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WO2024227678A1 - Moulages en mousse de polyuréthane de faible densité à peau lisse - Google Patents

Moulages en mousse de polyuréthane de faible densité à peau lisse Download PDF

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Publication number
WO2024227678A1
WO2024227678A1 PCT/EP2024/061346 EP2024061346W WO2024227678A1 WO 2024227678 A1 WO2024227678 A1 WO 2024227678A1 EP 2024061346 W EP2024061346 W EP 2024061346W WO 2024227678 A1 WO2024227678 A1 WO 2024227678A1
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weight
polyurethane foam
polymer
acid
polyols
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PCT/EP2024/061346
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English (en)
Inventor
Erhan Cubukcu
Martin Baumert
Massimo PATRIGNANI
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Basf Se
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Publication of WO2024227678A1 publication Critical patent/WO2024227678A1/fr

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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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • 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
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/3271—Hydroxyamines
    • C08G18/3278—Hydroxyamines containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/631—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyesters and/or polycarbonates
    • 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
    • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine 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
    • C08G2110/0033—Foam properties having integral skins
    • 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
    • C08G2110/0058—≥50 and <150kg/m3
    • 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
    • C08G2410/00—Soles

Definitions

  • the present invention relates to a process for producing polyurethane foam moldings, wherein a) organic polyisocyanates are mixed with b) polyols comprising b1) polyesterols and b2) polymer polyetherols having a proportion of primary OH groups of less than 50%, c) blowing agents, d) fillers and optionally e) chain extenders and/or crosslinkers, f) catalysts and g) other auxiliaries and/or additives to form a reaction mixture, the latter is introduced into a mold and allowed to react to form a polyurethane foam molding.
  • the present invention further relates to the use of such polyurethane foam moldings as shoe sole and slipper.
  • EP 1 790 675 and EP 1 756 187 disclose the use of polymer polyols based on polyetherol in polyesterol polyurethane systems.
  • the documents show, in the comparative example, that the use of polymer polyetherols leads to an integral foam having an unsatisfactory surface and a coarse cell structure.
  • WO 2011/070153 A2 relates to a method for producing polyurethane molded foam bodies, wherein a) organic polyisocyanates are mixed with b) polyols, containing b1) polyesterols and b2) polymer polyetherols having a fraction of primary OH groups of less than 50%, c) expanding agents, and optionally d) chain lengthening agents and/or crosslinking agents, e) catalysts and f) other auxiliary agents and/or additives, to form a reaction mixture, introduced in a mold and allowed to fully cure to form a polyurethane molded foam body and to the use of such polyurethane molded foam bodies as a shoe sole.
  • a polyurethane foam molding which can be obtained by a process in which a) organic polyisocyanates are mixed with b) polyols comprising b1) polyesterols and b2) polymer polyetherols having a proportion of primary OH groups to secondary OH groups of less than 50%, c) blowing agents, d) fillers, e) chain extenders and/or crosslinkers, f) catalysts and optionally g) other auxiliaries and/or additives to form a reaction mixture, the latter is introduced into a mold and allowed to react to form a polyurethane foam molding.
  • polyurethane foam moldings are polyurethane foams which are produced in a mold.
  • Integral polyurethane foams are, for the purposes of the invention, polyurethane foams in accordance with DIN 7726 having an outer zone which, due to the shaping process, has a higher density than the core.
  • the overall foam density averaged over the core and the outer zone is preferably from 80 g/l to 250 g/l, particularly preferably from 120 g/l to 200 g/l. Since integral polyurethane foams are also produced in a mold, the term polyurethane foam moldings also comprises integral polyurethane foams.
  • the organic and/or modified polyisocyanates (a) used for producing the polyurethane foam moldings of the invention comprise the aliphatiOc, cycloaliphatic and aromatic bifunctional or polyfunctional isocyanates known from the prior art (constituent a-1) and also any mixtures thereof.
  • Examples are 4,4'-methanedi(phenyl diisocyanate), 2,4'-methanedi(phenyl diisocyanate), mixtures of monomeric methanedi(phenyl isocyanates) and homologues of methanedi (phenyl diisocyanate) having a larger number of rings (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene 2,4- or 2,6-diisocyanate (TDI) or mixtures of the isocyanates mentioned.
