WO1988000214A1 - Polymeres de polyurethane prepares a partir de resines de glycol d'alkylene melangees - Google Patents

Polymeres de polyurethane prepares a partir de resines de glycol d'alkylene melangees Download PDF

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Publication number
WO1988000214A1
WO1988000214A1 PCT/US1987/001457 US8701457W WO8800214A1 WO 1988000214 A1 WO1988000214 A1 WO 1988000214A1 US 8701457 W US8701457 W US 8701457W WO 8800214 A1 WO8800214 A1 WO 8800214A1
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Prior art keywords
glycol
polymer
average molecular
carrier system
molecular weight
Prior art date
Application number
PCT/US1987/001457
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English (en)
Inventor
Stephen D. Reduker
Charles K. Kliment
Original Assignee
Tyndale Plains-Hunter, Ltd.
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Filing date
Publication date
Application filed by Tyndale Plains-Hunter, Ltd. filed Critical Tyndale Plains-Hunter, Ltd.
Publication of WO1988000214A1 publication Critical patent/WO1988000214A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208—Tissues; Wipes; Patches
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87—Polyurethanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/20—Pills, tablets, discs, rods
    • A61K9/2004—Excipients; Inactive ingredients
    • A61K9/2022—Organic macromolecular compounds
    • A61K9/2031—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, polyethylene oxide, poloxamers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/20—Pills, tablets, discs, rods
    • A61K9/28—Dragees; Coated pills or tablets, e.g. with film or compression coating
    • A61K9/2806—Coating materials
    • A61K9/2833—Organic macromolecular compounds
    • A61K9/2853—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, polyethylene oxide, poloxamers, poly(lactide-co-glycolide)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
    • A61K9/703—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms characterised by shape or structure; Details concerning release liner or backing; Refillable patches; User-activated patches
    • A61K9/7038—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer
    • A61K9/7046—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds
    • A61K9/7069—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. polysiloxane, polyesters, polyurethane, polyethylene oxide
    • 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
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/58—Adhesives
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • 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
    • 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
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • 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 polyurethane polymers, and in particular to hydrophilic polyurethane polymers prepared from a combination of certain alkylene glycols and to coatings, films, carrier systerns and various articles based on the polymers.
  • the polyurethane polymers of the cited patents vary from gel-like to soft and pliable and in the dry state from soft to hard and machinable. Suggested uses are as coatings, linings, dialysis membranes, absorbents, controlled release agents, swellable fabrics, gauzes, solubilizing packaging components, water transmitting coated
  • Hydrophilic polyurethane polymers have also been disclosed in which the chemical configuration is specifically tailored to provide certain features and characteristics. For instance, in U.S. Patent No. 4,156,066,. there is described a hydrophilic polyur- ethane having lactone groups in the polymer backbone. The lactone may be opened by hydrolytic cleavage to form carboxylic groups which render the polymer soluble in alkaline medium.
  • Other specialized hydrophilic polyurethane polymers are the polyurethane diacrylates of U.S. Patent No. 4,359,558 and the polyurethane quaternary ammonium salts of U.S. Patent No. 4,451,635.
  • a polyurethane polymer of the hydrophilic type has now been found, the formulation and properties of which are not obviously derivable from the known art and the provision of said polymer and its uses constitute the object and purpose of the invention.
  • novel polyurethane of the invention is a hydrophilic, thermoplastic, essentially linear polymer which is obtained by reacting, in the
  • the proportions in which the long-chain polyglycol and the low molecular weight glycol are used depends on the hydrophobic-hydrophilic balance that is desired in the final polymer product. Increasing molecular weight of the long-chain polyoxyethylene glycol and/or the amount of this component imparts strong hydrophilic properties to the polymer. This effect may be counter-balanced by increasing the proportions of
  • the polyurethane polymer of the invention will overall fall within the average molecular weight range of from about 10,000 to 200,000, the polymer being further defined as comprising the reaction product of: (A) an alkylene glycol component comprising a mixture of (1) ethylene glycol and/or diethylene glycol, (2) a polyoxyethylene glycol having an average molecular weight of from about 400 to about 20,000 and (3) a polyoxytetramethylene glycol having an average molecular weight of from about 650 to about 2,900; (B) an organic diisocyanate; and (C) a minor amount of water.
