US4880883A
Expired / Lapsed
US
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Biocompatible polyurethanes modified with lower alkyl sulfonate and lower alkyl carboxylate
Assignee: Wisconsin Alumni Research Foundation
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Filing: 1987-06-03
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Granted: 1989-11-14
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Expires: 2007-06-03
Abstract
Abstract Modified-polyurethane block copolymers and devices formed therefrom demonstrate excellent biocompatibility 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.
Inventors
- 👤 Timothy G. Grasel
- 👤 Stuart L. Cooper
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 14:42
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/83; A; A61; A61L; A61L27/00; A61L27/14; A61L27/18; C08G18/08; C08G18/0804; C08G18/0819
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
102 words
A biocompatible, substantially solid polyurethane composition comprising 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 C 2 -C 14 alkyl or aryl diol or diamine or hydroxy-functional amine and (c) a polyol having a number average molecular weight from about 500 to about 3000, respectively, the copolymer being modified wherein about 5 to about 25 percent of the urethane hydrogen atoms of the copolymer are replaced with a combination of lower alkyl (C 1 -C 6 ) sulfonate groups and lower alkyl (C 1 -C 6 ) carboxylate groups.
Claim 2
Dependent Claim
102 words
A biocompatible, substantially solid polyurethane composition comprising 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 C 2 -C 14 alkyl or aryl diol or diamine or hydroxy-functional amine and (c) a polyol having a number average molecular weight from about 500 to about 3000, respectively, the copolymer being modified wherein about 5 to about 25 percent of the urethane hydrogen atoms of the copolymer are replaced with a combination of lower alkyl (C 1 -C 6 ) sulfonate groups and lower alkyl (C 1 -C 6 ) carboxylate groups.
Claim 3
Dependent Claim
36 words
The polyurethane composition 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.
Claim 4
Dependent Claim
27 words
The polyurethane composition 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.
Claim 5
Dependent Claim
40 words
The polyurethane composition of claim 1 wherein the hydroxy-functional amine is represented by the formula (HOR) 2 NR 1 SO 3 H wherein each R and R 1 are independently selected from lower alkyl (C 1 -C 6 ) groups.
Claim 6
Dependent Claim
31 words
The polyurethane composition of claim 1 wherein said polyol is selected from the group consisting of polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyisobutylene, 1,4-polybutadiene, polyethylene adipate, polytetramethylene adipate, polycaprolactone and polydimethylsiloxane.
Claim 7
Dependent Claim
22 words
The polyurethane composition of claim 1 wherein the number average molecular weight of the polyol is from about 500 to about 2000.
Claim 8
Dependent Claim
18 words
The polyurethane composition of claim 1 wherein the number average molecular weight of the polyol is about 1000.
Claim 9
Dependent Claim
31 words
The polyurethane composition of claim 1 wherein the mole ratio of organic diisocyanate, C 2 -C 14 alkyl or aryl diol or diamine or hydroxy-functional amine and polyol is about 3/2/1.
Claim 10
Dependent Claim
43 words
The polyurethane composition of claim 1 wherein about 10 to about 15 percent of the urethane hydrogen atoms of the copolymer are replaced with lower alkyl (C 1 -C 6 ) sulfonate groups and lower alkyl (C 1 -C 6 ) carboxylate groups.
Claim 11
Dependent Claim
18 words
The polyurethane composition of claim 1 including an equimolar ratio of isocyanate to hydroxyl and amine functional groups.
Claim 12
Dependent Claim
87 words
A biocompatible substantially solid poly(tetramethylene oxide)-based polyurethane composition comprising a polyether-polyurethane copolymer based on a mole ratio of about 1.5/1.0/1.0 to about 10/9/1 of an organic diisocyanate, a C 2 -C 14 alkyl or aryl diol or diamine and polytetramethylene oxide having a number average molecular weight of from about 500 to about 3000, respectively, the copolymer being modified wherein about 5 to about 25 percent of the urethane hydrogen atoms of the copolymer are replaced with a combination of propyl sulfonate groups and propyl carboxylate groups.
Claim 13
Dependent Claim
87 words
A biocompatible substantially solid poly(tetramethylene oxide)-based polyurethane composition comprising a polyether-polyurethane copolymer based on a mole ratio of about 1.5/1.0/1.0 to about 10/9/1 of an organic diisocyanate, a C 2 -C 14 alkyl or aryl diol or diamine and polytetramethylene oxide having a number average molecular weight of from about 500 to about 3000, respectively, the copolymer being modified wherein about 5 to about 25 percent of the urethane hydrogen atoms of the copolymer are replaced with a combination of propyl sulfonate groups and propyl carboxylate groups.
Claim 14
Dependent Claim
37 words
The poly(tetramethylene oxide)-based polyurethane composition of claim 11 wherein said organic diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene dissocyanate, methylene bis(p-phenyl isocyanate), 1,5-naphthalene diisocyanate, methylene bis(p-cyclohexylisocyanate), 1,6-hexane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.
Claim 15
Dependent Claim
30 words
The poly(tetramethylene oxide )-based polyurethane composition of claim 11 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.
Claim 16
Dependent Claim
21 words
The poly(tetramethylene oxide)-based polyurethane composition of claim 11 wherein said polytetramethylene oxide has a number average molecular weight of about 1000.
Claim 17
Dependent Claim
32 words
The poly(tetramethylene oxide)-based polyurethane composition of claim 11 wherein the mole ratio of organic diisocyanate, C 2 -C 14 , alkyl or aryl diol or diamine and polytetramethylene oxide is about 3/2/1.
