WO1995006670A1 - Low friction, hydrophilic, biocompatible compositions - Google Patents

Low friction, hydrophilic, biocompatible compositions Download PDF

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Publication number
WO1995006670A1
WO1995006670A1 PCT/US1994/009867 US9409867W WO9506670A1 WO 1995006670 A1 WO1995006670 A1 WO 1995006670A1 US 9409867 W US9409867 W US 9409867W WO 9506670 A1 WO9506670 A1 WO 9506670A1
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Prior art keywords
polymer blend
polymer
polyurethane
poly
blend
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PCT/US1994/009867
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French (fr)
Inventor
Adrian S. Fox
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Nepera, Inc.
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Publication date
Application filed by Nepera, Inc. filed Critical Nepera, Inc.
Priority to AU76428/94A priority Critical patent/AU7642894A/en
Publication of WO1995006670A1 publication Critical patent/WO1995006670A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses

Definitions

  • This invention relates to the field of polymer blends. More particularly, the invention relates to hydrophilic blends of polyurethane and poly (alkylene oxides) , and to use of those blends in a variety of applications including lubricous coating compositions.
  • Lubricous hydrophilic coatings for a variety of uses are described in the prior art. For example, forming a linear polyurethane polymer and then dispersing it in water is well known in the art. See U.S. Pat. Nos. 3,412,054 and 4,094,838 which describe modified, water dispersible urethanes.
  • Lubricous urethane coated articles for insertion into the human body are described in U.S. Pat. Nos. 4,100,309 and 4,119,094. Articles such as catheters and condoms described in these patents have been obtained by applying polyvinylpyrrolidone polyurethane interpolymer coatings to a substrate.
  • PVP Polyvinylpyrrolidone
  • the invention is directed to polymer blends of an organic solvent-soluble, thermoplastic polyurethane and a second component of poly (alkylene oxide) . These blends surprisingly retain slipperiness when exposed for long periods to aqueous environments.
  • organic solvent-soluble thermoplastic polyurethanes can be blended, or alloyed with polyethylene oxide (“PEO") or other poly alkylene oxides such as polypropylene oxide, either by use of a common solvent or solvent mixture, or by conventional melt blending techniques.
  • PEO polyethylene oxide
  • the resulting urethanes exhibit highly lubricous properties in aqueous environments, as well as surprising retention of lubricous properties in aqueous environments.
  • a hydrophilic urethane polymer blend which comprises a first polymer component of an organic solvent-soluble, thermoplastic polyurethane and a second polymer component of hydrophilic poly (alkylene oxide) , preferably poly ethylene oxide ("PEO") .
  • the polyurethane is derived from any of aromatic polyisocyanate or aliphatic polyisocyanate and any of polyether polyol or polyester polyol.
  • the polyurethane can be crosslinked during or subsequent to including the polyurethane in the blend.
  • the polymer blend may contain at least one additional polymer component which is compatible therewith.
  • these additional polymer components include homopolymers or copolymers of monomers such as hydroxyethylmethacrylate, acrylic acid, methacrylic acid, vinyl acetate, vinyl alcohol and vinyl etheralpha-olefins , vinyl chloride, vinylidene chloride, hydroxyethylmethacrylate, acrylic acid, methacrylic acid, vinyl acetate, vinyl alcohol and vinyl ether.
  • the alkylene oxide is poly(ethylene oxide) present in 1 to 15% by weight of the blend.
  • the polymer blends of the invention can be provided in the form of a solid, as well as solvent solutions thereof. Solvent solutions of these polymers can be employed to provide coatings by applying the solution to a substrate followed by evaporation of the solvent. Films or sheets also can be prepared from the polymer blends of the invention.
