Derivatized microfibrillar polysaccharide

• US 6,602,994 B1
• Filed: 02/10/1999
• Issued: 08/05/2003
• Est. Priority Date: 02/10/1999
• Status: Expired due to Term

• Current Assignee: Hercules, LLC (Ashland Global Holdings, Inc.)
• Original Assignee: Hercules Incorporated (Ashland Global Holdings, Inc.)
• Inventors: Chan, Anita N., Cash, Mary Jean, Gelman, Robert Alan, Conner, Herbert Thompson, Lusvardi, Kate Marritt, Cowan, Patrick Joseph, Tise, Frank Peine, Thompson, Samuel Anthony
• Primary Examiner(s): Wilson, James O.
• Assistant Examiner(s): White, Everett
• Application Number:
  US09/248,246
• Time in Patent Office: 1,637 Days
• Field of Search: 536/30, 536/43, 536/44, 536/84, 536/90, 536/91, 536/92, 536/95, 536/96, 536/97, 536/99, 536/100
• US Class Current: 536/30
• CPC Class Codes: A61K 8/027 Fibers; Fibrils
• CPC Class Codes: A61K 8/731 Cellulose; Quaternized cellulose derivatives
• CPC Class Codes: A61Q 11/00 Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
• CPC Class Codes: A61Q 17/04 Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: A61Q 19/08 Anti-ageing preparations
• 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 11/12 substituted with carboxylic radicals , e.g. carboxymethylcellulose [CMC]
• CPC Class Codes: C08B 11/20 Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
• CPC Class Codes: C08B 15/00 Preparation of other cellulose derivatives or modified cellulose , e.g. complexes
• CPC Class Codes: C08B 37/00 Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof cellulose D21; microbiological processes C12P
• CPC Class Codes: D21H 17/26 Ethers thereof
• CPC Class Codes: D21H 21/10 Retention agents or drainage improvers
• CPC Class Codes: D21H 21/16 Sizing or water-repelling agents
• CPC Class Codes: D21H 21/18 Reinforcing agents
• CPC Class Codes: D21H 21/20 Wet strength agents

Abstract

A method for producing derivatized microfibrillar polysaccharide, including but not limited to cellulose, derivatized by steric and/or electrostatic forces, where the electrostatic forces are provided by anionic charge or by a combination of both anionic and cationic charge, by stabilizing and/or microfibrillating a polysaccharide starting material. A method of modifying the rheological properties of a composition of matter using derivatized microfibrillar polysaccharide. Method of improving coatings, paper manufacture, and the stability of emulsions, dispersions, and foams using a derivatized microfibrillar polysaccharide. Compositions that include derivatized microfibrillar polysaccharide, including paper compositions, comestible compositions, non-comestible spreadable compositions, and emulsions, dispersion, and foams.

Claims

1. A derivatized microfibrillar polysaccharide, derivatized to comprise substituents that provide electrostatic and/or steric functionality, said electrostatic functionality comprising anionic charge, wherein the derivatized microfibrillar polysaccharide is characterized by forming a gel in water at at least one point in the concentration range of from about 0.05 wt. % to about 0.99 wt. % based on the total weight of the gel.

2. The derivatized microfibrillar polysaccharide of claim 1, wherein the polysaccharide in said derivatized microfibrillar polysaccharide comprises at least one of cellulose, hemicellulose, chitin, chitosan, guar gum, pectin, alginate, agar, xanthan, starch, amylose, amylopectin, alternan, gellan, mutan, dextran, pullulan, fructan, locust bean gum, carrageenan, glycogen, glycosaminoglycans, murein, bacterial capsular polysaccharides, and derivatives thereof.

3. The derivatized microfibrillar polysaccharide of claim 2, wherein said polysaccharide is at least one of cellulose, chitin, chitosan, pectin, agar, starch, carrageenan, and derivatives thereof.

4. The derivatized microfibrillar polysaccharide of claim 3, comprising derivatized microfibrillar cellulose.

5. The derivatized microfibrillar polysaccharide of claim 4, wherein said cellulose is obtained from at least one of chemical pulps, mechanical pulps, thermal mechanical pulps, chemical-thermal mechanical pulps, recycled fibers, newsprint, cotton, soybean hulls, pea hulls, corn hulls, flax, hemp, jute, ramie, kenaf, manila hemp, sisal hemp, bagasse, corn, wheat, bamboo, velonia, bacteria, algae, fungi, microcrystalline cellulose, vegetables, and fruits.

6. The derivatized microfibrillar polysaccharide of claim 5, wherein said cellulose is obtained from at least one of optionally bleached wood pulps produced from sulfite, kraft, or prehydrolyzed kraft pulping processes;

cotton linters;

fruits; and

vegetables.

7. The derivatized microfibrillar cellulose of claim 4, comprising at least one of microfibrillated hydroxyethyl cellulose, microfibrillated ethylhydroxyethyl cellulose, microfibrillated carboxymethylcellulose, microfibrillated carboxymethylhydroxyethyl cellulose, microfibrillated hydroxypropylhydroxyethyl cellulose, microfibrillated methyl cellulose, microfibrillated methylhydroxypropyl cellulose, microfibrillated methylhydroxyethyl cellulose, microfibrillated carboxymethylmethyl cellulose, microfibrillated hydrophobically modified carboxymethylcellulose, microfibrillated hydrophobically modified hydroxyethyl cellulose, microfibrillated hydrophobically modified hydroxypropyl cellulose, microfibrillated hydrophobically modified ethylhydroxyethyl cellulose, microfibrillated hydrophobically modified carboxymethylhydroxyethyl cellulose, microfibrillated hydrophobically modified hydroxypropylhydroxyethyl cellulose, microfibrillated hydrophobically modified methyl cellulose, microfibrillated hydrophobically modified methylhydroxypropyl cellulose, microfibrillated hydrophobically modified methylhydroxyethyl cellulose, microfibrillated hydrophobically modified carboxymethylmethyl cellulose, microfibrillated nitrocellulose, microfibrillated cellulose acetate, microfibrillated cellulose sulfate, microfibrillated cellulose vinyl sulfate, microfibrillated cellulose phosphate, and microfibrillated cellulose phosphonate.

