WO1999047072A1 - Polyurethanes de polyether hydrophile contenant de l'acide carboxylique - Google Patents

Polyurethanes de polyether hydrophile contenant de l'acide carboxylique Download PDF

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Publication number
WO1999047072A1
WO1999047072A1 PCT/US1999/005653 US9905653W WO9947072A1 WO 1999047072 A1 WO1999047072 A1 WO 1999047072A1 US 9905653 W US9905653 W US 9905653W WO 9947072 A1 WO9947072 A1 WO 9947072A1
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Prior art keywords
diol
polymer
water
glycol
reaction mixture
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PCT/US1999/005653
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English (en)
Inventor
Murray H. Reich
John Teffenhart
Jirina Kuzma
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Tyndale Plains-Hunter, Ltd.
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Priority to AU29056/99A priority Critical patent/AU2905699A/en
Publication of WO1999047072A1 publication Critical patent/WO1999047072A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04—Macromolecular materials
    • A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2210/00—Compositions for preparing hydrogels

Definitions

  • This invention relates to hydrophilic polyether polyurethanes having improved strength, good adhesion to different substrates, solubility in basic media, enhanced washability and which dissolve in neutral to slightly basic media to produce low viscosity solutions.
  • the polymers are specifically adapted for use as adhesives, absorbents, coatings of woven and nonwoven materials and rubber products, films, cosmetic applications, electroconductive surgical pads, shaving preparations, body and facial hair removal products, and antifogging agents.
  • the present invention also relates to novel hydrophilic polyether polyurethanes which can be coated onto plastics, elastomers and woven and nonwoven cloth into which can be incorporated long and short chain materials such as a drug, pharmaceutically active agent, fragrance, long chain material, and enzyme for imparting controlled release of the drug, fragrance and material, and which coated materials can have an extended material, pharmaceutically active agent and drug release.
  • Coated rubber products and cloths have improved slip and absorptivity and coated gloves have improved dry, damp and wet donnability.
  • U.S. 4,156,066 and 4,156,067 relate to a polyether polyurethane which cont ns a lactone group in the backbone and the polymer is subsequently swelled in a polar solvent such as acetone.
  • the lactone group is ring opened with caustic to obtain a polymer with a carboxyl group in the polymer chain.
  • These polymers have high solubility in neutral to base solutions, improved washability with ammonia and amines.
  • U.S. 4,743,673 describes a polymer containing an ester group which is neutralized in order to convert the sodium salts to carboxylic acid groups.
  • This patent teaches that since carboxyl groups decarboxylate isocyanates, and since existing acidic diols were expensive, that the acid should to be shielded as an ester group. This process is complicated, lengthy and tedious.
  • the polymer is made in two steps and the solvent must be added during the reaction in order to drive the reaction to completion. Then the polymer must be saponified, dissolved and the mixture is refluxed at the boiling temperature of the solvent for up to 11 hours, in order to make a water insoluble polymer which dissolves in water upon the addition of ammonia.
  • the resulting polymer comprises a linear polyester diol.
  • U.S. Patent 3,412,054 teaches the reaction of 4 to about 15% 2,2-di (hydroxymethyl) alkanoic acid with an isocyanate in order to produce polymers which become water soluble upon reaction with ammonia or an amine to form a quaternary salt.
  • This patent teaches that the carboxyl group in alkanoic acidic diols does not react significantly with isocyanates to hinder the introduction of carboxylic acid groups into the polymer chain.
  • the quaternary salts provide many hydrophilic sites which renders the urethane polymer water compatible if not water-soluble.
  • U.S. Patent 5,120,816 relates to high strength hydrophilic polyether-polyester polyurethanes prepared at water levels in the reaction mixture of about 1.0 to 2.5%. This patent teaches that high tear strength polyether polyurethanes are achieved with less than 1% water. The hydrophilic polymers described in this patent are insoluble in water and polar solvents.
  • hydrophilic polyether polyurethanes produce polymers having excellent hydrophilicity, improved absorptivity, slip and biocompatibility, enhanced washability, superior slip, good adhesion, solubility in aqueous/polar solvents and which can form clear solutions in neutral to slightly basic aqueous solutions.
  • the hydrophilic and amphiphilic polymers of this invention can be used as absorbent, to form gels, to coat rubber, woven and nonwoven cloth of natural and synthetic materials such as polyethylene, polyester, polytetrafluroethylene, dacron and polypropylene for use as sutures, implanted vascular grafts and as coatings of polytetrafluoroethylene material for use in securing implants wherein such vascular grafts and implants comprise a material such as drugs, enzymes, pharmaceutically active agents (PAA), anticoagulants, endothilial and blood vessel growth factors and antibiotics, including but not limited to heparin, tissue plasminogen activator, and the like and wherein the rate of release of such material is controlled by the type and concentration of polymer.
  • PAA pharmaceutically active agents
  • anticoagulants anticoagulants
  • endothilial and blood vessel growth factors and antibiotics including but not limited to heparin, tissue plasminogen activator, and the like and wherein the rate of release of such material is controlled
  • hydrophilic polyurethanes are produced by reacting: (A) a diol component comprising a polyoxyalkylene diol; (B) a alkylene glycol; (C) a diisocyanate; (D) a catalyst selected from amines and salts of metals such as bismuth, calcium, sodium, lead, lithium, potassium, tin, zinc and zirconium, (E) water in an amount constituting from about 0.001% to about 0.6% of the combined weight of the reactants; and (F) an 2,2-di- (hydroxymethyl) alkanoic acid, preferably 2,2-di-(hydroxymethyl) propionic acid, in which the ratio of NCO to OH in the water, diol and glycol is from about 0.80 to about 1.1.
  • a diol component comprising a polyoxyalkylene diol
  • B a alkylene glycol
  • C a diisocyanate
  • D a catalyst selected from amines and salts of metals such as
  • the polymer can be formed without alkylene glycol in the reaction mixture.
  • the polymers are particularly useful as absorbents and as coatings of woven and nonwoven materials, rubber goods, metals, skin, elastomers and plastics, and for use in medical devices, cosmetic and industrial applications, and to control the release of additives such as drugs, pharmaceutically active agents (PAA) long chain materials and fragrances.
  • PAA pharmaceutically active agents
  • the resulting polymer is a hydrophilic polyether polyurethane consisting of polyoxyalkylene units, so called soft segments and alkylene units, so-called hard segments connected through urethane linkages. Also interspersed in the polymer chain are small amounts of diol with appending carboxyl groups.
  • the polymer chain also includes precise amounts of urea groups which originate from the reaction of water with isocyanate groups and modify the adhesive of the polymer. It has been found that precisely controlling the combination of the different groups in specific proportions provides unique polymer properties such as hydrophilicity, biocompatibility, absorptivity, superior adhesive and excellent properties for use in cosmetic applications.
  • the polymers are produced from (A) polyoxyethylene diol having a molecular weight of 4,000 to 20,000; (B) a hydrophobic diol selected from polyoxypropylene diol, polyoxytetramethylene diol, polydimethylsiloxane polyoxyethylenecopolymer, polybutylene oxide, and polyether polycarbonate diol, (C) an aliphatic diisocyanate, (D) water in the amount comprising about 0.01% to about 0.5% by weight of the reaction mixture; (E) a catalyst selected from amines and salts of metals such as bismuth, calcium, magnesium, sodium, lead, lithium, potassium, tin, zinc and zirconium, (F) a 2,2-di-(hydroxymethyl) alkanoic acid, the ratio of NCO to OH in the water, diol, and glycol mixture being about 0.80 to about 1.10.
  • the polymers can be used in medical devices, cosmetic and industrial applications such as shaving preparations and razors, antiperspirants, skin and hair care, body and facial hair removal products, and animal grooming products and as coatings of woven and nonwoven materials, elastomers, plastics, metals for use for rubber gloves and in medical devices.
  • the polymers have the advantages of solubility in dilute (neutral to basic) aqueous solutions, sprayablity, biocompatibility, absorptivity, adhesion, lubricity, soft feel .and cross-linkability. In these applications, hydrophilicity is advantageous to provide breathabiliity and softness in a hydrated state.
  • the polymers are specifically adapted to coat metal, skin, hair, glass and plastics for use in medical devices.
  • the polymers are useful for forming gels in glycerine/water, water, and propylene glycol/water solutions and can be used in foams, cosmetic, animal grooming products, antiperspirants, and depilatories, gels, lotions and creams and shaving preparations.
  • the polymers of this embodiment are particularly useful in and as coatings of medical devices, more specifically for use as infusion therapy catheters, including peripherally inserted catheters, intravenous catheters (IV), central venous, dialysis and cardiovascular catheters, shaving products, mechanical and synthetic heart valves, stents, ports, introducers, valves, shunts, vascular grafts, breathable and water-resistant films, and for cosmetic, medical and therapeutic lotions and creams and products, and for biocompatible extrudable materials which soften and swell to controlled amounts.
  • IV intravenous catheters
  • dialysis and cardiovascular catheters shaving products
  • mechanical and synthetic heart valves stents, ports, introducers, valves, shunts, vascular grafts, breathable and water-resistant films
  • cosmetic, medical and therapeutic lotions and creams and products and for biocompatible extrudable materials which soften and swell to controlled amounts.
  • the polymers can be used as coatings of elastomers, polymers, glass, including treated and untreated latex rubber and polyolefins such as ethylene-propylene copolymers, polyethylene and polypropylene, polystyrene, butadiene and isoprene copolymers and terpolymers of styrene acrylonitrile and carboxylic acid containing monomers, high impact polystyrene, polyether polyamides, polyurethane, polyurethane-polycarbonate, and the like, metals including stainless steel, aluminum, brass, bronze, copper, silicon, silicon dioxide, nickel and chrome coated metal, brass, bronze, silicon chips, and the like, natural and synthetic woven and nonwoven materials.
  • treated and untreated latex rubber and polyolefins such as ethylene-propylene copolymers, polyethylene and polypropylene, polystyrene, butadiene and isoprene copolymers and terpolymers of st
  • Coated materials can be used to control the release rate of drugs, enzymes, PAA, fragrances and other materials.
  • the substrates can be coated with a primer and also can be treated with plasma energy and oxidative gases to enhance bonding of the primer and the topcoat.
  • the amphiphilic polyether polyurethanes of this invention bond to a wide variety of substrates, impart enhanced slip and biocompatiblity to the surfaces, and also can serve as a primer for more hydrophilic polymers.
  • the amphiphilic polyether polyurethanes are especially valuable for certain medical devices and shaving systems because the polyurethanes of this invention have the advantages of extrudability, improved slip, biocompatibility, absorptivity, cross-linkability and adhesive properties compared to hydrophobic polymers.
  • the present invention is based on the discovery that a class of hydrophilic polyether polyurethane polymers more fully described herein formed from the reaction product of a diol component selected from a hydrophilic or hydrophobic diol, an alkylene glycol, an aliphatic diisocyanate, water, a catalyst and a 2,2-di- (hydroxymethyl) alkanoic acid are advantageous in medical devices, cosmetic and industrial applications such as a skin and hair care product, shaving preparation and razor, absorbents, adhesives and gels.
  • the polymers are suitable as a coating of catheter, implant, vascular graft, guidewire, rubber product, woven and nonwoven cloth. The coating provides controlled release of a drugs, pharmaceutically active agent, long and short chain materials.
  • the polymers can be soluble in water and can thicken aqueous solutions, enhancing their value as coatings.
  • the polymers impart improved soft feel, breathability, lubricity, slip, adhesion to skin and hair, and washability, which is advantageous in cosmetic and shaving applications.
  • a first aspect of the present invention pertains to a hydrophilic polyether polyurethane polymer comprising the reaction product of a polyoxyethylene diol having a molecular weight of from about 3,000 to about 20,000; an organic diisocyanate, an 2,2-di-(hydroxymethyl) alkanoic acid, and water in an amount comprising from about 0.001% to about 0.95% by weight of the reaction mixture, in which the NCO/OH ratio is from about 0.6 to about 1.1.
  • polyoxyethylene diols are available from Union Carbide Corporation under the trademark and designation Carbowax, such as Carbowax® 3360, Carbowax® 4500, Carbowax® 8000, and Carbowax® 1450 wherein numbers represent the number average molecular weight.
  • Carbowax such as Carbowax® 3360, Carbowax® 4500, Carbowax® 8000, and Carbowax® 1450 wherein numbers represent the number average molecular weight.
  • the amount by weight of the reaction mixture of the polyoxyethylene diol can vary from at least about 40%, preferably about 50%, more preferably about 60%, still more preferably about 65%, and most preferably about 70%, and the average molecular weight of the polyoxyalkylene diol can vary from about 400 to about 20,000.
