ISSN 1070-4272, Russian Journal of Applied Chemistry, 2016, Vol. 89, No. 6, pp. 955−959. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.V. Pestov, O.V. Koryakova, Yu.O. Privar, S.Yu. Bratskaya,
2016, published in Zhurnal Prikladnoi Khimii, 2016, Vol. 89, No. 6, pp. 796−801.
A New Approach to Preparation of Granulated Materials
Based on Chitosan and Its Imidazole Derivative
A. V. Pestov
, O. V. Koryakova
, Yu. O. Privar
, and S. Yu. Bratskaya
Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences,
ul. Sof ’i Kovalevskoi 22, Yekaterinburg, 620137 Russia
Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences,
pr. 100-letiya Vladivostoka, Vladivostok, 690022
Received April 20, 2016
Abstract—A new approach to preparation of granulated materials based on chitosan and N-(5-methyl-4-imidazolyl)-
methyl chitosan was developed. The procedure is simple and efﬁ cient and involves the use of glutaraldehyde as
cross-linking agent without using precipitants. The composition and structural features of the materials obtained
were determined by elemental analysis and Fourier IR spectroscopy. The dependence of the degree of material
swelling on the degree of functionalization with glutaraldehyde was determined. The polymer granules were used
as support for Pd
-containing catalysts for reduction of organic compounds.
Functionalization is widely used for expanding the
range and, hence, the application ﬁ eld of practically
important properties of the known and commercially
available polymers [1, 2]. It allows varying the solubility,
ionogenic properties, lipophilic-hydrophilic balance,
and many other characteristics of polymers. Another
factor determining the possibility of successful use of
commercially available polymers in various branches is
the availability of methods for forming various types of
materials [3, 4]: monolithic massive items, rods, threads,
ﬁ lms, granules, powders, and tubes.
In view of wide use of chitosan and its derivatives
in modern medical [5, 6], sorption [7, 8], and catalytic
[9, 10] technologies, it is necessary to develop speciﬁ c
and efﬁ cient methods for forming materials of various
types from chitosan.
In contrast to synthetic carbon-chain polymers,
preparation of granules of polysaccharides is a nontrivial
problem, because in this case it is principally impossible
to melt the polymer. In the case of chitosan, preparation
of granules is often based on precipitation. The polymer
in the form of spherical granules is precipitated from
aqueous solution using sodium hydroxide [11, 12],
sodium tripolyphosphate [13, 14], phosphate buffer
solution , or organic solvents [16–18]. The drawbacks
of this approach are the need for using inorganic or organic
precipitants and a drop-feeding or spraying  device.
The use of such devices, in turn, requires dilute solutions
of the polymer. The size of the formed spherical granules
obtained using a precipitant is primarily determined by the
nozzle diameter and shape, which considerably reduces
the efﬁ ciency of this method for reproducible preparation
of granules, including those of minimal size, and restricts
the possibilities of their use.
This study is aimed at developing a new approach to
the preparation of granulated forms of chitosan and its
derivatives, including materials intended for use as sup-
ports for metal-containing catalysts of organic reactions.
The following substances were used in the study:
Sonat chitosan (DD = 0.84, MM = 250 kDa, ash residue
0.19%; the degree of deacetylation, DD, was estimated
Н NMR spectroscopy, and the molecular mass, by
viscometry ); N-(5-methyl-4-imidazolyl)methyl