WO2022073835A1 - Procédé de production de mousses ou d'hydrogels de polyuréthane à l'aide d'allongeurs de chaîne amine - Google Patents

Procédé de production de mousses ou d'hydrogels de polyuréthane à l'aide d'allongeurs de chaîne amine Download PDF

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WO2022073835A1
WO2022073835A1 PCT/EP2021/076899 EP2021076899W WO2022073835A1 WO 2022073835 A1 WO2022073835 A1 WO 2022073835A1 EP 2021076899 W EP2021076899 W EP 2021076899W WO 2022073835 A1 WO2022073835 A1 WO 2022073835A1
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weight
optionally
isocyanate
components
mol
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PCT/EP2021/076899
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Jim Thompson
Jan SUETTERLIN
Marc-Stephan Weiser
Sascha Plug
Rafael METHLING
Sebastian Doerr
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Covestro Deutschland Ag
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
    • 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
    • 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
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • 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
    • 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
    • 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
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • 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
    • C08G2110/0091—Aerogels; Xerogels

Definitions

  • compositions comprising A) isocyanate-functional prepolymers obtainable by the reaction of Al) low molecular weight diisocyanates of molar mass from 140 to 278 g/mol, with A2) polyalkylene oxides having an OH functionality of two or more and optionally A3) further isocyanate-reactive components differing from A2); B) water in an amount of at least 2% by weight, based on the total weight of the composition; C) optionally polyisocyanates composed of at least two low molecular weight, aliphatic diisocyanates; D) optionally catalysts: E) optionally salts of weak acids, the corresponding free acids of which have a pKA in water at 25°C of > 3.0 and ⁇ 14.0; F) optionally surfactants; G) optionally mono- or polyhydric alcohols or polyols; H) optionally hydrophilic polyisocyanates; I) a) isocyanate-functional prepolymers obtainable by the reaction of Al) low molecular weight
  • Water absorbing polyurethanes are useful for many applications such as foam or hydrogel based wound dressings, incontinence pads or hydrogel contact lenses.
  • Foams are highly porous materials with low density. In the case of wound dressing foams, densities are often around 100 g/L. With increasing density the material may be called a porous hydrogel until it is a pure and compact hydrogel without any visible pores. There is no sharp boundary between the two extremes.
  • foams and hydrogels important mechanical properties, such as tensile strength at break, drastically decline upon swelling of the foams or hydrogels when coming into contact with fluids.
  • water absorbing polyurethanes in the form of foams or hydrogels that retain high wet-tensile-strength-at-break (oB.wet) despite good water absorption are desirable.
  • dividing OB.wet by density (D) delivers a value that accounts for density differences and therefore normalizes the value of wet-tensile-strength-at-break (oB.wet) with respect to the density.
  • oB.wet wet-tensile-strength-at-break
  • Foams with good wet-tensile-strength-at-break are already known.
  • a foam from prepolymer example 4 of US2006142529 was synthesized (comparative example 1 in this document) and used to obtain a foam with an excellent (oB,wet/D)-S 2 value of 0.61.
  • all foams in US2006142529 were synthesized from prepolymers that were not distilled after synthesis, hence, containing more than at least 8% residual diisocyanate. Due to the low vapor pressure of diisocyanate monomers foam or hydrogel manufacturers require an exhaustion system for safe manufacturing of foams and hydrogels.
  • An aim that has not been achieved to date in the production of polyurethane foams or hydrogels, especially in the use thereof in medical applications, is to provide an efficient process and allows for a cost efficient processability leading to a foam with good and almost unchanged properties both in dry and in wet state.
  • compositions for the production of foams that allow the manufacturing of foams or hydrogels that provide high water absorption and/or high wet-tensile- strength-at-break (oB.wet), especially high values of (oB,wet/D)-S 2 .
  • One aim of the present invention was that of at least partly overcoming at least one disadvantage of the prior art. Furthermore, it was a goal to find favourable prepolymers that are easily pumpable and show good properties when mixed with components comprising water.
  • a further goal of the invention was to provide foams with good wet strength performance as indicated by (oB,wet/D)-S 2 values of at least 0.30, especially together with the properties and production features as mentioned above.
  • the invention firstly relates to a process for producing polyurethane foams or hydrogels, in which compositions comprising
  • polyalkylene oxides having an OH functionality of two or more, preferably within a range from 2 to 6, preferably within a range from 2 to 5, or preferably 2 to 4,
  • A3) optionally further isocyanate-reactive components differing from A2) ;
  • G optionally mono- or polyhydric alcohols or polyols;
  • Hl low molecular weight diisocyanates of molar mass from 140 to 278 g/mol and/or polyisocyanates preparable therefrom and having an average isocyanate functionality of 2 to 6 with
  • a polyamine with at least two amine groups or two ammonium groups, preferably a diamine; are provided, eventually foamed and cured, wherein the ratio of amine groups stemming from component I) to isocyanate groups of all components A) to I) is in a range of 0.1 to 1.2 wherein the isocyanate containing components, especially components A), C) and H), do not exceed a residual diisocyanate content of 8% by weight, based on the total weight of the polyurethane foam or hydrogel.
  • the prepolymers A) have a residual monomer content of below 1% by weight, preferably below 0.8% by weight, more preferably below 0.75% by weight, especially preferably below 0.5% by weight, based on the total weight of the prepolymer.
  • the components A), C) and H) have a residual diisocyanate content of below 5% by weight, more preferably below 3% by weight, especially preferably below 2% by weight, even more preferably below 0.5% by weight, most preferably below 0.1% by weight, based on the total weight of the components A), C) and H).
  • the residual diisocyanate content according to the invention means the content of diisocyanates which have a molar mass from 140 to 278 g/mol.
