Biocompatible polyurethane devices wherein polyurethane is modified with lower alkyl sulfonate and lower alkyl carboxylate

• US 5,017,664 A
• Filed: 04/05/1989
• Issued: 05/21/1991
• Est. Priority Date: 06/03/1987
• Status: Expired due to Fees

• Current Assignee: Wisconsin Alumni Research Foundation (University of Wisconsin System)
• Original Assignee: Wisconsin Alumni Research Foundation (University of Wisconsin System)
• Inventors: Grasel, Timothy G., Cooper, Stuart L.
• Primary Examiner(s): Foelak, Morton
• Assistant Examiner(s): Daley, Dennis R.
• Application Number:
  US07/333,991
• Time in Patent Office: 776 Days
• Field of Search: 525/454, 528/49, 528/71, 604/266
• US Class Current: 525/454
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08G 18/0819 containing anionic or anionogenic groups
• CPC Class Codes: C08G 18/83 Chemically modified polymers
• CPC Class Codes: C08L 75/04 Polyurethanes

Abstract

Modified-polyurethane block copolymers and devices formed therefrom demonstrate excellent biocompatibilty and improved physical and mechanical properties. In a preferred embodiment, from about 5 to about 25 percent of urethane hydrogen atoms are replaced with propyl sulfonate and propyl carboxylate groups to provide the modified copolymer.

Claims

1. A biocompatible device having at least one surface which includes a polyether-polyurethane copolymer based on a mole ratio of about 1.5/0.5/1.0 to about 10/9/1 of an organic diisocyanate, a C₂ -C₁₄ alkyl or aryl diol or diamine and a polyol having a number average molecular weight from about 500 to about 3000, the copolymer being modified wherein about 5 to about 25 percent of the urethane hydrogen atoms are replaced with a combination of lower alkyl (C₁ -C₆) sulfonate groups and lower alkyl (C₁ -C₆) carboxylate groups.

2. The device of claim 1 wherein said organic diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, methylene bis(p-phenyl isocyanate), 1,5-naphthalene diisocyanate, methylene bis(p-cyclohexyl isocyanate), 1,6-hexane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.

3. The device of claim 1 wherein said diol or diamine is selected from the group consisting of 1,4-butanediol, ethylene diamine, 4,4'"'"'-methylene bis(2-chloroaniline), ethylene glycol and hexanediol.

4. The device of claim 1 wherein said polyol is selected from the group consisting of polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyisobutylene, polybutadiene, polyethylene adipate, polytetramethylene adipte, polycaprolactone and polydimethylsiloxane.

5. A biocompatible device for biomedical applications including surgical implantations, blood contacting procedures and the like, said device comprising a polyurethane composition which includes a polyether-polyurethane copolymer based on a mole ratio of about 1.5/0.5/1.0 to about 10/9/1 of (a) an organic diisocyanate, (b) a C₂ -C₁₄ alkyl or aryl diol or diamine and (c) a polyol having a number average molecular weight from about 500 to about 3000, the copolymer being modified wherein about 5 to about 25 percent of the urethane hydrogen atoms are replaced with a combination of propyl sulfonate groups and propyl carboxylate groups.

6. The device of claim 5 wherein said organic diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, methylene bis(p-phenyl isocyanate), 1,5-naphthalene diisocyanate, methylene bis(p-cyclohexyl isocyanate), 1,6-hexane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.

7. The device of claim 5 wherein said diol or diamine is selected from the group consisting of 1,4-butanediol, ethylene diamine, 4,4'"'"'-methylene bis(2-chloroaniline), ethylene glycol and hexanediol.

8. The device of claim 5 wherein said polyol is selected from the group consisting of polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyisobutylene, polybutadiene, polyethylene adipate, polytetramethylene adipate, polycaprolactone and polydimethylsiloxane.

9. A biocompatible device having a blood- or tissue-containing portion comprising a poly(tetramethylene oxide) -based polyurethane composition which comprises a polyether-polyurethane copolymer based on a 3/2/1 mole ratio of an organic diisocyanate, a C₂ -C₁₄ alkyl or aryl diol or diamine and a polytetramethylene oxide having a number average molecular weight of about 1000, the copolymer being modified wherein about 5 to about 25 percent of the urethane hydrogen atoms are replaced with a combination of propyl sulfonate groups and propyl carboxylate groups.

10. The device of claim 9 wherein said organic diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, methylene bis(p-phenyl isocyanate), 1,5-naphthalene diisocyanate, methylene bis(p-cyclohexyl isocyanate), 1,6-hexane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.

11. The device of claim 9 wherein said diol or diamine is selected from the group consisting of 1,4-butanediol, ethylene diamine, 4,4'"'"'-methylene bis(2-chloroaniline), ethylene glycol and hexanediol.

12. A device for biomedical use comprising a poly(tetramethylene oxide)-based polyurethane composition which comprises a polyether-polyurethane copolymer based on a 3/2/1 mole ratio of methylene bis(p-phenyl isocyanate), 1,4-butanediol and polytetramethylene oxide having a number average molecular weight of about 1000, the copolymer being modified wherein about 5 to about 25 percent of the urethane hydrogen atoms are replaced with a combination of propyl sulfonate groups and propyl carboxylate groups.