ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 11, pp. 1902!1905. + Pleiades Publishing, Ltd., 2007.
Original Russian Text + T.K. Chalov, E.E. Ergozhin, A.I. Nikitina, T.V. Kovrigina, K.Kh. Khakimbolatova, 2007, published in Zhurnal Prikladnoi Khimii,
2007, Vol. 80, No. 11, pp. 1878!1881.
AND POLYMERIC MATERIALS
Mechanism of Polycondensation of Allyl Bromide,
Epichlorohydrin Oligomer, and Polyethylenimine
T. K. Chalov, E. E. Ergozhin, A. I. Nikitina,
T. V. Kovrigina, and K. Kh. Khakimbolatova
Bekturov Institute of Chemical Sciences, Ministry of Education and Science of the Kazakhstan Republic,
Received January 31, 2007; in final form, September 2007
Abstract-The kinetics of polycondensation of allyl bromide, epichlorohydrin oligomer, and polyethyl-
enimine was studied. The rate constants and activation energies were determined.
The kinetic parameters and relationships of chemi-
cal reactions are the main quantitative characteristics
necessary for providing a basis for efficient control of
chemical processes . In studying kinetic character-
istics of practically all reactions, one of the most
important experimental problems is determination of
how the concentrations of the reaction participants
vary in time. A very promising and convenient meth-
od for studying kinetics and mechanism of chemical
reactions, among them polymerization and polycon-
densation in solutions, is classic polarography, in
which the error in determination of the monomer con-
centration is 233 rel %.
Previously  we developed procedures of syn-
thesis of anion exchangers based on allyl bromide,
epichlorohydrin oligomer, and polyethylenimine, and
studied their main physicochemical characteristics .
Here we report on a polarographic study of the ki-
netics of polycondensation of the above compounds.
Dimethylformamide (DMF) of pure grade was
dried over calcium hydride and distilled at 443
45oC/15 mm Hg; n
1.4300 (bp 153oC/1013 hPa ).
Epichlorohydrin (ECH) of chemically pure grade
was dried over calcium hydride and distilled; the frac-
tion boiling at 1153116oC/918 kPa was collected; n
1.4380 (bp 161.1oC; n
Epichlorohydrin oligomer (ECHO) was synthesized
in the presence of the M-14 catalyst, activated alu-
), taken in an amount of 1%
of the monomer weight. The reaction mixture was
heated for 2 h at 30350oC and for 53 6hat60380oC
with stirring at a constant rate and then cooled. The
reaction product was dissolved in benzene, precipi-
tated with water3ethanol mixture (2 : 1), and filtered
off. The resulting viscous brown product was dried
at room temperature in a vacuum to constant weight.
Allyl bromide (AB) was of chemically pure grade,
1.4690 (bp 71.3oC/1013 hPa).
Polyethylenimine (PEI) (MW 1 0 10
) was used in
the form of 50% aqueous solution. The content of
titratable nitrogen in anhydrous sample was 29.3%.
Polycondensation of ECHO with AB and PEI in
a weight ratio of 1 : 1 : 1 was performed in DMF at
40370oC for 4 h. Samples were withdrawn from the
reaction mixture at certain intervals and diluted with
a large excess of DMF to completely stop the reac-
tion. Then, the content of the monomer, allyl bromide,
in the samples was determined polarographically.
The polarographic study was performed in a tem-
perature-controlled cell at 25+ 0.2oC on a PU-1 po-
larograph with a capillary characteristic at an open
= 4.38 mg
. Saturated calomel
electrode was used as a reference electrode. Oxygen
was removed from the solution by argon bubbling for
5 min. The polarography was performed using an
0.02 M solution of (C
NI in 50% DMF as a sup-
It should be noted that, among three reactants (AB,
ECHO, and PEI), only allyl bromide is polarographic-