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 is that of antioxidant.
quantitative criterion of the antioxidant A On the other hand, to determine the
effectiveness, 3 is incorrect. 4 The opposite, purely antioxidant effectiveness we must know the
empirical approach, which consists of studying the dependence of the rate of polymer oxidation Wp
variation of the properties of polymer containing on the antioxidant concentration [A], i.e. find an
various concentration of the antioxidant during unambiguous method of dividing Wo2 into its
its processing and subsequent use, needs too components Wp and Wa- The simplest of these
much time and work and sometimes cannot be values is the rate of direct antioxidant oxidation
used, for example, when the polymeric materials Wa, which may be described by the second-order
are to be used over several decades. There is law Wa = k~[A][O2]. However, in a polymer at
therefore a need for methods of evaluation of high antioxidant concentration the rate of such a
antioxidant effectiveness which require a rela- simple reaction may differ markedly from simple
tively short time and are not dependent on ideas second-order kinetics because of the difference in
concerning the mechanism of antioxidant action, reactivities of the same antioxidant molecules
305

with antioxidants | (1) and IV (2). of antioxidant concentration either until this concentration becomes equal to its solubility in the polymer or until the upper critical concentra. Oxygen consumption in the course of PE oxidation oxidant concentrations were plates 0-1 cm thick. approach. The volatile the antioxidant concentration. Tyuleneva. 7 In the first case.1 C6H~--C(CH3)2--C6H4--NH c --C6H4---C(CHa)2--C6H5 IV The device used for investigation of polymer __ ! I 0 1OO 200 oxidation has been described elsewhere. at high Mw/Mn = 15.6-di-tert-butylphenol (I). The value of Wmi. Experiments concentrations Wa = ka[A][O2] and consider Wp to have shown that antioxidants I and IV. reveal the possible difficulties of its application decreasing in the middle of the induction period we investigated the dependence of the oxygen and increasing at its end (Fig. and aromatic 0"3 l ) amine 4.04 tool kg -1. which be monotonically decreasing with [A]. and may be a non-linear function of oxygen pressure of 300mm Hg. (Fig. consumption rate in high-density polyethylene The curves of initial rate of oxygen consump- oxidation on concentration of several anti. Thus we consumption during oxidation of PE containing may assume that at relatively small antioxidant the various antioxidants studied. Fig. Shlyapnikov present in different elements of the polymer temperature.butylphenol) (antioxidant 2246) (II). possess straight-line asymptotes.6.e. and were oxidized at 200°C and an structure. (biphenols).306 N. 3 (monophenol and monoamine) and Fig. the ester of 3. but the shapes of the curves Wo2 vs [A] for EXPERIMENTAL the various antioxidants differ markedly.tert.5-di-tert- butyl-4-hydroxyphenylpropionic acid and dieth- ylene glycol (Phenozan-28) (III). te-dimethylbenzyl)diphenyl- amine produced by Uniroyal Chemical Co. [A]o = 0. at 200°C and oxygen pressure of 300 mm made by pressing of PE powder at room Hg. it will rapidly increase. K. Figures 1 and 2 show the kinetic curves of oxygen in the second. Antioxidants were alkylated phenols: 2. In the presence of biphenols il and III. where e([A]) is a decreasing function either The rates of oxygen consumption in the approaching zero or becoming zero at a certain presence of monophenol I and monoamine IV [A] value. N. 2). i. tion vs antioxidant concentration are presented in oxidants at 200°C and an oxygen pressure of Fig. passing through a mini- mum. increasing at its end effectiveness. the rate of oxygen consumption changes.methyl. induction period. Kolesnikova. In all cases. N. Wp beginning from a certain value of [A] will remain constant.4. . 1). We therefore had to Wo2 = Wmi n + e([A]) + ka[A][O2] (3) combine in pairs I and IV. A. which each contain two active groups. The curves of Wo2 vs [A] for both biphenols I1 and I!1 High-density polyethylene (PE). 4 300 mm Hg. will be the remain approximately constant throughout in quantitative characteristic of antioxidant most of the induction period. RESULTS A N D DISCUSSION tion is reached.2'.4'-bis-(cr. contain one active group in the molecule. 2 2. Yu.2 (Naugard 445) (IV): v {HO C6HE(t-C4Hg)2 E --CHECH2COO CH2CH2}20 III t- 8 o. 1.methylene-bis (4.5 Time (rain) The samples of PE containing various anti. To show the possibilities of the method and to the rates change in a more complicated manner. has been used. then II and IIl. 6 products (mainly water) were absorbed with solid The value of Wp must be a decreasing function KOH. Mw= 108000. ~0. are ing a certain limit Wmin: much less effective than II and I11.

6 mol kg -~ s -~ for IV.9 c 0.6 mol kg -1 s -1 for !II. The minima of the oxidation rates straight-line asymptote.. i. the uncertainty is not too great. antioxidant concentrations when e ( [ A ] ) ~ 0. the PE 15 oxidation rate increases non-linearly with anti- oxidant concentration.4 x 10 . the minimal value of the oxidation (2) becomes rate in the presence of this antioxidant. I i I I i 0 5 3O0 800 Time (rain) FA] x 102 (tool kg -1) Fig. 3. at 200°C and oxygen Hg. with antioxidants I | (1) and I l l (2). Fig. this asymptote intersects in the presence of these antioxidant occur at greater antioxidant concentrations than in the presence of II and lll.20 2 0'15 A 3 2 E '7 0-10 E -6 E 2 § . at 200°C and oxygen pressure of 300 mm initial antioxidant concentration.05 >. [A]o = pressure of 300 mm Hg. 2. 7 x 1 0 .e. 0. . eqn y = Wmin.e. when the ex. and by extrapolating experimental values of Wo2 to [A] = 0 we may I I | I calculate fairly definite values of Wmi.. As a result. Initial rate of oxygen consumption as a function of initial antioxidant concentration. equal to 0 10 20 FA] x 102 (mol kg -1) 4 x 10 . These values are 0 . with antioxidants ! (1) and IV (2). at 200°C and oxygen The m e t h o d proposed also gives additional pressure of 300 mm Hg. 6 Although these effects make deciphering of the experimen- tal dependence of Wo2 on [A] difficult. After passing through a minimum.6 mol kg -~ s -1 for l and 5x 10 . and minimal values of the 230 oxidation rate are several times greater. the ordinate axis at the point x = [ A ] = 0 . this dependence may be explained as the result of specific features of the ) 1 reaction in the presence of m o n o p h e n o P or by lO physical effects: with increasing antioxidant concentration the ratio of its molecules possess- E ing increased reactivity increases. with antioxidants !I (1) and !I! (2). information: the values of induction periods.04 mol kg -1. Thus in the simplest case.ka[m][o2] (4) 1. i. Oxygen consumption in the course of PE oxidation Fig. Antioxidant effectiveness in polyolefins 307 230~ 0. Initial rate of oxygen consumption as a function of induction period.l s -1 for II and W o 2 = Wmin -~. all of the curves are shifted to the region of greater rates and antioxidant concentrations. For antioxidants ! and IV.6 m o l k g . 4. the situation is more perimental curve of Wo2 vs [A] possesses a complicated.

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