WO1989003860A1 - Compositions elastomeres sensibles a l'humidite - Google Patents

Compositions elastomeres sensibles a l'humidite Download PDF

Info

Publication number
WO1989003860A1
WO1989003860A1 PCT/US1988/003577 US8803577W WO8903860A1 WO 1989003860 A1 WO1989003860 A1 WO 1989003860A1 US 8803577 W US8803577 W US 8803577W WO 8903860 A1 WO8903860 A1 WO 8903860A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
active agent
water
rubber
weight
Prior art date
Application number
PCT/US1988/003577
Other languages
English (en)
Inventor
Ellsworth E. Faust
Charles K. Kliment
Francis E. Gould
Original Assignee
Tyndale Plains-Hunter, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tyndale Plains-Hunter, Ltd. filed Critical Tyndale Plains-Hunter, Ltd.
Publication of WO1989003860A1 publication Critical patent/WO1989003860A1/fr

Links

Classifications

    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • A61L15/225—Mixtures of macromolecular compounds
    • 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
    • A61L29/049—Mixtures of macromolecular compounds
    • 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
    • A61L31/041—Mixtures of macromolecular compounds
    • 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
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • A61L9/042—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating with the help of a macromolecular compound as a carrier or diluent
    • 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
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C08L21/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C08L7/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/10—Latex
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B42/00—Surgical gloves; Finger-stalls specially adapted for surgery; Devices for handling or treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives

Definitions

  • This invention relates to el astomer composi tions. More particul arly, the invention pertains to moisture sensitive el astomer compositions comprising a composite of a rubber polymer and a hydrophil ic polyurethane polymer.
  • rubber incl uding natural and synthetic types, as a class is highly resistant to the ef fects of moisture.
  • rubber is the material of choi ce for fabri cating a great variety of water repellant articles, particularly fabrics and coatings.
  • a moisture sensitive rubber is desirable.
  • rubber films and membranes having increased moisture permeability and transmission would be useful in fabricating prophylatic devices such as condoms as well as bandages, finger cots and surgical gloves. Rubber that absorbs water accompanied by swelling would be useful as self-sealing caulks and gaskets in an aqueous environment. Because of their relatively high water absorbency, these materials would also be suitable for holding and controlling the release of active ingredients as exemplified by medications, flavors, fragrances, insecticides, germicides, spermicides and the like.
  • moisture sensitive means that the rubber compositions of the invention undergo changes in physical behavior such as swelling on exposure to a moist environment such as body fluids or tissues. Examples of these changes and how they can give rise to useful properties are described above and hereinafter.
  • the moisture sensitive rubber compositions of the invention are prepared by first forming a homogeneous blend of a curable rubber component and a hydrophilic polyurethane and then subjecting the blend to curing conditions to effect curing of the rubber component.
  • the curing conditions may cause crosslinking of the polyurethane component as well.
  • a generally suitable procedure consists in mixing the curable rubber component (in the form of a rubber latex or as a solution or dispersion in an organic solvent) with a solution or water-based emulsion of the hydrophilic polyurethane polymer. Curing of the composition is performed in the usual manner, i.e., by heating in the presence of rubber curing agents.
  • Exemplary and satisfactory curing agents include sulfur, zinc oxide, dimethyl zinc and methyl or ethyl dithiocarbamate or any mixture thereof.
  • the uncured blends including the curing system are first stripped of volatile components such as water or solvents.
  • the stripped blends can then be pressure formed or extruded to give the desired shape.
  • films or membranes such as condoms or gloves
  • dipping or casting is the usual forming method.
  • the foregoing and other rubber shaping techniques are well known in the art and therefore need not be described in detail.
  • curable rubber component includes uncured natural rubber as well as various synthetic curable rubber components commonly used in the preparation of synthetic rubbers and elastomers.
  • Representative synthetic rubber components include those derived from unsaturated hydrocarbon monomers and mixtures thereof, such as isoprene, chloroprene, butadiene, SBR (styrene/butadiene rubber), isobutene/isoprene and EPDM (ethylene/propylene/butadiene).
  • Synthetic rubber monomers and latices produced therefrom, as well as other chemicals used in the manufacture of rubber and useful in the invention are well known and are commercially available from a number of chemical suppliers. A lengthy description of these materials is, therefore, unnecessary for the practice and understanding of the invention.
  • hydrophilic polyurethane polymers employed in carrying out the invention are known materials, the description and preparation of which are set forth, for example, in U. S. Patent Nos. 3,822,238, 3,975,350, 4,156,066, 4,156,067, 4,255,550, 4,359,558 and 4,451,635, incorporated herein by reference.
  • Such polymers are resins obtained by reacting a polyisocyanate with a resin having two or more reactive terminal hydrogens and containing various polar sites which appear in the final polymer product and are responsible for its hydrophilic character.
  • Illustrative polar sites include ether groups, carboxylic acid groups, sulfhydryl groups, sulfonium groups, sulfonic groups and quaternary ammonium groups.
  • An adduct of dihydroxy compounds such as ethylene glycol or propylene glycol with ethylene oxide, propylene oxide, ethylene imine, propylene imine, dioxolane or any mixtures of same;
  • An adduct of trihydroxy compounds such as glycerol or trimethylol propane with ethylene oxide, propylene oxide, ethylene imine, propylene imine, dioxol ane or any mixtures of same ;
  • An adduct of tetrahydroxy compounds such as erythritol or pentaerythritol with ethylene oxide, propyl ene oxide, ethyl ene imine, propylene imine, dioxolane or any mixtures of same;
  • An adduct of polyhydroxy compounds such as anhydroenneaheptitol , sorbitol, mannitol , hydrolyzed l ow molecul ar weight polyvinyl acetate, sucrose or lactose wi th ethylene oxide, propylene oxide, ethyl ene imine, propylene imine, dioxolane or any mixtures of same;
