Poly(ethylene oxide) coated surfaces

• US 20030087099A1
• Filed: 11/26/2002
• Published: 05/08/2003
• Est. Priority Date: 11/17/1995
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Leung, Gladys, Merrill, Edward W.
• Granted Patent: US 6,616,982 B2
• Time in Patent Office: Days
• US Class Current: 428/413
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: B05D 7/04 to surfaces of films or sheets producing layered products by applying coatings of pasty or pulverulent plastics B29C41/00
• CPC Class Codes: C08J 2465/02 Polyphenylenes
• CPC Class Codes: C08J 7/04 Coating
• CPC Class Codes: C08J 7/0427 with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: Y10T 428/261 In terms of molecular thickness or light wave length
• CPC Class Codes: Y10T 428/264 Up to 3 mils
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

Methods are provided for the fabrication of hydrophilic coatings on hydrophobic surfaces. In one embodiment, a polyethylene oxide (PEO) coating is fabricated on the surface of a polymeric material by contacting the surface with a methacrylic acid or acrylic acid monomer. The monomer first is reacted, for example by irradiation with an electron beam, to polymerize and covalently attach the monomer to the surface, to improve the hydrophilicity of the polymeric material. A coating of PEO molecules is subsequently attached to the polymer surface by hydrogen bond complexation. The PEO coating then may be covalently grafted onto the surface, for example, by irradiation grafting with an electron beam. The covalent grafting of a coating of the methacrylic or acrylic monomers to the surface greatly improves the wettability of the surface, and facilitates the covalent or non-covalent attachment of a coating of PEO to the polymer surface. Thus, hydrophilic PEO coatings can be fabricated on hydrophobic polymer surfaces, to improve the biocompatibility and other properties of the polymer surfaces.

Claims

1. A method for the fabrication of a hydrophilic coating on the surface of a hydrophobic material, the method comprising:

a) contacting the surface of a hydrophobic material with a monomer comprising an unsaturated group which is capable of reacting with the surface to enhance the hydrophilicity of the surface;

b) reacting the monomer with the surface, thereby to enhance the hydrophilicity of the surface; and

c) attaching poly(ethylene oxide) molecules to the hydrophilic surface of the support material, after step b), thereby to form a poly(ethylene oxide) coating on the surface.

2. The method of claim 1 wherein, in step b), the monomer is reacted with the surface by irradiation with an electron beam.

3. The method of claim 2 wherein the monomer is covalently reacted with the surface and polymerized to form a coating on the surface, in step b).

4. The method of claim 2 wherein the monomer is a selected from the group consisting of methacrylic acid, monovalent metal salts of methacrylic acid, methacryloyl chloride, acrylic acid, monovalent salts of acrylic acid, acryloyl chloride, hydroxyethyl methacrylate, glycidyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.

5. The method of claim 4 wherein the monomer is methacrylic acid.

6. The method of claim 1 wherein the hydrophobic surface comprises a polymer selected from the group consisting of polyalkylenes, polyarylalkylenes, polyvinyls, poly(alkyl methacrylates), poly(alkylene terephthalates), polydiolefins, polysiloxanes and polyurethanes.

7. The method of claim 1 wherein the surface comprises a polymer selected from the group consisting of polyethylene, polypropylene, poly(methyl methacrylate), poly(vinyl chloride), poly(vinylidene fluoride), poly(ethylene terephthalate), and polystyrene.

8. The method of claim 7 wherein the polyethylene (PE) is selected from the group consisting of high density PE, low density PE, ultra high molecular weight PE and PE copolymers.

9. The method of claim 1 wherein the surface comprises a polymer selected from the group consisting of polybutadiene, polyisoprene, copolymers of isoprene, copolymers of butadiene, silicone rubber, segmented polyurethane and plasticized polyvinylchloride.

10. The method of claim 1 wherein step c) comprises:

i) contacting the surface with poly(ethylene oxide) molecules thereby to adsorb the poly(ethylene oxide) molecules to the surface;

ii) removing poly(ethylene oxide) molecules which are not adsorbed to the surface, thereby to leave essentially a monolayer of poly(ethylene oxide) molecules adsorbed on the surface; and

iii) covalently grafting the poly(ethylene oxide) to the surface, thereby to form essentially a monolayer of the poly(ethylene) oxide on the surface.