  • the amounts of polyalkylene oxides A2), the optionally further isocyanate-reactive components, differing from A2), A3), and the low molecular weight, preferably aliphatic diisocyanates Al) are preferably adjusted such that, for every 1 mol of OH groups of the combined components A2) and A3), there are provided 1.1 to 20 mol, preferably 1.5 to 10 mol and more preferably 2 to 5 mol of NCO groups of the low molecular weight, preferably aliphatic diisocyanate Al).
  • the amounts of polyalkylene oxides A2), the optionally further isocyanate-reactive components A3) and the low molecular weight, preferably aliphatic diisocyanates Al) are preferably adjusted such that, for every 1 mol of isocyanate reactive groups of the combined components A2) and A3), there are provided 1.1 to 20 mol, preferably 1.5 to 10 mol and more preferably 2 to 5 mol of NCO groups of the low molecular weight, preferably aliphatic diisocyanate Al).
  • the reaction can be effected in the presence of urethanization catalysts such as tin compounds, zinc compounds, amines, guanidines or amidines, or in the presence of allophanatization catalysts such as zinc compounds.
  • urethanization catalysts such as tin compounds, zinc compounds, amines, guanidines or amidines
  • allophanatization catalysts such as zinc compounds.
  • catalysts as mentioned later as representative of component D) may also be present when reacting components Al) to A3) to receive the prepolymer Al). However, it is preferred not to use a catalyst when reacting component Al) to A3).
  • the reaction is typically performed at 25°C to 140°C, preferably 60°C to 100°C.
  • excess isocyanate preferably the excess of low molecular weight, preferably aliphatic diisocyanate is then removed, preferably by thin-fdm distillation using a thin-fdm evaporator.
  • acidic or alkylating stabilizers such as benzoyl chloride, isophthaloyl chloride, methyl tosylate, chloropropionic acid, HC1, dibutyl phosphate or antioxidants such as di-tert-butylcresol or tocopherol.
  • the NCO content of the isocyanate-functional prepolymers A) is 1.5% to 8% by weight.
  • Examples of low molecular weight, aliphatic diisocyanates of component Al) are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), pentamethylene diisocyanate (PDI), bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylene diisocyanate, bisisocyanatomethylcyclohexane, bisisocyanatomethyltricyclodecane, xylene diisocyanate, tetramethylxylylene diisocyanate, norbomane diisocyanate, cyclohexane diisocyanate or diisocyanatododecane, preference being given to hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), pentamethylene diisocyanate (
  • aromatic diisocyanates are used as component Al), these are preferably toluene 2,4-diisocyanate (2,4- TDI), toluene 2,6-diisocyanate (2,6-TDI) or 2,2 ’-methylene diphenyl diisocyanate (2,2’-MDI), 2.4'- methylene diphenyl diisocyanate (2,4’-MDI), 4,4 ’-methylene diphenyl diisocyanate (4,4’-MDI), or mixtures of at least two of these.
  • Polyalkylene oxides of component A2) may be any polyalkylene oxides that the person skilled in the art would use for the purpose.
  • Polyalkylene oxides of component A2) are preferably copolymers of ethylene oxide and propylene oxide having an oxyethylene unit content, based on the total amount of the oxyalkylene groups present, of 50 to 100 mol%, preferably 60 to 90 mol%, started from polyols or amines.
  • Preferred starters of this kind are selected from the group consisting of ethylene glycol, propane-1, 3-diol, propane-1,2 diol (propylene glycol), dipropylene glycol, butane- 1,4-diol, glycerol, trimethylolpropane (TMP), sorbitol, pentaerythritol, triethanolamine, ammonia and ethylenediamine, or a mixture of at least two of these.
  • the polyalkylene oxides of component A2) typically have number-average molecular weights of 250 to 10 000 g/mol, preferably of 300 to 2800 g/mol, more preferably 350 to 1500 g/mol.
  • polyalkylene oxides of component A2) have OH functionalities of 2 to 6, preferably of 2 to 5, more preferably of 2 to 4.
  • component A3) is a polyol. More preferably, A3) is a diol.
  • A3) is linear, especially a linear diol.
  • component A3) is selected from the group consisting of 1,2-ethandiol, 2-(2-hydroxyethoxy)ethan-l-ol, 1,2 propanediol, 1,3 propanediol, 1,2 butanediol, 1,3 butanediol, 1,4 butanediol, 1,2 pentanediol, 1,3 pentanediol, 1,4 pentanediol, 1,5 pentanediol, 1,2 hexanediol, 1,3 hexanediol, 1,4 hexanediol, 1,5 hexanediol, 1,6 hexanediol, 1,2 heptanediol, 1,3 heptanediol, 1,4 heptanediol, 1,5 heptanediol, 1,6 hexaned
  • A3) is selected from the group consisting of 1,2-ethandiol, 2- (2-hydroxyethoxy)ethan-l-ol, 1,3 propanediol, 1,4 butanediol, 1,6 hexanediol, 1,8 octanediol, 1,10 decanediol, 1,12 dodecanediol or mixtures of at least two thereof.
  • mono- and polyhydric alcohols or mono- and polyfunctional amines that are known per se to the person skilled in the art, and mixtures thereof.
  • mono- or polyhydric alcohols or polyols that are different to those of the component A2), such as ethanol, propanol, butanol, decanol, tridecanol, hexadecanol, ethylene glycol, neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, monofunctional polyether alcohols and polyester alcohols, polyetherdiols and polyesterdiols or mixtures of at least two of these.
  • mono- or polyfunctional amines include butylamine, ethylenediamine or amine-terminated polyalkylene glycols (e.g. Jeffamine®).
