WO2001085822A1 - Stabilisants pour mousses polyurethane - Google Patents

Stabilisants pour mousses polyurethane Download PDF

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Publication number
WO2001085822A1
WO2001085822A1 PCT/EP2001/004633 EP0104633W WO0185822A1 WO 2001085822 A1 WO2001085822 A1 WO 2001085822A1 EP 0104633 W EP0104633 W EP 0104633W WO 0185822 A1 WO0185822 A1 WO 0185822A1
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Prior art keywords
weight
groups
polyol
foam
stabilizer
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PCT/EP2001/004633
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German (de)
English (en)
Inventor
Bert Klesczewski
Robert-Joseph Kumpf
Original Assignee
Bayer Aktiengesellschaft
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Priority to AU2001267370A priority Critical patent/AU2001267370A1/en
Publication of WO2001085822A1 publication Critical patent/WO2001085822A1/fr

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    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/142—Polyethers
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • 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
    • C08G18/635—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto unsaturated polymers
    • 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
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/005—< 50kg/m3
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Definitions

  • the invention relates to foam stabilizers which are free of silicon atoms and their use for the production of polyurethane and / or polyisocyanurate foams.
  • Polyurethane foams are used e.g. B. for thermal insulation, energy absorption, sound absorption and as a material for the manufacture of mattresses, cushions, etc. used.
  • the properties of the foam formed depend to a particular extent on the structure and the chemical composition of the foam stabilizer used.
  • Polysiloxane-polyoxyalkylene block copolymers are generally used as foam stabilizers. These stabilizers are highly effective and can be adapted to the foaming system and the foaming process by suitable selection of the structure and composition. However, due to the way in which they are manufactured, they always contain a considerable proportion of cyclic siloxanes which, when the foam is used later, have undesirable effects such as worsened fire behavior and outgassing (“fogging”).
  • Polymer 39 (1998) 2049 describes fluorine-containing stabilizers for rigid polyurethane foams which have a fluorine content of 50-70% by weight and consist of block copolymers of methyl methacrylate and (fluoroalkyl) acrylates. However, they do not develop the full spectrum of action of a conventional foam stabilizer and are best used in combination with one.
  • the high fluorine content causes poor compatibility with conventional raw materials such as polyols and also very high costs.
  • EP-A 351 614 describes the production and use of oligomeric acrylates with 5 to 30% by weight of fluorine, which are prepared in accordance with DE-OS 23 10 357, as
  • Emulsifier for perfluoroalkanes in polyol formulations are considered Foam stabilizers alone are ineffective and associated with high costs due to their high fluorine content.
  • Foam stabilizers have now been found which can be obtained by copolymerizing a poly (oxyalkylene) polyol having double bonds and an acrylate containing fluorine atoms.
  • the invention therefore relates to foam stabilizers with a fluorine content of 0.1 to 4.5% by weight, which can be obtained by copolymerizing a poly (oxyalkylene) polyol containing double bonds with at least 10% by weight polyoxyethylene units and an acrylate containing fluorine atoms ,
  • Double bonded poly (oxyalkylene) polyols are known, for example, from US Pat. Nos. 3,652,639, 3,823,201, 4,460,715, 4,390,645, 5,093,412 and 4,342,840. Double bonded poly (oxyalkylene) polyols are obtained by the reaction of
  • Poly (oxyalkylene) polyols with cyclic unsaturated carboxylic anhydrides e.g. B. maleic anhydride and subsequent reaction with oxirane and / or methyloxirane
