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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
  • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
  • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
  • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
  • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • 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
  • A61L15/425—Porous materials, e.g. foams or sponges
• • 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• • 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
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

• the present invention relates to hydrophilic polyurethane foams, blends used to prepare these foams, absorptive devices comprising the foams and methods for their preparation.
• hydrophilic polyurethane foams for example as an absorbent material
• hydrophilic polyurethane foams for example as an absorbent material
• hydrophilic polyurethane foams are usually more expensive than the conventional cellulosic absorbent materials used in such devices and have therefore not been extensively used in commercial absorptive devices.
• British Patent No. 1429711 see also United States Patent Nos.
• 3812618, 3812619, 3874694, 3889417, 3928138, 3929574 and 4137200 discloses a hydrophilic polyurethane foam formed by reacting with water an isocyanate capped polyoxyethylene glycol prepolymer.
• British Patent No. 2188055 discloses hydrophilic polyurethane foams formed by reacting with water the reaction product of polyisocyanate which has a functionality of greater than 2 and polyalkylene glycol mono alkyl or alkaryl ether. These prepolymers require to be mixed with only relatively low aaounts of water, thus obviating the need for an elaborate drying stage. The foams are therefore more economical to manufacture than previously known hydropilic foans.
• reaction rates of aliphatic isocyanate based polyurethane foam systems tend to be undesirably slow for commerical use unless high levels of ethylene oxide containing residues are incorporated into the reactive system.
• Such dressings need to be able to absorb aqueous materials such as wound exudate and to be produced quickly and economically to compare favourably with conventional fabric and pad dressings.
• the present invention seeks to provide a polyurethane foam which is hydrophilic and has good dimensional stability when produced in thin flat sheets and which can be produced rapidly and economically.
• the present invention provides a polyurethane hydrophilic foam, suitable for use as first aid dressing which and comprise residues of a aromatic isocyanate, of an aliphatic isocyanate, of a polyoxyalkylene monoether and of a polyoxyalkylene polyol such as a polyether polyol.
• the present invention further provides an absorptive device which comprises a hydrophilic polyurethane foam of the invention.
• the absorptive device of the invention is preferably a medical or hygienic device such as a vound dressing eg. a first aid dressing, sanitary towel, diaper, incontinence pad tampon, or the like.
• the invention provides a process for preparing a hydrophilic polyurethane foam of the invention which comprises blending at least one aromatic based prepolymer with at least one aliphatic based prepolymer. An aqueous phase is then added to effect the foaming reaction and the foam formed is allowed to set.
• a hydrophilic polyurethane foam comprising residues of a first isocyanate prepolymer derived from a polyoxyalkylene mono ether and an aromatic isocyanate containing at least two isocyanate groups and residues of a second isocyanate prepolymer derived from a polyoxyalkylene mono ether and an aliphatic isocyanate containing at least two isocyanate groups and in which at least one of said isocyanate prepolymers contains residues from a polyether polyol.
• the present invention also provides a hydrophilic polyurethane foam formed by blending at least one of said aromatic isocyanate based prepolymers and at least one aliphatic isocyanate based prepolymers and subsequently adding an aqeous phase to catalyse the foaming reaction wherein at least one of the prepolymers is additionally derived from a polyether polyol .
• control over a wider range of processing variables and foam properties can be achieved than was hitherto possible.
• Processing variables which may re controlled more readily than was previously possible include efficiency of mixing and ease of dispensing, cre ⁇ m time, rise time, gel time and cure time.
• Foam properties which may be controlled more readily according to the process of tie invention include softness and resiliency, density, cell size and structure, water content and capacity, linear swell on hydration and rate of wicking.
• foams displaying excellent water uptake, water capacity and strength have been found.
• the foams also possess a lower level of extractables. Furthermore they can be formed into tiin sheets which show excellent conformability.
• the prepolymer blend should contain at least 10w/w% of the solids weight of aliphatic based prepolymer. Similarly it has been fc_nd that the blend should contain at least 10w/w% of the solids weight of aromatic based prepolymer. Aptly the ratio of aromatic isocyanate to aliphatic isocyanate prepolymers will be from 25-75 to 75:25 weight percent. More aptly the ratio of prepolymers will be about 50:50 weight percent.
• the hydrophilic polyurethane foams of the invention can be formed by mixing the blend with a stoichiometric amount of water. It is preferred, however, to mix the blend with a low molar excess of water for example 10% by weight of water. It has been found that this low molar excess of water can be easily absorbed by the hydrophilic foam.