  • An adduct of polybasic acids such as trimellitic acid, pyromell itic acid, mel litic acid, pyrophosphoric acid, and low mol ecul ar wei ght polyacrylic and methacrylic acids with ethylene oxide, propylene oxide, ethylene imine, dioxol ane or any mixtures of same;
  • amino compounds such as ammonia, ethylene diamine, diethylene triamine, triethylene tetraamine with ethylene oxide, propylene oxide, ethylene imine, dioxolane or any mixtures of same;
  • Suitable diacids include maleic, adipic, azelaic, sebacic, phthalic, itaconic acid or any mixture of same.
  • the term "slightly branched" indicates only methyl or ethyl substituents on the polyamide backbone, the ethyl substituent being less than 1%;
  • Hydrammonium or quaternary ammonium salts of ethylene or propylene imine adducts of polyhydroxy compounds from categories 1 to 4.
  • the resins of classes 1-15 above will fall within an equivalent weight range above 140, preferably above 170 and up to about 2000.
  • a ratio of carbon atoms to oxygen and/or amine and/or imine nitrogen atoms ranging from about 1.2:1 to about 2.8:1 is required.
  • the ratio is 1.33:1 to 2.8:1, more preferably 1.33:1 to 2.5:1.
  • the aforedescribed polyurethane polymers may vary in their hydrophilicity from polymers that are water soluble to polymers which are water insoluble but which nevertheless will absorb water (e.g., at least 10% by weight), usually accompanied by swelling. Hydrophilic character can be controlled by balancing the type and number of polar sites against the type and size of the inert portion of the polymer molecule following the guide lines given in the cited patents.
  • a representative polyurethane useful in the invention is prepared by reacting a diisocyanate with a mixture of one or more low molecular weight alkylene glycols such as diethylene glycol and one or more long-chain poloxyalkylene glycol resins in which the oxyalkylene units contain 2 to 4 carbon atoms.
  • Hydrophilic character in these polyurethanes is determined by varying the ratio of low molecular weight alkylene glycol and long-chain polyoxyalkylene glycol. Extreme hydrophilicity of the polymer, even water solubility, is achieved by employing a predominant amount of the highly polar polyoxyethylene glycol.
  • Minimal hydrophilicity results when employing a predominant amount of a poly oxyalkylene glycol in which the oxyalkylene contains higher numbers of carbon atoms, that is, three or more.
  • Intermediate hydrophilicity can be realized by using a mixture of the polyoxyalkylene glycol s or glycols having varying ratios of high to low oxyalkylene units in the resin chain.
  • a highly suitable hydrophilic polyurethane polymer for preparing the moisture sensitive rubber compositions of the invention comprises the reaction product of a mixture of an organic diisocyanate, a low molecular weight alkylene glycol, such as ethylene glycol and/or diethylene glycol, a water-soluble poloxy ethylene glycol having a number average molecular weight of from about 400 to about 20,000, and water, the reaction mixture having an NCO/OH ratio of from about 0.5 to 1.0, preferably about 0.8 to 0.98 and wherein the percent by weight in the reaction mixture of the low molecular weight glycol is no more than about 20%, the water content is no more than about 0.5% and the weight percent of the diisocyanate is from about 5% to about 60%.
  • An especially preferred polymer is produced by reacting on a 100% weight basis from about 12% to about 55% of methylene bis (cyclohexy 1-4,4'-isocyanate), from about 2% to about 20% of the low molecular weight alkylene glycol such as diethylene glycol, from about 25% to about 85% of a polyoxy ethylene having a number average molecular weight of from about 1000 to about 8000 and from about 0.1% to about 0.5% water.
  • methylene bis(cyclohexyl4,4'-isocyanate) can be used in preparing suitable hydrophilic polyurethane polymers. These other diisocyanates include both aliphatic and aromatic types although the aliphatics are preferred.
  • Representative members are tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexylene 1,2-diisocynate, cyclohexylene 1,4-diisocyanate, and aromatic diisocyanates such as 2,4- and 2,6-tolylene diisocyanates. Also suitable are the isocyanate equivalents which form urethane linkages as exemplified by nitrile carbonates, such as adiponitrile carbonate.
  • alkylene glycols and poly oxyalkylene glycols are known entities which can be purchased from chemical supply houses.
  • Typical commercial products are the polyoxy ethylene glycols manufactured by the Union Carbide Corporation, such as CARBCWAX ® 1450, CARBOWAX ® 4500 and CARBOXWAX ® 8000.
  • the numbers refer to average molecular weights.
  • the glycol components and water are formed into a homogeneous mixture which is then reacted with the diisocyanate.
  • the reaction is catalyzed by known catalysts, examples of which are tin salts and organic tin esters such as dibutyl tin dilaurate, tertiary amines such a triethyl diamine (DABCO), N,N,N,N'-tetramethyl-1,3-butane diamine, and other recognized catalysts for urethane polymer synthesis.
