Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing the same

• US 8,324,290 B2
• Filed: 06/26/2009
• Issued: 12/04/2012
• Est. Priority Date: 06/27/2008
• Status: Active Grant

• Current Assignee: Cardiac Pacemakers Incorporated (Boston Scientific Corporation)
• Original Assignee: Cardiac Pacemakers Incorporated (Boston Scientific Corporation)
• Inventors: Desai, Shrojalkumar, Schwarz, Marlene C., Boden, Mark, Krishnan, Mohan, Smith, Michael C., Strickler, Frederick H., Cooke, Daniel J.
• Primary Examiner(s): ZIMMER, MARC S
• Application Number:
  US12/492,483
• Publication Number:
  US 20100023104A1
• Time in Patent Office: 1,257 Days
• Field of Search: None
• US Class Current: 523/105
• CPC Class Codes: A61L 27/18 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 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• 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 18/4854 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 18/6204 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 18/7657 containing two or more aromatic rings
• CPC Class Codes: C08L 75/00 Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers

Abstract

The present invention pertains to polyisobutylene urethane, urea and urethane/urea copolymers, to methods of making such copolymers and to medical devices that contain such polymers. According to certain aspects of the invention, polyisobutylene urethane, urea and urethane/urea copolymers are provided, which comprise a polyisobutylene segment, an additional polymeric segment that is not a polyisobutylene segment, and a segment comprising a residue of a diisocyanate. According to other aspects of the invention, polyisobutylene urethane, urea and urethane/urea copolymers are provided, which comprise a polyisobutylene segment and end groups that comprise alkyl-, alkenyl- or alkynyl-chain-containing end groups.

Claims

1. An implantable or insertable medical device comprising a polymeric region that comprises:

a polyisobutylene urethane, urea or urethane/urea copolymer comprising a polyisobutylene segment, a segment comprising a residue of a diisocyanate and an additional polymeric segment comprising a residue of a polyether diol, wherein the additional polymeric segment is a soft polymeric segment, and wherein a molar ratio of the polyisobutylene to additional polymeric segment is from 1.5;

0.5 to 0.5;

1.5.

2. The copolymer of claim 1, wherein the additional polymeric segment comprises a residue of a polytetramethylene oxide diol, or a polyhexamethylene oxide diol.

3. The copolymer of claim 1, wherein the polyisobutylene segment comprises a residue of a polyisobutylene diol or a polyisobutylene diamine.

4. The copolymer of claim 1, wherein the diisocyanate is selected from an aromatic diisocyanate, an aliphatic diisocyanate and combinations thereof.

5. The copolymer of claim 1, wherein the diisocyanate is selected from 4,4′

-methylenediphenyl diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, para-phenylene diisocyanate, 3,3′

-tolidene-4,4′

-diisocyanate, 3,3′

-dimethyl-diphenylmethane-4,4′

-diisocyanate, and combinations thereof.

6. The copolymer of claim 1, further comprising a chain extender residue.

7. The copolymer of claim 6, wherein the chain extender residue is selected from an aliphatic diol, an aromatic diol, a combination of aliphatic and aromatic diols, an aliphatic diamine, an aromatic diamine and a combination of aliphatic and aromatic diamines.

8. The copolymer of claim 6, wherein the chain extender is an alpha,omega-C₁-C10-alkane diol.

9. The copolymer of claim 6, wherein the chain extender is selected from 1,2-ethane diol, 1,4-butanediol, 1,6-hexanediol, a low molecular weight polyisobutylene diol, and a low molecular weight poly(stryrene-b-isobutylene-b-styrene)diol.

10. The copolymer of claim 1, further comprising end groups that comprise alkyl, alkenyl or alkynyl chains ranging from 1 to 17 carbons atoms in length.

11. The copolymer of claim 10, wherein the end groups are selected from [—

CH₂]_nCH₃ groups, [—

CH₂]_n—

C(CH₃)₃ groups, [—

CH₂]_n—

CF₃ groups, [—

CH₂]_n—

C(CF₃)₃ groups, [—

CH₂]_n—

CH₂OH groups, [—

CH₂]_n—

C(OH)₃ groups, [—

CH₂]_n—

C₆H₅ groups, [—

CH.₂]_n-b-[—

CH₂O]_n—

CH₃ groups, [—

CH₂]_n-b-[—

CH₂O]_n—

CH₂CH₂C(CH₃)₃ groups, [—

CH₂]_n-b-[—

CH₂O]_n—

CH₂CH₂CF₃ groups, [—

CH₂]_n-b-[—

CH₂O]_n—

CH₂CH₂C(CF₃)₃ groups, [—

CH₂]_n-b-[—

CH₂O]_n—

CH₂CH₂OH groups, [—

CH₂]_n-b-CH₂O′

—

C(OH)₃ groups, [—

CH₂]_n-b-[—

CH₂O]_n—

CH₂CH₂—

C₆H₅ groups and combinations thereof, where n ranges from 1 to 20.

12. The implantable or insertable medical device of claim 1, wherein the medical device is selected from a stent, a heart valve, an implantable electrical lead, a pacemaker, a defibrillator and a heart failure device.

13. The implantable or insertable medical device of claim 1, wherein the medical device comprises an implantable electrical lead and wherein the polymeric region is a polymeric layer disposed over an electrical conductor.

14. The implantable or insertable medical device of claim 13, wherein the electrical lead is selected from a cardiac lead and a neurostimulation lead.

15. The implantable or insertable medical device of claim 1, wherein said polymeric region further comprises a therapeutic agent.

16. The implantable or insertable medical device of claim 1, wherein said polymeric region further comprises a filler material selected from a silicate material, alumina, silver nanoparticles, and silicate/alumina/silver nanoparticle composites.

17. The copolymer of claim 1 wherein the additional polymer segment comprises poly(tetramethylene oxide).

18. The copolymer of claim 1 wherein a molar ratio of the diisocyanate to polyisobutylene to additional polymer is from 2:

1.5;

0.5 to 2;

0.5;

1.5.

19. A pacemaker lead comprising a polyisobutylene urethane, urea or urethane/urea copolymer, the copolymer comprising a polyisobutylene segment, a segment comprising a residue of a diisocyanate and an additional polymeric segment comprising a polyether segment, wherein a molar ratio of the polyisobutylene segment to the polyether segment is from 1.5:

0.5 to 0.5;

1.5.

20. The pacemaker lead of claim 19 wherein the polyether segment comprises a poly(tetramethylene oxide) segment.

21. The pacemaker lead of claim 20 wherein the polyether segment comprises a residue of a saturated poly(tetramethylene oxide) diol segment.