  • Organic solvent-soluble, thermoplastic polyurethanes constitute a well known family of resins.
  • these polyurethanes are prepared by the reaction of aromatic and/or aliphatic polyisocyanates with polyester and/or polyether polyols, or by reaction of substantially linear, isocyanate-capped urethane prepolymers with polyols of the aforestated type.
  • Useful polyisocyanates for providing these urethanes include but are not limited to cyclohexylene- 1,4-diisocyanate, m-phenylene diisocyanate, 3,3-diphenyl- 4,4-biphenylene diisocyanate, 4,4-biphenylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,5- naphthalene diisocyanate, cumene-2,4-diisocyanate, 2,4- diisocyanatodiphenylether, 5,6-dimethyl-l,3- pheylenediisocyanate, 2,4-dimethyl-l,3-phenylene- diisocyanate, 2,4-dimethyl-l,3-phenylenediisocyanate, 4,4-diisocyanatodiphenylether, 9,10-anthracene diisocyanate, 2,4-diisocyanatotoluene, 1,
  • polyester polyols for reaction with these isocyanates include but are not limited to polyester polyols obtained from the condensation of polycarboxylic acids, preferably dicarboxylic acids such as adipic, sebacic, phthalic, isophthalic, terephthalic, oxalic, malonic, ricinoleic, succinic, maleic, cyclohexane-1,2-dicarboxylic, cyclohexane-1,4- dicarboxylic, polyacrylic, naphthalene-1,2-dicarboxylic, fumaric, itaconic, most preferably ricinoleic and the like with polyalcohols, preferably diols such as ethylene glycol, diethylene glycol, pentaglycol, glycerol, sorbitoi, triethanolamine, di(betahydroxyethyl)ether, and the like, and/or amino-alcohols such as ethanolamine, 3- aminopropanol, 4-a
  • Useful organic solvent-soluble thermoplastic polyurethanes which may be employed with the poly (alkylene oxide) include but are not limited to polyurethanes based on polytetramethylene ether glycol- diphenylmethane diisocyanate, polytetramethylene ether glycol-isoferrone isocyanate, poly(l,4-oxybutylene)glycol diphenylmethane diisocyanate, poly(l,4-oxybutylene)glycol isoferrone isocyanate, polyethylene glycol- diphenylmethane diisocyanate, polyethylene glycol- isoferone isocyanate, polypropylene glycol diphenylmethane diisocyanate, polypropylene glycol- isoferrone isocyanate, polycaprolactone-diphenylmethane diisocyanate, polycaprolactone isoferrone isocyanate, polyethylene adipate diphenylmethane diiso
  • polyurethanes useful in the invention preferably are substantially linear to provide solubility and thermoplasticity
  • they can be crosslinked after blending with the poly(alkylene oxide) component, e.g., by adding a sufficient quantity of crosslinking agent to a solvent solution of the polymers, or by incorporating the crosslinking agent into the melt-blended polymer mixture while the mixture is still in the plastic state.
  • crosslinking agents which can be utilized for this purpose include but are not limited to isocyanates, polycarboxylic acids, peroxide and organotitanates.
  • poly(alkylene oxides) as used herein shall be understood to include homopolymers of poly(ethylene oxide) (“PEO") , and copoly ers of oxides such as (PEO) , poly (propylene oxide) , and the like. Copolymers of the foregoing prepared with minor amounts of, for example, up to 30 weight percent of one or a mixture of other vinyl monomers copolymerizable with the poly (alkylene oxides) , preferably copolymerizable with PEO, are also included.
  • PEO poly(ethylene oxide)
  • copoly ers of oxides such as (PEO) , poly (propylene oxide) , and the like.
  • Copolymers of the foregoing prepared with minor amounts of, for example, up to 30 weight percent of one or a mixture of other vinyl monomers copolymerizable with the poly (alkylene oxides) , preferably copolymerizable with PEO, are also included.
  • the blends of polyurethane and poly (alkylene oxide) of the invention can be provided by conventional melt blending techniques and apparatus, e.g., a two-roll heated mill, helical screw extruder.
