WO2006066763A1 - Procede de production d'elastomeres de polyurethanne microcellulaires - Google Patents

Procede de production d'elastomeres de polyurethanne microcellulaires Download PDF

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Publication number
WO2006066763A1
WO2006066763A1 PCT/EP2005/013405 EP2005013405W WO2006066763A1 WO 2006066763 A1 WO2006066763 A1 WO 2006066763A1 EP 2005013405 W EP2005013405 W EP 2005013405W WO 2006066763 A1 WO2006066763 A1 WO 2006066763A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane elastomers
microcellular polyurethane
aii
elastomers according
phosphorus content
Prior art date
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PCT/EP2005/013405
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German (de)
English (en)
Inventor
Markus SCHÜTTE
Diane Terese Langer
Original Assignee
Basf Aktiengesellschaft
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Priority to CN2005800431336A priority Critical patent/CN101080428B/zh
Publication of WO2006066763A1 publication Critical patent/WO2006066763A1/fr

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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
    • C08G18/08—Processes
    • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
    • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
    • 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
    • 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
    • C08G18/28—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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5353—Esters of phosphonic acids containing also nitrogen
    • 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
    • C08G2110/0066—≥ 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
    • C08G2410/00—Soles

Definitions

  • Polyurethane integral foams often referred to as microcellular polyurethane elastomers and hereinafter also referred to as MPE, have been known for a long time and are used, for example, for the production of shoe soles. They are described, for example, in the Kunststoffhandbuch, volume 7 "Polyurethane", 3rd edition, page 376 et seq., They are prepared by reacting polyisocyanates with compounds having at least two isocyanate-reactive hydrogen atoms as compounds having at least two hydrogen atoms reactive with isocyanate groups These materials are often used to produce high performance materials such as high elasticity, high tensile and tear strength or low abrasion, while at the same time processing such systems with high process reliability, a disadvantage of microcellular polyester-based polyurethane elastomers The low resistance to hydrolysis is caused by the intrinsic susceptibility of the ester groups to hydrolytic degradation, and the cleavage of the ester groups causes a reduction in the molar mass e of the polymer and
  • polyester alcohols based on adipic acid 1,4-butanediol, 1,6-hexanediol and neopentyl glycol are used.
  • substitution or partial substitution of the polyester alcohols for hydrolysis-resistant polyether alcohols is described.
  • EP 965 582 describes the use of acid anhydrides
  • DE 19 710 978 describes the use of a combination of lactones and carbodiimides.
  • the solutions to be taken from the prior art usually have disadvantages. In some cases, higher hydrolysis resistances are achieved, but at the same time only insufficient use properties are obtained before aging. In addition, some solutions can not be realized in practice due to the higher input costs. This can be done, for example, in the case of the use of special len polyester alcohols or high amounts of certain additives occur. Another disadvantage of many of the prior art solutions to be taken is the reduction of the storage stability of the components. Furthermore, many solutions have too low an efficacy, especially if extremely high demands are made on the hydrolysis resistance.
  • phosphites generally in microcellular polyurethane elastomers is known and is described e.g. in Kunststoffhandbuch, volume 7 "Polyurethane", 3rd edition, page 120 ff.
  • phosphites are used as antioxidants, and their use in combination with typical antioxidants, such as sterically hindered phenols, leads to a synergistic effect Effect, combined with a significant increase in the effect of preventing thermal oxidation processes.
  • JP 61128904 describes the use of 4-14% by weight of phosphite esters in polyester-based microcellular polyurethane elastomers. Phosphites based on phenol and long-chain alkyl radicals are used as yellowing inhibitors. The phosphites are used in the prepolymer.
