Functionalized polyurethanes

• US 6,177,523 B1
• Filed: 07/14/1999
• Issued: 01/23/2001
• Est. Priority Date: 07/14/1999
• Status: Expired due to Fees

• Current Assignee: Cardiotech International
• Original Assignee: Cardiotech International
• Inventors: Teffenhart, John, Reich, Murray H.
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): BISSETT, MELANIE D
• Application Number:
  US09/353,222
• Time in Patent Office: 559 Days
• Field of Search: 525/459, 525/460, 525/450, 525/454, 525/453, 528/56, 528/57, 528/55, 528/58, 524/840, 524/839, 524/591
• US Class Current: 525/459
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/44 Polycarbonates
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/6692 with compounds of group C08G18/34
• CPC Class Codes: C08G 18/765 alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• CPC Class Codes: C08G 18/833 by nitrogen containing compounds by azo compounds C08G18/85

Abstract

The present invention relates to functionalizable and crosslinkable polyurethanes formed of a polyurethane intermediate including one or more ester groups which react with an amine equivalent to form an amide unit. The polyurethane intermediate comprises the reaction product of alkyl ester of dihydroxypolyacid or dimethylolalkanoic acid, a polyoxyalkylene diol and an organic diisocyanate. The polyurethane is reacted with a solution of an amine equivalent and a solvent or an amine. An article of manufacture can be formed from the polyurethane.

Claims

1. A polyurethane comprising the reaction product of a poyurethane intermediate comprising an alkyl ester of dimethylolalkanoic acid or dihydroxypolyacid;

a polyoxyalkylene diol; and

an organic diisocyanate; and

a solution of an amine equivalent and a solvent having less than about 50% by weight of water, said amine equivalent including one or more amine groups wherein said polyurethane comprises an amide.

2. The polyurethane of claim 1 wherein said amine equivalent is employed in an amount of about equal to or about less than an equivalent amount by weight of amine to ester to crosslink said polyurethane.

3. The polyurethane of claim 1 wherein said amine equivalent is employed in an amount of about one to about two times the equivalent amount by weight of amine to ester to functionalize and crosslink said polyurethane.

4. The polyurethane of claim 1 wherein said amine equivalent is employed in an amount of about two to about ten times the equivalent amount by weight of amine to ester to functionalize said polyurethane.

5. The polyurethane of claim 1 wherein said alkyl ester of dimethylolalkanoic acid or dihydroxypolyacid is present in an amount of about 0.01% to about 30% by weight of the reaction mixture.

6. The polyurethane of claim 5 wherein said alkyl ester is present in an amount of about 0. 10% to about 8% by weight of the reaction mixture.

7. The polyurethane of claim 4 wherein said alkyl ester of dimethylolalkanoic acid or dihydroxypolyacid is selected from the group consisting of dihydroxy benzoic acid ester, glyceric acid ester, straight chain and branched alkyl esters of tartaric acid and trihydroxy n-butyric acid containing carbon lengths of 1-20 or butyl, propyl, ethyl, hexyl, octyl, decyl, methyl, nonyl, stearyl, and dodecyl 2,2-di(hydroxymethyl)propionic acid and trihydroxy n-butyric acid ester.

8. The polyurethane of claim 1 wherein the reaction product of said polyurethane intermediate further comprises an alkylene glycol selected from ethylene glycol, 2,-4-pentane diol, 2-methyl-1,3 propanediol, propylene glycol, 1-4-butane diol, neopentyl glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, diethylene glycol, hexane diol, 2,-4-pentane diol, cyclohexanediol, cyclohexanedimethanol, 2,2-dimethylolpropionic acid and 2-ethyl-1,3-hexane.

9. The polyurethane of claim 1 wherein the reaction product of said polyurethane intermediate further comprises:

water in an amount of about 0.001% to about 0.80% by weight of the reaction mixture in an equivalent molecular weight ratio of NCO/OH of the diol, the alkyl glycol and the water of about 0.4 to about 1.2.

10. The polyurethane of claim 1 wherein said polyoxyalkylene diol is selected from the group consisting of polyoxyethylene diol having a number average molecular weight of about 100 to about 20,000, polyoxypropylene diol having a number average molecular weight of about 200 to about 4,000, polydimethylsiloxane polyoxyalkylene copolymer having a number average molecular weight of about 400 to about 3000, polyoxytetramethylene diol having a number average molecular weight of about 400 to about 3,000, polybutylene oxide having a number average molecular weight of about 1000 to about 4000 and polyether polycarbonate diol having an average molecular number weight of about 400 to about 3,000;

and wherein said reaction product of said polyurethane intermediate further comprises water in an amount of about 0.02% to about 0.45% by weight of the reaction mixture and an equivalent mole weight ratio of NCO to OH of about the diol and water 0.80 to about 0.99 and wherein said polyurethane intermediate is substantially amphiphilic.