  • you can e.g. by esterification of poly (oxyalkylene) polyols with acrylic acid, methacrylic acid or their derivatives by reaction of poly (oxyalkylene) polyols with allyl glycidyl ether, by reaction of poly (oxyalkylene) polyols with an unsaturated isocyanate such as isocyanatoalkyl acrylate, isocyanatomethacrylate or by reaction obtained from poly (oxyalkylene) polyols with an NCO-functional adduct from an isocyanate with hydroxyethyl acrylate or hydroxypropyl acrylate. Esterification products of poly (oxyalkylene) polyols with acrylic acid, methacrylic acid or their derivatives are preferably used.
  • Suitable poly (oxyalkylene) polyols are obtained by polyaddition of alkylene oxides such as oxirane, methyloxirane, ethyloxirane, decyloxirane or phenyloxirane, preferably methyloxirane, ethyloxirane or oxirane, on starter compounds with active hydrogen atoms.
  • alkylene oxides such as oxirane, methyloxirane, ethyloxirane, decyloxirane or phenyloxirane, preferably methyloxirane, ethyloxirane or oxirane
  • ammonia or compounds which have at least one primary are used as starter compounds or have secondary amino group, for example aliphatic amines such as 1,2-diaminoethane, oligomers of 1,2-diaminoethane (for example diethylene triamine, triethylene tetramine or pentaethylene hexamine), ethanolamine or diethanol
  • Amines such as 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 2,3-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 2,5-diaminotoluene, 2,6- Diamino toluene, 2,2'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane or aromatic amines obtained by acid-catalyzed condensation of aniline with formaldehyde.
  • Suitable starter compounds are those with two or more hydroxyl end groups such as water, triethanolamine, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaeryfhritol, or sorbitol
  • the starter compounds can be used alone or as mixtures.
  • Polyether polyols which can be used according to the invention in the polyol component have a number-average molar mass of 150 to 12500 g / mol, preferably 2000 to 12500 g / mol and a mathematical functionality between one and six.
  • the proportion of oxyethylene groups in relation to the proportion of the other oxyalkylene groups in poly (oxyalkylene) polyols and the type of arrangement of the oxyethylene and other oxyalkylene groups influences the miscibility with customary polyurethane raw material components and others for foaming important properties such as cell structure.
  • Suitable poly (oxyalkylene) polyols have a proportion of oxyethylene units in the total amount of poly (oxyalkylene) units between 10 and 80% by weight.
  • a proportion of oxyethylene units of between 10 and 60% by weight is preferred, particularly preferably between 10 and 40% by weight.
  • the different oxyalkylene units can be bound randomly or in blocks. However, the block-like arrangement is preferred.
  • the fluorine content of the stabilizers according to the invention is 0.1 to 4.5% by weight, preferably 0.5 to 3.5% by weight, particularly preferably 1.5 to 3.0% by weight.
  • the alkyl radical can have a linear or branched structure.
  • the radical R F preferably has a fluorine content by weight of between 50 and 80% by weight.
  • agents which reduce the viscosity are preferably added to the stabilizers according to the invention.
  • agents which reduce the viscosity are preferably added to the stabilizers according to the invention.
  • solvents known to the person skilled in the art, such as aliphatic or aromatic hydrocarbons, aliphatic ketones, amides, ethers, alcohols, amines, etc. Those compounds are preferably used which have boiling points at atmospheric pressure above 100 ° C. and / or have groups which are reactive toward isocyanates.
  • the viscosity-reducing additive particularly preferably consists of toluene,
  • the stabilizers according to the invention are used in the production of polyurethane in amounts of approximately 0.1 to 5% by weight, based on the total amount of polyol. It is of course possible, in addition to that of the invention Stabilizers to use other stabilizers with a different structure, if necessary, or additional additives.
  • the stabilizers according to the invention can be added to both the polyol component and the isocyanate component of the polyurethane formulation. - subject of