  • JP 63278962 describes UV-stable polyester-based MPE for shoe soles. Phosphites are used as antioxidant aids together with sterically hindered phenols as antioxidant. The proportion by weight is 1 wt .-%.
  • JP 63305162 describes a UV stabilization package for polyester alcohol-based MPE. Here is u.a.
  • the proportion by weight is 0.5% by weight.
  • JP 05214240 describes a UV protection for PUR shoe soles which i.a. Contains thiophosphites in amounts of about 1%.
  • JP 2003147057 describes the use of polycarbonate diols in shoe systems. The example mentions that about 2% by weight of TPP is added to the prepolymer.
  • JP 61128904, JP 63278962 and JP 05214240 generally describe the use of phosphites in polyester-based MPE as antioxidant aids.
  • the documents JP 63278962 and JP 63305162 mention that i.a. aromatic phosphites can be used as an antioxidant in the isocyanate-reactive component.
  • the document JP 2003147057 describes the use of aromatic phosphites in microcellular polyurethane elastomers based on polyether carbonate alcohols.
  • the object of the present application was to provide a hydrolysis protection agent for polyester alcohol-based MPE, which allows a high effect at low input and guarantees high efficiency regardless of the polyester alcohol used.
  • the object could be achieved by the use of a special hydrolysis protection agent a), consisting of a combination of ai) an aromatic phosphite with a phosphorus content of 9.00 to 11, 00 wt .-%, preferably 9.90 to 10 , 10 wt .-% and in particular 9.95 to 10.05 wt .-% and aii) an amine compound such as triethylenediamine, wherein the molar ratio between ai) and aii) preferably 0.005 to 4.0, particularly preferably. 0.1 to 3.0, and especially 0.5 to 2.0. is.
  • the component ai) is preferably used in the isocyanate-containing component (B component) and aii) in the isocyanate-reactive component (A component).
  • MPE can be prepared by reacting polyisocyanates with compounds having at least two isocyanate-reactive hydrogen atoms, characterized in that it is a combination of a) consisting of ai) an aromatic phosphite having a phosphorus content of 9.00 to 11 , 00 wt .-%, and aii) of an amine compound, wherein the molar ratio between ai) and aii) is 0.005 to 4.0.
  • the invention furthermore relates to a process for the preparation of MPE by reacting polyisocyanates with compounds having at least two isocyanate-reactive hydrogen atoms, characterized in that the reaction in the presence of a), which comprises a combination consisting of ai) an aromatic phosphite with phosphorus content of 9.00 to 11.00 wt%, and aii) an amine compound, wherein the molar ratio between ai) and aii) is 0.005 to 4.0.
  • a which comprises a combination consisting of ai) an aromatic phosphite with phosphorus content of 9.00 to 11.00 wt%, and aii) an amine compound, wherein the molar ratio between ai) and aii) is 0.005 to 4.0.
  • the invention also provides the use of a combination of ai) an aromatic phosphite having a phosphorus content of 9.00 to 11, 00 wt .-%, and aii) an amine compound as a hydrolysis protection for MPE.
  • the invention also relates to shoe soles comprising the microcellular polyurethane elastomers according to the invention.
  • the molar ratio between ai) and aii) is preferably 0.1 to 3.0, and more preferably 0.5 to 2.0.
  • the phosphorus content of component ai) is preferably 9.90 to 10.10 wt .-% and in particular 9.95 to 10.05 wt .-%.
  • the component ai) used is preferably triphenyl phosphite (TPP). 4
  • amine compounds aii) primary, secondary and preferably tertiary amines can be used. These are preferably those amines which are customarily used as catalysts for the preparation of polyurethanes.
  • tertiary amines selected from the groups comprising triethylamine, triethylenediamine, tributylamine, dimethylbenzylamine, N, N 1 N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N , N ', N'-tetramethylhexane-1,6-diamine, dimethylcyclohexylamine, pentamethyldipropylenetriamine, penta-methyldiethylenetriamine, 3-methyl-6-dimethylamino-3-azapentol, dimethylaminopropylamine, 1,3-bisdimethylaminobutane, bis ( 2-dimethylaminoethyl) ether, N-ethylmorpholine, N-methylmorpholine, N-cyclohexylmorpholine, 2-dimethylaminoethoxyethanol, dimethylethanolamine, tetramethyl
  • the amount of tertiary amines used as a catalyst is sufficient to achieve the required stabilizing effect in combination with the aromatic phosphites ai).