  • the number average molecular weight of the polyoxyethylene diol can vary from about 4,000 to about 12,000, and still more preferably from about 5,000 to about 10,000.
  • the polymers can include about 0.01% to about 10% by weight of a low molecular weight alkylene glycol selected from ethylene glycol, propylene glycol, 2-ethyl-l-l, 3-hexanediol, tripropylene glycol, triethylene glycol, 2-4-pentane diol, 2-methyl-l,3-propanediol,2,-methyl-l,3- pentanediol,l,6-hexanediol, 1,4-butanediol, cyclohexanediol, cyclohexanedimethanol, dipropylene glycol, diethylene glycol, and mixtures thereof, a catalyst selected from organic acid salts of metals such as bismuth, barium, calcium, lead, magnesium, lithium, potassium, tin, iron, zinc and zirconium.
  • a catalyst selected from organic acid salts of metals such as bismuth, barium, calcium, lead, magnesium, lithium,
  • the alkylene glycols can be purchased at chemical supply houses.
  • propylene glycol can be purchased from Aldrich Chemical Company as 1,2-propane diol.
  • the amount of the alkylene glycol (hard segments) component can be from about 0.01% to about 20%, preferably from about 0.05% to about 15%, more preferably from about 0.1% to about 12%, still more preferably from about 0.5% to about 10%, and most preferably from about 1.0% to about 8% by weight of the reaction mixture.
  • hydrophilic polyether polyurethane can be formed wihout alkylene glycol in the reaction mixture.
  • the diisocyanate used in the present invention can include both aliphatic and aromatic types and mixtures thereof although the aliphatics are preferred.
  • An especially preferred isocyanate is methylene bis(cyclohexyl-4-isocyanate).
  • diisocyanates are trimethyl hexamethylene diisocyanate and isophorone diisocyanate.
  • Representative examples of the preferred aliphatic diisocyanates include, but are not limited to tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylene diisocyanate, trimethylene hexamethylene diisocyanate, cyclohexyl 1,2-diisocyanate, cyclohexylene 1,4-d ⁇ socyanate, .and aromatic diisocyanates such as 2,4-toluene diisocyanates and 2,6-toluene diisocyanates.
  • isocyanate equivalents which form urethane linkages as exemplified by nitrile carbonates, such as adipontirile carbonate of the formulas (U.S. Patent No. 4,810, 543 of common ownership therewith).
  • the amount of diisocyanate can vary from about 3% to about 50%, preferably from about 3.5% to about 40%, more preferably from about 4% to about 30%, still more preferably from about 4.5% to about 25% by weight of the reaction mixture.
  • the amount of water by weight in the reaction mixture is in the range of from about 0.01% to about 0.50%, and more preferably from about 0.02% to about 0.40% of the reaction mixture, and most preferably from about 0.02% to about 0.35%.
  • the amount of 2,2-di-(hydroxymethyl) alkanoic acid in the reaction mixture is in the range from about 0.05% to about 30%, preferably from about 0.1% to about 20%, more preferably from about 0.15% to about 10%, still more preferably from about 0.2% to about 8%, and most preferably from about 0.25% to about 3.0% by weight of the reaction mixture.
  • the 2,2-di-(hydroxymethyl) alkanoic acid is dimethylolpropionic acid.
  • the final reaction product has an acidic value of at least about 0.1, preferably at least about 0.2.
  • the ratio of NCO to OH of the hydroxyl groups from the diol, alkylene glycol, amines, and water in the reaction mixture is preferably in the range from about 0.70 to about 1.02, and most preferably from about 0.75 to about 0.99.
  • the most preferred ratio of NCO to OH is from about 0.80 to about 0.99.
  • the most preferred weight average molecular weight of the polymer is from about 10,000 to about 500,000, preferably from about 40,000 to about 300,000.
  • the preferred molecular weight of the polymer is from about 50,000 to about 300,000 and for certain cosmetic applications, the preferred molecular weight of the polymer is from about 25,000 to about 50,000.
  • the sum of all ingredients, including the diols, glycols, water, and diisocyanate in the reaction mixture totals 100 parts by weight.
  • the catalyst is selected from dibutyl tin dilaurate, stannous octoacte, bismuth neodecanate and bismuth octoate. These polymers are useful for certain applications such as improved slip absorptive and wet strength polymers.
  • Polymers can be formed from a reaction mixture without the low molecular weight alkylene, a polyoxyethylene diol, about 0.04% to about 2.0% by weight of the reaction mixture dimethylolpropionic acid, about 0.001% to about 0.20% of water by weight of the reaction mixture, to an NCO/OH ratio of about 0.90 to about 0.99 and about 0.5 cc to about 8 cc of catalyst per pound of reactants in the reaction mixture, more preferably, about 0.8 cc to about 5 cc of the catalyst per pound of reactants is used in the reaction mixture.
  • the amount of catalyst provides complete reaction of the isocyanate and produces polymers having a molecular weight greater than 30,000 with substantially improved slip, absorptivity, wet strength and extrudability properties.
  • the catalyst is selected from stannous octoate, dibutyl tin dilaurate, bismuth octoate and bismuth neodecanate.
  • the polymers of this .aspect can form hazy to clear solutions in water which can be clarified by neutralizing the solutions with a base such ammonia, aminomethylpropanol, triethanolamine and the like.
  • the polymers can increase the viscosity of water.
  • the solubility of polymer in water is affected by amount of water, catalyst and dimethylolpropionic acid in the reaction mixture and by the NCO/OH ratio. The solubility of these polymers in water enhances their value in cosmetic applications.
  • a polymer made with 0.10% by weight of water with two percent b * y weight of the acid-diol in the reaction mixture forms a clear solution in neutral slightly basic solution water at about 2% concentration and polymer made with 0.33% by weight water in the reaction mixture is insoluble in water.
  • the polymers find application as thickeners, in adhesives, wound dressings, cosmetic products.
  • the polymer is suitable as coatings of guide wires, catheters, D ' acron, polyethylene and polypropylene, boat surfaces, and metals, and for use in adhesives.
  • films containing these polymers can be used as adhesives to metal, hair, glass, and skin with/without a commercial adhesive due to their superior adhesive and hydrophilic properties.
  • the polymers also can reduce the elution rate of drugs, PAA, and long chain materials from films and coatings such as appetite suppressants because they bond amino groups.
  • the polymer can irritate the skin and open the pores, permitting more drug to be introduced into the body.
  • the acid containing polymers can be mixed with commercial adhesives such as those made by Monsanto Corporation under the trademark of Gelva adhesives to improve adhesion and moisture vapor transmission rates.
  • the polymers can be used as coatings of blood collection containers, coronary, urinary and biliary stents, and infusion therapy catheters.
  • the hydrophilic polymers of this aspect do not significantly alter the structure and composition of the complex proteins. This property enhances their use in wound dressings, sorting devices, coatings of rubber products, catheters, guide wires, cannula, ports, introducers, valves, tubing, and a wide range of medical devices.
  • the improved slip polymers allow aqueous solutions of a wide range of molecules to pass through a sorting medical device such as a computer chip because of improved slip, biocompatability, high water absorptivity, low to nonadsorption of complex proteins and cells, and smoothness of the coating.
  • the improved slip polymers comprising about 0.01% to about 0.20% by weight water in the reaction mixture can be used to form water soluble polymers which are spreadable for use in cosmetics, make-up and as coatings of skin, plastics, metals, and rubber. Solutions of water- soluble polymer produce breathable, soft, water-absorptive films formed without alkylene glycol in the reaction mixture.
  • Polymers of this aspect comprising about 0.01% to about 2.0% dimethylolpropionic acid, about 0.01% to about 0.25% water by weight in the reaction mixture and about 0.7 cc to about 5 cc catalyst per pound of the reactants and an NCO/OH ratio of about 0.90 to about 0.99 form improved water absorptive and extrudable polymers that can be used as absorbents and improved slip polymers.
  • about 0.1% to about 3% of an alkylene glycol can be added for certain applications.
  • the high slip polymers comprising about 0.25% to about 0.5% water by weight in the reaction mixture can be extruded to form tough, water absorbable products that can be used for
  • isocyanate primers such as Adcote 533 made by Morton Corporation and Desmophen 670A-80 and BL31- 75 made by Bayer Corporation can be coated onto the hydrophobic surface.
  • the polyether polyurethanes of this aspect impart excellent biocompatibility and superior slip, low protein and cell adhesion properties to medical devices enhancing their value in shunts, stents, cardiovascular and infusion therapy catheters, introducers, blood collection units, arterial and venous grafts, mechanical and synthetic heart valves, and the like.
  • a second aspect of the present invention relates to a hydrophilic polyurethane suitable for medical devices, cosmetic and industrial applications comprising the reaction product of: (A) a polyoxyethylene diol having a number average molecular weight of about 4,000 to about 20,000, (B) a hydrophobic diol selected from polyoxypropylene diol, block copolymers of ethylene oxide and propylene oxide, polybutylene oxide, polydimethylsiloxane polyoxyethylenecopolymer, polyether polycarbonate diol and polyoxytetramethylene diol having number average molecular weights of about 200 to about 3,500, (C) a diisocyanate, (D) water in an amount of about 0.01% to abou 0.5% of the reaction mixture, and (E) 2,2-di(hydroxymethyl) alkanoic acid in an equivalent mole weight ratio of NCO to OH of the water, diol and glycol of from about 0.80 to about 1.04.
  • A a polyoxyethylene diol having
  • At least about 0.10% by weight of the hydrophobic diol is used in the reaction mixture.
  • Polyoxypropylene diols are available from various sources such as from ARCO under the trademark of NIAX® PPG 1025, PPG-425, PPG-725, PPG 4025 and PPG 2025 and Acclaim 2200 and Acclaim 4200 wherein the numbers represent the number average molecular weight except in the case of Acclaim where the number average molecular weight values are 2000 and 4000 respectively.
  • polyoxytetramethylene diols are available from E.I. Dupont de Nemours as Terathanes 600, 1000, 1400, 2000, 2900 and from Nippoly America as CD250.
  • polydimethylsiloxane polyoxyethylenecopolymers having a number average molecular weight of about 700 to about 2400 are available from OSI as Silwets, Dow Corning as Q4-3667, Q2481, Q2 5211 and from GE as GE Silicones as 1 161-11-925, 1 161-1 1-926, 1161-1032, 1161- 11-928 and polybutylene oxides are available from Dow Company as XAS.1096.01 and .05.
  • Polyetherpolycarbonate diols having a number average molecular weight of 1000 and 2000 are available, for example, from BASF as PolyTHFCD-1000 and PolyTHF CD-2000, CD4200, CD4201 and Nippollan 980 and Nippollan 981 are available from Nippoly America Corp.
  • block copolymers of ethylene oxide and propylene oxide having a number average molecular weight of about 1,000 to about 2,500 can also be used in the reaction.
  • a propylene oxide terminated block of ethylene glycol manufactured by BASF under the tradename Pluronic R and an ethylene oxide terminated block of propylene glycol manufactured by BASF under the tradename of Pluronic can be used for the polyoxyalkylene diol in the reaction.
  • Pluronic R an ethylene oxide terminated block of propylene glycol manufactured by BASF under the tradename of Pluronic
  • propylene oxide to ethylene diamine are made by BASF under the tradename of Pluronics and Pluronic R such as F64, F127, L35, L92, F68, L82, 17R2 and 25R2.
  • the 2,2-di-(hydroxymethyl) alkanoic acid is preferably dimethylolpropionic acid.
  • the amount of dimethylolpropionic acid is from about 0.01% to about 30%, preferably from about 0.05% to about 20%, more preferably from about 0.10% to about 10%, still more preferably from about 0.15% to about 6.0%, and most preferably from about 0.20% to about 3.0% by weight of the reaction mixture'.
  • the final reaction product has an acid value of at least about 0.05.
  • the reaction mixture can include a catalyst selected from an amine or salts of metals such as bismuth, calcium magnesium, potassium, lead, lithium, tin, zinc, and zirconium,
  • the reaction mixture can include an alkylene glycol is selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, cyclohexanediol, 1,4-butanediol, 1,6- hexanediol, cyclohexanedimethanol, tripropylene glycol and triethylene glycol, preferably, cyclohexanedimethanol, diethylene glycol and dipropylene glycol, and more preferably diethylene glycol.