  • polymeric MDI polymeric MDI
  • tetramethylene diisocyanate tetramethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TDI tolylene 2,4- or 2,6-diisocyanate
  • the 4,4'-MDI which is preferably used can comprise from 0 to 20% by weight of 2,4'-MD I and small amounts, up to about 10% by weight, of allophanate- or uretonimine-modified polyisocyanates. It is also possible to use small amounts of polyphenylenepolymethylene polyisocyanate (polymeric MDI). The total amount of these high-functionality polyisocyanates should not exceed 5% by weight of the isocyanate used.
  • the polyisocyanate component (a) is preferably used in the form of polyisocyanate prepolymers.
  • These polyisocyanate prepolymers can be obtained by reacting above-described polyisocyanates (a-1), for example at temperatures of from 30 to 100°C, preferably about 80°C, with polyols (a-2) to form the prepolymer.
  • Polyols (a-2) are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.1.
  • Customary chain extenders or crosslinkers are optionally added to the polyols mentioned in the preparation of the isocyanate prepolymers. Such substances are described below under e).
  • Polyols b) comprise polyesterols b1) and polymer polyetherols b2) having a proportion of primary OH groups to secondary OH groups of less than 50% and optionally also polymer polyesterols b3) and/or further polyols, for example polyetherols b4).
  • polyesterols b1) it is possible to use polyesterols which are customarily used in polyurethane chemistry.
  • Polyesterols b1) can be prepared, for example, from organic dicarboxylic acids having from 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having from 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms.
  • dicarboxylic acids are, for example: succin- ic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used either individually or in admixture with one another. It is also possible to use the corresponding carboxylic acid derivatives, e.g. dicarboxylic esters of alcohols having from 1 to 4 carbon atoms or dicarboxylic anhydrides, instead of the free dicarboxylic acids.
  • dicarboxylic acid mixtures of succinic, glutaric and adipic acid in weight ratios of, for example, 20-35: 35-50: 20-32, and in particular adipic acid.
  • dihydric and polyhydric alcohols, in particular diols are: ethanediol, diethylene glycol, 1,2- or 1 ,3-propanediol, dipropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,10-decanediol, glycerol and trimethylolpropane.
  • polyester polyols derived from lactones, e.g. E-caprolactone, or hydroxycarboxylic acids, e.g. a>-hydroxycaproic acid.
  • the organic, e.g. aromatic and preferably aliphatic, polycarboxylic acids and/or polycarboxylic acid derivatives and polyhydric alcohols can be polycondensed in the absence of catalysts or preferably in the presence of esterification catalysts, advantageously in an atmosphere of inert gas such as nitrogen, carbon monoxide, helium, argon, etc., in the melt at temperatures of from 150 to 250°C, preferably from 180 to 220°C, optionally under reduced pressure, to the desired acid number which is preferably less than 10, particularly preferably less than 2.
  • inert gas such as nitrogen, carbon monoxide, helium, argon, etc.
  • the esterification mixture is polycondensed at the abovementioned temperatures to an acid number of from 80 to 30, preferably from 40 to 30, under atmospheric pressure and subsequently under a pressure of less than 500 mbar, preferably from 50 to 150 mbar.
  • Possible esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts.
  • the polycondensation can also be carried out in the liquid phase in the presence of diluents and/or entrainers such as benzene, toluene, xylene or chlorobenzene to azeotropically distill off the water of condensation.
  • the organic polycarboxylic acids and/or polycarboxylic acid derivatives and polyhydric alcohols are advantageously polycondensed in a molar ratio of 1 :1-1.8, preferably 1 :1.05- 1.2.
  • the polyester polyols obtained preferably have a functionality of 2 to 4, in particular from 2 to 3, and a number average molecular weight of from 480 to 3000 g/mol, preferably 1000 to 3000 g/mol.
  • polyetherols b4) it is also possible to use further polyols, for example polyetherols b4).
  • polyetherols b4) it is possible to use all polyetherols which are customarily used in polyurethane chemistry.
  • Polyetherols b4) can be prepared by known methods, for example from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical by anionic polymerization using alkali metal hydroxides or alkali metal alkoxides as catalysts with addition of at least one starter molecule comprising 2 or 3 reactive hydrogen atoms in bound form or by cationic polymerization using Lewis acids such as antimony pentachloride or boron fluoride etherate.