  • an alkylene glycol component comprising a mixture of (1) ethylene glycol and/or diethylene glycol, (2) a polyoxyethylene glycol having an average molecular weight of from about 400 to about 20,000 and (3) a polyoxytetramethylene glycol having an average molecular weight of from about 650 to about 2,900
  • B an organic diisocyanate
  • C a minor amount of water.
  • the mixture of alkylene glycols will comprise, per 100 parts by weight of total reaction mixture (A+B+C), of (i) from about 2 parts to about 15 parts by weight of ethylene glycol and/or diethylene glycol, (ii) from about 10 to
  • a more preferred alkylene glycol formulation comprises (i) from about 4 to about 10 parts by weight of ethylene glycol and/or diethylene glycol, (ii) from about 22 parts to about 59 parts by weight of polyoxyethylene glycol and (iii) from about 20 to about 40 parts by weight of polyoxytetramethylene glycol on the same basis.
  • the proportions of alkylene glycol and diisocyanate will be such as to provide an NCO/OH ratio of about 1 to slightly less than 1, usually about 0.98, i.e., from about 1:1 to about 0.98:1.
  • Enough water should be present in the reaction mixture to assist in the workup of the mixture, e.g., by lowering the viscosity. While this is achievable in some cases without foaming, by reason of trace amounts of water often present in commercial alkylene glycols or which result from pickup of atmospheric moisture by the alkylene glycols due to their hygroscopicity, preferably sufficient water will be present or added to cause foaming of the polyurethane as it is formed. Generally, trace amounts up to about 0.5 parts by weight of water based on the weight of the total reaction mixture will be effective, and for foaming, from about 0.1 to about 0.5 part by weight
  • the diisocyanates used in the present invention include both aliphatic and aromatic types and mixtures thereof although the aliphatics are preferred.
  • Representative members are tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl- hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, diethylbenzene diisocyanate, decamethylene 1,10-diisocyanate, cyclohexylene 1,2- diisocyanate and cyclohexylene 1,4-diisocyanate, and aromatic isocyanates such as 2,4- and 2,6-tolylene diisocyanate.
  • An especially preferred isocyanate is methylene di(cyclohexyl isocyanate). Somewhat less preferred diisocyanates are trimethyl hexamethylene diisocyanate and isophorone diisocyanate.
  • polyoxyethylene glycols are known entties which are readily available from chemical suppliers.
  • the glycol components are formed into a homogeneous mixture which is then reacted with the diisocyanate.
  • the reaction is catalyzed by known catalysts for such reaction, suitable ones being tin salts
  • organic tin esters such as dibutyl tin dilaurate, tertiary amines such as triethyl diamine (DABCD) , N,N,N',N'-tetramethyl-1,3-butane diamine and other recognized catalysts for urethane polymer synthesis.
  • DABCD triethyl diamine
  • the polymer of the invention absorbs water in aqueous media accompanied by varying degrees of swelling depending on the particular polymer composition. Water absorption is determined by immersing the polymer in water at 20°C for 24 hours and weighing the polymer in the dry state and after removal from the water, and expressing the gain as % (by weight of polymer) of water absorbed.
  • the hydrophilic polyurethane polymer of the present invention is dimensionally stable upon repeated exposure to water and exhibits high mechanical strength, especially in the wet stage. These characteristics translate into superior film products made from the polymer such as, for example, condoms and gloves.
  • Other uses include coatings, molding compounds, absorbents, carrier systems for active agents including a nonleachable carrier system, a leachable carrier system, and wherein the carrier system is disposed in liquid medium, e.g. a body fluid, or in a gaseous medium such as air, ion exchange resins, and such manufactured articles as dialysis membranes, dentures, cannulae, e.g. feeding tubes, contact lenses, packaging components, burn dressings, contraceptive devices, sutures, surgical
  • implants for treating neurological disorders.
