1070-4272/05/7805-0798+2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 5, 2005, pp. 798!801. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 5,
2005, pp. 814!817.
Original Russian Text Copyright + 2005 by Kiryukhin, Kichigina, Zubakova, Moskvina.
AND POLYMERIC MATERIALS
Radiation-Initiated Copolymerization of N-Vinylpyrrolidone
with Triethylene Glycol Dimethacrylate
D. P. Kiryukhin, G. A. Kichigina, L. B. Zubakova, and I. Yu. Moskvina
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, Russia
Received June 16, 2004; in final form, March 2005
Abstract-The kinetics of radiation-initiated copolymerization of N-vinylpyrrolidone with triethylene glycol
dimethacrylate was studied. The variation of the composition of the 3D cross-linked copolymer and of the
amount of N-vinylpyrrolidone homopolymer in the course of the process at various initial monomer ratios was
Polyvinylpyrrolidone and its copolymers are used
in various branches of chemistry, medicine, and food
and perfumery industries . The use of triethylene
glycol dimethacrylate (TGM-3) as a long-chain cross-
linking agent in copolymerization with N-vinylpyrro-
lidone (N-VP) allows preparation of sorbents that
efficiently recover polyphenols from food and per-
fumery liquids and are used for stabilization and clari-
fication of juices, wine materials, and strong drinks
. The sorbent performance is largely determined
by the composition and structure of the copolymer.
The sorption properties of the sorbent are due to the
presence of carbonyl oxygen atoms in N-VP units.
However, as TGM-3 is more reactive than N-VP, it is
difficult to prepare the product of the required struc-
ture in a high yield.
The goal of this study was to examine the kinetic
relationships of radiation-initiated (
copolymerization of N-VP with TGM-3 and find the
optimal conditions for preparing the sorbent. The
reaction was monitored calorimetrically. A combina-
tion of the calorimetry with radiation initiation is very
convenient for studying the block polymerization of
a cross-linking system, as it allows the reaction rate to
be measured directly during the process and the de-
gree of conversion of double bonds in the monomers
to be estimated up to high conversions.
N-Vinylpyrrolidone was purified by double distilla-
tion in a vacuum, and TGM-3, by threefold filtration
through a column packed with activated alumina. To
perform the reaction, a monomer mixture of a definite
composition was placed in glass calorimetric cells,
deoxygenated, and sealed.
The radiation copolymerization was monitored
calorimetrically . A calorimeter with the reaction
cell was placed in the chamber of a Gammatok-100
g-ray installation, theromstated at the required temper-
ature, and irradiated at a dose rate of 1.5 Gy s
the course of the experiment, we monitored how the
rate of the heat release due to the polymerization
varies in time. The degree of conversion and reaction
rate were calculated using the following heats of poly-
merization (kJ mol
): 58.6 for N-VP  and 114.0
for TGM-3 .
After the reaction completion, the product was
precipitated with diethyl ether and dried to constant
weight in a vacuum, after which the total polymer
yield was determined gravimetrically. To remove the
soluble linear homopolymer of N-VP (PVP), the prod-
uct was washed with distilled water, and the insoluble
cross-linked copolymer was dried. The yield of PVP
was calculated from the difference between the total
yield of the polymer and the yield of the insoluble
The composition of the 3D copolymers were deter-
mined by elemental analysis for nitrogen.
To study the copolymerization of N-VP with
TGM-3, we took samples of N-VP, TGM-3, and their
mixtures with various initial molar ratios of the mono-
mers. The calorimetric curves of the polymerization of
N-VP and TGM-3 and of their copolymerization in the
course of g-irradiation at 295 K are shown in Fig. 1a,
and the time dependences of the consumption of the