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1 ,3-propylene oxide, 1,2- or 2,3-butylene oxide and preferably ethylene oxide and 1 ,2-propylene oxide. It is also possible to use multimetal cyanide compounds, known as DMC catalysts, as catalysts.
  • the alkylene oxides can be used individually, alternatively in succession or as mixtures. Preference is given to mixtures of 1 ,2-propylene oxide and ethylene oxide.
  • Possible starter molecules are water or 2- and 3-functional alcohols such as ethylene glycol, 1,2- and 1,3- propanediol, diethylene glycol, dipropylene glycol, 1 ,4-butanediol, glycerol or trimethylolpropane.
  • the polyether polyols preferably polyoxypropylene-polyoxyethylene polyols, preferably have a functionality of from 2 to 3 and number average molecular weights of from 1000 to 8000 g/mol, preferably from 2000 to 6000 g/mol. Preference is given to using, based on the weight of the polyesterol b1) , less than 50% by weight, particularly preferably less than 20%, very particularly preferably less than 5% by weight, of polyetherol and in particular no polyetherol.
  • polymer polyols are known and commercially available.
  • Polymer polyols are prepared by free-radical polymerization of the monomers, preferably acrylonitrile, styrene and optionally further monomers, a macromer and, if appropriate, a moderator using a free-radical initiator, usually azo or peroxide compounds, in a polyetherol or polyesterol as continuous phase.
  • Polymer polyols which have been prepared in a polyetherol as continuous phase are referred to as polymer polyetherols
  • polymer polyols which have been prepared in a polyesterol as continuous phase are referred to as polymer polyesterols b3).
  • the polyetherol or the polyesterol which represents the continuous phase and thus the dispersion medium is frequently also referred to as carrier polyol.
  • carrier polyol The preparation of polymer polyols is described, for example, in the patent documents US 4568705, US 5830944, EP 163188, EP 365986, EP 439755, EP 664306, EP 622384, EP 894812 and WO 00/59971.
  • This preparation is usually an in-situ polymerization of acrylonitrile, styrene or preferably mixtures of styrene and acrylonitrile, e.g. in a weight ratio of from 90:10 to 10:90, preferably from 70:30 to 30:70.
  • Possible carrier polyols are all polyols described under b1) and b4).
  • the polyetherols for preparing the polymer polyetherols have a content of primary OH groups of less than 50% by weight, particularly preferably less than 30% and in particular less than 10%.
  • Macromers also referred to as stabilizers, are linear or branched polyetherols or polyester polyols which have molecular weights of > 1000 g/mol and comprise at least one terminal, reactive ethylenic unsaturated group.
  • the eth- ylenically unsaturated group can be attached to an existing polyol by reaction with carboxylic acids such as acrylic acid, carboxylic acid halides such as acryloyl chloride, carboxylic anhydrides such as maleic anhydride, fumaric acid, acrylate and methacrylate derivatives, ethylenically unsaturated epoxides such as 1-vinylcyclohexene 3,4-epoxide, 1- butadiene monoxide, vinyl glycidyl ether, glycidyl methacrylate and allyl glycidyl ether and also isocyanate derivatives such as 3-isopropenyl-1,1 -dimethylbenzyl isocyan
  • a further route is preparation of a polyol by alkoxidation of propylene oxide and ethylene oxide using starter molecules having hydroxyl groups and ethylenic unsaturation.
  • Examples of such macromers are described in the documents US 4390645, US 5364906, EP 0461800, US 4997857, US 5358984, US 5990232, WO 01/04178 and US 6013731.
  • the macromers are built into the polymer chain. This results in formation of copolymers which have polyether or polyester blocks and polyacrylonitrile-styrene blocks and act as phase compatibilizers in the interface between continuous phase and dispersed phase and suppress agglomeration of the polymer polyol particles.
  • the proportion of macromers can be up to greater than 90% by weight and is usually from 1 to 60% by weight, preferably from 1 to 40% by weight and particularly preferably from 1 to 15% by weight, in each case based on the total weight of the monomers used for preparing the polymer polyol.
  • moderators also referred to as chain transfer agents.
  • the moderators decrease the molecular weight of the copolymers being formed by chain transfer of the growing free radical, as a result of which the crosslinking between the polymer molecules is reduced, which in turn influences the viscosity and the dispersion stability and also the filterability of the polymer polyols.