  • blood oxygenators for treating neurological disorders.
  • intrauterine devices for treating neurological disorders.
  • vascular prostheses for example, vascular prostheses, oral delivery systems, battery separator plates, eye bandages, corneal prostheses, antifog coatings, surgical drapes, oxygen exchange membranes, artificial fingernails, finger cots, adhesives, gas permeable membranes, and protective and drag resistant coatings.
  • the temperature continued to rise to about 80°C and the mass foamed.
  • the pan was placed in an oven and he l d at 100 °C for about one hour to complete formation of the polymer.
  • the substituted polymer of Examples 1 and 2 is much more soluble in lower alcohols, which is an advantage for dipping manufacturing procedures, and is soft and pliable in its dry state, while the nonsubsti- tuted, prior art polymer is tough and parchmentlike.
  • Both of the polymers from Example 1 and Example 2 are especially suitable for preparation of condoms, diaphragms, electronic and surgical gloves and similar products, where high tensile and tear strength in both dry and wet state is essential.
  • a typical prior art hydrophilic polyurethane was prepared by reacting 27.5 parts of CARBOWAX 1450, 19.1 parts of diethylene glycol, 0.1 parts of water, and 53.4 parts of DESMODUR W by the procedure as previously described.
  • the 20% substituted polymer of this group has the following composition: 22.4 parts of CARBOWAX
  • the polymer from Example 2 was placed in a Carver press at 104.4 °C to 115.5°C and 3,000 pounds pressure and formed into a sheet 1-1.2 mm thick.
  • the po lymer plate was coated on one si de with a layer of GELVA" RA 788 adhesive (vinylacetate acrylic multpolymer adhesive, Monsanto, St. Louis, MO) using a doctor blade.
  • GELVA RA 788 adhesive
  • the soft polymeric sheet was adapted to the gum-contacting surface of a full upper denture, pressed into place and the excess cut off with a scalpel.
  • the polymer After swelling in water, the polymer further softens and owing to its water content, exhibits water spreading on its surface.
  • the advantage of this type of denture liner is two-fold: the soft layer cushions the denture and prevents erosion of the gums, and the hydrophilic surface increases the adhesion.
  • Example 2 The polymer from Example 1 was dissolved in chloroform as a 10% solids solution, and a film 3 mil thick was cast on release paper. When the last remnants of the solvent evaporated, a polyurethane/ polyacrylic hydrophilic adhesive (Tyndale Plains-Hunter
  • the finished film when used as a wound dressing composite has a Moisture Vapor transmission Rate of 1,250 g/m 2 /24 hours and oxygen permeability of 13 g O 2 /m 2 /24 hours.
  • the cast films with the hydrophilic adhesive was tested as a transdermal patch. On rats, the film was found to release indomethacin at a rate of 6 g/cm 2 /24 hours.
  • a film was cast from the polymer of Example 1, using a formulation containing 10% by weight of polymer and 1% sodium bicarbonate in a solvent blend of 60 parts ethyl alcohol, 10 parts isopropyl alcohol and 20 parts water. After the film was dried to constant weight, it was eluted in distilled water at 25°C. The elution rate of the sodium bicarbonate from the film was found to be 280 mg/10 hours.
  • a 10% solution of the polymer from Example 1 was prepared in chloroform. Commercial tablets of antibiotic were coated with the polymer solution. Ninety-eight percent (98%) of the drug present, that is, 0.98 g, eluted at 37 °C in distilled water in 15 hours.
  • the elution rate in distilled water was 290 mg/20 hours. This experiment was repeated with the ground tablets placed in capsules, prepared from the above-mentioned polymer solution by dipping on a Teflon ⁇ mandrel. The elution rate was slightly slower, about 250 mg/20 hours.
  • Pfizer Agricultural Division, New York, NY containing 90 grains sulfamethazine, 90 grains sulfanilamide and 60 grains sulfathiazole each in 824 mg of electrolyte salts, were coated with a solution of 10% solids of the polymer from Example 2 in 90% ethyl alcohol.
