Method of making anti-microbial polymeric surfaces

• US 20040086568A1
• Filed: 01/05/2004
• Published: 05/06/2004
• Est. Priority Date: 02/28/2001
• Status: Active Grant

• Current Assignee: Covalon Technologies Incorporated
• Original Assignee: Covalon Technologies Incorporated
• Inventors: Ditizio, Valerio, DiCosmo, Frank
• Granted Patent: US 8,840,927 B2
• Time in Patent Office: Days
• US Class Current: 424/486
• CPC Class Codes: A61L 2300/104 Silver, e.g. silver sulfadiazine
• CPC Class Codes: A61L 2300/404 Biocides, antimicrobial agents, antiseptic agents
• CPC Class Codes: A61L 2300/606 Coatings
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 27/54 Biologically active materials, e.g. therapeutic substances A61L27/227 takes precedence
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 29/16 Biologically active materials, e.g. therapeutic substances A61L29/048 takes precedence
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/16 Biologically active materials, e.g. therapeutic substances A61L31/047 takes precedence

Abstract

The present invention is a method for the modification of the surfaces of polymeric materials with polymer coatings that may be subsequently treated to be lubricious and anti-microbial. The method comprises incubating a photo-initiator-coated polymeric material with an aqueous monomer that is capable of free radical polymerization and exposing the incubating polymeric material to UV light creating a modified surface on said polymeric material. The method may additionally comprise adding a silver component to the modified surface. The silver component may be provided as a silver salt coating or a silver salt contained within a hydrogel bonded to the acrylate modified polymeric material surface.

Claims

1. A polymeric composite comprising;

a polymeric body made of a polymeric material selected from the group consisting of polyurethanes, polyamides, polyesters, polyethers, polyorganosiloxanes, polysulfones, polytetrafluoroethylene and polysiloxanes, said polymeric body having a stable polyacrylate modified surface, said surface being hydrophilic, lubricious and having a silver agent rendering said surface anti-microbial.

2. The polymeric composite of claim 1, wherein said polymeric material is silicone.

3. The polymeric composite of claim 2, wherein said polymeric material is provided as a device selected from the group consisting of implants, catheters, stents, wound dressings, cardiac valves, tubings, pins and clips.

4. The polymeric composite of claim 3, wherein said silver agent comprises a silver salt selected from the group consisting of silver lactate, silver phosphate, silver citrate, silver acetate, silver benzoate, silver chloride, silver carbonate, silver iodide, silver iodate, silver nitrate, silver laurate, silver sulfadiazine, silver palmitate and mixtures thereof.

5. The polymeric composite of claim 4, wherein said stable polyacrylate modified surface is made by the free radical polymerization of a monomer selected from the group consisting of acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 4-vinylbenzoic acid, itaconic acid, and mixtures thereof.

6. A method for making a lubricious anti-microbial modified surface on a polymeric material, the method comprising:

incubating a photo-initiator-coated polymeric material with an aqueous monomer capable of free radical polymerization;

exposing the incubating polymeric material to UV light creating a modified polymeric surface on said polymeric material;

ionizing said modified polymeric surface; and

adding a silver agent to said ionized modified polymeric surface.

7. The method of claim 6, wherein said polymeric material is selected from the group consisting of polyurethanes, polyamides, polyesters, polyethers, polyorganosiloxanes, polysulfones, polytetrafluoroethylene and polysiloxanes.

8. The method of claim 7, wherein said polymeric material is silicone.

9. The method of claim 8, wherein said polymeric material is, provided as a device selected from the group consisting of implants, catheters, stents, wound dressings, cardiac valves, tubings, pins and clips.

10. The method of claim 9, wherein said monomer is selected from the group consisting of acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 4-vinylbenzoic acid, itaconic acid, and mixtures thereof.

11. The method of claim 10, wherein said photo-initiator is selected from the group consisting of peresters. α

-hydroxyketones, benzil ketals, benzoins and their derivatives and mixtures thereof.

12. The method of claim 11, wherein said photo-initiator is selected from the group consisting of 2,2-dimethoxy-2-phenyl-acetophenone, p-benzoyl tert-butylperbenzoate and mixtures thereof.