11. The polyurethane of claim 1 wherein said polyoxyalkylene diol comprises:

a hydrophilic diol of polyoxyethylene diol having a number average molecular weight from about 400 to about 10,000 at about 10% to about 95% by weight of the reaction mixture mixed with a portion of hydrophobic polyoxyalkylene diol of about 15% to about 30% by weight of the reaction mixture, said hydrophobic polyoxyalkylene diol selected from polyoxytetramethylene diol having a number average molecular weight of from about 200 to about 4,000, polyoxypropylene diol having a number average molecular weight of from about 400 to about 4,000, polyether polycarbonate diol having a number average molecular weight of about 1,000 to about 2,000, polybutylene oxide having a number average molecular weight of about 1000 to about 4000, and polydimethylsiloxane polyoxyalkylene copolymer having a number average molecular weight of about 500 to about 3,000 wherein the polyoxyalkylene is selected from polyoxyethylene and polyoxypropylene;

an alkylene glycol selected from ethylene glycol, propylene glycol, 2-ethyl-1,3-hexane diol, tripropylene glycol, 1,4-butane diol, neopentyl glycol, triethylene glycol, 2,-4-pentane diol, 2-methyl-1,3 propanediol, hexane diol, cyclohexanediol, cyclohexanedimethanol, dipropylene glycol, 2,2-dimethylolpropionic acid and diethylene glycol;

and wherein said reaction product of the polyurethane intermediate further comprises water in an amount of about 0.05% to about 0.70% by weight of the reaction mixture in an equivalent mole weight ratio of NCO to OH of the diol, alkylene glycol and water of about 0.90 to about 1.0.

12. The polyurethane of claim 11 wherein said ester acid is the alkyl ester of dimethylolpropionic acid in an amount of from about 0.02% to about 25% by weight of the reaction mixture.

13. The polyurethane of claim 1 wherein said polyoxyalkylene diol comprises at least about 60% by weight of the reaction mixture of polyoxyethylene diol having a number aerage molecular weight of about 200 to about 20,000 wherein said polyurethane intermediate is substantially hydrophilic.

14. The polyurethane of claim 10 wherein said ester acid is the alkyl ester of 2,2-dimethylolpropionic acid in an amount of from about 0.3% to about 5% by weight of the reaction mixture.

15. The polyurethane of claim 1 wherein said polyoxyalkylene diol comprises:

about 5% to about 80% by weight of a hydrophobic diol selected from the group consisting of a polyoxypropylene diol and polyoxytetramethylene diol having a number average molecular weight from about 200 to about 6,000, polybutylene oxide having a number average molecular weight of about 1000 to about 4000, polydimethylsiloxane polyoxyethylene copolymer having a number average molecular weight of about 500 to about 3,000 and polyetherpolycarbonate diol and having a number average molecular weight of about 1000 to about 4000; and

about 1% to about 40% by weight of a hydrophilic diol of polyoxyethylene;

and wherein said reaction product of said polyurethane intermediate further comprises water in an amount of about 0.01% to about 0.70% by weight of the reaction mixture in an equivalent mole weight ratio of NCO to OH of the hydroxyl groups of the diols alkylene glycol and water from about 0.7 to about 1.2.

16. The polyurethane of claim 15 wherein said hydrophobic diol is polyether polycarbonate diol in an amount of about 5% to about 70% by weight and polydimethylsiloxane polyoxyethylene copolymer in an amount of about 5% to about 50% by weight of the reaction mixture.

17. The polyurethane of claim 1 wherein said amine is selected from the group consisting of ethylene diamine, butyl diamine, butyl amine, propanediamine, butanediamine, pentane diamine, propyl amine, pentylamine, ethylene amine, heptyl amine, triethylene tetraamine, diethylenetriamine, hexylamine, hexanediamine, octanediamine, nonanediamine, decyldiamine, diaminotoluene, phenylenediamine, benzidazole, benzothiazoles, toluene, xylylenediamine, 1,4-diaminocyclohexane, 2-methylpentamethylene diamine, benzene diamine, glycine, diglycolamine, ethanolamine, fatty amine and polyoxyalkylene amines and diamines.

