Cellulose interpolymers and method of oxidation

• US 7,879,994 B2
• Filed: 11/23/2004
• Issued: 02/01/2011
• Est. Priority Date: 11/28/2003
• Status: Active Grant

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: Watterson, Thelma Lee, Lambert, Juanelle Little, Carty, Susan Northrop, Lindblad, Margaretha Soderqvist, Malcolm, Michael Orlando, Kuo, Chung-Ming, Posey-Dowty, Jessica Dee, Buchanan, Charles Michael, Wood, Matthew Davie, Buchanan, Norma Lindsey
• Primary Examiner(s): Jiang; Shaojia Anna
• Assistant Examiner(s): Lau; Jonathan S
• Application Number:
  US10/995,750
• Publication Number:
  US 20050192434A1
• Time in Patent Office: 2,261 Days
• Field of Search: 536/64, 536/124
• US Class Current: 536/64
• CPC Class Codes: A61K 47/38 Cellulose; Derivatives thereof
• CPC Class Codes: A61K 9/19 lyophilised , i.e. freeze-dried, solutions or dispersions lyophilised products with subsequent particle size reduction A61K9/14; granules or pellets made by lyphilisation A61K9/1682; solid oral dosage forms made by lyophilisation A61K9/2095; lyophilisation additives A61K47/00
• CPC Class Codes: A61K 9/2054 Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
• CPC Class Codes: A61K 9/2866 Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
• CPC Class Codes: A61K 9/4891 Coated capsules; Multilayered drug free capsule shells with drug coating for immediate release A61K9/4808; osmotic devices A61K9/0004
• CPC Class Codes: C08B 15/02 Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
• CPC Class Codes: C08B 15/04 Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
• CPC Class Codes: C08B 3/04 Cellulose formate
• CPC Class Codes: C08B 3/06 Cellulose acetate , e.g. mono-acetate, di-acetate or tri-acetate
• CPC Class Codes: C08B 3/08 of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
• CPC Class Codes: C08B 3/16 Preparation of mixed organic cellulose esters , e.g. cellulose aceto-formate or cellulose aceto-propionate
• CPC Class Codes: C08B 3/22 Post-esterification treatments, including purification
• CPC Class Codes: C08B 3/24 Hydrolysis or ripening
• CPC Class Codes: C08L 1/10 Esters of organic acids , i.e. acylates
• CPC Class Codes: C08L 1/12 Cellulose acetate
• CPC Class Codes: C08L 1/14 Mixed esters, e.g. cellulose acetate-butyrate
• CPC Class Codes: C09D 17/00 Pigment pastes, e.g. for mixing in paints artists' paints C09D5/06

Abstract

This invention provides cellulose ester interpolymers, and methods of oxidizing cellulose interpolymers and cellulose ester interpolymers. The invention also provides routes to access carboxylated cellulose ester derivatives with high acid numbers wherein the carboxyl group is attached directly to the cellulose backbone by a carbon-carbon bond. Through functionalization of an intermediate aldehyde, the corresponding cationic or zwitterionic cellulose ester derivatives can also be accessed. The interpolymers of the present invention have a number of end-use applications, for example, as binder resins in various types of coating compositions and as drug delivery agents.

Claims

1. A cellulose ester interpolymer wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolymer are in the alcohol oxidation state, and consisting of anhydroglucose units

2. The cellulose ester interpolymer of claim 1, having an apparent degree of substitution per anhydroglucose unit of X of 0.05 to 1.0, and an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of at least about 0.6.

3. The cellulose ester interpolymer of claim 1, having an apparent degree of substitution per anhydroglucose unit of X of 0.2 to 1.0, and an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8.

