Polysaccharide-Polyamine Copolymers For Removal Of Phosphate

• US 20180099007A1
• Filed: 03/18/2016
• Published: 04/12/2018
• Est. Priority Date: 03/20/2015
• Status: Active Grant

• Current Assignee: Howard University
• Original Assignee: Howard University
• Inventors: Mitchell, James W., Yang, Dazhi
• Granted Patent: US 10,849,927 B2
• Time in Patent Office: Days
• CPC Class Codes: A61K 31/738 Cross-linked polysaccharides
• CPC Class Codes: A61K 31/785 Polymers containing nitrogen
• CPC Class Codes: A61K 9/14 Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles microspheres A61K9/16; microcapsules A61K9/50; nanocapsules, nanoparticles of the matrix type A61K9/51
• CPC Class Codes: A61P 7/08 Plasma substitutes; Perfusion solutions; Dialytics or haemodialytics; Drugs for electrolytic or acid-base disorders, e.g. hypovolemic shock artificial tears A61P27/04
• CPC Class Codes: B01J 20/264 derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
• CPC Class Codes: B01J 20/267 Cross-linked polymers
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28078 Pore diameter
• CPC Class Codes: B01J 20/28085 being more than 50 nm, i.e. macropores
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: C08B 15/06 containing nitrogen , e.g. carbamates
• CPC Class Codes: C08F 251/02 on to cellulose or derivatives thereof
• CPC Class Codes: C08G 2101/00 Manufacture of cellular products
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08G 73/0206 Polyalkylene(poly)amines
• CPC Class Codes: C08G 81/00 Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers involving only carbon-to-carbon unsaturated bond reactions C08F299/00 ; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42
• CPC Class Codes: C08G 83/002 Dendritic macromolecules
• CPC Class Codes: C08J 2205/022 Hydrogel, i.e. a gel containing an aqueous composition
• CPC Class Codes: C08J 2207/10 Medical applications, e.g. biocompatible scaffolds
• CPC Class Codes: C08J 2387/00 Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08J 9/16 : Making expandable particles
• CPC Class Codes: C08L 1/08 : Cellulose derivatives
• CPC Class Codes: C08L 3/20 : Oxidised amylose; Oxidised amylopectin
• CPC Class Codes: C08L 5/02 : Dextran; Derivatives thereof
• CPC Class Codes: C08L 5/08 : Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

Abstract

Covalently cross-linked copolymers are described herein. More specifically, polysaccharide-polyamine copolymeric matrices or structures and cationic copolymeric matrices are described herein. The polysaccharide-polyamine copolymers, when protonated, can form cationic copolymeric matrices having exceptionally high densities of cationic sites. In one form, the covalently cross-linked copolymers provide a three-dimensional structure, especially when hydrated.

Claims

1. A polysaccharide-polyamine copolymer having an amino functionality which will provide a protonatable copolymeric material having a three-dimensional structure with cationic sites through protonation, the polysaccharide-polyamine copolymer comprising:

a selectively oxidized polysaccharide having a 2,3-dialdehyde moiety; and

amino polymers which provide an amino functionality, the amino polymers cross linking the oxidized polysaccharides to provide a particulate polysaccharide-polyamine copolymer having an amino functionality which when protonated will provide the cationic copolymeric material with a nitrogen content of at least 12.3 wt. %, both the polysaccharide-polyamine copolymer and cationic copolymeric material being water insoluble.

2. The polysaccharide-polyamine copolymer of claim 1, wherein the amino polymers have a nitrogen content of at least 24.5 wt. %, based on the weight of the amino polymers and a molecular weight in the range of from about 15,000 to about 900,000.

3. The polysaccharide-polyamine copolymer of claim 1, wherein the selectively oxidized polysaccharide are selected from the group consisting of selectively oxidized cellulose, selectively oxidized starch, selectively oxidized amylose, selectively oxidized chitosan, selectively oxidized dextran, selectively oxidized glycogen, selectively oxidized chitin and mixtures thereof, the polysaccharide having been oxidized in an amount effective to provide the 2,3-dialdehyde moiety which is reactive with the amino polymers.

4. The polysaccharide-polyamine copolymer of claim 1, wherein the selectively oxidized polysaccharide have β

-1,4-glycosidic bonds or β

-1,6-glycosidic bonds.