  • Water as component B) is employed in at least 2% by weight, preferably of at least 5% by weight, or preferably of at least 10% by weight, or preferably within a range from 2% to 40% by weight, or preferably within a range from 5% to 30% by weight, or preferably within a range from 10% to 25% by weight, based on the total weight of the composition.
  • any compounds of component C) that are optionally to be used are polyisocyanates obtainable by reaction of low molecular weight diisocyanates having amolar mass of 140 to 278 g/mol, such as biurets, oxadiazinetrione, allophanates, isocyanurates, iminooxadiazinediones or uretdiones of the aforementioned low molecular weight diisocyanates. Preference is given to using preferably aliphatic diisocyanates for component C).
  • the 4-membered or 6-membered ring oligomers of low molecular weight diisocyanates have a functionality within a range from 2 to 6, or preferably within a range from 2.1 to 5.5, or preferably within a range from 2.5 to 5.
  • the component C) has a residual diisocyanate content of below 1% by weight, preferably below 0.8% by weight, more preferably below 0.75% by weight, especially preferably below 0.5% by weight, based on the total weight of the component C).
  • Examples of low molecular weight, aliphatic diisocyanates of component C) are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), pentamethylene diisocyanate (PDI), bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylene diisocyanate, bisisocyanatomethylcyclohexane, bisisocyanatomethyltricyclodecane, xylene diisocyanate, tetramethylxylylene diisocyanate, norbomane diisocyanate, cyclohexane diisocyanate or diisocyanatododecane, preference being given to hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), pentamethylene diisocyanate (
  • aromatic polyisocyanates are used as component C), these are preferably toluene 2,4-diisocyanate (2,4-TDI), toluene 2,6-diisocyanate (2,6-TDI) or 2,2’-methylene diphenyl diisocyanate (2,2’-MDI), 2,4 ’-methylene diphenyl diisocyanate (2,4 ’-MDI), 4,4 ’-methylene diphenyl diisocyanate (4,4 ’-MDI), or mixtures of at least two of these.
  • the content of isocyanate groups elevated by the use of component C) ensures better foaming since more CO2 is formed in the isocyanate-water reaction.
  • catalysts can be used in component D). These are typically the compounds known to the person skilled in the art from polyurethane technology. Preference is given here to compounds from the group consisting of catalytically active metal salts, amines, amidines and guanidines.
  • Examples include dibutyltin dilaurate (DBTL), tin acetate, 1,8- diazabicyclo[5.4.0]undecene-7 (DBU), l,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4- diazabicyclo[3.3.0]octene-4 (DBO), N-ethylmorpholine (NEM), triethylenediamine (DABCO), pentamethylguanidine (PMG), tetramethylguanidine (TMG), cyclotetramethylguanidine (TMGC), n- decyltetramethylguanidine (TMGD), n-dodecyltetramethylguanidine (TMGDO), dimethylaminoethyltetramethylguanidine (TMGN), 1,1,4,4,5,5-hexamethylisobiguanidine (HMIB), phenyltetramethylguanidine (TMGP) and hexamethylene
  • amines Preference is given to the use of amines, amidines, guanidines or mixtures thereof as catalysts of component D).
  • DBU l,8-diazabicyclo[5.4.0]undecene-7
  • DBN l,5-diazabicyclo[4.3.0]nonene-5
  • DABCO triethylenediamine
  • salts of weak acids the corresponding free acids of which have a pKA in water at 25°C of > 3.0 and ⁇ 14.0.
  • suitable salts of weak acids are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and sodium hydrogencarbonate, sodium acetate, potassium acetate, sodium citrate, potassium citrate, sodium benzoate, potassium benzoate, also including any desired mixtures of these salts. It is preferable when the salts of weak acids are selected from the group of sodium hydroxide, sodium hydrogencarbonate and sodium carbonate. In this case, the result is a particularly short reaction time.
  • compounds of component F may be used, where such additives may in principle be any of the anionic, cationic, amphoteric and nonionic surfactants that are known per se, and mixtures of these.
  • additives may in principle be any of the anionic, cationic, amphoteric and nonionic surfactants that are known per se, and mixtures of these.
  • EO/PO block copolymers Preference is given to using solly the EO/PO block copolymers as component F).
  • compounds of component G may be used.
  • These are in principle all the mono- and polyhydric alcohols that are known per se to the person skilled in the art, and mixtures of these.
  • mono- or polyhydric alcohols or polyols such as ethanol, propanol, butanol, decanol, tridecanol, hexadecanol, ethylene glycol, neopentyl glycol, butanediol, hexanediol, decanediol, trimethylolpropane, glycerol, pentaerythritol, monofunctional polyether alcohols and polyester alcohols, polyetherdiols and polyesterdiols or mixtures of at least two of these.
  • the ratio of the monohydroxyfunctional polyalkylene oxides H2) to the low molecular weight diisocyanates Hl) is typically adjusted such that, for every 1 mol of OH groups of the monohydroxyfunctional polyalkylene oxides, there are 1.25 to 20 mol, preferably 2 to 15 mol and more preferably 5 to 13 mol of NCO groups of the low molecular weight diisocyanate Hl). This is followed by allophanatization or biuretization and/or isocyanurate formation or uretdione formation. If the polyalkylene oxides H2) are bonded to the preferably aliphatic diisocyanates Hl) via urethane groups, allophanatization preferably takes place thereafter. It is further preferable that isocyanate structural units are formed.
  • a preferred alternative preparation of the hydrophilic polyisocyanates H) is typically effected by reaction of 1 mol of OH groups of the monohydroxyfunctional polyalkylene oxide component H2) with 1.25 to 20 mol, preferably with 2 to 15 mol and more preferably 5 to 13 mol of NCO groups of a polyisocyanate Hl) having an isocyanate functionality of 2 to 6, based on aliphatic or aromatic diisocyanates, preferably aliphatic diisocyanates.
