Coatings for implantable devices comprising poly(hydroxy-alkanoates) and diacid linkages

• US 8,758,801 B2
• Filed: 11/27/2012
• Issued: 06/24/2014
• Est. Priority Date: 07/30/2004
• Status: Expired due to Fees

• Current Assignee: Abbott Cardiovascular Systems Incorporated (Abbott Laboratories Incorporated)
• Original Assignee: Abbott Cardiovascular Systems Incorporated (Abbott Laboratories Incorporated)
• Inventors: Pacetti, Stephen Dirk, Glauser, Thierry
• Primary Examiner(s): Switzer, Juliet C
• Assistant Examiner(s): HELM, CARALYNNE E
• Application Number:
  US13/686,392
• Publication Number:
  US 20130116380A1
• Time in Patent Office: 574 Days
• Field of Search: None
• US Class Current: 424/426
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: C08G 63/66 Polyesters containing oxygen in the form of ether groups C08G63/42, C08G63/58 take precedence
• CPC Class Codes: C09D 167/00 Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09D177/12; based on polyester-imides C09D179/08; Coating compositions based on derivatives of such polymers

Abstract

Coatings for an implantable medical device and a method of fabricating thereof are disclosed, the coatings including block-polymers comprising at least one poly(hydroxyacid) or poly(hydroxy-alkanoate) block, at least one block of a biologically compatible polymer and at least one type of linking moiety.

Claims

1. A polymer having the formula:

2. The polymer of claim 1, wherein the poly(hydroxyacid) or poly(hydroxy-alkanoate) is one of poly(lactide-co-glycolide);

poly(L-lactide);

poly(D-lactide);

poly(D,L-lactide);

poly(L-lactide-co-glycolide);

poly(D,L-lactide-co-glycolide);

poly(L-lactide-co-caprolactone);

poly(D,L-lactide-co-caprolactone);

poly(L-lactide-co-D,L-lactide);

poly(L-lactide-co-trimethylene carbonate);

poly(D,L-lactide-co-trimethylene carbonate);

poly(L-lactic acid);

poly(D-lactic acid);

poly(D,L-lactic acid);

or a combination thereof.

3. The polymer of claim 1, wherein Y is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,4-hydroxymethylbenzene, serinol, dihydroxyacetone, any linear or branched C₂ to C₁₂ hydrocarbon with two primary hydroxyl groups, or any linear or branched C₂ to C₁₂ with unsaturation and two primary hydroxyl groups.

4. The polymer of claim 1 wherein the poly(hydroxyacid) or poly(hydroxy-alkanoate) is one of poly(L-lactide);

poly(D-lactide);

poly(D,L-lactide);

poly(L-lactide-co-D,L-lactide);

poly(L-lactic acid);

poly(D-lactic acid);

poly(D,L-lactic acid);

or a combination thereof.

5. The polymer of claim 1 wherein the linking moiety is derived from at least one of or any combination of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, brassylic acid, dodecane-1,12-dicarboxylic acid, tridecane-1,13-dicarboxylic acid, thapsic acid, fumaric acid, maleic acid, and 1,3-acetonedicarboxylic acid.

6. The polymer of claim 1 wherein the linking moiety is derived from at least one of or any combination of glutaric acid, adipic acid, pimelic acid, brassylic acid, dodecane-1,12-dicarboxylic acid, tridecane-1,13-dicarboxylic acid, thapsic acid, fumaric acid, maleic acid, and 1,3-acetonedicarboxylic acid.

7. The polymer of claim 1 wherein each A is a poly(D,L-lactide) block.

8. The polymer of claim 7 wherein n is about 10.

20. A coating made with the polymer of claim 1.

21. A medical device comprising the coating of claim 20.

9. A method of making a polymer comprising:

reacting a hydroxy-terminated polymeric, biocompatible moiety with a diacid or anhydride to make a first block;

making a second block by ring opening polymerization with a cyclic hydroxy-alkanoate using a dihydric initiator;

coupling the first block to the second block using a coupling agent, facilitated by a catalyst, such that a final block copolymer is formed having the formula;

10. The method of claim 9, wherein the hydroxy-terminated polymeric, biocompatible moiety is poly(ethylene glycol) (PEG).

11. The method of claim 9, wherein the cyclic hydroxy-alkanoate is lactide.

12. The method of claim 10, wherein the dihydric initiator is 1,3-propanediol.

13. The method of claim 9, wherein the coupling agent is 1,3-dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC).

14. The method of claim 9, wherein the catalyst is N-dimethylaminopyridine (DMAP), diazabicycloundecane (DBU), N-(methylpolystyrene)-4-(methylamino)pyridine, or 4-pyrrolidinopyridine.

15. The method of claim 9, wherein Y is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,4-hydroxymethylbenzene, serinol, dihydroxyacetone, any linear or branched C₂ to C₁₂ hydrocarbon with two primary hydroxyl groups, or any linear or branched C₂ to C₁₂ with unsaturation and two primary hydroxyl groups.

16. The method of claim 9, wherein the poly(hydroxyacid) or poly(hydroxy-alkanoate) is one of poly(lactide-co-glycolide);

poly(L-lactide);

poly(D-lactide);

poly(D,L-lactide);

poly(L-lactide-co-glycolide);

poly(D,L-lactide-co-glycolide);

poly(L-lactide-co-caprolactone);

poly(D,L-lactide-co-caprolactone);

poly(L-lactide-co-D,L-lactide);

poly(L-lactide-co-trimethylene carbonate);

poly(D,L-lactide-co-trimethylene carbonate);

poly(L-lactic acid);

poly(D-lactic acid);

poly(D,L-lactic acid);

or a combination thereof.

17. The method of claim 9 wherein the linking moiety is derived from at least one of or any combination of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, brassylic acid, dodecane-1,12-dicarboxylic acid, tridecane-1,13-dicarboxylic acid, thapsic acid, fumaric acid, maleic acid, and 1,3-acetonedicarboxylic acid.

18. The method of claim 9 further comprising:

depositing the final block copolymer on a region of an implantable portion of a medical device.

19. The method of claim 18 wherein the medical device is a stent.