Preparation of poly alpha-1,3-glucan esters and films made therefrom

Patent metadata

Field	Value
Publication number	US-9278988-B2
Application number	US-201314136226-A
Country	US
Kind code	B2
Filing date	Dec 20, 2013
Priority date	Dec 27, 2012
Publication date	Mar 8, 2016
Grant date	Mar 8, 2016

Abstract

Poly alpha-1,3-glucan ester compounds are disclosed herein with a degree of substitution of about 0.05 to about 3.0. Also disclosed are methods of producing poly alpha-1,3-glucan ester compounds and films made therefrom.

First claim

What is claimed is:

1. A composition comprising a poly alpha-1,3-glucan ester compound represented by the structure:

wherein
(i) n is at least 6,
(ii) each R is independently an H or acyl group, and
(iii) the compound has a degree of substitution of about 0.05 to about 3.0;
wherein the compound contains two or more types of said acyl group.

2. The composition of claim 1 , wherein the two or more types of said acyl group are selected from the group consisting of acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, and octanoyl.

3. The composition of claim 2 , wherein at least one acyl group is an acetyl group.

4. The composition of claim 3 , wherein the degree of substitution with said acetyl group is about 0.05 to about 2.6.

5. The composition of claim 2 , wherein the two or more types of said acyl group are:
(i) acetyl and propionyl, or
(ii) acetyl and butyryl.

6. A method of producing a poly alpha-1,3-glucan ester compound, the method comprising:
(a) contacting poly alpha-1,3-glucan in a reaction that is substantially anhydrous with at least one acid catalyst, at least one acid anhydride, and at least one organic acid, wherein two or more types of acyl group are esterified to the poly alpha-1,3-glucan thereby producing a poly alpha-1,3-glucan ester compound represented by the structure:

 wherein
(i) n is at least 6,
(ii) each R is independently an H or acyl group, and
(iii) the compound has a degree of substitution of about 0.05 to about 3.0, wherein the compound contains two or more types of acyl group; and

(b) optionally, isolating the poly alpha-1,3-glucan ester compound produced in step (a).

7. The method of claim 6 , wherein the poly alpha-1,3-glucan is acid-exchanged with an organic acid before contacting step (a) to remove water from the poly alpha-1,3-glucan.

8. The method of claim 6 , wherein the acid catalyst is an inorganic acid.

9. The method of claim 8 , wherein the inorganic acid is sulfuric acid or perchloric acid.

10. The method of claim 6 , wherein:
the acid anhydride is one or more of acetic anhydride, propionic anhydride, or butyric anhydride; and
the organic acid is one or more of acetic acid, propionic acid, or butyric acid.

11. The method of claim 10 , wherein:
(i) the acid anhydrides are propionic anhydride and acetic anhydride, and the organic acids are propionic acid and optionally acetic acid, wherein the poly alpha-1,3-glucan ester compound produced in the reaction is a poly alpha-1,3-glucan acetate propionate;
(ii) the acid anhydride is propionic anhydride, and the organic acids are propionic acid and acetic acid, wherein the poly alpha-1,3-glucan ester compound produced in the reaction is a poly alpha-1,3-glucan acetate propionate;
(iii) the acid anhydrides are butyric anhydride and acetic anhydride, and the organic acids are butyric acid and optionally acetic acid, wherein the poly alpha-1,3-glucan ester compound produced in the reaction is a poly alpha-1,3-glucan acetate butyrate; or
(iv) the acid anhydride is butyric anhydride, and the organic acids are butyric acid and acetic acid, wherein the poly alpha-1,3-glucan ester compound produced in the reaction is a poly alpha-1,3-glucan acetate butyrate.

12. The method of claim 6 , wherein the poly alpha-1,3-glucan is further contacted with an organic solvent in step (a).

13. The method of claim 6 , wherein step (a) comprises:
(i) cooling the reaction;
(ii) cooling a mixture containing the poly alpha-1,3-glucan, acid catalyst and organic acid, and then adding the acid anhydride to the mixture;
(iii) cooling a mixture containing the acid anhydride and organic acid, and then adding the poly alpha-1,3-glucan and acid catalyst to the mixture; or
(iv) cooling a mixture containing the acid catalyst and organic acid, and then adding the poly alpha-1,3-glucan and acid anhydride to the mixture.

14. The method of claim 6 , wherein at least two acid anhydrides are contacted with poly alpha-1,3-glucan in step (a).

15. A method of producing poly alpha-1,3-glucan acetate, the method comprising:
(a) contacting poly alpha-1,3-glucan in a reaction that is substantially anhydrous with acetic anhydride, acetic acid, and at least one acid catalyst, wherein poly alpha-1,3-glucan triacetate is produced;
(b) isolating the poly alpha-1,3-glucan triacetate produced in step (a);
(c) contacting the poly alpha-1,3-glucan triacetate with acetic acid and water to form a preparation;
(d) applying steam pressure of about 3-10 kg/cm 2 to the preparation to raise its temperature up to 260° C., wherein poly alpha-1,3-glucan acetate is produced having a degree of substitution of 0.05 to 2.70; and
(e) optionally, isolating the poly alpha-1,3-glucan acetate produced in step (d).

16. The method of claim 15 , wherein the temperature of step (d) is raised to about 140-160° C.

17. A method of producing a poly alpha-1,3-glucan ester compound, the method comprising:
(a) providing a poly alpha-1,3-glucan ester compound represented by the structure:

 wherein
(i) n is at least 6,
(ii) each R is independently an H or acyl group, and
(iii) the compound has a degree of substitution of about 0.05 to about 3.0;

(b) subjecting the poly alpha-1,3-glucan ester compound of step (a) to hydrolysis conditions, thereby producing a poly alpha-1,3-glucan ester compound with a reduced degree of substitution compared to the poly alpha-1,3-glucan ester compound of step (a); and
(c) optionally, isolating the poly alpha-1,3-glucan ester compound produced in step (b).

18. The method of claim 17 , wherein the hydrolysis conditions comprise water, organic acid, and a temperature up to 260° C.

19. The method of claim 18 , wherein the hydrolysis conditions further comprise a pressure of about 3-10 kg/cm 2 .

20. The method of claim 17 , wherein the poly alpha-1,3-glucan ester compound provided in step (a) is poly alpha-1,3-glucan triacetate, and wherein the poly alpha-1,3-glucan ester compound produced in step (b) has a degree of substitution of 0.05 to 2.70.

Assignees

• Du Pont

Inventors

• Kasat Rahul B
• Paullin Jayme L

Classifications

• C07H13/04 Primary

  having the esterifying carboxyl radicals attached to acyclic carbon atoms · CPC title

• C08B37/0009 Primary

  alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof · CPC title

• C08J2305/00

  Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00 · CPC title

• C08L5/00

  Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00 · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title