  • additional amines when using other than amine catalysts or when using smaller amounts of amine catalysts than required for adequate stabilization. These will not be the tertiary amines used as catalysts in the process to exclude catalysis disturbances.
  • the hydrolysis protection agent a) in an amount of 0.0001 to 3, 0.0005 to 2 and 0.001 to 1, 6 wt .-%, based on the weight of the MPE used.
  • the polyisocyanates used in the process according to the invention include the known from the prior art aliphatic, cycloaliphatic and aromatic isocyanates and any mixtures thereof. Examples are diisocyanate 4,4 'diphenylmethane ⁇ , the mixtures of monomeric diphenylmethane diisocyanates and higher-nuclear homologues of diphenylmethane diisocyanate (polymeric MDI), tetramethylene 5 013405
  • O is diisocyanate, hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI) or mixtures thereof.
  • 4,4'-MDI and / or HDI is used.
  • the most preferred 4,4'-MDI may contain minor amounts, up to about 10% by weight, of allophanate- or urethane-onimine-modified polyisocyanates. It is also possible to use small amounts of polyphenylenepolymethylene polyisocyanate (crude MDI). The total amount of these high-functionality polyisocyanates should not exceed 5% by weight of the isocyanate used.
  • the 4,4'-MDI may contain small amounts, preferably at most 10% by weight, of 2,4'-MDI.
  • the polyisocyanates can also be used in the form of polyisocyanate prepolymers. These prepolymers are known in the art. The preparation is carried out in a manner known per se, by reacting polyisocyanates described above, for example at temperatures of about 8O 0 C, with the compounds described below with isocyanate-reactive hydrogen atoms to the prepolymer.
  • the polyol-polyisocyanate ratio is generally chosen so that the NCO content of the prepolymer 8 to 25 wt .-%, preferably 10 to 22 wt .-%, particularly preferably 13 to 20 wt .-% is.
  • polyester alcohols are used as compounds with isocyanate-reactive hydrogen atoms.
  • the polyester alcohols are generally obtained by condensation of polyfunctional alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, with polyfunctional carboxylic acids having 2 to 12 carbon atoms, for example succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, and / or terephthalic acid and mixtures thereof.
  • polyfunctional alcohols preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms
  • polyfunctional carboxylic acids having 2 to 12 carbon atoms
  • suitable dihydric and polyhydric alcohols are ethylene glycol, diethylene glycol, 1,4-butanediol, 1, 5-pentanediol, and / or 1, 6-hexanediol and mixtures thereof.
  • the polyester alcohols may also be branched.
  • the branched polyester alcohols preferably have a functionality of more than 2 to 3, in particular from 2.2 to 2.8. Furthermore, the branched polyester alcohols preferably have a number-average molecular weight of from 500 to 5000 g / mol, more preferably from 2000 to 3000 g / mol.
  • the polyester alcohols used for the process according to the invention have an average theoretical functionality of 2 to 4, preferably of more than 2 to less than 3 and the above-mentioned number average molecular weights.
  • polyester alcohols used can in principle also be used in a mixture with polyether alcohols. However, since such mixtures often have insufficient phase stability, the use of such mixtures is not preferred.
  • the compounds having two active hydrogen atoms also include the optionally used chain extenders.
  • Suitable chain extenders are known in the art. Preference is given to using 2-functional alcohols having molecular weights below 400 g / mol, in particular in the range from 60 to 150 g / mol. Examples are ethylene glycol, 1,3-propanediol, diethylene glycol, butanediol-1, 4, glycerol or trimethylolpropane, and mixtures thereof. Preferably, ethylene glycol is used.
  • the chain extender if used, is usually present in an amount of from 1 to 15% by weight, preferably from 3 to 12% by weight, more preferably from 4 to 10% by weight, based on the total weight of the two compounds Isocyanatat phenomenon reactive hydrogen atoms used.
  • blowing agents it is possible to use generally known chemically or physically active compounds.
  • chemically acting blowing agent water can preferably be used.
  • physical blowing agents are inert (cyclo) aliphatic hydrocarbons having from 4 to 8 carbon atoms which evaporate under the conditions of polyurethane formation. The amount of blowing agent used depends on the desired density of the foams.