  • the proportion of moderators is usually from 0.5 to 25% by weight, based on the total weight of the monomers used for preparing the polymer polyol.
  • Moderators which are usually employed for preparing polymer polyols are alcohols such as 1 -butanol, 2-butanol, isopropanol, ethanol, methanol, cyclohexane, toluenes, mercaptans, such as ethanethiol, 1 -heptanethiol, 2-octanethiol, 1- dodecanethiol, thiophenol, 2-ethylhexyl thioglycolate, methyl thioglycolate, cyclohexyl mercaptan and also enol ether compounds, morpholines and a-(benzoyloxy)styrene. Preference is given to using alkyl mercaptan.
  • peroxide or azo compounds e.g. dibenzoyl peroxide, lauroyl peroxide, t-amylperoxy 2-ethylhexanoate, di-t-butyl peroxide, diisopropyl peroxide carbonate, t-butylperoxy 2- ethylhexanoate, t-butyl perpivalate, t-butyl perneodecanoate, t-butyl perbenzoate, t-butyl percrotonate, t-butyl perisobutyrate, t-butylperoxy 1-methylpropanoate, t-butylperoxy 2-ethylpentanoate, t-butylperoxy octanoate and di-t-butyl perphthalate, 2,2’-azobis(2,4-dimethylvaleronitrile), 2,2'-azo
  • the free-radical polymerization for preparing polymer polyols is usually carried out at temperatures of from 70 to 150°C and a pressure of up to 20 bar.
  • Preferred reaction conditions for preparing polymer polyols are temperatures of from 80 to 140°C at a pressure of from atmospheric pressure to 15 bar.
  • Polymer polyols are prepared in continuous processes using stirred vessels with continuous inflow and outflow, cascades of stirred vessels, tube reactors and loop reactors with continuous inflow and outflow, or in discontinuous processes by means of a batch reactor or a semi batch reactor.
  • the reaction for preparing the polymer polyols can also be carried out in the presence of an inert solvent.
  • inert solvents which can be used are: benzene, toluene, xylene, acetonitrile, hexane, heptane, dioxane, ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Preference is given to benzene, xylene and toluene.
  • Suitable ethylenically unsaturated monomers for preparing the solid component of the polymer polyol are, for example, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1 ,7-octadiene, styrene, alpha-methylstyrene, 2- methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene and similar derivatives; substituted styrenes such as cyanostyrene, nitrostyrene, N,N-dimethylaminostyrene, acetoxystyrene, methyl 4-vinylbenzoate,
  • acrylonitrile, styrene, in particular styrene and acrylonitrile in a ratio of from 1 :3 to 3:1 are used as ethylenically unsaturated monomers.
  • the polymerization is optionally also carried out using a moderator and using a free-radical initiator.
  • the solid component comprises acrylonitrile, styrene and macromer, with the proportion of acrylonitrile being from 10 to 75% by weight and preferably from 25 to 35% by weight, the proportion of styrene being from 30 to 90% by weight, preferably from 55 to 70% by weight, and the proportion of macromer being from 1 to 10% by weight, preferably from 3 to 6% by weight, based on the total weight of the solid component of the polymer polyol.
  • the polymer polyol has a solids content of from 10 to 90% by weight, particularly preferably from 15 to 60% by weight and in particular from 20 to 55% by weight, based on the total weight of the polymer polyol.
  • the solids content, based on the total weight of the polyol component b) is preferably from 1 to 10% by weight, particularly preferably from 2 to 7% by weight and in particular from 2.5 to 6% by weight.
  • the solids content of polymer polyols is calculated from the percentage ratio of the monomers used and the macromer to the carrier polyols used and is usually determined gravimetrically on the finished polymer polyol from the percentage ratio of the mass of solid to total mass of the polymer polyol.
  • the proportion of polymer polyetherol b2) in the total weight of the polyol component b) is preferably from 0.5 to 20% by weight.
  • the proportion of polymer polyesterol b3) in the total weight of the polyol component b) is preferably from 0 to 30% by weight, particularly preferably from 1 to 10% by weight.
  • the ratio of polymer polyetherol b2) to polymer polyesterol b3) is preferably from 1 :20 to 20:1 , particularly preferably from 1 :5 to 5: 1.
  • a combination of polymer polyetherol b2) and polymer polyesterol b3) is preferably used for producing polyurethane foam moldings having a height of at least 1.5 cm, particularly preferably at least 5 cm.