  • the polyurethane and poly (alkylene oxide) blends also can be provided by dissolving the poly (alkylene oxide) in a solvent to provide a solution which is added to the urethane.
  • the solvent preferably is capable of dissolving both the urethane and poly (alkylene oxide) components to provide a single-phase solution.
  • Solvents which are suitable for use with poly(alkylene oxides) such as PEO include but are not limited to trichloroethane, methyl ethyl ketone, tetrahydrofuran, toluene, vinyl toluene, benzene, methyl cyclohexanone, methyl propyl ketone, and mixtures thereof. Additional solvents may be added to accelerate drying, reduce solvency toward particular substrates, etc. In each of these alternatives, commercially available PEO having a molecular weight of 100,000- 4,000,000 Daltons may be used. PEO with a molecular weight of 4,000,000 Daltons is especially preferred.
  • the urethane blends of the invention can contain from 1 to 15 weight percent, preferably from 1 to about 10 weight percent of poly (alkylene oxide) .
  • Additional materials which may be incorporated into the polymer blends herein, include but are not limited to organic and inorganic salts, alcohols, amines, acids, polymer latices, resin or wax dispersions, fillers, fibers, cellulosics, surfactants, pigments, dyes, enzymes, proteins, chelates, thickeners, stabilizers, dyes, fragrances, and so forth.
  • blends of the invention are numerous and diverse and include surface coatings, foams, fibers, films, or solid articles which absorb water and impart wettability or a reduced coefficient of friction in aqueous environments.
  • the blends can be combined with and adhered to a virtually unlimited variety of substrates including metal and resin foils, woven and non-woven webs of natural and synthetic fibers, etc.
  • Uses of the materials of the invention therefore include, but are not limited to, coatings for catheters, condoms, invasive devices and test probes which are lubricous only when wet.
  • antifog coatings for lenses, windows, etc. may include antifog coatings for lenses, windows, etc., drag reducing coatings for ships, burn and wound dressings, contact lenses, antistatic coatings, hydrophilic fibers and matrices for controlled release of pharmaceuticals, dyes, fragrances, salts and the like.
  • the blends of this invention also may be employed as carriers for a variety of releasable materials including biologically active substances having curative or therapeutic value for human beings or non- human animals. Included among the biologically active materials which are suitable for incorporation into the blends of the present invention are: hypnotics, sedatives, tranquilizers, anti-convulsants, muscle relaxants, antiparkinson agents, analgesics, antipyretic agents, anti-inflammatory agents, local anesthetics, anti-spasmodics, antiulcer agents, antivirals, antibacterials, antifungals, antimalarials, sympathomimetic agents, cardiovascular agents, diuretics, antiparasitic agents, antitumor agents and hypoglycemic agents, and the like.
  • a silicone rubber tube is dip-coated for 90 seconds in a solution prepared from 2.0 g. of poly(ethylene oxide) of 4,000,000 Daltons molecular weight (Polyox® WSR-301, Union Carbide Corp.) in 48.0 g. of a 50:50 weight percent mixture of tetrahydrofuran and toluene, to which is added with slow agitation 50 g. of a solution of 5.0 g of a linear poly(ether- urethane) (Pellethane® 2363, Dow Chemical Co.), dissolved in 95 g. of a 50:50 weight percent mixture of tetrahydrofuran and toluene.
  • the silicone rubber tubing is dried for one hour at ambient temperature followed by 15 minutes at 60°C. The resulting clear, dried coating on the tubing is smooth and uniform. Upon immersion in a physiological saline solution, the surface of the tubing becomes highly lubricous and remains slippery to the touch after soaking in the saline solution for 48 hours.
  • a vinyl Foley catheter is dip-coated in the resulting solution for 90 seconds, after which the catheter is dried in a circulating air oven for about 8 hours at 50- 60°C.