8. The derivatized microfibrillar cellulose of claim 4, wherein said derivatized microfibrillar cellulose forms a gel in water throughout the concentration range of between about 0.01 wt. % and about 100 wt. % solids based on the total weight of the gel.

9. The derivatized microfibrillar cellulose of claim 4, wherein said derivatized microfibrillar cellulose forms a gel in water throughout the concentration range of between about 0.01 wt. % and about 50 wt. % solids based on the total weight of the gel.

10. The derivatized microfibrillar cellulose of claim 4, wherein said derivatized microfibrillar cellulose forms a gel in water at at least one point in the concentration range of from about 0.05 wt. % up to about 0.99 wt. % solids based on the total weight of the gel.

11. The derivatized microfibrillar cellulose of claim 4, comprising carboxymethylcellulose.

12. The derivatized microfibrillar polysaccharide of claim 4, wherein said derivatized microfibrillar cellulose forms a gel in water at a concentration of less than about 1 wt. % solids based on the total weight of the gel.

13. The derivatized microfibrillar polysaccharide of claim 1, further comprising a solvent, wherein said derivatized microfibrillar polysaccharide is substantially insoluble in said solvent.

14. The derivatized microfibrillar polysaccharide of claim 13, wherein said solvent is water, alcohol, or oil.

15. The derivatized microfibrillar polysaccharide of claim 14, wherein said solvent is water.

16. The derivatized microfibrillar polysaccharide of claim 15, wherein said derivatized microfibrillar polysaccharide is derivatized to comprise substituents that provide electrostatic functionality.

17. The derivatized microfibrillar polysaccharide of claim 15, wherein said derivatized microfibrillar polysaccharide is derivatized to comprise substituents that provide steric functionality.

18. The derivatized microfibrillar polysaccharide of claim 17, having a molar substitution of less than about 3.0.

19. The derivatized microfibrillar polysaccharide of claim 18, wherein said molar substitution is less than about 1.5.

20. The derivatized microfibrillar polysaccharide of claim 19, wherein said molar substitution is less than about 1.0.

21. The derivatized microfibrillar polysaccharide of claim 20, wherein said molar substitution is less than about 0.5.

22. The derivatized microfibrillar polysaccharide of claim 18, wherein said molar substitution is between about 0.5 and 3.0.

23. The derivatized microfibrillar polysaccharide of claim 17, wherein said substituents comprise at least one of hydroxyethyl groups;

hydroxypropyl groups;

methyl groups;

ethyl groups;

straight- or branched-chain alkyl, alkenyl, or alkynyl groups having from about 4 to about 30 carbons;

aryl, arylalkyl, arylalkenyl, cyclic, and herterocyclic hydrocarbons having from about 4 to about 30 carbons;

or combinations thereof.

24. The derivatized microfibrillar polysaccharide of claim 23, further wherein said derivatized microfibrillar polysaccharide is a derivatized microfibrillar cellulose.

25. The derivatized microfibrillar cellulose of claim 24, wherein said microfibrillar cellulose is further derivatized to provide electrostatic functionality with a degree of substitution of less than about 0.35.

26. The derivatized microfibrillar cellulose of claim 25, wherein said degree of substitution is less than about 0.20.

27. The derivatized microfibrillar cellulose of claim 26, wherein said degree of substitution is between about 0.02 and about 0.2.

28. The derivatized microfibrillar cellulose of claim 27, wherein said degree of substitution is between about 0.10 and about 0.2.

29. The derivatized microfibrillar polysaccharide of claim 1, wherein said derivatized microfibrillar polysaccharide comprises electrostatically derivatized microfibrillar cellulose having a degree of substitution of less than about 0.5.

30. The derivatized microfibrillar polysaccharide of claim 29, wherein said degree of substitution is less than about 0.35.

31. The derivatized microfibrillar polysaccharide of claim 30, wherein said degree of substitution is less than about 0.2.

32. The derivatized microfibrillar polysaccharide of claim 31, wherein said degree of substitution is less than about 0.18.

33. The derivatized microfibrillar polysaccharide of claim 32, wherein said degree of substitution is less than about 0.1.

34. The derivatized microfibrillar polysaccharide of claim 29, wherein said degree of substitution is between about 0.02 and about 0.5.

35. The derivatized microfibrilliar polysaccharide of claim 34, wherein said degree of substitution is between about 0.05 and about 0.2.

36. The derivatized microfibrillar polysaccharide of claim 1, derivatized to comprise substituents that provide electrostatic functionality in the form of anionic charge, wherein the degree of substitution representing substituents that provide electrostatic functionality in the form of anionic charge is at least about 0.02.

37. The derivatized microfibrillar polysaccharide of claim 1, wherein said anionic charge is provided by carboxyl, sulfate, sulfonate, phosphonate, or phosphate groups, or combinations thereof.

38. Microfibrillar carboxymethylcellulose having a degree of substitution of between about 0.10 and about 0.20.

39. A paper composition comprising derivatized microfibrillar cellulose derivatized to comprise groups that provide electrostatic and/or steric functionality, further wherein said electrostatic functionality comprises the presence of anionic charge.

40. The paper composition of claim 39, wherein said derivatized microfibrillar cellulose is microfibrillar carboxymethylcellulose.