11. The method of claim 1 wherein step c) comprises:

i) contacting the surface with poly(ethylene oxide) molecules, thereby to adsorb the poly(ethylene oxide) molecules to the surface;

ii) removing a portion of the poly(ethylene oxide) molecules which are not adsorbed to the surface thereby to leave a multilayer of poly(ethylene oxide) molecules on the surface; and

iii) covalently grafting the poly(ethylene oxide) molecules to the surface, thereby to form a thin multilayer film of poly(ethylene oxide) on the surface.

12. The method of claim 10 or 11 wherein the poly(ethylene oxide) molecules are covalently grafted to the surface by irradiation of the poly(ethylene oxide) molecules on the surface with an electron beam.

13. The method of claim 12 wherein the hydrophobic material is a gas permeable hard contact lens.

14. The method of claim 13 wherein the monomer is methacrylic acid.

15. The method of claim 1 wherein the hydrophobic material is selected from the group consisting of membranes, prostheses, stents, sutures, catheters, artificial hearts, ventricular assist devices, polymeric particles, and polymeric films or a coating thereon.

16. The method of claim 10 or 11 wherein the PEO is selected from the group consisting of linear PEO, polyethylene glycol and a PEO star macromolecule.

17. The method of claim 16 wherein the PEO is a linear PEO with a molecular weight between about 1000 and 5,000,000 daltons.

18. The method of claim 16 further comprising covalently attaching terminal PEO hydroxyl groups on the surface to at least one biological molecule or polymer thereof.

19. The method of claim 11 wherein the PEO multilayer film, formed in step iii), is on the order of about 0.1 to 100 μ

m thick when in contact with water.

20. The method of claim 11 wherein the poly(ethylene oxide), contacted with the surface in step i), has a molecule weight of one million or greater.

21. A hydrophobic material comprising a hydrophilic coating on a surface thereof, wherein the hydrophilic coating comprises a first layer of monomers comprising an unsaturated group covalently grafted to the surface and at least partially polymerized, and a second layer of poly(ethylene oxide) (“

PEO”

) molecules grafted to the first layer.

22. The material of claim 21 wherein the first and second layers are grafted to the surface by irradiation with an electron beam.

23. The material of claim 21 wherein the monomer grafted to the surface and at least partially polymerized is selected from the group consisting of methacrylic acid, monovalent metal salts of methacrylic acid, methacryloyl chloride, acrylic acid, monovalent salts of acrylic acid, acryloyl chloride, hydroxyethyl methacrylate, glycidyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.

24. The material of claim 21 wherein the hydrophobic surface comprises a polymer selected from the group consisting of polyalkylenes, polyarylalkylenes, polyvinyls, poly(alkyl methacrylates), poly(alkylene terephthalates), polydiolefins, polysiloxanes and polyurethanes.

25. The material of claim 21 wherein the surface comprises a polymer selected from the group consisting of polyethylene, polypropylene, poly(methyl methacrylate), poly(vinyl chloride), poly(vinylidene fluoride), poly(ethylene terephthalate), and polystyrene.

26. The material of claim 25 wherein the polyethylene (PE) is selected from the group consisting of high density PE, low density PE, ultra high molecular weight PE, and PE copolymers.

27. The material of claim 21 wherein the surface comprises a polymer selected from the group consising of polybutadiene, copolymers of butadiene, polyisoprene, copolymers of isoprene, silicone rubber, segmented polyurethane and plasticized polyvinylchloride.

28. The material of claim 21 wherein the material is a gas permeable hard contact lens.

29. The material of claim 21 wherein the monomer is methacrylic acid.

30. The material of claim 21 selected from the group consisting of membranes, prostheses, stents, sutures, catheters, artificial hearts, ventricular assist devices, polymeric particles, and polymeric films or a coating thereon.

31. The material of claim 21 wherein the PEO is selected from the group consisting of linear PEO, polyethylene glycol, and a PEO star macromolecule.

32. The material of claim 31 further comprising at least one biological molecule or polymer thereof covalently attached to terminal hydroxyl groups on the PEO coating.

33. The material of claim 31 wherein the poly(ethylene oxide) coating is on the order of about 0.1 and 100 μ

m thick when in contact with water.