ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 8, pp. 1374!1377. + Pleiades Publishing, Inc., 2006.
Original Russian Text + E.E. Ergozhin, T. Hirotsu, B.A. Mukhitdinova, S.A. Shoinbekova, A.I. Nikitina, G.N. Zhunusova, 2006, published
in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 8, pp. 1388!1390.
Cationic Polymerization of Redox Monomers Derived
from Monoethanolamine Vinyl Ether
and Various Quinones
E. E. Ergozhin, T. Hirotsu, B. A. Mukhitdinova, S. A. Shoinbekova,
A. I. Nikitina, and G. N. Zhunusova
Bekturov Institute of Chemical Sciences, Ministry of Education and Science of the Republic of Kazakhstan,
National Institute of Advanced Industrial Science and Technology!AIST, Tsukuba, Japan
Received February 21, 2006
Abstract-Cationic polymerization of redox monomers derived from monoethanolamine vinyl ether and
various chlorinated quinones in aqueous3organic solutions in the presence of HCl was studied. Optimal re-
action conditions were found, and the kinetic characteristics of the reactions were calculated.
The new redox monomers prepared from mono-
ethanolamine vinyl ether (MEAVE) and chlorinated
quinones (chloranil, CA; 2,3-dichloro-1,4-naphtho-
quinone, DCNPQ; 2,3-dichloro-5,6-dicyano-1,4-ben-
zoquinone, DCDCQ)  can be classed with substi-
tuted vinyl ethers (VEs) CH
=CHOR, namely, with
ethanolamine VEs. It is known  that the polymeri-
zation activity of VEs depends on the structure of
the organic residue. For example, aliphatic VEs poly-
merize considerably more readily than vinyl aryl
ethers. Also, introduction of a halogen substituent
into the monomer molecule enhances its activity in
polymerization . Furthermore, chlorine substituents
significantly alter the properties of a polymer, espe-
cially its solubility and softening point, which are
higher compared to the unsubstituted analog.
Vinyl alkyl ethers polymerize most readily under
the action of ionic, in particular, acid catalysts .
It has been shown [3, 4] that radical homopolymeri-
zation of vinyl ethers occurs considerably more dif-
ficultly than the cationic polymerization. Therefore,
it is interesting to study how the chemical structure
of redox monomers affects their reactivity in cationic
In this study, we examined the features of cationic
polymerization of redox monomers in the DMF3water
mixture in the presence of HCl.
Redox monomers derived from MEAVE and chlor-
anil (disubstituted derivative MEAVE3CA3MEAVE),
MEAVE and 2,3-dichloro-1,4-naphthoquinone (MEA-
VE3DCNPQ), and MEAVE and 2,3-dichloro-5,6-di-
cyano-1,4-benzoquinone (MEAVE3DCDCQ) were
prepared as described in .
The polymerization of the redox monomers was
performed at 7327oC for 237hinDMF3water mix-
tures, volume ratio from 4 : 0 to 1 : 3, in the presence
of HCl (0.0730.61 M). The reaction progress was
monitored by polarographic measurement of the con-
centration of the unchanged monomer and by gravi-
metric determination of the precipitated polymer.
The polarograms were recorded on a PU-1 polaro-
graph in a temperature-controlled cell at 25+0.5oC,
using a mercury dropping electrode with the open-cir-
cuit capillary characteristic m
= 4.38 mg
the supporting electrolyte was a phosphate buffer
solution (pH 7.4) in 25% DMF. Saturated calomel
electrode was a reference electrode. The solutions
were deoxygenated by bubbling of argon for 5 min.
Ethanolamine vinyl ethers are considerably less
active than vinyl alkyl ethers in reactions occurr-
ing by the ionic mechanism , because of the pres-