ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 12, pp. 2178–2179. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.V. Kurzin, A.N. Evdokimov, O.S. Pavlova, V.B. Antipina, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81, No. 12,
Esters of Amylose, Cellulose, and Tall Oil Fatty Acids
A. V. Kurzin, A. N. Evdokimov, O. S. Pavlova, and V. B. Antipina
St. Petersburg State Technological University of Vegetable Polymers, St. Petersburg, Russia
Received May 14, 2008
Abstract—The possibility of preparing amylose and cellulose esters by esterification and acylation with
chlorides of tall oil fatty acids was examined.
Esters of carbohydrates and higher fatty acids
(HFAs), the so-called liposaccharides, are promising
and valuable nonionic surfactants used in various
branches of industry and in medicine . Polysaccha-
ride esters form a particular group of liposaccharides.
The main procedures for their preparation are based on
acylation with HFAs under the conditions of acid or
base catalysis, and also on ester interchange of alkyl
esters of acids with polysaccharides [1–4].
A promising renewable source of fatty acids is tall
oil, a by-product from kraft pulp production. The main
components of tall oil fatty acids (TOFAs) are unsatu-
acids: oleic, linoleic, and linolenic . A search
for new applications of tall products is a topical prob-
lem of pulp-and-paper and resin industry. Previously,
we have prepared liposaccharides from sucrose ,
xylitol , and tall oil fatty acids.
The goal of this study was to prepare TOFA esters
of amylose and cellulose.
Use of strong Brønsted acids as acylation cata-
lysts leads to formation of dark tarry products. A more
efficient synthetic route to polysaccharide esters is
the reaction of activated polymers with acid chlorides
in the presence of tertiary amines.
Chlorides of higher unsaturated acids are usually
prepared by treatment of the acids with phosphorus
halides or thionyl chloride, but side processes occur in
the latter case. For the experiments, we chose phospho-
rus trichloride, which is successfully used in synthesis
of chlorides of higher fatty unsaturated acids, including
Among the catalysts reported in the literature for
esterification of carbohydrates with HFAs, a particular
place is occupied by anhydrides and chlorides of acetic
acid derivatives (methoxyacetic, chloroacetic, trifluoro-
acetic acids). Positive results have also been obtained
with free trichloroacetic acid used as catalyst (impeller).
The degree of substitution of the reaction product
was calculated from the difference between the saponi-
fication number and acid number. For the amylose es-
ter prepared with TOFA chlorides, it was 0.38, and for
the ester prepared using trichloroacetic acid, 0.45.
The low acid numbers (less than 1 mg KOH/g product)
show that the product hardly contains any amount of
starting fatty acids. The appearance of new ester bonds
is also confirmed by comparison of the IR spectra of
the starting amylose and its esterification products.
Absorption bands characteristic of stretching vibrations of
ester C=O groups (1730 cm
) and of double bonds in
hydrocarbon residues of TOFAs (1680–1620 cm
appear in the IR spectra, whereas bands of the reagents
used, including C–Cl stretching vibration bands (800–
), are absent.
The polymers obtained are structurally similar
to surfactants widely used today for stabilization of
dispersions and control over rheological properties
(Emulsan etc.) .
TOFAs (A grade, Segezha Pulp-and-Paper Com-
bine, Joint-Stock Company) were additionally purified
by vacuum distillation, with the fraction boiling at
170–205°С/1 mm Hg collected. Bleached coniferous
pulp (Kotlas Pulp-and-Paper Combine, Joint-Stock
Company) was disintegrated to separate fibers. TOFA