  • Examples of such polyisocyanates Hl) are biuret structures, isocyanurates or uretdiones based on preferably aliphatic diisocyanates.
  • the polyisocyanate Hl) and the polyalkylene oxide H2) are preferably joined to one another via a urethane group or a urea group, preference being given particularly to linkage via urethane groups.
  • the component H) has a residual diisocyanate content of below 1% by weight, preferably below 0.8% by weight, more preferably below 0.75% by weight, especially preferably below 0.5% by weight, based on the total weight of the component H).
  • the polyamine preferably the diamine of component I) can be any polyamine that the person skilled in the art would select for the process to form a foam or hydrogel.
  • the polyamine of component I) comprises secondary or primary amine groups or both, more preferably solely primary amine groups.
  • the polyamine is able to react with an NCO-group by building a urea group.
  • the amine groups are terminally positioned.
  • the polyamine has a molecular weight in a range of from 50 to 400 g/mol, more preferably in a range of from 60 to 300 g/mol.
  • the backbone of the diamine is a hydrocarbon chain without hetero atoms.
  • the backbone of the polyamine is a linear hydrocarbon chain.
  • a linear hydrocarbon chain, according to the invention is an unbranched alkylene-group.
  • the polyamine is linear and comprises secondary amine groups. More preferably, the polyamine is linear and comprises primary amine groups.
  • the polyamine is a diamine which is linear and comprises secondary amine groups. More preferably, the polyamine is a diamine which is linear and comprises primary amine groups
  • the polyamine has at least two ammonium groups.
  • the polyamine is provided at least partially in the form of an ammonium salt like ammoniumformate or ammoniumhydrogencarbonate, more preferably as an ammoniumhydrogencarbonate.
  • the component I) is preferably selected from the group consisting of a diamine or a triamine or both.
  • a triamine are diethylenetriamine and dipropylenetriamine.
  • the component I) preferably comprises a diamine which is selected from the group consisting of 1,2- ethane diamine 1,3-propane diamine, 1,4- butane diamine, 1,5-pentamethylenediamine, 1,6- hexamethylenediamine, 1,7-heptamethylenediamine, 1,8 -octamethylenediamine, 1,10- decamethylenediamine, 1, 12-dodecamethylenediamine or a mixture of at least two thereof.
  • a diamine which is selected from the group consisting of 1,2- ethane diamine 1,3-propane diamine, 1,4- butane diamine, 1,5-pentamethylenediamine, 1,6- hexamethylenediamine, 1,7-heptamethylenediamine, 1,8 -octamethylenediamine, 1,10- decamethylenediamine, 1, 12-dodecamethylenediamine or a mixture of at least two thereof.
  • component I) comprises an aliphatic polyamine, preferably an aliphatic diamine, more preferably a linear aliphatic diamine as the polyamine I).
  • the diamine is selected from the group consisting of 1,3-butane diamine, 1,4- propane diamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8- octamethylenediamine, 1,10-decamethylendiamine, 1,12-dodecamethylendiamine or a mixture of at least two thereof.
  • the polyamine I) is provided as ammonium salt, more preferably as ammoniumhydrogencarbonate .
  • the component I) comprises the polyamine as ammonium salt, preferably as ammoniumhydrogencarbonate or ammoniumformate, more preferably as ammonium salt of 1,6- hexamethylenediamine, especially preferably as hexane- 1,6-diammonium hydrogencarbonate.
  • the hydrogenecarbonate is used as the anion of the ammoniumhydrogencarbonate.
  • the ammoniumhydrogencarbonate salt can be formed by the addition of carbon dioxide, for example in the form of dry ice either as solid or fluid, to an aqueous solution of the polyamine.
  • the ammonium salt is in equilibrium with a small amount of the un-protonated amine of the polyamine I).
  • un-protonated amine of the component I) with at least component A
  • C) and H new un-protonated amine is reformed from the rest ammonium salt.
  • Carbondioxide evolves as gas during this process.
  • the isocyanate-containing components especially components A), C) and H), have a total isocyanate content within a range from 2% to 12% by weight, more preferably in a range from 2% to 10% by weight, even more preferably in a range from 2% to 8% by weight, based on the total amount of the isocyanate-containing components.
  • the isocyanate-containing components, especially components A), C) and H) have a content of urethane groups of 1.0 to 3.5 mol/kg, based on the total amount of the isocyanate-containing components.
  • the isocyanate-containing components, especially components A), C) and H) have a total isocyanate content within a range from 3% to 7% by weight or preferably within a range from 4% to 6.5% by weight, and preferably a content of urethane groups within a range from 1.5 to 3.0 mol/kg, or preferably within a range from 1.7 to 2.8 mol/kg, based in each case on the total amount of the isocyanate-containing components.
  • linear diisocyanates Preference is given to using linear diisocyanates in the production of polyurethane foams or hydrogels of the invention. More particularly, preference is given to using exclusively linear diisocyanates for components Al), C) and Hl).
  • the reaction can be effected in the presence of urethanization catalysts such as tin compounds, zinc compounds, amines, guanidines or amidines, or in the presence of allophanatization catalysts such as zinc compounds.
  • urethanization catalysts such as tin compounds, zinc compounds, amines, guanidines or amidines
  • allophanatization catalysts such as zinc compounds.
  • the reaction is typically performed at 25°C to 140°C, preferably at 60°C to 100°C.
  • the excess of low molecular weight, preferably aliphatic diisocyanate is then removed, preferably by thin-fdm distillation.
