Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 5, pp. 871−874.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
K.Kh. Khakimbolatova, E.E. Ergozhin, T.K. Chalov, T.V. Kovrigina, A.I. Nikitina, 2009, published in Zhurnal Prikladnoi Khimii, 2009,
Vol. 82, No. 5, pp. 817−820.
ORGANIC SYNTHESIS AND INDUSTRIAL
Kinetics of Polycondensation of Allyl Bromide
and Monoethanolamine Vinyl Ether
with Resorcinol Diglycidyl Ether
K. Kh. Khakimbolatova, E. E. Ergozhin, T. K. Chalov, T. V. Kovrigina, and A. I. Nikitina
Bekturov Institute of Chemical Sciences, Ministry of Education and Science of the Kazakhstan Republic,
Received April 23, 2008
Abstract—Polycondensation of resorcinol diglycidyl ether, monoethanolamine vinyl ether, and allyl bromide in
dimethylformamide solution was studied. The kinetic parameters of the process were determined.
The use of epoxy and allyl compounds allows
production of polymers with longer service life, due to
improved physicomechanical properties and enhanced
resistance to heat and chemicals. This particularly concerns
ion-exchange materials which in the course of operation
are in contact with oxidants, acids, or alkalis. Therefore,
search for new synthetic routes to ion exchangers based on
allyl and epoxy monomers is a topical problem.
Previously we prepared various polyfunctional anion
exchangers derived from allyl halides, diglycidyl ethers
of benzenediols, and di- and polyamines [1–3], and also
from allyl bromide (AB), epichlorohydrin oligomer,
and polyethylenimine . The structure of reactants
signiﬁ cantly affects the cell size in three-dimensional ion
exchanger networks, which, in turn, affects the degree
of recovery of various metal ions. In particular, network
anion exchangers prepared from allyl bromide, resorcinol
diglycidyl ether (RDGE), and polyethylenepolyamine
efﬁ ciently sorb transition metal ions . The use of
monoethanolamine vinyl ether (MEAVE) for their
synthesis is due to the fact that this is a proton-donor
compound, and such compounds are known  to activate
the epoxy ring. Furthermore, incorporation of MEAVE,
which contains nitrogen and oxygen atoms bearing lone
electron pairs, into anion exchangers should enhance
their complexing ability. We have developed a procedure
for preparing new polyelectrolytes by condensation of
RDGE, MEAVE, and AB, followed by their thermal
curing with hexamethylenediamine (HMDA).
This study concerns kinetic features of polycondensation
of resorcinol diglycidyl ether, monoethanolamine vinyl
ether, and allyl bromide.
Allyl bromide was of chemically pure grade, n
1.4690, bp 71.3°C. Resorcinol diglycidyl ether was
distilled at 80°C/20 mm Hg. Monoethanolamine vinyl
ether was treated with sodium metal and distilled with
collection of the fraction boiling at 114°C, n
Pure grade dimethylformamide (DMF) was dried over
calcium hydride and distilled at 44–45°C/15 mm Hg; n
1.4300 (bp 153°C, n
Polycondensation of RDGE, MEAVE, and AB was
performed at their weight ratio of 1 : 1 : 1, allowing
preparation of the ion exchangers in the highest yield,
in DMF at 70–80°C. The reaction time was varied
from 15 min to 5 h. At deﬁ nite intervals, samples of
the reaction mixture were withdrawn and multiply
diluted DMF to fully stop the reaction. Then the
content of AB (E
–1.41 V) and MEAVE (E
was determined by classical polarography using as
supporting electrolyte 0.2 M LiCl in 50% DMF. Under
these conditions, RDGE is polarographically inactive.
Therefore, the reaction order was determined only with
respect to AB and MEAVE concentrations.