  • coated granules were spread outdoors, using a spreader delivering 15.4 lbs/acre.
  • the area, which was originally infested with ticks was completely free of ticks for a period of four weeks, despite heavy rainfall and high temperatures.
  • Control spreading using only the insecticide on the granules (no polymer) in the same concentration, was effective only for 24 hours in controlling the tick population.
  • a solution was prepared from 4 parts of the polymer from Example 2, 0.09 parts of a leveling agent Silwet" L-7604 organosilicone fluid, manufactured by Union Carbide Silicones Division, Danbury, CT), 90 parts of ethyl alcohol and 5 parts of water.
  • Silwet L-7604 organosilicone fluid
  • the solution was weighed into aerosol cans. After capping with the valve and dip tube assembly, the can were filled with DYMEL ⁇ 22 (fluorocarbon propellant, manufactured by E.I. DuPont and de Nemours, Wilmington, Delaware) in a ratio of 40 parts solution, 25 parts propellant.
  • DYMEL ⁇ 22 fluorocarbon propellant, manufactured by E.I. DuPont and de Nemours, Wilmington, Delaware
  • the samesolution may also be used for saturating nonwoven pads, packaged in foil envelopes to prevent a loss of solvent.
  • a latex Foley urinary catheter was dip-coated with a solution made from 3 parts of polymer from
  • Example 1 and 97 parts of dichloroethane. After air drying, the dipping was repeated. The coating was cured at 80°C for 5 minutes.
  • the coated catheter While the uncoated latex has a coefficient of friction of 0.4 (as measured according to ASTM D-1894- 75), the coated catheter has a coefficient of friction in fully hydrated state of 0.18.
  • a solution prepared from 7 parts of polymer from Example 1, 88 parts of 200 proof SDA ethyl alcohol and 5 parts of water was used as a wrinkle patch.
  • the film is removed by applying water and stripping, usually. in one piece.
  • the resulting spray was used as a deodorant.
  • the films prevent moisture transport in the liquid form, but does not prevent moisture vapor transmission.
  • the subject remains "dry", with no visible sweat formation on the skin.
  • the hydrated film releases slowly the fragrance over a period of several hours.
  • Example 2 The polymer of Example 2 was cut into thin strips and fed into a 1 inch Killian vented extruder and continuously extruded.
  • the extrusion conditions were set as follows:
  • the die was selected to give a thin-wall tubing of French 2 size.
  • Example M The extrusion conditions of Example M were repeated except that a die was elected to give a rod having a diameter of 3.5 mm.
  • the rod can be used as an implantable storage device for both human and veterinary drugs.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dermatology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Birds (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Gerontology & Geriatric Medicine (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Surgery (AREA)
  • Hematology (AREA)
  • Materials Engineering (AREA)
  • Biomedical Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Un polymère de polyuréthane hydrophile, thermoplastique de stabilité dimensionnelle et de résistance mécanique améliorées ayant un poids moléculaire moyen compris entre 10.000 environ et 200.000 environ est produit en faisant réagir A) un diisocyanate organique avec B) un mélange de composants de glycol comprenant i) du glycol d'éthylène et/ou du glycol de diéthylène, ii) un glycol de polyoxyéthylène ayant un poids moléculaire moyen compris entre 400 environ et 20.000 environ et iii) un glycol de polyoxytétraméthylène ayant un poids moléculaire moyen compris entre 650 environ et 2.900 environ, et C) une petite quantité d'eau. Les polymères sont particulièrement utiles pour produire des objets en forme de films tels que des gants et des préservatifs. D'autres utilisations possibles sont les revêtements à faible coefficient de friction, les implants dans le corps humain ainsi que les milieux de libération d'un agent actif.