  • an alkylene glycol is selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, cyclohexanediol, 1,4-butanediol, 1,6- hexanediol, cyclohexanedimethanol, tripropylene glycol and triethylene glycol, preferably, cyclohexanedimethanol, diethylene glycol and dipropylene glycol, and more preferably
  • the amount of the alkylene glycol (hard segments) is from about 0.01% to about 20%, preferably from about 0.05% to about 15%, more preferably from about 0.1% to about 12%, still more preferably from about 0.5% to about 10%, and most preferably from about 1.0% to about 5% by weight of the reaction mixture.
  • the hydrophilic polyurethane can be formed without alkylene glycol in the reaction mixture.
  • the preferred weight average molecular weight of the polymer is from about 10,000 to about 500,000, preferably from about 40,000 to about 300,000.
  • the preferred molecular weight is from about 40,000 to about 300,000 and for certain cosmetic applications the preferred molecular
  • 15 weight is from about 25,000 to about 50,000.
  • polymers of this aspect with about 0.1% to about 20% by weight of the reaction mixture of polydimethylsiloxane polyoxyethylenecopolymer (PDMS) having a number average molecular weight of about 500 to about 1,500, about 0.1% to about 4% by weight of the reaction mixture of dimethylolpropionic acid and an amount of water of about 0.01% to about 0.25% by weight of the reaction mixture and a NCO/OH ratio of about 0.80 to about 0.96 can be dissolved in water and provide improved slip, biocompatible and absorptive polymers.
  • PDMS polydimethylsiloxane polyoxyethylenecopolymer
  • the viscosity of the aqueous solution and solubility of polymer in water are affected by the amount of water and amount and molecular weight of PDMS, type and amount of catalyst used in the reaction mixture and the NCO/OH ratio.
  • the same polymer formed with PDMS having a number average molecular weight of about 2,400 is insoluble in water.
  • Polymers formed with alkylene glycol of about 0.01% to about 0.15% by weight of the reaction mixture of water and about 0.01% to about 10% by weight of the reaction mixture of a hydrophobic diol with an NCO/OH ratio of about 0.80 to about 0.98 and using at least about 0.8cc of catalyst per pound of polymer can produce high molecular weight polymers, having a molecular weight of greater than 40,000, with improved slip, improved water absorptivity and biocompatibility for use as coatings and absorbents.
  • the polymer can be formed without alkylene glycol in the reaction mixture.
  • the polymers 16 their improved hydrophilicity, biocompatibility, low cell and protein adhesion can be used to transport proteins, drugs, cells, blood and vitamins without significantly modifying their structure and effectiveness.
  • the polymers can be used as coatings of and in blood collection containers, coronary, urinary and biliary stents, cardiovascular, dialysis, infusion therapy catheters, guide wires, sorting devices, cannula, ports, valves, tubing, shunts, stents, introducers, arterial and venous grafts for the arterial and peripheral system, implants, mechanical and synthetic heart valves.
  • the hydrophilic polymers of this aspect do not significantly alter the structure and composition of the complex proteins.
  • the high slip polymers allow aqueous solutions of a wide range of molecules to pass through a sorting device such as a computer chip because of high slip, biocompatability, high water absorptivity, low to nonadsorption of complex proteins and cells, and smoothness of the coating.
  • the polymers can be used to form water soluble, spreadable polymers for use in cosmetics, make-up and as coatings of skin, plastics, metals, and rubber. Solutions of water- soluble polymer produce breathable, soft, water-absorptive films.
  • the high slip polymers comprising about 0.25% to about 0.5% water by weight in the reaction mixture and those produced with about 0.02% to about 0.20% of water and about 0.80 cc to about 6 cc of catalyst per pound of polymer to about 0.85 to about 0.99 NCO/OH ratio can be extruded to form tough, water absorbable products that can be used for medical devices, absorbents, cosmetics, shaving razor strips, and industrial applications.
  • the polymers can be coextruded over other plastics possessing lower expansion values.
  • isocyanate primers such as Adcote 533 made by Morton Corporation and Desmophen 670A-80
  • the polymers of this aspect and the first aspect can be used to make gels for use in burn and wound care dressings.
  • the gels are made by adding the polymer to water, water/glycerine and water/propylene glycol mixtures, stirring the mixture in a heated vessel or on a roller mill, and then mixing for about one hour at about 80 °C to about 95 °C. The procedure is repeated until a homogeneous gel is obtained.
  • mixtures of water, glycerine, polymer, and propylene glycol can be added to a heated vessel with an agitator and slowly heated and mixed to obtain uniform gels. The viscous mixtures are extruded through a film die.
  • the gels comprise about 3% to about 30% polymer, preferably about 4% to about 25% polymer and about 5% to about 60% of propylene glycol and glycerine, more preferably from about 8% to about 50% of glycol and glycerine.
  • propylene glycol/water gels PG
  • the ratio of PG/water is preferably from about 10/90 to about 30/70
  • the ratio of glycerine/water is preferably from about 10/90 to about 50/50.
  • the polymers of this aspect are specifically adapted for use in cosmetic applications such as shaving preparations and coatings, antiperspirants, animal grooming products, and facial and body hair removal products in which the polymers are soluble in water, ethanol/water mixtures and dilute neutral to basic aqueous solutions to form low viscosity solutions.
  • the polymers also have the advantages in cosmetic applications of ease of forming improved gels in mixtures of hydrophilic and hydrophobic medi.a, improved sprayablity of solutions, and of forming films with excellent hydrophilicity, breathability, washability, high moisture and oxygen transmission rates, and soft feel. It has been found that the cosmetic properties can be affected by small changes in the level of water, ratio of NCO/OH, and the level of the di(hydroxymethyl) alkanoic acid in the
  • the polymers are useful for adhesives, cosmetic applications such as shaving preparations, animal grooming products, depilatories, and antiperspirants, improved slip coatings, drug delivery systems for its improved absorptivity, as a thickener, and for pH sensitive applications.
  • the polymer can be used in improved absorptive coatings and gels formed from the polymer in propylene glycol water, water and glycerine water solutions.
  • polymers of this aspect having an amount of water of about 0.01% to about 0.25% by weight of the reaction mixture, polydimethylsiloxane polyoxyethylenecopolymer having a number average molecular weight of about 500 to about 1500 in an amount by weight of the reaction mixture of about 0.1% to about 20% and a NCO/OH ratio of about 0.75 to about 0.98 can form low viscosity solutions in water and ethanol water mixtures that are useful in forming creams, lotions, and gels for use in cosmetic applications.
  • the viscosity and molecular weight of the polymers can be adjusted to suit the needs of an application by changes of about 0.02% water in the reaction mixture and of about 0.02 in the NCO/OH ratio.
  • the polymers comprising PDMS form solutions in neutralized water that are useful in forming creams, lotions, and gels for use in cosmetic applications.
  • the films formed from these products have a soft feel, are tough, highly water absorptive, breathable and washable.
  • the concentration of polymer in the solution is less than about 15%, preferably less than about 10%, more preferably less than about 8%, still more preferably less than about 7% by weight of the mixture.
  • the solution can include at least about 5% water, preferably at least about 10% water, more preferably at least about 15% water, still more preferably at least about 30% water.
  • hydrophilic polyether polyurethane polymers of this aspect formed with a hydrophobic diol and polyoxyethylene diol can form low viscosity solutions in aqueous polar solvents for use in cosmetic products, antiperspirants, shaving preparations and razors, animal grooming, body and facial hair removal products, and coatings of medical devices, metals, plastics and rubber products.
  • the coatings and cosmetic products possess soft feel, slip, biocompatiblity, absorptivity, washability, adhesion to skin and hair, and soft feel. Breathability and biocompatibility have the advantages of promoting a healthy skin when used in skin products.
  • a third aspect of the present invention relates to hydrophilic polyether polyurethane polymers comprising the reaction product of a higher molecular weight polyoxyethylene diol having a number average molecular weight of about 4,000 to about 20,000, B) a hydrophobic diol selected from polyoxypropylene, block copolymers of ethylene oxide and propylene oxide, polybutylene oxide, polydimethylsiloxane polyoxyethylenecopolymer, polyether polycarbonate diol and polyoxytetramethylene diol having a number average molecular weights of about 200 to about 3,500, (C) a lower molecular weight polyoxyethylene diol having a number average molecular weight of about 200 to about 2,500, (D) water in an amount of about 0.01% to about 0.5% of the reaction mixture, (E) a diisocyanate, and (F) 2,2-di(hydroxymethyl)alkanoic acid in an equivalent mole weight ratio of NCO to OH of the water, diol and
  • the 2,2-di-(hydroxymethyl) alkanoic acid is preferably dimethylolpropionic acid.
  • the amount of dimethylolpropionic acid is preferably from about 0.1% to about 10%, more preferably from about 0.15% to about 6.0%, still more preferably from about 0.2% to about 6.0%, and most
  • the final reaction product has an acid value of at least about 0.02, preferably at least about 0.05, more preferably at least about 0.08 and most preferably at least about 0.1.
  • the amount of water by weight in the reaction mixture is from about 0.01% to about 0.5%, more preferably from about 0.01% to about 0.4%, still more preferably from about 0.015% to about 0.3%, and most preferably from about 0.02% to about 0.25%.
  • the amount of lower molecular weight polyoxyethylene diol having a number average molecular weight of about 200 to about 2,500 is about 0.1% to about 35%, more preferably from about 0.5% to about 25% by weight of the reaction mixture.
  • the high molecular weight polyoxyethylene diol has a number average molecular weight preferably of about 4,000 to about 15,000, preferably from about 4,500 to about 10,000, more preferably from about 6,000 to about 10,000 and the amount of the high molecular weight polyoxyethylene diol is at least about 45%, preferably at least about 50%, more preferably at least about 55%, still more preferably at least about 60%, and most preferably at least about 65% of the reaction mixture.
  • the NCO/OH ratio is from about 0.70 to
  • the amount by weight of diisocyanate in the reaction mixture for this aspect is from about 3% to about 40%, preferably from about 3.5% to about 35%, more preferably from about 4% to about 30%, and most preferably from about 4.5% to about 25%.
  • the amount of the hydrophobic diol is from about 0.1% to about 20% by weight of the reaction mixture, more preferably from about 0.15% to about 15%, and most
  • the number average molecular weight of the hydrophobic diol is from about 200 to about 3,000, and more preferably from about 250 to about 2,500.
  • the reaction can include a catalyst selected from an amine and salts of a metal such as bismuth, calcium, magnesium, lithium, potassium, lead, tin, zinc, and zirconium.
  • a catalyst selected from an amine and salts of a metal such as bismuth, calcium, magnesium, lithium, potassium, lead, tin, zinc, and zirconium.
  • the polymer can include about 0.01% to about 10% by weight of a low molecular weight alkylene glycol selected from ethylene glycol, propylene glycol, 2-ethyl-l-l,3-hexanediol, tripropylene glycol, triethylene glycol, 2,-4-pentane diol, 2-methyl-l,3-propanediol, 2,-methyl-l,3- pentanediol, 1,6-hexanediol, 1,4-butanediol, cyclohexanediol, cyclohexanedimethanol, dipropylene glycol, diethylene glycol, and mixtures thereof.
  • a low molecular weight alkylene glycol selected from ethylene glycol, propylene glycol, 2-ethyl-l-l,3-hexanediol, tripropylene glycol, triethylene glycol, 2,-4-pentane diol, 2-methyl-l
  • Gels, solutions, lotions, foams, and creams for shaving preparations, facial and body hair removal materials, depilatories and animal grooming products can be made with optional components that are well known to those skilled in the art.
  • the optional components are emulsifiers such as anionic or nonionic surfactants; preservatives such as methyl paraben, propyl paraben, coloring agents, perfume oils, propellants for foams, waxes, vitamins, drugs, depilatory agents such as thioglycolic acid, foaming agents for shaving creams, and chelating agents such as ethylenediaminetetr.aacetic acid.
  • the polymer is dissolved in an aqueous solution and the solution is cooled to about 50° to about 90°C and the other ingredients are added.
  • the preservatives are added at about 35° to 50°C.
  • the preferred level of the low molecular weight polyoxyethylene diol is from about 1% to about 25%, the preferred amount
  • the preferred amount of hydrophobic diol is about 0.1% to about 15%, more preferably about 0.2% to about 10% by weight of the reaction mixture, and the preferred NCO/OH ratio is from about 0.84 to about 0.98.
  • the polymers have high slip, good adhesion to metals, skin, plastics, and hair, and possess pH-sensitive viscosities, they are specifically adapted for use in coatings of guidewires, silicon computer chips, catheters, plastics such as polyurethane, silicone rubber, polystyrene, polyolefins, wires ⁇ or bone healing units, knives, metals, and pipe.
  • plastics such as polyurethane, silicone rubber, polystyrene, polyolefins, wires ⁇ or bone healing units, knives, metals, and pipe.
