Polymer Degradation and Stability 22 (1988) 195-203

Polymerization Products of p-Benzoquinone as Bound

Antioxidants for Styrene-Butadiene Rubber: Part I
Preparation of Quinone Polymers

M a g d y W. Sabaa, T a r e k M. M a d k o u r
& A h m a d y A. Yassin*

Department of Chemistry, Faculty of Science,

University of Cairo, Giza, Egypt

(Received 16 December 1987; accepted 2 February 1988)

ABSTRACT

p-Benzoquinone was polymerized either cationically using dilute sulfuric

acid or borontrifluoride-acetic acid complex or anionically by the use of
sodium ethoxide in ethanol as polymerization catalysts. The number average
molecular weights of the polymerization products varied between 10 000 and
47000 depending on the nature of the catalyst and its concentration. The
elemental and spectral analyses proved that both quinone and hydroquinone
nuclei are present in the polymeric chains obtained from both mechanisms.
The quinone/hydroquinone ratio wasfound to vary depending on the nature of
the catalyst. The products obtained are thermally stable up to ~-200° C, and
highly susceptible to both oxidation and reduction. Mechanisms for both
types of polymerization are proposed.

INTRODUCTION

The susceptibility of natural and synthetic rubbers to oxidative degradation

is one of the main problems encountered in the rubber industry. 1'2 A large
number of antioxidants have been produced to protect the rubber from
oxidative deterioration, but in spite of the antioxidizing potency of the
currently used antioxidants (hindered phenols and aromatic amines), they
* To whom all correspondenceshould be addressed.
195
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Ltd, England. Printed in Great Britain
196 Magdy W. Sabaa, Tarek M. Madkour, Ahmady A. Yassin

are liable either to bloom on the surface of the finished product or to leach
from it on exposure to the action of solvents. This may be attributed either to
the low molecular weight of these antioxidants or to their inability to bind
chemically with the rubber matrix. 3'4 For this reason, great efforts have been
directed recently towards the production of new types of antioxidant
characterized by high molecular weights, 5'6 or by their ability to bond
chemically with the rubber chains, 6'7 thus avoiding their volatilization or
leaching.
It is known that p-benzoquinone and hydroquinone are effective
inhibitors for the radical polymerization of various monomers. Consequent-
ly, it is expected that both materials can similarly intervene in the radical
chain degradation process of rubber oxidation. However, the ease of
sublimation of p-benzoquinone at the high temperatures of vulcanization
has led to the idea that it might be polymerized to thermally stable products
that can withstand the effect of temperature. For this reason, use was made
of the fact that p-benzoquinone undergoes polymerization in the presence of
Lewis acids in organic solvents to form polyquinones of low molecular
weight a - 11 or in the solid phase to form quinone-tin polymers with various
tin contents depending on the molar ratio of tin chloride and quinone used in
their preparation. 12-14 Preliminary investigations with p-benzoquinone
have shown that products of higher molecular weights may be obtained if
the polymerization reaction is carried out in an aqueous medium using
cationic catalysts or much higher in the presence of an anionic catalyst. It is
the purpose of the present study to investigate the possibility of developing a
new class of polymeric bonding antioxidant based on p-benzoquinone and
their use as antioxidants for both natural and synthetic rubbers.

EXPERIMENTAL

Materials

1,4-Benzoquinone (Prolabo, France) was twice crystallized from benzene

(m.p. 115.7°C) and boron trifluoride (as 40% in acetic acid) was obtained
from Koch-light Laboratory Ltd, Colnbrook, UK.

Cationic polymerization of p-benzoquinone

Distilled water (500ml), 30g of p-benzoquinone (0.277mole) and the
appropriate amount of catalyst (either HzSO 4 or BF3-acetic acid complex)
were refluxed for 5 h. Two concentrations of the catalyst were used, 0-8%
and 6.3% by weight based on the weight of the solvent. A brittle brownish-
black solid mass was formed.
 Polymerization products of p-benzoquinone as antioxidants for SBR: 1 197

Anionic polymerization of p-benzoquinone

A mixture of 300ml of absolute ethanol, 15g of p-benzoquinone and a
freshly prepared solution of sodium ethoxide obtained by dissolving 1 g of
sodium metal in 40 ml of absolute ethyl alcohol was allowed to stand at
room temperature (25°C) for 2 days. A brown powder was obtained on
complete vaporization of the solvent.

