EP-4739728-A1 - TUNABLE POLYISOBUTYLENE POLYURETHANE

Abstract

A polymeric material having a polyisobutylene polyurethane. The polyisobutylene having soft segments including a polyisobutylene diamine residue, and hard segments including bis-cyclic carbonate residue.

Inventors

• HSU, YEN-HAO
• BODEN, MARK W.

Assignees

• Boston Scientific Scimed, Inc.

Dates

Publication Date

20260513

Application Date

20240702

Claims (20)

1. 1 . A polymeric material comprising: a polyisobutylene polyurethane including: soft segments including a polyisobutylene diamine residue; and hard segments including bis-cyclic carbonate residue.
2. 2. The polymeric material of claim 1 , wherein the polyisobutylene polyurethane is free of urea linkages.
3. 3. The polymeric material of claim 1 or claim 2, wherein the hard segments further include ethanol side chains.
4. 4. The polymeric material of any of claims 1-3, wherein the hard segments further include modifying moieties covalently bonded to a polymer backbone.
5. 5. The polymeric material of claim 4, wherein the modifying moieties are from bromine-terminated polyethylene glycol (PEG-Br), quaternary ammonium bromineterminated derivatives (small molecule or polymer-based), bromine-terminated polyvinylpyrrilidone (PVP-Br) or bromine-terminated poly (2-methyl-2-oxazoline).
6. 6. The polymeric material of claim 4, wherein the modifying moieties from 8-bromo- 1 ,1 ,1 ,2,2,3,3,4,4,5,5,6,6-tridecafluoro-octane, bromine-terminated polytetrafluoroethylene (PTFE-Br) or bromine-terminated polydimethylsiloxane (PDMS- Br).
7. 7. A medical device comprising: a polymeric material including: a polyisobutylene polyurethane including: soft segments including a polyisobutylene diamine residue; and hard segments including bis-cyclic carbonate residue.
8. 8. The medical device of claim 7, wherein the hard segments further include modifying moieties covalently bonded to a polymer backbone.
9. 9. The medical device of claim 8, wherein the modifying moieties are only present at surfaces of the polyisobutylene polyurethane.
10. 10. The medical device of claim 8, wherein the modifying moieties are present throughout the polyisobutylene polyurethane.
11. 11. A method of making a polymeric material, the method comprising: forming amino-terminated polyisobutylene from hydroxyl-term inated polyisobutylene; and performing ring-opening polymerization with bis-cyclic carbonate and the aminoterminated polyisobutylene to form polyisobutylene polyurethane.
12. 12. The method of claim 11 , wherein forming the amino-terminated polyisobutylene includes adding methanesulfonyl chloride and ammonia to hydroxyl-term inated polyisobutylene.
13. 13. The method of claim 11 or claim 12, wherein the bis-cyclic carbonate and the amino-terminated polyisobutylene are present in the ring-opening polymerization in equal molar amounts.
14. 14. The method of any of claims 11-13, and further comprising performing a SN2 reaction with the polyisobutylene polyurethane to form a modified polyisobutylene polyurethane.
15. 15. The method of claim 1 wherein the SN2 reaction includes bromine-terminated polyethylene glycol (PEG-Br), quaternary ammonium bromine-terminated derivatives (small molecule or polymer-based), bromine-terminated polyvinylpyrrilidone (PVP-Br) or bromine-terminated poly (2-methyl-2-oxazoline).
16. 16. The method of claim 14, wherein the SN2 reaction includes 8-bromo- 1 ,1 ,1 ,2,2,3,3,4,4,5,5,6,6-tridecafluoro-octane, bromine-terminated polytetrafluoroethylene (PTFE-Br) or bromine-terminated polydimethylsiloxane (PDMS- Br).
17. 17. The method of claim 14, and further comprising forming the polyisobutylene polyurethane into a medical device.
18. 18. The method of claim 17 wherein the SN2 reaction is performed before forming the medical device.
19. 19. The method of claim 17 wherein the SN2 reaction is performed after forming the medical device.
20. 20. The method of claim 19 wherein the SN2 reaction includes a polymer or molecule having a leaving group and a modifying moiety, wherein the leaving group is selected from the group consisting of bromide, iodide, chloride, tosylates and mesylates, and wherein the modifying moiety is selected from the group consisting of polyacrylates, acrylic acid copolymers, polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyoxazolines, quaternary ammonium-functionalized polymers or molecules glycosaminoglycans and peptides.

