1070-4272/05/7810-1600 C 2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 10, 2005, pp. 1600!1604. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 10, 2005,
Original Russian Text Copyright + 2005 by Ergozhin, Chalov, Rozhkova, Iskakova.
AND ION-EXCHANGE PROCESSES
Epichlorohydrin-Based Polyfunctional Ion Exchangers
E. E. Ergozhin, T. K. Chalov, A. G. Rozhkova, and R. A. Iskakova
Bekturov Institute for Chemical Research, Ministry of Education
and Science of the Republic of Kazakhstan, Almaty, Kazakhstan
Received May 3, 2005
Abstract-Polyfunctional polyelectrolytes were synthesized by polycondensation of epichlorohydrin oligomer
in the presence of allyl bromide. The polycondensation conditions were optimized, and composition and
the properties of the resulting ion exchangers were studied.
Thanks to their high reactivity toward aliphatic
and aromatic amines, epoxy compounds are widely
used for preparation of various high-performance ion-
exchange materials . However, synthesis of
thermally and chemically resistant ion exchangers
with advanced sorption characteristics mostly involves
many steps, requiring rigorous conditions.
With epichlorohydrin oligomer (ECHO) contain-
ing functional groups with close reactivities used as
a starting reagent, it is possible to prepare ion ex-
changers with a more regular structure and advanced
In this study, we synthesized and characterized
Epichlorohydrin oligomers were obtained in the pres-
ence of 1 wt % M-14 catalyst, activated aluminosili-
). The reaction mixture was heated for
2hat30350oC and for 536hat60380oC under con-
tinuous stirring, and then cooled. The product was dis-
solved in benzene, the solution was filtered, and the
product was precipitated by adding a 1 : 2 water3alco-
hol mixture. The resulting brown viscous mass was
vacuum-dried at room temperature to constant weight.
The polycondensation of ECHO with polyamines
was performed in various solvents. The mixture was
stirred for 6 h at 60380oC to the onset of gelation.
The gel was transferred into a porcelain bottle and
cured for 14324hat803100oC. The polyamines used
were polyethylenimine (PEI), hexamethylenediamine
(HMDA), and polyethylenepolyamine (PEPA). Also
poly-2-methyl-5-vinylpyridine (PMVP) was used.
The polycondensation of ECHO with allyl bromide
(AB) and amines was carried out in DMF at 40370oC
for 3 h. The prepolymerization was performed at var-
ious component ratios. The resulting gel was cured in
an oven, crushed, and washed with distilled water.
Finally, the product was converted from the OH form
to the Cl form.
The static exchange capacity (SEC) and moisture
content W were determined by the standard proce-
The infrared spectra were registered on a Specord
M-80/M85 spectrophotometer (in pellets with KBr
+ 1 mg of substance).
It is known that the properties of ion-exchange
polymers depend on the ratio of the starting reactants,
their concentration in the reaction mixture, solvent,
temperature, and reaction time.
Performing polycondensation in a solvent enables
synthesis of polymers under considerably milder con-
ditions. Without solvent, the process is very fast and
yields an inhomogeneous product. Therefore, a proper
selection of a solvent in modification of ECHO with
polyamines enables polycondensation under homo-
geneous conditions before gelation.
The effect of a solvent on the conversion of ECHO,
judged from the exchange capacity and chlorine con-
tent, is illustrated in Table 1. This effect appeared to
Table 1. Effect of a solvent on the properties of the poly-
mers (ECHO : PEPA : solvent = 1.0 : 2.0 : 1.0 weight parts;
t = 4 h; and T =80oC)
³ SEC, ³ Chlorine ³ V
³ mg-equiv g
³ content, % ³ ml g
Hexane ³ 7.4 ³ 5.3 ³ 4.2
DMF ³ 8.8 ³ 4.6 ³ 4.4
Acetone ³ 8.1 ³ 4.3 ³ 4.2
Static exchange capacity in 0.1 N HCl; the same in Tables 236.