl-2-nitrosopropane (MNP, XVII) at very
short times and similar concentrations were
formed from DPN (XIVa) and a-phenyl-N-
methyl nitrone (PMN, XIVc). The formation of
hydroperoxide is markedly reduced in PVC
during processing by a combination of a spin trap
(e.g. MNP or PMN) and a basic HCl scavenger,
DBTM (see below). PMN is a particularly
effective synergist (see Fig. 4) and this combina-
tion is also a photostabilser ‘for PVC.34
The formation of macroalkyl radicals in PVC
during processing is then the primary source of
completely eliminate the formation of either
hydroperoxides or hydrogen choride by means of
alkyl radical traps. Allylic unsaturation is formed
following the initial spin trapping process and is a
potential source of further HCl elimination and
hydroperoxide formation. Consequently, HCl
scavengers and peroxide decomposers effectively
synergise with spin traps. All the most effective
PVC stabilisers are in fact HCl scavengers but
most of them have an additional function For
example the dialkyl tin maleates (e.g. DBTM,
XII, Scheme 12) contains a dienophilic function
24
which interrupts conjugated unsaturation.“” This
is a palliative effect since it has no influence on
the initial radical generating step. The tin
thioglycollates liberate thioglycollic esters on
reaction with HCl (Scheme 13) which, in the
presence of free radicals, readily add to
monoenic unsaturation and in particular vinyl
groups formed at the chain ends This process
removes allylic methylene groups, thus increasing
the oxidative stability of the polymer chain, and
the chemistry has also been used to bind phenolic
antioxidants and light stabilisers containing a
thiol group to PVC during pocessing by the
mechanism outlined in Scheme 4.35

cb 8
*

Scheme l2. Dual role of tin maleates in PVC during

processing.

UC1 / Cl
oct2sn(scs2uJaIct)2 -

+
oct2sn
DOTG ‘scE2couoct

I-
Esai2axloct

I
4 8 12 16 20
Processing Time. min cEl,=aics,~-
octococa2s(o)~
Fig. 4. Formation of peroxides in PVC containing spin traps ~Inu -
MNP and PMN (2 X lo-’ mol g-‘) during processing at
180°C. All samples, including control, contained 2.9 X lo-’
mol g-’ DBTM. (From J. Appl. Polym. Sci., 34 (1987)
‘!?L4Ytn2t3cn2cs
2673.) Scheme 13. Multifunctional role of thioglycollates.
324 G. Scott

