ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 11, pp. 2008–2013. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.M. Misin, N.N. Glagolev, M.V. Misin, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81, No. 11, pp. 1893–1898.
Modification of Commercial Oligomers with Diphenyldiacetylene
and p-Diethynylbenzene Polymers
V. M. Misin, N. N. Glagolev, and M. V. Misin
Emanuel’ Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia
Received May 4, 2008
Abstract—Diphenyldiacetylene and p-diethynylbenzene homopolymers and copolymers exhibit high resis-
tance to heat and thermal oxidation. Their composites with commercial oligomers were examined.
It is well known that substituted polyacetylenes
exhibit a set of unique physicochemical properties al-
lowing preparation on their basis of diverse materials
for electronics, information recording, and catalysis
[1–3]. Within the class of substituted polyacetylenes,
polydiphenyldiacetylene (poly-DPD) and poly-p-di-
ethynylbenzene (poly-DEB) exhibit high resistance to
heat and thermal oxidative degradation [1, 4]. Further-
more, there are indications that polyconjugated poly-
mers inhibit thermal and thermal oxidative degradation
of various substances and polymeric materials [4, 5].
However, these studies dealt with samples of polycon-
jugated polymers that had been prepared under the
conditions causing formation of defective structures of
macrochains. The polymers were insoluble and con-
tained virtually no reactive functional groups. Further-
more, the suggested procedures for preparing the poly-
mers were difficult to implement in industry.
For example, in thermal polymerization of DPD in
the bulk, the insoluble fraction content was as high as
61%. Macromolecules of the polymer contained both
polyene and polyacene fragments [6, 7]. Polymeriza-
tion of DPD in the presence of coordination initiators
[6, 8, 9] led to the formation of polyenes of low mo-
lecular weight with a low conversion.
In thermal polymerization of DEB, both ethynyl
groups of the monomer opened. This led to the forma-
tion of a nonmelting insoluble colored polymer of
three-dimensional network structure . In the pres-
ence of coordination initiators [11–16], thickly cross-
linked insoluble polyphenylenes or branched oligo-
phenylenes containing no more than 2–4 –C≡CH
groups were obtained.
Later the synthesis of DPD  and DEB [18, 19]
homopolymers and of their random copolymers 
under mild conditions (anionic initiators, temperature
lower than 60°C) allowed preparation for systematic
studies of polymers in which the chains were nonde-
fective and had proved intramolecular structure. Here
we demonstrate for the first time the possibility of us-
ing these polymers for the modification of commercial
oligomers of various classes.
AND POLYMERIC MATERIALS
All the synthesized polyconjugated polymers were
powders readily soluble in organic solvents. Thermo-
plastic poly-DPD and thermosetting poly-DEB had the
structure of substituted polyenes. These units were also
present in thermosetting random copolymers of DEB
and DPD in 3 : 1 (CPL-1) and 1 : 3 (CPL-2) ratios.
To prepare a carborane-containing polymer (poly-
DEB-B), to a toluene solution of poly-DEB we added
toluene solutions of decaborane and dimethylaniline.
The reaction mixture was washed with HCl and water,