EP1664145A2 - Procede de production de mousses de polyurethane integrales - Google Patents

Procede de production de mousses de polyurethane integrales

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Publication number
EP1664145A2
EP1664145A2 EP04703771A EP04703771A EP1664145A2 EP 1664145 A2 EP1664145 A2 EP 1664145A2 EP 04703771 A EP04703771 A EP 04703771A EP 04703771 A EP04703771 A EP 04703771A EP 1664145 A2 EP1664145 A2 EP 1664145A2
Authority
EP
European Patent Office
Prior art keywords
weight
oxide
less
organic
ethylene oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04703771A
Other languages
German (de)
English (en)
Inventor
Peter Falke
Heinz-Jürgen SCHRÖDER
Ulf Sattler
Paul Cappellani
Adriano Trinaistich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1664145A2 publication Critical patent/EP1664145A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/4804—Two or more polyethers 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G2110/0083—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

  • polyurethane foams by reacting organic and / or modified organic polyisocyanates or prepolymers with higher-functionality compounds with at least two reactive hydrogen atoms, for example polyoxyalkylene polyamines and / or preferably organic polyhydroxy compounds, in particular polyetherols, with molecular weights of 300 to 6000, and optionally chain extenders and / or crosslinking agents with molecular weights up to about 400 in the presence of catalysts, blowing agents, flame retardants, auxiliaries and / or additives is known and has been described many times.
  • a comprehensive overview of the production of polyurethane foams is e.g. in the plastic manual, volume VII, "Polyurethane", 1st edition 1966, published by Dr. R.
  • WO-A-98/23659 discloses the use of polyether alcohols for safety clothing, in particular safety shoes.
  • polyester alcohol-based polyurethanes are generally used in the production of shoe soles, since sols containing polyether alcohol have inadequate resistance to oil and oils. own interest.
  • the outsoles produced have bulk densities of greater than 800 kg / m3 (midsoles greater than 400 kg / m3).
  • the ethylene oxide content of such polyether alcohols is stated to be a maximum of 40% by weight.
  • US Pat. No. 5,996,253 proposes polyurethane elastomers which have a low rebound resilience and a low hardness. No blowing agents are used here, which means correspondingly high sole densities.
  • US-A-3 793 241 discloses water-driven integral foams.
  • an isocyanate component is made from a TDI polyethylene glycol prepolymer in a blend with a polyisocyanate (PMDI).
  • PMDI polyisocyanate
  • This isocyanate component is then foamed with a mixture of a polypropylene glycol and ice water. The process is very complex.
  • DE-A-40 32 148 deals with integral foams which are foamed exclusively with water as a blowing agent.
  • the polyether alcohols used consist of propylene oxide-containing polyols with an ethylene oxide endcap and a filler-containing polymer polyol.
  • WO-A-99/33893 describes shoe soles which, for reasons of reactivity, have an ethylene oxide endcap of 5 to 35% by weight. Solid particles are introduced through the proportionate use of polymer polyols.
  • EP-A-10 141 098 discloses integral foams. Polyols with secondary OH groups are made accessible for processing via a prepolymer variant.
  • US Pat. No. 4,559,366 uses freons for the production of shoe soles, polyols with ethylene oxide fractions of up to 50% by weight also being used in the prepolyers used.
  • US-A-3 839 138 and US-A-3 781 231 disclose hydrophilic foams which are used as shoe soles.
  • the ethylene oxide-rich polyols used are processed as prepolymers.
  • the isocyanate prepolymers produced in this way are then reacted with hydrophobic polyols, this reaction having to be carried out in the presence of ice water - a complex treatment.
  • the invention was based on the object of producing easy-to-process integral polyurethane foams using both tolylene diisocyanate and, in particular, diphenyl methane diisocyanate isomers which have good solvent resistance, viscoelastic and shock-absorbing properties.
  • the invention thus relates to a process for the production of integral polyurethane foams by reacting organic and / or modified organic polyisocyanates (a) with a polyether mixture (b) and chain extenders (c) and, if appropriate, further compounds (d) which are reactive toward isocyanates in the presence of Water and / or other blowing agents (e), catalysts (f) and optionally further auxiliaries and additives (g), which is characterized in that the polyether mixture (b) has a functionality of 2 to 3 and consists of
  • the invention further relates to the integral polyurethane foams themselves produced by this process and to their use for shoe soles, automobile safety parts and in vehicle construction.