  • the "height” of the polyurethane foam molding is the greatest distance in the mold for producing the polyurethane foam molding according to the invention in the rise direction of the foam.
  • blowing agents c) are present in the production of polyurethane foam moldings. These blowing agents c) comprise water. Apart from water, generally known chemically and/or physically acting compounds can additionally be used as blowing agents c).
  • chemical blowing agents are compounds which react with isocyanate to form gaseous products, for example water or formic acid.
  • Physical blowing agents are compounds which are dissolved or emulsified in the starting materials for polyurethane production and vaporize under the conditions of polyurethane formation.
  • hydrocarbons for example, hydrocarbons, halogenated hydrocarbons and other compounds, for example perfluorinated alkanes such as perfluorohexane, chlorofluorocarbons and ethers, esters, ketones, acetals or mixtures thereof, for example (cyclo)aliphatic hydrocarbons having from 4 to 8 carbon atoms or fluorinated hydrocarbons such as Solkane® 365 mfc from Solvay Fluorides LLC.
  • a mixture comprising at least one of these blowing agents and water is used as blowing agent; in particular, water is used as only blowing agent. If no water is used as only blowing agent, preference is given to using exclusively physical blowing agents.
  • the water content is from 0.1 to 2% by weight, preferably from 0.2 to 1 .5% by weight, particularly preferably from 0.3 to 1 .2% by weight, based on the total weight of the components a) to g).
  • hollow microspheres comprising physical blowing agent are added as additional blowing agent in the reaction of the components a) to g).
  • the hollow microspheres can also be used in admixture with the abovementioned blowing agents.
  • the hollow microspheres usually comprise a shell of thermoplastic polymer and are filled in the core with a liquid, low-boiling substance based on alkanes.
  • the production of such hollow microspheres is described, for example, in US 3 615 972.
  • the hollow microspheres generally have a diameter of from 5 to 50 .m. Examples of suitable hollow microspheres can be obtained under the trade name Expancell® from Akzo Nobel.
  • the hollow microspheres are generally added in an amount of from 0.5 to 5% by weight, based on the total weight of the components b), c) and e).
  • inorganic fillers such as siliceous minerals, for example sheet silicates such as antigorite, bentonite, serpentine, hornblendes, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminum oxides, titanium oxides, zinc oxides and iron oxides, metal salts such as chalk and barite, and inorganic pigments such as cadmium sulfide, zinc sulfide and also glass, etc. may be used. Preference is given to using calcium carbonate, kaolin (china clay), aluminum silicate and coprecipitates of barium sulfate and aluminum silicate.
  • sheet silicates such as antigorite, bentonite, serpentine, hornblendes, amphiboles, chrysotile and talc
  • metal oxides such as kaolin, aluminum oxides, titanium oxides, zinc oxides and iron oxides
  • metal salts such as chalk and barite
  • inorganic pigments such
  • Possible organic fillers are, for example: carbon black, melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and/or aliphatic dicarboxylic esters and in particular carbon fibers.
  • calcium carbonate is used as filler, most preferably in the range from 5 to 20 wt.-% based on the, based on the weight of the components a) to g). CaCOs improves skin formation and avoids double skin at low densities.
  • the mean particle size of the filler is in the range from 1 - 10 m.
  • the inorganic and organic fillers can be used individually or as mixtures and are advantageously added to the reaction mixture in amounts of from 0.5 to 50% by weight, preferably from 5 to 20% by weight, based on the weight of the components a) to g). Most preferably the filler is dispersed in the polyol components b) before combining it with the isocyanate component a).
  • chain extenders and/or crosslinkers e use is made of substances having a molecular weight of preferably less than 500 g/mol, particularly preferably from 60 to 400 g/mol, with chain extenders having 2 hydrogen atoms which are reactive toward isocyanates and crosslinkers having 3 hydrogen atoms which are reactive toward isocyanate. These can preferably be used individually or in the form of mixtures. Preference is given to using diols and/or triols having molecular weights of less than 400, particularly preferably from 60 to 300 and in particular from 60 to 150.