However, the tin thioglycollates have yet 6. Lattimer, R.P., Layer, R.W. & Rhee, C.K., In
Atmospheric Oxidation and Antioxidants, Vol. II, ed G.
another function since they, their derived thiols Scott, Elsevier, 1993, Ch. 7.
and thiol adducts to double bonds, are all 7. Lacoste, J., Adam, C., Siampiringue, N. & Lemaire, J..
effective hydroperoxide decomposers and the Eur. Polym. J.. 30 (1994) 433.
8. Scott. G., Atmospheric Oxidation and Antioxidants,
exceptional heat stabilising activity of the Elsevier, 1965, p. 24.
thioglycollates is almost certainly associated with 9. Scott, G. In Atmospheric Oxidation and Antioxidants,
their abilities to scavenge HCl, remove unsatura- Vol. II, ed G. Scott, Elsevier, 1993, Ch. 3.
tion and destroy hydroperoxides in a non-radical 10. Pike. M. & Watson, W.F., J. Polym. Sci., 9 (1952) 229.
11. Watson, W.F., Trans. IRI, 29 (1953) 32.
process.“6 12. Aberghini, D.P. & Sukarnek, P.C.. J. App. Polym. Sci.,
16 (1972) 1701.
13. Sohma, J., In Developments in Polymer Degradation-2,
ed. N. Grassie, App. Sci. Pub., 1979, Ch. 4.
4 CONCLUSIONS 14. Ayrey, G., Moore, C.G. & Watson, W.F.. J. Polym.
Sci., 19 (1956) 1.
15. Ceresa, R.J. & Watson, W.F., J. App. Pol. Sci,, 11
1. The initiating process in many polymer (1959) 101.
degradation reactions involves peroxidic 16. Scott, G. In Atmospheric Oxidation and Antioxidants,
species formed in the polymer during Vol. If, Elsevier, 1993, Ch. 5.
17. Al-Malaika, S., Nooshin, H. & Scott, G., unpublished
manufacture and/or during processing. work.
2. Mechanical scission of the polymer chain to 1X. Scott, G., Atmospheric Oxidation and Antioxidants,
give macroalkyl radicals under conditions of Elsevier, 1965, p. 469. et seq.
19. Katbab. A.A. & Scott. G.. Chem. & fnd., (1980) 573:
high shear during mixing and extrusion is a Eur. Polym. J., 17 (1981) 559.
precursor to hydroperoxide formation. 20. Dweik, H.S. & Scott, G., Rubb. Chem. Tech., 57 (1984)
3. Agents which trap and/or oxidise macro- 735.
alkyl radicals are inhibitors of molar mass 21. Dweik, H.S. & Scott, G., Rubb. Chem. Tech., 57 (1984)
908.
change during polymer processing. 22. Scott. G., Rubb. Chem. Tech., 58 (1985) 269: J. Nat.
4. Nitroxyl radicals and their cognate Rubb. Res., 5 (1990) 163.
hydroxylamines formed during processing 23. Nethsinghe, L.P. & Scott, G., Eur. Polym. J., 20 (1984)
213.
are effective catalytic antioxidants during 24. Gilead, D. & Scott, G. In Developments in Polymer
subsequent service. Stabilisation-5.ed. G. Scott. App. Sci. Pub., 1982, p.
80.
25. Bagheri, R., Chakraborty, K.B. & Scott, G., J. App.
Polym. Sci., 22 (1984) 1573.
ACKNOWLEDGEMENTS 26. Chakraborty, K.B., Scott, G. & Yaghmour, H., J. App.
Polym. Sci., 30 (1985) 189. .
27. Al-Malaika, S., Omikorede. E.O. & Scott, G., Polym.
I am grateful to Dr K.B. Chakraborty and Dr S. Comm.. 27 (1986) 173; J. App. Polym. Sci., 33 (1987)
Al-Malaika for their contributions to the above 703.
28. Scott. G., Macromol. Chem., Macromol. Symp., 27
studies and to Dr H. Nooshin, Dr J. Li and Dr X.
(1989) 1.
Xing for their permission to report previously 29. Scott, G. In Atmospheric Oxidation and Antioxidants,
unpublished work. Vol. II, Elsevier, 1993, Ch. 8.
30. Adeniyi, J.B. & Scott, G., Polym. Deg. Stab., 17 (1987)
117.
31. Ceresa, R.J., Plast. Inst. Trans., 28 (1960) 202.
REFERENCES 32. Scott, G., Li, J. & Xing, X., unpublished work.
33. Cooray, B.B. & Scott, G., Developments in Polymer
Stabilisation-2. ed. G. Scott, App. Sci. Pub., 1980, Ch.
1. Grassie, N. & Scott, G., Polymer Degradation and 7.
Stabilisation, Cambridge University Press, 1985. 34. Adeniyi, J.B., Al-Malaika, S. & Scott, G., J. App.
2. Gray, J.A., J. Chem. Sot., (1953) 741. Chem., 34 (1987) 2673.
3. Rtinby, B. & Rabek. J.F. (eds), Singlet Oxygen, Wiley, 35. Cooray, B.B. & Scott, G., Europ. Polvm. J., 16 (1980)
1978. 1145: 17 (1981) 379.
4. Ng, H.C. & Guillet, J.E., ibid, Ch. 27. 36. Cooray, B.B. & Scott, G., Polym. Deg. Stab., 2 (1980)
5. Scott, G., ibid, Ch. 23. 35.