Polysiloxane-containing polyurethane elastomeric compositions

• US 6,313,254 B1
• Filed: 05/17/1999
• Issued: 11/06/2001
• Est. Priority Date: 09/23/1996
• Status: Expired due to Term

• Current Assignee: AorTech International, PLC
• Original Assignee: Cardiac CRC Nominees Pty., Limited
• Inventors: McCarthy, Simon John, Gunatillake, Pathiraja Arachchillage, Meijs, Gordon Francis
• Primary Examiner(s): Moore, Margaret G.
• Application Number:
  US09/147,971
• Time in Patent Office: 904 Days
• Field of Search: 528/28, 528/26, 428/15, 428/423.1, 428/904
• 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 98 wt % of at least one polysiloxane macrodiol and about 2 to 40 wt % of at least one polyether and/or polycarbonate macrodiol and processes for its preparation.

Claims

1. A polyurethane elastomeric composition comprising a hard segment and a soft segment, wherein the soft segment is formed from (a) about 2 wt. % to about 40 wt. % of at least one polyether, about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol, wherein the polyether macrodiol is a compound of the formula:

wherein

m is an integer of 4 or more; and

n is an integer from 2 to 50; and

(b) about 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol of formula (I);

 

wherein

R₁, R₂, R₃, R₄, R₅, and R₆ are each independently an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and

n is an integer from 1 to 100;

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

2. The polyurethane elastomeric composition of claim 1 wherein the soft segment is formed from about 10 wt. % to about 30 wt. % of at least one polyether macrodiol, about 10 wt. % to about 30 wt. % of at least one polycarbonate macrodiol, or about 10 wt. % to about 30 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol.

3. The polyurethane elastomeric composition of claim 1 wherein the soft segment is formed from about 70 wt. % to about 90 wt. % of at least one polysiloxane macrodiol.

4. The polyurethane elastomeric composition of claim 1 wherein the soft segment is formed from (a) about 10 wt. % to about 30 wt. % of at least one polyether macrodiol, about 10 wt. % to about 30 wt. % of at least one polycarbonate macrodiol, or about 10 wt. % to about 30 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol;

and (b) from about 70 wt. % to about 90 wt. % of at least one polysiloxane macrodiol.

5. The polyurethane elastomeric composition of claim 1 wherein the hard segment is present in about 30 wt. % to about 50 wt. % of the polyurethane elastomeric composition.

6. The polyurethane elastomeric composition of claim 1 wherein the polysiloxane macrodiol is polydimethylsiloxane.

7. The polyurethane elastomeric composition of claim 1 wherein the molecular weight of the polysiloxane macrodiol is about 200 to about 6000.

8. The polyurethane elastomeric composition of claim 1 wherein the molecular weight of the polysiloxane macrodiol is about 400 to about 1500.

9. The polyurethane elastomeric composition of claim 1 wherein the polyether macrodiol is polytetramethylene oxide, polypentamethylene oxide, polyhexamethylene oxide, polyheptamethylene oxide, polyoctamethylene oxide, or polydecamethylene oxide.

10. The polyurethane elastomeric composition of claim 1 wherein the polycarbonate macrodiol is a poly(alkylene carbonate), a polycarbonate prepared by reacting an alkylene carbonate with an alkane diol, or a silicon-based polycarbonate.

11. The polyurethane elastomeric composition of claim 1 wherein the hard segment is derived from a diisocyanate and a chain extender.

12. The polyurethane elastomeric composition of claim 11 wherein the diisocyanate is 4,4′

-methylenediphenyl diisocyanate;

methylene bis diisocyanate;

p-phenylene diisocyanate;

cis-cyclohexane-1,4-diisocyanate;

trans-cyclohexane-1,4-diisocyanate;

a mixture of cis-cyclohexane-1,4-diisocyanate and trans-cyclohexane-1,4-diisocyanate;

1,6-hexamethylene diisocyanate;

2,4-toluene diisocyanate;

cis-2,4-toluene diisocyanate;

trans-2,4-toluene diisocyanate;

a mixture of cis-2,4-toluene diisocyanate and trans-2,4-toluene diisocyanate;

p-tetramethylxylene diisocyanate;

or m-tetramethylxylene diisocyanate.

