1070-4272/02/7511-1791$27.00C2002 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 75, No. 11, 2002, pp. 1791!1794. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 11,
2002, pp. 1826!1829.
Original Russian Text Copyright + 2002 by Ergozhin, Chalov, Iskakova, Sarsenov.
AND ION-EXCHANGE PROCESSES
Anion Exchangers Based on Glycidyl Derivatives of Aromatic
Diamines and Some Allyl Halides
E. E. Ergozhin, A. K. Chalov, R. A. Iskakova, and S. K. Sarsenov
Bekturov Institute of Chemical Sciences, Ministry of Education and Science of Kazakhstan Republic,
Received April 9, 2002
Abstract-Polyfunctional three-dimensional network anion exchangers were prepared by condensation of
tetraglycidyl-4,4`-diaminodiphenylmethane with allyl halides and amines. The optimal preparation conditions
were determined; the properties of the resulting product as influenced by the nature of the initial monomers
Owing to high static exchange capacity (SEC) and
thermal and chemical stability, polyelectrolytes based
on nitrogen-containing epoxy compounds are widely
used in hydrometallurgy of rare metals, in recovery of
metal ions from spent solutions and wastewaters, and
in other branches of industry.
Condensation of tetraglycidyl diamines with poly-
ethylenepolyamine (PEPA), polyethylenimine (PEI),
polyxylylenepolyamine, and hexamethylenediamine
(HMDA) in methanol yielded selective polyfunctional
anion exchangers with high exchange capacity .
Utilization of long-chain aromatic nitrogen-containing
epoxy resins in combination with heteroatoms of 3S3,
3,or3O3 type between phenyl rings improves
the sorption and kinetic properties of the resulting
sorbents with respect to polyvanadate ions [4, 5].
To obtain ion-exchange materials possessing high
thermal and radiation stability, we prepared anion
exchangers based on glycidyl derivatives of 4,4`-di-
aminodiphenyl sulfide, 4,4`-diaminodiphenyl oxide,
PEPA, and PEI .
The goal of this work was to prepare highly por-
ous three-dimensional network anion exchangers
based on tetraglycidyl-4,4`-diaminodiphenylmethane
(TGDADPM), allyl halides (AHs), and di- and poly-
TGDADPM was synthesized according to ; the
content of the epoxy groups was determined by the
procedure given in .
The condensation of AH with TGDADPM was per-
formed in dimethylformamide (DMF) at 13325oC
with subsequent curing at 803120oC. Then, the gel
was crushed, sieved, and the fraction with a particle
size of 0.25 mm was taken.
The static exchange capacity (mg-equiv g
ture content, swellability g, and thermal and chemical
stability of the resulting anion exchangers were deter-
mined by the standard procedures .
The IR spectra of the initial and final products (thin
films or KBr pellets, 200 mg KBr per 1 mg com-
pound) were recorded on a Specord M 80/M 85 spec-
To determine the optimal preparation conditions,
we examined the effect of various factors such as the
ratio of the initial components, temperature, curing
conditions, and process time on the product properties.
The effect of the initial component ratio is of par-
ticular importance, because the content of amine in
the polymer determines the properties of the resulting
product. It was found that, with increasing content of
amine, both SEC and swellability increase, and the
strongest effect is observed with PEPA, which is
probably due to its structure. As seen from the NMR
data [10, 11], PEPA contains significant amounts of
diethylenetriamine with two primary and one sec-
ondary amino groups. Since primary amino groups
are the most reactive, they are involve in the reaction
first. In the case of PEI, despite significant content of
nitrogen (16%), more branched structure of the poly-
amine causes strong cross-linking and thus hinders
accessibility of the corresponding functional groups.
Double bonds, a certain fraction of which is cleaved
with atmospheric oxygen , also strongly affect the