PCT/US1987/001457 1986-06-26 1987-06-15 Polymeres de polyurethane prepares a partir de resines de glycol d'alkylene melangees WO1988000214A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US87915686A 1986-06-26 1986-06-26
US879,156 1986-06-26

Publications (1)

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WO1988000214A1 true WO1988000214A1 (fr) 1988-01-14

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Cited By (17)

* Cited by examiner, † Cited by third party
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EP0335308A2 (fr) * 1988-03-31 1989-10-04 W.R. Grace & Co.-Conn. Dispositif enduit de polymère polyurée-uréthane n'absorbant pas les protéines
EP0348105A2 (fr) * 1988-06-17 1989-12-27 PolyMedica Industries, Inc. Polyuréthane polyéther segmenté
EP0352984A1 (fr) * 1988-07-22 1990-01-31 Allergan, Inc Manchon synthétique pour instruments de chirurgie
EP0404517A1 (fr) * 1989-06-21 1990-12-27 Superior Healthcare Group, Inc. Cathéter expansible à base d'élastomère thermoplastique de polyétheruréthane hydrophilique
EP0408558A1 (fr) * 1988-03-09 1991-01-23 Tyndale Plains-Hunter, Ltd. Polyurethanes hydrophiles prepares a partir d'oxyalcene glycol
EP0454293A2 (fr) * 1990-04-23 1991-10-30 C.R. Bard, Inc. Revêtements organiques flexibles lubrifiants
EP0482467A2 (fr) * 1990-10-15 1992-04-29 Nisshinbo Industries, Inc. Adhésif chirurgical
EP0502591A2 (fr) * 1991-03-06 1992-09-09 W.R. Grace & Co.-Conn. Dispositif enduit de polymère polyurée-uréthane n'absorbant pas les protéines
EP0586132A1 (fr) * 1992-09-03 1994-03-09 Becton, Dickinson and Company Mélanges de polyuréthane thermoplastiques
EP0700779A3 (fr) * 1994-08-10 1996-06-26 Von Borries Horst Bandes perméables pour la construction et procédé pour leurs fabrications
WO2008089163A1 (fr) * 2007-01-18 2008-07-24 Lubrizol Advanced Materials, Inc. Polyuréthanes très perméables à l'humidité
WO2009108678A1 (fr) * 2008-02-26 2009-09-03 Lubrizol Advanced Materials, Inc. Polyuréthannes à transmission de vapeur humide élevée
FR2954150A1 (fr) * 2009-12-17 2011-06-24 Oreal Utilisation d'un ou plusieurs composes adhesifs sensibles a la pression en tant qu'agent pour le traitement de la transpiration humaine
WO2013030148A1 (fr) 2011-08-29 2013-03-07 Bayer Intellectual Property Gmbh Polyuréthanes thermoplastiques hydrophiles et utilisation desdits polyuréthanes thermoplastiques hydrophiles dans la technique médicale
US8637629B2 (en) 2007-01-18 2014-01-28 Lubrizol Advanced Materials, Inc. High moisture vapor transmissive polyurethanes
CN112079986A (zh) * 2020-09-21 2020-12-15 兰州科天健康科技股份有限公司 一种水性聚氨酯乳液及其制备方法和用途
WO2020257880A1 (fr) * 2019-06-28 2020-12-30 Eudaemon Technologies Pty Ltd Hydrogels de polyuréthane moulés

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US4433072A (en) * 1978-12-15 1984-02-21 Hospal-Sodip, S.A. Mixtures of polymers for medical use
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US4359558A (en) * 1980-11-12 1982-11-16 Tyndale Plains-Hunter, Ltd. Polyurethane diacrylate compositions
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Cited By (27)

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Publication number Priority date Publication date Assignee Title
US5169720A (en) * 1986-11-18 1992-12-08 W. R. Grace & Co.-Conn. Protein non-adsorptive polyurea-urethane polymer coated devices
EP0408558A1 (fr) * 1988-03-09 1991-01-23 Tyndale Plains-Hunter, Ltd. Polyurethanes hydrophiles prepares a partir d'oxyalcene glycol
EP0408558A4 (en) * 1988-03-09 1991-03-20 Tyndale Plains-Hunter, Ltd. Hydrophilic polyurethanes prepared from mixed oxyalkylene glycols
EP0335308A3 (en) * 1988-03-31 1990-12-19 W.R. Grace & Co.-Conn. (A Connecticut Corp.) Protein non-adsorptive polyurea-urethane polymer coated devices
EP0335308A2 (fr) * 1988-03-31 1989-10-04 W.R. Grace & Co.-Conn. Dispositif enduit de polymère polyurée-uréthane n'absorbant pas les protéines
EP0348105A2 (fr) * 1988-06-17 1989-12-27 PolyMedica Industries, Inc. Polyuréthane polyéther segmenté
EP0348105A3 (en) * 1988-06-17 1990-07-04 Matrix Medica, Inc. Segmented polyether polyurethane
EP0352984A1 (fr) * 1988-07-22 1990-01-31 Allergan, Inc Manchon synthétique pour instruments de chirurgie
EP0404517A1 (fr) * 1989-06-21 1990-12-27 Superior Healthcare Group, Inc. Cathéter expansible à base d'élastomère thermoplastique de polyétheruréthane hydrophilique
EP0454293A2 (fr) * 1990-04-23 1991-10-30 C.R. Bard, Inc. Revêtements organiques flexibles lubrifiants
EP0454293A3 (en) * 1990-04-23 1992-05-13 C.R. Bard, Inc. Flexible lubricious organic coatings
EP0482467A2 (fr) * 1990-10-15 1992-04-29 Nisshinbo Industries, Inc. Adhésif chirurgical
EP0482467A3 (en) * 1990-10-15 1993-03-03 Nisshinbo Industries, Inc. Surgical adhesive
EP0502591A2 (fr) * 1991-03-06 1992-09-09 W.R. Grace & Co.-Conn. Dispositif enduit de polymère polyurée-uréthane n'absorbant pas les protéines
EP0502591A3 (en) * 1991-03-06 1993-03-10 W.R. Grace & Co.-Conn. Protein non-adsorptive polyurea-urethane polymer coated devices
EP0586132A1 (fr) * 1992-09-03 1994-03-09 Becton, Dickinson and Company Mélanges de polyuréthane thermoplastiques
EP0700779A3 (fr) * 1994-08-10 1996-06-26 Von Borries Horst Bandes perméables pour la construction et procédé pour leurs fabrications
US8637629B2 (en) 2007-01-18 2014-01-28 Lubrizol Advanced Materials, Inc. High moisture vapor transmissive polyurethanes
WO2008089163A1 (fr) * 2007-01-18 2008-07-24 Lubrizol Advanced Materials, Inc. Polyuréthanes très perméables à l'humidité
WO2009108678A1 (fr) * 2008-02-26 2009-09-03 Lubrizol Advanced Materials, Inc. Polyuréthannes à transmission de vapeur humide élevée
FR2954150A1 (fr) * 2009-12-17 2011-06-24 Oreal Utilisation d'un ou plusieurs composes adhesifs sensibles a la pression en tant qu'agent pour le traitement de la transpiration humaine
WO2011073345A3 (fr) * 2009-12-17 2012-05-03 L'oreal Utilisation d'un ou de plusieurs composés adhésifs sensibles à la pression à titre d'agents pour le traitement de la transpiration chez l'homme
WO2013030148A1 (fr) 2011-08-29 2013-03-07 Bayer Intellectual Property Gmbh Polyuréthanes thermoplastiques hydrophiles et utilisation desdits polyuréthanes thermoplastiques hydrophiles dans la technique médicale
WO2020257880A1 (fr) * 2019-06-28 2020-12-30 Eudaemon Technologies Pty Ltd Hydrogels de polyuréthane moulés
CN114096290A (zh) * 2019-06-28 2022-02-25 尤达莫恩科技私人有限公司 模制聚氨酯水凝胶
CN112079986A (zh) * 2020-09-21 2020-12-15 兰州科天健康科技股份有限公司 一种水性聚氨酯乳液及其制备方法和用途
CN112079986B (zh) * 2020-09-21 2022-07-12 兰州科时西西里健康科技有限公司 一种水性聚氨酯乳液及其制备方法和用途

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