1070-4272/01/7401-0145$25.00C2001 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 74, No. 1, 2001, pp. 145!148. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 1,
2001, pp. 138!142.
Original Russian Text Copyright C 2001 by Nud’ga, Petrova, Ben’kovich, Petropavlovskii.
AND POLYMERIC MATERIALS
Comparative Study of Reactivity of Cellulose, Chitosan,
and Chitin!Glucan Complex in Sulfoethylation
L. A. Nud’ga, V. A. Petrova, A. D. Ben’kovich, and G. A. Petropavlovskii
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received July 20, 2000
Abstract-Sulfoethylation of the chitin3glucan complex, isolated from mycelium of the mold fungus Asper-
gillus niger, by substitution with sodium b-chloroethylsulfonate or addition of sodium vinylsulfonate is
examined. A comparative study is made of the reactivity of the chitin3glucan complex, chitosan, and cellulose
in the both reactions. The sorption characteristics of the sulfoethylated products with respect to Cu(II) and
Cr(III) are determined.
It is known that introduction of sulfo groups in
cellulose and some other polysaccharides makes them
water-soluble. Solutions of the resulting sulfo deriva-
tives are stable in polymineral media, which is im-
portant in view of their use in metallurgy and oil pro-
duction. Also sulfo derivatives can be used as cation
exchangers and blood anticoagulants. Thus, chitin was
sulfonated to synthesize a full analog of heparin .
The sulfoethyl group imparts the same properties to
polysaccharides as the sulfo group, but additionally
makes the resulting ether more resistant to hydrolysis
in acid and alkaline solutions, since it is bound to the
skeleton chain of the polysaccharide by an ether bond.
It was reported also that sulfoalkyl derivatives of
polysaccharides can exhibit biological, particularly
anti-AID activity .
It is known  that sulfoethyl derivatives of
cellulose and chitosan can be obtained, having a
degree of substitution (DS) sufficiently high to make
them water-soluble. At the same time, despite the fact
that chitin3glucan complexes (CGCs) show promise
as a source of chitin (utilization of various biochemi-
cal work wastes), there is only limited information on
preparation of sulfoethyl derivatives of CGC . The
fact that chitin3glucan complexes contain both chitin
and glucan fragments makes it possible to compare
the CGC reactivity with that of cellulose and chitin
in the same reactions.
Depending on an alkylating agent, sulfoalkylation
can proceed either as substitution (with haloalkylsul-
fonates) or addition (with vinylsulfonate or alkane
sultones). For alkylation of cellulose all the three
types of reagents were used; selection of a reagent was
governed by the length of the alkyl residue. Thus, for
synthesis of sulfomethyl and sulfoethyl cellulose
ethers haloalkylsulfonates were used . Sulfoethyl
cellulose was also obtained by addition of sodium
vinylsulfonate  (this reaction is also known as sul-
fovinylation, despite the fact the product is a saturated
sulfoethyl ether). In the case of higher homologs al-
kane sultones were also used .
Study of cellulose sulfoethylation by reaction of
the first type showed that the yield increases when the
reaction is performed in a diluent . Additionally,
this reduces the degradation of the macromolecules
and improves the uniformity of the substituent distri-
bution along the polysaccharide chain. Also the use of
a diluent improves the product solubility and the qual-
ity of its solutions. It was demonstrated that the best
suited diluents are branched alcohols or their mixtures
with xylene. The optimal temperature of the reaction
is 80oC from the viewpoint of competition of hydroly-
sis of sodium b-chloroethylsulfonate (b-NaCES) and
substitution of the cellulose hydroxyls. The degree
of substitution attained in this reaction was no more
that 0.8, whereas in reaction of the second type [with
sodium vinylsulfonate (NaVS)] products were ob-
tained with SD of about 2.0.
In this work for CGC sulfoethylation we used sub-
stitution with b-NaCES and addition of NaVS.
In the case of substitution the reaction is written as
R(OH) + ClR
Na + NaOH 6 R3OR
+ NaCl + H