Abstract

The invention is directed to polymer blends of an organic solvent-soluble, thermoplastic polyurethane and a second polymer component of poly (alkylene oxide). These blends retain slipperiness when exposed for long periods to aqueous environments.

Description

LOW FRICTION. HYDROPHILIC. BIOCOMPATIBLE COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to the field of polymer blends. More particularly, the invention relates to hydrophilic blends of polyurethane and poly (alkylene oxides) , and to use of those blends in a variety of applications including lubricous coating compositions.
BACKGROUND OF THE INVENTION
Lubricous hydrophilic coatings for a variety of uses are described in the prior art. For example, forming a linear polyurethane polymer and then dispersing it in water is well known in the art. See U.S. Pat. Nos. 3,412,054 and 4,094,838 which describe modified, water dispersible urethanes.
Lubricous urethane coated articles for insertion into the human body are described in U.S. Pat. Nos. 4,100,309 and 4,119,094. Articles such as catheters and condoms described in these patents have been obtained by applying polyvinylpyrrolidone polyurethane interpolymer coatings to a substrate.
Polyvinylpyrrolidone ("PVP") is a commercially available hydrophilic compound. However, since PVP is water soluble, it guickly can be leached from coating compositions and other materials formulated therewith by aqueous fluids. The value of urethane compositions containing PVP for use as lubricous coatings therefore is limited due to leaching of PVP into the surrounding aqueous medium.
A need therefore exists for lubricous urethane coating materials which avoid the limitations associated with PVP. SUMMARY OF THE INVENTION
The invention is directed to polymer blends of an organic solvent-soluble, thermoplastic polyurethane and a second component of poly (alkylene oxide) . These blends surprisingly retain slipperiness when exposed for long periods to aqueous environments.
Applicants have discovered that organic solvent-soluble thermoplastic polyurethanes can be blended, or alloyed with polyethylene oxide ("PEO") or other poly alkylene oxides such as polypropylene oxide, either by use of a common solvent or solvent mixture, or by conventional melt blending techniques. The resulting urethanes exhibit highly lubricous properties in aqueous environments, as well as surprising retention of lubricous properties in aqueous environments.
In accordance with the invention, a hydrophilic urethane polymer blend is provided which comprises a first polymer component of an organic solvent-soluble, thermoplastic polyurethane and a second polymer component of hydrophilic poly (alkylene oxide) , preferably poly ethylene oxide ("PEO") . The polyurethane is derived from any of aromatic polyisocyanate or aliphatic polyisocyanate and any of polyether polyol or polyester polyol. The polyurethane can be crosslinked during or subsequent to including the polyurethane in the blend. The polymer blend may contain at least one additional polymer component which is compatible therewith. These additional polymer components include homopolymers or copolymers of monomers such as hydroxyethylmethacrylate, acrylic acid, methacrylic acid, vinyl acetate, vinyl alcohol and vinyl etheralpha-olefins , vinyl chloride, vinylidene chloride, hydroxyethylmethacrylate, acrylic acid, methacrylic acid, vinyl acetate, vinyl alcohol and vinyl ether. Preferably, the alkylene oxide is poly(ethylene oxide) present in 1 to 15% by weight of the blend. Conveniently, the polymer blends of the invention can be provided in the form of a solid, as well as solvent solutions thereof. Solvent solutions of these polymers can be employed to provide coatings by applying the solution to a substrate followed by evaporation of the solvent. Films or sheets also can be prepared from the polymer blends of the invention.
Surprisingly, exposure of the blends of this invention to saline solutions for prolonged periods does not cause the blend of the invention to experience significant loss of lubricous properties.
DETAILED DESCRIPTION OF THE INVENTION
Organic solvent-soluble, thermoplastic polyurethanes constitute a well known family of resins. In general, these polyurethanes are prepared by the reaction of aromatic and/or aliphatic polyisocyanates with polyester and/or polyether polyols, or by reaction of substantially linear, isocyanate-capped urethane prepolymers with polyols of the aforestated type.
Useful polyisocyanates for providing these urethanes include but are not limited to cyclohexylene- 1,4-diisocyanate, m-phenylene diisocyanate, 3,3-diphenyl- 4,4-biphenylene diisocyanate, 4,4-biphenylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,5- naphthalene diisocyanate, cumene-2,4-diisocyanate, 2,4- diisocyanatodiphenylether, 5,6-dimethyl-l,3- pheylenediisocyanate, 2,4-dimethyl-l,3-phenylene- diisocyanate, 2,4-dimethyl-l,3-phenylenediisocyanate, 4,4-diisocyanatodiphenylether, 9,10-anthracene diisocyanate, 2,4-diisocyanatotoluene, 1,4-anthracene diisocyanate, 2,4,6-toluene triisocyanate, 2,4-toluene diisocyanate, isophorone diisocyanate and p,p*,p",- triphenylmethane triisocyanate.
