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[11]
[45]
Hayes
[54] N,O-CARBOXYMETHYL CHITOSAN AND
PREPARATIVE METHOD THEREFOR
[75] Inventor:
426/302
Field of Search ........................................ .. 536/20
References Cited
3,560,480
2/ 1971
4,063,016 12/1977
4,195,175
.... .. 536/20
4,301,067 1 1/ 1981
Koshugi .... ..
4,304,905 12/1981
Koshugi ..
4,308,377 12/1981
Koshugi ........ ..
Publishing Co.
Koshugi et a1., Chem. Abst., vol. 95, 1981, p.
45101(m).
Hirano et a1, Chem. Abst., v01. 95, 1981, p. 113891.
[52]
[56]
4,619,995
[51]
[58]
Patent Number:
Date of Patent:
536/20
[57]
ABSTRACT
A novel chitosan derivative, having carboxymethyl
substituents on some of both the amino and primary
OTHER PUBLICATIONS
8 Claims, No Drawings
4,619,995
the acetyl substituents on the copolymer, usually by 25 General Chemistry of the USSR by L. A. Nudga, E. A.
hydrolysis, to leave a copolymer having generally from
Plisko, and S. N. Danilov (Zh. Obshch. Khim. 1973,
13 to 17 percent of N-acetyl glucosamine monomer
43(12), 2752-6), who disclosed the preparation of O
units and correspondingly from 87 to 83 percent of
carboxymethyl chitosan. The speci?c O-alkylation was
glucosamine units in its structure.
Naturally occuring chitin, contaminated as it is with
inorganic salts, most commonly some form of calcium
carbonate, and with various proteins, must generally be
processed to remove most, if not all, of the contami
readily understood why it would be advantageous to 55 N,Ocarboxymethyl chitosan, are water soluble and
obtain materials of consistent composition, so that mate
4,619,995
tially one mol of the acid for each 1.8 to 2.2 mols of
45
4,619,995
tones.
phase.
for the chitosan prepared therefrom to be prepared 65 reaction is completed in three hours at 60 C. and in two
under consistent and uniform conditions, and (c) for the
hours at 70 C.
carboxymethylation of the chitosan to form the prod
Following completion of the reaction, the excess
ucts of this invention to be carried out under carefully
sodium hydroxide must be neutralized and the extrane
4,619,995
effective than the previously mentioned methanol, par 20 istics or properties of solubility, viscosity, and degree of
ticularly if excise tax regulations must be taken into
erty for thin ?lms when it is desired to separate thereby 60 ence of gel with an aqueous solution creates an abnor
mally high viscosity in the solution and renders dif?cult
or impossible the formation of a completely smooth ?lm
on a substrate, eg. on an apple; hence it is most desirable
mixture. Gas permeation studies have shown that ?lms
to have gel-free solutions for such commercial applica
of N,O-carboxymethyl chitosan are, for example, sub
stantially eight times more permeable to acetylene than 65 tions, but for other commercial applications, eg. coating
hatchery eggs, ?lm smoothness is of less significance. In
they are to ethylene when these gases are in admixture.
most cases the gel can be dissolved by heating the solu
Thus this selective permeability of the ?lm for these
tion; solutions that have been heated to dissolve gel
two gases will permit the concentration of acetylene
4,619,995
have lower viscosities than initially but higher viscosi
ties than those solutions which are initially gel-free.
Inasmuch as the degree of substitution of carboxy
methyl groups on chitosan is of some signi?cance with
regard to the water solubility of the material, additional
comment on this factor becomes appropriate. A degree
of substitution of 1.0 for carboxymethyl chitosan indi
10
value less than one indicates that not all the monomer
slurry of chitin, (b) slowly adding a strong aqueous
units are substituted. Theoretically each monomer unit
sodium hydroxide solution to the stirred slurry over a
could have substitution on the N-position and on each 15 period of 10 to 30 minutes and in a proportion to pro
30
EXAMPLE 2
ent from the reactant chitosan and also from the prior
11
4,619,995
12
tially 70 C.,
(d) maintaining the stirred slurry at the reaction tem
perature for a reaction period of substantially two
to twelve hours and suf?cient to complete reaction
between the chitosan and sodium monochloroace
tate to form N,O-carboxymethyl chitosan,
(e) adding to the slurry a small portion of water and
a portion of glacial acetic acid in amounts suf?cient
respectively to enable measurement of the pH of
60
65