Melt processable polyurethaneurea copolymers and method for their preparation

• US 5,250,649 A
• Filed: 06/29/1990
• Issued: 10/05/1993
• Est. Priority Date: 06/29/1990
• Status: Expired due to Term

• Current Assignee: Becton, Dickinson & Co
• Original Assignee: Becton, Dickinson & Co
• Inventors: Onwumere, Fidelis C., Solomon, Donald D.
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): Truong, Duc
• Application Number:
  US07/546,825
• Time in Patent Office: 1,194 Days
• Field of Search: 528/44, 528/28, 528/54, 528/76, 528/77, 528/83, 528/84
• US Class Current: 528/44
• CPC Class Codes: A61L 29/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 29/16 Biologically active materials, e.g. therapeutic substances A61L29/048 takes precedence
• CPC Class Codes: C08G 18/482 Mixtures of polyethers containing at least one polyether containing nitrogen
• CPC Class Codes: C08G 18/5024 containing primary and/or secondary amino groups
• CPC Class Codes: C08G 18/6674 with compounds of group C08G18/3203
• CPC Class Codes: C08L 75/12 from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Abstract

Melt processable polyurethaneureas are prepared from a diisocyanate, a polyglycol, a diol chain extender and an amine terminated polyether. Water may be included as a reactant, and the polymer may contain an additive such as a radiopaque material and a coating of an antithrombogenic agent or an antimicrobial agent. The invention includes a one-pot bulk polymerization method for preparation of the polymers.

Claims

1. A melt processable polyurethaneurea consisting essentially of a product reaction of a diisocyanate, a polyetherglycol, a diol chain extender, an amine terminated polyether and atmospheric moisture as a curing agent, said polyurethaneurea having a mino end caps as a result of being cured with said atmospheric moisture.

2. The polyurethaneurea of claim 1 wherein said diisocyanate is selected from the group consisting of 4,4'"'"'-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), and hexamethylene diisocyanate.

3. The polyurethaneurea of claim 1 wherein said polyetherglycol is selected from the group consisting of polyethyleneglycol and polytetramethylene ether glycol.

4. The polyurethaneurea of claim 1 wherein said diol is selected from the group consisting of 1,4-butanediol, ethylene glycol;

diethylene glycol;

triethylene glycol;

1,2-propanediol;

1,3-propanediol;

1,6-hexanediol;

1,4-bis-hydroxymethyl cyclohexane, and hydroquinone dihyroxyethyl ether.

5. The polyurethaneurea of claim 1 wherein said amino terminated polyether is selected from the group consisting of amine terminated polyethylene oxide, amine terminated polypropylene oxide and amine terminated polytetramethylene oxide.

6. The polyurethaneurea of claim 1 further including a component selected from the group consisting of a radiopaque material, an antithrombogenic agent, an antimicrobial agent and water.

7. A melt processable polyurethaneurea consisting essentially of a product from the reaction of a polyisocyanate, chain extender, polyglycol, polymeric amine terminated soft segment component selected from the group consisting of an amine terminated polyether, polyester, polyurea and polysiloxane, and atmospheric moisture as a curing agent, said polyurethaneurea having amino end caps as a result of being cured with said atmospheric moisture.

8. The polyurethaneurea of claim 7 wherein said component has a linkage selected from the group consisting of a urea, ester, siloxane and ether linkage in the polymer chain.

9. The polyurethaneurea of claim 7 wherein said chain extender is selected from the group consisting of a diol, diamine, amino alcohol and water.

10. The polyurethaneurea of claim 7 wherein said polyglycol is selected from the group consisting of a polysiloxane lycol, a polyester lycol and a polyether glycol.

11. A melt processable polyurethaneurea consisting essentially of a product from the reaction of 4,4'"'"'-diphenylmethane diisocyanate, 1,4-butanediol, polytetramethyleneether glycol, amine terminated polypropylene oxide and atmospheric moisture as a curing agent, said polyurethane having amino end caps as a result of being cured with said atmospheric moisture.

12. The polyurethaneurea of claim 11 further consisting essentially of an agent selected from the group consisting of a radiopaque agent, an antithrombogenic agent and an antimicrobial agent.

13. A method for producing a melt processable polyurethaneurea consisting essentially of combining with mixing a diisocyanate and a mixture of a polyetherglycol, a diol chain extender and an amine terminated polyether at a temperature sufficient to induce an exotherm to give a clear and uniform melt of polyurethaneurea and curing said polyurethaneurea with said atmospheric moisture.

14. The method of claim 13 wherein said combining step is performed with a diisocyanate selected from the group consisting of 4,4'"'"'-diphenylmethane diisocyanate, toluene diiso cyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), and hexamethylene diisocyanate.

15. The method of claim 13 wherein said combining step is performed with a polyetherglycol selected from the group consisting of polyethyleneglycol and polytetramethylene ether glycol.

16. The method of claim 13 wherein said combining step is performed with a diol selected from the group consisting of 1,4-butanediol, ethylene glycol;

diethylene glycol;

triethylene glycol;

1,2-propanediol;

1,3-propanediol;

1,6-hexanediol;

1,4-bis-hydroxymethyl cyclohexane and hydroquinone dihydroxyethyl ether.

17. The method of claim 13 wherein said combining step is performed with an amine terminated polyether selected from the group consisting of polyethylene oxide, polypropylene oxide and polytetramethylene oxide.

18. The method of claim 13 wherein said combining step is performed with a reagent selected from the group consisting of water and a radiopaque material.

19. The method of claim 13 further consisting essentially of extruding said polyurethaneurea into a tubing and coating said tubing with an agent selected from the group consisting of an antithrombogenic agent and an antimicrobial agent.

20. The method of claim 13 further consisting essentially of coextruding said polyurethaneurea into a tubing having a coextruded stripe which includes a radiopaque material.

21. A method for producing a melt processable polyurethaneurea consisting essentially of combining with mixing a polyisocyanate, a polyglycol, a chain extender and an amine terminated polyether at a temperature sufficient to induce an exotherm to give a clear and uniform melt of thermoplastic polyurethaneurea and curing said polyurethaneurea with said atmospheric moisture.

22. The method of claim 21 wherein said combining step is performed with a polyglycol selected from the group consisting of a silicone glycol, a polyester lycol, polylactone lycol and a polyether glycol.

23. A method for producing a melt processable polyurethaneurea consisting essentially of adding 4,4'"'"'-diphenylmethane diisocyanate, with mixing, to a mixture of 1,4-butanediol, polytetramethylene ether glycol and an amine terminated polypropylene oxide at a temperature sufficient to induce an exotherm to give a clear uniform melt of a polyurethaneurea and moisture curing said polyurethaneurea.