Description

TUNABLE POLYISOBUTYLENE POLYURETHANE CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The application claims priority to U.S. Provisional Application No. 63/317,732, filed July 3, 2023, which is herein incorporated by reference in its entirety. TECHNICAL FIELD [0002] The present disclosure relates to polymeric materials. More specifically, the disclosure relates to polyisobutylene-polyurethane block copolymers, methods for making polyisobutylene-polyurethane block copolymers, and medical devices containing polyisobutylene-polyurethane block copolymers. BACKGROUND [0003] Polymeric materials are widely used in the field of medical devices. For example, polymeric materials such as silicone rubber, polyurethane, and fluoropolymers are used as coating and/or insulating materials for medical leads, stents, catheters, and other devices. [0004] Thermoplastic polyurethanes (TPUs) can be used in either short-term or long-term implantable devices, such as catheters, polymer discs, and coatings. Block copolymers are polymeric materials made of alternating sections of polymerized monomers. Polyisobutylene polyurethane is a TPU formed from hard segments (such as diisocyanates) and soft segments (hydroxyl-term inated polymers such as polyether, polycarbonate, poly-c-caprolactone and polyisobutylene). The mechanical (such as hardness and stretchability) and thermal (such as crystallinity and glassy transition) properties of polyisobutylene polyurethane can be tuned, for example, by varying the weight percentage of the hard and soft segments. [0005] However, one challenge with existing polyisobutylene polyurethane manufacturing processes is the formation of undesired urea linkage groups, which can cause unpredictable variation in the molecular weight and thermal and/or mechanical properties of the polyurethane. [0006] Additionally, non-covalently bound coatings have been used on polyisobutylene polyurethanes to reduce or prevent biofilm accumulation on the polymer surface. However, a covalently bound coating would provide an improved coating and sufficient lubricity while also preventing biofilm accumulation. SUMMARY [0007] Example 1 is a polymeric material having a polyisobutylene polyurethane. The polyisobutylene having soft segments including a polyisobutylene diol residue, and hard segments including bis-cyclic carbonate residue. [0008] Example 2 is the polymeric material of Example 1 , wherein the polyisobutylene polyurethane is free of urea linkages. [0009] Example 3 is the polymeric material of Example 1 , wherein the hard segments further include ethanol side chains. [0010] Example 4 is the polymeric material of Example 1 , wherein the hard segments further include modifying moieties covalently bonded to a polymer backbone. [0011] Example 5 is the polymeric material of Example 4, wherein the modifying moieties are from bromine-terminated polyethylene glycol (PEG-Br), quaternary ammonium bromine-terminated derivatives (small molecule or polymer-based), bromine-terminated polyvinylpyrrilidone (PVP-Br) or bromine-terminated poly (2-methyl- 2-oxazoline). [0012] Example 6 is the polymeric material of Example 4, wherein the modifying moieties are from 8-bromo-1 ,1 ,1 ,2,2,3,3,4,4,5,5,6,6-tridecafluoro-octane, bromineterminated polytetrafluoroethylene (PTFE-Br) or bromine-terminated polydimethylsiloxane (PDMS-Br). [0013] Example 7 is a medical device having a polymeric material. The polymeric material has soft segments including a polyisobutylene diamine residue and hard segments including bis-cyclic carbonate residue. [0014] Example 8 is the medical device of Example 7, wherein the hard segments further include modifying moieties covalently bonded to a polymer backbone. [0015] Example 9 is the medical device of Example 8, wherein the modifying moieties are only present at surfaces of the polyisobutylene polyurethane. [0016] Example 10 is the medical device of Example 8, wherein the modifying moieties are present throughout the polyisobutylene polyurethane. [0017] Example 11 is a method of making a polymeric material that includes forming amino-terminated polyisobutylene from hydroxyl-term inated polyisobutylene; and performing ring-opening polymerization with bis-cyclic carbonate and the aminoterminated polyisobutylene to form polyisobutylene polyurethane. [0018] Example 12 is the method of Example 11 , wherein forming the aminoterminated polyisobutylene includes adding methanesulfonyl chloride and ammonia to hydroxyl-term inated polyisobutylene. [0019] Example 13 is the method of Example 11 , wherein the bis-cyclic carbonate and the amino-terminated polyisobutylene are present in the ring-opening polymerization in equal molar amounts. [0020] Example 14 is the method of Example 11 , and further comprising performing a SN2 reaction with the polyisobutylene polyurethane to form a modified polyisobutylene polyurethane. [0021] Example 15 is the method of Example 14 wherein the SN2 reaction includes bromine-terminated polyet