Polyisobutylene-Based Polyurethanes

• US 20100179298A1
• Filed: 01/12/2010
• Published: 07/15/2010
• Est. Priority Date: 01/12/2009
• Status: Active Grant

• Current Assignee: University Of Massachusetts
• Original Assignee: University Of Massachusetts
• Inventors: Ojha, Umaprasana, Faust, Rudolf
• Granted Patent: US 9,574,043 B2
• Time in Patent Office: Days
• US Class Current: 528/75
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/26 Mixtures of macromolecular compounds
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 29/049 Mixtures of macromolecular compounds
• CPC Class Codes: A61L 29/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 29/085 Macromolecular materials
• 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: A61L 31/10 Macromolecular materials
• CPC Class Codes: C08G 18/32 Polyhydroxy compounds; Polyamines; Hydroxyamines
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/4063 Mixtures of compounds of group C08G18/62 with other macromolecular compounds
• 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 18/6204 Polymers of olefins unsaturated polymers of conjugated dienes C08G18/69
• CPC Class Codes: C08G 18/6511 compounds of group C08G18/3203
• CPC Class Codes: C08G 18/7671 containing only one alkylene bisphenyl group
• CPC Class Codes: C08L 75/04 Polyurethanes

Abstract

An elastomeric polymer, comprising (1) a hard segment in the amount of 10% to 60% by weight of the elastomeric polymer, wherein the hard segment includes a urethane, urea or urethaneurea; and (2) a soft segment in the amount of 40% to 90% by weight of the elastomeric polymer. The soft segment comprises (a) at least 2% by weight of the soft segment of at least one polyether macrodiol, and/or at least one polycarbonate macrodiol; and (b) at least 2% by weight of the soft segment of at least one polyisobutylene macrodiol and/or diamine.

Claims

1. An elastomeric polymer, comprising:

(1) a hard segment in the amount of 10% to 60% by weight of the elastomeric polymer, wherein the hard segment includes a urethane, urea or urethaneurea; and

(2) a soft segment in the amount of 40% to 90% by weight of the elastomeric polymer,

wherein the soft segment comprises;

(a) at least 2% by weight of the soft segment of at least one polyether macrodiol, and/or at least one polycarbonate macrodiol; and

(b) at least 2% by weight of the soft segment of at least one polyisobutylene macrodiol and/or diamine,

wherein the number average molecular weight of the elastomeric polymer is not less than about 40 kilodaltons.

2. The elastomeric polymer of claim 1, wherein the number average molecular weight of the elastomeric polymer is not less than about 50 kilodaltons.

3. The elastomeric polymer of claim 1, wherein the at least one polyether macrodiol is a compound of formula

HO—

[CH(R)—

(CH₂)_k—

O]_l—

H,

wherein;

R, for each occurrence, is independently a C1-C12 alkyl or H;

k is an integer not less than 1; and

l is an integer not less than 1.

4. The elastomeric polymer of claim 1, wherein the at least one polyisobutylene macrodiol or diamine is of formula:

wherein;

each X is independently —

OH, —

NH₂ or —

NHR₄;

R₁ is an initiator residue;

R₂ and R₃ and R₄ is each independently a C1-C16 alkyl, a C3-C16 cycloalkyl, a C2-C16 alkenyl, a C3-C16 cycloalkenyl, a C2-C16 alkynyl, a C3-C16 cycloalkynyl, or a C6-C18 aryl, wherein, for each occurrence, R₂ or R₃ is, independently, optionally substituted with one or more groups selected from halo, cyano, nitro, dialkylamino, trialkylamino, C1-C16 alkoxy and C1-C16 haloalkyl; and

n and m are each, independently, integers from 1 to 500.

5. The elastomeric polymer of claim 1, wherein the soft segment includes:

(a) the at least one polyether and the at least one polycarbonate; and

(b) at least 2% by weight of the soft segment of the at least one polyisobutylene.

6. The elastomeric polymer of claim 1, wherein the soft segment includes:

(a) about 10% to about 90% by weight of the soft segment of the at least one polyisobutylene; and

(b) either

about 10% to about 90% by weight of the soft segment of the at least one polyether,

 

or

about 10% to about 90% by weight of the soft segment of the at least one polycarbonate,

 

or

about 10% to about 90% by weight of the soft segment of the at least one polyether and the at least one polycarbonate.