  • acidic or alkylating stabilizers such as benzoyl chloride, isophthaloyl chloride, methyl tosylate, chloropropionic acid, HC1 or antioxidants such as di-tert-butylcresol or tocopherol.
  • the NCO content of the hydrophilic polyisocyanates H) is preferably 0.3% to 23% by weight, more preferably 2% to 21% by weight and most preferably 3% to 18% by weight.
  • Examples of low molecular weight, aliphatic diisocyanates of component Hl) are hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), pentamethylene diisocyanate (PDI), bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylene diisocyanate, bisisocyanatomethylcyclohexane, bisisocyanatomethyltricyclodecane, xylene diisocyanate, tetramethylxylylene diisocyanate, norbomane diisocyanate, cyclohexane diisocyanate or diisocyanatododecane, preference being given to hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), butylene diisocyanate (BDI), pentamethylene diisocyanate
  • aromatic diisocyanates are used as component Hl), these are preferably toluene 2,4-diisocyanate (2,4- TDI), toluene 2,6-diisocyanate (2,6-TDI) or 2,2 ’-methylene diphenyl diisocyanate (2,2’-MDI), 2.4'- methylene diphenyl diisocyanate (2,4’-MDI), 4,4 ’-methylene diphenyl diisocyanate (4,4’-MDI), or mixtures of at least two of these.
  • polyisocyanates H2 examples are polyisocyanates having an average isocyanate functionality of 2 to 6 with isocyanurate, urethane, allophanate, biuret, iminooxadiazinetrione, oxadiazinetrione and/or uretdione groups, based on the preferably aliphatic and/or cycloaliphatic diisocyanates mentioned in the paragraph above.
  • Components H2) used are preferably higher molecular weight compounds with biuret, iminooxadiazinedione, isocyanurate and/or uretdione groups, based on hexamethylene diisocyanate, isophorone diisocyanate and/or 4,4'-diisocyanatodicyclohexylmethane. Preference is further given to isocyanurates. Very particular preference is given to structures based on hexamethylene diisocyanate.
  • the monohydroxyfunctional polyalkylene oxides H2) have an OH number of 15 to 250, preferably of 28 to 112, and an oxyethylene unit content of 50 to 100 mol%, preferably of 60 to 100 mol%, based on the total amount of the oxyalkylene groups present.
  • Monohydroxyfunctional polyalkylene oxides in the context of the invention are understood to mean compounds that have only one isocyanate-reactive group, i.e. one group that can react with an NCO group.
  • Suitable starter molecules are especially saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n- butanol, isobutanol, sec-butanol, diethylene glycol monobutyl ether, and aromatic alcohols such as phenol or monoamines such as diethylamine.
  • Preferred starter molecules are saturated monoalcohols of the aforementioned type. Particular preference is given to using diethylene glycol monobutyl ether or n- butanol as starter molecules.
  • the monohydroxyfunctional polyalkylene oxides H2) typically have number-average molecular weights of 220 to 3700 g/mol, preferably of 250 to 2800 g/mol, or preferably of 300 to 2000 g/mol.
  • the monohydroxyfunctional polyalkylene oxides H2) preferably have an OH group as isocyanatereactive group.
  • components A) to I) are used in the following amounts:
  • hydrophilic polyisocyanate component H) polyamine I) in an amount wherein the ratio of amine groups stemming from component I) to isocyanate groups of all components A) to I) is in a range of 0.1 to 1.2.
  • components A) to I) are used in the following amounts:
  • components A) to I) are used in the following amounts:
  • the NCO content of the isocyanate- functional prepolymers A) is 1.5% to 8% by weight, more preferably 2% to 7.5% by weight and most preferably 3% to 7% by weight.
  • prepolymer A) has a proportion by weight of low molecular weight diisocyanates having a molar mass of 140 to 278 g/mol of below 1.0% by weight, preferably of below 0.5% by weight, preferably of below 0.3% by weight, or preferably of below 0.1% by weight, based on the Prepolymer A).
  • the proportion by weight of low molecular weight diisocyanates is preferably adjusted via distillation.
  • aliphatic isocyanates are used as component Al), more preferably exclusively aliphatic isocyanates.
  • Examples of aliphatic isocyanates have already been mentioned above.
  • Preferred aliphatic isocyanates are HDI or IPDI or mixtures thereof, especially preferred HDI.
  • linear diisocyanates in the production of polyurethane foams or hydrogels are used. More particularly, preference is given to using exclusively linear diisocyanates for components Al), C) and Hl).
  • the isocyanate-functional prepolymer A has a viscosity a viscosity at RT/ 23°C/ 25°C, determined according to DIN 53019 of ⁇ 50 000 mPas, preferably of ⁇ 25 000 mPas, or preferably of ⁇ 10 000 mPas, or preferably within a range from 100 to 20 000 mPas.
  • the components A), C) and H) have a residual diisocyanate content of below 5% by weight, preferably below 3% by weight, more preferably below 2% by weight, especially preferably below 0.5% by weight, most preferably below 0. 1% by weight based on the total weight of the components A), C) and H).
  • a residual diisocyanate content of below 5% by weight, preferably below 3% by weight, more preferably below 2% by weight, especially preferably below 0.5% by weight, most preferably below 0. 1% by weight based on the total weight of the components A), C) and H).
  • component B) with all other components, especially D), E), F) G) and I), apart from the prepolymer mixture,
  • the temperature in at least one of steps I), to IV). is chosen within a range from 2 to 70°C, or preferably within a range from 10 to 50°C, or preferably from 20 to 40°C.
  • components B), D), E), F), G) and I) may be provided separately or in any combination and order to the mixture of step II). or III).
  • the mixture, after step IV). is applied to a substrate and allowed to cure.
