N,O-carboxymethyl chitosan and preparative method therefor

• US 4,619,995 A
• Filed: 12/24/1984
• Issued: 10/28/1986
• Est. Priority Date: 12/24/1984
• Status: Expired due to Term

• Current Assignee: Nova Chem Limited
• Original Assignee: Nova Chem Limited
• Inventors: Hayes, Ernest R.
• Primary Examiner(s): Brown, Johnnie R.
• Application Number:
  US06/685,559
• Time in Patent Office: 673 Days
• Field of Search: 536/20
• US Class Current: 536/20
• CPC Class Codes: A23B 7/16 Coating with a protective layer; Compositions or apparatus therefor A23B7/08 takes precedence
• CPC Class Codes: C08B 37/003 Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof

Abstract

A novel chitosan derivative, having carboxymethyl substituents on some of both the amino and primary hydroxyl sites of the glucosamine units of the chitosan structure, is disclosed, together with methods for its preparation starting from either chitosan or chitin.

Claims

1. N,O-carboxymethyl chitosan having a degree of substitution of carboxymethyl groups per glucosamine monomer unit in the chitosan of less than 1.0, with carboxymethyl groups being substituted on hydroxyl oxygen atoms of the glucosamine monomer units of the chitosan and carboxymethyl groups being substituted on nitrogen atoms of the glucosamine monomer units of the chitosan.

5. A polymer film selectively permeable to various gases, said film consisting of N,O-carboxymethyl chitosan having a composition as defined in claim 1.

2. A method for the preparation of N,O-carboxymethyl chitosan which comprises

(a) dispersing solid chitosan in a liquid medium of the group consisting of isopropyl alcohol, n-butanol, isobutanol, methyl ethyl ketone, toluene, and ethanol-toluene mixtures containing at least 72 mol percent toluene, to form a slurry,

(b) steeping the chitosan in caustic medium by adding strong aqueous sodium hydroxide solution to the slurry, in a proportion of three to eight mols sodium hydroxide per mol of glucosamine monomer unit in the chitosan, with stirring to maintain the chitosan dispersed in the caustic medium for a period of from 0.5 to 1.0 hours,

(c) thereafter adding monochloroacetic acid to the caustic medium, in a proportion of substantially one mol of the acid for each 1.8 to 2.2 mols of sodium hydroxide in the caustic medium, and heating the slurry with continued stirring to a reaction temperature of from substantially 40°

C. to substantially 70°

C.,

(d) maintaining the stirred slurry at the reaction temperature for a reaction period of substantially two to twelve hours and sufficient to complete reaction between the chitosan and sodium monochloroacetate 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 sufficient respectively to enable measurement of the pH of the suspending liquid, and to bring the pH of the slurry to substantially 7.0, and

(f) recovering the N,O-carboxymethyl chitosan product from the slurry by separating the solid thereof and washing same with solvents to remove extraneous salts without dissolving the product.

3. A method as claimed in claim 2, including preliminary preparation of the chitosan dispersed and steeped in said liquid medium by

(a) dispersing granular sized chitin in the liquid medium, to form a slurry of chitin,

(b) slowly adding a strong aqueous sodium hydroxide solution to the stirred slurry over a period of ten to 30 minutes and in a proportion to provide substantially five to nine mols sodium hydroxide per mol N-acetyl glucosamine units in the chitin,

(c) heating the stirred slurry to a temperature in the range of 75°

C. to 100°

C. and maintaining it in this range for a period of 2.5 to 3.5 hours,

(d) allowing the slurry to cool to ambient room temperature and to steep until the chitin has been deacetylated to chitosan and the chitosan has steeped in the caustic medium for a brief period not exceeding one hour.

4. A method as claimed in claim 3 in which the brief period is of 0.5 to 1.0 hour duration.

6. A water resistant gel made from an aqueous solution of N,O-carboxymethyl chitosan by reaction of said solution with a material of the group consisting of cross-linking dialdehydes, cross-linking diketones, and aqueous solutions of ions of metals of the group consisting of iron, copper, mercury, nickel, silver, zinc, and calcium.

7. A gel as claimed in claim 6, in which the aqueous N,O-carboxymethyl chitosan solution is a 1% solution and the material is a solution of metal ions having a concentration of 100 to 10,000 ppm.

8. A gel as claimed in claim 6, in which the material is a dialdehyde in a proportion of from 0.5:

1 to 1;

1 by weight of the N,O-carboxymethyl chitosan.