  • the component (bl) consists of at least one at least two-functional polyetherol with an OH number of 20 to 80 mg KOH / g, preferably 25 to 60 mg KOH / g, based on propylene oxide and / or butylene oxide and ethylene oxide with an ethylene oxide content of more than 40 wt .-%, preferably more than 60 wt .-%, each based on the total amount of alkylene oxide used.
  • the polyetherols used advantageously have a proportion of primary OH groups of greater than 40%, preferably of 60 to 85%.
  • polyetherols based on ethylene glycol, glycerol or trimethylpropane as starters with an ethylene oxide end block.
  • Polyetherols based on ethylene glycol and / or glycerol with an ethylene oxide endcap are preferably used.
  • polyetherols (b1) described further at least two-functional polyetherols based on propylene oxide and / or butylene oxide and ethylene oxide with an OH number of 20 to 160 mg KOH / g, preferably 25 to 60 mg KOH / g, and an ethylene oxide content may optionally be used of less than 25% by weight, preferably from 5 to 23% by weight, in each case based on the total amount of alkylene oxide (b3) used.
  • polyetherols based on glycerin, trimethylpropane, diethylene glycol and propylene glycol are considered
  • the polyetherols of component (bl) are preferably used in a proportion of at least 50% by weight, preferably more than 60% by weight, based on the total weight of the polyetherols of components (bl) and (b3) used.
  • the component (b2) consists of at least one at least two-functional polyetherol based on propylene oxide and / or butylene oxide with an OH number of less than 600 mg KOH / g, preferably less than 150 mg KOH / g.
  • polyetherols based on propylene glycol glycerol and ethylene glycol and propylene oxide.
  • Polypropylene glycol based on propylene glycol or glycerin is preferably used.
  • the total amount by weight of components (bl) and (b3) is greater than the amount by weight of component (b2).
  • the ratio of the total amount by weight of (bl) and (b3) to the amount by weight (b2) is advantageously more than 4, particularly preferably more than 5.5.
  • the polyetherols mentioned are prepared by known processes, as described, for example, below.
  • chain extenders and optionally crosslinking agents (c) are used in total in an amount of less than 15% by weight, preferably from 2 to 12% by weight, advantageously from 3 to 10% by weight, based in each case on the preparation of the integral polyurethane foams Total weight of components (b) to (g) used.
  • Difunctional compounds such as glycols, eg. B. ethylene glycol and diethylene glycol, butanediol-1, 4, propylene glycol and dipropylene glycol.
  • Compounds (c) which crosslink the polymer chains with one another can also be used in small amounts in component (c).
  • Such crosslinkers have functionalities greater than two.
  • a suitable crosslinking agent is, for example, glycerol.
  • all other substances described for this purpose in the literature can also be used as chain extenders and wetting agents.
  • the chain extenders and optionally crosslinking agents (c) used according to the invention have molecular weights of less than 300, preferably from 60 to 200.
  • the polyetherols of component (b) and the chain extenders (c) it is also possible to use further compounds (d) containing hydrogen atoms that are reactive toward isocyanates.
  • Compounds with at least two reactive hydrogen atoms and an average molecular weight from 300 are primarily suitable for this. It is expedient to use those having a functionality of 2 to 8, preferably 2 to 3, and an average molecular weight of 300 to 8000, preferably 500 to 5000.
  • the hydroxyl number of the polyhydroxyl compounds is generally 20 to 250 and preferably 28 to 60.
  • polyether polyols used in components (b) and (d) are obtained by known processes, for example by anionic polymerization with alkali metal hydroxides, such as Sodium or potassium hydroxide or alkali alcoholates, e.g. Sodium methylate, sodium or potassium ethylate or potassium isopropylate as cataly-
  • alkali metal hydroxides such as Sodium or potassium hydroxide or alkali alcoholates, e.g. Sodium methylate, sodium or potassium ethylate or potassium isopropylate as cataly-
  • catalysts and with the addition of at least one starter molecule which contains 2 to 8, preferably 2 to 3, bonded reactive hydrogen atoms, or by cationic polymerization with Lewis acids, such as antimony pentachloride, borofluoride etherate and others. , or bleaching earth as catalysts or by double metal cyanide catalysis from one
  • Alkylene radical produced can also be integrated into the polyether structure for special purposes.
  • Suitable alkylene oxides are, for example, tetrahydrofuran,
  • 1,3-propylene oxide 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • starter molecules are: water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'-dialkyl-substituted
  • 35 diamines with 1 to 4 carbon atoms in the alkyl radical such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1-butylenediamine, 1,2-, 1,3- , 1,4-, 1,5- and 1,6-hexamethylene diamine, phenylenediamine, 2,3-, 2,4- and 2,6-toluenediamine and
  • alkanolamines such as Ethanolamine, N-methyl and N-ethylethanolamine