Useful polyester polyols for reaction with these isocyanates include but are not limited to polyester polyols obtained from the condensation of polycarboxylic acids, preferably dicarboxylic acids such as adipic, sebacic, phthalic, isophthalic, terephthalic, oxalic, malonic, ricinoleic, succinic, maleic, cyclohexane-1,2-dicarboxylic, cyclohexane-1,4- dicarboxylic, polyacrylic, naphthalene-1,2-dicarboxylic, fumaric, itaconic, most preferably ricinoleic and the like with polyalcohols, preferably diols such as ethylene glycol, diethylene glycol, pentaglycol, glycerol, sorbitoi, triethanolamine, di(betahydroxyethyl)ether, and the like, and/or amino-alcohols such as ethanolamine, 3- aminopropanol, 4-aminopropenol, 5-aminopentanol- 1,6- aminohexanol, 10-aminodecanol, 6-amino-5-methyl-hexanol- 1, p-hydroxymethylbenzylamine, and the like.
Useful organic solvent-soluble thermoplastic polyurethanes which may be employed with the poly (alkylene oxide) include but are not limited to polyurethanes based on polytetramethylene ether glycol- diphenylmethane diisocyanate, polytetramethylene ether glycol-isoferrone isocyanate, poly(l,4-oxybutylene)glycol diphenylmethane diisocyanate, poly(l,4-oxybutylene)glycol isoferrone isocyanate, polyethylene glycol- diphenylmethane diisocyanate, polyethylene glycol- isoferone isocyanate, polypropylene glycol diphenylmethane diisocyanate, polypropylene glycol- isoferrone isocyanate, polycaprolactone-diphenylmethane diisocyanate, polycaprolactone isoferrone isocyanate, polyethylene adipate diphenylmethane diisocyanate, polyethylene adipate-isophorone isocyanate, polytetramethylene adipate-diphenylmethane diisocyanate, polytetramethylene adipate-isoferrone isocyanate, polyethylene propylene adipate-diphenylmethane diisocyanate, and polyethylene-propylene adipate- isophorone isocyanate.
Although polyurethanes useful in the invention preferably are substantially linear to provide solubility and thermoplasticity, they can be crosslinked after blending with the poly(alkylene oxide) component, e.g., by adding a sufficient quantity of crosslinking agent to a solvent solution of the polymers, or by incorporating the crosslinking agent into the melt-blended polymer mixture while the mixture is still in the plastic state. Examples of crosslinking agents which can be utilized for this purpose include but are not limited to isocyanates, polycarboxylic acids, peroxide and organotitanates.
The term "poly(alkylene oxides)" as used herein shall be understood to include homopolymers of poly(ethylene oxide) ("PEO") , and copoly ers of oxides such as (PEO) , poly (propylene oxide) , and the like. Copolymers of the foregoing prepared with minor amounts of, for example, up to 30 weight percent of one or a mixture of other vinyl monomers copolymerizable with the poly (alkylene oxides) , preferably copolymerizable with PEO, are also included.
The blends of polyurethane and poly (alkylene oxide) of the invention can be provided by conventional melt blending techniques and apparatus, e.g., a two-roll heated mill, helical screw extruder. The polyurethane and poly (alkylene oxide) blends also can be provided by dissolving the poly (alkylene oxide) in a solvent to provide a solution which is added to the urethane. The solvent preferably is capable of dissolving both the urethane and poly (alkylene oxide) components to provide a single-phase solution. Solvents which are suitable for use with poly(alkylene oxides) such as PEO include but are not limited to trichloroethane, methyl ethyl ketone, tetrahydrofuran, toluene, vinyl toluene, benzene, methyl cyclohexanone, methyl propyl ketone, and mixtures thereof. Additional solvents may be added to accelerate drying, reduce solvency toward particular substrates, etc. In each of these alternatives, commercially available PEO having a molecular weight of 100,000- 4,000,000 Daltons may be used. PEO with a molecular weight of 4,000,000 Daltons is especially preferred.
The urethane blends of the invention can contain from 1 to 15 weight percent, preferably from 1 to about 10 weight percent of poly (alkylene oxide) . Additional materials which may be incorporated into the polymer blends herein, include but are not limited to organic and inorganic salts, alcohols, amines, acids, polymer latices, resin or wax dispersions, fillers, fibers, cellulosics, surfactants, pigments, dyes, enzymes, proteins, chelates, thickeners, stabilizers, dyes, fragrances, and so forth.
Applications for the blends of the invention are numerous and diverse and include surface coatings, foams, fibers, films, or solid articles which absorb water and impart wettability or a reduced coefficient of friction in aqueous environments. When the blends are provided in the form of a sheet, film, or coating, the blends can be combined with and adhered to a virtually unlimited variety of substrates including metal and resin foils, woven and non-woven webs of natural and synthetic fibers, etc. Uses of the materials of the invention therefore include, but are not limited to, coatings for catheters, condoms, invasive devices and test probes which are lubricous only when wet. Other uses may include antifog coatings for lenses, windows, etc., drag reducing coatings for ships, burn and wound dressings, contact lenses, antistatic coatings, hydrophilic fibers and matrices for controlled release of pharmaceuticals, dyes, fragrances, salts and the like.