18. The polyurethane of claim 1 wherein an alkylene glycol is added to said alkyl ester of dimethylolalkanoic acid or dihydroxypolyacid said alkylene glycol being selected from the group of ethylene glycol, 2,-4-pentane diol, 2-methyl-1,3 propanediol, propylene glycol, dipropylene glycol, 1,4-butane diol, neopentyl glycol, triethylene glycol, tripropylene glycol, diethylene glycol, hexane diol, cyclohexanediol, cyclohexanedimethanol, 2,2-dimethylolpropionic acid and 2-ethyl-1,3-hexane diol, and mixtures thereof.

19. The polyurethane of claim 1 wherein said amine equivalent is a monoamine and is employed in an amount of about 0.2 to about 1.2 the equivalent amount by weight of amine to functionalize said polyurethane.

20. The polyurethane of claim 19 wherein said amine equivalent is vinylamine.

21. The polyurethane of claim 1 further comprising a catalyst selected from the group of Lewis acid, phosphoric acid, sulfuric acid, stannous octoate, dibutyl tin dilaurate, acetic anhydride, acetic acid chloride, phosphorus pentoxide, zinc chloride, tetrabutyl titanate, unblocked and amine-blocked alkane sulfonic and aromatic sulfonic acid.

22. The polyurethane of claim 1 wherein said solvent is selected from the group consisting of ethanol, methyl ethyl ketone, pyrrolidone, dimethylacetamide, dimethylformamide, isopropanol, methanol and butanol.

24. The polyurethane of claim 1 wherein the alkyl ester is butyl, ethyl, methyl or propyl dimethylolpriopionic acid.

25. An article of manufacture formed from the polyurethane of claim 1.

26. The article of manufacture of claim 25 wherein said article is a coating.

27. The article of manufacture of claim 25 wherein said article is a film.

28. The article of manufacture of claim 25 wherein said article is a medical device selected from the group consisting of an infusion therapy catheter, midline catheter, intravenous catheters, synthetic heart valve, synthetic vein, artery, scar flattener, cardiovascular therapy catheter, stent, port, dilator, and dialysis catheter.

29. An article of manufacture formed from the polyurethane of claim 3.

30. The article of manufacture of claim 29 further comprising a compound selected from the group consisting of phenol, isocyanate, carboxylic acid, mercaptan, silanol and epoxy.

31. The article of manufacture of claim 29 further comprising an active agent selected from the group consisting of pharmacologically active agent, antithrombogenic agent, anticancer agent, cellular growth agent and anticoagulent agent.

32. An article of manufacture of claim 1 further comprising a second polyurethane comprising a second polyurethane intermediate comprising the reaction product of an alkyl ester of dimethylolalkanoic acid or dihydroxypolyacid, a second polyoxyalkylene diol and a second organic diisocyanate.

33. The polyurethane of claim 1 further comprising a vinyl monomer selected from an alkyl ester of acrylic, methacrylic, maleic or itaconic acid, wherein said amine equivalent is present in an amount of about 0.2 to about 1.0 equivalent amount by weight of amine to ester to bond said vinyl monomer to said polyurethane intermediate.

35. The polyurethane of claim 1 wherein the reaction of the alkyl ester of dihydroxypolyacid and said amine equivalent is performed under substantially oxygen- free conditions.

23. A polyurethane comprising the reaction product of a polyurethane intermediate comprising of dimethylolalkanoic acid;

a polyoxyalkylene diol;

an organic diisocyanate; and

an amine equivalent, said amine equivalent including one or more amine groups said polyurethane intermediate being crosslinked with an epoxy containing material selected from bisphenol-epichorohydrin, cycloaliphatic epoxy resins, epoxidized fatty acids, glycidyl methacryalate, glycidyl acrylate with a catalyst selected from a Lewis acid, tetrabutyl titanate, amine-blocked and unblocked alkane, aromatic sulfonic acid, benzyldimethyl amine, benzyldimethyl ammonium chloride, dimethylcyclohexylatnine, triethylenediamine, triethylenetetramine and triphenylphosphine wherein said polyurethane comprises an amide.

34. A polyurethane comprising the reaction product of a poyurethane intermediate comprising an alkyl ester of dimethylolalkanoic acid or dihydroxypolyacid;

a polyoxyalkylene diol;

an organic diisocyanate; and

an amine equivalent, said amine equivalent including one or more amine groups wherein said polyurethane comprises an amide.

36. An article of manufacture formed of the polymer of claim 34.

37. The article of manufacture of claim 36 comprising a molded article.

38. The article of manufacture of claim 37 wherein said article is formed by extrusion.