  • the reaction of the polyisocyanates with the compounds with two active hydrogen atoms is optionally carried out in the presence of catalysts and of auxiliaries and / or additives, such.
  • Catalysts for the preparation of the microcellular polyurethane elastomers according to the invention can be the customary and known polyurethane-forming catalysts, for example organic metal compounds, such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and / or strongly basic amines, such as diazabicyclooctane, bis (N, N-dimethylaminoethyl) ether or the above-mentioned amines.
  • the catalysts are preferably used in an amount of from 0.01 to 10% by weight, preferably from 0.02 to 5% by weight, based on the reaction mixture.
  • amines in particular tertiary amines, are preferably used as catalysts.
  • the amines can, as described above, individually or as any mixtures with one another set. These act simultaneously in the microcellular polyurethane elastomers as component aii).
  • organic amines known from the prior art tertiary amines are useful.
  • suitable are organic amines, such as triethylamine, triethylenediamine, tributylamine, dimethylbenzylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ' , N'-tetramethylhexane-1,6-diamine, dimethylcyclohexylamine, pentamethyldipropylenetriamine, pentamethyldiethylenetriamine, 3-methyl-6-dimethylamino-3-azapentol, dimethylaminopropylamine, 1,3-bis-dimethylaminobutane, bis (2-dimethylaminoethyl) - ether, N-ethylmorpholine, N-methylmorpholine, N-cyclohexylmorpholine, 2-dimethylamin
  • the catalysts which can be used in a mixture with the tertiary amines are, as described above, mainly organic metal compounds, in particular tin compounds, such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and / or bismuth compound.
  • the catalysts are preferably mixed with the compounds having at least two isocyanate-reactive hydrogen atoms. In principle, it is also possible to mix at least the organic metal compounds with the polyisocyanates.
  • the polyisocyanates are referred to as the isocyanate component and the compounds having at least two isocyanate-reactive hydrogen atoms, which is usually used in admixture with the catalysts, optionally the blowing agents and additives, as a polyol component.
  • the isocyanate component and the polyol component are usually reacted in amounts such that the equivalent ratio of NCO groups to the sum of the reactive hydrogen atoms is 1: 0.8 to 1: 1, 25, preferably 1: 0.9 to 1 : 1, 15 is.
  • a ratio of 1: 1 corresponds to an NGO index of 100.
  • the reaction to the microcellular polyurethane elastomer is preferably carried out in densified forms.
  • the molds are preferably made of metal, for example steel or aluminum, or else of plastic, for example epoxy resin.
  • the starting components are mixed at temperatures of 15 to 90 ° C., preferably at 20 to 35 ° C., and if appropriate under elevated pressure, introduced into the preferably closed molding tool.
  • the mixing can be carried out during introduction by known in the art high or low pressure mixing heads.
  • the mold temperature is generally between 20 and 90 0 C, preferably between 30 and 60 ° C.
  • the amount of the reaction mixture introduced into the mold is such that the resulting molded articles have a density of from 250 to 600 g / l or from 800 to 1200 g / l, preferably from 400 to 600 g / l or from 820 to 1050 g / l , exhibit.
  • the degrees of compression of the resulting microcellular polyurethane elastomers are between 1, 1 and 8.5, preferably between 1.2 and 5, particularly preferably between 1, 5 and 4.
  • microcellular polyurethane elastomers according to the invention can be used for steering wheels, safety clothing and preferably for shoe soles.
  • 100 parts by weight of the polyol component and the specified in Table 1 parts by weight of the isocyanate component were thoroughly mixed at 23 ° C and the mixture in a tempered at 50 0 C, plate-shaped aluminum mold with dimensions of 20cm x 20 cm ⁇ 1 cm in such an amount that after foaming and curing in the closed mold, a microcellular polyurethane elastomer plate with a total density of 550 g / l resulted.
  • Amine catalyst 33% strength by weight solution of triethylenediamine in ethylene glycol (Lupragen ® N 202) BASF AG
  • Table 1 Composition of the systems V1-V3 (comparative examples) and 1-4 (examples according to the invention).
  • Table 2 Aging results of samples V1-V3 and 1-4.
  • a) residual tensile strength or residual strain in% of the initial value after 2 weeks of aging.

