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US5000955A Expired / Lapsed US ⏱️ 0.0 years remaining

Thermally reversible polyurethane hydrogels and cosmetic, biological and medical uses

Assignee: Tyndale Plains Hunter Ltd
•
Filing: 1990-07-23
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Granted: 1991-03-19
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Expires: 2010-07-23
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Abstract

Abstract Thermally reversible polyurethane hydrogels are formed by adding water to a gel forming hydrophilic polyurethane polymer produced by reacting under anhydrous conditions a non-aromatic organic diisocyanate with a glycol component in an NCO/OH mole weight ratio of from about 0.900/1 to about 0.980/1, the glycol component having a number average molecular weight of from about 1000 to 3500 wherein the percentage by weight of the diisocyanate in the reaction mixture is from about 7% to about 20%. The hydrogels are solids at room temperature but liquify at higher temperatures such as body temperature and therefore are useful as carriers for the protection, delivery and sustained release of a variety of active agents including pharmaceuticals, cosmetics, living cells and organisms.

Inventors

  • 👤 Francis E. Gould
  • 👤 Christian W. Johnston
  • 👤 George E. Seems

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-04 06:19
CPC Classifications
A; A61; A61K; A61K8/00; A61K8/02; A61K8/04; A61K8/042; A61K47/00; A61K47/30; A61K47/34; A61K8/18; A61K8/72; A61K8/84; A61K8/87; A61K9/00; A61K9/20; A61K9/2004; A61K9/2022; A61K9/2031; A61Q; A61Q13/00; A61Q15/00; A61Q17/00; A61Q19/00; C; C08; C08G; C08G18/00; C08G18/06; C08G18/28; C08G18/40; C08G18/48; C08G18/4833; C08G18/65; C08G18/66; C08G18/6666; C08G18/667; C08G18/6674; C08G18/70; C08G18/72; C08G18/73; C08G18/74; C08G18/75; C08G18/758; C12; C12N; C12N1/00; C12N1/20; A61Q1/00; A61Q1/02; A61Q1/10; A61Q19/007; A61Q19/08; C08G2210/00; Y; Y10; Y10S; Y10S524/00; Y10S524/916