  • the curing is preferably conducted at a temperature within a range from 20 to 50°C. With the aid of convection ovens or infrared dryers, the curing and simultaneous drying can also be conducted in higher temperature ranges, for example between 50 and 200°C.
  • the polyurethane foams or hydrogels according to the invention are preferably produced by mixing components A), produced from components Al), A2) and optionally A3) and optionally D), optionally with C) and/or H), in any sequence, and then with a mixture of B) and I) and optionally D), E), F), G), foaming the mixture and curing, preferably by chemical crosslinking.
  • components A), C) and H) are pre-mixed with one another.
  • Any salts E) to be used and any surfactants F) are preferably added to the reaction mixture in the form of their aqueous solutions, preferably together with component B).
  • the foaming can in principle be effected by means of the carbon dioxide formed in the reaction of the isocyanate groups with water, but the use of other blowing agents is likewise possible.
  • blowing agents from the class of the hydrocarbons such as C3-C6- alkanes, e.g. butanes, w-pentane, /.so-pcntanc. cyc/o-pcntanc.
  • halogenated hydrocarbons such as dichloromethane, dichloromonofluoromethane, chlorodifluoroethanes, 1,1- dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane, especially chlorine-free hydrofluorocarbons such as difluoromethane, trifluoromethane, difluoroethane, 1,1,1,2-tetrafluoroethane, tetrafluoroethane (R 134 or R 134a), 1,1,1,3,3-pentafluoropropane (R 245 fa), 1,1, 1,3,3, 3-hexafluoro- propane (R 256), 1,1,1,3,3-pentafluorobutane (R 365 mfc), heptafluoropropane or else sulfur hexafluoride. Mixtures of these blowing agents are also usable.
  • the subsequent curing is typically performed at 23°C.
  • the oxyethylene unit content of A2 is > 50% by weight, or preferably > 55% by weight, or preferably > 60% by weight, based on the total amount of the oxyalkylene groups present.
  • the isocyanate-functional prepolymer A) of ⁇ 5, or preferably of ⁇ 4, or preferably of ⁇ 3, or preferably within a range from 1 to 5, or preferably within a range from 1.5 to 4.5.
  • the polyalkylene oxide A2) has an OH number within a range from 25 to 450 mg KOH/g, preferably within a range from 50 to 400, or preferably within a range from 75 to 250.
  • the present invention further provides the polyurethane foams or hydrogels produced by the process according to the invention, and for the use of the hydrophilic, preferably aliphatic polyurethane foams or hydrogels as a constituent of a wound dressing, a cosmetic article or an incontinence product.
  • the polyurethane foams or hydrogels according to the invention are preferably produced by mixing components A), produced from components Al), A2) and optionally A3), optionally D), optionally with C) and/or H), in any sequence, and then with a mixture of B) and I) and optionally D), E), F), G), foaming the mixture and curing, preferably by chemical crosslinking.
  • components A), C) and H) are pre-mixed with one another.
  • Any salts E) to be used and any surfactants F) are preferably added to the reaction mixture in the form of their aqueous solutions.
  • the polyurethane foams or hydrogels according to the invention are hydrophilic and have preferably aliphatic units.
  • the polyurethane foams according to the invention or the polyurethane foams produced in accordance with the invention preferably have a porous, at least partly open-cell structure with cells in communication with one another.
  • the density of the polyurethane foams is preferably 50 to 300 g/1.
  • the polyurethane foams have good mechanical strength and high elasticity. Typically, tensile strengthdry values are greater than 40 kPa, elongation at break values greater than 30% with a density in the range from 50 to 300 g/1 (determination in each case by the standards as described later under Methods).
  • the polyurethane foams can be processed by methods known per se to give essentially two-dimensional or thin three-dimensional materials which can then be used, for example, as a constituent of a wound dressing, of a cosmetic article or of an incontinence product.
  • slabstock foams are cut to the desired thickness by standard methods, to obtain two- dimensional materials having a thickness of typically from 10 pm to 5 cm, preferably from 0.1 mm to 1 cm, more preferably from 0.1 mm to 6 mm, most preferably from 0.2 mm to 6 mm.
  • the two-dimensional materials described can alternatively be obtained directly by application and optionally foaming of the composition according to the invention to a substrate, for example an optionally pretreated paper, a film, a nonwoven or a textile.
  • a mixture of the starting materials as described in the PCT application numbered WO 2011/006608 is applied to a substrate by means of a coating bar, and then the optional foaming follows after the coating.
  • the gap height of the coating bar is generally in the range from 0.2 to 20 mm, preferably from 0.5 to 5 mm and most preferably from 0.8 to 2 mm.
  • the film width of the coating bar to be used can be matched to the particular end use. Examples are film widths between 10 and 5000 mm, preferably between 20 and 2000 mm.
  • a further layer is applied to the top side of the polyurethane foam or hydrogel, preferably before the polyurethane foam or hydrogel has dried.
  • the polyurethane foams generally contain only a small water-extractable proportion of not more than 2% by weight, preferably of not more than 1% by weight, meaning that they contain only very small amounts of chemically unbound constituents.
  • polyurethane foams or hydrogels may be bonded, laminated or coated with further materials, for example based on hydrogels, (semi-)permeable films, foam films, coatings, hydrocolloids or other foams.
  • the polyurethane foams or hydrogels according to the invention are particularly suitable for production of wound dressings.
  • the polyurethane foams or hydrogels here may be in direct or indirect contact with the wound. However, preference is given to using the polyurethane foams or hydrogels in direct contact with the wound in order to assure, for example, optimal absorption of wound fluid.
  • the polyurethane foams or hydrogels that are used as wound dressing must additionally be sterilized in a further process step.
