Hydrocyclosiloxane membrane prepared by plasma polymerization process

• US 5,463,010 A
• Filed: 11/12/1993
• Issued: 10/31/1995
• Est. Priority Date: 11/12/1993
• Status: Expired due to Term

• Current Assignee: Shigemasa Osaki
• Original Assignee: Surface Engineering Technologies Division of Innerdyne Incorporated
• Inventors: Dolence, Eric K., Osaki, Shigemasa, Hu, Chen-Ze, Sanders, Clifton G.
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): MOORE, MARGARET G
• Application Number:
  US08/152,176
• Time in Patent Office: 718 Days
• Field of Search: 528/31, 528/25, 528/28, 528/32
• US Class Current: 528/25
• CPC Class Codes: B01D 69/127 using electrical discharge or plasma-polymerisation
• CPC Class Codes: B05D 1/62 Plasma-deposition of organic layers plasma deposition in general C23C14/00, C23C16/00
• CPC Class Codes: C08G 77/04 Polysiloxanes
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Plasma polymerized membranes comprising polymerized aliphatic hydrocyclosiloxane monomers optionally copolymerized with co-monomers and methods for their preparation are described. These methods may be used to coat substrates to impart properties such as hydrophobicity, thromboresistance, gas permeability and biocompatibility.

Claims

1. A composition of matter comprising a membrane formed from the plasma polymerization of hydrocyclosiloxane monomer of the general formula:

##STR5## where R is an aliphatic group having 1 to about 5 carbon atoms and n is an integer from 2 to about 10.

2. A composition of claim 1, wherein n is 7 to 10.

3. A composition of claim 1, wherein n is 4 to 6.

4. A composition of claim 1, wherein n is 2 to 3.

5. A composition of claim 1, wherein said hydrocyclosiloxane monomer is selected from the group consisting of 1,3,5,7-tetramethylhydrocyclotetrasiloxane, 1,3,5,7,9-pentamethylhydrocyclopentasiloxane, 1,3,5,7,9,11-hexamethylhydrocyclohexasiloxane, and a mixture of 1,3,5,7,9-pentamethylcyclopentasiloxane and 1,3,5,6,9,11-hexamethylcyclohexasiloxane monomers.

6. A composition of claim 1, wherein said membrane has a FTIR spectra characterized by absorption bands at 2960 cm^-1, 2902 cm^-1, 2170 cm^-1, 1260 cm^-1, 1025 cm^-1 and 1143 cm^-1.

7. A composition of claim 1, wherein said membrane exhibits FTIR spectra substantially the same as FIG. 3.

8. A composition of claim 1, wherein said membrane exhibits FTIR spectra substantially the same as FIG. 4.

9. A composition of claim 1, wherein said membrane exhibits ESCA spectra substantially the same as FIGS. 9A to 9C.

10. A composition of claim 1, wherein said membrane exhibits ESCA spectra substantially the same as FIGS. 10A to 10C.

31. A composition of any one of claims 1 to 10, wherein said membrane is biocompatible.

33. A composition of any one of claims 1 to 10, wherein said membrane is gas permeable.

36. A composition of any one of claims 1 to 10, wherein said membrane is thromboresistant.

11. A composition comprising a membrane formed from the plasma copolymerization of a hydrocyclosiloxane monomer of the general formula:

##STR6## where R is a aliphatic group and n is an integer from 2 to about 10, and a co-monomer selected from the group consisting of fluorocarbon monomers, organo-based monomers selected from the group consisting of ethylene, allylamine, N-trimethylsilylallylamine, hydrocarbons, N-protected unsaturated amines, N-unprotected unsaturated amines, N-protected cyclic aliphatic amines, N-unprotected cyclic aliphatic amines, mercaptans, nitriles and organophosphorus compounds; and

functionalizing monomers selected from the group consisting of N₂, CO₂, NH₃ and SO₂.

12. A composition of claim 11, wherein n is 7 to 10.

13. A composition of claim 11, wherein n is 4 to 6.

14. A composition of claim 11, wherein n is 2 to 3.

15. A composition of claim 11, wherein said hydrocyclosiloxane monomer is selected from the group consisting of 1,3,5,7-tetramethylhydrocyclotetrasiloxane, 1,3,5,7,9-pentamethylhydrocyclopentasiloxane, 1,3,5,7,9,11-hexamethylhydrocyclohexasiloxane, and a mixture of 1,3,5,7,9-pentamethylcyclopentasiloxane and 1,3,5,6,9,11-hexamethylcyclohexasiloxane monomers.