  • catalysts examples of which are tin salts and organic tin esters such as dibutyl tin dilaurate, tertiary amines such a triethyl diamine (DABCO), N,N,N,N'-tetramethyl-1,3-butane diamine, and other recognized catalysts for urethane polymer synthesis.
  • sufficient water will be present or added to cause foaming of the polyurethane polymer as it is formed.
  • water Generally, from about 0.1 to about 0.5 part by weight of water based on 100 parts by weight of the total reaction mixture will be effective.
  • compositions of the invention should generally contain at least about 50% by weight of the hydrophobic rubber component in order to provide the requisite elasticity or rubbery character. Such formulations are preferred when the compositions of the invention are used in the manufacture of prophylatic devices and other film articles requiring a high rate of water vapor transmission.
  • the hydrophilic polyurethane polymers may be insoluble in water but soluble in organic solvents.
  • the water sensitive rubber compositions of the invention preferably contain on a solids weight basis from about 5% to about 50% of the solvent soluble polyurethane, and [polyurethane is used] from about 5% to 20% when a water soluble polyurethane is used.
  • the moisture sensitive rubber compositions of the invention are particularly useful in the manufacture of film products having controlled moisture transmission such as prophylatic devices (pessaries, condoms), surgical gloves, surgical membranes and dressings, and the like.
  • Coatings can be prepared by spraying a substrate or article with a solvent solution or emulsion (latex) of the uncured composition which is then cured in place.
  • the rubber compositions of the invention can also be cast, extruded, pressed, calendered or molded into a variety of useful shapes and configurations such as rods, bulk articles and tubing (for example, surgical catheters). Other applications are caulking and sealant materials.
  • a further use of the rubber compositions of the invention is as an active agent release medium. This is effected by adding an active agent to the uncured composition followed by curing. On exposure of such formulations to aqueous conditions, the active agents are slowly leached out in a controlled manner. Active agents which can be dispersed by this technique include biostats or biocides such as germicides, insecticides and spermicides; insect repellants; detergents including soaps; various drugs and medicines, cosmetics, fragrances, flavors and the like.
  • a general procedure for producing the aforedescribed articles and materials comprises stripping water or solvents from the uncured polyurethane polymer/rubber blend and then pressure forming or extruding to the desired shape. Films and membranes are produced by dipping or casting, followed by curing.
  • the rubber compositions of the invention when cured usually exhibit an equilibrium water content of at least about 10% by weight. Equilibrium water content is determined by immersing a sample of the composition in water at 20°C for 24 hours and weighing the composition in the dry state and after removal from water, and expressing the gain as % (by weight of composition) of water absorbed.
  • the elastomer compositions thus are hydrophilic despite the inherent hydrophobicity of the rubber component.
  • a rubber latex formulation was prepared as follows. To 80.0 parts of a 62.5% solids natural rubber latex were added with agitation 1.3 parts of a 68% solids sulfur dispersion, 0.3 parts of a 60% solids zinc oxide dispersion and 1.0 part of a 50% solids zinc dimethyldithiocarbamate dispersion (sold as Methyl Zimate ® by R.T. Vanderbilt Co.). Water, 45.0 parts was then added to reduce the latex solids level to 40%.
  • a polyurethane solution was prepared by dissolving and reacting in 588 parts of water, a hydrophilic polyurethane formed from 59.2 parts of CARB0WAX ® 8000, 25.0 parts of CARBOWAX ® 1450, 2.6 parts of diethylene glycol and 13.1 parts of methylene bis (4-cyclohexylisocyanate).
  • the cured film exhibited tensile strength of 3,667 psi and an ultimate elongation of 740%. After immersion in water overnight at ambient temperature, the tensile strength measured 1,799 psi with ultimate elongation of 840%.
  • 0.75 inch diameter disks were die cut from the dry film ad kept under water for 2 days.
  • the disks exhibited a water content of 30% and a linear expansion of 9%.
  • Specimens kept immersed for 12 days showed no further uptake of water.
  • a film was cast from the rubber latex alone, air dried and cured at 110°C for 30 minutes. This film had a tensile strength of 2,489 psi and ultimate elongation of 867%. The water content of this film after two days immersion in water was determined to be 4.5% with a linear expansion of 2.3%.
