Polysiloxane-containing polyurethane elastomeric compositions

• US 20030018156A1
• Filed: 12/13/2000
• Published: 01/23/2003
• Est. Priority Date: 09/23/1996
• Status: Active Grant

• Current Assignee: AorTech International, PLC
• Original Assignee: Cardiac CRC Nominees Pty., Limited
• Inventors: McCarthy, Simon John, Gunatillake, Pathiraja Arachchillage, Meijs, Gordon Francis
• Granted Patent: US 6,627,724 B2
• Time in Patent Office: Days
• US Class Current: 528/26
• CPC Class Codes: A61L 15/26 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof A61L15/225 takes precedence
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 29/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 31/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds A61L31/041 takes precedence
• CPC Class Codes: C08G 18/44 Polycarbonates
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/4858 Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/6511 compounds of group C08G18/3203
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: Y10S 428/904 Artificial leather
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

The present invention relates to a material having improved mechanical properties, clarity, processability and/or degradation resistance comprising a polyurethane elastomeric composition which includes a soft segment derived from at least one polysiloxane macrodiol and at least one polyether and/or polycarbonate macrodiol. This material can function as a degradation resistant material or biomaterial and is particularly useful in the manufacture of medical devices, articles or implants which contact living tissues or bodily fluids. The present invention also provides a polyurethane elastomeric composition which includes a soft segment derived from about 60 to about 98 wt. % of at least one polysiloxane macrodiol and about 2 to about 40 wt. % of at least one polyether and/or polycarbonate macrodiol and processes for its preparation.

Claims

1. A material having improved mechanical properties, clarity, processability and/or degradation resistance comprising a polyurethane elastomeric composition which includes a soft segment derived from at least one polysiloxane macrodiol and at least one polyether and/or polycarbonate macrodiol.

2. A material according to claim 1, wherein the improved mechanical properties are tensile strength, tear strength, abrasion resistance, Durometer hardness, flexural modulus and/or related measures of flexibility.

3. A material according to claim 1 or claim 2, wherein the improved resistance to degradation is resistance to free radical, oxidative, enzymatic and/or hydrolytic processes and/or to degradation when implanted as a biomaterial.

4. A material according to any one of the preceding claims, wherein the improved processability is ease of processing by casting and/or thermal means.

5. A material according to any one of the preceding claims which is a degradation resistant material.

6. A material according to any one of the preceding claims which is an in vivo degradation resistant material.

7. A material according to any one of the preceding claims which is a biomaterial.

8. A material according to any one of the preceding claims, wherein the soft segment is derived from about 60 to about 98 wt % of at least one polysiloxane macrodiol and about 2 to about 40 wt % of at least one polyether and/or polycarbonate macrodiol.

9. A material according to any one of the preceding claims wherein the soft segment is derived from about 70 to about 90 wt % of at least one polysiloxane macrodiol and about 30 to about 10 wt % of at least one polyether and/or polycarbonate macrodiol.

10. A material according to any one of the preceding claims, wherein the soft segment is derived from about 80 wt % of at least one polysiloxane macrodiol and about 20 wt % of at least one polyether and/or polycarbonate macrodiol.

11. A material according to any one of the preceding claims, wherein the polysiloxane macrodiol is represented by the formula (I)

12. A material according to any one of the preceding claims, wherein the polysiloxane macrodiol is polydimethylsiloxane (PDMS).

13. A material according to any one of the preceding claims, wherein the molecular weight range of the polysiloxane macrodiol is about 200 to about 6000.

14. A material according to any one of the preceding claims, wherein the molecular weight range of the polysiloxane macrodiol is about 400 to about 1500.

15. A material according to any one of the preceding claims, wherein the polyether macrodiol is represented by the formula (II)

HO—

[(CH₂)_m—

O]_n—

H  

 

(II)

wherein

m is an integer of 4 or more; and

n is an integer of 2 to 50.

16. A material according to any one of the preceding claims, wherein the polyether macrodiol is polytetramethylene oxide (PTMO), polypentamethylene oxide (PPMO), polyhexamethylene oxide (PHMO), polyheptamethylene diol, polyoctamethylene oxide (POMO) or polydecamethylene oxide (PDMO).

17. A material according to any one of the preceding claims, wherein the polycarbonate macrodiol is a poly(alkylene carbonate), a polycarbonate prepared by reacting an alkylene carbonate with an alkanediol or a silicon-based polycarbonate.

18. A material according to any one of the preceding claims, wherein the soft segment contains both the polyether and polycarbonate macrodiols in the form of a mixture or a copolymer.

19. A material according to any one of the preceding claims, wherein the polyurethane elastomeric composition further includes a hard segment derived from both a diisocyanate and a chain extender.

20. A material according to claim 19, wherein the diisocyanate is selected from 4,4′

-methylenediphenyl diisocyanate (MDI), methylene bis (cyclohexyl) diisocyanate (H₁₂MDI), p-phenylene diisocyanate (p-PDI), trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (DICH), 2,4-toluene diisocyanate (2,4-TDI) or its isomers or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI) and m-tetramethylxylene diisocyanate (m-TMXDI).

21. A material according to claim 19 or claim 20, wherein the chain extender is selected from 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonadiol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexane dimethanol, p-xyleneglycol and 1,4-bis(2-hydroxyethoxy) benzene.