The blends of this invention also may be employed as carriers for a variety of releasable materials including biologically active substances having curative or therapeutic value for human beings or non- human animals. Included among the biologically active materials which are suitable for incorporation into the blends of the present invention are: hypnotics, sedatives, tranquilizers, anti-convulsants, muscle relaxants, antiparkinson agents, analgesics, antipyretic agents, anti-inflammatory agents, local anesthetics, anti-spasmodics, antiulcer agents, antivirals, antibacterials, antifungals, antimalarials, sympathomimetic agents, cardiovascular agents, diuretics, antiparasitic agents, antitumor agents and hypoglycemic agents, and the like.
The following non-limiting examples further illustrate the invention.
Example 1
To a solution of 2.5 g. of poly(ethylene oxide) of 600,000 Daltons molecular weight (Polyox® WSR-205, Union Carbide Corp.) in 47.5 g. of a 50:50 (weight percent) mixture of trichloroethane and methylethyl ketone is added with slow agitation 50 g. of a solution of 4.8 g of 4,4'-diisocyanate diphenylmethane terminated ricinoleate prepolymer (Vorite® 689, CasChem, Inc.) and 5.2 g. of a ricinoleate polyol (Polycin® 936, CasChem, Inc.), dissolved in 90 g. of a 50:50 weight percent mixture of trichlorehane and methylethyl ketone. A vinyl Foley catheter is dip-coated in the resulting solution for 90 seconds. The coated catheter is dried in a circulating air oven for about 8 hours at 50-60°C. The resulting clear, dried coating on the catheter is smooth and uniform. Upon immersion in a physiological saline solution, the surface of the catheter becomes highly lubricous and remains slippery to the touch after soaking in the saline solution for 48 hours.
Example 2
A silicone rubber tube is dip-coated for 90 seconds in a solution prepared from 2.0 g. of poly(ethylene oxide) of 4,000,000 Daltons molecular weight (Polyox® WSR-301, Union Carbide Corp.) in 48.0 g. of a 50:50 weight percent mixture of tetrahydrofuran and toluene, to which is added with slow agitation 50 g. of a solution of 5.0 g of a linear poly(ether- urethane) (Pellethane® 2363, Dow Chemical Co.), dissolved in 95 g. of a 50:50 weight percent mixture of tetrahydrofuran and toluene. The silicone rubber tubing is dried for one hour at ambient temperature followed by 15 minutes at 60°C. The resulting clear, dried coating on the tubing is smooth and uniform. Upon immersion in a physiological saline solution, the surface of the tubing becomes highly lubricous and remains slippery to the touch after soaking in the saline solution for 48 hours.
Example 3
A stainless steel percutaneous cardiovascular follower wire, pretreated with a 5% hydrochloric acid etching solution, is dip-coated for 2-minutes in a solution formed from 3.0 g. of poly(ethylene oxide) of 600,000 Daltons molecular weight (Polyox® WSR-205, Union Carbide Corp.) dissolved in 47.0 g. of a 50:50 weight percent mixture of trichloroethane and methylethyl ketone to which is added with slow agitation 50 g of a solution of 3.8 g of a 4,4 '-diisocyanatodiphenylmethane terminated ricinoleate prepolymer (Vorite® 689, CasChem, Inc.) and 6.2 g. of a ricinoleate polyol (Polycin® 943, CasChem, Inc.), dissolved in 90 g. of a 50:50 weight percent mixture of trichloroethane and methylethylketone. The wire is dried in a circulating air oven for about 8 hours at 50-60°C. The resulting clear, dried coating on the stainless steel wire is smooth and uniform. Upon immersion in a physiological saline solution, the surface of the wire becomes highly lubricous and remains slippery to the touch after soaking in the saline solution for 48 hours. Example 4
To a solution of 2.5 g. of a poly(ethylene-co- propylene oxide) of 600,000 Daltons molecular weight(available from BASF Corp.) in 47.5 g. of a 50:50 (weight percent) mixture of trichloroethane and methylethyl ketone is added with slow agitation 50 g. of a solution of 4.8 g of 4,4 '-diisocyanate diphenylmethane terminated ricinoleate prepolymer (Vorite® 689, CasChem, Inc.) and 5.2 g. of a ricinoleate polyol (Polycin® 936, CasChem, Inc.), dissolved in 90 g. of a 50:50 weight percent mixture of trichlorehane and methylethyl ketone. A vinyl Foley catheter is dip-coated in the resulting solution for 90 seconds, after which the catheter is dried in a circulating air oven for about 8 hours at 50- 60°C.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification, or from practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the scope and spirit of the invention being indicated by the following claims.

