Polysaccharide-polyamine copolymers for removal of phosphate

Patent metadata

Field	Value
Publication number	US-10849927-B2
Application number	US-201615560131-A
Country	US
Kind code	B2
Filing date	Mar 18, 2016
Priority date	Mar 20, 2015
Publication date	Dec 1, 2020
Grant date	Dec 1, 2020

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.

First claim

What is claimed is:

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,
wherein the amino polymers are in a branched or dendritic form.

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 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 μm to about 10 mm.

9. 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 μm to about 10 mm and pore sizes of less than about 50 μm.

10. A method of making the polysaccharide-polyamine copolymer and copolymeric materials which when protonated have cationic sites of claim 1 , 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.

11. The method claim 10 , 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.

12. The method of claim 10 , 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.

13. The method of claim 10 , 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.

14. The method of claim 10 , wherein the selectively oxidized polysaccharides have β-1,4-glycosidic bonds.

15. The method of claim 10 , wherein the selectively oxidized polysaccharides have β-1,6-glycosidic bonds.

16. The method of claim 10 , 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.

17. The method of claim 10 , wherein the particulate polysaccharide-polyamine copolymer and copolymeric material has particulates having sizes in the range of from about 100 μm to about 10 mm and pore sizes of less than about 50 μm.

Assignees

• Univ Howard

Inventors

• Mitchell James W
• Yang Dazhi

Classifications

• C08G81/00

  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 title

• A61K31/785 Primary

  Polymers containing nitrogen · CPC title

• B01J20/267

  Cross-linked polymers · CPC title

• C08G73/0206

  Polyalkylene(poly)amines · CPC title

• B01J20/28004

  Sorbent size or size distribution, e.g. particle size · CPC title