OUTER LAYER HAVING ENTANGLEMENT OF HYDROPHOBIC POLYMER HOST AND HYDROPHILIC POLYMER GUEST

• US 20100150983A1
• Filed: 02/15/2010
• Published: 06/17/2010
• Est. Priority Date: 10/30/2001
• Status: Active Grant

• Current Assignee: Colorado State University Research Foundation
• Original Assignee: Colorado State University Research Foundation
• Inventors: JAMES, Susan P., ZHANG, Min, BEAUREGARD, Guy
• Granted Patent: US 8,524,886 B2
• Time in Patent Office: Days
• US Class Current: 424/423
• CPC Class Codes: A61P 43/00 Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
• CPC Class Codes: B05D 5/00 Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• CPC Class Codes: B29C 67/24 characterised by the choice of material
• 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: C08B 37/0072 Hyaluronic acid, i.e. HA or hyaluronan; Derivatives thereof, e.g. crosslinked hyaluronic acid (hylan) or hyaluronates
• CPC Class Codes: C08J 9/42 with macromolecular compounds
• CPC Class Codes: C08L 101/00 Compositions of unspecified macromolecular compounds
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/26 Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
• CPC Class Codes: C08L 5/08 Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31971 Of carbohydrate

Abstract

An outer layer having an entanglement comprising an intermingling of cloaked hydrophilic guest and a hydrophobic polymer host, wherein molecules of the guest have been crosslinked with each other. Under certain circumstances, using complexes of the guest may be desirable or even necessary. The intermingling of the guest and host includes a physical tangling, whether it also comprises crosslinking by primary bonding (e.g., chemical/covalent bonding) there-between. Also a method of producing an outer layer having such an entanglement, including the steps of: temporarily cloaking at least a portion of the hydrophilic groups of the guest; intermingling at least a portion of the cloaked groups with a porous polymeric structure by diffusing the guest with cloaked groups into at least a portion of the structure'"'"'s pores; within the pores, crosslinking at least a portion of the molecules of the guest with the guest; and removing the cloaking. Cloaking may be performed by silylation or acylation. Intermingling may be performed by producing a mixture of guest and host (whether in solution, powdered, granular, etc., form); next, a crosslinking of the guest with itself is performed; then, the mixture is molded into the outer layer.

Claims

1-6. -6. (canceled)

7. A system comprising an outer layer having an entanglement comprising a hydrophobic polymer host and a hydrophilic guest, said outer layer being formed into a structure comprising a base comprising the hydrophobic polymer of the host;

wherein the hydrophilic guest comprises a compound selected from the group consisting of polyions, polysaccharides, salts of glycosaminoglycans, nucleic acids, polyvinylpyrrolidones, peptides, polypeptides, proteins, lipoproteins, polyamides, polyamines, polyhydroxy polymers, polycarboxy polymers, phosphorylated derivatives of carbohydrates, sulfonated derivatives of carbohydrates, interleukin-2, interferon, and phosphorothioate oligomers;

the entanglement comprises an intermingling of cloaked hydrophilic groups of the hydrophilic guest with the hydrophobic polymer host, and crosslinked molecules of the hydrophilic guest with the guest and

said cloaked groups having been returned to an initial hydrophilic state to produce a generally hydrophilic outer surface of the layer,

and wherein said generally hydrophilic outer surface of the layer is selected from the group consisting of;

a bearing surface;

a flexible barrier surface separating a first and second area;

a transparent member surface;

an in vivo implant surface;

a drag reduction surface;

a reaction resin surface;

a topical dressing surface; and

a dental splint surface.

8. An outer layer having an entanglement comprising a hydrophobic porous polymeric host structure and a hydrophilic guest, comprising:

the hydrophilic guest comprises a compound selected from the group consisting of polyions, polysaccharides, salts of glycosaminoglycans, nucleic acids, polyvinylpyrrolidones, peptides, polypeptides, amino acids, proteins, lipoproteins, polyamides, polyamines, polyhydroxy polymers, polycarboxy polymers, phosphorylated derivatives of carbohydrates, sulfonated derivatives of carbohydrates, interleukin-2, interferon, and phosphorothioate oligomers; and

the entanglement comprising an intermingling of cloaked hydrophilic groups of the hydrophilic guest diffused into a plurality of pores of the porous polymeric host structure, and crosslinked molecules of the hydrophilic guest with the guest; and

said cloaked groups having been returned to an initial hydrophilic state to produce a generally hydrophilic outer surface of the layer.

9. An outer layer having an entanglement comprising a hydrophobic polymer host and a hydrophilic guest, comprising:

the hydrophilic guest comprises a compound selected from the group consisting of polyions, polysaccharides, salts of glycosaminoglycans, nucleic acids, polyvinylpyrrolidones, peptides, polypeptides, amino acids, proteins, lipoproteins, polyamides, polyamines, polyhydroxy polymers, polycarboxy polymers, phosphorylated derivatives of carbohydrates, sulfonated derivatives of carbohydrates, interleukin-2, interferon, and phosphorothioate oligomers; and

the entanglement comprises an intermingling of acylated hydrophilic groups of the hydrophilic guest in a powdered form with a powdered form of the host, and crosslinked molecules of the hydrophilic guest with the guest;

said acylated groups having been returned to an initial hydrophilic state to produce a generally hydrophilic outer surface of the layer; and

the layer produced by way of a thermal molding of said powdered form of the guest with the host.