  • the polymers can be incorporated into razor strips, and pre- and post-shaving preparations.
  • the polymers can be mixed with aqueous media to form gels for burn and wound care dressings and trans-dermal delivery of drugs by iontophoresis, as described above related to the polymer of aspects one, two and aspect three described below.
  • the polymers can be used in foams for shaving preparations and other cosmetic applications.
  • the gels are tough, hydrophilic, possess enhanced washability, superior water absorptivity and adhesiveness to metals, glass, skin ⁇ hair, plastics and pH-sensitive viscosities.
  • the gels can be used in the trans-dermal delivery of drugs.
  • the polymers form films with excellent breathability, high moisture and oxygen transmission rates, and superior feel.
  • the films may be formed by extruding the polymer through a film die and by solvent casting.
  • the polymer can be dissolved in suitable solvents such as tetrahydrofuran, ethanoi, ketones, water, propylene glycol, the solution is poured over a suitable flat surface, and the solvent is allowed to evaporate.
  • the high slip, water absorptivity and high moisture vapor transmission rate of the polymers enhance their use in skin lotions, thickeners, breathable films, nail polish, face make-up,
  • antiperspirants and shaving preparations such as stable and quick breaking foams, lotions, and creams.
  • the increased hydrophilicity and superior slip of the polymers enhance their use as high slip coatings.
  • the polymers can be mixed with water, an alkylene glycol and glycerine to form flowable viscous gels which can be squeezed out of tubes to provide a moist healing environment for wounds.
  • the gels are especially useful, because the acidic gels provide an improved healing environment and a so being pH sensitive, can be readily removed with a slightly neutr rinse.
  • the acid-containing polymers may absorb certain additives that are not readily adsorbed by non-acid containing polymers.
  • the gels can be used to fill wound or holes in an emergency, and then to wash them out with a slightly basic rinse.
  • the gels may be used for the delivery of drugs, because of their high absorptivity and for improved adhesion, and also, the gels, due to their acidity, may absorb different types of drugs. Also, improved adhesive gels can improve the contact of the gel with the skin, extremely important in iontophoresis and trans-dermal delivery of drugs.
  • the concentration of polymer in the media is preferably from about 5% to about 30%, more preferably from about 8% to about 25%, and most preferably from about 10% to about 22%.
  • the concentration of polymer in the media is preferably from about 0.01% to about 10%, preferably from about 0.02% to about 8%, and most preferably from about 0.03% to about 6%.
  • the adhesive qualities of the gels are advantageous for shaving applications and hair removal products, because of the improved ability to stick to the hair. And the washability, high moisture vapor transmission rates and breathability of the films are useful after the solvents have evaporated
  • the .amount of water is about 0.01% to about 0.3% and the NCO/OH ratio is from about 0.80 to about 0.98, more preferably the amount of water is from about 0.02% to about 0.25% and the NCO/OH ratio is from about 0.80 to about 0.98.
  • the alkanoic acid is from about 0.1% to about 2.5%
  • the NCO/OH ratio is from about 0.88 to about 0.98
  • the amount of water is from about 0.20% to about 0.35%.
  • the urethane forming reaction is preferably catalyzed by known catalysts such as bismuth, potassium, lead, zinc, zirconium, calcium, magnesium, lithium, tin salts and organotin esters. Included among the catalysts are stannous octoate, dibutyl tin dilaurate, potassium octoate, bismuth neodecanate, bismuth octoate and tertiary amines such as triethylene diamine, N,N,N',N'-tetramethyl-l,3-butane diamine, preferably tin-containing catalysts, and more preferably, potassium octoate, bismuth neodecanate, bismuth octoate, stannous octoate and dibutyl tin dilaurate.
  • the catalyst is used in an amount effective for catalytic reaction, from about 0.5cc to about 6 cc of catalyst per pound of
  • desiccant fillers such as ZeoChem, Zeolites, molecular sieves, glycerine, barytes, and calcium sulfate in the primer and topcoats of coatings of rubber products reduce tack and increases water absorptivity at low humidity levels. It has also been found that the use of about 0.5% to about 50% of filler, based upon polymer solids, unexpectedly improves dry, damp and wet donnability of rubber latex gloves.
  • Preferred fillers added to the polymer are cornstarch, zeolites, barytes, and high slip hydrophilic polymers such as polyvinylpyrrolidone (PVP) and polyoxyethylene oxide (Polyox).
  • filler preferably Zeolite Type 5 A, PVP, polyox, and cornstarch is added.
  • Silicones, surfactants, fatty acid amines, polyetherdiamines and diglycoldiamines can be added as antiblocking agents in combination with the polymer and as a postdip.
  • solutions used for coating rubber products contain about 0.05% to about 10% of polymer comprising about 1% to about 15% of PDMS, preferably about 0.10% to about 5% of polymer.
  • the coating mixture has the advantage of simplifying the coating system since the coating can be dissolved in water and ethanol and water mixtures and can be applied on-line at any stage of the dipping and spraying process without curing or cross-linking the polymers and without leaving any residual odor on the hands due to certain lubricants. Small amounts of commercial antioxidants can also be added to prevent oxidation during the curing of the rubber.
  • the coating mixture has the advantage of simplifying the coating system since the coating can be dissolved in water and in ethanol and water and can be applied on-line at any stage of the dipping and spraying process without leaving any residual odor on the hands due to certain lubricants. Small amounts of commercial antioxidants can also be added to prevent oxidation during the curing of the rubber.
  • the hydroxylamines and the JefFamines are manufactured by Huntsman Corporation.
  • Amines for use in the coating solution are selected from the group of ethanolamines such as ethylene diamine, monoethanolamine, diethanolamine, diglycol-amine, triethanolamine propylene diamine, polyether diamines based on propylene oxide and ethylene oxice such as triethylene glycol diamine, and other amines and diamines such as those made by Huntsman Corporation under the tradenames of EDR-148, ED-600, ED-900, ED-2001, D-400, Dl-230 ,D-2000, D- 4,000 and D-230, ratty acid amines such as hexadecyldimethylamine, dodecyldimethylamine and octadecyldimethylamine, aminoethylpopanol, propylene diamine.
  • Surfactants are selected from ammonium salts of alkyl phosphate made by Vanderbilt Corporation under the tradename of Darvan L and dimethylpolysiloxanes made by GE Silicones under the tradenames of SM2130, 2138 and 2153.
  • the amines used in the coating solution are fatty acid amines, aminopropanol, triethanolamine and diglycoldiamine.
  • the diamines can react with the acid groups to form more insoluble materials and the amines can bind the polymer to a substrate.
  • Polymers of the above-described aspects can be used to coat metals, plastics, synthetic and natural woven and nonwoven cloth.
  • Suitable cloths include cloths formed of polyester, polytetrafluoroethylene, polyethylene, polypropylene, acrylic, silk, wool, cotton, Teflon® and Dacron®. Teflon® and Dacron® are trademarks of Dupont.
  • the coated cloths can be used to suture implants, mechanical heart valves, animal heart valves, and synthetic heart valves to tissue and muscle.
  • the coated cloth can be used as an implant.
  • the coated cloth can be formed into tubing for use as vascular grafts such as synthetic veins and arteries for the arterial and peripheral system.
  • the coated cloth can be used as a carrier to absorb a drug, cell, enzyme, and short and
  • suitable agents used in the coated cloth include pharmacogologically active agent, anticoagulant, antithrobomgenic agent, anticancer drug, cellular growth material, anti-infective agent, and antibiotic.
  • the coated cloth comprising the absorbed material can be used as a medical device and also implanted into the human and animal bodies as a vascular graft.
  • Suitable antithrombogenic agents are prostaglandin, urokinase, streptokinase, tissue plasminogen activator (tPA), coumadin, dicumerol, protamine sulfate, hirudin and heparinoids.
  • Preferred antithrobomgenic agents are sulfonated heparinoids, such as dextran sulfonate, most preferably heparin, albumin or a salt thereof.
  • Suitable anti-coagulant agents which are antibodies (for example antibodies directed against platelet receptor Gpib or Gpib, against platelet receptor GPib/IIIa, or against von Willebrand Factor (vWF)) and also such agents with vasoactive properties (such as Prostacyclin and Nitric Oxide).
  • Suitable pharmaceutically active agents include growth factor regulators in particular antibodies.
  • Suitable antibodies include antibodies directed against Platelet-derived Growth Factor (PDGF), Fibroblastic Growth Factor (FGF), Transforming Growth Factor beta (TGF), Insulin-like Growth factor (IGF), Interleukins (LL1-8), Endothelin, Trombin, or Endothelial adhesion molecules, for example ICAM-1.
  • PDGF Platelet-derived Growth Factor
  • FGF Fibroblastic Growth Factor
  • TGF Transforming Growth Factor beta
  • IGF Insulin-like Growth factor
  • LL1-8 Interleukins
  • the woven or nonwoven cloth can be formed by dipping the woven or nonwoven cloth into a solution of the polymer in a solvent.
  • the solvent evaporates for about one
  • coated cloth 28 minute to about sixty minutes at room temperature to form a coated cloth.
  • the coated cloth is heated at an elevated temperature for about 1 minute to about sixty minutes to substantially remove the solvent.
  • the coated cloth is allowed to cool to room temperature.
  • the coated cloth is dipped into a solution comprising the above-described agents and materials to be incorporated into the coating.
  • the coated cloth is allowed to dwell in the solution from about 0.01 second to about one week, preferably about half second to about thirty hours.
  • the coated cloth is removed and the solvent is allowed to evaporate at room temperature and then placed in an oven at about 20°C to about 120°C depending upon the nature of the agent or material incorporated into the coating.
  • coated cloth including tPA is heated at about 15°C to about 40°C, but not above 40 °C.
  • a coated cloth comprising tPA can be used as a vascular graft and to suture an implant and heart valve to tissue and muscle.
  • the polymers of the above-described aspects can also be used to coat implants and medical devices such as stents, valves, oxygenators, needles, gaskets, infusion therapy, urinary and cardiovascular catheters and guidewires, and other devices.
  • the catheters and guidewires can be coated with the polymers of this aspect to facilitate the insertion and withdrawal of the devices.
  • the agent or material to be incorporated into the coating depends upon the specific purpose of the medical device.
  • a stainless steel stent to be inserted into an artery can be coated with the high slip and high abso ⁇ tive polymers of aspect four and five described above, preferably polymers of aspect four and then the coated stent can be dipped into a solution of tPA as an anticoagulent. After drying the coated stent at low temperatures, the stent can be sterilized and implanted into a human, the coated stent reduces the body's tendency to form clots due to a foreign object.
  • Coated materials will release additives in the substrate such as drugs, pharmaceutically active agents, fragrances, and hydrophilic polymers such as PVP and Polyox at a lower rate in an aqueous media due to the coating.
  • This property enhances their use in products including but not limited to medical devices, cosmetics and shaving applications. It has been found that the materials can be absorbed in a short period of time, for example, from about 0.01 minute to about 48 hours, and can remain captured within the hydrated hydrophilic polymer helix for a much longer period, for example from about one minute to about four months, and can retain its activity for an extended period, for as long as one year and longer
  • polymers of the above-described aspects can be coated over amphiphilic and hydrophobic polymers and the amphiphilic and hydrophobic polymers such as are described in U.S. 4,789,520, can be coated over this aspect. Also, polymers of the above-described aspects can be coated over both hydrophobic and amphiphilic polymers, providing a multi-layer system.
  • the polymers can also be used as coatings of rubber products and rubber gloves to enhance dry, damp and wet donnability, as described in aspects one and two.
  • the polymers can be coated onto a variety of substrates and the coated materials can absorb and release different types of materials due to their high abso ⁇ tivity and acidity.
  • the polymers can be used to control the release of fragrances, drugs, long chain materials from medical devices, cosmetic products and medical creams such as skin and hair care products and antiperspirants.
  • the drugs can be entrapped in the polymer hydrogels, thereby decreasing the rate of elution.
  • the coatings have improved slip, biocompatibility and abso ⁇ tivity.