7. The polyurethane elastomeric polymer of claim 1, wherein the soft segment includes from about 10% to about 30% by weight of the soft segment of the at least one polycarbonate.

8. The elastomeric polymer of claim 1, wherein the soft segment includes from about 10% to about 30% by weight of the soft segment of the at least one polyether and the at least one polycarbonate.

9. The elastomeric polymer of claim 1, wherein the soft segment includes from about 10% to about 30% by weight of the soft segment of the at least one polyether.

10. The elastomeric polymer of claim 1 wherein the soft segment includes from about 10% to about 90% by weight of the soft segment of the at least one polyisobutylene.

11. The elastomeric polymer of claim 1, wherein the soft segment includes from about 70% to about 90% by weight of the soft segment of the at least one polyisobutylene.

12. The elastomeric polymer of claim 1, wherein the hard segment is present in the amount of from about 30% to about 50% by weight of the elastomeric polymer.

13. The elastomeric polymer of claim 1, wherein the polyisobutylene macrodiol is hydroxyallyl telechelic polyisobutylene.

14. The elastomeric polymer of claim 1, wherein the polyisobutylene macrodiol is hydroxyalkyl telechelic polyisobutylene.

15. The elastomeric polymer of claim 14, wherein the polyisobutylene macrodiol is hydroxypropyl telechelic polyisobutylene.

16. The elastomeric polymer of claim 1, wherein the polyisobutylene diamine is aminoallyl telechelic polyisobutylene.

17. The elastomeric polymer of claim 1, wherein the number average molecular weight of the at least one polyisobutylene macrodiol is about 400 Da to about 6000 Da.

18. The elastomeric polymer of claim 1, wherein the number average molecular weight of the at least one polyisobutylene macrodiol is about 1000 Da to about 3000 Da.

19. The elastomeric polymer of claim 1, wherein the at least one polyether macrodiol includes at least one member selected form the group consisting of poly(ethylene oxide) diol, polypropylene oxide) diol, poly(trimethylene oxide) diol, poly(tetramethylene oxide) diol, poly(hexamethylene oxide) diol, poly(heptamethylene oxide) diol, poly(octamethylene oxide) diol and poly(decamethylene oxide) diol.

20. The elastomeric polymer of claim 1, wherein the at least one polycarbonate macrodiol includes at least one poly(alkylene carbonate).

21. The elastomeric polymer of claim 1, wherein the hard segment is formed by reacting a diisocyanate with a chain extender.

22. The elastomeric polymer of claim 21 wherein the diisocyanate includes at least one member selected from the group consisting of 4,4′

-methylenephenyl diisocyanate;

methylene diisocyanate;

p-phenylene diisocyanate;

cis-cyclohexane-1,4-diisocyanate;

trans-cyclohexane-1,4-diisocyanate;

a mixture of cis 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; and

m-tetramethylxylene diisocyanate.

23. The elastomeric polymer of claim 21, wherein the chain extender includes at least one member selected from the group consisting of 1,4-butanediol;

1,5 pentanediol;

1,6-hexanediol;

1,8-octanediol;

1,9-nonanediol;

1,10-decanediol, 1,12-dodacanediol;

1,4-cyclohexane dimethanol;

p-xyleneglycol and 1,4-bis(2-hydroxyethoxy)benzene.

24. The elastomeric polymer of claim 21, wherein the chain extender includes at least one member selected from the group consisting of 1,4-diaminobutane;

1,5-diaminopentane;

1,6-diaminohexane;

1,8-diaminooctane;

1,9-diaminononane;

1,10-diamonodecane, 1,12-diaminododacane;

1,4-diaminocyclohexane;

2,5-diaminoxylene and isophoronediamine and water.

25. The elastomeric polymer of claim 21, wherein the diisocyanate is 4,4′

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

26. The elastomeric polymer of claim 1, wherein:

the soft segment is formed from a hydroxyallyl telechelic polyisobutylene, and

the hard segment is formed from 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol.

27. The elastomeric polymer of claim 1, wherein:

the soft segment is formed from a hydroxyallyl telechelic polyisobutylene and poly(tetramethylene oxide) diol; and

the hard segment is formed from 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol.

