Polymer Degradation and Stability 39 (1993) 305-308

Evaluation of antioxidant effectiveness in

polyolefins
N. N. Kolesnikova, N. K. Tyuleneva & Yu. A. Shlyapnikov
Institute of Chemical Physics, 117334, Moscow, Russia

(Received 4 March 1992; accepted 14 April 1992)

Antioxidants added to a polymer take part not only in reactions leading to

retardation of the polymer oxidation, but also in many other stages of the
oxidation process, including direct interaction with oxygen. Their effectiveness
in polyolefins can be evaluated by analysing the dependence of oxygen
consumption rate on initial antioxidant concentration.

which are always subjective.

INTRODUCTION
We have recently described a method of
registration of very slow oxygen consumption in
The problem of quantitative evaluation of
the course of the induction period of inhibited
antioxidant effectiveness in a polymer is compli-
oxidation of a polymer? The method makes it
cated and ambiguous. Various antioxidants can
possible to observe the oxidation kinetics in the
differ not only in effectiveness, but also in the
stage during which it was until that time
principles of the oxidation process retardation.
considered that the reaction could not be
Even antioxidants belonging to the same class of
observed; however, it was not possible to
chemical compound can differ markedly in the
separate the parallel processes of oxygen
regularities of their action. 1,2 There may be
consumption in the oxidation of polymer and in
various reasons for these differences. 1,2 This is
the oxidation of the antioxidant (reaction
why the use of the rate constant of only one
A + O2). The observed rate of oxygen consump-
reaction, the chain termination,
tion is
ktl
RO2 + A ~ products (1) Wo~ = Wp + Wa (2)

where Wp is the rate of polymer oxidation and Wa

though proposed by many researchers as a
quantitative criterion of the antioxidant A
effectiveness, 3 is incorrect. 4 The opposite, purely
empirical approach, which consists of studying the
variation of the properties of polymer containing
various concentration of the antioxidant during
its processing and subsequent use, needs too
much time and work and sometimes cannot be
used, for example, when the polymeric materials
are to be used over several decades. There is
therefore a need for methods of evaluation of
antioxidant effectiveness which require a rela-
tively short time and are not dependent on ideas
concerning the mechanism of antioxidant action,
305
is that of antioxidant.
On the other hand, to determine the
antioxidant effectiveness we must know the
dependence of the rate of polymer oxidation Wp
on the antioxidant concentration [A], i.e. find an
unambiguous method of dividing Wo2 into its
components Wp and Wa- The simplest of these
values is the rate of direct antioxidant oxidation
Wa, which may be described by the second-order
law Wa = k~[A][O2]. However, in a polymer at
high antioxidant concentration the rate of such a
simple reaction may differ markedly from simple
second-order kinetics because of the difference in
reactivities of the same antioxidant molecules
306 N. N. Kolesnikova, N. K. Tyuleneva, Yu. A. Shlyapnikov
present in different elements of the polymer
structure, and may be a non-linear function of
the antioxidant concentration. 6
The value of Wp must be a decreasing function
of antioxidant concentration either until this
concentration becomes equal to its solubility in
the polymer or until the upper critical concentra-
tion is reached. 7 In the first case, Wp beginning
from a certain value of [A] will remain constant;
in the second, it will rapidly increase. Thus we
may assume that at relatively small antioxidant
concentrations Wa = ka[A][O2] and consider Wp to
be monotonically decreasing with [A], approach-
ing a certain limit Wmin:
Wo2 = Wmi n + e([A]) + ka[A][O2]
where e([A]) is a decreasing function either
approaching zero or becoming zero at a certain
[A] value. The value of Wmi. will be the
quantitative characteristic of antioxidant
effectiveness.
To show the possibilities of the method and to
reveal the possible difficulties of its application
we investigated the dependence of the oxygen
consumption rate in high-density polyethylene
oxidation on concentration of several anti-
oxidants at 200C and an oxygen pressure of
300 mm Hg.
EXPERIMENTAL
High-density polyethylene (PE), Mw= 108000,
Mw/Mn = 15.4, has been used. Antioxidants were
alkylated phenols: 2,6-di-tert-butylphenol (I),
2,2'- methylene-bis (4- methyl- 6- tert- butylphenol)
(antioxidant 2246) (II), the ester of 3,5-di-tert-
butyl-4-hydroxyphenylpropionic acid and dieth-
ylene glycol (Phenozan-28) (III), and aromatic
amine 4,4'-bis-(cr, te-dimethylbenzyl)diphenyl-
amine produced by Uniroyal Chemical Co.
(Naugard 445) (IV):
{HO C6HE(t-C4Hg)2
--CHECH2COO CH2CH2}20
C6H~--C(CH3)2--C6H4--NH
--C6H4---C(CHa)2--C6H5
The device used for investigation of polymer
oxidation has been described elsewhere.5
The samples of PE containing various anti-
oxidant concentrations were plates 0-1 cm thick,
made by pressing of PE powder at room
temperature, and were oxidized at 200C and an
oxygen pressure of 300mm Hg. The volatile
products (mainly water) were absorbed with solid
KOH.
RESULTS A N D DISCUSSION
Figures 1 and 2 show the kinetic curves of oxygen
consumption during oxidation of PE containing
the various antioxidants studied. Experiments
have shown that antioxidants I and IV, which
contain one active group in the molecule, are
much less effective than II and I11, which each
contain two active groups. We therefore had to
(3)
combine in pairs I and IV, then II and IIl.
The rates of oxygen consumption in the
presence of monophenol I and monoamine IV
remain approximately constant throughout in
most of the induction period, increasing at its end
(Fig. 1). In the presence of biphenols il and III,
the rates change in a more complicated manner,
decreasing in the middle of the induction period
and increasing at its end (Fig. 2).
The curves of initial rate of oxygen consump-
tion vs antioxidant concentration are presented in
Fig. 3 (monophenol and monoamine) and Fig. 4
(biphenols). In all cases, the rate of oxygen
consumption changes, passing through a mini-
mum, but the shapes of the curves Wo2 vs [A] for
the various antioxidants differ markedly. The
curves of Wo2 vs [A] for both biphenols I1 and I!1
possess straight-line asymptotes, i.e. at high
2
0"3 l
)
~0.2
v
E
III t-
8 o.1
c
IV
__ ! I
0 1OO 200
Time (rain)
Fig. 1. Oxygen consumption in the course of PE oxidation
induction period, at 200C and oxygen pressure of 300 mm
Hg, with antioxidants | (1) and IV (2), [A]o = 0.04 tool kg -1.
 Antioxidant effectiveness in polyolefins 307