Purification of the reaction products

The brown mass obtained by both cationic and anionic mechanisms was
washed repeatedly with hot water until free from catalyst, unreacted
benzoquinone, hydroquinone, quinhydrone and the low molecular weight
fractions formed. The solid residue was then filtered, dried and milled to
form a deep brown powder. The purified product was freely soluble in
acetone, dioxane, tetrahydrofuran, dimethylformamide and cyclohexanone,
sparingly soluble in methyl and ethyl alcohols and completely insoluble in
ether, carbon tetrachloride, benzene and chlorobenzene.

Identification of the polymerization products

The quinonoid nature of the reaction products was proved by the Craven
test. 15 In this test, the material is treated with a mixture of equal volumes of a
concentrated solution of ammonia and ethyl alcohol followed by the
addition of a few drops of ethyl cyanoacetate. A green or blue color
develops when the benzoquinone derivatives retain unsubstituted positions
in the quinonoid ring. The intensity of color increases as the number of the
unsubstituted positions increases. Moreover, the test is so sensitive that it
can differentiate easily between the parent p-benzoquinone and its quinoid
derivatives as various colors are developed. In spite of the fact that the
hydroquinone nuclei in the polymerization products are susceptible to
oxidation under the condition of the test to form the corresponding
quinonoid derivatives, the quinonoid nuclei in these products was further
proved by an absorption band in the 1610-1660cm -1 region of the IR
spectrum which is characteristic of the quinonoid structures.

Reducing properties
The polymerization products were found to discharge the color of both
bromine in carbon tetrachloride and potassium permanganate, which
indicates their susceptibility for oxidation.

Oxidizing properties
The products are also susceptible to reduction by zinc dust and hydrochloric
198 Magdy W. Sabaa, Tarek M. Madkour, Ahmady A. Yassin

acid. The resulting colorless material is easily reoxidized on exposure to air,

reforming the original brown product. It seems that an equilibrium is
maintained in the polymer between the hydro- and benzoquinone forms
giving a polyquinhydrone, through both intra- and intermolecular H-
bonding.

Oxidation of the polymerization products

The polymerization products were susceptible to oxidation by either

potassium permanganate in acetone or iodine in tetrahydrofuran. However,
oxidation by KMnO4 leads to loss of the quinonoid nature indicating that
oxidation is not restricted to the transformation of the hydroquinone nuclei
to the corresponding quinonoid units. For this reason, oxidation was
restricted to that effected by iodine solution, which was added gradually until
oxidation was complete. The oxidized products were then filtered, washed
successively with distilled water and ethanol, dried and milled to form a deep
brown powder.

RESULTS AND DISCUSSION

The elemental analysis of the polymerization products obtained by both

mechanisms and their oxidized forms is given in Table 1. The table also
shows the effect of the type and concentration of the catalyst used on the
molecular weight of the final products. The elementary analysis data are in

TABLE 1
Elemental Analysis of Quinone Polymers and Some Molecular Weights

Type of catalyst Catalyst %C %H %0 ~1.a

concentration
(%)