Claims Analysis

Total Claims: 33
Claim 1
Independent Claim 147 words
A thermally reversible hydrogel, comprising water and a gel forming hydrophilic polyurethane polymer, produced by reacting under anhydrous conditions an alkylene diisocyanate, bicycloalkane diisocyanate in which the rings are connected via ring carbon atoms by a single bond, or dicycloalkylalkane diisocyanate in which the rings are connected via ring carbon atoms through an alkylene chain, with a glycol component comprising one or more polyoxyethylene glycols, optionally mixed with one or more lower molecular weight ethylene glycols, in a mole weight ratio of NCO/OH of from about 0.900/1 to about 0.980/1, the total glycol component having a number average molecular weight of from about 1000 to about 3500 and wherein the amount by weight of the diisocyanate in the anhydrous reaction mixture is from about 7% to about 20%, mixing the reaction product in an aqueous medium, heating the mixture with stirring until homogeneous, and cooling the mixture.
Claim 2
Dependent Claim 147 words
A thermally reversible hydrogel, comprising water and a gel forming hydrophilic polyurethane polymer, produced by reacting under anhydrous conditions an alkylene diisocyanate, bicycloalkane diisocyanate in which the rings are connected via ring carbon atoms by a single bond, or dicycloalkylalkane diisocyanate in which the rings are connected via ring carbon atoms through an alkylene chain, with a glycol component comprising one or more polyoxyethylene glycols, optionally mixed with one or more lower molecular weight ethylene glycols, in a mole weight ratio of NCO/OH of from about 0.900/1 to about 0.980/1, the total glycol component having a number average molecular weight of from about 1000 to about 3500 and wherein the amount by weight of the diisocyanate in the anhydrous reaction mixture is from about 7% to about 20%, mixing the reaction product in an aqueous medium, heating the mixture with stirring until homogeneous, and cooling the mixture.
Claim 3
Dependent Claim 20 words
The hydrogel of claim 1 wherein the amount by weight of the diisocyanate is from about 10% to about 15%.
Claim 4
Dependent Claim 21 words
The hydrogel of claim 1 wherein the concentration by weight of the polyurethane polymer is from about 1% to about 15%.
Claim 5
Dependent Claim 19 words
The hydrogel of claim 1 wherein the concentration of the polyurethane polymer is from about 3% to about 7%.
Claim 6
Dependent Claim 34 words
The hydrogel of claim 1 wherein the glycol component is a mixture of a lower molecular weight ethylene glycol and a polyoxyethylene glycol having a number average molecular weight of up to about 10,000.
Claim 7
Dependent Claim 34 words
The hydrogel of claim 1 wherein the glycol component is a mixture of diethylene glycol and at least one polyoxyethylene glycol having a number average molecular weight of from about 1450 to about 8000.
Claim 8
Dependent Claim 14 words
The hydrogel of claim 1 wherein the diisocyanate is 4,4'-dicyclohexylmethane diisocyanate or hexamethylene diisocyanate.
Claim 9
Dependent Claim 11 words
The hydrogel of claim 1 wherein the diisocyanate is 4,4'-dicyclohexylmethane diisocyanate.
Claim 10
Dependent Claim 28 words
The hydrogel of claim 6 wherein the glycol component is a mixture of diethylene glycol and a polyoxyethylene glycol having a number average molecular weight of about 1450.
Claim 11
Dependent Claim 28 words
The hydrogel of claim 6 wherein the glycol component is a mixture of diethylene glycol and a polyoxyethylene glycol having a number average molecular weight of about 4500.
Claim 12
Dependent Claim 28 words
The hydrogel of claim 6 wherein the glycol component is a mixture of diethylene glycol and a polyoxyethylene glycol having a number average molecular weight of about 8000.
Claim 13
Dependent Claim 40 words
The hydrogel of claim 6 wherein the glycol component is a mixture of diethylene glycol, a polyoxyethylene glycol having a number average molecular weight of about 1450 and a polyoxyethylene glycol having a number average molecular weight of about 8000.
Claim 14
Dependent Claim 161 words
An active agent carrier system comprising an active agent and as the carrier vehicle therefore a hydrophilic, thermally reversible hydrogel comprising water and a gel forming polyurethane polymer produced by reacting under anhydrous conditions an alkylene diisocyanate, bicycloalkane diisocyanate in which the rings are connected via ring carbon atoms by a single bond, or dicycloalkylalkane diisocyanate in which the rings are connected via ring carbon atoms through an alkylene chain, with a glycol component comprising one or more polyoxyethylene glycols, optionally mixed with one or more lower molecular weight ethylene glycols, in a mole weight ratio of NCO/OH of from about 0.900/1 to about 0.980/1, the total glycol component having a number average molecular weight of from about 1000 to about 3500 and the percentage by weight of the diisocyanate in the anhydrous reaction mixture is from about 7% to about 20%, mixing the reaction product in an aqueous medium, heating the mixture with stirring until homogeneous, and cooling the mixture.
Claim 15
Dependent Claim 161 words
An active agent carrier system comprising an active agent and as the carrier vehicle therefore a hydrophilic, thermally reversible hydrogel comprising water and a gel forming polyurethane polymer produced by reacting under anhydrous conditions an alkylene diisocyanate, bicycloalkane diisocyanate in which the rings are connected via ring carbon atoms by a single bond, or dicycloalkylalkane diisocyanate in which the rings are connected via ring carbon atoms through an alkylene chain, with a glycol component comprising one or more polyoxyethylene glycols, optionally mixed with one or more lower molecular weight ethylene glycols, in a mole weight ratio of NCO/OH of from about 0.900/1 to about 0.980/1, the total glycol component having a number average molecular weight of from about 1000 to about 3500 and the percentage by weight of the diisocyanate in the anhydrous reaction mixture is from about 7% to about 20%, mixing the reaction product in an aqueous medium, heating the mixture with stirring until homogeneous, and cooling the mixture.
Claim 16
Dependent Claim 19 words