  • sterilization the processes known per se to the person skilled in the art are used, in which sterilization is effected by thermal treatment, chemical substances such as oxyethylene, or irradiation, for example by gamma irradiation.
  • the irradiation can optionally be effected under protective gas atmosphere.
  • the polyurethane foams or hydrogels according to the invention made from preferably aliphatic diisocyanates, especially component Al) and optionally Hl), have the great advantage that they are not discoloured on irradiation, especially on irradiation with gamma rays.
  • a further aspect of the invention is a polyurethane foam or polyurethane hydrogel which as obtained according to the process according to the invention as described above.
  • a further aspect of the invention is a wound dressing or an incontinence product which is obtainable using polyurethane foams or hydrogels according to the invention.
  • Desmodur® H hexamethylenediisocyanate.
  • the content of hexamethylenediisocyanate is > 98.2% by weight commercial product of Covestro Deutschland AG.
  • Polyethylene glycol prepared by ethoxylation of propylene glycol, OH-number: 190 mg KOH / g, commercial product of Covestro GmbH AG
  • Poly(ethyleneglycol-ran-propylenglycol) is a difunctional polyether (MERCK).
  • MERCK difunctional polyether
  • the molar mass and fraction of ethylene oxide units were determined via 1 H-NMR spectroscopy in deutorated chloroform solvent to be 1870 g/mol and 80.4%, respectively.
  • Hexamethylene diamine commercial product of ABCR, Germany, purity 98%.
  • Pluronic PE 6800 commercial product of BASF, Ludwigshafen, Germany dry ice: commercial product of Nippon Gases, Germany
  • Viscosities of prepolymers were determined according to DIN 53019-1-2008-09. Unless stated otherwise the temperature was 23 °C.
  • NCO contents were determined according to DIN-EN ISO 11909-2007-05. pH-value pH was measured using a Knick 765 Calimatic pH-meter at 23 °C.
  • Residual diisocyanate contents were determined according to DIN EN ISO 10283:2007.
  • the height of foam samples was measured by a compressed air caliper connected to a display (Heidehain MT25P).
  • Foam samples of the dimensions 5 x 5 cm were punched out of the foam sheet. The sample height was determined as described previously at five locations and averaged. Subsequently, the samples were weighed using a Mettler Toledo XS603S balance and the density (D) was calculated.
  • the urethane content can be calculated from the stoichiometry of the urethane-forming reaction between hydroxyl groups and isocyanate groups. Since the hydroxyl groups are fully converted to urethane groups in all examples, the following formula can be used for calculation: % by wt. of hydroxyl component ⁇ OHN
  • OHN denotes hydroxyl number of the hydroxyl component used or the corresponding average value for multiple components.
  • Examples of possible hydroxyl components are mono- or polyfunctional alcohols or polyols. Specific examples are described under Al), A3), G) or H2).
  • edge length expansion factor S was calculated as follows
  • Elongation at break (eb, wet) and wet-tensile-strength-at-break (ob.wet) in the wet (swollen) state were determined according to DIN EN ISO 527-2 except for the following deviations.
  • the samples were immersed in deionized water for 30 min prior to punching out the tensile specimens.
  • Prepolymer 1 (according to US2006142529, example 4)
  • the product had a viscosity of 2100 mPas.
  • the urethane content was calculated to be 2.2 mol/kg.
  • Prepolymer 4 (according to WO19137879, example 1)
  • Aqueous phase 2 (not inventive)
  • Aqueous phase 3 (not inventive)
  • Aqueous phase 4 (inventive)
  • Aqueous phase 5 (inventive)
  • the prepolymers from the examples were placed into a 500 mL PP beaker (Sarstedt, Germany) and stirred using Disperlux green 037 stirrer at 930 rpm for 15 seconds. Subsequently, a defined amount of aqueous phase (see Table 1) was added. It was stirred for another 5 seconds. Then the mixture was coated on a release paper (Felix Schoeller Y 05200) using a 1500 pm coating bar. After 40 seconds a pin holed release paper (Felix Schoeller Y05200) was placed on top. The foam was allowed to dry over night at 23°C.
  • Aliphatic prepolymers containing more than 1% residual diisocyanate like comparative example 2 in this document can be used to produce foams with excellent wet strength performance as indicated by the outstanding (oB,wet/D)-S 2 value of 1.42.
  • Similar prepolymers that differ only by the subsequent removal of the residual diisocyanate monomer are known.
  • example 1 of WO19137879 leads to a prepolymer that retained a rather low viscosity of 5140 mPas after distillation.
  • the (oB,wet/D)-S 2 value of foams produced from this prepolymer dropped drastically to 0.28 (see non- inventive example 4 as described above in table 1).
  • comparative prepolymer 3 was designed in a way that it resembles the chemical composition of prepolymer 4 (similar HDI and polyol content of 35% and 65%, respectively) but differs in the fact that the residual diisocyanate was removed via distillation.
  • Aromatic foam 1 and aliphatic foam 2 show excellent (oB,wet/D)-S 2 values > 0.30 but were prepared from the respective prepolymers 1 and 2 that contain more than 8% monomeric diisocyanates (component Al).
  • Prepolymers 3 and 4 contain less than 8% diisocyanates because residual diisocyanate was removed by distillation.
  • Foam 4 was prepared via a non-inventive method without a polyamine as component I).
  • the (ob,wet/D)-S 2 value was only 0.28.
  • Foam 5 was prepared employing a polyamine as component I) in an amount that resulted in a NH/NCO-ratio of 0.4. Due to component I) the (ob,wet/D)-S 2 value increased to 0.40.
  • Foam 6 was prepared by further increasing the amount of component I) until a NH/NCO-ratio of 0.8 was reached.