Claim 18
Dependent Claim
70 words
A biocompatible poly(tetramethylene oxide)-based polyurethane composition comprising a polyetherpolyurethane copolymer based on a 3/2/1 mole ratio of about 1.5/0.5/1.0 to about 10/9/1 of methylene bis(p-phenyl isocyanate), 1,4-butanediol, and polytetramethylene oxide having a number average molecular weight from about 500 to about 3000, wherein about 5 to about 25 percent of the urethane hydrogen atoms of the copolymer are replaced with a combination of propyl sulfonate groups and propyl carboxylate groups.
Claim 19
Dependent Claim
70 words
A biocompatible poly(tetramethylene oxide)-based polyurethane composition comprising a polyetherpolyurethane copolymer based on a 3/2/1 mole ratio of about 1.5/0.5/1.0 to about 10/9/1 of methylene bis(p-phenyl isocyanate), 1,4-butanediol, and polytetramethylene oxide having a number average molecular weight from about 500 to about 3000, wherein about 5 to about 25 percent of the urethane hydrogen atoms of the copolymer are replaced with a combination of propyl sulfonate groups and propyl carboxylate groups.
Claim 20
Dependent Claim
36 words
The poly(tetramethylene oxide)-based polyurethane composition of claim 16 wherein about 10 to about 15 percent of the urethane hydrogen atoms of the copolymer are replaced with a combination of propyl sulfonate groups and propyl carboxylate groups.
Claim 21
Independent Claim
104 words
A method for the production of a modified and substantially solid polyether-polyurethane copolymer composition which is biocompatible and which provides improved physical and mechanical properties, said method comprising the steps of: (a) providing a polyether-polyurethane copolymer based on a 3/2/1 mole ratio of an organic diisocyanate, a C 2 -C 14 alkyl or aryl diol or diamine and a polyol; (b) modifying the copolymer by replacing up to about 25 percent of the urethane hydrogen atoms thereof with a combination of propyl sulfonate groups and propyl carboxylate groups in the presence of a solvent; and (c) removing the solvent by drying the modified copolymer.
Claim 22
Independent Claim
104 words
A method for the production of a modified and substantially solid polyether-polyurethane copolymer composition which is biocompatible and which provides improved physical and mechanical properties, said method comprising the steps of: (a) providing a polyether-polyurethane copolymer based on a 3/2/1 mole ratio of an organic diisocyanate, a C 2 -C 14 alkyl or aryl diol or diamine and a polyol; (b) modifying the copolymer by replacing up to about 25 percent of the urethane hydrogen atoms thereof with a combination of propyl sulfonate groups and propyl carboxylate groups in the presence of a solvent; and (c) removing the solvent by drying the modified copolymer.
Claim 23
Dependent Claim
29 words
The method according to claim 18 wherein up to about 20 percent of said urethane hydrogen atoms are replaced by treatment with 1,3-propane sultone to provide a modified-urethane material.
Claim 24
Dependent Claim
29 words
The method according to claim 19 further including the step of treating the modified copolymer with a carboxyl-substituted C 1 -C 6 halide to provide a further modified-urethane material.
Claim 25
Independent Claim
120 words
A method for the production of a modified and substantially solid poly(tetramethylene oxide)-based polyurethane composition comprising a polyether-polyurethane copolymer which is biocompatible and which demonstrates improved physical and mechanical properties, said method comprising the steps of: (a) providing a polyether-polyurethane copolymer based on a 3/2/1 mole ratio of an organic diisocyanate, a C 2 -C 14 alkyl or aryl diol or diamine and polytetramethylene oxide having a number average molecular weight of about 1000; (b) modifying the copolymer by replacing from about 5 to about 25 percent of the urethane hydrogen atoms thereof with a combination of propyl sulfonate groups and propyl carboxylate groups in the presence of a solvent; and (c) removing the solvent by drying the modified copolymer.
Claim 26
Independent Claim
120 words
A method for the production of a modified and substantially solid poly(tetramethylene oxide)-based polyurethane composition comprising a polyether-polyurethane copolymer which is biocompatible and which demonstrates improved physical and mechanical properties, said method comprising the steps of: (a) providing a polyether-polyurethane copolymer based on a 3/2/1 mole ratio of an organic diisocyanate, a C 2 -C 14 alkyl or aryl diol or diamine and polytetramethylene oxide having a number average molecular weight of about 1000; (b) modifying the copolymer by replacing from about 5 to about 25 percent of the urethane hydrogen atoms thereof with a combination of propyl sulfonate groups and propyl carboxylate groups in the presence of a solvent; and (c) removing the solvent by drying the modified copolymer.
Claim 27
Dependent Claim
36 words
The method according to claim 21 wherein said organic diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, methylene bis(phenyl isocyanate), 1,5-naphthalene diisocyanate, methylene bis(p-cyclohexyl isocyanate), 1,6-hexane diisocyanate, isophorone diisocyanate and cyclohexyl diisocyanate.
Claim 28
Dependent Claim
27 words
The method according to claim 21 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.
Claim 29
Dependent Claim
29 words
The method according to claim 21 wherein up to about 20 percent of said urethane hydrogen atoms are replaced by treatment with 1,3-propane sultone to provide a modified-urethane material.
Claim 30
Dependent Claim
30 words
The method according to claim 24 further including the step of treatment the modified copolymer with a carboxy-substituted C 1 -C 6 alkyl halide to provide a further modified-urethane material.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1992-11-13 | 1993-05-15 | 1993-11-14 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-11-13 | 1997-05-15 | 1997-11-14 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-11-13 | 2001-05-15 | 2001-11-14 | $7700.00 | Window Closed / Lapsed |