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Sabaa 1988
Sabaa 1988
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*
ABSTRACT
INTRODUCTION
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
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.
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
TABLE 1
Elemental Analysis of Quinone Polymers and Some Molecular Weights
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 +
Termination
(C) + C 2 H s O H • C2HsONa
(d)
o'. ~ o~ o. ........ o
Polyquinones prepared using sodium ethoxide catalyst:
OH I- OH ........ O OH . . . . . . . O -[ OH
. . . . .
1J
o. ....... o
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