5. The polysaccharide-polyamine copolymer of claim 1, wherein the selectively oxidized polysaccharide have β

-1,4-glycosidic bonds.

6. The polysaccharide-polyamine copolymer of claim 1, wherein the selectively oxidized polysaccharide is selected from the group consisting of selectively oxidized cellulose, selectively oxidized chitosan, selectively oxidized chitin, selectively oxidized amylose and mixtures thereof.

7. The polysaccharide-polyamine copolymer of claim 1, wherein the amino polymers which provide a cationic amino functionality are selected from the group consisting of polyethylenimine, poly(allylamine) and polypropylenimine tetramine and mixtures thereof.

8. The polysaccharide-polyamine copolymer of claim 1, wherein the amino polymers are in a branched or dendritic form.

9. The polysaccharide-polyamine copolymers of claim 1, wherein the particulates of the polysaccharide-polyamine copolymer and cationic copolymeric material have sizes in the range of from about 100 μ

m to about 10 mm.

10. The polysaccharide-polyamine copolymer of claim 1, wherein the particulate polysaccharide-polyamine copolymer and cationic copolymeric material has particulates having sizes in the range of from about 100 μ

m to about 10 mm and pore sizes of less than about 50 μ

m.

11. A method of making a polysaccharide-polyamine copolymer and copolymeric materials which when protonated have cationic sites, the method comprising:

reacting selectively oxidized polysaccharides having a 2,3 di-aldehyde moieties with amino polymers, the reaction providing a particulate polysaccharide-polyamine copolymer and copolymeric material having an amino functionality in an amount which when protonated provides a cationic copolymeric material with a nitrogen content of at least 12.3 wt. %, based upon the weight of the cationic copolymeric material, both the polysaccharide-polyamine copolymer and copolymeric material being water insoluble.

12. The method claim 11, wherein the selectively oxidized polysaccharides are selected from the group consisting of consisting of selectively oxidized cellulose, selectively oxidized starch, selectively oxidized amylose, selectively oxidized chitosan, selectively oxidized dextran, selectively oxidized glycogen, selectively oxidized chitin and mixtures thereof, the polysaccharide having been oxidized in an amount effective to provide the 2,3 di-aldehyde moiety which is reactive with the amino polymers.

13. The method of claim 11, wherein the amino polymers have a nitrogen content of at least 24.5 wt. %, based on the weight of the amino polymers, and a molecular weight in the range of from about 15,000 to about 900,000.

14. The method of claim 11, wherein the amino polymers which provide a cationic amino functionality are selected from the group consisting of polyethylenimine, poly(allylamine) and polypropylenimine tetramine and mixtures thereof.

15. The method of claim 11, wherein the selectively oxidized polysaccharides have β

-1,4-glycosidic bonds.

16. The method of claim 11, wherein the selectively oxidized polysaccharides have β

-1,6-glycosidic bonds.

17. The method of claim 11, wherein the selectively oxidized polysaccharides is selected from the group consisting of selectively oxidized cellulose, selectively oxidized chitosan, selectively oxidized chitin, selectively oxidized amylose and mixtures thereof.

18. The method of claim 11, wherein the particulate polysaccharide-polyamine copolymer and copolymeric material has particulates having sizes in the range of from about 100 μ

m to about 10 mm and pore sizes of less than about 50 μ

m.

19. A method to effect removal of phosphate from an aqueous phosphate solution, the method comprising applying a protonated particulate polysaccharide-polyamine copolymeric material having a three-dimensional structure, the particulate polysaccharide-polyamine polymeric material comprising:

selectively oxidized polysaccharide having a 2,3 di-aldehyde moiety; and

amino polymers which provide a cationic amino functionality, the amino polymers covalently cross linking the selectively oxidized polysaccharide to provide a particulate polysaccharide-polyamine copolymer and copolymeric material having an amino functionality which when protonate will provide the cationic copolymeric material with a nitrogen content of at least 12.3 wt. %, the cationic particulate polysaccharide-polyamine copolymer and cationic copolymeric material being water insoluble.

