FLUOROPOLYMER-BASED MEDICAL IMPLANT COATING COMPOSITIONS

• US 20090264539A1
• Filed: 04/16/2009
• Published: 10/22/2009
• Est. Priority Date: 04/16/2008
• Status: Active Grant

• Current Assignee: Boston Scientific Scimed (Boston Scientific Corporation)
• Original Assignee: Boston Scientific Scimed (Boston Scientific Corporation)
• Inventors: Lasch, James, Rolf, David, Seethamraju, Kasyap, Kocur, Gordon
• Granted Patent: US 8,475,844 B2
• Time in Patent Office: Days
• US Class Current: 514/772.600
• CPC Class Codes: A61L 2420/06 Coatings containing a mixture of two or more compounds
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/16 Biologically active materials, e.g. therapeutic substances A61L31/047 takes precedence
• CPC Class Codes: A61P 7/02 Antithrombotic agents; Anticoagulants; Platelet aggregation inhibitors
• CPC Class Codes: C08F 214/186 with non-fluorinated comonomers
• CPC Class Codes: C08F 220/10 Esters
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 27/16 Homopolymers or copolymers or vinylidene fluoride
• CPC Class Codes: C08L 33/06 of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Abstract

Polymers of fluorinated monomers and acrylate and alkyl acrylates are disclosed which demonstrate improved performance as coatings for implantable devices. Such coatings may, for example, be used to release a bioactive agent from the medical device. One specific application lies in drug-eluting coatings for stents.

Claims

1. A copolymer composition, said copolymer composition comprising:

a fluoromonomer unit; and

,

an acrylate monomer unit selected from the group consisting of acrylate monomer units of formula I, acrylate monomer units of formula II, acrylate monomer units of formula III, and combinations thereof,

wherein when R¹ is a C₆-C₁₀ aryl, a 5- to 12-membered heterocyclic group, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, or C₃-C₆ cycloalkyl; and

R² is hydrogen, a C₆-C₁₀ aryl, a 5- to 12-membered heterocyclic group, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, or C₃-C₆ cycloalkyl, and further wherein R¹ and R² may be the same or different.

2. The copolymer composition of claim 1, wherein the mole % of acrylate is 50% or lower.

3. The copolymer composition of claim 1, wherein the mole % of acrylate is selected from the group consisting of 10-20%, 10-50%, and 25-50%.

4. The copolymer composition of claim 1, having a glass transition temperature of less than 35°

C.

5. The copolymer composition of claim 4, having a glass transition temperature of less than 20°

C.

6. The copolymer of claim 1, wherein the fluoromonomer unit is selected from the group consisting of vinylidene difluoride, hexfluoropropylene and combinations thereof.

7. The copolymer composition of claim 1, wherein the copolymer composition comprises a random copolymer, a block copolymer, or a graft copolymer.

8. The copolymer composition of claim 1, wherein the acrylate monomer unit is selected from the group consisting of methylmethacrylate, ethylmethacrylate, butylmethacrylate, hexylmethacrylate, methacrylate, n-butylacrylate, ethylacrylate, and any combination thereof.

9. The copolymer composition of claim 1, further comprising a bioactive agent.

10. The copolymer composition of claim 9, wherein said bioactive agent is an antithrombotic agent.

11. The copolymer composition of claim 1, further comprising an additional monomer unit wherein said additional monomer unit is present at less than 10 mole % of the composition.

12. A copolymer composition, said copolymer composition comprising:

a fluoromonomer unit; and

,

an acrylate monomer unit of formula IV,

wherein Y is selected from the group consisting of

—

COOH, —

NH₂, —

SH, —

OH, —

Si(OCH₃)₃,

13. The copolymer of claim 12, wherein the fluoromonomer unit is selected from the group consisting of vinylidene difluoride, hexfluoropropylene and combinations thereof.

14. The copolymer composition of claim 12, wherein the mole % of acrylate is 50% or lower.

15. The copolymer composition of claim 12, wherein the mole % of acrylate is selected from the group consisting of 10-20%, 10-50%, and 25-50%.

16. The copolymer composition of claim 12, having a glass transition temperature of less than 35°

C.

17. The copolymer composition of claim 16, having a glass transition temperature of less than 20°

C.

18. The copolymer composition of claim 12, wherein the copolymer composition comprises a random copolymer, a block copolymer, or a graft copolymer.

19. The copolymer composition of claim 12, further comprising a bioactive agent.

20. The copolymer composition of claim 19, wherein said bioactive agent is an antithrombotic agent.

21. The copolymer composition of claim 12, further comprising an additional monomer unit wherein said additional monomer unit is present at less than 10 mole % of the composition.

22. A copolymer composition, said copolymer composition comprising:

a fluoromonomer unit; and

,

an acrylate monomer unit of formula V, formula VI, or a combination thereof.

23. The copolymer composition of claim 22, wherein the fluoromonomer unit is selected from the group consisting of vinylidene difluoride, hexfluoropropylene and combinations thereof.

24. The copolymer composition of claim 22, wherein the mole % of acrylate is 50% or lower.

25. The copolymer composition of claim 22, wherein the mole % of acrylate is selected from the group consisting of 10-20%, 10-50%, and 25-50%.

26. The copolymer composition of claim 22, having a glass transition temperature of less than 35°

C.

27. The copolymer composition of claim 26, having a glass transition temperature of less than 20°

C.

28. The copolymer composition of claim 22, wherein the copolymer is a random copolymer a block copolymer, or a graft copolymer.

29. The copolymer composition of claim 22, further comprising a bioactive agent.

30. The copolymer composition of claim 29, wherein said bioactive agent is an antithrombotic agent.

31. The copolymer composition of claim 22, further comprising an additional monomer unit wherein said additional monomer unit is present at less than 10 mole % of the composition.

32. A polymer blend composition, said composition comprising:

a fluoropolymer; and

,

an polyacrylate having an acrylate monomer unit selected from the group consisting of acrylate monomer units of formula I, acrylate monomer units of formula II, acrylate monomer units of formula III, and combinations thereof,

wherein when R¹ is a C₆-C₁₀ aryl, a 5- to 12-membered heterocyclic group, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, or C₃-C₆ cycloalkyl; and

R² is hydrogen, a C₆-C₁₀ aryl, a 5- to 12-membered heterocyclic group, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, or C₃-C₆ cycloalkyl, and further wherein R¹ and R² may be the same or different.

33. The polymer blend of claim 32, further comprising a third polymer, said third polymer being substantially free of fluoromonomers and acrylate monomers.