Abstract

Procédé de production d'élastomères de polyuréthanne microcellulaires qui peuvent être obtenus par mise en réaction de polyisocyanates avec des composés ayant au moins deux atomes d'hydrogène réagissant avec les groupes isocyanate. Lesdits élastomères sont caractérisés en ce qu'ils contiennent une combinaison (a) constituée (ai) d'un phosphite aromatique ayant une teneur en phosphore de 9,00 à 11,00 % en poids, et (aii) d'un composé amine, le rapport molaire entre (ai) et (aii) 0,005 allant jusqu'à 4,0.
PCT/EP2005/013405 2004-12-17 2005-12-14 Procede de production d'elastomeres de polyurethanne microcellulaires WO2006066763A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2005800431336A CN101080428B (zh) 2004-12-17 2005-12-14 生产微孔聚氨酯弹性体的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004061609.4A DE102004061609B4 (de) 2004-12-17 2004-12-17 Mikrozelluläre Polyurethan-Elastomere, herstellbar durch Umsetzung von Polyisocyanaten enthaltend 4,4'-Diphenylmethandiisocyanat, Verfahren zur Herstellung solcher mikrozellulären Polyurethan-Elastomere und deren Verwendung
DE102004061609.4 2004-12-17

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WO2006066763A1 true WO2006066763A1 (fr) 2006-06-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008074701A1 (fr) * 2006-12-20 2008-06-26 Basf Se Élastomère cellulaire anisotrope
WO2008074705A1 (fr) * 2006-12-20 2008-06-26 Basf Se Élastomère cellulaire anisotrope
US7985780B2 (en) 2005-02-22 2011-07-26 Basf Se Cylindrical mouldings based on cellular polyurethane elastomers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2710901A1 (de) * 1976-03-12 1977-09-15 Prb Sa Polyurethan mit integrer haut und verfahren zur herstellung desselben
DE3008811A1 (de) * 1979-03-09 1980-09-18 Prb Sa Verfahren zum herstellen von polyurethan mit integralhaut und polyurethan
US4477600A (en) * 1983-09-23 1984-10-16 Stauffer Chemical Company Polyurethane foams having low scorch discoloration

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2710901A1 (de) * 1976-03-12 1977-09-15 Prb Sa Polyurethan mit integrer haut und verfahren zur herstellung desselben
DE3008811A1 (de) * 1979-03-09 1980-09-18 Prb Sa Verfahren zum herstellen von polyurethan mit integralhaut und polyurethan
US4477600A (en) * 1983-09-23 1984-10-16 Stauffer Chemical Company Polyurethane foams having low scorch discoloration

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7985780B2 (en) 2005-02-22 2011-07-26 Basf Se Cylindrical mouldings based on cellular polyurethane elastomers
WO2008074701A1 (fr) * 2006-12-20 2008-06-26 Basf Se Élastomère cellulaire anisotrope
WO2008074705A1 (fr) * 2006-12-20 2008-06-26 Basf Se Élastomère cellulaire anisotrope
US8282851B2 (en) 2006-12-20 2012-10-09 Basf Se Anisotropic cellular elastomers

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Publication number Publication date
DE102004061609B4 (de) 2014-06-26
DE102004061609A1 (de) 2006-07-06
CN101080428A (zh) 2007-11-28
KR20070100937A (ko) 2007-10-15
CN101080428B (zh) 2011-02-02

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