• Suitable polyoxyalkylene mono ethers for preparing the prepolymer components of the blend of the present invention may be polyoxyalkylene monoalkyl or monoalkaryl ethers.
• the mono ethers are polyalkylene glycol monoethers.
• the alkylene moiety of the mono ethers may contain 1 to 4 carbons.
• Preferred polyalkylene glycol mono alkaryl ethers are those in which the alkylene group is ethylene.
• Suitable polyalkylene glycol mono alkaryl ethers include those in which the a-ryl moeity is phenyl.
• Preferred ethers are those in which the alkyl moeity contains from 1 to 20 carbon atoms eg. octyl or nonyl.
• Suitable polyalkylene glycol mono alkyl ethers for forming the reaction product are those in which the alkyl group contains 1 to 20 carbon atoms.
• Alkylene favoured ethers are those in which the alkyl group is a methyl group.
• Another class of preferred polyalkylene glycol mono alkyl ethers are those in which the alkyl group contains 10 to 18 carbon atoms, eg. lauryl or cetyl.
• Preferred polyalkylene glycol mono alkyl ethers are those in which the alkylene group is ethylene.
• the polyalkylene glycol alkyl or alkaryl ether can suitably have an average molecular weight of 180 to 6000.
• Apt ethers are polyethylene glycol mono lauryl ethers having an average molecular weight of approximately 1090 and 360 known as Brij 35 and Brij 30 respectively, available from Honeywell Atlas and polyethylene glycol mono methyl ethers having an average molecular weight of approximately 500 and 5000 known as PEG monomethylether molecular weight 550 and 5000 respectively, available from Aldrich Chemicals.
• Suitable polyethylene glycol mono nonyl phenyl ethers are commercially available under the Trade names Antarox CO-320, Antarox Co-990, available from GAF (Great England) Co. Ltd.
• Apt polyethylene glycol mono nonyl phenyl ethers are Dowafax 9N6 and 9N20 having an average molecular wieght in the range of 400-500 and 1100-1200 respectively and available from K+K Greeft Ltd.
• the ethylene oxide molecular weight can vary in the range 220 to 2200.
• the polyethylene glycol mono alkyl or alkaryl ether used in the invention will normally contain water. It is preferred, however, that the ether contains less than 1% by weight water, to limit the number of urea groups formed in the reaction with the polyisocyanate during the prepolymer formulation.
• the polyether polyol residues present in at least one of the blend prepolymers may be derived from polyhydric alcohols, alkylene polyamines, alkylene amines, cyclic amines, amides and polycarboxylic acids.
• suitable polyols may be derived from hydrophilic reactant ⁇ .
• a particularly suitable hydrophilic reactant is ethylene oxide.
• Preferred polyether polyols are derived from ethylene oxide and aliphatic polyhydric alcohols. Suitable alcohols may have from 2 to £ carbon atoms eg. ethylene glycol, pentaerythritol, procylene glycol, 2,3-butylene glycol, glycerol, 1,5-per.oanediol and the like.
• the polyether polyols may be derived from the polymerisation of ethylene oxide in _____ presence of the above mentioned di- or polyfunctional reactants.
• polyether polyols for the preparation of foams of the present invention are polyether triols.
• Preferred polyether triols are polyoxypropylene (PPG) ether triols, end-capped with polyethylene oxide (PEG).
• PEG polyethylene oxide
• the PEG may comprise 2 to 30w/w% of the polyether triol.
• the PEG comprises 5 to 15w/w% of the rolyether.
• Apt polyoxypropylene ether triols, end-capped with PEG have an average molecular weight of 700 to 7000.
• the PPG ether triols, end capped with PEG will have an average molecular weight in the range of 3000-3500 eg. Arcol 132 available from Arco Chemical Products Europe.
• At least one of the blend prepclymers may further be derived from a copolymer polyether triol derived from the polyether polyols described herein.
• a particularly preferred copolymer polyether is based on PPG and PEG blocks.
• the PEG may be present in the range of 40 to 75w/w of the copoljmer. More suitably the PEG may comprise 45-55w/v%.
• the PEG comprises 45w/w% of the copolymer.
• a preferred copolymer polyether is Voranol CP1421 which has an average molecular weight in the range of 3000-3500 and is supplied by Dow Chemicals Europe.