4. The cellulose ester interpolymer of claim 1, having an acid number greater than 10.

5. The cellulose ester interpolymer of claim 1, having an acid number greater than 30.

6. The cellulose ester interpolymer of claim 1, having an acid number greater than 30 and less than 150.

7. The cellulose ester interpolymer of claim 1, having an acid number greater than 30 and less than 130.

8. The cellulose ester interpolymer of claim 1, having an acid number greater than 30 and less than 90.

9. The cellulose ester interpolymer of claim 1, wherein R₁, R₂, R₃, R₄, and R₅ are independently selected from the group consisting of hydrogen, acetyl, propionyl, butyryl, or a mixture thereof.

10. The cellulose ester interpolymer of claim 1, having a weight average molecular weight of at least 5,000 g/mol.

11. The cellulose ester interpolymer of claim 1, having a range of molecular weight of between 10,000 g/mol and 900,000 g/mol.

12. The cellulose ester interpolymer of claim 1, having a degree of polymerization of at least 10.

13. The cellulose ester interpolymer of claim 1, having a degree of polymerization of at least 25.

14. The cellulose ester interpolymer of claim 1, having a degree of polymerization of between 25 and 50.

15. The cellulose ester interpolymer of claim 1, having a degree of polymerization of at least 250.

16. The cellulose ester interpolymer of claim 1, wherein at least one of R₃ is hydrogen.

17. A cellulose ester interpolymer wherein the C2 and C3 positions of each of the monomer units of the cellulose ester interpolymer are in the alcohol oxidation state, and comprising a plurality of anhydroglucose units having a C6 carboxy group and wherein the cellulose ester interpolymer has an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of at least about 0.6 and an acid number of greater than 10, wherein said cellulose ester interpolymer consists of anhydroglucose units, anhydroglucuronic acid units, esters of anhydroglucose units, and esters of anhydroglucuronic acid units.

18. The cellulose ester interpolymer of claim 17 having an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8.

19. The cellulose ester interpolymer of claim 17 having an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8, and an acid number of greater than 30 and less than 150.

20. The cellulose ester interpolymer of claim 17 having an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8, and an acid number of greater than 30 and less than 130.

21. The cellulose ester interpolymer of claim 17 having an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8, and an acid number of greater than 30 and less than 90.

22. The cellulose ester interpolymer of claim 17, wherein said C₂-C₁₂ acyl is acetyl, propionyl, butyryl, or a mixture thereof.

23. The cellulose ester interpolymer of claim 17 having a random distribution throughout the cellulose ester interpolymer of anhydroglucose units having C6 carboxy groups.

24. The cellulose ester interpolymer of claim 17, having a weight average molecular weight of at least 5,000 g/mol.

25. The cellulose ester interpolymer of claim 17, having a range of molecular weight of between 10,000 g/mol and 900,000 g/mol.

26. The cellulose ester interpolymer of claim 17, having a degree of polymerization of at least 10.

27. The cellulose ester interpolymer of claim 17, having a degree of polymerization of at least 25.

28. The cellulose ester interpolymer of claim 17, having a degree of polymerization of between 25 and 50.

29. The cellulose ester interpolymer of claim 17, having a degree of polymerization of about 250.

30. The cellulose ester interpolymer of claim 17, further comprising a plurality of anhydroglucose units having a primary alcohol group at C6.

31. A cellulose ester interpolymer having a degree of polymerization of at least 10, an acid number of greater than 10, and a random distribution throughout the cellulose ester interpolymer of anhydroglucose units having a C6 carboxy group, wherein the C2 and C3 positions of each of the monomer units of the cellulose ester interpolymer are in the alcohol oxidation state, wherein said cellulose ester interpolymer consists of anhydroglucose units, anhydroglucuronic acid units, esters of anhydroglucose units, and esters of anhydroglucuronic acid units.

32. The cellulose ester interpolymer of claim 31, having an acid number of greater than 30.

33. The cellulose ester interpolymer of claim 31, having an acid number of greater than 30 and less than 150.

34. The cellulose ester interpolymer of claim 31, having a weight average molecular weight of at least 5,000 g/mol.

35. The cellulose ester interpolymer of claim 31, further comprising a plurality of anhydroglucose units having a primary alcohol group at C6.