13. The method of claim 6, wherein said aqueous monomer additionally comprises a photo-initiator.

14. The method of claim 13, wherein said photo-initiator is selected from the group consisting of 2,2-dimethoxy-2-phenyl-acetophenone, p-benzoyl tert-butylperbenzoat and mixtures thereof.

15. The method of claim 14, wherein said silver agent is added by immersing said ionized modified polymeric material having an ionized modified surface in a silver salt solution.

16. The method of claim 14, wherein a hydrogel is covalently bound to said modified polymeric surface.

17. The method of claim 16, wherein said hydrogel comprises a crosslinked matrix of gelatin and poly (ethylene oxide) sequestering a silver agent

18. The method of claim 15 or 17, wherein said silver agent comprises a silver salt selected from the group consisting of silver lactate, silver phosphate, silver citrate, silver acetate, silver benzoate, silver chloride, silver carbonate, silver iodide, silver iodate, silver nitrate, silver laurate, silver sulfadiazine, silver palmitate and mixtures thereof.

19. A method for making a lubricious anti-microbial modified surface on a polymeric material, the method comprising:

precoating a polymeric material with a photo-initiator;

immersing the precoated polymeric material in an aqueous solution of vinyl carboxylic acid monomer and exposing the incubating polymeric material to UV light to create a modified non-lubricious polyacrylate surface on said polymeric material;

ionizing said polyacrylate surface of said polymeric material by immersion in an aqueous base;

saturating the polyacrylate surface with cations by immersion in an electrolyte solution;

providing silver to said cation-saturated polyacrylate surface.

20. The method of claim 19, wherein said precoated polymeric material is further washed and dried prior to immersion in monomer.

21. The method of claim 19, wherein said polymeric material is selected from the group consisting of polyurethanes, polyamides, polyesters, polyethers, polyorganosiloxanes, polysulfones, polytetrafluoroethylene and polysiloxanes.

22. The method of claim 21, wherein said polymeric material is silicone.

23. The method of claim 22, wherein said polymeric material is provided as a device selected from the group consisting of implants, catheters, stents, wound dressings, cardiac valves, tubings, pins and clips.

24. The method of claim 23, wherein said monomer is selected from the group consisting of acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 4-vinylbenzoic acid, itaconic acid, and mixtures thereof.

25. The method of claim 24, wherein said photo-initiator is selected from the group consisting of peresters, α

-hydroxyketones, benzil ketals, benzoins and their derivatives and mixtures thereof.

26. The method of claim 25, wherein said photo-Initiator is selected from the group consisting of 2,2-dimethoxy-2-phenyl-acetophenone, p-benzoyl tert-butylperbenzoate and mixtures thereof.

27. The method of claim 26, wherein said aqueous monomer solution additionally comprises a photo-initiator.

28. The method of claim 27, wherein said photo-initiator is selected from the group consisting of 2,2-dimethoxy-2-phenyl-acetophenone, p-benzoyl tert-butylperbenzoate and mixtures thereof.

29. The method of claim 28, wherein silver is provided by immersing said ionized polymeric material in a silver salt solution.

30. The method of claim 28, wherein silver is provided by covalently binding a hydrogel to said ionized polyacrylate surface, said hydrogel sequestering a silver salt.

31. The method of claim 29 or 30, wherein said silver salt is selected from the group consisting of silver lactate, silver phosphate, silver citrate, silver acetate, silver benzoate, silver chloride, silver carbonate, silver iodide, silver iodate, silver nitrate, silver laurate, silver sulfadiazine, silver, palmitate and mixtures thereof.

32. The method of claim 19, wherein said neutralizing electrolyte solution has a pH of at least about 8.0.

33. The method of claim 32, wherein said cation-saturating electrolyte solution is selected from the group consisting of sodium lactate, sodium acetate, sodium citrates disodium phosphate, potassium acetate, potassium citrate, dipotassium phosphate and mixtures thereof.

34. The method of claim 33, wherein said electrolyte solution is sodium lactate.