  • the corresponding mixtures are also an invention. These contain either at least one compound with at least two groups reactive toward isocyanate groups and 0.1 to 5% by weight of at least one stabilizer according to the invention or at least one organic polyisocyanate and 0.1 to 5% by weight of at least one stabilizer according to the invention.
  • the mixtures can also contain chemical and / or physical blowing agents.
  • Water is preferably used as the chemical blowing agent, which provides carbon dioxide as the blowing gas by reaction with isocyanate groups. Water is preferred in an amount of 2 to 8% by weight, particularly preferably 2 to 4% by weight.
  • Non-flammable physical blowing agents such as e.g. Dichloromethane, dichloromonofluoromethane, difluoromethane, trifluoromethane,
  • the invention further relates to foams containing polyurethane groups which contain at least one stabilizer according to the invention and a process for the production of such foams from at least difunctional polyisocyanates, compounds with at least two hydrogen atoms which are reactive toward isocyanates, blowing agents and foam stabilizers and, if appropriate, catalysts and other additives, in which at least one stabilizer according to the invention is used as a foam stabilizer.
  • Organic di- or polyisocyanates or polyisocyanate prepolymers are used as at least difunctional polyisocyanates in the process according to the invention.
  • Suitable di- or polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as described in Justus Liebigs Annalen der Chemie 562 (1949) 75, for example those of the formula
  • n is an integer from 2 to 4, preferably 2, and
  • Q is an aliphatic hydrocarbon residue with 2 to 18, preferably 6 to 10 C atoms, a cyclo aliphatic hydrocarbon residue with 4 to 15, preferably 5 to 10 C atoms, an aromatic hydrocarbon residue with 6 to 15, preferably 6 to 13 C. -Atoms, or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13, carbon atoms.
  • Polyisocyanates as described in DE-OS 28 32 253 are preferred.
  • the technically easily accessible polyisocyanates for example 2,4- and 2,6-tolylene diisocyanate and any other, are generally used with particular preference Mixtures of these isomers (“TDI”), polyphenyl-polymethylene polyisocyanates, as they are produced by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (polyisocyanates containing) modified polyisocyanates "), especially those modified
  • Prepolymers of the isocyanates mentioned and organic compounds with at least one hydroxyl group can also be used. Examples include one to four hydroxyl-containing polyol or polyester with (number average) molecular weights from 60 to 1400.
  • Very particularly preferred are the polyisocyanates industrially obtainable under the name “polymeric diphenylmethane diisocyanate” with a functionality higher than 2.0 and from them prepared prepolymers use.
  • Compounds with at least two hydrogen atoms which are reactive toward isocyanates are used for foam production. These are generally introduced into the foam-forming reaction mixture as part of a polyol component. Examples of such compounds are polyether and polyester polyols.
  • Polyether polyols are obtained by polyaddition of alkylene oxides, such as oxirane, methyloxirane, ethyloxirane, Decyloxiran or phenyloxirane, 'preferably methyl oxirane, ethyl oxirane or oxirane to starter compounds having active hydrogen atoms.
  • starter compounds used are ammonia or compounds which have at least one primary or secondary amino group, such as, for example, aliphatic amines such as 1,2-diaminoethane, oligomers of 1,2-diaminoethane (for example diethylene triamine, triethylene tetramine or pentaethylene hexamine), ethanolamine or diethanolamine.
  • Amines such as 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 2,3-di- minotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,2'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 4,4'-diamino-diphenylmethane or aromatic amines obtained by acid-catalyzed condensation of aniline with formaldehyde.
  • Other suitable starter compounds are those with two or more hydroxyl end groups such as water,
  • Triethanolamine 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1, 2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose.
  • the starter compounds can be used alone or as mixtures.
  • polyether polyols which can be used in the polyol component have (number average) molar masses from 150 to 12500 g / mol.