Claims

THE CLAIMS What is claimed is:
1. A stable hydrophilic polymer blend comprising a first component of an organic solvent- soluble thermoplastic polyurethane and a second polymer component of a poly(alkylene oxide) .
2. The polymer blend of claim 1 wherein the polyurethane is derived from an aromatic polyisocyanate and a polyether polyol.
3. The polymer blend of claim l wherein the polyurethane is derived from an aliphatic polyiosocyanate and a polyether polyol.
4. The polymer blend of claim 1 wherein the polyurethane is derived from an aromatic polyisocyanate and a polyester polyol.
5. The polymer blend of claim 1 wherein the polyurethane is derived from an aliphatic polyisocyanate and a polyester polyol.
6. The polymer blend of claim 1 containing at least one additional polymer component which is compatible therewith.
7. The polymer blend of claim 7 wherein the additional polymer component is a homopolymer or copolymer of at least one monomer selected from the group of alpha-olefin, vinyl chloride, and vinylidene chloride.
8. The polymer blend of claim 7 wherein the additional polymer component is a homopolymer or copolymer of at least one monomer selected from the group of hydroxyethylmethacrylate, acrylic acid, methacrylic acid, vinyl acetate, vinyl alcohol and vinyl ether.
9. The polymer blend of claim 1 in the form of a solid.
10. The polymer blend of any one of claims 1- 10 wherein said alkylene oxide is poly(ethylene oxide).
11. The polymer blend of claim 10 wherein said poly(ethylene oxide) is present in 1 to 15% by weight of said blend.
12. A solvent solution of the polymer blend of claim 1.
13. A coating obtained from application of the solvent solution of claim 12 to a substrate followed by evaporation of the solvent.
14. A film or sheet prepared from the polymer blend of claim 1.
15. The polymer blend of claim 1 in which the polyurethane component is crosslinked subsequent to fabrication of the blend.
PCT/US1994/009867 1993-08-30 1994-08-29 Low friction, hydrophilic, biocompatible compositions WO1995006670A1 (en)

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AU76428/94A AU7642894A (en) 1993-08-30 1994-08-29 Low friction, hydrophilic, biocompatible compositions

