Silane copolymer coatings

• US 6,329,488 B1
• Filed: 11/10/1998
• Issued: 12/11/2001
• Est. Priority Date: 11/10/1998
• Status: Expired due to Fees

• Current Assignee: C.R. Bard, Inc. (Becton, Dickinson & Co)
• Original Assignee: C.R. Bard, Inc. (Becton, Dickinson & Co)
• Inventors: Walsh, Kevin, Terry, Richard N.
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): Robertson, Jeffrey B.
• Application Number:
  US09/189,240
• Time in Patent Office: 1,127 Days
• Field of Search: 528/28, 528/29, 427/2.28
• US Class Current: 528/28
• CPC Class Codes: A61L 2400/10 Materials for lubricating medical devices
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 29/14 Materials characterised by their function or physical properties , e.g. lubricating compositions
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3893 containing silicon
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08L 75/00 Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: C09D 175/08 from polyethers
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

The invention is drawn to silane copolymers prepared from the reaction of one or more polyisocyanates with one or more lubricious polymers having at least two functional groups, which may be the same or different, that are reactive with an isocyanate functional group and with one or more organo-functional silanes having at least two functional groups, which may be the same or different, that are reactive with an isocyanate functional group and at least one functional group reactive with a silicone rubber substrate. The silane copolymer coatings of the invention are elastic, lubricious, and resist wet abrasion. They are useful as coatings for polysiloxane (rubber) and other difficult to coat substrates, especially for medical devices, such catheters.

Claims

1. An article of manufacture comprising a polysiloxane rubber substrate and a silane copolymer coating wherein the coating comprises an organo-functional silane having at least one functional group that is reactive with an isocyanate group and an isocyanate-containing polymer and wherein the coating forms a layer covering the surface of the rubber substrate.

2. The article of claim 1 wherein the substrate is a medical device.

3. The article of claim 2 wherein the medical device is a catheter.

4. The article of claim 1 wherein the silane copolymer coating is the reaction product of (1) one or more polyisocyanates with (2) one or more polymers having at least two functional groups, which may be the same or different, that are reactive with isocyanate, and with (3) one or more organo-functional silanes having at least two functional groups, which may be the same or different, that are reactive with isocyanate, and having at least one functional group reactive with a silicone rubber substrate.

5. A process for preparing a silane copolymer comprising reacting (1) one or more polyisocyanates with (2) one or more polymers having at least two functional groups, which may be the same or different, that are reactive with an isocyanate functional group and with (3) one or more organo-functional silanes having at least two functional groups, which may be the same or different, that are reactive with an isocyanate functional group, and having at least one functional group reactive with a silicone rubber substrate.

6. The process of claim 5 further comprising the addition of a solvent.

7. The process of claim 5 further comprising the addition of a catalyst that is catalytic for the reaction between an isocyanate and a polymer having at least two functional groups which may be the same or different, that are reactive with isocyanate.

8. The process of claim 5 wherein the polymer having at least two functional groups, which may be the same or different, that are reactive with an isocyanate functional group is a polyol.

9. The process of claim 8 wherein the polyol is a diol.

10. The process of claim 9 wherein the diol is selected from the group consisting of poly(ethylene adipates), poly(diethyleneglycol adipates), polycaprolactone diols, polycaprolactone-polyadipate copolymer diols, poly(ethylene-terephthalate)diols, polycarbonate diols, polytetramethylene ether glycol, polyethylene glycol, ethylene oxide adducts of polyoxypropylene diols, and ethylene oxide adducts of polyoxypropylene triols.

11. The process of claim 10 wherein the polyethylene glycol is a polyethylene glycol.

12. The process of claim 11 wherein the polyethylene gylcol has a molecular weight of approximately 1450.

13. The process of claim 11 wherein the polyethylene glycol has a molecular weight of approximately 8000.

14. The process of claim 5 wherein the polyisocyanate is a diisocyanate.

15. The process of claim 14 wherein the diisocyanate is selected from the group consisting of 4,4′

-diphenylmethane diisocyanate and position isomers thereof, 2,4- and 2,6-toluene diisocyanate (TDI) and position isomers thereof, 3,4-dichlorophenyl diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate (HMDI), 4,4′

-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI) and position isomers thereof, isophorone diisocyanate (IPDI), and adducts of diisocyanates.

16. The process of claim 15 wherein the diisocyanate is dicyclohexylmethane-4,4′

-diisocyanate (HMDI).

17. The process of claim 5 wherein the organo-functional silane is an amino-functional alkoxysilane.

18. The process of claim 17 wherein the amino-functional alkoxysilane is N-(2-aminoethyl)-3-aminopropyl-methyldimethoxy silane.