• the ratio of triol equivalents _o mono ether equivalents may be varied to alter the processing variables and the foam properties. It has been found that suitably the ratio of triol equivalents to mono ether equivalents is in the range of 1.3:1 to 10:1, more suitably from 1:1 to 5:1 and preferably about 3:1.
• the i ⁇ ocyanates used for forming the blend prepolymers will have a functionality of at least 2.
• both the aliphatic aromatic isocyanates will have a functionality of less than about 2.5.
• Suitable aliphatic polyisocyanates for use in the invention include 4 , 4 '-dicyclohexyl nethane di-isocyanate (Desraodur W) which has a functionality of 2.0 and is available from Bayer A.G. and hexamethylene di-isocyanate.
• Suitable aromatic isocyanates for forming the blend prepolymers are polymeric methylene di-isocyanates.
• Polymeric methylene di-isocyanates comprise a mixture of 4,4'-diphenyl methane diisocyanates and one or more of polyaeric homologues.
• Apt polymeric methylene di-isocyanates are known as suprasec VM 10, VM 20 and VM 50 available from ICI and have a functionality of 2.07, 2.13 and 2.49 respectively.
• aromatic isocyanates which may be used include toluene di-isocyanate, methylene-bis-( 4-phenyl isocyanate) , 3,3'-bitolylene-4,4'-di-isocyanate, 1,4-phenylene di-isocyanate, naphthalene-1,5-*-di-isoc ⁇ anate and the like.
• a favoured blend for forming foams of the present invention comprises an aliphatic based prepolymer derived from polyoxyethylene glycol r ⁇ ono-nonyl phenyl ether, a polyoxypropylene ether triol, end-capped with PEG, a copolymer poplyether triol and 4,4'-dicyclohexyl methane di-isocyanate (Desm ⁇ dur W) .
• the blend further comprises an aromatic based prepolymer derived from a polyoxyethylene gylcol mono-nonyl phenyl ether, a polyoxypropylene ether triol, end-capped with PEG and a polymeric methylene di-isocyanate comprising a mixture of , '-diphenyl methane di-isocyanate and one or more polymeric homologues.
• the isocyanate and reactive hydrogen containing compound are present in an amount to ensure that the prepolymers contain an excess of isoycanate groups.
• the isocyanate to hydroxyl ratio (NCO:OH) is at least 2:1.
• the NCO:OH ratio should be less than 6:1.
• the NCO:OH ratio is in the range of 2.7:1 and 4:1.
• the prepolymers employed in the invention contain an excess of isocyanate groups.
• they contain an excess of at least 2 w/w% NCO groups, more suitably upto 12%w/w excess NCO groups.
• the prepolymers contain an excess of 5 tc 7w/w% NCO groups.
• the mono ethers and pclyols will be pre-dried to a water content of less than 1%.
• the blend can be reacted with an aqueous phase to form a hydrophilic polyurethane foam of the invention.
• the hydrophilic polyurethane so formed will normally be a cross-linked hydrophilic polyurethane foam.
• the hydrophilicity of the foam is believed to be dependent on the oxyethylene groups. Varying the weight % of oxyethylene groups in the constituents of the blend, can provide the hydrophilic polyurethane foams of the invention with a wide range of water absorption properties.
• the hydrophilic foam will absorb at least 5% by weight of its weight of water.
• the water absorption of the hydrophilic polyurethane foams aptly range from 25% to 95% by weight of polymer.
• Preferred hydrophilic polyurethane foams of the invention have a water absorption of 50% to 92% by weight of polymer.
• the water absorption of the foam is determined by weighing a 1cm cube of the foam, then immersing the foam in water (at 20°C) for 24 hours, removing excess water by lightly blotting the foam with absorbent paper and then re-weighing the foam cube. The water absorption of the foam (% by weight) can then be calculated as
• the hydrophilic polyurethane foam of the invention will normally be an open cell foam.
• the open cell foam can suitably have a density of 20 to 350 Kg/m 3 and can preferably have a density of 4 to 150Kg/m 3 .
• the hydrophilic polyurethane fo__n can be in a sheet, moulded or particulate form.
• hydrophilic polyurethane foams of the invention can be used in absorptive devices for example as an absorbent component thereof.
• the prepolymer forming reaction may be catalysed.
• Suitable catalysts include Dioctyl tin dilaurate (Metatin 812 ES) ; dioctyl tin mercaptide ester (Metatin 813 and Metatin 713); cibutyl tin dilaurate (T-12); stannous octate (T-rt and Bismuth neodecanoate (Coscat 83).
