ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 4, pp. 663! 667. + Pleiades Publishing, Ltd., 2008.
Original Russian Text + Yu.N. Biglova, R.Kh. Yumagulova, S.V. Kolesov, Yu.B. Monakov, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81,
No. 4, pp. 627! 631.
AND POLYMERIC MATERIALS
Effect of Fullerene C
on Copolymerization Parameters
of Methyl Methacrylate with Compounds Containing Allyl Bond
Yu. N. Biglova, R. Kh. Yumagulova, S. V. Kolesov, and Yu. B. Monakov
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Received August 13, 2007
Abstract-The effect of fullerene C
on copolymerization of methyl methacrylate with compounds, one
of which is a typical allyl monomer and the other is a vinyl monomer with a side allyl bond, was examined.
The kinetic parameters of the reactions and the copolymerization constants of monomers in the absence
and in the presence of fullerenes were determined. Based on the UV spectrometric data, the material balance
was calculated and a variation of the molar extinction coefficient of fullerene was revealed.
The synthesis of practically important fullerene-
containing polymers requires solving many problems.
In view of the fact that these macromolecular com-
pounds well combine the characteristics of both poly-
mers and fullerenes, procedures for introduction of
fullerenes into the composition of polymer chains are
being actively developed .
Fullerene can be introduced into both the main
chain and side chain by radical copolymerization of
vinyl and allyl monomers of various structures. As
a consequence, the resulting substances have the char-
acteristics that strongly differ from those of the initial
substances. The presence of a covalently bonded ful-
lerene affects the size and shape of a polymer globule
as a whole and fundamentally changes the optical and
dielectric characteristics of macromolecules .
Highly symmetric fullerene molecules are also
widely used as structural units of polymer chains in
synthesis of macromolecular products [5, 6].
Here, we discuss the common and specific features
of the influence of fullerene C
on the radical copoly-
merization of methyl methacrylate (MMA) with allyl
methacrylate (AMA) and allyl chloride (AC) on
the basis of the kinetic dependences, composition
of copolymers, and data of UV spectroscopy and gel
Methyl and allyl methacrylates were purified to
remove the stabilizing agent with an 8% KOH solu-
tion, washed with water to neutral reaction, dried
, and twice distilled in a vacuum. For
polymerization, we took a fraction of MMA with bp
48oC/ 70 mm Hg and AMA with bp 73oC/53 mm Hg.
Allyl chloride was purified by distillation at atmo-
spheric pressure in an inert medium, bp 44oC. Ben-
zoyl peroxide was three times recrystallized from
methanol and dried in a vacuum at room temperature
to constant weight, mp 108oC (with decomposition).
In all the experiments, the initiator concentration
was the same: 2.0 0 10
The copolymerization was performed in the bulk
at 60 + 0.05oC. The process kinetics was studied by
the dilatometric method . Fullerene C
in the form of a saturated solution in o-dichloroben-
] = 9.3 0 10
The content of C
in the samples was measured by
UV spectroscopy on a Shimadzu UV VIS NIR 3100
device, using chloroform as a solvent. The molar ex-
tinction coefficients of fullerenes at the absorption
peaks, e, were determined from the calibration de-
pendences of the optical density on the concentration
of the solutions with [C
] = 2.0 0 10
32.0 0 10
which had the optical density of 3.6 and lower in
the transparency range of chloroform, 2503750 nm.
We also found the e values of monomers at the wave-
lengths of the absorption peaks of C
. The 7.0 0
35.0 0 10
M solutions of the monomers in
the range of the main absorption peak of C
had the optical density of 0.095 and