230~
0.20
2

0'15

A 3
2
E '7
0-10
E -6
E 2
,9
c
0.05
>,,,

I i I
I i
0 5
3O0 800
Time (rain) FA] x 102 (tool kg -1)

Fig. 2. Oxygen consumption in the course of PE oxidation Fig. 4. Initial rate of oxygen consumption as a function of
induction period, at 200C and oxygen pressure of 300 mm initial antioxidant concentration, at 200C and oxygen
Hg, with antioxidants !I (1) and !I! (2), [A]o = pressure of 300 mm Hg, with antioxidants I | (1) and I l l (2).
0.04 mol kg -1.

the ordinate axis at the point x = [ A ] = 0 ,

antioxidant concentrations when e ( [ A ] ) ~ 0, eqn
(2) becomes
W o 2 = Wmin -~- ka[m][o2]
Thus in the simplest case, when the ex-
perimental curve of Wo2 vs [A] possesses a
straight-line asymptote, this asymptote intersects
230
15
) 1
lO
E ing increased reactivity increases. 6 Although
I I | I
0 10
FA] x 102 (mol kg -1)
Fig. 3. Initial rate of oxygen consumption as a function of
initial antioxidant concentration, at 200C and oxygen
pressure of 300 mm Hg, with antioxidants ! (1) and IV (2).
y = Wmin, i.e. the minimal value of the oxidation
rate in the presence of this antioxidant. These
values are 0 . 7 x 1 0 - 6 m o l k g - l s -1 for II and
(4) 1.4 x 10 - 6 mol kg -1 s -1 for !II.
For antioxidants ! and IV, the situation is more
complicated. The minima of the oxidation rates
in the presence of these antioxidant occur at
greater antioxidant concentrations than in the
presence of II and lll, and minimal values of the
oxidation rate are several times greater. As a
result, all of the curves are shifted to the region
of greater rates and antioxidant concentrations.
After passing through a minimum, the PE
oxidation rate increases non-linearly with anti-
oxidant concentration; this dependence may be
explained as the result of specific features of the
reaction in the presence of m o n o p h e n o P or by
physical effects: with increasing antioxidant
concentration the ratio of its molecules possess-
these effects make deciphering of the experimen-
tal dependence of Wo2 on [A] difficult, the
uncertainty is not too great, and by extrapolating
experimental values of Wo2 to [A] = 0 we may
calculate fairly definite values of Wmi, equal to
20
4 x 10 - 6 mol kg -~ s -1 for l and 5x
10 - 6 mol kg -~ s -~ for IV.
The m e t h o d proposed also gives additional
information: the values of induction periods, i.e.
308 N. N. Kolesnikova, N. K. Tyuleneva, Yu. A. Shlyapnikov
of the period of antioxidant action. As seen from
Figs 1 and 2, these periods at the same reaction
conditions (200C and oxygen pressure of
300 m m Hg) and the same antioxidant concentra-
tion [ A ] 0 = 0 . 0 4 m o l k g -1 are 65, 600, 660 and
160rain respectively for I, il, IIl and IV.
Although there is no unambiguous connection
between minimal oxidation rate and induction
period, we see that the more effective anti-
oxidants II and If! ensure the longest induction
periods (600 and 660 min), whereas the weaker
antioxidants ! and IV give relatively short ones
(25 and 160 min). On the other hand, it can be
seen that duration of the induction period is
too rough a characteristic of antioxidant
effectiveness. Undoubtedly, after selection of the
best antioxidant using any m e t h o d based on
kinetic data, other characteristics of the corn-
pound and its effect on the polymer properties
must also be determined.
REFERENCES
1. Shlyapnikov, Yu. A., Kinet. Katal., 7,3 (1982) 1018.
2. Shlyapnikov, Yu. A., Kiryushkin, S. G. & Mar'in, A. P.,
Antioxidative Polymer Stabilization. Khimiya, Moscow,
1987.
3. Denisov, E. T., Usp. Khim., 42 (1973) 361.
4. Shlyapnikov, Yu. A., Usp. Khim., 50 (1981) 1105; Russ.
Chem. Rev., 50 (1981) 581.
5. Tyuleneva, N. K., Kiryushkin, S. G. & Shlyapnikov, Yu.
A., Dokl. Akad. Nauk SSSR, 279 (1984) 145;
Shlyapnikov, Yu. A., Kiryushkin, S. G., Tyuleneva, N.
K., Iring, M. & Fodor, Zs., Polym. Bull., 19 (1988) 449.
6. Kolesnikova, N. N. & Shlyapnikov, Yu. A., Eur. Polym.
J., 23, (1987) 633.
7. Shlyapnikov, Yu. A., Pure & Appl. Chem., 52 (1980)
337.