  • reaction mixtures for all aspects and preferrably aspects one and two without alkylene glycol can be heated for about 20 minutes to about two hours at 70 °C to about
  • the viscosity of the polymer of aspects one and two at about 3% concentration in 60/40 propylene glycol/water is at least about 50 cps, more preferably at least about 500 cps, and more preferably at least about 5000 cps, and preferably, the polymers have a viscosity of at least 500 cps at about 2% concentration in water. Most preferably the polymers are insoluble in water at about 2% concentrate and in propylene glocol water at about 3% concentrate.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to a water level of 0.028% and 744 parts of the dried diol was added to 20.8 parts of diethylene glycol and 0.098 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 79 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added during which period the temperature decreased. The NCO/OH ratio was 0.98. When the temperature reached about 65°C, 2.25 ml of dibutyl tin dilaurate was added, and the mass exothermed to about 68°C. The mass was heated at 100°C for about one hour to complete formation of the polymer. The polymer formed a thick viscous gel at 5% concentration in 55/45
  • the viscosity of the hazy gel was 850,000 cps. Addition of dilute ammonia did not clarify the gel and did not visibly affect the viscosity.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.2045% of water, and 744 parts of the dried diol was added to 20.8 parts of diethylene glycol, 18.6 parts of dimethylol propionic acid, and 5.51 parts of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 135 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added during which the temperature decreased. The NCO/OH ratio was 0.50. When the temperature reached about 60°C, 2.25 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm to about 65°C.
  • the mass was placed in an oven and held at 100°C for 1.5 hours to complete formation of the polymer.
  • the polymer dissolved in 55/45 ethanol/water to give a millcy solution having a viscosity of 11 cps.
  • dilute ammonia the viscosity did not change and it became clear.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.053% of water, and 473 parts of the dried diol was added to 13.2 parts of diethylene glycol, 11.5 parts of dimethylolpropionic acid, and 0.12 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 69.7 parts of methylene bis- cyclohexyl-4-4'-diisocyanate were added during which the temperature decreased. The NCO/OH ratio was 0.90. When the temperature reached about 64°C, .75 ml of dibutyl tin dilaurate was added. The mass was held at 100°C for about one hour
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.030% of water, and 744 parts of the dried diol was added to 20.8 parts of diethylene glycol, 18.6 parts of dimethylolpropionic acid, and 0.078 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 60 parts of methylene bis-cyclohexyl- 4-4'-diisocyanate were added. The NCO/OH ratio was 0.50. When the temperature reached about 75°C, 2.25 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for 1.5 hours. The polymer was dissolved in water at 2% concentration to produce a solution with 4 cps viscosity.
  • the polymer dissolved in 55/45 ethanol/water to give a slightly hazy solution having a viscosity of 9 cps.
  • the solution had a viscosity of 7.5 cps, and became clear.
  • a batch of 14580 parts of polyoxyethylene diol of 8000 molecular weight was added to a five gallon electrically heated reactor and heated under vacuum to dry the diol.
  • the dried diol was added to 408 parts of diethylene glycol and 356 parts of dimethylolpropionic acid, and the mixture was heated to 105C in order to melt the ingredients.
  • the mixture was allowed to cool to about 175F and the water analyzed as 0.20%. Then 40 grams of water was added.
  • a separate reactor had 2835 parts of methylene bis(cyclohexyl-4-isocyanate). To the diols was added 38 cc of dibutyl tin dilaurate. Then the isocyanate was heated to about 100°F and the liquids were forced out under nitrogen pressure at about .152 ratio. The NCO/OH ratio was 0.85.
  • the polymer was collected in polypropylene tubs.
  • the polymer was dissolved in 55/42 ethanol/water at 3% to give a viscosity of 24.3 cts..
  • the polymer had a weight average molecular weight of about l5O,000.
  • the polymer was insoluble in 60/40 propylene glycol/water at 3% concentration.
  • the polymer was dissolved at 4% concentration in a solution of 75 parts tetrahydrofuran and 25 parts ethanol and a latex rubber Foley catheter was dipped into the solution.
  • the Foley catheter had a slip of 0.053 after two hours of immersion in water. Comparable uncoated catheter had a slip of more than 0.10.
  • the polymer can be used as a high slip coating for guidewires, razors, plastics, polyurethanes, polyethylene, polypropylene, nonwoven cloth, silicone rubber, natural and synthetic rubbers, catheters, knives, medical devices ' , silicon computer chips, and wires for pacers and bone healing electrical units.
  • the polymer can be used as a filler for bone castings.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.0385% of water, and 744 parts of the dried diol was added to 20.8 parts of diethylene glycol, 18.6 parts of dimethylolpropionic acid, and 0.01 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 100 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.85. When the temperature reached about 68°C, 2.25 ml of dibutyl tin dilaurate was added and the mass
  • the slightly hazy solution had a viscosity of 9 cps and at 2.5% it had viscosity of 11.2 cps.
  • the polymer dissolved in 55/45 ethanol/water to give a hazy solution having a viscosity of 11 cps.
  • the slightly hazy solution had a viscosity was 19 cps.
  • dilute ammonia to bring the pH to 9.0, the viscosity of the former was 11.5 cps and that of the latter was 12.5 cps. Both solutions were clear.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.048% of water, and 744 parts of the dried diol was added to 21 parts of diethylene glycol, 38 parts of dimethylolpropionic acid, and 0.071 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then ' , 132 parts of methylene bis- cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.85. When the temperature reached about 73°C, 2.25 ml of dibutyl tin dilaurate was added. The mass was heated at 100°C for 1.5 hours to complete formation of the polymer.
  • the polymer dissolved at 2.0% concentration in water and the solution had a viscosity of 9.5 and at 2.5% concentration the viscosity was 13.5 cps. Both solutions had a slight haze. At 5% concentration, the polymer dissolved in 55/45 ethanol/water to give a viscosity of 10 cps and at 5% in 30/65 ethanol/water, for a viscosity of 20 cps. Both solutions were hazy. Dilute ammonia was added to increase the pH to 9. The viscosity of the former was 10 and that of the latter was 13 cps. Both solutions were clear.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.050% of water, and 474 parts of the dried diol was added to 13 parts of diethylene glycol, 12 parts of dimethylolpropionic acid, and 0.15 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 73 parts of methylene bis-cyclohexyl- 4-4'-diisocyanate were added. The NCO/OH ratio was 0.94. When the temperature reached about 61°C, 1.5 ml of dibutyl tin dilaurate was added. The mass was heated at 100°C for about one hour.
  • the polymer was dissolved at 5% concentration in 55/45 and 30/65 ethanol/water, giving viscosities of 12.0 and 23.5 cps, respectively. WTien the pH was raised with dilute ammonia, the viscosities were 9 and 14.4 cps, respectively,
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.088% of water, and 744 parts of the dried diol was added to 21 parts of diethylene glycol, 4.3 parts of dimethylolpropionic acid, and 0.020 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 81 parts of methylene bis-cyclohexyl- 4-4'-diisocyanate were added. The NCO/OH ratio was 0.85. When the temperature reached about 61°C, 2.25 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation of the polymer.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.037% of water, and 744 parts of the dried diol was added to 21 parts of diethylene glycol, 19 parts of dimethylolpropionic acid, and 0.023 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 115 parts of methylene bis- cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.98. When the temperature reached about 65°C, 2.25 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete the polymerization.
  • the polymer dissolved in 55/45 ethanol/water to give a clear solution with 5 pH and a viscosity of 1680 cps. Adding 2 cc dilute ammonia to 180 grams of solution reduced the viscosity of 225 cps. Both solutions were clear. Sodium bicarbonate also clarified the solution.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.208% of water, and 744 parts of the dried diol was added to 21 parts of diethylene glycol, 19 parts of dimethylolpropionic acid, and 2.90 part of water. The mixture was heated until a homogeneous melt was obtained. Then, 106 parts of methylene bis-cyclohexyl-4-4'- diisocyanate were added. The NCO/OH ratio was 0.50. When the temperature was about 63 °C, 2.25 ml of dibutyl tin dilaurate was added. The mass was allowed to exotherm, and then heated at 100°C for 1.5 hours.
  • the polymer produced a milky solution having a viscosity of 12.5 cps, and at 5% in 30/60 ethanol/water the milky solution had a viscosity of 15.0 cps. Both solutions became clear upon the addition of dilute ammonia, with viscosities of 14 and 13 cps, and solutions of 2% and 2.5% polymer in water had viscosities
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.271% of water, and 736 parts of the dried diol was added to 21 parts of diethylene glycol, 38 parts of dimethylolpropionic acid, and 0.271 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 145 parts of methylene bis- cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.75. When the temperature reached about 59°C, 1.85 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation of the polymer.
  • the polymer formed a milky solution in 55/45 ethanol/water having a viscosity of 9.0 cps.
  • the mixture was made basic with dilute ammonia to provide a water clear solution having a viscosity of 15.3 cps.
  • the polymer can be used as an anti-graffiti coating and for use in cosmetic applications including shaving preparations, facial and body hair removal products, animal grooming products and antiperspirants.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.276% of water, and 736 parts of the dried diol was added to 21 parts of diethylene glycol, 24 parts of dimethylolpropionic acid, and 0.270 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 124 parts of methylene bis- cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.75 When the temperature reached about 56°C, 1.85 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation of the
  • the polymer formed a milky solution in 55/45 ethanol/water at a concentration of 5%.
  • the pH was 5.0 and the viscosity was 9.0 cps.
  • the pH of about 20 cc of solution was increased to about 7 with dilute ammonia, potassium hydroxide, sodium bicarbonate, and lithium acetate dihydrate.
  • the slightly basic solutions were water clear, and the viscosity of solution with ammonia was 15 cps.
  • the polymers can be used in anti-graffiti coatings, and cosmetic applications including shaving preparations, facial and body hair removal products and antiperspirants.
  • Example 14 Polyoxyethylene diol having an average molecular weight of 8000 and polyoxyethylene diol having an average molecular weight of 1450 were heated under vacuum to 0.2075% of water, and 269 parts of the 8000 and 114 parts of the higher molecular weight glycol were added to 12 parts of diethylene glycol, 18 parts of dimethylolpropionic acid, and 0.10 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 88 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.92. When the temperature reached about 65°C, stannous octoate was added, and the mass was allowed to exotherm.
  • the mass was heated at 100°C for about one hour to complete formation of the polymer.
  • the polymer dissolved in slightly basic 55/45 ethanol/water at a concentration of 5% to produce a clear solution with a viscosity of 12 cps.
  • the solution was poured on a glass plate to form a film.
  • the film required more force to remove from the glass plate than did a similar film made from Example 1.
  • the film of this example did not dissolve in water but was readily removed by a solution of sodium bicarbonate in water.
  • the polymers can be used as anti-graffiti coatings and as coatings in paint booths.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.156% of water and 756 parts of the dried diol was added to 21 parts of diethylene glycol, 39 parts of dimethylolpropionic acid, and 0.25 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 136 parts of methylene bis-cyclohexyl-4- 4'-diisocyanate were added. The NCO/OH ratio was 0.75. When the temperature reached about 66°C, 1.85 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation of the polymer.
  • the polymer dissolved in a slightly basic 55/45 ethanol/water solution at a concentration of 5% to produce a clear solution with a viscosity of 11 cps.
  • the polymer was used to make an excellent film with improved breathability, washability, adhesion, and moisture vapor transmission rate and the polymer can be used in cosmetic applications including shaving preparations, facial and body hair removal products, and antiperspirants, and to promote a healthy skin.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.032% of water and 736 of the dried diol was added to 21 parts of diethylene glycol, 18 parts of dimethylolpropionic acid, and 2.06 parts of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 113 parts of methylene bis-cyclohexyl-4- 4'-diisocyanate were added. The NCO/OH ratio was 0.75. When the temperature reached about 65°C, 1.85 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation of the polymer. The polymer dissolved in a slightly basic 55/45 ethanol/water solution at a concentration of 5% to
  • the polymer 40 produce a clear solution with a viscosity of 13 cps.
  • the polymer had a kinematic viscosity of 6.50 cts in 55/42/3 ethanol/water/polymer solution.
  • the polymer can be used in cosmetic applications including shaving creams, lotions, and foams, facial and body hair removal products, and antiperspirants.
  • the cosmetic films had improved breathability, washability, adhesion, and moisture vapor and oxygen transmission rate and can be used to maintain a healthy skin due its excellent breathability properties.
  • Example 17 Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.060% of water and 736 parts of the dried diol was added to 21 parts of diethylene glycol, 18 parts of dimethylolpropionic acid, and 2.84 parts of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 139 parts of methylene bis- cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.85. When the temperature reached about 64°C, 1.85 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation of the polymer.
  • the polymer had a molecular weight of 76,000 and dissolved in a slightly basic 55/45 ethanol/water solution at a concentration of 5% to give a viscosity of 18 cps.
  • the polymer had a kinematic viscosity of 14.7 cts in 55/42/3 ethanol/water/polymer solution.
  • the polymer was used in cosmetic applications including shaving creams, lotions, and foams, facial and body hair removal products, and antiperspirants.
  • the polymer can be used in animal grooming products.
