Process for activating polysaccharides, polysaccharides produced by this process, and use thereof

• US 5,939,544 A
• Filed: 11/06/1997
• Issued: 08/17/1999
• Est. Priority Date: 03/25/1995
• Status: Expired due to Fees

• Current Assignee: Rhodia Acetow AG
• Original Assignee: Rhodia Acetow AG
• Inventors: Steinmeier, Hans, Karstens, Ties
• Primary Examiner(s): Lee, Howard C.
• Application Number:
  US08/913,782
• Time in Patent Office: 649 Days
• Field of Search: 536/56, 536/124
• US Class Current: 536/124
• CPC Class Codes: C08B 1/00 Preparatory treatment of cellulose for making derivatives thereof , e.g. pre-treatment, pre-soaking, activation
• CPC Class Codes: C08B 1/06 Rendering cellulose suitable for etherification etherification per se C08B11/00
• CPC Class Codes: C08B 30/12 Degraded, destructured or non-chemically modified starch , e.g. mechanically, enzymatically or by irradiation; Bleaching of starch preparation of chemical derivatives of starch C08B31/00
• 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
• CPC Class Codes: C08B 37/0096 Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
• CPC Class Codes: D01F 2/02 from solutions of cellulose in acids, bases or salts
• CPC Class Codes: D01F 2/24 from cellulose derivatives

Abstract

The process for activating polysaccharides consists of contacting the polysaccharide with liquid ammonia at an initial pressure which is higher than atmospheric pressure and at a temperature of at least approximately 25° C., the amount of liquid ammonia being sufficient at least for wetting the surface of the polysaccharide starting material which is then expanded. The volume available for the polysaccharide/liquid ammonia system is enlarged in the manner of an explosion by lowering the pressure by at least 5 bar. The process is particularly suitable for activating cellulose, guar gum, starch and chitin. The process enables cellulose to be modified in a novel manner. The activated polysaccharides display higher reactivity and improved elimination of reagents during acylation, alkylation, silylation, xanthogenation and carbomoylation with largely homogeneous reaction processes.

Claims

1. A process of activating a polysaccharide, which comprises the steps of:

a) contacting said polysaccharide with liquid ammonia at a pressure higher than atmospheric pressure and at a temperature of at least about 25°

C., wherein the quantity of liquid ammonia suffices to at least wet the surface of said polysaccharide to obtain a mixture of liquid ammonia and said polysaccharide; and

b) subjecting said mixture to a pressure release, the volume available for the polysaccharide and liquid ammonia system is increased in an explosion-like manner while reducing the pressure by at least 5 bars.

2. The process according to claim 1, wherein said explosion-like increase in volume takes place within a period of less than one second.

3. The process according to claim 1, wherein said polysaccharide and the liquid ammonia in step a) are brought in contact in a pressure device, and the pressure of the polysaccharide and liquid ammonia mixture is released in step b) by transferring the mixture into an explosion chamber having a volume larger than that of the pressure device.

4. The process according to claim 1, wherein the pressure in step a) is set to between about 5 and 46 bars.

5. The process according to claim 4, wherein the pressure in step a) is between about 25 and 30 bars.

6. The process according to claim 3, wherein the temperature in the pressure device in step a) is set to between 25 to 85°

C.

7. The process according to claim 6, wherein the temperature is between about 55°

and 65°

C.

8. The process according to claim 1, wherein in step b) the pressure is reduced in an explosion-like manner by at least about 10 bars.

9. The process according to claim 1, wherein in step a) said mixture consists of 1 part by mass of said polysaccharide and at least 1 part by mass of liquid ammonia.

10. The process according to claim 9, wherein the amount of liquid ammonia is about 5-10 parts by mass.

11. The process according to claim 1, wherein the ammonia evaporated by the explosion-like increase in volume in step b) is condensed to liquid ammonia and fed back into the process.

12. The process according to claim 1, wherein step b) is carried out in an explosion chamber and prior to feeding into said chamber the polysaccharide and liquid ammonia mixture, said explosion chamber is kept under vacuum.

13. The process according to claim 1, wherein said polysaccharide has a polyhexose structure.

14. The process according to claim 1, wherein said polysaccharide has a polymerization degree DP not less than 150.

15. The process according to claim 14, wherein said polysaccharide is cellulose.

16. The process according to claim 15, wherein said cellulose is a compact chemical cellulose material with a density of about 0.6 to 0.8 g/cm³.

17. The process according to claim 1, wherein said polysaccharide is a member selected from the group consisting of cellulose, starch, chitin and a galactomannan.

18. The process according to claim 17, wherein said galactomannan is guar gum.

19. The process according to claim 1, wherein said polysaccharide in step a) has a water content of less than about 12% by mass.

20. The process according to claim 1, wherein said polysaccharide in step a) contains less than 18% by mass of foreign substances.

21. The process according to claim 1, wherein said polysaccharide in step a) is free of proteins.

22. The process according to claim 1, wherein after step b) in order to remove adhering ammonia, the product is subjected to vacuum or is heated or both subjected to vacuum and heated.

23. An exploded crystalline cellulose which exhibits an X-ray diffraction spectrum with peaks at the following diffraction angles 2θ

and with the relative intensities;

Peak 11.25±

1 with the relative intensity of about 15 to 25;

Peak 17±

1 with the relative intensity of about 25 to 40;

Peak 20.5±

1 with the relative intensity of 100 (reference value).

24. The cellulose according to claim 23, which exhibits a LODP-value of about 50 to 200.

25. The cellulose according to claim 24, wherein said LODP value is about 100-160.

26. The cellulose according to claim 24, which is in the form of a fluff with a density of less than about 0.2 g/cm³.

27. The cellulose according to claim 26, wherein the density is less than about 0.1 g/cm³.

28. The cellulose according to claim 27, wherein said fluff has an ammonia content of less than about 0.5% by mass.

29. The method of producing cellulose derivatives by reaction with an acylation, alkylation, silylation, xanthogenation or a carbamoylation reagent which consists of reacting said cellulose according to claim 23 with said reagent.

30. The method of preparing a solution of cellulose for wet spinning which consists of forming a solution from the crystalline cellulose according to claim 23.