  • polyester polyols with (number average) molar masses from 100 to 30,000 g / mol, preferably 150 to, can also be present in the polyol component
  • dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, azelaic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, malonic acid and succinic acid.
  • the pure dicarboxylic acids and any mixtures thereof can be used.
  • the corresponding * dicarboxylic acid derivatives such as. B.
  • Dicarboxylic acid mono- or diesters of alcohols having one to four carbon atoms Such esters are formed, for example, when polyester waste is recycled.
  • Dicarboxylic anhydrides such as phthalic anhydride or maleic anhydride can also be used as the acid component.
  • the alcohol components used for the esterification are preferably: ethylene glycol, diethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, Glycerin, trimethylolpropane, pentaerythritol or mixtures thereof.
  • Polyester polyols from lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example ⁇ - Hydroxycarboxylic acids can be used.
  • the polyol component can also contain polyether ester polyols, such as are obtainable, for example, by reaction of phthalic anhydride with diethylene glycol and subsequent reaction with oxirane.
  • suitable polyols which may be contained in the polyol component are polyfunctional alcohols or amines or amino alcohols or mixtures thereof and their oxypropylated and or oxyethylated secondary products or also polyester polyols which are obtained by esterification of polyfunctional alcohols with polyfunctional carboxylic acids. Modified polyols can also be used in the polyol component, as described by
  • Grafting of polyols with styrene and or aryl nitrile, as polyurea dispersions or as PIPA polyols can be obtained.
  • compounds with at least two isocyanate-reactive hydrogen atoms and a molecular weight of 32 to 399 are optionally used. This is taken to mean hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl group-containing compounds, preferably compounds containing hydroxyl groups and / or amino groups, which serve as chain extenders or crosslinking agents.
  • Chain extenders and / or crosslinking agents are, for example, glycerol, ethylene glycol, diethanolamine, triethanolamine and triisopropanolamine.
  • catalysts can optionally be added which accelerate the reaction between the isocyanate component and the polyol component.
  • suitable catalysts are organic tin compounds such as tin (II) salts of organic carboxylic acids, for example Tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin (IV) salts, for example dibutyltin diacetate, dibutyltin dilaurate and dioctyltin diacetate.
  • tin (II) salts of organic carboxylic acids for example Tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate
  • dialkyltin (IV) salts for example dibutyltin diacetate, dibutyltin d
  • Suitable catalysts are amines such as dimethylaminopropylurea, dimethylaminopropylamine, bis (dimethylaminopropyl) amine, diazabicyclooctane, dimethylethanolamine, triethylamine, dimethylcyclohexylamine,
  • the catalyst component preferably contains at least one aliphatic amine. A combination of several catalysts can also be used.
  • further additives are optionally used, for example paraffins or fatty alcohols or dimethylpolysiloxanes and pigments or dyes, furthermore stabilizers against the effects of aging and weathering, plasticizers such as dioctyl phthalate and fungistatic and bacteriostatic substances.
  • plasticizers such as dioctyl phthalate and fungistatic and bacteriostatic substances.
  • flame retardants are also added, preferably those which are liquid and / or in one or more of those used for foam production
  • Components are soluble.
  • Commercially available phosphorus-containing flame retardants are preferably used, for example tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl) phosphate, Tetrakis (2-chloroethyl) ethylene diphosphate, dimethyl methane phosphonate, diethyl ethane phosphonate, diethanolaminomethylphosphonic acid diethyl ester.
  • Halogen and / or phosphorus-containing, flame-retardant polyols are also suitable.
  • the flame retardants are preferably used in an amount of at most 35% by weight, preferably at most 20% by weight, based on the polyol component.