  • the polymeric film had improved breathability and moisture vapor transmission rate which promotes a healthy skin.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.099% of water and 306 parts of the dried diol was added to 34 parts of a block copolymer of ethylene oxide and propylene oxide made by BASF under the tradename of F 127, 9.5 parts of diethylene glycol, 27 parts of dimethylolpropionic acid, and 1.30 parts of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 77 parts of methylene bis-cyc ⁇ ohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.65.
  • the polymer can be dissolved in slightly basic 55/45 ethanol/water at a concentration of 5% to produce a clear solution with a viscosity of less than 20 cps.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0 072% of water, and 343 parts of the dried diol was added to 18 parts of polyoxypropylene glycol of 425 molecular weight, 10 parts of diethylene glycol, 18 parts of dimethylolpropionic acid, and 0.43 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 79 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was 0.85.
  • the polymer dissolved in 55/45 ethanol/water at a concentration of 5% to produce a clear solution with a viscosity of 12 cps.
  • the polymer can be used to make an improved cosmetic products including shaving
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.061% of water, and 736 parts of the dried diol was added to 21 parts of diethylene glycol, 59 parts of dimethylolpropionic acid, and 1.11 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 185 parts of methylene bis- cyclohexyl-4-4'-diis ⁇ cyanate were added. NCO/OH ratio was 0.85. When the temperature reached about 63 °C, 1.85 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation of the polymer.
  • the polymer had a molecular weight of 21,000 and dissolved in slightly basic 55/45 ethanol/water solution at a concentration of 5% was clear and had a viscosity of 10 cps.
  • the polymer had a kinematic viscosity of 6.15 cts in 55/42/3 ethanol/water/polymer solution.
  • the polymer can be used in cosmetic applications including creams and lotions, moisturizing lotions and creams, shaving preparations, facial and body hair removal products, depilatories, and antiperspirants.
  • the hydrophilic film had improved breathability and can be used to promote a healthy skin.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.215% of water, and 736 parts of the dried diol was added to 21 parts of diethylene glycol, 59 parts of dimethylolpropionic acid, and 1.81 parts of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 168 parts of methylene bis- cyclohexyl-4-4'-diisocyanate were added. NCO/OH ratio was 0.65. WT en the temperature
  • the polymer had a molecular weight of 15,000 and dissolved in slightly basic 55/45 ethanol/water solution at a concentration of 5% was clear and had a viscosity of 10 cps.
  • the polymer had a kinematic viscosity of 4.60 cts in 55/42/3 ethanol/water/polymer solution.
  • the polymer can be used in to give superior cosmetic products including shaving lotions, creams and foams, moisturizing lotions and creams, facial creams, animal grooming products, facial and body hair removal products, and antiperspirants, and superior coatings of guidewires, catheters, plastics, elastomers, polyolefins, silicone rubber, metals, steel, brass, silicon, bronze and polyurethane to enhance slip and biocompatibility.
  • the coatings are useful in industrial applications, and medical devices.
  • the cosmetic films had improved washability, adhesion to skin, breathability, a soft feel, and promote a healthy skin.
  • Example 22 Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.060% of water, and 736 parts of the dried diol was added to 21 parts of diethylene glycol, 18 parts of dimethylolpropionic acid, and .96 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 114 parts of methylene bis-cyclohexyl-4- 4'-diisocyanate were added. NCO/OH ratio was 0.85. When the temperature reached about 63 °C, 1.85 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation of the polymer. The polymer dissolved in slightly basic 55/45 ethanol/water solution at a concentration of 5% was clear and had a viscosity of 14 cps. The polymer had a molecular weight of 40,000 and can be
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.060% of water, and 336 parts of the dried diol was added to 9.3 parts of diethylene glycol, 27 parts of dimethylolpropionic acid, 8.2 parts of diglycolamine and .002 part of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 73 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added. NCO/OH ratio was 0.65. When the temperature reached about 65°C, 0.92 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm.
  • the mass was heated at 100°C for about one hour to complete formation of the polymer.
  • the polymer dissolved in slightly basic 55/45 ethanol/water solution at a concentration of 5% was clear.
  • the polymer had a kinematic viscosity of 5.93 cts in 55/42/3 ethanol/water/polymer solution.
  • the polymer can be used in cosmetic applications including shaving preparations, depillatories, and antiperspirants. Cosmetic films had excellent breathability, washability and adhesion, and promote a healthy skin.
  • Polyoxyethylene diol having an average molecular weight of 8000 and polyoxyethylene diol having an average molecular weight of 1450 were heated under vacuum to 0.132% of water,
  • the masK was heated at 100°C for about one hour to complete formation of the polymer.
  • the polymer dissolved in slightly basic 55/45 ethanol/water solution at a concentration of 5% was clear and had a viscosity of 8 cps.
  • the polymer can be used to give superior cosmetic products such as shaving preparations, facial and body hair removal products, and antiperspirants.
  • the cosmetic films had excellent breathability, washability, adhesion, and promote a healthy skin.
  • a batch of 13147 parts of polyoxethylene diol having an average molecular weight of 8000 was added to a five-gallon electrically heated reactor and heated under vacuum to dry the glycol.
  • the dried diol was added to 368 parts of diethylene glycol and 321 parts of dimethylolpropionic acid, and the mixture was heated to 105°C in order to melt the ingredients.
  • the mixture was allowed to cool to about 175°F to about 185°F and the water level was analyzed by Karl Fisher method as 0.0675%. Then, 19.41 grams of water was added to the mixture to bring the total water to 28.75 grams of water.
  • a separate reactor contained 2073 parts of methylene bis(cyclohexyl-4-isocyanate). To the diols was added 33.04 cc of dibutyl tin dilaurate. Then the isocyanate was heated to about 110° -115°F, and both liquids were forced out under nitrogen pressure using a piston cylinder at
  • the polymer was dissolved at 3% solids in 55/45/5 ethanol/water/polymer solution and gave viscosities of 11. cps using a Brookfield viscometer.
  • the polymer had a kinematic viscosity of 7.67 cts in 55/42/3 ethanol/water/polymer solution.
  • the polymer had a molecular weight of 40,000.
  • the coatings are useful in industrial applications and medical devices.
  • a batch of 13147 parts of polyoxethylene glycol having an average molecular weight of 8000 was added to a five-gallon electrically heated reactor and heated under vacuum to dry the glycol.
  • the dried diol was added to 368 parts of diethylene glycol and 321 parts of dimethylolpropionic acid, and the mixture was heated to 105°C in order to melt the ingredients
  • the mixture was allowed to cool to about 175°F to about 185°F and a sample of the mixture was taken and analyzed for its water content by Karl Fisher method.
  • the mixture had a water content of .0625% water and 26.66 grams of water was added to the mixture to bring the total water to 35.31 grams of water.
  • a separate reactor contained 2162 parts of methylene bis(cyclohexyl-4-isocyanate).
  • the diols was added 33.04 cc dibutyl tin dilaurate. Then the diisocyanate was heated to about 110° -115°F, and both liquids were forced out under nitrogen pressure using a piston cylinder at about a ratio of 0.1555. Twelve shots of liquid were pumped into a polypropylene tub and heated for one hour at 100°C. The NCO/OH ratio was 0.85.
  • the polymer was dissolved at 3% solids in 55/45/5 ethanol/water/polymer solution and gave viscosities of 11.5 cps using a Brookfield viscometer.
  • the polymer had a kinematic viscosity of 9.81 cts in 55/42/3 ethanol/water/polymer solution, and a molecular weight of 49,000.
  • the polymer can be used in cosmetic applications such as shaving lotions, creams and foams, moisturizing lotions and creams, facial creams, urinary and baby rash creams and lotions, animal grooming products, facial and body hair removal products, and antiperspirants, and in coatings of guidewires, catheters, metals, plastics, elastomers, including polyolefins, silicon, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and in medical devices.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.028% of water, and 736 parts of the dried diol was added to 21 parts of cyclohexanedimethanol, 18 parts of dimethylolpropionic acid, and 1.21 parts of water. The mixture was heated with stirring until a homogeneous melt was obtained. Then, 102 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added. NCO/OH ratio was 0.85. When the temperature reached about 65°C, 1.85 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100°C for about one hour to complete formation
  • the polymer can be dissolved in slightly basic 55/45 ethanol/water solution at a concentration of 5% to give a low viscosity clear solution.
  • the polymer can be used in cosmetic applications including shaving lotions, creams and foams, moisturizing lotions and creams, facial creams, animal grooming products, facial and body hair removal products, and antiperspirants, and in coatings of guidewires, catheters, metals, plastics, elastomers, including polyolefins, silicon, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and in medical devices.
  • Example 28 Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.048% of water and 744 parts of the dried diol was added to 21 parts of diethylene glycol, 4.3 parts of dimethylolpropionic acid, and 0.37 part of water. The mixture was heated with stirring until a homogenous melt was obtained. Then, 88 parts of methylene bis-cyclohexyl-4-4'- diisocyanate were added. The NCO/OH ratio was about 0.98. When the temperature reached abut 65C, 2.25 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100C for about one hour to complete formation of the polymer.
  • the polymer had a weight average molecular weight of 141,000. At a 5% concentration the polymer dissolved in 55/45 ethanol water to give a solution with a viscosity of 180 cps. At a concentration of 3% in 60/40 propylene glycol/water, the solution had a viscosity of 5300 cps.
  • a gel made with 19% of polymer in 20/80 propylene glycol/water was tough, exceptionally clear and adhered to the glass. The viscosity of the gel can be reduced by raising the pH above 7.0. Gels containing lower concentrations of polymer can be used to keep wounds and burns moist during the healing process.
  • the polymer was dissolved at 4% concentration in 75/25
  • the Foley catheter had a slip of 0.053 after two hours of immersion in water. Comparable uncoated catheter had a slip of more than 0.10.
  • the polymer can be used as a high slip and biocompatible coating for guidewires, razors, catheters, silicon computer chips, and wires for bone healing electrical units.
  • the polymers can be used in shaving lotions, creams and foams, moisturizing and facial lotions and creams, animal grooming products, depillatories and antiperspirants, and in coatings of metals, elastomers "and plastics including polyolefins, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and medical devices.
  • the polymer can be used as a filler for bone castings.
  • Example 29 Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.037% of water and 744 parts of the dried diol was added to 21 parts of diethylene glycol, 18.6 parts of dimethylol propionic acid, and 0.23 part of water. The mixture was heated with stirring until a homogenous melt was obtained. Then, 115 parts of methylene bis-cyclohexyl- 4-4'-diisocyanate were added. The NCO/OH ratio was about 0.98. When the temperature reached abut 65C, 2.25 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100C for about one hour to complete formation of the polymer.
  • the polymer had a weight average molecular weight of 63,000. At a 5% concentration the polymer dissolved in 55/45 ethanol water to give a solution with a viscosity of 1680 cps, and a reduced viscosity of 225 cps upon the addition of 2 cc ammonia to 180 grams of the solution. At a concentration of 3% in 60/40 propylene glycol/water, the solution had a viscosity of 144 cps. A gel made with 19% of polymer in 20/80 propylene glycol/water was tough, exceptionally clear,
  • Gels containing lower concentrations of polymer can be used to keep wounds and burns moist during the healing process.
  • the polymer can be used as a high slip coating for guidewires, razors, catheters, silicon computer chips, wires for bone healing electrical units.
  • the polymers can be used in shaving lotions, creams and foams, moisturizing lotions and creams, facial creams, animal grooming products, facial and body hair removal products, and antiperspirants, and in coatings of metals, plastics, elastomers, including polyolefins, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and in medical devices.
  • the polymer can be used as a filler for bone castings.
  • Example 30 Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to 0.062% of water and 470 parts of the dried diol was added to 13.2 parts of diethylene glycol, 11.4 parts of dimethylol propionic acid, and 0.55 part of water. The mixture was heated with stirring until a homogenous melt was obtained. Then, 76 parts of methylene bis-cyclohexyl- 4-4'-diisocyanate were added. The NCO/OH ratio was about 0.90. When the temperature reached about 61C, 1.44 ml of dibutyl tin dilaurate was added, and the mass was allowed to exotherm. The mass was heated at 100C for about one hour to complete formation of the polymer.
  • the polymer had a weight average molecular weight of 46,000. At a 5% concentration the polymer dissolved in 55/45 ethanol water to give a solution with a viscosity of 13 cps, and a reduced viscosity of 12 cps upon the addition of 2 cc ammonia to 180 grams of the solution. At a concentration of 3% in 60/40 propylene glycol/water, the solution had a viscosity of 64 cps. At a
  • a gel made with 19% of polymer in 20/80 propylene glycol/water was tough, exceptionally clear, and adhered to the glass, displaying improved adhesive properties compared to gels made using polymer without the alkanoic acid. Gels containing lower concentrations of polymer can be used to keep wounds and burns moist during the healing process.