  • dialkanolamines such as e.g. Example, diethanolamine, N-methyl and N-ethyldiethanolamine
  • trialkanolamines such as. B. triethanolamine, and ammonia.
  • alkanolamines such as Ethanolamine, N-methyl and N-ethylethanolamine
  • dialkanolamines such as e.g. Example, diethanolamine, N-methyl and N-ethyldiethanolamine
  • trialkanolamines such as. B. triethanolamine, and ammonia.
  • polyhydric especially di- and / or trihydric alcohols, such as ethanediol, 1,2-and 2,3-propanediol, diethyl lenglycol, dipropylene glycol, 1,4-butanediol, 1, 6-hexanediol, glycerin, trimethylolpropane, pentaerythritol.
  • di- and / or trihydric alcohols such as ethanediol, 1,2-and 2,3-propanediol, diethyl lenglycol, dipropylene glycol, 1,4-butanediol, 1, 6-hexanediol, glycerin, trimethylolpropane, pentaerythritol.
  • the polyether polyols preferably polyoxypropylene and polyoxypropylene polyoxyethylene polyols, have a functionality of preferably 2 to 8 and in particular 2 to 3 and molecular weights of 300 to 8000, preferably 300 to 6000 and in particular 1000 to 5000 and suitable polyoxytetramethylene glycols a molecular weight of up to approximately 3500.
  • polyether polyols are polymer-modified polyether polyols, preferably graft polyether polyols, in particular those based on styrene and / or acrylonitrile, which are obtained by in situ polymerization of acrylonitrile, styrene or preferably mixtures of styrene and acrylonitrile, e.g.
  • polyether polyol dispersions which are used as a disperse phase, usually in an amount of 1 to 50% by weight, preferably 2 to 25% by weight.
  • -% include: e.g. Polyureas, polyhydrazides, tert.
  • polyether polyamines and / or other polyols selected from the group of polyester polyols, polythioether polyols, polyester amides, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates or mixtures of at least two of the polyols mentioned.
  • the hydroxyl number of the polyhydroxyl compounds is generally 20 to 80 and preferably 28 to 56.
  • Suitable polyester polyols can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, by customary processes.
  • the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are catalyst-free 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 from 150 to 250 ° C, preferably 180 to 220 ° C, optionally under reduced pressure to the desired acid number, which is advantageously less than 10, preferably less than 2, polycondensed.
  • inert gas such as nitrogen, carbon monoxide, helium, argon, etc.
  • hydroxyl-containing polyacetals include the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4, 4 '-dihydroxyethoxydiphenyldimethylmethane, hexanediol and formaldehyde. Suitable polyacetals can also be prepared by polymerizing cyclic acetals.
  • Suitable hydroxyl-containing polycarbonates are those of the type known per se, which can be obtained, for example, by reacting diols, such as 1,3-propanediol, 1,3-butanediol, 4 and / or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, eg Diphenyl carbonate, or phosgene can be produced.
  • diols such as 1,3-propanediol, 1,3-butanediol, 4 and / or 1,6-hexanediol
  • diethylene glycol triethylene glycol or tetraethylene glycol
  • diaryl carbonates eg Diphenyl carbonate
  • phosgene phosgene
  • polyether polyamines can be prepared from the above-mentioned polyether polyols by known processes. Examples include the cyanoalkylation of polyoxyalkylene polyols and subsequent hydrogenation of the nitrile formed (US Pat. No. 3,266,050) or the partial or complete amination of polyoxyalkylene polyols with amines or ammonia in the presence of hydrogen and catalysts (DE-A-1 215 373).
  • the compounds of component (d) can be used individually or in the form of mixtures.
  • the integral polyurethane foams according to the invention are obtained by reacting components (b), (c) and optionally (d) with organic and / or modified organic polyisocyanates (a) in the presence of water and / or other blowing agents (e), catalysts (f) and optionally other auxiliaries and additives (g).
  • the foams are produced according to the invention with key figures of less than 110, preferably 90 to 105.
  • Suitable organic polyisocyanates (a) for producing the integral polyurethane foams according to the invention are the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyvalent isocyanates known per se.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical such as 1, 12-dodecane diisocyanate, 2-ethyl-tetramethylene diisocyanate-1, 4, 2-methylpentamethylene diisocyanate-1, 5, tetramethylene diisocyanate-1, 4 and preferably hexamethylene diisocyanate-1, 6; cycloaliphatic diisocyanates, such as cyclohexane-1, 3- and-1, 4-diisocyanate and any mixtures of these isomers, l-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI), 2,4- and 2 , 6-hexahydrotoluenediisocyanate and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, 4,4'-
  • Toluene diisocyanate mixtures of diphenylmethane diisocyanate isomers, mixtures of diphenylmethane diisoeyanate and crude MDI or tolylene diisocyanate with diphenyl methane diisocyanate and / or crude MDI are preferably used. Mixtures with proportions of 2,4′-diphenylmethane diisocyanate of more than 30% by weight are particularly preferably used.