  • reaction components are usually reacted according to the known one-step process, the prepolymer process or the semi-prepolymer process, machine equipment often being used, e.g. B. those described in U.S. Patent 2,764,565. Details of processing devices that are also suitable according to the invention are given in
  • the foaming is carried out in closed molds.
  • the reaction mixture is introduced into a mold.
  • the foamable reaction mixture foams in the mold and forms the shaped body.
  • the procedure can be such that enough foamable reaction mixture is introduced into the mold that the foam formed just fills the mold. But you can also work so that you have more foamable
  • the foams according to the invention are preferably produced in such a way that the NCO / OH index, ie the stoichiometric ratio between reactive isocyanate groups and hydroxyl groups multiplied by 100, is between 65 and 350.
  • the NCO / OH index is particularly preferably 70 to 120.
  • the invention also relates to the use of the foams according to the invention as cushioning material for e.g. B. seats, backrests and armrests and headrests in automobiles, rail vehicles, aircraft and watercraft and in furniture for private and public applications.
  • Polyol A polypropylene oxide-polyether polyol with a calculated molecular weight of 630 based on sucrose / propylene glycol
  • Polyol B polypropylene oxide-polyether polyol with a calculated molecular weight 345 based on ethylenediamine
  • Polyol C polypropylene oxide-polyether polyol with a calculated molecular weight 560 based on o-tolylene diamine
  • Polyol D Polypropylene oxide-polyether polyol with a calculated molecular weight of 1000 based on propylene glycol
  • Polyol E Polypropylene oxide-polyethylene oxide-polyether polyol with a calculated molecular weight of 6000 based on trimethylolpropane, in which 20% by weight styrene / acrylonitrile in the weight ratio
  • 60:40 were polymerized in situ based on polyol F: polyester polyol with a calculated molecular weight of 530
  • Diethylene glycol, phthalic anhydride and adipic acid Polyol G polyether polyester polyol with a calculated molecular weight of 360, produced by adding methyloxirane to a polyester polyol made from phthalic anhydride, diethylene glycol and sorbitol polyol H: Ixol ® 251, flame-retardant polyol with a hydroxyl number of 330,
  • Tegostab ® B-8421 Siloxane-based rigid foam stabilizer (Th. Goldschmidt AG, Goldschmidtstr. 100, D-45127 Essen)
  • Example 2 The procedure was as in Example 1, except that N, N-dimethylformamide was used instead of toluene.
  • the product (stabilizer D) was obtained as a clear, storage-stable liquid with a viscosity of 5560 mPa * s (at 20 ° C.) and a fluorine content of 2.3% by weight.
  • Example 2 The procedure was as in Example 1, except that the amount (2,2,3,3,3-pentafluoropropyl) acrylate was 15 g.
  • the product (comparative product 1) was obtained as a milky, storage-stable liquid with a viscosity of 11600 mPa * s (at 20 ° C.) with a
  • Example 3 The procedure was as in Example 3, but the amount of (3,3,4, 4,5,5, 6,6,7,7,8,8,8-tri-decafluorooctyl) acrylate was 10 g.
  • the product (comparative product 2) was obtained as a milky, storage-stable liquid with a viscosity of 11600 mPa * s (at 20 ° C.) with a fluorine content of 5.0% by weight.
  • Example 4 The procedure was as in Example 1, but the polymerization was carried out without (2,2,3,3,3-pentafluoropropyl) acrylate. A clear liquid (comparative product 3) with a viscosity of 4660 mPa * s (at 20 ° C.) was obtained. Comparative Example 4 Preparation of a Stabilizer (Comparative Product 4)
  • Example 4 The procedure was as in Example 3, but the polymerization was carried out without (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) acrylate. A clear liquid (comparative product 4) with a viscosity of 7180 mPa * s (at 20 ° C.) was obtained.
  • Examples 5-8 were repeated, but the comparative products 1-4 were used as stabilizers. In all four cases, no polyurethane foam could be produced because the foaming mixture collapsed when it rose.
  • Example 9 The procedure was as in Example 9 except that 8 g Zonyl ® TA-N (Fa. DuPont) were used. A two-phase, cloudy mixture was obtained. (Comparative product 5)
  • Example 10 was repeated using Comparative Product 5 as