  • Possible chain extenders/crosslinkers are, for example, aliphatic, cycloaliphatic and/or araliphatic diols having from 2 to 14, preferably from 2 to 10, carbon atoms, e.g. ethylene glycol, 1 ,3-propanediol, 1 , 10-decanediol, 1,2-, 1,3-, 1,4- dihydroxyclohexane, diethylene glycol, dipropylene glycol and 1 ,4-butanediol, 1 ,6-hexanediol and bis(2-hydroxy- ethyl)hydroquinone, triols, such as 1,2,4-, 1 ,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane, and low molecular weight hydroxyl-comprising polyalkylene oxides based on ethylene oxide and/or 1 ,2-propylene oxide and the abovementioned diols and/or triol
  • chain extenders, crosslinkers or mixtures thereof are advantageously used in amounts of from 1 to 60% by weight, preferably from 1 .5 to 50% by weight and in particular from 2 to 40% by weight, based on the weight of the components b) and e).
  • catalysts f) for producing the polyurethane foams preference is given to using compounds which strongly accelerate the reaction of the polyols b) and optionally chain extenders and crosslinkers d) with the organic, optionally modified polyisocyanates a).
  • amidines such as 2, 3-dimethy I- 3,4,5,6-tetrahydropyrimidine
  • tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N- methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'- tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, bis(dimethyl- aminoethyl) ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1- azabicyclo[3.3.0]octane and preferably 1,4-diazabicyclo[2.2.2]octane and alkanolamine
  • organic metal compounds preferably organic tin compounds such as tin(ll) salts of organic carboxylic acids, e.g. tin(ll) acetate, tin(ll) octoate, tin(ll) ethylhexanoate and tin(ll) laurate, and the dialkyltin(IV) salts of organic carboxylic acids, e.g.
  • dibutyltin diacetate dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate
  • bismuth carboxylates such as bismuth(lll) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate, or mixtures thereof.
  • the organic metal compounds can be used either alone or preferably in combination with strongly basic amines. If the component b) is an ester, preference is given to using exclusively amine catalysts.
  • auxiliaries and/or additives g) can additionally be added to the reaction mixture for producing the polyurethane foams. Mention may be made by way of example of surface-active substances, foam stabilizers, cell regulators, further mold release agents, dyes, pigments, hydrolysis inhibitors, odor-absorbing substances and fungistatic and/or bacteriostatic substances.
  • Preferably surface-active agents are used as wetting or dispersing agents to prevent separation of the filler d) and enhance its performance.
  • Wetting and dispersing agents reduce viscosity and avoids settlement of solid parti- cles/fillers.
  • Possible surface-active substances are, for example, compounds which serve to aid homogenization of the starting materials and are also optionally suitable for regulating the cell structure. Mention may be made by way of example of emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids and also salts of fatty acids with amines, e.g. diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salts of sulfonic acids, e.g.
  • alkali metal or ammonium salts of dodecylbenzenesulfonic or dinaphthylmethanedisulfonic acid, and ricinoleic acid foam stabilizers such as siloxane-oxyalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil esters or ricinoleic esters, Turkey red oil and peanut oil, and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • Oligomeric acrylates having polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying action, the cell structure and/or stabilizing the foam.
  • copolymers with acidic groups are used as dispersing agent for fillers, such as calcium car- bonate.
  • Most preferable polyethylene glycol ester of phosphoric acid is used as dispersing agent with calcium carbonate as filler.
  • the surface-active substances are usually employed in amounts of from 0.01 to 5 parts by weight, based on 100 parts by weight of the component b).
  • the present invention further provides a process for producing a polyurethane foam molding, in particular an integral polyurethane foam, in which the components a) to d) and optionally e), f) and/or g) are mixed with one another in such amounts that the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of the reactive hydrogen atoms of the components (b), (c) and (e) is from 1 :0.8 to 1 :1.25, preferably from 1 :09 to 1 :1.15.
  • the polyurethane foam moldings of the invention are preferably produced by the one-shot process by means of the low-pressure or high-pressure technique in closed, advantageously heated molds.
  • the molds usually comprise metal, e.g. aluminum or steel.
  • the starting components a) to g) are for this purpose preferably mixed at a temperature of from 15 to 90°C, particularly preferably from 25 to 55°C, and the reaction mixture is introduced, optionally under superatmospheric pressure, into the mold. Mixing can be carried out mechanically by means of a stirrer or a stirring screw or under high pressure in the countercurrent injection process.
  • the mold temperature is advantageously from 20 to 160°C, preferably from 30 to 120°C, particularly preferably from 30 to 60°C.