  • modified polyvalent isocyanates ie products obtained by chemical reaction of organic di- and / or polyisocyanates, are also frequently used. Examples include di- and / or polyisocyanates containing ester, urea, biuret, ophllophanate, carbodiid, isocyanurate, uretdione and / or urethane groups.
  • the di- or polyoxyalkylene glycols can be used individually or as mixtures, for example: diethylene, dipropylene glycol, polyoxyethylene, polyoxypropylene and polyoxypropylene polyoxyethylene glycols, triols and / or tetrols.
  • Prepolymers containing NCO groups and having NCO contents of 25 to 3.5% by weight, preferably 21 to 14% by weight, based on the total weight, prepared from the polyester and / or preferably polyether polyols described below are also suitable and 4,4'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-tolylene diisocyanates or crude MDI.
  • NCO contents 43 to 15, preferably 31 to 21% by weight, based on the total weight, for example based on 4,4'-, 2,4 ', have also proven useful.
  • modified polyisocyanates can be used together or with unmodified organic polyisocyanates such as e.g. 2,4'-, 4, 4'-diphenylmethane diisocyanate, crude MDI, 2,4- and / or 2,6-toluenediisocyanate are mixed.
  • unmodified organic polyisocyanates such as e.g. 2,4'-, 4, 4'-diphenylmethane diisocyanate, crude MDI, 2,4- and / or 2,6-toluenediisocyanate are mixed.
  • NCO group-containing prepolymers which are advantageously formed by reacting at least parts of components (a), (b) and, if appropriate, (c), (d) and / or (e), in particular those which at least partially contain component (bl).
  • water is used as blowing agent (s) in proportions of 1 to 10% by weight, preferably in an amount of 0.1 to 5% by weight and particularly preferably of 0.1 to 2% by weight, in each case based on the total weight of components (b) to (g) used.
  • the water can be added in combination with other conventional blowing agents.
  • CFCs chlorofluorocarbons
  • aliphatic and / or cycloaliphatic hydrocarbons in particular pentane and cyclopentane or acetals, such as methylyl, are particularly suitable as alternative blowing agents.
  • These physical blowing agents are usually added to the polyol component of the system.
  • the Isocyanate component or as a combination of both the polyol component and the isocyanate component. It is also possible to use them together with highly and / or perfluorinated hydrocarbons, in the form of an emulsion of the polyol component.
  • emulsifiers if they are used, it is customary to use oligomeric acrylates which contain bound polyoxyalkylene and fluoroalkane radicals as side groups and have a fluorine content of approximately 5 to 30% by weight.
  • Such products are well known from plastic chemistry, e.g. B. EP-A-0351614.
  • the amount of the blowing agent or blowing agent mixture optionally used in addition to water is advantageously 1 to 10% by weight, preferably 1 to 3% by weight, based in each case on the total weight of components (b) to (e).
  • the catalysts (e) used for the production of the integral polyurethane foams according to the invention are, in particular, compounds which react the reaction of the reactive hydrogen atoms, in particular compounds containing hydroxyl groups, of components (b), (c), (d) and (e) with the organic, if appropriate accelerate modified polyisocyanates (a) strongly.
  • Organic metal compounds preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, for. B. tin (II) acetate, tin (II) octoate,
  • organic carboxylic acids e.g. B. dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate.
  • the organic metal compounds are used alone or preferably in combination with strongly basic amines.
  • Examples include amidines such as 2,3-dimethyl-3, 4, 5, 6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, dirnethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetr- ⁇ ⁇ t_ethylhexanediamine-1,6, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether , Bis (dimethylaminopropyl) urea, dimethylpiperazine, 1, 2-dimethylimidazole, 1-azabicyclo- (3, 3, 0) -octane and preferably 1, 4-diazabicyclo- (2, 2.2)
  • Suitable catalysts are: tris (dialkylaminoalkyl) -s-hexahydrotriazines, especially tris (N, N-dimethylamino-propyl) -s-hexahydrotriazine, tetraalkylammonium hydroxides, such as
  • Tetramethylammonium hydroxide such as sodium hydroxide and alkali alcoholates such as sodium methylate and potassium isopropylate, as well as alkali salts of long-chain fatty acids with 10 to 20 carbon atoms and optionally pendant OH groups.
  • auxiliaries and / or additives (g) can be incorporated into the reaction mixture for producing the integral polyurethane foams according to the invention.
  • auxiliaries and / or additives (g) include flame retardants, stabilizers, fillers, dyes, pigments and hydrolysis protection agents, as well as substances with a functionalist and bacteriostatic effect.
  • Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, dimethyl methane phosphonate, diethanolaminomethylphosphonic acid diethyl ester and commercially available halogen-containing flame retardant polyols.
  • inorganic or organic flame retardants such as red phosphorus, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, such as e.g. Melamine, or mixtures of at least two flame retardants, e.g. Ammonium polyphosphates and melamine and optionally corn starch or ammonium polyphosphate, melamine and expandable graphite and / or optionally aromatic polyesters are used to flame retard the polyisocyanate polyaddition products. Additions of melamine have proven particularly effective. In general, it has proven useful to 5 to
  • surface-active substances ie compounds
  • stabilizers which serve to support the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the plastics.
  • emulsifiers such as the sodium salts of castor oil sulfates or fatty acids, and salts of fatty acids with amines, for example oleic acid diethylamine, stearic acid diethanolamine, ricinoleic acid diethanolamine, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene- and disulphonic acid or disulfonic acid
  • Foam stabilizers such as siloxane-oxalkylene copolymers and other organopolylsiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and peanut oil, and cell
  • Mainly organopolysiloxanes that are water-soluble are used as stabilizers. These are polydimethylsiloxane residues to which a polyether chain of ethylene oxide and propylene oxide is grafted.
  • the surface-active substances are usually used in amounts of 0.01 to 5 parts by weight, based on 100 parts by weight of components (b) to (g).
  • Fillers in particular reinforcing fillers, are understood to be the conventional organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating agents, etc., which are known per se.
  • inorganic fillers such as silicate minerals, for example sheet silicates, such as antigorite, serpentine, hornblende, ampiboles, chrisotile and talc, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts such as chalk, heavy spar and inorganic pigments, such as cadmium sulfide and zinc sulfide, as well as glass etc.
  • kaolin china clay
  • aluminum silicate and coprecipitates made from barium sulfate and aluminum silicate
  • natural and synthetic fibrous minerals such as wollastonite, metal and in particular glass fibers of various lengths, which are optionally sized could be.
  • suitable organic fillers are: carbon, rosin, cyclopentadienyl resins and graft polymers as well as cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and in particular carbon fibers.
  • the inorganic and organic fillers can be used individually or as mixtures and are advantageously added to the reaction mixture in amounts of 0.5 to 50% by weight, preferably 1 to 40% by weight, based on the weight of components (a) to (g), but the content of mats, nonwovens and fabrics made of natural and synthetic fibers can reach values up to 80.
  • the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of the reactive hydrogen atoms of components (b) to 10 (g) is thus 0.90 to 1.10: 1, preferably 0.95 to 1.05: 1.
  • Integral polyurethane foams by the process according to the invention are advantageously produced by the one-shot process, for example with the aid of high-pressure or low-pressure technology 15 in open or closed molds, for example metallic molds.
  • the starting components are at a temperature from 15 to 90 ° C, preferably from 20 to 60 ° C and in particular from 20 to
  • the mixing can be carried out mechanically by means of a stirrer, by means of a stirring screw or by a
  • the mold temperature is advantageously 20 to 110 ° C, preferably 30 to 60 ° C and in particular 35 to 55 ° C.
  • the integral 40 foams produced by the process according to the invention have a density of 100 to 800 kg / m 3 , preferably of 250 to 600 kg / m 3 .
  • the Shore A hardness is determined according to DIN 53505.
  • the swelling behavior of the integral foams in hydrocarbons is less than 10%, preferably 1 to 5%. This means that such foams are suitable for use in the presence of these media.
  • the swelling behavior is determined after 5 minutes' storage in cyclopentane (as an increase in volume).
  • the integral foams according to the invention have good solvent resistance and excellent shock-absorbing properties.
  • Examples 1, 2 and 4 isocyanate mixture of 20 Tl Lupranat.RTM MI, 5 20 parts Lupranat.RTM M20A and 60 Tl Lupranat ® MES;...
  • Example 3 NCO prepolymer with 20.5% by weight NCO content
  • Example 5 Isocyanate mixture of 80 parts of Lupranat® MI and 10 20 parts of Lupranat® M20A.
  • Polyol bl polyether alcohol based on propylene and ethylene oxide (73% by weight), OH number 42 mg KOH / g, BASF;
  • polyol b2 polyether alcohol based on propylene oxide, OH number 56 mg KOH / g, BASF;
  • Polyol b3 polyether alcohol based on propylene and ethylene oxide (14% by weight), OH number 36 mg KOH / g, BASF; 20
  • Silicon Stabilizer - B 8409 (Goldschmidt);