  • As a result (ob,wet/D)-S 2 further increased to 0.50. Consequently, it could be demonstrated that employing component I) effectively increases (oB,wet/D)-S 2 . Surprisingly, it could be shown that a foam with good (ob,wet/D)-S 2 value could be reached even with low residual diisocyanate amounts.

Abstract

L'invention concerne un procédé de production de mousses ou d'hydrogels de polyuréthane, dans lequel des compositions comprenant A) des prépolymères à fonction isocyanate pouvant être obtenus par la réaction de A1) diisocyanates de faible poids moléculaire de masse molaire de 140 à 278 g/mol, avec A2) des oxydes de polyalkylène ayant une fonctionnalité OH de deux ou plus, A3) éventuellement d'autres composants réactifs vis-à-vis de l'isocyanate différant d'A2) ; B) de l'eau en une quantité d'au moins 2 % en poids, par rapport au poids total de la composition ; C) éventuellement des polyisocyanates pouvant être obtenus par réaction d'au moins deux diisocyanates de faible poids moléculaire, de préférence aliphatiques, les diisocyanates ayant une masse molaire de 140 à 278 g/mol, D) éventuellement des catalyseurs ; E) éventuellement des sels d'acides faibles, dont les acides libres correspondants ont un pKA dans l'eau à 25 °C ≥ 3,0 et ≤ 14,0 ; F) éventuellement des tensioactifs ; et G) éventuellement des mono-alcools ou alcools polyhydriques ou polyols ; H) éventuellement des polyisocyanates hydrophiles pouvant être obtenus par réaction H1) de diisocyanates de faible poids moléculaire ayant une masse molaire de 140 à 278 g/mol et/ou des polyisocyanates pouvant être préparés à partir de ceux-ci et ayant une fonctionnalité isocyanate moyenne de 2 à 6 avec H2) des oxydes de polyalkylène monohydroxyfonctionnels d'indice OH de 10 à 250 et de teneur en unités oxyéthylène de 50 à 100 % en moles, par rapport à la quantité totale des groupes oxyalkylène présents, I) une polyamine comportant au moins deux groupes amine ou deux groupes ammonium, de préférence une diamine, les composants contenant de l'isocyanate, en particulier des composants A), C) et H), ne dépassent pas une teneur en diisocyanate résiduel de 8 % en poids, par rapport au poids total de la mousse ou de l'hydrogel de polyuréthane et le rapport des groupes amine issus du composant I) à des groupes isocyanate de tous les composants A) à I) est dans une plage de 0,1 à 1,2. Ces mousses ou hydrogels sont utilisés dans des pansements, des articles cosmétiques ou des produits pour l'incontinence.
PCT/EP2021/076899 2020-10-05 2021-09-30 Procédé de production de mousses ou d'hydrogels de polyuréthane à l'aide d'allongeurs de chaîne amine WO2022073835A1 (fr)

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US3903232A (en) 1973-10-09 1975-09-02 Grace W R & Co Dental and biomedical foams and method
US4137200A (en) 1973-10-09 1979-01-30 W. R. Grace & Co. Crosslinked hydrophilic foams and method
US5849850A (en) 1994-11-22 1998-12-15 Imperial Chemical Industries Plc Process for making flexible foams
US20060142529A1 (en) 2004-02-06 2006-06-29 Verena Thiede Hydrophilic polyurethane polymers derived from a mdi-based isocyanate-terminated prepolymer
EP2143744A1 (fr) 2008-07-09 2010-01-13 Bayer MaterialScience AG Mousses de polyuréthane hydrophile et aliphatique
WO2011006608A1 (fr) 2009-07-15 2011-01-20 Bayer Materialscience Ag Procédé de fabrication de nappes de mousses de polyuréthane aliphatique hydrophiles
EP2470580A2 (fr) 2009-08-29 2012-07-04 Bayer MaterialScience AG Mousses de polyuréthane aliphatiques hydrophiles
WO2012150224A1 (fr) * 2011-05-04 2012-11-08 Bayer Intellectual Property Gmbh Mousse de polyuréthane hydrophile au gonflement volumique minime
EP2632501A1 (fr) 2010-10-27 2013-09-04 Bayer Intellectual Property GmbH Mousses polyuréthanne aliphatiques hydrophiles
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US3903232A (en) 1973-10-09 1975-09-02 Grace W R & Co Dental and biomedical foams and method
US4137200A (en) 1973-10-09 1979-01-30 W. R. Grace & Co. Crosslinked hydrophilic foams and method
US5849850A (en) 1994-11-22 1998-12-15 Imperial Chemical Industries Plc Process for making flexible foams
US20060142529A1 (en) 2004-02-06 2006-06-29 Verena Thiede Hydrophilic polyurethane polymers derived from a mdi-based isocyanate-terminated prepolymer
EP2143744A1 (fr) 2008-07-09 2010-01-13 Bayer MaterialScience AG Mousses de polyuréthane hydrophile et aliphatique
WO2011006608A1 (fr) 2009-07-15 2011-01-20 Bayer Materialscience Ag Procédé de fabrication de nappes de mousses de polyuréthane aliphatique hydrophiles
EP2470580A2 (fr) 2009-08-29 2012-07-04 Bayer MaterialScience AG Mousses de polyuréthane aliphatiques hydrophiles
EP2632501A1 (fr) 2010-10-27 2013-09-04 Bayer Intellectual Property GmbH Mousses polyuréthanne aliphatiques hydrophiles
WO2012150224A1 (fr) * 2011-05-04 2012-11-08 Bayer Intellectual Property Gmbh Mousse de polyuréthane hydrophile au gonflement volumique minime
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