22. A material according to claim 20 or claim 21, wherein the diisocyanate is MDI and the chain extender is 1,4-butanediol.

23. A material according to any one of claims 19 to 22, wherein the hard segment is about 30 to about 60 wt % of the composition.

24. Use of the polyurethane elastomeric composition as defined in any one of the preceding claims as a material having improved mechanical properties, clarity, processability and/or degradation resistance.

25. The polyurethane elastomeric composition as defined in any one of claims 1 to 23 when used as a material having improved mechanical properties, clarity, processability and/or degradation resistance.

26. A device or article which is composed wholly or partly of the polyurethane elastomeric composition as defined in any one of claims 1 to 23.

27. A device or article according to claim 26 which is a medical device, article or implant.

28. A device or article according to claim 26 or claim 27 which is a cardiac pacemaker or defibrillator, catheter, implantable prosthesis, cardiac assist device, heart valve, vascular graft, extra-corporeal device, artificial organ, pacemaker lead, defibrillator lead, blood pump, balloon pump, A-V shunt, biosensor, membrane for cell encapsulation, drug delivery device, wound dressing, artificial joint, orthopaedic implant or soft tissue replacement.

29. A device or article according to claim 26 which is selected from artificial leather, shoe soles, cable sheathing, varnishes, coatings, structural components for pumps or vehicles, mining ore screens, conveyor belts, laminating compounds, textiles, separation membranes, sealants and adhesive components.

30. Use of the polyurethane elastomeric composition as defined in any one of claims 1 to 23 in the manufacture of a device or article.

31. A polyurethane elastomeric composition as defined in any one of claims 1 to 23 when used in the manufacture of a device or article.

32. A polyurethane elastomeric composition which includes a soft segment derived from about 60 to about 98 wt % of at least one polysiloxane macrodiol and about 2 to about 40 wt % of at least one polyether and/or polycarbonate macrodiol.

33. A composition according to claim 32, wherein the soft segment is derived from about 70 to about 90 wt % of at least one polysiloxane macrodiol and about 2 to about 40 wt % of at least one polyether and/or polycarbonate macrodiol.

34. A composition according to claim 32 or claim 33, wherein the soft segment is derived from about 80 wt % of at least one polysiloxane macrodiol and about 20 wt % of at least one polyether and/or polycarbonate macrodiol.

35. A composition according to any one of claims 32 to 34, wherein the polysiloxane macrodiol is represented by the formula (I)

36. A composition according to any one of claims 32 to 35, wherein the polysiloxane macrodiol is polydimethylsiloxane (PDMS).

37. A composition according to any one of claims 32 to 36, wherein the polyether macrodiol is represented by the formula (II)

HO—

[(CH₂)_m—

O]_n—

H  

 

(II)

wherein

mn is an integer of 4 or more; and

n is an integer of 2 to 50.

38. A composition according to any one of claims 32 to 37, wherein the polyether macrodiol is polytetramethylene oxide (PTMO), polypentamethylene oxide (PPMO), polyhexamethylene oxide (PHMO), polyoctamethylene oxide (POMO) or polydecamethylene oxide (PDMO).

39. A composition according to any one of claims 32 to 38, wherein the polycarbonate macrodiol is a poly(alkylene carbonate), a polycarbonate prepared by reacting an alkylene carbonate with an alkanediol or a silicon-based polycarbonate.

40. A composition according to any one of claims 32 to 39 which further includes a hard segment derived from a diisocyanate and a chain extender.

41. A composition according to any one of claims 32 to 40, wherein the diisocyanate is selected from 4,4′

-methylenediphenyl diisocyanate (MDI), methylene bis (cyclohexyl) diisocyanate (H₁₂MDI), p-phenylene diisocyanate (p-PDI), trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6hexamethylene diisocyanate (DICH), 2,4-toluene diisocyanate (2,4-TDI) or its isomers or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI) and m-tetramethylxylene diisocyanate (m-TMXDI).

42. A composition according to any one of claims 32 to 41, wherein the chain extender is selected from 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonadiol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexane dimethanol, p-xyleneglycol and 1,4-bis(2-hydroxyethoxy) benzene.

43. A composition according to any one of claims 40 to 42 which includes a soft segment derived from 80 wt % of PDMS and 20 wt % of PHMO or PTMO and a hard segment derived from MDI and BDO.

44. A process for preparing a composition according to any one of claims 40 to 43 which includes the steps of:

(a) mixing the polysiloxane macrodiol, polyether and/or polycarbonate macrodiol and chain extender, and

(b) reacting the mixture with the diisocyanate.

45. A process according to claim 44, wherein step (a) is performed at a temperature in the range of about 45 to about 100°

C.

46. A process according to claim 44 or claim 45, wherein step (a) occurs in the presence of a catalyst.

47. A process according to claim 46, wherein the catalyst is dibutyl tin dilaurate.

48. A process for preparing a composition according to any one of claims 40 to 43 which includes the steps of:

(a) reacting the diisocyanate with the polysiloxane macrodiol and polyether and/or polycarbonate macrodiol to form a prepolymer having terminally reactive diisocyanate groups; and

(b) reacting the prepolymer with the chain extender.