ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 1, pp. 100 !103. + Pleiades Publishing, Ltd., 2008.
Original Russian Text + A.I. Bol’shakov, S.I. Kuzina, D.P. Kiryukhin, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81, No. 1, pp. 104 !107.
AND POLYMERIC MATERIALS
Spontaneous Polymerization of Acrylamide
in Preactivated Glycerol
A. I. Bol’shakov, S. I. Kuzina, and D. P. Kiryukhin
Institite of Chemical Physics Problems, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received August 30, 2007
Abstract-Spontaneous polymerization of acrylamide in acrylamide3glycerol mixture was studied.
It is commonly believed that spontaneous poly-
merization of monomers is initiated by random forma-
tion of active centers (radicals, ions, etc.) caused by
various factors. The polymerization can also be ini-
tiated by impurities present in monomers and solvents.
These impurities can form specific compounds cap-
able of decomposing under certain conditions to form
active intermediates. For example, the presence of
hydroperoxide impurities in monomers can induce
spontaneous formation of polysulfones [1, 2].
We reported previously  that spontaneous poly-
merization of acrylamide was observed in acrylamide3
glycerol mixture on adding finely dispersed acryl-
amide monomer to glycerol without any initiatior. In
this study we examined the mechanism of formation
of active centers initiating the spontaneous polymeri-
zation of acrylamide in glycerol.
Acrylamide recrystallized from acetone was ground
in an agate mortar to 100-mm particles. Glycerol
(analytically pure grade, main substance content
99.3%) was used without additional purification.
The main impurities in glycerol were iron, lead, and
silver sulfates and chlorides, and also fatty acid esters.
Glycerol was irradiated with light [l>236 nm (in-
tensity 7.6 0 10
) and l>360 nm
(intensity 4.1 0 10
)] and with g-rays
Co, radiation dose rate 0.5 Gy s
Finely dispersed acrylamide monomer (20%) was
added to glycerol, and the resulting suspension was
thoroughly stirred. Since dissolved atmospheric oxy-
gen does not affect the acrylamide polymerization,
the acrylamide3glycerol suspension was not degassed.
After the polymerization completion, the reaction
mixture was washed with ethanol to remove glycerol,
and then ethanol was removed by evacuation. The
ESR spectra were recorded on an EPR-21 radiospec-
trometer at 77 K (wavelength 3 cm, UHF field power
W). The electronic absorption spectra were
recorded on a Specord-40 M spectrophotometer in
a 1-cm optical cell. The gaseous products of photoly-
sis were analyzed on an MI-1201 mass spectrometer.
The peroxy compounds were determined by iodomet-
Experiments on spontaneous polymerization of
acrylamide in glycerol of various batches showed that
this phenomenon was poorly reproducible. Since in
glycerol of some batches polymerization was not
observed, we suggested that it is the glycerol activity
that is responsible for spontaneous polymerization of
acrylamide. In particular, it is possible that commer-
cial glycerol contains active species inducing poly-
merization. These active species can be either com-
plexes of glycerol with impurities or other compounds
formed in glycerol in its production and storage under
the action of light, irradiation, heating, and other
We found that glycerol is activated with both the
daylight and g-ray irradiation, and this effect occurs
at small radiation doses and short exposure time. As
seen from Fig. 1, the maximal yield of the polymer
(70%) is reached at the irradiation dose of about
0.5 kGy or upon photolysis (l>360 nm) for 30 min.
Hence, both the photolysis and radiolysis of glycerol
are accompanied by formation of stabilized active
intermediates initiating polymerization of acrylamide.
Figure 2 shows the dependence of the polymer
yield on the wavelength of light used for preactivation