10. A method of producing an outer layer having an entanglement comprising a hydrophobic porous polymeric structure and a hydrophilic guest, the method comprising the steps of:

temporarily cloaking at least a portion of the hydrophilic groups of the guest;

intermingling at least a portion of said cloaked guest with the porous polymeric structure by diffusing the cloaked guest into at least a portion of the structure'"'"'s pores;

within said pores, crosslinking at least a portion of the molecules of the guest with the guest; and

removing said cloaking to produce a generally hydrophilic outer surface of the outer layer.

11. The method of claim 10 wherein:

the guest is a polysaccharide;

said intermingling is performed using complexes of the guest comprising an QN⁺ group, where QN⁺ represents a long-chain paraffin ammonium cation;

said cloaking said hydrophilic groups of said complexes comprises performing a silylation using a silylating agent; and

said step of removing further comprises performing a hydrolysis reaction.

12. The method of claim 10 wherein:

the hydrophobic porous polymeric structure is a molded form comprising ultra high molecular weight polyethylene;

said polysaccharide is hyaluronic acid;

said intermingling is performed using complexes of the guest comprising an QN⁺ group, where QN⁺ represents a cation selected from the group consisting of alkyltrimethylammonium chloride, alkylamine hydrochloride, alkylpyridinium chloride, alkyldimethylbenzyl ammonium chloride, alkyltrimethylammonium bromide, alkylamine hydrobromide, alkylpyridinium bromide, and alkyldimethylbenzyl ammonium bromide; and

further comprising the step of dissociating said QN⁺ groups from said guest complexes in a salt solution.

13. The method of claim 10 wherein:

the guest comprises a compound selected from the group consisting of polyions, polysaccharides, salts of glycosaminoglycans, nucleic acids, polyvinylpyrrolidones, peptides, polypeptides, amino acids, proteins, lipoproteins, polyamides, polyamines, polyhydroxy polymers, polycarboxy polymers, phosphorylated derivatives of carbohydrates, sulfonated derivatives of carbohydrates, interleukin-2, interferon, and phosphorothioate oligomers;

said cloaking said hydrophilic groups comprises performing a silylation using a silylating agent; and

said crosslinking further comprises exposing said cloaked guest within said pores to a crosslinker; and

further comprising the step of thermally forming the layer into a preselected shape.

14. The method of claim 13 wherein:

said polyhydroxy polymers comprise a polymer selected from the group consisting of polyvinyl alcohol and polyethylene glycol;

said polycarboxy polymers comprise a polymer selected from the group consisting of carboxymethylcellulose, alginic acid, sodium alginate, and calcium alginate;

said intermingling is performed using complexes of the guest; and

said step of removing further comprises performing a hydrolysis reaction; and

further comprising the step of returning the guest complexes to a pre-complex state by dissociation of a group therefrom.

15. A system comprising the layer produced according to the method of claim 10 thermally-formed with a base comprising the hydrophobic porous polymer of the structure into a preselected form;

and wherein said generally hydrophilic outer surface of the layer is selected from the group consisting of;

a bearing surface;

a flexible barrier surface separating a first and second area;

a transparent member surface;

an in vivo implant surface;

a drag reduction surface;

a reaction resin surface;

a topical dressing surface; and

a dental splint surface.

16. A method of producing an outer layer having an entanglement comprising a hydrophobic polymer host and a hydrophilic guest, comprising the steps of:

temporarily cloaking at least a portion of the hydrophilic groups of the hydrophilic guest, by performing acylation thereon;

entangling the guest and the host by producing a mixture comprising said acylated guest and the host, and crosslinking at least a portion of the molecules of the guest with the guest; and

molding said mixture into the outer layer.

17. The method of claim 16 wherein the guest comprises a compound selected from the group consisting of polyions, polysaccharides, salts of glycosaminoglycans, nucleic acids, polyvinylpyrrolidones, peptides, polypeptides, amino acids, proteins, lipoproteins, polyamides, polyamines, polyhydroxy polymers, polycarboxy polymers, phosphorylated derivatives of carbohydrates, sulfonated derivatives of carbohydrates, interleukin-2, interferon, and phosphorothioate oligomers;

and further comprising the steps of drying said acylated guest complexes, said mixture is in powdered form, and further comprising the step of removing said cloaking to produce a generally hydrophilic outer surface of the outer layer.

18. The method of claim 17 wherein:

the guest is a polysaccharide;

said entangling is performed using complexes of the guest comprising an QN³⁰ group, where QN⁺ represents a long-chain paraffin ammonium cation;

said performing acylation further comprises using an acid chloride; and

said removing further comprises performing a hydrolysis reaction.

19. The method of claim 16 wherein:

the guest is hyaluronic acid;

said entangling is performed using complexes of the guest represented according to the expression HA⁻

-QN⁺, where HA represents hyaluronic acid and QN⁺ represents a cation;

said cloaked hydrophilic groups of the guest complexes comprise acylated functional groups; and

at least a portion of said crosslinking to occur during said step of molding said mixture; and

further comprising, prior to said step of molding, the step of removing said cloaking to produce a generally hydrophilic outer surface of the outer layer.

20. A system comprising the layer produced according to the method of claim 16 laminated onto a structure comprising the hydrophobic polymer material of the host, forming a preselected form.

21. The system of claim 19 wherein said cloaking is removed to produce a generally hydrophilic outer surface of the outer layer, and said outer surface is selected from the group consisting of:

a bearing surface;

a flexible barrier surface separating a first and second area;

a transparent member surface;

an in vivo implant surface;

a drag reduction surface;

a reaction resin surface;

a topical dressing surface; and

a dental splint surface.