1070-4272/01/7409-1577$25.00C2001 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 74, No. 9, 2001, pp. 1577!1580. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 9,
2001, pp. 1530!1532.
Original Russian Text Copyright + 2001 by Ermilov, Shibalovich, Nikolaev.
AND POLYMERIC MATERIALS
of N,N,N-Trimethylammonioethyl Methacrylate Methyl Sulfate
F. V. Ermilov, V. G. Shibalovich, and A. F. Nikolaev
St. Petersburg State Technological Institute, St. Petersburg, Russia
Received March 5, 2001
Abstract-The kinetic features of initiation of N, N,N-trimethylammonioethyl methacrylate methyl sulfate
polymerization in the presence of manganese(III) bis(acetylacetonate) nitrate and p-nitrosoaniline were studied
by the inhibited polymerization method. The kinetic parameters of initiation were calculated, and participation
of the monomer in the initiation stage was established.
In radical polymerization, the initiation stage is the
most energy-consuming and the slowest, as compared
to chain propagation and termination, and, as a rule,
it determines the overall polymerization rate .
A kinetic study of inhibited polymerization of
N,N,N-trimethylammonioethyl methacrylate methyl
sulfate (TMAEMA3MS) under the action of manga-
nese(III) bis(acetylacetonate) nitrate (MN) was per-
formed in aqueous solution in the temperature range
203 40oC in the presence of radical scavenger, p-ni-
trosoaniline (p-NA). The concentrations of the reac-
tants (M) were as follows: inhibitor 6 0 10
35 0 10
initiator 6.3 0 10
, and monomer 1.4132.82.
With p-NA added, we observed a clearly pro-
nounced induction period t
(Figs. 1a, 1b) within
which no polymerization occurred, and after exhaus-
tion of p-NA the copolymerization occurred at a con-
stant rate equal to the polymerization rate in the
absence of the inhibitor.
The duration of the induction period linearly de-
pends on the inhibitor concentration, which suggests
the absence of side reactions between the inhibitor and
monomer (Fig. 2).
The constancy of the ratio [Z]/t
([Z] is the
inhibitor concentration) suggests that the inhibitor is
consumed only in reactions with primary radicals
generated by decomposition of MN.
The facts that the induction period is proportional
to the initial inhibitor concentration and that after the
end of the induction period no inhibition is observed
in the examined concentration range allow us to use
the following equation  for calculating the initiation
is the initiation rate (mol l
] is the
initial p-NA concentration (M), and t
is the induc-
tion period (s). The initiation constant K
) can be
Fig. 1. Kinetic curves of inhibited polymerization of
TMAEMA3MS in the presence of p-NA at 20oC: (a) con-
version and (t) time. TMAEMA3MS concentration, M:
(a) 1.49 and (b) 2.82. p-NA concentration c 0 10
(a) (1)0,(2) 0.67, (3) 1.25, and (4) 5.0; (b) (1)0,(2) 1.0,
(3) 2.0, and (4) 5.0.