  • Example II To 37.5 parts of the formulated rubber latex of Example I was added 11.4 parts of the aqueous solution of the polyurethane of Example I along with 62.1 parts of water. A film was cast, air dried and cured as in Example I. Tensile strength of the dry film was determined to be 3,966 psi with ultimate elongation of 868%. After hydrating the film for 24 hours in water at ambient temperature, the wet tensile strength was 2,658 psi and ultimate elongation 960%. Water content after two days immersion in water was found to be 21% and the linear expansion was 7%.
  • a styrene/butadiene latex was prepared as follows. To 72.4 parts of a 69% solids Pliolite ® 5356 synthetic styrene/butadiene rubber latex (Goodyear Co.) were added 1.1 parts of a 68% solids sulfur dispersion, 0.6 part of a 60% solids zinc oxide dispersion, 0.8 part of a 50% solids Ethyl .pa Zimate ® dispersion (R.T. Vanderbilt Co.) and 56. 2 parts water.
  • the water content of the film was determined to be 19% after two days immersion in water at ambient temperature.
  • a film cast from the formulated and cured latex alone exhibited a water content of 9% after two days of water immersion.
  • Example I To 38.3 parts of the rubber latex of Example I were added 23.2 parts of an aqueous sol ution containing 7.2% of a polyurethane formed from 57.6 CARBOWAX ® 8000, 24.4% of CARBOWAX ® 1450, 3.0 parts of diethylene glycol, 0.15% water and 14.9 parts of methylene bis(cyclohexylisocyanate).
  • a film was cast from the mixture, air dried and cured as described in Example I.
  • the water content of the film after two days water immersion at ambient temperature, was found to be 24% while the linear expansion was measured at 10%.
  • Tensile strength of the wet film was 2,638 psi and ultimate elongation 840%.
  • the water content and linear expansion values of the film remained constant after 39 days of water immersion.
  • Example I To 25 parts of the rubber latex of Example I were added 75 parts of a 50/50 (by wt.) ethanol/water mixture and 18.7 parts of a polyurethane solution prepared by dissolving in 70 parts of a 90/10 (vol.) ethanol water mixture a polyurethane polymer formed from 54.4 parts CARBCWAX ® 1450, 7.2 parts of diethylene glycol, 2.4 parts of gluconic acid delta lactone, 0.3 part water and 35.8 parts of methylenebis(cycloexylisocyanate), followed by the addition of 70 parts of water to reduce the solids level of the solution to 17.6% and the ethanol content of the volatile portion to 45%. A film was cast from the mixture, air dried and cured for 30 minutes at 110° C. After a two day water immersion at ambient temperature, the water content and linear expansion of the polymer were found to be 27% and 11%, respectively.
  • a polyurethane solution prepared by dissolving in 70 parts of a 90/10 (vol.) ethanol
  • the tensile strength of the dry film was 2,054 psi and the ultimate elongation 1,100%. After two days immersion in water, the tensile strength of the wet film was determined to be 2,146 psi and the ultimate elongation 1,000%.
  • a film was cast from the mixture, air dried and cured at 110°C for 30 minutes. After immersion for two days in water at ambient temperature, the water content of the film was found to be 18% and the linear expansion 6%.
  • a nonaqueous blend of 70% SBR synthetic rubber and 30% water insoluble hydrophilic polyurethane was prepared by mixing the following components:
  • a film was cast from the mixture, air dried and then heated to 120°C for 20 minutes. After two days immersion in water at ambient temperature, the water content of the film and its linear expansion were found to be 23% and 11%, respectively.
  • a film was cast from the blend of natural rubber latex and the aqueous solution of the water soluble polyurethane of Example I and air dried in vacuum at room temperature.
  • the resulting uncured dried film was subjected to 5,000 psi at 50°C in a hydraulic press to form a plate 1.2 mm in thickness. After curing at 120°C for 40 minutes, the plate was immersed in water for two days. The water content and linear expansion of the plate were then measured and found to be 29% and 9%, respectively.
  • a blend of the rubber latex and water insoluble hydrophilic polyurethane of Example V was cast as a film and air dried under vacuum at 30°C to constant weight.
  • the resulting dry uncured film was cut into small (5x5 mm) pieces and the pieces fed into a laboratory hand extruder preheated to 60°C.
  • a tube having an OD of 7 mm and an ID of 4 mm was extruded at
  • the tube was suspended in an oven and cured at 120°C for 60 minutes. After immersion in water for two days at ambient temperature, the water content and linear expansion were determined and found to be 26% and 10%, respectively.
  • the tube is suitable for use as a urinary catheter or drain tube for body fluids.
  • IGEPAL ® CO 630 surfactant was rel eased during the first hour.
  • Example A To the mixture of rubber latex and hydrophilic polymer of Example A was added 0.5 parts of tetracycline. The mixture was processed, dried and extruded as described in Example A. The resulting tube was placed in distilled water at 37°C and the elution of tetracycline was monitored every hour by taking samples from the mixed solution. It was found that the tetracycline elution was fairly steady at 4-6 mg/hour during the 24 hour period. TABLE I