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des stabilisants pour mousses, qui sont exempts d'atomes de silicium et leur utilisation pour produire des mousses polyuréthane et/ou polyisocyanurate.
PCT/EP2001/004633 2000-05-08 2001-04-25 Stabilisants pour mousses polyurethane WO2001085822A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001267370A AU2001267370A1 (en) 2000-05-08 2001-04-25 Stabilizers for polyurethane foams

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10022370A DE10022370A1 (de) 2000-05-08 2000-05-08 Stabilisatoren für Polyurethanschäume
DE10022370.2 2000-05-08

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WO2001085822A1 true WO2001085822A1 (fr) 2001-11-15

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EP1688448A1 (fr) * 2003-11-26 2006-08-09 Asahi Glass Company Ltd. Mousse polyurethanne souple, son procede de production, et feuille de vehicule automobile la contenant
EP1790682A1 (fr) * 2005-11-25 2007-05-30 Goldschmidt GmbH Copolymères de polyéther greffés et leur utilisation comme stabilisateur en mousse de polyuréthanne
EP1884529A1 (fr) * 2005-05-25 2008-02-06 Asahi Glass Company, Limited Mousse souple en polyurethanne, son procede de fabrication, et siege d'automobile utilisant cette mousse souple en polyurethanne
EP2028223A1 (fr) * 2007-08-23 2009-02-25 Bayer MaterialScience AG Copolymères en bloc EO/PO en tant que stabilisateurs pour mousses PUR
EP2085414A1 (fr) * 2006-11-20 2009-08-05 Asahi Glass Company, Limited Procédé destiné à produire une mousse polyuréthane dure
EP2085413A1 (fr) * 2006-11-20 2009-08-05 Asahi Glass Company, Limited Procédé de fabrication de polyol à dispersion polymère
EP2284207A1 (fr) * 2008-05-30 2011-02-16 Asahi Glass Company, Limited Résine synthétique sous forme de mousse rigide et son procédé de fabrication
CN112341596A (zh) * 2020-10-28 2021-02-09 山东一诺威聚氨酯股份有限公司 预制型聚氨酯发泡弹性体材料及其制备方法、施工的球场及其施工方法

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FR3092837B1 (fr) * 2019-02-18 2021-08-27 Gaztransport Et Technigaz Copolymeres methacrylates, et leurs utilisations pour la preparation de mousse polyurethane

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1688448A1 (fr) * 2003-11-26 2006-08-09 Asahi Glass Company Ltd. Mousse polyurethanne souple, son procede de production, et feuille de vehicule automobile la contenant
EP1688448A4 (fr) * 2003-11-26 2009-02-18 Asahi Glass Co Ltd Mousse polyurethanne souple, son procede de production, et feuille de vehicule automobile la contenant
EP1884529A1 (fr) * 2005-05-25 2008-02-06 Asahi Glass Company, Limited Mousse souple en polyurethanne, son procede de fabrication, et siege d'automobile utilisant cette mousse souple en polyurethanne
EP1884529A4 (fr) * 2005-05-25 2011-10-12 Asahi Glass Co Ltd Mousse souple en polyurethanne, son procede de fabrication, et siege d'automobile utilisant cette mousse souple en polyurethanne
EP1790682A1 (fr) * 2005-11-25 2007-05-30 Goldschmidt GmbH Copolymères de polyéther greffés et leur utilisation comme stabilisateur en mousse de polyuréthanne
EP2085414A1 (fr) * 2006-11-20 2009-08-05 Asahi Glass Company, Limited Procédé destiné à produire une mousse polyuréthane dure
EP2085413A1 (fr) * 2006-11-20 2009-08-05 Asahi Glass Company, Limited Procédé de fabrication de polyol à dispersion polymère
EP2085414A4 (fr) * 2006-11-20 2012-11-07 Asahi Glass Co Ltd Procédé destiné à produire une mousse polyuréthane dure
EP2085413A4 (fr) * 2006-11-20 2012-11-07 Asahi Glass Co Ltd Procédé de fabrication de polyol à dispersion polymère
WO2009024266A1 (fr) * 2007-08-23 2009-02-26 Bayer Materialscience Ag Copolymères séquencés eo/po utilisés comme agents stabilisants pour des mousses polyuréthane
EP2028223A1 (fr) * 2007-08-23 2009-02-25 Bayer MaterialScience AG Copolymères en bloc EO/PO en tant que stabilisateurs pour mousses PUR
EP2284207A1 (fr) * 2008-05-30 2011-02-16 Asahi Glass Company, Limited Résine synthétique sous forme de mousse rigide et son procédé de fabrication
EP2284207A4 (fr) * 2008-05-30 2011-06-15 Asahi Glass Co Ltd Résine synthétique sous forme de mousse rigide et son procédé de fabrication
CN112341596A (zh) * 2020-10-28 2021-02-09 山东一诺威聚氨酯股份有限公司 预制型聚氨酯发泡弹性体材料及其制备方法、施工的球场及其施工方法
CN112341596B (zh) * 2020-10-28 2022-04-19 山东一诺威聚氨酯股份有限公司 预制型聚氨酯发泡弹性体材料及其制备方法、施工的球场及其施工方法

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