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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

L'invention concerne un procédé permettant de produire des mousses de polyuréthane intégrales, par réaction de polyisocianates organiques et/ou organiques modifiés (a), avec un mélange polyétherol (b) et des prolongateurs de chaîne (c), en présence d'eau et/ou d'autres agents moussants (e) et de catalyseurs (f). Ledit procédé se caractérise en ce que le mélange polyéthérol (b) présente une fonctionnalité de l'ordre de 2 à 3 et comprend b1) au moins un polyéthérol au moins bifonctionnel, à base d'oxyde de propylène et/ou d'oxyde de butylène et d'oxyde d'éthylène, avec une proportion d'oxyde d'éthylène supérieure à 40 % en poids, par rapport à la quantité totale d'oxyde d'alkylène utilisée, avec un indice hydroxyle de l'ordre de 20 à 80 KOH/g et b2) au moins un polyéthérol au moins bifonctionnel, à base d'oxyde de propylène et/ou d'oxyde de butylène, avec un indice hydroxyle inférieur à 600 mg KOH/g. La réaction intervient à des indices inférieurs à 110. La quantité en poids total de (b1) est supérieure à celle de (b2) et la proportion de prolongateurs de chaîne (c) est inférieure à 15 % en poids, par rapport au poids total des constituants (b) à (f). L'invention concerne en outre les mousses de polyuréthane intégrales en soi, obtenues à l'aide dudit procédé et leur utilisation pour fabriquer des semelles de chaussures, des éléments de sécurité automobile, ainsi que dans le cadre de la construction de véhicules.
EP04703771A 2003-01-27 2004-01-21 Procede de production de mousses de polyurethane integrales Withdrawn EP1664145A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10303172A DE10303172A1 (de) 2003-01-27 2003-01-27 Verfahren zur Herstellung von Polyurethanintegralschaumstoffen
PCT/EP2004/000459 WO2004067607A2 (fr) 2003-01-27 2004-01-21 Procede de production de mousses de polyurethane integrales