20. The method to effect removal of phosphate as recited in claim 19, wherein the selectively oxidized polysaccharides are selected from the group consisting of consisting of selectively oxidized cellulose, selectively oxidized starch, selectively oxidized amylose, selectively oxidized chitosan, selectively oxidized dextran, selectively oxidized glycogen, selectively oxidized chitin and mixtures thereof, the polysaccharide having been oxidized in an amount effective to provide the 2,3 di-aldehyde moiety which is reactive with the amino polymers.

21. The method to effect removal of phosphate of claim 19, wherein the amino polymers have a nitrogen content of at least 24.5 wt. %, based on the weight of the amino polymers, and a molecular weight in the range of from about 15,000 to about 900,000.

22. The method to effect removal of phosphate of claim 19, the selectively oxidized polysaccharides are selected from the group consisting of selectively oxidized cellulose, selectively oxidized starch, selectively oxidized amylose, selectively oxidized chitosan, selectively oxidized dextran, selectively oxidized glycogen, selectively oxidized chitin and mixtures thereof, the polysaccharide having been oxidized in an amount effective to provide the 2,3 di-aldehyde moiety which is reactive with the amino polymers.

23. The method to effect removal of phosphate of any of the preceding method of removal claim 19, wherein the amino polymers which provide a cationic amino functionality are selected from the group consisting of polyethylenimine, poly(allylamine) and polypropylenimine tetramine and mixtures thereof.

24. The method to effect removal of phosphate of any of the preceding method of removal claim 19, wherein the selectively oxidized polysaccharides have β

-1,4-glycosidic bonds.

25. The method to effect removal of phosphate of claim 19, wherein the selectively oxidized polysaccharides have β

-1,6-glycosidic bonds.

26. The method to effect removal of phosphate of claim 19, wherein the selectively oxidized polysaccharide is selected from the group consisting of selectively oxidized cellulose, selectively oxidized chitosan, selectively oxidized chitin, selectively oxidized amylose and mixtures thereof.

27. The method to effect removal of phosphate of claim 19, wherein the particulate polysaccharide-polyamine copolymer and copolymeric material has particulates having sizes in the range of from about 100 m to about 10 mm and pore sizes of less than about 50 μ

m.

28. A cationic copolymeric material comprising a protonated polysaccharide-polyamine copolymer having a three-dimensional structure, the polysaccharide-polyamine copolymer material comprising:

selectively oxidized polysaccharide having a 2,3 di-aldehyde moiety; and

amino polymers which provide a cationic amino functionality, the amino polymers covalently cross linking the oxidized polysaccharide to provide a particulate polysaccharide-polyamine copolymer and copolymeric material having an amino functionality which when protonated will provide the cationic copolymeric material with a nitrogen content of at least 12.5 wt. %, the cationic copolymer and cationic polymeric material being water insoluble.

29. The cationic copolymeric material of claim 28, wherein the amino polymers have a nitrogen content of at least 24.5 wt. %, based on the weight of the amino polymers, and a molecular weight in the range of from about 15,000 to about 900,000.

30. The cationic copolymeric material of claim 28, the selectively oxidized polysaccharides are selected from the group consisting of selectively oxidized cellulose, selectively oxidized starch, selectively oxidized amylose, selectively oxidized chitosan, selectively oxidized dextran, selectively oxidized glycogen, selectively oxidized chitin and mixtures thereof, the polysaccharide having been oxidized in an amount effective to provide the 2,3 di-aldehyde moiety which is reactive with the amino polymers.

31. The cationic copolymeric material of claim 28, wherein the selectively oxidized polysaccharides have β

-1,4-glycosidic bonds.

32. The cationic copolymeric material of claim 28, wherein the selectively oxidized polysaccharides have β

-1,6-glycosidic bonds.

33. The cationic copolymeric material of claim 28, wherein the selectively oxidized polysaccharide is selected from the group consisting of selectively oxidized cellulose, selectively oxidized chitosan, selectively oxidized chitin, selectively oxidized amylose and mixtures thereof.

34. The cationic copolymeric material of claim 28, wherein the amino polymers which provide a cationic amino functionality are selected from the group consisting of polyethylenimine, poly(allylamine) and polypropylenimine tetramine and mixtures thereof.

35. The cationic copolymeric material of claim 28, wherein the particulate polysaccharide-polyamine copolymer and copolymeric material has particulates having sizes in the range of from about 100 μ

m to about 10 mm and pore sizes of less than about 50 μ

m.