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WO1996039204A1 (en) * 1995-06-03 1996-12-12 Jeremy Watson Lubricious coatings
WO1997029160A1 (en) * 1996-02-09 1997-08-14 Surface Solutions Laboratories, Inc. Water-based hydrophilic coating compositions and articles prepared therefrom
WO2000030696A1 (en) * 1998-11-20 2000-06-02 Coloplast A/S A method for sterilising a medical device having a hydrophilic coating
US6776998B1 (en) * 1998-07-14 2004-08-17 Commonwealth Scientific And Industrial Research Organisation Biocidal packaging system
US6986868B2 (en) 1998-11-20 2006-01-17 Coloplast A/S Method for sterilizing a medical device having a hydrophilic coating
WO2007016182A2 (en) * 2005-07-28 2007-02-08 Cardiac Pacemakers, Inc. Lubricious eluting polymer blend and coating made from the same
WO2008074838A1 (en) * 2006-12-21 2008-06-26 Novartis Ag Process for the coating of biomedical articles
WO2010142502A1 (en) * 2009-06-09 2010-12-16 Huntsman International Llc Materials comprising a matrix and process for preparing them
US9080061B2 (en) 2006-05-03 2015-07-14 Surface Solutions Laboratories Coating resins and coating with multiple crosslink functionalities

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Cited By (23)

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Publication number Priority date Publication date Assignee Title
US6020071A (en) * 1995-06-03 2000-02-01 Jeremy Watson Lubricious coatings
WO1996039204A1 (en) * 1995-06-03 1996-12-12 Jeremy Watson Lubricious coatings
WO1997029160A1 (en) * 1996-02-09 1997-08-14 Surface Solutions Laboratories, Inc. Water-based hydrophilic coating compositions and articles prepared therefrom
US6238799B1 (en) 1996-02-09 2001-05-29 Surface Solutions Laboratories, Inc. Articles prepared from water-based hydrophilic coating compositions
US6866936B2 (en) 1996-02-09 2005-03-15 Surface Solutions Laboratories, Inc. Articles with hydrophilic coating
US6776998B1 (en) * 1998-07-14 2004-08-17 Commonwealth Scientific And Industrial Research Organisation Biocidal packaging system
EP2065061A3 (en) * 1998-11-20 2009-08-26 Coloplast A/S A method for sterilising a medical device having a hydrophilic coating
WO2000030696A1 (en) * 1998-11-20 2000-06-02 Coloplast A/S A method for sterilising a medical device having a hydrophilic coating
EP1252898A2 (en) * 1998-11-20 2002-10-30 Coloplast A/S A method for sterilising a medical device having a hydrophilic coating
EP1252898A3 (en) * 1998-11-20 2003-02-05 Coloplast A/S A method for sterilising a medical device having a hydrophilic coating
US6986868B2 (en) 1998-11-20 2006-01-17 Coloplast A/S Method for sterilizing a medical device having a hydrophilic coating
US9138510B2 (en) 1998-11-20 2015-09-22 Coloplast A/S Sterilized ready-to-use catheter
WO2007016182A2 (en) * 2005-07-28 2007-02-08 Cardiac Pacemakers, Inc. Lubricious eluting polymer blend and coating made from the same
JP2009502345A (en) * 2005-07-28 2009-01-29 カーディアック・ペースメーカーズ・インコーポレーテッド Lubricating eluting polymer blends and coatings made therefrom
EP2172230A3 (en) * 2005-07-28 2012-08-15 Cardiac Pacemakers, Inc. Lubricious eluting polymer blend and coating made from the same
WO2007016182A3 (en) * 2005-07-28 2007-08-02 Cardiac Pacemakers Inc Lubricious eluting polymer blend and coating made from the same
US9080061B2 (en) 2006-05-03 2015-07-14 Surface Solutions Laboratories Coating resins and coating with multiple crosslink functionalities
WO2008074838A1 (en) * 2006-12-21 2008-06-26 Novartis Ag Process for the coating of biomedical articles
JP2010513966A (en) * 2006-12-21 2010-04-30 ノバルティス アーゲー Method for coating biomedical articles
US8158192B2 (en) 2006-12-21 2012-04-17 Novartis Ag Process for the coating of biomedical articles
WO2010142502A1 (en) * 2009-06-09 2010-12-16 Huntsman International Llc Materials comprising a matrix and process for preparing them
CN102482489A (en) * 2009-06-09 2012-05-30 亨茨曼国际有限公司 Materials comprising a matrix and process for preparing them
US9926479B2 (en) 2009-06-09 2018-03-27 Huntsman International Llc Materials comprising a matrix and process for preparing them

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