  • reaction mixture of the components a) to g) at reaction conversions of less than 90%, based on the isocyanate groups is referred to as reaction mixture.
  • the amount of reaction mixture introduced into the mold is calculated so that the moldings obtained, in particular integral foam, have a density of preferably from 80 g/l to 500 g/l, particularly preferably from 150 g/l to 450 g/l.
  • the degrees of compaction for producing the integral polyurethane foams of the invention are in the range from 1 .1 to 8.5, preferably from 1 .7 to 7.0.
  • the polyurethane foam moldings of the invention are preferably used as shoe sole and particularly preferably as (through)sole, for example for street shoes, sports shoes, sandals, slippers and boots.
  • the integral polyurethane foams of the invention are used as throughsole for sports shoes or as sole material of high-heeled ladies' shoes.
  • the thickness of the sole at the thickest point is preferably more than 3 cm, particularly preferably more than 5 cm.
  • polyurethane foams according to the invention can be used in the interior of vehicles, for example in cars as steering wheels, headrests or gearstick knobs or as armrests. Further possible uses are as armrests for chairs or as motor-cycle seats.
  • Polyol 1 Polyesterol based on adipic acid, monoethylene glycol, diethylene glycol and glycerol and having an
  • Polyol 2 Polyesterol based on a mixture of succinic acid, glutaric acid and adipic acid, monoethylene glycol and glycerol and having an OH number of 58 mg KOH/g and a viscosity of 430 mPas at 100°C
  • Polyol 3 Polyesterol based on a mixture of succinic acid, glutaric acid, adipic and monoethylene glycol and having an OH number of 56 mg KOH/g and a viscosity of 650 mPas at 75°C.
  • Polyol 4 Graft polyol based on a polyetherol (based on glycerol, propylene oxide and ethylene oxide and having an ethylene oxide/propylene oxide mixed cap, an OH number of 56 mg KOH/g and a viscosity of 460 mPas at 25°C) and having a solids content of 45% by weight.
  • a polyetherol based on glycerol, propylene oxide and ethylene oxide and having an ethylene oxide/propylene oxide mixed cap, an OH number of 56 mg KOH/g and a viscosity of 460 mPas at 25°C
  • Polyol 5 Graft polyol PM 245® from Synthesia based on polyesterol and having an OH number of 60 mg
  • DA Dispersing agent (polyethylene glycol ester of phosphoric acid).
  • F Filler (Calcium carbonate, mean particle size 5 pm)
  • Prepolymer 1 (Prepol):
  • Prepolymer 2 (Prepo 2):
  • inventive examples E1 and E2 and the comparative examples C1 to C3 were carried out.
  • the components indicated in Table 1 were mixed with the indicated isocyanate prepolymers at the isocyanate index indicated and in each case firstly free-foamed and secondly introduced into a sole mold having the heel height in cm (HH) indicated in the table so as to form moldings having a density of 200 g/l.
  • the density of the free-foamed polyurethane foam in g/l (density fr) is likewise shown in Table 1.
  • the moldings had a good surface quality.
  • the molding from example C3 had a coarse, inhomogeneous cell structure in the upper third of the sole, which cell structure could be compressed under load (human body) and thus had an adverse effect on the stability of the shoe.
  • the integral polyurethane foam as per example E2 showed a homogeneous microcel lular foam structure.
  • Table 1 Composition in parts per weight and properties of Examples E1 and E2 and Comparative Examples C1 - C3

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Un procédé de production de moulages en mousse de polyuréthane, dans lequel a) des polyisocyanates organiques sont mélangés avec b) des polyols comprenant b1) des polyesterols et b2) des polyétherols polymères ayant une proportion de groupes OH primaires de moins de 50 %, c) des agents gonflants, d) des charges et éventuellement e) des allongeurs de chaîne et/ou des agents de réticulation, f) des catalyseurs et g) d'autres auxiliaires et/ou additifs pour former un mélange réactionnel, ce dernier est introduit dans un moule et laissé réagir pour former un moulage de mousse de polyuréthane. La présente invention concerne en outre l'utilisation de tels moulages en mousse de polyuréthane en tant que semelle de chaussure et pantoufle.
PCT/EP2024/061346 2023-05-02 2024-04-25 Moulages en mousse de polyuréthane de faible densité à peau lisse WO2024227678A1 (fr)

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