Sulfuric acid 0-8 64"18 3"20 32-62 40 059

Sulfuric acid 6'3 66"02 3'15 30"83 15 368
BF3-acetic acid complex 0"8 68'50 3"40 28-10 33760
BF3-acetic acid complex 6"3 69"10 3"10 27-80 10833
Sodium ethoxide 65'34 3"61 31-05 47 869
Sulfuric acid, oxidized by iodine 0-8 67'59 2-76 29"65
Sodium ethoxide, oxidized by iodine 65-01 2-80 32'19

a The number average molecular weights were measured using a Knaur electronic membrane
osmometer.
 Polymer&ation products of p-benzoquinone as antioxidants for SBR: 1 199

accordance with the presence of both hydro- and benzoquinone nuclei in the
polymer chains. This is further proved by the presence of IR absorption
bands of substituted benzenoid structures at 820, 1200-1210, and
1480-1510cm -~ and of quinonoid nuclei at 1610-1660cm -a. This is in
addition to the absorption in the 3460-3480 cm- a region which character-
izes both intra- and intermolecular H-bonding.
The chemical and spectral analysis data lead to the conclusion that the
polymerization of p-benzoquinone may be represented by the following
mechanism.
In the presence of cationic catalyst:
Init&tion
0 OH OH

[A] -

O O O
where HA is either H2SO 4 or BF 3. CH3COOH complex [A]- is either
[HSO4]- or [CH3COO I -
Propagation
OH 0
U
[A]- + I ~
II
0 0
OH 0 OH 0

OH OH OH OH
(a)

~
0 OH [- OH 1 OH

(a)+n~ [A]-

0 OH L OH J. 0
(b)
200 Magdy W. Sabaa, Tarek M. Madkour, Ahmady A. Yassin

Termination

(b) -"; + HA

OH L OH J. 0
(c)
(c) oxida,io,by...... ,edb~.zoq.i.... , partially oxidized polyhydroquinone.
In the presence of anionic catalyst:
Initiation
- -

@
0

+ C2HsO-Na +
*C2HsOH~ Na + • ,~

O O
O- 0
H

Na + ~. Na +
C2H50~ C2HsO~
OH OH
(a)
Propagation
0 0 O
H
(a) + Na + ~ ,

OH OH
0 OH
Na +

OH 0
(b)
0

(b)+n Na +

0 ~-~° or. [ Vo. ] Vo.

(c)
 Polymerization products of p-benzoquinone as antioxidants for SBR: 1 201

Termination

(C) + C 2 H s O H • C2HsONa

(d)

(d) oxidationby...... todb~°~oqoi.... ~ partially oxidized polyhydroquinone.

The initiation step of the cationic mechanism involves the abstraction of a

proton from the catalyst by the benzoquinone molecule resulting in the
formation ofa semiquinone cation. The latter, being the actual active center,
adds monomer molecules during the propagation step and leads to the
formation of the growing cation. Termination takes place by abstraction of
a proton from the growing cation by the catalyst anion, resulting in the
formation of a chain terminal benzoquinone nucleus. The polymeric
molecule thus formed undergoes partial oxidation by the unreacted
benzoquinone to form partially oxidized polyhydroquinone. This latter step
in the proposed mechanism is in accordance with both the elemental analysis
and the IR data of the various polymerization products. On the other hand,
initiation of the anionic mechanism is effected through the formation of a
semiquinone anion as a result of the interaction of the parent quinone with
the ethoxide catalyst. The active anion formed adds the monomeric
molecules in the propagation step. Termination takes place through
abstraction of a proton from the solvent molecules (ethanol) by the growing
anion, resulting in the formation of a polymeric molecule with a chain
terminal hydroquinone nucleus. The polyhydroquinone formed undergoes
partial oxidation by the unreacted benzoquinone to form partially oxidized
polyhydroquinone.

Thermal stability of the polymerization products

As the thermal stability of the products, especially at the molding

temperature of the rubber (-150°C), is considered to be of prime
importance for their application as antioxidants, the various products have
been heated slowly in an air oven up to 200°C. N o detectable weight loss,
decomposition or even melting was observed.
Probable structures suggested by elemental analysis and IR data are as
follows.
202 Magdy W. Sabaa, Tarek M. Madkour, Ahmady A. Yassin

Polyquinones prepared using either H2SO 4 or BFa-acetic acid complex:

o'. ~ o~ o. ........ o
Polyquinones prepared using sodium ethoxide catalyst:

OH I- OH ........ O OH . . . . . . . O -[ OH

. . . . .

1J

o. ....... o

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