13. The polyurethane elastomeric composition of claim 11 wherein the chain extender is 1,4-butanediol;

1,6-hexanediol;

1,8-octanediol;

1,9-nonanediol;

1,10-decanediol;

1,12-dodecanediol;

1,4-cyclohexane dimethanol;

p-xyleneglycol;

or 1,4-bis(2-hydroxyethoxy) benzene.

14. The polyurethane elastomeric composition of claim 11 wherein the diisocyanate is 4,4′

-methylenediphenyl diisocyanate and wherein the chain extender is 1,4-butanediol.

15. A polyurethane elastomeric composition comprising a hard segment and a soft segment wherein the soft segment is formed from about (a) 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol;

and (b) about 2 wt. % to about 40 wt. % of at least one polyether macrodiol, about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol, wherein the polyether macrodiol is a compound of the formula;

wherein m is an integer of 4 or more; and

n is an integer from 2 to 50; and

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

16. The polyurethane elastomeric composition of claim 15 wherein the soft segment is derived from about 70 wt. % to about 90 wt. % of polysiloxane macrodiol.

17. The polyurethane elastomeric composition of claim 15 wherein the soft segment is derived from about 10 wt. % to about 30 wt. % of at least one polyether macrodiol, about 10 wt. % to about 30 wt. % of at least one polycarbonate macrodiol, or about 10 wt. % to about 30 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol.

18. The polyurethane elastomeric composition of claim 15 wherein the soft segment is derived from (a) about 70 wt. % to about 90 wt. % of at least one polysiloxane macrodiol;

and (b) about 10 wt. % to about 30 wt. % of at least one polyether macrodiol, about 10 wt. % to about 30 wt. % of at least one polycarbonate macrodiol, or about 10 wt. % to about 30 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol.

19. The polyurethane elastomeric composition of claim 15 wherein the hard segment is present in about 30 wt. % to about 50 wt. % of the polyurethane elastomeric composition.

20. The polyurethane elastomeric composition of claim 15 wherein the polysiloxane macrodiol is polydimethylsiloxane.

21. The polyurethane elastomeric composition of claim 15 wherein the polyether macrodiol is polytetramethylene oxide, polypentamethylene oxide, polyhexamethylene oxide, polyoctamethylene oxide, or polydecamethylene oxide.

22. The polyurethane elastomeric composition of claim 15 wherein the polycarbonate macrodiol is a poly(alkylene carbonate), a polycarbonate prepared by reacting an alkylene carbonate with an alkane diol, or a silicon-based polycarbonate.

23. The polyurethane elastomeric composition of claim 15 further comprising a hard segment derived from a diisocyanate and a chain extender.

24. The polyurethane elastomeric composition of claim 23 wherein the diisocyanate is 4,4′

-methylenediphenyl diisocyanate;

methylene bis diisocyanate;

p-phenylene diisocyanate;

cis-cyclohexane-1,4-diisocyanate;

trans-cyclohexane-1,4-diisocyanate;

a mixture of cis-cyclohexane-1,4-diisocyanate and trans-cyclohexane-1,4-diisocyanate;

1,6-hexamethylene diisocyanate;

2,4-toluene diisocyanate;

cis-2,4-toluene diisocyanate;

trans-2,4-toluene diisocyanate;

a mixture of cis-2,4-toluene diisocyanate and trans-2,4-toluene diisocyanate;

p-tetramethylxylene diisocyanate;

or m-tetramethylxylene diisocyanate.

25. The polyurethane elastomeric composition of claim 23 wherein the chain extender is 1,4-butanediol;

1,6-hexanediol;

1,8-octanediol;

1,9-nonanediol;

1,10-decanediol;

1,12-dodecanedioi;

1,4-cyclohexane dimethanol;

p-xyleneglycol;

or 1,4-bis(2-hydroxyethoxy) benzene.

26. The polyurethane elastomeric composition of claim 15 comprising a soft segment derived from polydimethylsiloxane, and a hard segment derived from 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol.

27. The polyurethane elastomeric composition of claim 15 comprising a soft segment derived from polydimethylsiloxane and polyhexamethylene oxide;

and a hard segment derived from 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol.

