Polyisobutylene-based polyurethanes

• US 9,574,043 B2
• Filed: 01/12/2010
• Issued: 02/21/2017
• Est. Priority Date: 01/12/2009
• Status: Active Grant

• Current Assignee: University Of Massachusetts
• Original Assignee: University Of Massachusetts
• Inventors: Faust, Rudolf, Ojha, Umaprasana
• Primary Examiner(s): WASHVILLE, JEFFREY D
• Application Number:
  US12/685,858
• Publication Number:
  US 20100179298A1
• Time in Patent Office: 2,597 Days
• Field of Search: None
• US Class Current: 1/1
• 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, consisting of:

(1) a hard segment in the amount of 32% to 36% by weight of the elastomeric polymer, wherein the hard segment consists of;

a urethane, urea or urethane urea;

optionally at least one chain extender; and

optionally at least one diisocyanate residue; and

(2) a soft segment in the amount of 64% to 68% by weight of the elastomeric polymer, wherein the soft segment consists of;

(a) about 10% to about 30% by weight of the soft segment of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol; and

(b) about 70% to about 90% 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 40 kilodaltons, and wherein the at least one polyether macrodiol is selected from the group consisting of 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.

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

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

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

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

6. The elastomeric polymer of claim 5, wherein the polyisobutylene macrodiol is hydroxypropyl telechelic polyisobutylene.

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

8. 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.

9. 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.

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

11. The elastomeric polymer of claim 1, wherein the hard segment comprises a diisocyanate residue and a chain extender.

12. The elastomeric polymer of claim 11 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.

13. The elastomeric polymer of claim 11, 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.

14. The elastomeric polymer of claim 11, 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.

15. The elastomeric polymer of claim 11, wherein the diisocyanate is 4,4′

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

16. The elastomeric polymer of claim 1, wherein:

the polyisobutylene macrodiol of the soft segment comprises a hydroxylalkyl telechelic polyisobutylene residue, and

the hard segment comprises a 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol chain extender.

17. The elastomeric polymer of claim 1, wherein:

the polyisobutylene macrodiol of the soft segment comprises a hydroxylalkyl telechelic polyisobutylene residue, a poly (alkylene carbonate) residue, and a poly(tetramethylene oxide) diol residue; and

the hard segment comprises a 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol chain extender.

18. The elastomeric polymer of claim 1, wherein:

the polyisobutylene macrodiol of the soft segment comprises a hydroxylalkyl telechelic polyisobutylene residue, a poly (alkylene carbonate) residue, and a poly(hexamethylene oxide) diol residue;

the hard segment comprises a 4,4′

-methylenediphenyl diisocyanate and 1,4-butanediol chain extender.

19. The elastomeric polymer of claim 1, wherein the polyisobutylene macrodiol of the soft segment comprises

(a) a hydroxyallyl difunctional polyisobutylene residue;

(b) a poly (alkylene carbonate) residue; and

(c) a poly(tetramethylene oxide) diol or poly(hexamethylene oxide) diol residue;

and

the hard segment comprises

(d) a 4,4′

-methylenediphenyl diisocyanate; and

(e) 1,4-butanediol chain extender.

20. 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.

21. 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.

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

23. An article of manufacture, comprising:

an elastomeric polymer, said elastomeric polymer, consisting of;

(1) a hard segment in the amount of 10% to 60% by weight of the elastomeric polymer, wherein the hard segment consists of;

a urethane, urea or urethane urea;

optionally at least one chain extender; and

optionally at least one diisocyanate residue; and

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

(a) about 10% to about 30% by weight of the soft segment of a combination of at least one polyether macrodiol and at least one polycarbonate macrodiol;

(b) about 70% to about 90% by weight of the soft segment of at least one polyisobutylene macrodiol and/or diamine; and

(c),

wherein the number average molecular weight of the elastomeric polymer is not less than 40 kilodaltons, and wherein the article of manufacture is a medical device or an implant, and wherein the at least one polyether macrodiol is selected from the group consisting of 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.

24. The article of claim 23, wherein the number average molecular weight of the elastomeric polymer is not less than 50 kilodaltons.

25. The article of claim 23, wherein the medical device or implant is a fiber, film, engineering plastic, fabric, coating, and adhesive joint.

26. The article of claim 23, wherein the medical device or implant 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.

27. A process for preparing an 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 consists of;

(i) a hard segment in the amount of 32% to 36% by weight of the elastomeric polymer, wherein the hard segment includes a urethane, urea or urethaneurea;

(ii) a soft segment in the amount of 64% to 68% by weight of the elastomeric polymer, wherein the soft segment consists of;

at least 2% by weight of the soft segment of at least one polyether macrodiol, and 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 40 kilodaltons, and wherein the at least one polyether macrodiol is selected from the group consisting of 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; and

(iii) optionally a catalyst.

28. The article of claim 27, wherein the number average molecular weight of the elastomeric polymer is not less than 50 kilodaltons.

29. The process of claim 27, wherein the at least one polyisobutylene macrodiol or diamine of the soft segment is of the formula:

30. The process of claim 27 wherein mixture is formed at a temperature of about 45°

C. to about 120°

C.

31. The process of claim 27 wherein the mixture is formed in the presence of a catalyst.

32. The process of claim 31 wherein the catalyst is stannous octoate.

33. 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, at least one polycarbonate macrodiol, 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 consists of;

(i) a hard segment in the amount of 32% to 36% 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 64% to 68% by weight of the elastomeric polymer, wherein the soft segment consists of;

at least 2% by weight of the soft segment of the at least one polyether macrodiol, and the 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 40 kilodaltons, and wherein the at least one polyether macrodiol is selected from the group consisting of 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.

34. The process of claim 33, wherein the number average molecular weight of the elastomeric polymer is not less than 50 kilodaltons.

35. The process of claim 33, wherein the at least one polyisobutylene macrodiol or diamine of the soft segment is of the formula:

36. The process of claim 33 wherein the at least one polycarbonate macrodiol includes at least one poly(alkylene carbonate).

37. The process of claim 33 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.

38. The process of claim 33 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.

39. A pacemaker lead comprising a polymer, the polymer consisting of:

(1) a hard segment in the amount of 32% to 36% by weight of the elastomeric polymer, wherein the hard segment includes a urethane, urea or urethane urea; and

(2) a soft segment in the amount of 64% to 68% by weight of the elastomeric polymer, wherein the soft segment consists of;

(a) from 10% to 30% by weight of the soft segment of a combination of at least one poly(tetramethylene oxide) diol and at least one polycarbonate macrodiol; and

(b) from 70% to 90% by weight of the soft segment of at least one polyisobutylene macrodiol.

40. The pacemaker lead of claim 39 wherein the polymer has a Shore hardness of from 60A to 100A.