19. The process of claim 5 wherein the polyisocyanate is dicyclohexylmethane-4,4′

-diisocyanate (HMDI), the amino-functional alkoxysilane is N-(2-aminoethyl)-3-aminopropyl-methyldimethoxy silane, and the polyol is a polyethylene glycol having a molecular weight of approximately 1450.

20. The process of claim 5 comprising the steps of

(a) reacting one or more polyols with an excess of polyisocyanate in the presence of a catalyst to form a polyurethane-urea prepolymer having terminal isocyanate groups;

(b) reacting the prepolymer formed in step (a) with one or more organo-functional silanes having at least two functional groups, which may be the same or different, that are reactive with the isocanate groups on the polyurethane-urea prepolymer and having at least one functional group reactive with a silicone rubber substrate to form a silane copolymer; and

(c) stabilizing the copolymer formed in step (b) by treating the copolymer with an alcohol.

21. The process of claim 20 wherein step (a) further comprises the addition of a solvent.

22. The process of claim 20 wherein the catalyst is selected from the group consisting of N,N-dimethylaminoethanol, N,N-dimethyl-cyclohexamine-bis(2-dimethyl aminoethyl)ether, N-ethylmorpholine, N,N,N′

,N′

,N″

-pentamethyl-diethylene-triamine, 1-2(hydroxypropyl)imidazole, stannous octoate, dibutyl tin dilaurate, dioctyltin dilaurate, dibutyl tin mercaptide, ferric acetylacetonate, lead octoate, and dibutyl tin diricinoleate.

23. The process of claim 20 wherein the polyol is a diol.

24. The process of claim 23 wherein the diol is selected from the group consisting of, poly(ethylene adipates), poly(diethyleneglycol adipates), polycaprolactone diols, polycaprolactone-polyadipate copolymer diols, poly(ethylene-terephthalate)diols, polycarbonate diols, polytetramethylene ether glycol, polyethylene glycol, ethylene oxide adducts of polyoxypropylene diols, and ethylene oxide adducts of polyoxypropylene triols.

25. The process of claim 24 wherein the diol is a polyethylene glycol.

26. The process of claim 25 wherein the polyethylene glycol has a molecular weight of approximately 1450.

27. The process of claim 25 wherein the polyethylene glycol has a molecular weight of approximately 8000.

28. The process of claim 20 wherein the polyisocyanate is a diisocyanate.

29. The process of claim 28 wherein the diisocyanate is selected from the group consisting of 4,4′

-diphenylmethane diisocyanate and position isomers thereof, 2,4- and 2,6-toluene diisocyanate (TDI) and position isomers thereof, 3,4-dichlorophenyl diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate (HMDI), 4,4′

-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI) and position isomers thereof, isophorone diisocyanate (IPDI), and adducts of diisocyanates.

30. The process of claim 29 wherein the diisocyanate is dicyclohexylmethane-4,4′

-diisocyanate (HMDI).

31. The process of claim 20 wherein the organo-functional silane is an amino-functional alkoxysilane.

32. The process of claim 31 wherein the amino-functional alkoxysilane is N-(2-aminoethyl)-3-aminopropyl-methyldimethoxy silane.

33. The process of claim 5 comprising the steps of

(a) reacting one or more organo-functional silanes having at least two functional groups, which may be the same or different, that are reactive with an isocyanate functional group and having at least one functional group reactive with a silicone rubber substrate with an excess of polyisocyanate to form a polyurea prepolymer having terminal isocyanate groups;

(b) reacting the polyurea prepolymer formed in step (a) with one or more polyols in the presence of a catalyst to form a silane copolymer; and

(c) stabilizing the copolymer formed in step (b) by treating the copolymer with an alcohol.

34. The process of claim 33 wherein step (a) further comprises the addition of a solvent.

35. The process of claim 33 wherein the catalyst is selected from the group consisting of N,N-dimethylaminoethanol, N,N-dimethyl-cyclohexamine-bis(2-dimethyl aminoethyl)ether, N-ethylmorpholine, N,N,N′

,N′

,N″

-pentamethyl-diethylene-triamine, 1-2(hydroxypropyl)imidazole, stannous octoate, dibutyl tin dilaurate, dioctyl tin laurate, dibutyl tin mercaptide, ferric acetylacetonate, lead octoate, and dibutyl tin diricinoleate.

36. The process of claim 33 wherein the polyol is a diol.

37. The process of claim 36 wherein the diol is selected from the group consisting of, poly(ethylene adipates), poly(diethyleneglycol adipates), polycaprolactone diols, polycaprolactone-polyadipate copolymer diols, poly(ethylene-terephthalate)diols, polycarbonate diols, polytetramethylene ether glycol, polyethylene glycol, ethylene oxide adducts of polyoxypropylene diols, and ethylene oxide adducts of polyoxypropylene triols.