28. The elastomeric polymer of claim 1, wherein:

the soft segment is derived from a hydroxyallyl telechelic polyisobutylene and poly(hexamethylene oxide) diol; and

the hard segment is derived from 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol.

29. The elastomeric polymer of claim 1, wherein:

the soft segment is formed from (a) a hydroxyallyl difunctional polyisobutylene and (b) poly(tetramethylene oxide) diol or poly(hexamethylene oxide) diol; and

the hard segment is formed from (c) 4,4′

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

30. The polyurethane elastomeric polymer of claim 1, wherein the soft segment includes from about 5% to about 40% by weight of the soft segment of the at least one polycarbonate.

31. The elastomeric polymer of claim 1, wherein the soft segment includes from about 5% to about 40% by weight of the soft segment of the at least one polyether and the at least one polycarbonate.

32. The elastomeric polymer of claim 1, wherein the soft segment includes from about 5% to about 40% by weight of the soft segment of the at least one polyether.

33. The polyurethane elastomeric polymer of claim 1, wherein the soft segment includes from about 10% to about 20% by weight of the soft segment of the at least one polycarbonate.

34. The elastomeric polymer of claim 1, wherein the soft segment includes from about 10% to about 20% by weight of the soft segment of the at least one polyether and the at least one polycarbonate.

35. The elastomeric polymer of claim 1, wherein the soft segment includes from about 10% to about 20% by weight of the soft segment of the at least one polyether.

36. An article of manufacture, comprising:

an elastomeric polymer, said elastomeric polymer, including;

(1) a hard segment in the amount of 10% to 60% by weight of the elastomeric polymer, wherein the hard segment includes a urethane, urea or urethaneurea; and

(2) a soft segment in the amount of 40% to 90% by weight of the elastomeric polymer,

wherein the soft segment comprises;

(a) at least 2% by weight of the soft segment of at least one polyether macrodiol, and/or at least one polycarbonate macrodiol; and

(b) at least 2% by weight of the soft segment of at least one polyisobutylene macrodiol and/or diamine,

wherein the number average molecular weight of the elastomeric polymer is not less than about 40 kilodaltons.

37. The article of claim 36, wherein the number average molecular weight of the elastomeric polymer is not less than about 50 kilodaltons.

38. The article of claim 36, wherein the article is a fiber, film, engineering plastic, fabric, coating, and adhesive joint.

39. The article of claim 36, wherein the article is a medical device or an implant.

40. The article of claim 39, wherein the article is a cardiac pacemaker, a defibrillator, a catheter, an implantable prosthesis, a cardiac assist device, an artificial organ, a pacemaker lead, a defibrillator lead, a blood pump, a balloon pump, an a-V shunt, a biosensor, a membrane for cell encapsulation, a drug delivery device, a wound dressing, an artificial joint, an orthopedic implant or a soft tissue replacement.

41. A process for preparing a elastomeric polymer, comprising the steps of:

a) forming a mixture that includes at least one polyisobutylene macrodiol and/or diamine, at least one polyether macrodiol and a chain extender; and

b) reacting the mixture with a diisocyanate to yield an elastomeric polymer,

wherein the elastomeric polymer includes,

(i) a hard segment in the amount of 10% to 60% by weight of the elastomeric polymer, wherein the hard segment includes a urethane, urea or urethaneeurea; and

(ii) a soft segment in the amount of 40% to 90% by weight of the elastomeric polymer, wherein the soft segment comprises;

at least 2% by weight of the soft segment of at least one polyether macrodiol, and/or at least one polycarbonate macrodiol, and

at least 2% by weight of the soft segment of the at least one polyisobutylene macrodiol and/or diamine,

wherein the number average molecular weight of the elastomeric polymer is not less than about 40 kilodaltons.

42. The article of claim 41, wherein the number average molecular weight of the elastomeric polymer is not less than about 50 kilodaltons.

43. The process of claim 41, wherein the at least one polyether macrodiol is a compound of formula

HO—

[CH(R)—

(CH₂)_k—

O]_l—

H,

wherein;

R, for each occurrence is, independently, a C1-C12 alkyl or H;

k is an integer not less than 1; and

l is an integer not less than 1.

