AND POLYMERIC MATERIALS
Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 3, pp. 413−416.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © I.I. Gavrilova, E.F. Panarin, N.A. Nesterova, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 3, pp. 440−444.
Homopolymerization of N-Vinylamides in the Presence
of Water-Soluble Initiators and Preparation of Polyelectrolytes
from the Polymerization Products
I. I. Gavrilova, E. F. Panarin, and N. A. Nesterova
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
e -mail: firstname.lastname@example.org
Received December 26, 2011
Abstract—Homopolymerization of vinylformamide and N-methyl-N-vinylacetamide in water in the presence of
2,2'-azobis(2-methylpropanediamine) dihydrochloride and of the hydrogen peroxide–ammonium hydroxide system
was examined. Hydrolysis of polyvinylformamide, poly-N-methyl-N-vinylacetamide, and poly-N-vinylacetamide
with hydrochloric acid at 100°С was studied.
Poly-N-vinylamides are water-soluble polymers used
in biotechnology and medicine. Cyclic N-vinylamides,
N-vinylpyrrolidone and N-vinylcaprolactam, have been
studied fairly well [1–3], whereas open-chain N-vinyl-
amides were given little attention until recently. At the
same time, these monomers contain a protected amino
group and are of interest for the synthesis of cationic
polyelectrolytes (ﬂ occulants) and carrier polymers con-
taining an amino group.
Here we report on a comparative study of the
homopolymerization of vinylformamide (VFA) and
N-methyl-N-vinylacetamide (N-MVAA) in water in
the presence of water-soluble initiator 2,2'-azobis(2-
methylpropanediamine) dihydrochloride (MPC) and of
the redox system hydrogen peroxide (H
OH). This system is used in industry for
the synthesis of poly-N-vinylpyrrolidone (P-N-VP). Po-
lymerization of VFA in organic solvents is a heterophase
process. Vinylformamide units form strong hydrogen
bonds between macromolecular chains [3, 4], which
prevents the solubility of the homopolymer. Preliminary
experiments (Table 1) showed that N-MVAA is less
reactive than VFA, which may be due to stronger steric
hindrance produced by substituents at the N atom in N-
MVAA chains, compared to VFA:
Table 1 shows that, to reach high conversion of N-
MVAA, it is necessary to perform the polymerization for
a two times longer period compared to VFA.
VFA and N-MVAA (Aldrich) were puriﬁ ed by vacuum
distillation, bp 65.0°С (4 mm Hg), n
1.4920, d 1.014;
bp 70.0°С (25 mm Hg), n
1.4830, d 0.956, respectively.
Polymerization was performed at 60°С in sealed am-
pules under argon, with variation of the monomer and
initiator concentrations. With the NН
the ratio of its components was also varied. The polymers
were precipitated into acetone, and the precipitate was
vacuum-dried at room temperature to constant weight.