28. The polyurethane elastomeric composition of claim 15 comprising a soft segment derived from polydimethylsiloxane and polytetramethylene oxide;

and a hard segment derived from 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol.

29. The polyurethane elastomeric composition of claim 15 comprising a soft segment derived from (a) polydimethylsiloxane and (b) polyhexamethylene oxide or polytetramethylene oxide;

and a hard segment derived from (c) 4,4′

-methylenediphenyl diisocyanate and (d) 1,4-butanediol.

30. A device or article comprising an amount of a polyurethane elastomeric composition effective to render the device biocompatible, the polyurethane elastomeric composition comprising a hard segment and a soft segment, wherein the soft segment is formed from (a) about 2 wt. % to about 40 wt. % of at least one polyether macrodiol, about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol, wherein the polyether macrodiol is a compound of the formula:

wherein m is an integer of 4 or more; and

n is an integer from 2 to 50; and

(b) about 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol of formula (I);

 

wherein

R₁, R₂, R₃, R₄, R₅, and R₆ are each independently an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and

n is an integer from 1 to 100;

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

31. The device or article of claim 30 which is a medical device, article or implant.

32. The device or article of claim 31 which is a cardiac pacemaker, 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.

33. A device or article comprising a polyurethane elastomeric composition comprising a hard segment and a soft segment, wherein the soft segment is formed from (a) about 2 wt. % to about 40 wt. % of at least one polyether macrodiol, about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol, wherein the polyether macrodiol is a compound of the formula:

wherein m is an integer of 4 or more; and

n is an integer from 2 to 50; and

(b) about 60 wt. % to about 98 wt. % of polysiloxane macrodiol of formula (I);

 

wherein

R₁, R₂, R₃, R₄, R₅, and R₆ are each independently an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and

n is an integer from 1 to 100;

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition; and

wherein the device is artificial leather, a shoe sole, a cable sheathing, varnish, a coating, a structural component for a pump or vehicle, a mining ore screen, a conveyor belt, a laminating compound, a textile, a separation membrane, a sealant or an adhesive component.

34. A process for preparing a polyurethane elastomeric composition comprising:

a) mixing a polysiloxane macrodiol;

a polyether macrodiol, a polycarbonate macrodiol, or a mixture thereof; and

a chain extender; and

b) reacting the mixture with a diisocyanate to yield a polyurethane elastomeric composition comprising a hard segment derived from a diisocyanate and a chain extender; and

a soft segment derived from;

about 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol; and

about 2 wt. % to about 40 wt. % of at least one polyether macrodiol, about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol, wherein the polyether macrodiol is a compound of the fornula;

wherein m is an integer of 4 or more; and

n is an integer from 2 to 50; and

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

35. The process of claim 34 wherein step (a) is performed at a temperature of about 45°

C. to about 100°

C.

36. The process of claim 34 wherein step (a) occurs in the presence of a catalyst.

37. The process of claim 36 wherein the catalyst is dibutyl tin dilaurate.

38. A process for preparing a polyurethane elastomeric composition comprising:

b) reacting a diisocyanate a polysiloxate macrodiol; and

a polyether macrodiol, a polycarbonate macrodiol, or a mixture thereof;

to form a prepolymer having terminally reactive diisocyanate groups; and

a) reacting the prepolymer with a chain extender to yield a polyurethane elastomeric composition comprising a soft segment derived from (a) about 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol; and

(b) about 2 wt. % to about 40 wt. % of at least one polyether macrodiol, about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol, wherein the polyether macrodiol is a compoind of the formula;

wherein m is an integer of 4 or more; and

n is an integer from 2 to 50; and

wherein the polyurethane elalstomeric composition comprises a hard segment derived from a diisocyante and a chain extender;

wherein the hard segment is present in abut 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

39. The process of claim 38 wherein the diisocyanate is 4,4′

-methylenediphenyl diisocyanate;

methylene bis diisocyanate;

p-phenylene diisocyanate;

cis-cyclohexane-1,4-diisocyanate;

trans-cyclohexane-1,4-diisocyanate;

a mixture of cis-cyclohexane-1,4-diisocyanate and trans-cyclohexane-1,4-diisocyanate;

1,6-hexamethylene diisocyanate;

2,4-toluene diisocyanate;

cis-2,4-toluene diisocyanate;

trans-2,4-toluene diisocyanate;

a mixture of cis-2,4-toluene diisocyanate and trans-2,4-toluene diisocyanate;

p-tetramethylxylene diisocyanate;

or m-tetramethylxylene diisocyanate.