  • the polymer can be used as a high slip coating for guidewires, razors, catheters, silicon computer chips, wires for bone healing electrical units.
  • the polymers can be used in shaving lotions, creams and foams, moisturizing lotions and creams, facial creams, animal grooming products, facial and body hair removal products, and antiperspirants, and in coatings of metals, plastics, elastomers, including polyolefins, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and in medical devices.
  • the polymer can be used as a filler for bone castings.
  • a batch of 1311 1 parts of polyoxyethylene diol of 8000 molecular weight was added to a five gallon electrically heated reactor and heated under vacuum to dry the glycol.
  • the dried diol was added to 367 parts of diethylene glycol and 320 parts of dimethylolpropionic acid , and the mixture was heated to 105C in order to melt the ingredients.
  • the mixture was allowed to cool to about 175F and the water analyzed as 0.14%. Then 5.64 grams of water was added.
  • a separate reactor had 2109 parts of methylene bis(cyclohexyl-4-isocyanate). To the diols was added 133 cc of dibutyl tin dilaurate. Then the isocyanate was heated to about 100F and the liquids were forced out under nitrogen pressure at about 0.152 ratio. The NCO/OH ratio was
  • the polymer was collected in polypropylene tubs.
  • the polymer was dissolved in 55/45 ethanol/water at 5% to give a viscosity of 25 cps.
  • the polymer was dissolved at 5% concentration in 30/70 ethanol/water to give a viscosity of 3000 cps which dropped to 205 cps upon the addition of a few cc of ammonia to raise the pH.
  • the polymer was dissolved in 60/40 propylene glycol water at 3% concentration to give a viscosity of about 166 cps, and the polymer formed a tough exceptionally clear gel at 19% concentration in 20/80 propylene glycol/water with improved adhesion for use in bum and wound care dressings, pre- and post-shaving preparations. Gels containing lower concentrations of polymer can be used to keep wounds and burns moist during the healing process.
  • the polymer can be used as a high slip coating for guidewires, razors, catheters, knives, silicon computer chips, and wires for pacers and bone healing electrical units.
  • the polymers can be used in shaving lotions, creams and foams, moisturizing lotions and creams, facial creams, animal grooming products, facial and body hair removal products, and antiperspirants, and in coatings of metals, plastics, elastomers, including polyolefins, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and in medical devices.
  • the polymer can be used as a filler for bone castings.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to reduce the water level, and 734 parts of the dried diol was added to 52 parts of polyoxyethylene diol having a number average molecular weight of 1450, 49 parts of polyoxypropylene diol having a number average molecular weight of 425, and 4.5 parts of
  • the polymers can be used in shaving lotions, creams and foams, moisturizing lotions and creams, facial creams, animal grooming products, facial and body hair removal products, and antiperspirants, and in coatings of metals, plastics, elastomers, including polyolefins, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and in medical devices.
  • Example 33 Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to reduce the water level, and 699 parts of the dried diol was added to 50 parts of polyoxyethylene diol having a number average molecular weight of 1450, 47 parts of polyoxypropylene diol having a number average molecular weight of 425, and 18 parts of dimethylol propionic acid, and sufficient water to bring the total to .31 part. The mixture was heated with stirring until a homogenous melt was obtained. Then, 94 parts of methylene bis- cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was about 0.92.
  • the polymers can be used in shaving lotions, creams and foams, moisturizing lotions and creams, facial creams, animal grooming products, facial and body hair removal products, and
  • antiperspirants and in coatings of metals, plastics, elastomers, including polyolefins, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and in medical devices.
  • Polyoxyethylene diol having an average molecular weight of 8000 was heated under vacuum to reduce the water level, and 291 parts of the dried diol was added to 15 parts of polyoxyethylene diol having a number average molecular weight of 1450, 34 parts of polyoxypropylene diol having a number average molecular weight of 425, 9.5 parts of dipropylene glycol, and 27 parts of dimethylol propionic acid, and sufficient water to bring the total to .141 part.
  • the mixture was heated with stirring until a homogenous melt was obtained. Then, 92 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added. The NCO/OH ratio was about 0.85.
  • the polymers can be used in animal grooming products, facial and body hair removal products, and antiperspirants, and in coatings of metals, plastics, elastomers, including polyolefins, polystyrene, silicone rubber, polyurethane, steel, brass, bronze to enhance slip, adhesion and biocompatibility.
  • the coatings are useful in industrial applications and in medical devices.
  • PED polyoxyethylene diol
  • the polymer was cut into strips and granulated.
  • the polymer had viscosities of 540 cps at 2% concentration in water 98 cps at 3% concentration in propylene glycol/water.
  • the polymer can used as high s ⁇ p coating for rubber goods such as gloves and condoms, medical products and can be used as absorbents, as gels in wound dressings, to prepare skin and face creams, to form baby rash creams.
  • PED polyoxyethylene diol
  • dimethylolpropionic acid To 857 grams of polyoxyethylene diol (PED) having a number average molecular weight of 8000 was added 4.5 grams of dimethylolpropionic acid and the mixture was heated to 120C to dissolve the DMPA. The mixture was cooled to 80C and analyzed for water and 0.33 gram of water was added to bring the total to 0.73 grams. Then, 45 grams of methylene bis(cyclohexyl-4- isocyanate) was added at about 73 C. The ratio of NCO to OH groups was 0.94. To the mixture was added 5.6 cc of bismuth neodecanate. The mixture was allowed to exotherm and then half was heated in an oven for one hour at 100°C and another half was heated for an additional two hours at 60C.
  • PED polyoxyethylene diol
  • the polymers was cut into strips and granulated.
  • the polymer that was heated for a total of three hours was insoluble in water at 2% and had a viscosity of 225 cps at 3% concentration in propylene glycol/water.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used as absorbents, gels in wound dressings, to
  • the polymer was dissolved in water at 0.5% concentration, and 0.25% Armeen 16D, 0.10% Silicone 2140 emulsion and 75% Purmol 5 A, based on polymer solids was added. Chlorinated latex gloves were dipped into the solution for five seconds, allowed to dry, and then heated at about 85C for ten minutes. The gloves were removed from the oven, and allowed to dry. The gloves had excellent dry, damp and wet donnability.
  • PED polyoxyethylene diol
  • the polymers was cut into strips and granulated.
  • the polymer had a viscosity of 750 cps in water at 2% concentration and a viscosity of 385 cps at 3% concentration in propylene glycol/water.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used as absorbents, gels in wound dressings, to prepare skin and face creams, to form baby creams.
  • PED polyoxyethylene diol
  • the polymers was cut into strips and granulated.
  • the polymer had a viscosity was partially insoluble in water at 2% and had a viscosity of 112 cps at 3% concentration in propylene glycol/water.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used as absorbents, gels in wound dressings, to prepare skin and face creams, to form baby rash creams.
  • PED polyoxyethylene diol
  • dimethylolpropionic acid To 864 grams of polyoxyethylene diol (PED) having a number average molecular weight' of 8000 was added 4.5 grams of dimethylolpropionic acid and the mixture was heated to 120C to dissolve the DMPA. The mixture was cooled to 80C, heated in a vacuum oven and analyzed for water. Then water was added to bring the total to 0.28 grams. Then, 39 grams of methylene bis(cyclohexyl-4-isocyanate) was added at about 70C. The ratio of NCO to OH groups was 0.94. To the mixture was added 1.4 cc of dibutyl tin dilaurate. The mixture was allowed to exotherm and then was heated in an oven for one hour at 100°C.
  • PED polyoxyethylene diol
  • the polymers was cut into strips and granulated.
  • the polymer had a viscosity of 31 cps at 3% concentration in propylene glycol/water.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used as absorbents, gels
  • PED polyoxyethylene diol
  • polydimethylsiloxane polyoxyethylenecopolymer having a number average molecular weight of about 780 and 4.5 grams of dimethylolpropionic acid
  • the mixture was heated to 120C to dissolve the DMPA.
  • the mixture was cooled to 80C, heated in a vacuum oven and analyzed for water.
  • 0.054 gram water was added to bring the total to .28 gram.
  • 53 grams of methylene bis(cyclohexyl-4-isocyanate) was added at about 72C.
  • the ratio of NCO to OH groups was 0.94.
  • To the mixture was added 1.4 cc of dibutyl tin dilaurate. The mixture was allowed to exotherm and then was heated in an oven for one hour at 100°C.
  • the polymers was cut into strips and granulated.
  • the polymer had a viscosity of 38 cps at 3% concentration in propylene glycol/water.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin and face creams and to form baby rash creams.
  • PED polyoxyethylene diol
  • polydimethylsiloxane polyoxyethylenecopolymer having a number average molecular weight of about 780 and 18 grams of dimethylolpropionic acid
  • the mixture was heated to 120C to dissolve the DMPA.
  • the mixture was cooled to about 80C, heated in a vacuum oven and analyzed for water.
  • 1.38 gram of water was added to bring the total to 1.64 grams.
  • 130 grams of methylene bis(cyclohexyl-4-isocyanate) was added at about 70C.
  • the ratio of NCO to OH groups was 0.85.
  • To the mixture was added 1.4 cc of bismuth
  • the polymers was cut into strips and granulated.
  • the polymer had a viscosity of 15 cps at 3% concentration in propylene glycol/water and 36 cps at 2% in water.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin and face creams and to form baby rash creamsA
  • PED polyoxyethylene diol
  • dimethylolpropionic acid 9 grams
  • polydimethlsiloxane polyoxyethylenecopolymer having a number average molecular weight of about 800 and 21 grams of diethylene glycol
  • the mixture was heated to 115C to dissolve the DMPA.
  • the mixture was cooled to 80C, heated in a vacuum oven and analyzed for water.
  • 1.12 gram of water was added to bring the total to 1.64 grams.
  • 120 grams of methylene bis(cyclohexyl-4- isocyanate) was added at about 70C.
  • the ratio of NCO to OH groups was 0.85.
  • To the mixture was added 1.4 cc of bismuth neodecanate. The mixture was allowed to exotherm and then some was heated in an oven for one hour at 100°C and some was heated for one hour at lOOC.
  • the polymers was cut into strips and granulated.
  • the polymer dissolved in water at 2% concentration to give a clear solution with a viscosity of 290 cps.
  • the polymer can be used in skin and hair care products and as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin and face creams and to form baby rash creams.
  • the polymer was dissolved in water at 1.5% concentration, 0.15% diglycoldiamine, 0.50% Armen 16D and 0.50% Silicone 2140 emulsion was added. Chlorinated latex gloves were dipped into the solution for five seconds, allowed to dry, and then heated at about 90C for six minutes. The gloves were removed from the oven, and allowed to dry. The gloves had excellent dry, damp and wet donnability.
  • the polymers was cut into strips and granulated.
  • the polymer dissolved in water at 2% concentration to give a very slightly hazy solution with a viscosity of 190 cps.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin, hair and face creams, foams, solutions and lotions and to form baby rash creams.
  • the polymers was cut into strips and granulated.
  • the polymer dissolved in water at 2% concentration to give a slightly hazy solution with a viscosity of 14 cps.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin, hair and face creams, gels, foams, solutions and lotions and to form baby rash creams.
  • PED polyoxyethylene diol
  • polydimethylsiloxane polyoxyethylenecopolymer having a number average molecular weight of about 780 and 18 grams of dimethylolpropionic acid
  • the mixture was heated to 120C to dissolve the DMPA.
  • the mixture was cooled to about 80C, heated in a vacuum oven and analyzed for water.
  • 1.38 gram of water was added to bring the total to 1.64 grams.
  • 109 grams of methylene bis(cyclohexyl-4-isocyanate) was added at about 70C.
  • the ratio of NCO to OH groups was 0.85.
  • To the mixture was added 1.4 cc of bismuth neodecanate. The mixture was allowed to exotherm and then was heated in an oven for one hour
  • the polymers was cut into strips and granulated.
  • the polymer dissolved in water at 2% concentration to give a clear solution with a viscosity of 10 cps.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin, hair and face creams, foams, solutions, lotions and sprays and to form baby rash creams.
  • PED polyoxyethylene diol
  • polydimethylsiloxane polyoxyethylenecopolymer having a number average molecular weight of about 780
  • 21 grams of diethylene glycol and 18 grams of dimethylolpropionic acid was heated to 120C to dissolve the DMPA.
  • the mixture was cooled to about 80C, heated in a vacuum oven and analyzed for water. Then 0.42 gram of water was added to bring the total to 0.73 grams.