44. The process of claim 41, wherein the at least one polyisobutylene macrodiol or diamine of the soft segment is of the formula:

wherein;

each X is —

OH, —

NH₂ or —

NHR₄;

R₁ is an initiator residue;

R₂ and R₃ and R₄ is each independently a C1-C16 alkyl, a C3-C16 cycloalkyl, a C2-C16 alkenyl, a C3-C16 cycloalkenyl, a C2-C16 alkynyl, a C3-C16 cycloalkynyl, or a C6-C18 aryl, wherein, for each occurrence, R₂ or R₃ is, independently, optionally substituted with one or more groups selected from halo, cyano, nitro, dialkylamino, trialkylamino, C1-C16 alkoxy and C1-C16 haloalkyl; and

n and m are each independently integers from 1 to 500.

45. The process of claim 41 wherein mixture is formed at a temperature of about 45°

C. to about 120°

C.

46. The process of claim 41 wherein the mixture is formed in the presence of a catalyst.

47. The process of claim 46 wherein the catalyst is stannous octoate.

48. A process for preparing an elastomeric polymer, comprising the steps of:

a) reacting a diisocyanate with a mixture that includes at least one polyisobutylene macrodiol and/or diamine, and at least one polyether macrodiol to form a prepolymer having terminally reactive diisocyanate groups; and

b) reacting the prepolymer with a chain extender to yield an elastomeric polymer, wherein the elastomeric polymer includes;

(i) a hard segment in the amount of 10% to 60% by weight of the elastomeric polymer, wherein the hard segment includes a urethane, urea or urethaneurea; and

(ii) a soft segment in the amount of 40% to 90% by weight of the elastomeric polymer, wherein the soft segment includes;

at least 2% by weight of the soft segment of the at least one polyether macrodiol and/or at least one polycarbonate macrodiol, and

at least 2% by weight of the soft segment of the at least one polyisobuylene macrodiol and/or diamine,

wherein the number average molecular weight of the elastomeric polymer is not less than about 40 kilodaltons.

49. The process of claim 48, wherein the number average molecular weight of the elastomeric polymer is not less than about 50 kilodaltons.

50. The process of claim 48, wherein the at least one polyether macrodiol is a compound of formula

HO—

[CH(R)—

(CH₂)_k—

O]_l—

H,

wherein;

R, for each occurrence, is independently a C1-C12 alkyl or H;

k is an integer not less than 1; and

l is an integer not less than 1.

51. The process of claim 48, wherein the at least one polyisobutylene macrodiol or diamine of the soft segment is of the formula:

wherein;

each X is —

OH, —

NH₂ or —

NHR₄;

R₁ is an initiator residue;

R₂ and R₃ and R₄ is each independently a C1-C16 alkyl, a C3-C16 cycloalkyl, a C2-C16 alkenyl, a C3-C16 cycloalkenyl, a C2-C16 alkynyl, a C3-C16 cycloalkynyl, or a C6-C18 aryl, wherein, for each occurrence, R₂ or R₃ is, independently, optionally substituted with one or more groups selected from halo, cyano, nitro, dialkylamino, trialkylamino, C1-C16 alkoxy and C1-C16 haloalkyl; and

n and m are each independently integers from 1 to 500.

52. The process of claim 48 wherein the at least one polyether macrodiol includes at least one member of the group consisting of poly(ethylene oxide) diol, poly(propylene oxide) diol, poly(trimethylene oxide) diol, poly(tetramethylene oxide) diol, poly(hexamethylene oxide) diol, poly(heptamethylene oxide) diol, poly(octamethylene oxide) diol and poly(decamethylene oxide) diol.

53. The process of claim 48 wherein the at least one polycarbonate macrodiol includes at least one poly(alkylene carbonate).

54. The process of claim 48 wherein the chain extender includes at least one member of the group consisting of 1,4-butanediol;

1,5-pentanediol;

1,6-hexanediol;

1,8-octanediol;

1,9-nonanediol;

1,10-decanediol, 1,12-dodecanediol;

1,4-cyclohexane dimethanol;

p-xyleneglycol and 1,4-bis(2-hydroxyethoxy)benzene.

55. The process of claim 48 wherein the chain extender includes at least one member of the group consisting of 1,4-diaminobutane;

1,5-diaminopentane;

1,6-diaminohexane;

1,8-diaminooctane;

1,9-diaminononane;

1,10-diamonodecane, 1,12-diaminododacane;

1,4-diaminocyclohexane;

2,5-diaminoxylene and isophoronediamine and water.