The carrier system of claim 13 wherein the percentage of the diisocyanate is from about 10% to about 15%.
Claim 17
Dependent Claim 15 words
The active agent carrier system of claim 13 wherein the active agent is a pharmaceutical.
Claim 18
Dependent Claim 15 words
The active agent carrier system of claim 13 wherein the pharmaceutical is an anti-cancer drug.
Claim 19
Dependent Claim 16 words
The active agent carrier system of claim 13 wherein the active agent is a cosmetic agent.
Claim 20
Dependent Claim 19 words
The active agent carrier system of claim 17 wherein the cosmetic agent is a fragrance, deodorant or mixture thereof.
Claim 21
Dependent Claim 17 words
A skin protectant film produced by applying to the skin the thermally reversible hydrogel of claim 1.
Claim 22
Independent Claim 234 words
A method of delivering an active agent to a treatment zone comprising the steps of: (1) mixing the active agent with a thermally reversible hydrogel in its liquid state, the said hydrogel comprising water and a hydrophilic polyurethane polymer produced by reacting under anhydrous conditions, an alkylene diisocyanate, bicycloalkane diisocyanate in which the rings are connected via ring carbon atoms by a single bond, or dicycloalkylalkane diisocyanate in which the rings are connected via ring carbon atoms through an alkylene chain, with a glycol component comprising one or more polyoxyethylene glycols, optionally mixed with one or more lower molecular weight ethylene glycols, in a mole weight NCO/OH ratio of from about 0.900/1 to about 0.980/1, the total glycol component having a number average molecular weight of from about 1000 to 3500 and the percentage by weight of the diisocyanate in the anhydrous reaction mixture is from about 10% to about 15%, mixing the reaction product in an aqueous medium, heating the mixture with stirring until homogeneous, (2) lowering the temperature of the liquid hydrogel to convert it into the solid gel form with concomitant encapsulation therein of the active agent; (3) introducing the solid hydrogel containing the encapsulated active agent to the treatment zone; and (4) raising the temperature of the solid hydrogel to convert it to the liquid form, thereby freeing the active agent to exert its therapeutic effect at the treatment zone.
Claim 23
Independent Claim 234 words
A method of delivering an active agent to a treatment zone comprising the steps of: (1) mixing the active agent with a thermally reversible hydrogel in its liquid state, the said hydrogel comprising water and a hydrophilic polyurethane polymer produced by reacting under anhydrous conditions, an alkylene diisocyanate, bicycloalkane diisocyanate in which the rings are connected via ring carbon atoms by a single bond, or dicycloalkylalkane diisocyanate in which the rings are connected via ring carbon atoms through an alkylene chain, with a glycol component comprising one or more polyoxyethylene glycols, optionally mixed with one or more lower molecular weight ethylene glycols, in a mole weight NCO/OH ratio of from about 0.900/1 to about 0.980/1, the total glycol component having a number average molecular weight of from about 1000 to 3500 and the percentage by weight of the diisocyanate in the anhydrous reaction mixture is from about 10% to about 15%, mixing the reaction product in an aqueous medium, heating the mixture with stirring until homogeneous, (2) lowering the temperature of the liquid hydrogel to convert it into the solid gel form with concomitant encapsulation therein of the active agent; (3) introducing the solid hydrogel containing the encapsulated active agent to the treatment zone; and (4) raising the temperature of the solid hydrogel to convert it to the liquid form, thereby freeing the active agent to exert its therapeutic effect at the treatment zone.
Claim 24
Dependent Claim 21 words
The method of claim 20 wherein the hydrogel contains by weight from about 1% to about 15% of the polyurethane polymer.
Claim 25
Dependent Claim 21 words
The method of claim 20 wherein the hydrogel contains by weight from about 3% to about 7% of the polyurethane polymer.
Claim 26
Dependent Claim 34 words
The method of claim 20 wherein the glycol component is a mixture of a lower molecular weight ethylene glycol and a polyoxyethylene glycol having a number average molecular weight of up to about 10,000.
Claim 27
Dependent Claim 33 words
The method of claim 20 wherein the glycol component is a mixture of diethylene and at least one polyoxyethylene glycol having a number average molecular weight of from about 1450 to about 8000.
Claim 28
Dependent Claim 20 words
The method of claim 20 wherein the diisocyanate is selected from the class consisting of 4,4'-dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
Claim 29
Dependent Claim 11 words
The method of claim 20 wherein the diisocyanate is 4,4'-dicyclohexylmethane diisocyanate.
Claim 30
Dependent Claim 29 words
The method of claim 20 wherein the glycol component is a mixture of a diethylene glycol and a polyoxyethylene glycol having a number average molecular weight of about 1450.
Claim 31
Dependent Claim 29 words
The method of claim 20 wherein the glycol component is a mixture of a diethylene glycol and a polyoxyethylene glycol having a number average molecular weight of about 4500.
Claim 32
Dependent Claim 29 words
The method of claim 20 wherein the glycol component is a mixture of a diethylene glycol and a polyoxyethylene glycol having a number average molecular weight of about 8000.
Claim 33
Dependent Claim 40 words
The method of claim 20 wherein the glycol component is a mixture of diethylene glycol, a polyoxyethylene glycol having a number average molecular weight of about 1450 and a polyoxyethylene glycol having a number average molecular weight of about 8000.

References Cited (Backward Citations)

US3821136A Cited
US3822238A Cited
US3975350A Cited
US4155892A Cited
US4190566A Cited
US4202880A Cited
US4404296A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1994-03-18 1994-09-17 1995-03-19 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1998-03-18 1998-09-17 1999-03-19 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2002-03-18 2002-09-17 2003-03-19 $7700.00 Window Closed / Lapsed

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