40. The process of claim 38 wherein the polysiloxane macrodiol is a compound of formula (I):

wherein

R₁, R₂, R₃, R₄, R₅, and R₆ are each independently an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and

n is an integer from 1 to 100.

41. The process of claim 38 wherein the polyether macrodiol is polytetramethylene oxide, polypentamethylene oxide, polyhexamethylene oxide, polyheptamethylene oxide, polyoctamethylene oxide, or polydecamethylene oxide.

42. The process of claim 38 wherein the polycarbonate macrodiol is a poly(alkylene carbonate), a polycarbonate prepared by reacting an alkylene carbonate with an alkane diol, or a silicon-based polycarbonate.

43. The process of claim 38 wherein the chain extender is 1,4-butanediol;

1,6-hexanediol;

1,8-octanediol;

1,9-nonanediol;

1,10-decanediol;

1,12-dodecanediol;

1,4-cyclohexane dimethanol;

p-xyleneglycol;

or 1,4-bis(2-hydroxyethoxy) benzene.

44. A polyurethane elastomeric composition comprising a hard segment and a soft segment, wherein the soft segment is formed from (a) about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a copolymer of at least one polyether macrodiol and at least one polycarbonate macrodiol;

and (b) about 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol of formula (I);

wherein

R₁, R₂, R₃, R₄, R₅, and R₆ are each independently an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and

n is an integer from 1 to 100;

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

49. The polyurethane elastomeric composition of claims 44, 45, 46, 47 or 48 wherein the polycarbonate macrodiol is a poly(alkylene carbonate), a polycarbonate prepared by reacting an alkylene carbonate with an alkane diol, or a silicon-based polycarbonate.

45. A polyurethane elastomeric composition comprising a hard segment and a soft segment wherein the soft segment is formed from about (a) 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol;

and (b) about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a copolymer of at least one polyether macrodiol and at least one polycarbonate macrodiol;

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

46. A device or article comprising an amount of a polyurethane elastomeric composition effective to render the device biocompatible, the polyurethane elastomeric composition comprising a hard segment and a soft segment, wherein the soft segment is formed from (a) about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a copolymer of at least one polyether macrodiol and at least one polycarbonate macrodiol;

and (b) about 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol of formula (I);

wherein

R₁, R₂, R₃, R₄, R₅, and R₆ are each independently an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and

n is an integer from 1 to 100;

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

47. A process for preparing a polyurethane elastomeric composition comprising:

a) mixing a polysiloxane macrodiol;

a polyether macrodiol, a polycarbonate macrodiol, or a mixture thereof; and

a chain extender; and

b) reacting the mixture with a diisocyanate to yield a polyurethane elastomeric composition comprising a hard segment derived from a diisocyanate and a chain extender; and

a soft segment derived from;

about 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol; and

about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a copolymer of at least one polyether macrodiol and at least one polycarbonate macrodiol;

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.

48. A process for preparing a polyurethane elastomeric composition comprising:

a) reacting a diisocyanate with a polysiloxane macrodiol; and

a polyether macrodiol, a polycarbonate macrodiol, or a mixture thereof;

to form a prepolymer having terminally reactive diisocyanate groups; and

b) reacting the prepolymer with a chain extender to yield a polyurethane elastomeric composition comprising a soft segment derived from (a) about 60 wt. % to about 98 wt. % of at least one polysiloxane macrodiol; and

(b) about 2 wt. % to about 40 wt. % of at least one polycarbonate macrodiol, or about 2 wt. % to about 40 wt. % of a copolymer of at least one polyether macrodiol and at least one polycarbonate macrodiol;

wherein the polyurethane elastomeric composition comprises a hard segment derived from a diisocyanate and a chain extender;

wherein the hard segment is present in about 30 wt. % to about 60 wt. % of the polyurethane elastomeric composition and wherein the soft segment is present in about 40 wt. % to about 70 wt. % of the polyurethane elastomeric composition.