Publications (1)

Publication Number Publication Date
EP1664145A2 true EP1664145A2 (fr) 2006-06-07

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EP04703771A Withdrawn EP1664145A2 (fr) 2003-01-27 2004-01-21 Procede de production de mousses de polyurethane integrales

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EP (1) EP1664145A2 (fr)
CN (1) CN1329422C (fr)
DE (1) DE10303172A1 (fr)
WO (1) WO2004067607A2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009068515A1 (fr) * 2007-11-26 2009-06-04 Basf Se Mousse de polyuréthane intégrale contenant un dialkylester d'acide cyclohexanedicarboxylique comme agent de démoulage interne
ITMI20101084A1 (it) * 2010-06-16 2011-12-16 Dow Global Technologies Inc Suole poliuretaniche di scarpe preparate usando polioli a base di ossido di propilene
CN102898618A (zh) * 2012-09-24 2013-01-30 吴江市信许塑料鞋用配套有限公司 一种减震鞋底材料的制备方法
CN102875766A (zh) * 2012-09-24 2013-01-16 吴江市信许塑料鞋用配套有限公司 一种吸震鞋底材料的制备方法
CN103072232A (zh) * 2012-12-13 2013-05-01 杨厚基 一种利用废弃下脚料生产聚氨酯保温板的工艺及设备
CN105418888A (zh) * 2015-12-16 2016-03-23 芜湖馨源海绵有限公司 一种用于鞋帮制品的海绵及其制备工艺
CN111848905A (zh) * 2020-06-10 2020-10-30 武汉希睿思新材料科技有限公司 一种多孔隙的聚氨酯发泡减震材料及其制备方法

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JPS583488B2 (ja) * 1978-05-15 1983-01-21 株式会社ブリヂストン 軟質ポリエ−テルポリウレタンフオ−ムの製造方法
US4559366A (en) * 1984-03-29 1985-12-17 Jaquelyn P. Pirri Preparation of microcellular polyurethane elastomers
US4863976A (en) * 1988-04-26 1989-09-05 Dow Chemical Company Polyurethane foam prepared using high functionalilty cell openers
DE3942330A1 (de) * 1989-12-21 1991-06-27 Basf Ag Verfahren zur herstellung von flexiblen polyurethan-weichschaumstoffen mit viskoelastischen, koerperschalldaempfenden eigenschaften und hierzu verwendbare polyoxyalkylen-polyol-mischungen
GB9301995D0 (en) * 1993-02-02 1993-03-17 Ici Plc Process for making flexible foams
TW358815B (en) * 1994-06-16 1999-05-21 Huntsman Ici Chem Llc Process for preparing a flexible polyurethane foam
CN1210324C (zh) * 1995-12-08 2005-07-13 亨茨曼Ici化学品有限公司 聚氨酯弹性体

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Also Published As

Publication number Publication date
DE10303172A1 (de) 2004-07-29
CN1329422C (zh) 2007-08-01
WO2004067607A2 (fr) 2004-08-12
CN1771270A (zh) 2006-05-10
WO2004067607A3 (fr) 2006-04-13

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