• the catalysts may be added in the range of 0.5 to O.OOlv/w %.
• the aqueous phase may contain a catalyst to increase the rate of reaction.
• a suitable amount of water required to be added to the prepolymer blend can be the stoichiometric amount of water needed to react with the NCO groups in the prepolymers. It is preferred, however, in order to obtain a homogenous mixture of water and prepolymers to use up to 12. eg. 4 to 10% by weight of water and preferably 5% by veight water in the process.
• a suitable catalyst for the reaction is an alkali metal carbonate such as potassium carbonate which can be present in amounts of 0.5 to 1.5% by weight of the blend.
• water or an aqueous solution will normally be provided in liquid form which is mixed and reacted with the prepolymer blend.
• the water in the process can also be provided by a material such as a metal salt hydrate which releases water in liquid or vapour form when heated.
• Suitable metal hydrates for use in the invention include Na,B 4 0 7 .10H 2 0, Na 2 S0 4 .10H 2 0, Na 2 Si0 3 .9H 2 0 and MgS0 4 .7H 2 0 which is preferred.
• the metal salt hydrate which is preferably in particulate form is mixed into the prepolymer blend. The mixture can then be heated to a suitable temperature to release the water for reaction with the prepolymer blend.
• the foam can be formed into a sheet or a desired shape by casting the foaming mixture into a release carrier or into a shaped mould and allowing the mixture to rise and set.
• the foams produced by the process of the invention can then be incorporated into absorptive devices using conventional methods.
• the hydrophilic foams of the present invention may be used in the preparation of first aid dressings since they can be used to form thin flexible and conformable sheets which are ideally suited for making such dressings.
• the polyurethane foam composition of the invention may cast into first aid dressings, for example as disclosed in WO91/01706 and WO91/01707.
• first aid dressings for example as disclosed in WO91/01706 and WO91/01707.
• dressings may be cast to thicknesses of 0.5 to 20mm, more aptly from 0.75 to 4mm.
• PPG Polyoxypropylene
• PEG polyethylene oxide
• Copolymer polyether triol (Voranol CP 1421) 1 equiv.
• Tin catalyst 0.01 w/w%
• the aliphatic prepolymer is synthesised by first heating the triols and mono ether in an oven at 60°C to melt them. The melted triols and monc ether are then added to a 700ml flange flask followed by the di-isocyanate. The flask is fitted with an air-driven anchor stirrer, a lid, a dry nitrogen blanket and placed in a water bath at 60 ⁇ C. The components are stirred vigourously until homogenous. The tin catlayst is added via a dipo ⁇ able syringe, while the contents of the flask are being stirred continuously. The water bath is adjusted to 90°C and the reaction is allowed to continue for 60 minutes until completion, as indicated by the subsiding exotherm. After completion, the prepolymer is poured while still warm into an air-tight jar.
• the aromatic prepolymer is formed by following the same steps as indicated above for preparation of the aliphatic prepolymer, except that after adjusting the water bath to 90 ⁇ C, the reaction is allowed to proceed for 30 rather than 60 minutes.
• the aliphatic and aromatic prepolymers are then blended. When a homogenous prepolymer blend is obtained the aqueous phase is added to effect foaming.
• the foam formed possesses all the properties discussed above which render it ideally suited for use in absorptive devices, particularly first-aid dressings.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Epidemiology (AREA)
• Materials Engineering (AREA)
• Hematology (AREA)
• Dispersion Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 1991
  • 1991-08-20 GB GB919117913A patent/GB9117913D0/en active Pending
• 1992
  • 1992-08-19 GB GB9400982A patent/GB2273296B/en not_active Expired - Fee Related
  • 1992-08-19 ZA ZA926233A patent/ZA926233B/xx unknown
  • 1992-08-19 AU AU24404/92A patent/AU656997B2/en not_active Ceased
  • 1992-08-19 EP EP92917631A patent/EP0599932A1/en not_active Withdrawn
  • 1992-08-19 WO PCT/GB1992/001527 patent/WO1993004101A1/en not_active Application Discontinuation
  • 1992-08-19 CA CA002114411A patent/CA2114411A1/en not_active Abandoned
  • 1992-08-19 JP JP5504197A patent/JPH06510312A/ja active Pending
  • 1992-08-20 MX MX9204833A patent/MX9204833A/es not_active Application Discontinuation

Non-Patent Citations (1)

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