  • 114 grams of methylene bis(cyclohexyl- " 4-isocyanate) was added at about 70C.
  • the ratio of NCO to OH groups was 0.85.
  • To the mixture was added 1.4 cc of bismuth neodecanate. The mixture was allowed to exotherm and then was heated in an oven for one hour at 100°C.
  • the polymers was cut into strips and granulated.
  • the polymer dissolved in water at 2% concentration to give a slightly hazy solution with a viscosity of 12 cps.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin, hair and face creams, gels, foams, solutions and sprays and to form baby rash creams.
  • PED polyoxyethylene diol
  • polydimethylsiloxane polyoxyethylenecopolymer having a number average molecular weight of about 780 and 18 grams of dimethylolpropionic acid
  • the mixture can be heated to 120C to dissolve the DMPA.
  • the mixture can be cooled to about 80C, heated in a vacuum oven and analyzed for water.
  • 1.38 gram of water can be added to bring the total to 1.64 grams.
  • 109 grams of methylene bis(cyclohexyl-4-isocyanate) can be added at about 70C.
  • the .ratio of NCO to OH groups is 0.85.
  • To the mixture was added 1.4 cc of dibutyl tin dilaurate. The mixture is allowed to exotherm and then heated in an oven for one hour at 100°C.
  • the polymer is cut into strips and granulated.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin, hair and face creams, gels, solutions and foams and to form baby rash creams.
  • PED polyoxyethylene diol
  • polyoxypropylene diol having a number average molecular weight of 8000
  • the mixture was heated to 120C to dissolve the DMPA.
  • the mixture was cooled to about 80C, heated in a vacuum oven and analyzed for water. Then water was added to bring the total to 1.64 grams.
  • 124 grams of methyl ene bis(cyclohexyl-4-isocyanate) was added at about 70C.
  • the ratio of NCO to OH groups was 0.85.
  • To the mixture was added 1.4 dibutyl tin dilaurate. The mixture was allowed to exotherm and then heated in an oven for one hour at 100°C.
  • the polymer was cut into strips and granulated.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin and face solutions, gels, foams, creams, and baby rash creams.
  • PED polyoxyethylene diol
  • polyoxypropylene diol having a number average molecular weight of 8000 was added 27 grams of polyoxypropylene diol having a number average molecular weight of about 425, 22 grams of diethylene glycol, and 18 grams of dimethylolpropionic acid and the mixture CM be heated to 120C to dissolve the DMPA.
  • the mixture was cooled to about 80C, heated in a vacuum oven, analyzed for water, and then water was added to bring the total to 1.64 grams.
  • 132 grams of methylene bis(cyclohexyl-4-isocyanate) was added at about 70C.
  • the ratio of NCO to OH groups is 0.85.
  • To the mixture was added 1.4 cc of dibutyl tin dilaurate. The mixture was allowed to exotherm and then heated in an oven for one hour at 100°C.
  • the polymer is cut into strips and granulated.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin and face creams, gels, solutions and foams, and to form baby rash creams.
  • Example 50 To 715 grams of polyoxyethylene diol (PED) having a number average molecular weight of 8000 was added 27 grams of polydimethylsiloxane polyoxyethylenecopolymer having a number average molecular weight of about 780 and 18 grams of dimethylolpropionic acid and the mixture
  • 65 was heated to 120C to dissolve the DMPA.
  • the mixture was cooled to about 80C, heated in a vacuum oven and analyzed for water. Then water was added to bring the total to 1.64 grams. Then, 127 grams of methylene bis(cyclohexyl-4-isocyanate) was added at about 70C. The ratio of NCO to OH groups is 0.85.
  • To the mixture was added 1.4 cc of dibutyl tin dilaurate. The mixture was allowed to exotherm and then heated in an oven for one hour at 100° C.
  • the polymer is cut into strips and granulated.
  • the polymer can be used as high slip coating for rubbefgoods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings, to prepare skin and face creams, gels, solutions and foams, and to form baby rash creams.
  • PED polyoxyethylene diol
  • polyoxytetramethylene diol having a number average molecular weight of 8000
  • the mixture was heated to 120C to dissolve the DMPA.
  • the mixture was cooled to about 80C, heated in a vacuum oven and analyzed for water. Then water was added to bring the total to 0.73 grams.
  • 128 grams of methylene bis(cyclohexyl-4-isocyanate) was added at about 70C.
  • the ratio of NCO to OH groups was 0.85.
  • To the mixture was added 1.4 dibutyl tin dilaurate. The mixture was allowed to exotherm and then heated in an oven for one hour at 100°C.
  • the polymer is cut into strips and granulated.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin and face solutions, gels, foams, creams, to form shampoos, mousse, and baby rash creams.
  • PED polyoxyethylene diol
  • polyoxytetramethylene diol having a number average molecular weight of about 650 and 18 grams of dimethylolpropionic acid
  • the mixture was cooled to about 80C, heated in a vacuum oven and analyzed for water. Then water was added to bring the total to 1.64 grams.
  • 122 grams of methylene bis(cyclohexyl-4-isocyanate) was added at about 70C.
  • the ratio of NCO to OH groups is 0.85.
  • To the mixture was added 1.4 cc of dibutyl tin dilaurate. The mixture was allowed to exotherm and then heated in an oven for one hour at 100°C.
  • the polymer was cut into strips and granulated.
  • the polymer can be used as high slip coating for rubber goods such as gloves and condoms, medical products and can be used in absorbents, as gels in wound dressings and to prepare skin and face creams, gels, solutions and foams, to form baby rash creams.

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Abstract

On prépare un polyuréthane amélioré en faisant réagir un diol, un di-isocyanate organique et un acide carboxylique avec de l'eau choisie en quantité critique dans le mélange de réaction. Ce polyuréthane présente des caractéristiques améliorées d'adhérence, de pouvoir hydrophile et de résistance. Ce polymère a une texture au toucher améliorée et une meilleure lavabilité. Les solutions de ce polymère ont une faible viscosité dans des solutions aqueuses. On peut inclure dans ce polymère des agents actifs, tels que agents antithrombogènes, agents anticancéreux, agents de croissance cellulaire et anticoagulants. Un article élaboré peut être fabriqué avec une couche de ce polymère placé sur un substrat. L'article ainsi élaboré peut être utilisé dans un implant corporel pour suture, greffe veineuse, greffe vasculaire, veine synthétique et artère synthétique.
PCT/US1999/005653 1998-03-18 1999-03-15 Polyurethanes de polyether hydrophile contenant de l'acide carboxylique WO1999047072A1 (fr)

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AU29056/99A AU2905699A (en) 1998-03-18 1999-03-15 Hydrophilic polyether polyurethanes containing carboxylic acid

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US4069198A 1998-03-18 1998-03-18
US09/040,691 1998-03-18

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001070295A1 (fr) * 2000-03-22 2001-09-27 Zenon Kyriakides Stent coronarien enduit d'un antagoniste de recepteur d'endotheline
FR2840907A1 (fr) * 2002-06-14 2003-12-19 Polymerexpert Sa Polymere thermo-sensible ameliore susceptible de former des gels thermoreversibles a haut indice de viscosification
DE10243967A1 (de) * 2002-09-20 2004-04-15 Adiam Life Science Ag Gefäßprothese oder Gewebeflicken aus biokompatiblem Polyurethan und Verfahren zur Verbesserung des E-Moduls dieser Werkstücke
EP1567559A1 (fr) * 2002-11-12 2005-08-31 The Polymer Technology Group, Inc. Regulation de l'architecture moleculaire de surface polymere au moyen de groupes terminaux amphipathiques
WO2006083582A3 (fr) * 2005-02-04 2006-11-16 Procter & Gamble Structure absorbante comprenant une matiere absorbant l'eau
WO2007016251A2 (fr) * 2005-07-28 2007-02-08 Cook Incorporated Valve thromboresistante implantable
CN100480349C (zh) * 2007-01-05 2009-04-22 华南理工大学 一种改性水性聚氨酯胶粘剂的制备方法
EP2322154A2 (fr) * 2002-07-09 2011-05-18 Crossbeta Biosciences B.V. Procédés de détection et d'élimination de protéines à structure bêta croisée avec des composés liant les structure bêta croisées.
WO2012062700A1 (fr) * 2010-11-12 2012-05-18 Nolax Ag Membrane résorbable
WO2013131969A2 (fr) 2012-03-09 2013-09-12 Bayer Materialscience Llc Effet de la substance filmogène en polyuréthane sur l'efficacité d'un traitement de l'acné
CN110092879A (zh) * 2019-04-25 2019-08-06 陕西科技大学 一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3412054A (en) * 1966-10-31 1968-11-19 Union Carbide Corp Water-dilutable polyurethanes
US4743673A (en) * 1986-12-19 1988-05-10 Tyndale Plains-Hunter, Ltd. Hydrophilic carboxy polyurethanes
US5563233A (en) * 1994-11-16 1996-10-08 Tyndale Plains-Hunter, Ltd. Polyether polyurethane polymers and gels having improved absorption and slip properties
US5641574A (en) * 1993-05-24 1997-06-24 E. I. Du Pont De Nemours And Company Process for forming overcoat

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3412054A (en) * 1966-10-31 1968-11-19 Union Carbide Corp Water-dilutable polyurethanes
US4743673A (en) * 1986-12-19 1988-05-10 Tyndale Plains-Hunter, Ltd. Hydrophilic carboxy polyurethanes
US5641574A (en) * 1993-05-24 1997-06-24 E. I. Du Pont De Nemours And Company Process for forming overcoat
US5563233A (en) * 1994-11-16 1996-10-08 Tyndale Plains-Hunter, Ltd. Polyether polyurethane polymers and gels having improved absorption and slip properties

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FR2840907A1 (fr) * 2002-06-14 2003-12-19 Polymerexpert Sa Polymere thermo-sensible ameliore susceptible de former des gels thermoreversibles a haut indice de viscosification
WO2003106536A2 (fr) * 2002-06-14 2003-12-24 Polymerexpert Sa Polymeres thermosensibles et gels thermoreversibles obtenus a partir de ces polymeres
WO2003106536A3 (fr) * 2002-06-14 2004-04-01 Polymerexpert Sa Polymeres thermosensibles et gels thermoreversibles obtenus a partir de ces polymeres
EP2322154A3 (fr) * 2002-07-09 2011-10-05 Crossbeta Biosciences B.V. Procédés de détection et d'élimination de protéines à structure bêta croisée avec des composés liant les structure bêta croisées.
EP2322154A2 (fr) * 2002-07-09 2011-05-18 Crossbeta Biosciences B.V. Procédés de détection et d'élimination de protéines à structure bêta croisée avec des composés liant les structure bêta croisées.
DE10243967A1 (de) * 2002-09-20 2004-04-15 Adiam Life Science Ag Gefäßprothese oder Gewebeflicken aus biokompatiblem Polyurethan und Verfahren zur Verbesserung des E-Moduls dieser Werkstücke
EP1567559A1 (fr) * 2002-11-12 2005-08-31 The Polymer Technology Group, Inc. Regulation de l'architecture moleculaire de surface polymere au moyen de groupes terminaux amphipathiques
EP1567559A4 (fr) * 2002-11-12 2008-04-16 Polymer Technology Group Inc Regulation de l'architecture moleculaire de surface polymere au moyen de groupes terminaux amphipathiques
US7671162B2 (en) 2002-11-12 2010-03-02 Dsm Ip Assets B.V. Control of polymer surface molecular architecture via amphipathic endgroups
US7884171B2 (en) 2002-11-12 2011-02-08 Dsm Ip Assets B.V. Control of polymer surface molecular architecture via amphipathic endgroups
WO2006083582A3 (fr) * 2005-02-04 2006-11-16 Procter & Gamble Structure absorbante comprenant une matiere absorbant l'eau
WO2007016251A3 (fr) * 2005-07-28 2008-04-03 Cook Inc Valve thromboresistante implantable
WO2007016251A2 (fr) * 2005-07-28 2007-02-08 Cook Incorporated Valve thromboresistante implantable
CN100480349C (zh) * 2007-01-05 2009-04-22 华南理工大学 一种改性水性聚氨酯胶粘剂的制备方法
WO2012062700A1 (fr) * 2010-11-12 2012-05-18 Nolax Ag Membrane résorbable
EP2457598A1 (fr) * 2010-11-12 2012-05-30 nolax AG Membrane résorbable
WO2013131969A2 (fr) 2012-03-09 2013-09-12 Bayer Materialscience Llc Effet de la substance filmogène en polyuréthane sur l'efficacité d'un traitement de l'acné
CN110092879A (zh) * 2019-04-25 2019-08-06 陕西科技大学 一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法

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