16. A composition of claim 11, wherein said hydrocyclosiloxane is selected from the group consisting of 1,3,5,7-tetramethylhydrocyclotetrasiloxane, 1,3,5,7,9-pentamethylhydrocyclopentasiloxane, 1,3,5,7,9,11-hexamethylhydrocyclohexasiloxane, and a mixture of 1,3,5,7,9-pentamethylcyclopentasiloxane and 1,3,5,6,9,11-hexamethylcyclohexasiloxane monomers and said co-monomer is hexafluoropropylene.

17. A composition of claim 11, wherein said hydrocyclosiloxane is selected from the group consisting of 1,3,5,7-tetramethylhydrocyclotetrasiloxane, 1,3,5,7,9-pentamethylhydrocyclopentasiloxane, 1,3,5,7,9,11-hexamethylhydrocyclohexasiloxane, and a mixture of 1,3,5,7,9-pentamethylcyclopentasiloxane and 1,3,5,6,9,11-hexamethylcyclohexasiloxane monomers and said co-monomer is ethylene.

18. A composition of claim 11, wherein said hydrocyclosiloxane is selected from the group consisting of 1,3,5,7-tetramethylhydrocyclotetrasiloxane, 1,3,5,7,9-pentamethylhydrocyclopentasiloxane, 1,3,5,7,9,11-hexamethylhydrocyclohexasiloxane, and a mixture of 1,3,5,7,9-pentamethylcyclopentasiloxane and 1,3,5,6,9,11-hexamethylcyclohexasiloxane monomers and said co-monomer is N-trimethylsilylallylamine.

19. A composition of claim 11, wherein said hydrocyclosiloxane is selected from the group consisting of 1,3,5,7-tetramethylhydrocyclotetrasiloxane, 1,3,5,7,9-pentamethylhydrocyclopentasiloxane, 1,3,5,7,9,11-hexamethylhydrocyclohexasiloxane, and a mixture of 1,3,5,7,9-pentamethylcyclopentasiloxane and 1,3,5,6,9,11-hexamethylcyclohexasiloxane monomers and said co-monomer is selected from the group consisting of NH₃, SO₂, N₂, or CO₂.

20. A composition of claim 15, wherein said membrane has a FTIR spectra substantially as depicted in FIGS. 3B or 4.

21. A composition in claim 16, wherein said membrane has a FTIR spectra substantially as depicted in FIG. 5.

22. A composition of claim 17, wherein said membrane has a FTIR spectra substantially as depicted in FIG. 6.

23. A composition of claim 18, wherein said membrane has a FTIR spectra substantially as depicted in FIG. 7.

24. A composition of claim 19, wherein said membrane has a FTIR spectra substantially as depicted in FIG. 8.

25. A composition of claim 15, wherein said membrane has ESCA spectra substantially as depicted in FIGS. 9A to 9C.

26. A composition of claim 15, wherein said membrane has ESCA spectra substantially as depicted in FIGS. 10A to 10C.

27. A composition of claim 16, wherein said membrane has ESCA spectra substantially as depicted in FIGS. 11A to 11D.

28. A composition of claim 17, wherein said membrane has ESCA spectra substantially as depicted in FIGS. 12A to 12C.

29. A composition of claim 18, wherein said membrane has ESCA spectra substantially as depicted in FIGS. 13A to 13D.

30. A composition of claim 19, wherein said membrane has ESCA spectra substantially as depicted in FIGS. 14A to 14E.

32. A composition of any one of claims 11 to 30, wherein said membrane is biocompatible.

34. A composition of claim 25 or 26 wherein said membrane has an oxygen permeation rate from 0.4 to 20, CO₂ permeation rate from 1 to 50 (X10^-4 cm³ /cm² *sec*cmHg) and CO₂ /O₂ selectivity between 1.5 and 7.

35. A composition of any one of claims 11 to 30, wherein said membrane is gas permeable.

37. A composition of any one of claims 11 to 30, wherein said membrane is thromboresistant.