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Public Health (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Hematology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

On produit des compositions élastomères ayant des propriétés d'hydroabsorption en soumettant à des conditions de polymérisation un mélange homogène d'un latex de caoutchouc polymérisable et d'un polymère de polyuréthane hydrophile. Des membranes perméables à l'humidité, des matériaux d'étanchéité gonflant à l'eau, des piéces extrudées et des milieux à agents actifs sont produits à partir de cette composition.
PCT/US1988/003577 1987-10-14 1988-10-12 Compositions elastomeres sensibles a l'humidite WO1989003860A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10842387A 1987-10-14 1987-10-14
US108,423 1987-10-14

Publications (1)

Publication Number Publication Date
WO1989003860A1 true WO1989003860A1 (fr) 1989-05-05

Family

ID=22322104

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/003577 WO1989003860A1 (fr) 1987-10-14 1988-10-12 Compositions elastomeres sensibles a l'humidite

Country Status (2)

Country Link
AU (1) AU2812389A (fr)
WO (1) WO1989003860A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2260986A (en) * 1991-10-29 1993-05-05 Armstrong World Ind Inc Polyurethane-urea/polyethylene oxide polymers
US5261421A (en) * 1988-04-23 1993-11-16 Smith & Nephew Plc Gloves, their manufacture and use
US5342889A (en) * 1990-01-05 1994-08-30 The B. F. Goodrich Company Chain extended low molecular weight polyoxiranes for electrostatic applications
US5574104A (en) * 1990-01-05 1996-11-12 The B. F. Goodrich Company Chain extended low molecular weight polyoxiranes and electrostatic dissipating blend compositions based thereon
WO1999010398A2 (fr) * 1997-08-28 1999-03-04 Eastman Chemical Company Polymere de condensation modifie
WO1999037715A1 (fr) * 1998-01-22 1999-07-29 Wolff Walsrode Ag Melange de matieres plastiques exempt de latex
US6197878B1 (en) 1997-08-28 2001-03-06 Eastman Chemical Company Diol latex compositions and modified condensation polymers
US6329462B1 (en) 1999-06-18 2001-12-11 Eastman Chemical Company Nylon 6/silicone blends
US6340726B1 (en) 1999-03-03 2002-01-22 Eastman Chemical Company Silicone polymer diol compositions and condensation polymer/silicone polymer blends
US6353052B1 (en) 1999-06-18 2002-03-05 Eastman Chemical Company Amide-type polymer/silicone polymer blends and processes of making the same
US6403698B1 (en) 1999-03-03 2002-06-11 Eastman Chemical Company Polyamide/emulsion polymer blends
WO2004014449A1 (fr) * 2002-08-13 2004-02-19 Medtronic, Inc. Systeme d'administration de principe actif, dispositif medical et methode
WO2005030345A2 (fr) * 2003-09-26 2005-04-07 Invista Technologies S.A.R.L. Melanges d'alliage de polyurethanne et de caoutchouc naturel
EP2307066A1 (fr) * 2008-06-30 2011-04-13 C.R. Bard, INC. Cathéter à base d'un mélange de polyuréthanne/polyisoprène
CN108424531A (zh) * 2018-04-26 2018-08-21 西南科技大学 一种阳离子溴化丁基橡胶胶乳的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2150938A (en) * 1983-12-05 1985-07-10 Tyndale Plains Hunter Limited Hydrophilic polyurethane acrylate compositions
US4563490A (en) * 1980-07-21 1986-01-07 Czechoslovenska Akademie Ved Of Praha Composite polymeric material for biological and medical application and the method for its preparation
WO1986005796A1 (fr) * 1985-04-01 1986-10-09 Innocap Aktiebolag Composition elastique vulcanizable contenant un polymere d'urethane liquide et du caoutchouc solide vulcanise et utilisation de ladite composition
JPS6257457A (ja) * 1985-11-29 1987-03-13 Dainichi Color & Chem Mfg Co Ltd 水膨潤性樹脂

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4563490A (en) * 1980-07-21 1986-01-07 Czechoslovenska Akademie Ved Of Praha Composite polymeric material for biological and medical application and the method for its preparation
GB2150938A (en) * 1983-12-05 1985-07-10 Tyndale Plains Hunter Limited Hydrophilic polyurethane acrylate compositions
WO1986005796A1 (fr) * 1985-04-01 1986-10-09 Innocap Aktiebolag Composition elastique vulcanizable contenant un polymere d'urethane liquide et du caoutchouc solide vulcanise et utilisation de ladite composition
JPS6257457A (ja) * 1985-11-29 1987-03-13 Dainichi Color & Chem Mfg Co Ltd 水膨潤性樹脂

