1070-4272/01/7411-1813$25.00C2001 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 74, No. 11, 2001, pp. 1813!1816. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 11,
2001, pp. 1759!1762.
Original Russian Text Copyright + 2001 by Antonik, Lopyrev, Tiunov, Dolgushin.
AND ION-EXCHANGE PROCESSES
Quaternization of 1,1-Dimethylhydrazine with Chloromethylated
Polystyrene and Properties of Thus Prepared
L. M. Antonik, V. A. Lopyrev, M. P. Tiunov, and G. V. Dolgushin
Favorskii Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Novosibirsk Chemical Concentrates Plant, Joint-Stock Company, Novosibirsk, Russia
Received June 14, 2001
Abstract-Quaternization of 1,1-dimethylhydrazine with chloromethylated polystyrene is studied to optimize
the procedure of preparation of new anion-exchange resins. Sorption characteristics of the resulting resins and
their applicability to wastewater treatment to remove uranium are studied.
Cross-linked chloromethylated polystyrene (CMPS)
is the basic intermediate for fabrication of anion-
exchange resins. With primary and secondary amines,
weakly basic anion exchangers are formed, and with
tertiary amines, strongly basic anion exchangers .
1,1-Dimethylhydrazine (DMH) shows promise as an
aminating agent, since it can react with CMPS via
both the primary and secondary amino groups to form
anion-exchange resins with specific performance char-
acteristics. Such resins are of particular interest in
view of the fact that, being one of the basic compo-
nents of propellants, DMH is accumulated in vast
amounts in a number of countries. In context of the
existing disarmament agreements this work is also
of a social significance.
Commercial CMPS (purchased from the OMIS
Joint-Stock Company, Omsk) was washed with ace-
tone and dried to constant weight. The chlorine con-
tent in the copolymer was found to be 16.1%. 1,1-Di-
methylhydrazine was distilled at 63oC.
Quaternization of DMH with chloromethylated
polystyrene was carried out as follows. The polymer
(10 g) containing 0.43 mol of fixed chlorine was al-
lowed to swell in 24 ml of dioxane for 15 or 60 min
at room temperature. Then DMH in 50 ml of water
was added. The amount of the aminating agent in
the system is given in Table 1. The process was per-
formed at 35392oC. The resulting product was washed
with distilled water and dried to constant weight.
The resulting resin was tested for the thermal and
chemical resistance and anion-exchange performance
according the standard procedures [2, 3]. The polymer
samples in the H form (nitrogen content 8.4%) were
placed in vials with distilled water and allowed to
stand for 24 h at 80, 100, and 150oC. In studying
the chemical resistance, 1 g of the air-dry resin was
treated with 100 ml of 5 N NaOH, HNO
at 20oC for 24 h or at 100oCfor1to90h.
Then the samples were washed, dried, and analyzed
for the weight loss, nitrogen content, and exchange
capacity. Sorption of the salts listed in Table 2 was
studied with the resin in the corresponding salt and
OH forms. A 1-g sample of the dry resin was stirred
in 100 ml of 0.1 N salt solution until the equilibrium
was reached (constant pH). The concentrations of
in the equilibrium solution were
determined chelatometrically with Na
Murexide as an indicator, and that of Fe
, by titration
with 0.1 N KMnO
. The amount of absorbed metal
was estimated from the difference between the metal
concentration in the initial and equilibrium solutions.
Sulfate was determined by titration with Ba(NO
in the presence of the chelatometric indicator chloro-
phosphonazo III. The residual concentrations of
, and AsO
by titration with 0.1 N Na
amount of absorbed anions was determined from the
difference between their concentrations in the initial
and equilibrium solutions. The resin was tested as
a sorbent for wastewater treatment to remove uranium.
For comparison, several commercial sorbents were