38. The process of claim 37 wherein the diol is a polyethylene glycol.

39. The process of claim 38 wherein the polyethylene glycol has a molecular weight of approximately 1450.

40. The process of claim 38 wherein the polyethylene glycol has a molecular weight of approximately 8000.

41. The process of claim 33 wherein the polyisocyanate is a diisocyanate.

42. The process of claim 41 wherein the diisocyanate is selected from the group consisting of 4,4′

-diphenylmethane diisocyanate and position isomers thereof, 2,4- and 2,6-toluene diisocyanate (TDI) and position isomers thereof, 3,4-dichlorophenyl diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate (HMDI), 4,4′

-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI) and position isomers thereof, isophorone diisocyanate (IPDI), and adducts of diisocyanates.

43. The process of claim 42 wherein the polyisocyanate is dicyclohexylmethane-4,4′

-diisocyanate (HMDI).

44. The process of claim 33 wherein the organo-functional silane is an amino-functional alkoxysilane.

45. The process of claim 44 wherein the amino-functional alkoxysilane is N-(2-aminoethyl)-3-aminopropyl-methyldimethoxy silane.

59. The process of claim 7 where in the catalyst is a tertiary amine or a metallic catalyst.

60. The process of claim 7 wherein the catalyst is selected from the group consisting of N,N-dimethylaminoethanol, N,N-dimethyl-cyclohexamine-bis(2-dimethyl aminoethyl)ether, N-ethylmorpholine, N,N,N′

,N′

,N″

-pentamethyl-diethylene-triamine, 1-2(hydroxypropyl)imidazole, stannous octoate, dibutyl tin dilaurate, dioctyltin dilaurate, dibutyl tin mercaptide, ferric acetylacetonate, lead octoate, and dibutyl tin diricinoleate.

46. A silane copolymer comprised of one or more polyisocyaantes, one or more organo-functional silanes, and one or more polyols.

47. The silane copolymer of claim 46 comprised of dicyclohexylmethane-4,4′

-diisocyanate (HMDI), N-(2-aminoethyl)-3-aminopropyl-methyldimethoxy silane, and polyethylene glycol having a molecular weight of approximately 1450.

48. A coating comprising a silane copolymer wherein the copolymer comprises an organo-functional silane having at least one functional group that is reactive with an isocyanate group and an isocyanate-containing polymer.

49. The coating of claim 48 wherein the silane copolymer is a polyurethane-urea-silane copolymer.

50. The coating of claim 48 wherein the coating further comprises a hydrophilic polymer.

51. The coating of claim 50 wherein the hydrophilic polymer is selected from the group consisting of polyethylene oxide (PEO), polyethylene glycol (PEG), polysaccharides, hyaluronic acid and its salts and derivatives, sodium alginate, chondroitin sulfate, celluloses, chitin, chitosan, agarose, xanthans, dermatan sulfate, keratin sulfate, emulsan, gellan, curdlan, amylose, carrageenans, amylopectin, dextrans, glycogen, starch, heparin sulfate, and limit dextrins and fragments thereof;

synthetic hydrophilic polymers, poly(vinyl alcohol), and poly(N-vinyl)pyrrolidone (PVP).

52. A coating comprising a primer coat and top coat wherein the primer coat comprises an organo-functional silane having at least one functional group that is reactive with an isocyanate group and an isocyanate-containing polymer.

53. The coating of claim 52 wherein the primer coat is the reaction product of one or more polyisocyanates, one or more organo-functional silanes having at least two functional groups, which may be the same or different, that are reactive with isocyanate and at least one functional group reactive with a silicone rubber substrate, and a polyethylene glycol.

54. The coating of claim 53 wherein the polyethylene glycol has a molecular weight of approximately 1450.

55. The coating of claim 52 wherein the top coat is the combination of a polyethylene oxide and a reactive mixture of polyfunctional isocyanate and polyol.

56. The coating of claim 52 wherein the top coat is the combination of a polyvinyl pyrrolidone and a reactive mixture of polyfunctional isocyanate and polyol.

57. The coating of claim 52 wherein the top coat is the reaction product of one or more polyisocyanates, one or more organo-functional silanes having at least two functional groups, which may be the same or different, that are reactive with isocyanate and at least one functional group reactive with a silicone rubber substrate, and a polyethylene glycol.

58. The coating of claim 57 wherein the polyethylene glycol has a molecular weight of approximately 8000.