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5261421A (en) * 1988-04-23 1993-11-16 Smith & Nephew Plc Gloves, their manufacture and use
US5342889A (en) * 1990-01-05 1994-08-30 The B. F. Goodrich Company Chain extended low molecular weight polyoxiranes for electrostatic applications
US5574104A (en) * 1990-01-05 1996-11-12 The B. F. Goodrich Company Chain extended low molecular weight polyoxiranes and electrostatic dissipating blend compositions based thereon
GB2260986A (en) * 1991-10-29 1993-05-05 Armstrong World Ind Inc Polyurethane-urea/polyethylene oxide polymers
US6417239B1 (en) 1997-08-28 2002-07-09 Eastman Chemical Company Methods of making modified condensation polymers
WO1999010398A3 (fr) * 1997-08-28 2000-04-06 Eastman Chem Co Polymere de condensation modifie
US6197878B1 (en) 1997-08-28 2001-03-06 Eastman Chemical Company Diol latex compositions and modified condensation polymers
WO1999010398A2 (fr) * 1997-08-28 1999-03-04 Eastman Chemical Company Polymere de condensation modifie
US6417269B1 (en) 1997-08-28 2002-07-09 Eastman Chemical Company Methods of making modified condensation polymers
WO1999037715A1 (fr) * 1998-01-22 1999-07-29 Wolff Walsrode Ag Melange de matieres plastiques exempt de latex
US6340726B1 (en) 1999-03-03 2002-01-22 Eastman Chemical Company Silicone polymer diol compositions and condensation polymer/silicone polymer blends
US6403698B1 (en) 1999-03-03 2002-06-11 Eastman Chemical Company Polyamide/emulsion polymer blends
US6329462B1 (en) 1999-06-18 2001-12-11 Eastman Chemical Company Nylon 6/silicone blends
US6353052B1 (en) 1999-06-18 2002-03-05 Eastman Chemical Company Amide-type polymer/silicone polymer blends and processes of making the same
WO2004014449A1 (fr) * 2002-08-13 2004-02-19 Medtronic, Inc. Systeme d'administration de principe actif, dispositif medical et methode
WO2005030345A2 (fr) * 2003-09-26 2005-04-07 Invista Technologies S.A.R.L. Melanges d'alliage de polyurethanne et de caoutchouc naturel
WO2005030345A3 (fr) * 2003-09-26 2005-12-29 Invista Tech Sarl Melanges d'alliage de polyurethanne et de caoutchouc naturel
US7361707B2 (en) 2003-09-26 2008-04-22 Invista North America S.A.R.L. Alloy blends of polyurethane and latex rubber
US7537814B2 (en) 2003-09-26 2009-05-26 Invista North America S.A.R.L. Alloy blends of polyurethane and latex rubber
EP2307066A1 (fr) * 2008-06-30 2011-04-13 C.R. Bard, INC. Cathéter à base d'un mélange de polyuréthanne/polyisoprène
JP2011526814A (ja) * 2008-06-30 2011-10-20 シー．アール．バード，インコーポレイテッド ポリウレタン／ポリイソプレンブレンドカテーテル
EP2307066A4 (fr) * 2008-06-30 2013-05-15 Bard Inc C R Cathéter à base d'un mélange de polyuréthanne/polyisoprène
US8795573B2 (en) 2008-06-30 2014-08-05 C.R. Bard, Inc. Polyurethane/polyisoprene blend catheter
CN108424531A (zh) * 2018-04-26 2018-08-21 西南科技大学 一种阳离子溴化丁基橡胶胶乳的制备方法
CN108424531B (zh) * 2018-04-26 2021-05-11 西南科技大学 一种阳离子溴化丁基橡胶胶乳的制备方法

Also Published As

Publication number Publication date
AU2812389A (en) 1989-05-23

Similar Documents

Publication Publication Date Title
US4920172A (en) Hydrophilic polyurethane emulsions and materials produced therefrom
WO1989003860A1 (fr) Compositions elastomeres sensibles a l'humidite
US5008115A (en) Matrix for release of active ingredients
EP0338732B1 (fr) Matrice pour la libération d'ingrédients actifs
CA1042600A (fr) Mousses polyurethannes hydrophobes a liaison transversale
CA1338678C (fr) Polyurethanes hydrophiliques possedant une resistance amelioree
EP0338818B1 (fr) Récipient, procédé et composition pour régler le dégagement d'un liquide volatil d'une solution aqueuse
US4137200A (en) Crosslinked hydrophilic foams and method
CA2228505C (fr) Modificateurs de surface oligomeres fluores pour des polymeres et articles realises a partir de ceux-ci
US4789720A (en) Hydrophilic polyurethanes prepared from mixed oxyalkylene glycols
US6617014B1 (en) Foam composite
EP0907384B1 (fr) Dispositif medical
CA2048253C (fr) Eponge de polyurethanne a degagement rapide d'iode
US4810543A (en) Articles having low friction surfaces and production thereof
US5159050A (en) Polyurethane and medical article therefrom
WO1994022934A1 (fr) Copolymeres en blocs aleatoires
JPH0722952B2 (ja) 物品に滑らかな被覆を適用する方法
CA1202531A (fr) Liant, et non tisse qui le renferme
JPS6410542B2 (fr)
WO1988000214A1 (fr) Polymeres de polyurethane prepares a partir de resines de glycol d'alkylene melangees
US4690953A (en) Method of frothing aqueous ionic polyurethane dispersions and products produced therefrom
EP1606349A2 (fr) Gels polymeres a liberation controlee
FR2612198A1 (fr) Composition de polyurethane hydrophile et article qui en est produit
US2992940A (en) Treatment of cellular materials
JPH04353515A (ja) 香料を含有する室温硬化性エポキシ樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE