WO2001085822A1 - Stabilizers for polyurethane foams - Google Patents

Stabilizers for polyurethane foams Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
weight
groups
polyol
foam
stabilizer
Prior art date
Application number
PCT/EP2001/004633
Other languages
German (de)
French (fr)
Inventor
Bert Klesczewski
Robert-Joseph Kumpf
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU2001267370A priority Critical patent/AU2001267370A1/en
Publication of WO2001085822A1 publication Critical patent/WO2001085822A1/en

Links

Classifications

    • 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

Abstract

The invention relates to foam stabilizers, which do not contain any silicon atoms, and to their use for producing polyurethane foams and/or polyisocyanurate foams.

Description

Stabilisatoren für PolyurethanschäumeStabilizers for polyurethane foams
Die Erfindung betrifft Schaumstabilisatoren, welche frei von Siliciumatomen sind und ihre Verwendung zur Herstellung von Polyurethan- und/oder Polyisocyanurat- schäumen.The invention relates to foam stabilizers which are free of silicon atoms and their use for the production of polyurethane and / or polyisocyanurate foams.
Polyurethanschäume werden z. B. zur thermischen Isolierung, zur Energieabsorption, zur Schallabsorption und als Material zur Herstellung von Matratzen, Polstern etc. verwendet. Die Eigenschaften des gebildeten Schaums hängen in besonderem Maße von der Struktur und der chemischen Zusammensetzung des verwendeten Schaumstabilisators ab.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.
Als Schaumstabilisatoren werden im allgemeinen Polysiloxan-Polyoxyalkylen- Blockmischpolymerisate verwendet. Diese Stabilisatoren haben hohe Wirksamkeit und lassen sich durch geeignete Auswahl der Struktur und der Zusammensetzung dem Verschäumungssystem und dem Verschäumungsverfahren anpassen. Sie enthalten jedoch aufgrund der Herstellungsweise stets einen erheblichen Anteil an cyclischen Siloxanen, der bei der späteren Anwendung des Schaumes unerwünschte Wirkungen wie verschlechtertes Brandverhalten und Ausgasen („Fogging") zeitigt.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”).
In Polymer 39 (1998) 2049 sind fiuorhaltige Stabilisatoren für Polyurethanhartschäume beschrieben, die einen Fluorgehalt von 50-70 Gew.-% aufweisen und aus Blockcopolymeren von Methylmethacrylat und (Fluoralkyl)acrylaten bestehen. Sie entfalten jedoch nicht das volle Wirkungsspektrum eines herkömmlichen Schaum- Stabilisators und werden am besten in Kombination mit einem solchen eingesetzt.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.
Außerdem verursacht der hohe Fluorgehalt schlechte Verträglichkeit mit herkömmlichen Rohstoffen wie Polyolen und zusätzlich sehr hohe Kosten.In addition, the high fluorine content causes poor compatibility with conventional raw materials such as polyols and also very high costs.
EP-A 351 614 beschreibt Herstellung und Verwendung von oligomeren Acrylaten mit 5 bis 30 Gew.-% Fluor, die gemäß DE-OS 23 10 357 hergestellt werden, alsEP-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
Emulgator für Perfluoralkane in Polyolformulierungen. Solche Produkte sind als Schaumstabilisatoren allein unwirksam und aufgrund ihres hohen Fluorgehalts mit hohen Kosten verbunden.Emulsifier for perfluoroalkanes in polyol formulations. Such products are considered Foam stabilizers alone are ineffective and associated with high costs due to their high fluorine content.
Es wurden nun Schaumstabilisatoren gefunden, die durch Copolymerisation eines Doppelbindungen aufweisenden Poly(oxyalkylen)polyols und eines- Fluoratome enthaltenden Acrylats erhältlich sind.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.
Gegenstand der Erfindung sind daher Schaumstabilisatoren mit einem Fluorgehalt von 0,1 bis 4,5 Gew.-%, welche durch Copolymerisation eines Doppelbindungen aufweisenden Poly(oxyalkylen)polyols mit mindestens 10 Gew.-% Polyoxyethylen- einheiten und eines Fluoratome enthaltenden Acrylats erhältlich sind.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 ,
Doppelbindungen aufweisende Poly(oxyalkylen)polyole gehen beispielsweise aus US-PS 3 652 639, 3 823 201, 4460 715, 4 390 645, 5 093 412 und 4 342 840 hervor. Doppelbindungen aufweisende Poly(oxyalkylen)polyole werden durch Reaktion vonDouble 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(oxyalkylen)polyolen mit cyclischen ungesättigten Carbonsäureanhydriden, z. B. Maleinsäureanhydrid und anschliessender Umsetzung mit Oxiran und/oder Methyloxiran, Sie können z.B. durch Veresterung von Poly(oxyalkylen)polyolen mit Acryl- säure, Methacrylsäure bzw. deren Derivaten, durch Reaktion von Poly(oxyalkylen)- polyolen mit Allylglycidylether, durch Reaktion von Poly(oxyalkylen)polyolen mit einem ungesättigten Isocyanat wie Isocyanatoalkylacrylat, Isocyanatomethacrylat oder durch Reaktion von Poly(oxyalkylen)polyolen mit einem NCO-funktionellen Addukt aus einem Isocyanat mit Hydroxyethylacrylat oder Hydroxypropylacrylat erhalten. Bevorzugt werden Veresterungsprodukte von Poly(oxyalkylen)polyolen mit Acrylsäure, Methacrylsäure bzw. deren Derivaten verwendet.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.
Geeignete Poly(oxyalkylen)polyole werden erhalten durch Polyaddition von Alky- lenoxiden wie beispielsweise Oxiran, Methyloxiran, Ethyloxiran, Decyloxiran oder Phenyloxiran, vorzugsweise Methyloxiran, Ethyloxiran oder Oxiran an Starterver- bindungen mit aktiven Wasserstoffatomen. Als Starterverbindungen werden beispielsweise Ammoniak oder Verbindungen verwendet, die mindestens eine primäre oder sekundäre Aminogruppe aufweisen, z.B. aliphatische Amine wie 1,2-Diamino- ethan, Oligomere des 1,2-Diaminoethans (beispielsweise Diethylentriamin, Tri- ethylentetramin oder Pentaethylenhexamin), Ethanolamin oder Diethanolamin. 1,3- Diaminopropan, 1,3-Diaminobutan, 1,4-Diaminobutan, 1,2-Diaminohexan, 1,3-Di- aminohexan, 1,4-Diaminohexan, 1,5-Diaminohexan, 1,6-Diaminohexan, aromatischeSuitable 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. For example, 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 diethanolamine. 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, 1,2-diaminohexane, 1,3-diaminohexane, 1,4-diaminohexane, 1,5-diaminohexane, 1,6-diaminohexane, aromatic
Amine wie 1 ,2-Diaminobenzol, 1,3-Diaminobenzol, 1,4-Diaminobenzol, 2,3-Di- aminotoluol, 2,4-Diaminotoluol, 3,4-Diaminotoluol, 2,5-Diaminotoluol, 2,6-Di- aminotoluol, 2,2'-Diaminodiρhenylmethan, 2,4'-Diaminodiρhenylmethan, 4,4 '-Dia- minodiphenylmethan oder aromatische Amine, die durch säurekatalysierte Konden- sation von Anilin mit Formaldehyd erhalten werden. Weitere geeignete Starterverbindungen sind solche mit zwei oder mehr Hydroxylendgruppen wie beispielsweise Wasser, Triethanolamin, 1,2-Ethandiol, 1,2-Propandiol, 1,3-Propandiol, Diethy- lenglykol, Dipropylenglykol, Triethylenglykol, Tripropylenglykol, 1,2-Butandiol, 1,3-Butandiol, 1,4-Butandiol, 1,2-Hexandiol, 1,3-Hexandiol, 1,4-Hexandiol, 1,5- Hexandiol, 1,6-Hexandiol, Glycerol, Trimethylolpropan, Pentaeryfhrit, Sorbit oderAmines 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. 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, pentaeryfhritol, or sorbitol
Saccharose. Die Starterverbindungen können allein oder als Gemische verwendet werden. Erfindungsgemäß in der Polyolkomponente einsetzbare Polyetherpolyole weisen eine zahlenmittlere Molmasse von 150 bis 12500 g/mol, bevorzugt 2000 bis 12500 g/mol und eine rechnerische Funktionalität zwischen eins und sechs auf.Sucrose. 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.
Der Anteil an Oxyethylengruppen im Verhältnis zum Anteil der übrigen Oxyalkylen- gruppen in Poly(oxyalkylen)ρolyolen sowie die Art der Anordnung der Oxyethylen- und übrigen Oxyalkylengruppen beeinflusst, wie dem Fachmann bekannt ist, die Mischbarkeit mit üblichen Polyurethanrohstoffkomponenten und weitere für die Ver- schäumung wichtige Eigenschaften wie z.B die Zellstruktur. Geeignete Poly(oxy- alkylen)polyole weisen einen Anteil an Oxyethyleneinheiten an der gesamten Menge an Poly(oxyalkylen)einheiten zwischen 10 und 80 Gew.-% auf. Bevorzugt ist ein Anteil an Oxyethyleneinheiten zwischen 10 und 60 Gew.-%, besonders bevorzugt zwischen 10 und 40 Gew.-%. Die unterschiedlichen Oxyalkyleneinheiten können statistisch oder blockartig gebunden sein. Die blockartige Anordnung ist jedoch bevorzugt.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, as is known to the person skilled in the art, 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.
Der Fluorgehalt der erfindungsgemäßen Stabilisatoren beträgt 0,1 bis 4,5 Gew.-%, bevorzugt 0,5 bis 3,5 Gew.-%, besonders bevorzugt 1,5 bis 3,0 Gew.-%.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.
Für die Herstellung der erfindungsgemäßen Stabilisatoren geeignete, Fluoratome enthaltende Acrylate besitzen die allgemeine Formel CH2=CH-COOCH2Rp , wobei Rp für einen Alkylrest mit 2 bis 19 Kohlenstoffatomen steht, der einen Gewichtsanteil an Fluor zwischen 30 und 80 Gewichts-% aufweist. Der Alkylrest kann eine lineare oder verzweigte Struktur aufweisen. Bevorzugt weist der Rest RF einen Gewichtsanteil an Fluor zwischen 50 und 80 Gewichts-% auf.Acrylates containing fluorine atoms which are suitable for the preparation of the stabilizers according to the invention have the general formula CH2 = CH-COOCH 2 Rp, where Rp is an alkyl radical having 2 to 19 carbon atoms and having a fluorine content by weight of between 30 and 80% 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.
Zur Herstellung der erfindungsgemäßen Schaumstabilisatoren können auch Ge- mische von verschiedenen fluorhaltigen Acrylaten einerseits und/oder Gemische von verschiedenen Doppelbindungen aufweisenden Poly(oxyalkylen)polyolen eingesetzt werden.Mixtures of different fluorine-containing acrylates on the one hand and / or mixtures of different poly (oxyalkylene) polyols having different double bonds can also be used to produce the foam stabilizers according to the invention.
Bevorzugt werden bei oder nach der Herstellung den erfϊndungsgemäßen Stabilisa- toren 0,1 bis 50 Gew.-% an Mitteln, die die Viskosität erniedrigen, zugesetzt. Beispiele sind dem Fachmann bekannte Lösemittel wie aliphatische oder aromatische Kohlenwasserstoffe, aliphatische Ketone, Amide, Ether, Alkohole, Amine usw. Vorzugsweise werden solche Verbindungen eingesetzt, die Siedepunkte bei Atmosphärendruck von über 100°C besitzen und/oder gegenüber Isocyanaten reaktive Gruppen aufweisen. Besonders bevorzugt besteht der viskositätsmindernde Zusatz aus Toluol,During or after production, 0.1 to 50% by weight of agents which reduce the viscosity are preferably added to the stabilizers according to the invention. Examples are 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,
N,N-Dimethylformamid, N,N-Dimethylacetamid, Diethylenglykol, Dipropylenglykol und Tripropylenglykol oder Mischungen hieraus.N, N-dimethylformamide, N, N-dimethylacetamide, diethylene glycol, dipropylene glycol and tripropylene glycol or mixtures thereof.
Die erfindungsgemäßen Stabilisatoren werden bei der Polyurethanherstellung in Mengen von etwa 0,1 bis 5 Gew.-%, bezogen auf die Gesamtmenge Polyol, verwendet. Es ist selbstverständlich möglich, zusätzlich zu den beim erfindungsgemäßen Stabilisatoren weitere Stabilisatoren mit gegebenenfalls anderer Struktur oder zusätzlich andere Additive einzusetzen.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.
Die erfindungsgemäßen Stabilisatoren können sowohl der Polyol- wie auch der Iso- cyanatkomponente der Polyurethanformulierung zugesetzt werden. - Gegenstand derThe stabilizers according to the invention can be added to both the polyol component and the isocyanate component of the polyurethane formulation. - subject of
Erfindung sind auch die entsprechenden Mischungen. Diese enthalten entweder mindestens eine Verbindung mit mindestens zwei gegenüber Isocyanatgruppen reaktiven Gruppen und 0,1 bis 5 Gew.-% mindestens eines erfindungsgemäßen Stabilisators oder mindestens ein organisches Polyisocyanat und 0,1 bis 5 Gew.-% mindestens eines erfindungsgemäßen Stabilisators.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.
Die Mischungen können zudem auch noch chemische und/oder physikalische Treibmittel enthalten. Als chemisches Treibmittel wird bevorzugt Wasser eingesetzt, das durch Reaktion mit Isocyanatgruppen Kohlendioxid als Treibgas liefert. Bevorzugt wird Wasser in einer Menge von 2 bis 8 Gew.-%, besonders bevorzugt 2 bis 4 Gew.-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.
%, bezogen auf die Menge an Polyol- oder Isocyanatkomponente, eingesetzt. Kohlendioxid kann aber auch als Gas oder flüssig, online oder im Batch- Verfahren der Polyol- oder Isocyanatkomponente nach den an sich bekannten Verfahren zugesetzt werden. Im Treibmittel können auch nicht brennbare physikalische Treibmittel wie z.B. Dichlormethan, Dichlormonofluormethan, Difluormethan, Trifluormethan,%, based on the amount of polyol or isocyanate component, used. However, carbon dioxide can also be added as a gas or liquid, online or in a batch process to the polyol or isocyanate component according to the processes known per se. Non-flammable physical blowing agents such as e.g. Dichloromethane, dichloromonofluoromethane, difluoromethane, trifluoromethane,
Difluorethan, 1,1,1,2-Tetrafluorethan, Tetrafluorethan (R 134 oder R 134a), 1,1,1,3,3,3-Hexafluorpropan (R 356), 1,1,1,3,3-Pentafluorpropan (R 245fa), Chlor- difluorethane, l,l-Dichlor-2,2,2-Trifluorethan, 2,2-Dichlor-2-fluorethan, Heptafluor- propan und Schwefelhexafluorid verwendet werden. Auch Gemische dieser Treib- mittel sind verwendbar. Es können auch niedrigsiedende Kohlenwasserstoffe, z.B.Difluoroethane, 1,1,1,2-tetrafluoroethane, tetrafluoroethane (R 134 or R 134a), 1,1,1,3,3,3-hexafluoropropane (R 356), 1,1,1,3,3-pentafluoropropane (R 245fa), chlorodifluoroethane, l, l-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane, heptafluoropropane and sulfur hexafluoride can be used. Mixtures of these blowing agents can also be used. Low boiling hydrocarbons, e.g.
Pentan, Hexan und deren Isomere eingesetzt werden. Weitere geeignete Treibmittel sind Carbonsäuren wie Ameisensäure, Essigsäure, Oxalsäure und chemische Treibmittel, die im Verlauf des Schäumprozesses Gase freisetzen wie z.B. Carbamate. Bevorzugt werden diese Treibmittel in Kombination mit Wasser eingesetzt. Gegenstand der Erfindung sind weiterhin Polyurethangruppen enthaltende Schaumstoffe, die mindestens einen erfindungsgemäßen Stabilisator enthalten sowie ein Verfahren zur Herstellung derartiger Schaumstoffe aus mindestens difunktionellen Polyisocyanaten, Verbindungen mit mindestens zwei gegenüber Isocyanaten re- aktionsfähigen Wasserstoffatomen, Treibmitteln und Schaumstabilisatoren sowie gegebenenfalls Katalysatoren und anderen Additiven, bei dem mindestens ein erfindungsgemäßer Stabilisator als Schaumstabilisator eingesetzt wird.Pentane, hexane and their isomers are used. Other suitable blowing agents are carboxylic acids such as formic acid, acetic acid, oxalic acid and chemical blowing agents which release gases such as carbamates in the course of the foaming process. These blowing agents are preferably used in combination with water. 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.
Als mindestens difunktionelle Polyisocyanate werden im erfindungsgemäßen Ver- fahren organische Di- oder Polyisocyanate oder Polyisocyanatprepolymere verwendet. Als Di- oder Polyisocyanate kommen aliphatische, cycloaliphatische, aralipha- tische, aromatische und heterocyclische Polyisocyanate in Frage, wie sie in Justus Liebigs Annalen der Chemie 562 (1949) 75 beschrieben werden, beispielsweise solche der FormelOrganic 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
Q(NCO)n Q (NCO) n
in derin the
n eine ganze Zahl von 2 bis 4, vorzugsweise 2, undn is an integer from 2 to 4, preferably 2, and
Q einen aliphatischen Kohlenwasserstoffrest mit 2 bis 18, vorzugsweise 6 bis 10 C-Atomen, einen cyclo aliphatischen Kohlenwasserstoffrest mit 4 bis 15, vorzugsweise 5 bis 10 C-Atomen, einen- aromatischen Kohlen- wasserstoffrest mit 6 bis 15, vorzugsweise 6 bis 13 C-Atomen, oder einen araliphatischen Kohlenwasserstoffrest mit 8 bis 15, vorzugsweise 8 bis 13 C-Atomen bedeuten.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.
Bevorzugt sind Polyisocyanate, wie sie in der DE-OS 28 32 253 beschrieben werden. Besonders bevorzugt eingesetzt werden in der Regel die technisch leicht zugänglichen Polyisocyanate, z.B. das 2,4- und 2,6-Toluylendiisocyanat sowie beliebige Gemische dieser Isomeren ("TDI"), Polyphenyl-polymethylenpolyisocyanate, wie sie durch Anilin-Formaldehyd-Kondensation und anschließende Phosgenierung hergestellt werden ("rohes MDI") und Carbodiimidgruppen, Urethangruppen, Allopha- natgruppen, Isocyanuratgruppen, Harnstoffgruppen oder Biuretgruppen aufweisende Polyisocyanate ("modifizierte Polyisocyanate"), insbesondere solche modifiziertenPolyisocyanates 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
Polyisocyanate, die sich vom 2,4- und/oder 2,6-Toluylendiisocyanat bzw. vom 4,4'- und/oder 2,4'-Diphenylmethandiisocyanat ableiten. Verwendet werden können auch Prepolymere aus den genannten Isocyanaten und organischen Verbindungen mit mindestens einer Hydroxylgruppe. Beispielhaft genannt seien ein bis vier Hydro- xylgruppen aufweisende Polyol- oder Polyester mit (zahlenmittleren) Molekulargewichten von 60 bis 1400. Ganz besonders bevorzugt finden die unter dem Namen „polymeres Diphenylmethandiisocyanat" technisch erhältlichen Polyisocyanate mit einer höheren Funktionalität als 2,0 sowie aus ihnen hergestellte Prepolymere Verwendung.Polyisocyanates derived from 2,4- and / or 2,6-tolylene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate. 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.
Zur Schaumherstellung werden Verbindungen mit mindestens zwei gegenüber Isocyanaten reaktionsfähigen Wasserstoffatomen eingesetzt. Diese werden in der Regel als Bestandteil einer Polyolkomponente in das schaumbildende Reaktionsgemisch eingebracht. Beispiele für solche Verbindungen sind Polyether- und Polyesterpolyole.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.
Polyetherpolyole werden erhalten durch Polyaddition von Alkylenoxiden wie beispielsweise Oxiran, Methyloxiran, Ethyloxiran, Decyloxiran oder Phenyloxiran,' vorzugsweise Methyloxiran, Ethyloxiran oder Oxiran an Starterverbindungen mit aktiven Wasserstoffatomen. Als Starterverbindungen werden beispielsweise Ammoniak oder Verbindungen verwendet, die mindestens eine primäre oder sekundäre Ami- nogruppe aufweisen, wie beispielsweise aliphatische Amine wie 1,2-Diaminoethan, Oligomere des 1,2-Diaminoethans (beispielsweise Diethylentriamin, Triethylen- tetramin oder Pentaethylenhexamin), Ethanolamin oder Diethanolamin. 1,3-Dia- minopropan, 1,3-Diaminobutan, 1,4-Diaminobutan, 1,2-Diaminohexan, 1,3-Diami- nohexan, 1,4-Diaminohexan, 1,5-Diaminohexan, 1,6-Diaminohexan, aromatischePolyether 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. Examples of 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. 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, 1,2-diaminohexane, 1,3-diaminohexane, 1,4-diaminohexane, 1,5-diaminohexane, 1,6- Diaminohexane, aromatic
Amine wie 1,2-Diaminobenzol, 1,3-Diaminobenzol, 1,4-Diaminobenzol, 2,3-Dia- minotoluol, 2,4-Diaminotoluol, 3,4-Diaminotoluol, 2,5-Diaminotoluol, 2,6-Diamino- toluol, 2,2'-Diaminodiphenylmethan, 2,4'-Diaminodiphenylmethan, 4,4'-Diamino- diphenylmethan oder aromatische Amine, die durch säurekatalysierte Kondensation von Anilin mit Formaldehyd erhalten werden. Weitere geeignete Starterverbindungen sind solche mit zwei oder mehr Hydroxylendgruppen wie beispielsweise Wasser,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,
Triethanolamin, 1,2-Ethandiol, 1,2-Propandiol, 1,3-Propandiol, Diethylenglykol, Dipropylenglykol, Triethylenglykol, Tripropylenglykol, 1,2-Butandiol, 1,3-Butan- diol, 1,4-Butandiol, 1,2-Hexandiol, 1,3-Hexandiol, 1,4-Hexandiol, 1,5 -Hexandiol, 1,6-Hexandiol, Glycerol, Trimethylolpropan, Pentaerythrit, Sorbit und Saccharose. Die Starterverbindungen können allein oder als Gemische verwendet werden. Erfindungsgemäß in der Polyolkomponente einsetzbare Polyetherpolyole weisen (zahlenmittlere) Molmassen von 150 bis 12500 g/mol auf.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. According to the invention, polyether polyols which can be used in the polyol component have (number average) molar masses from 150 to 12500 g / mol.
Es können in der Polyolkomponente auch ein oder mehrere Polyesterpolyole mit (zahlenmittleren) Molmassen von 100 bis 30000 g/mol, bevorzugt 150 bisOne or more 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
10000 g/mol, besonders bevorzugt 200 bis 6000 g/mol aus aromatischen und/oder aliphatischen Dicarbonsäuren und mindestens zwei Hydroxylgruppen aufweisenden Polyolen eingesetzt werden. Beispiele für Dicarbonsäuren sind Phthalsäure, Isophthalsäure, Terephthalsäure, Fumarsäure, Maleinsäure, Azelainsäure, Glutar- säure, Adipinsäure, Korksäure, Sebacinsäure, Malonsäure und Bernsteinsäure. Es können die reinen Dicarbonsäuren sowie beliebige Mischungen daraus verwendet werden. Anstelle der freien Dicarbonsäuren können auch die entsprechenden* Di- carbonsäurederivate, wie z. B. Dicarbonsäuremono- oder -diester von Alkoholen mit ein bis vier Kohlenstoffatomen eingesetzt werden. Solche Ester entstehen beispiels- weise bei der Recyclisierung von Polyesterabfällen. Es können als Säurekomponente auch Dicarbonsäureanhydride wie Phthalsäureanhydrid oder Maleinsäureanhydrid eingesetzt werden. Als Alkoholkomponente zur Veresterung werden vorzugsweise verwendet: Ethylenglykol, Diethylenglykol, Tetraethylenglykol, 1,2-Propandiol, 1,3- Propandiol, 1,4-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, 1,10-Decandiol, Glycerin, Trimethylolpropan, Pentaerythrit bzw. Mischungen daraus. Es können auch Polyesterpolyole aus Lactonen, z.B. ε-Caprolacton oder Hydroxycarbonsäuren, z.B. ω- Hydroxycarbonsäuren, verwendet werden. Die Polyolkomponente kann auch Poly- etheresterpolyole enthalten, wie sie z.B. durch Reaktion von Phthalsäureanhydrid mit Diethylenglykol und nachfolgende Umsetzung mit Oxiran erhältlich sind.10000 g / mol, particularly preferably 200 to 6000 g / mol of aromatic and / or aliphatic dicarboxylic acids and at least two hydroxyl-containing polyols are used. Examples of 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. Instead of the free dicarboxylic acids, 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 ε-caprolactone or hydroxycarboxylic acids, for example ω- 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.
Weitere Beispiele geeigneter Polyole, die in der Polyolkomponente enthalten sein können, sind polyfunktionelle Alkohole oder Amine oder Aminoalkohole oder Mischungen aus diesen sowie deren oxypropylierte und oder oxyethylierte Folgeprodukte oder auch Polyesterpolyole, die durch Veresterung mehrfach funktioneller Alkohole mit mehrfach funktionellen Carbonsäuren erhalten werden. In der Polyol- komponente können auch modizifierte Polyole verwendet werden, wie sie durchFurther examples of 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
Pfropfung von Polyolen mit Styrol und oder Arylnitril, als Polyharnstoffdispersionen oder als PIPA-Polyole erhalten werden.Grafting of polyols with styrene and or aryl nitrile, as polyurea dispersions or as PIPA polyols can be obtained.
Bei der Herstellung der erfindungsgemäßen Schäume werden gegebenenfalls Ver- bindungen mit mindestens zwei gegenüber Isocyanaten reaktionsfähigen Wasserstoffatomen und einem Molekulargewicht von 32 bis 399 mitverwendet. Man versteht hierunter Hydroxylgruppen und/oder Aminogruppen und/oder Thiolgruppen und/oder Carboxylgruppen aufweisende Verbindungen, vorzugsweise Hydroxylgruppen und/oder Aminogruppen aufweisende Verbindungen, die als Kettenverlän- gerungsmittel oder Vernetzungsmittel dienen. Diese Verbindungen weisen in derIn the production of the foams according to the invention, 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. These connections point in the
Regel 2 bis 8, vorzugsweise 2 bis 4, gegenüber Isocyanaten reaktionsfähige Wasserstoffatome auf. Beispiele hierfür werden in DE-OS 28 32253 beschrieben. In einer bevorzugten Ausführungsform kommen Mischungen von mindestens zwei dieser Kettenverlängerungs- und/oder Vernetzungsmittel zum Einsatz. Bevorzugte Ketten- verlängerungs- und/oder Vernetzungsmittel sind beispielsweise Glycerin, Ethylen- glykol, Diethanolamin, Triethanolamin und Triisopropanolamin.Rule 2 to 8, preferably 2 to 4, hydrogen atoms reactive towards isocyanates. Examples of this are described in DE-OS 28 32253. In a preferred embodiment, mixtures of at least two of these chain extenders and / or crosslinking agents are used. Preferred chain extenders and / or crosslinking agents are, for example, glycerol, ethylene glycol, diethanolamine, triethanolamine and triisopropanolamine.
Bei der Herstellung der erfindungsgemäßen Schäume können gegebenenfalls Katalysatoren zugesetzt werden, die die Reaktion zwischen der Isocyanatkomponente und der Polyolkomponente beschleunigen. Beispiele für geeignete Katalysatoren sind organische Zinnverbindungen wie Zinn(II)salze organischer Carbonsäuren, z.B. Zinn(II)acetat, Zinn(II)octoat, Zinn(II)ethylhexoat und Zinn(II)laurat und die Dial- kylzinn(IV)salze z.B. Dibutylzinndiacetat, Dibutylzinndilaurat und Dioctylzinndi- acetat. Weitere Beispiele für geeignete Katalysatoren sind Amine wie Dimethyl- aminopropylharnstoff, Dimethylaminopropylamin, Bis (dimethylaminopropyl)amin, Diazabicyclooctan, Dimethylethanolamin, Triethylamin, Dimethylcyclohexylamin,In the production of the foams according to the invention, catalysts can optionally be added which accelerate the reaction between the isocyanate component and the polyol component. Examples of 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. Further examples of suitable catalysts are amines such as dimethylaminopropylurea, dimethylaminopropylamine, bis (dimethylaminopropyl) amine, diazabicyclooctane, dimethylethanolamine, triethylamine, dimethylcyclohexylamine,
Dimethylbenzylamin, Pentamethyldiethylentriamin, N,N,N',N'-Tetramethylbutan- diamin, N-Methylmorpholin, Bis(dimethylaminoethyl)ether und Tris(dialkylamino- alkyl)-s-hexahydrotriazine. Bevorzugt enthält die Katalysatorkomponente mindestens ein aliphatisches Amin. Es kann auch eine Kombination mehrerer Katalysatoren verwendet werden.Dimethylbenzylamine, pentamethyldiethylenetriamine, N, N, N ', N'-tetramethylbutanediamine, N-methylmorpholine, bis (dimethylaminoethyl) ether and tris (dialkylaminoalkyl) -s-hexahydrotriazine. The catalyst component preferably contains at least one aliphatic amine. A combination of several catalysts can also be used.
Zur Herstellung der erfindungsgemäßen Schäume werden gegebenenfalls noch weitere Additive verwendet, beispielsweise Paraffine oder Fettalkohole oder Dimethyl- polysiloxane sowie Pigmente oder Farbstoffe, ferner Stabilisatoren gegen Alterungs- und Witterungseinflüsse, Weichmacher wie Dioctylphthalat und fungistatisch und bakteriostatisch wirkende Substanzen. Diese werden meist der Polyolkomponente in Mengen von 0 bis 10 Gewichtsteilen, bevorzugt 0 bis 5 Gewichtsteilen zugesetzt.To produce the foams according to the invention, 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. These are usually added to the polyol component in amounts of 0 to 10 parts by weight, preferably 0 to 5 parts by weight.
Gegebenenfalls werden auch Flammschutzmittel zugesetzt, bevorzugt solche, die flüssig und/oder in einer oder mehreren der zur Schaumherstellung eingesetztenIf necessary, flame retardants are also added, preferably those which are liquid and / or in one or more of those used for foam production
Komponenten löslich sind. Bevorzugt kommen handelsübliche phosphorhaltige Flammschutzmittel zum Einsatz, beispielsweise Trikresylphosphat, Tris(2-chlor- ethyl)phosρhat, Tris(2-chlorpropyl)phosphat, Tris(2,3-dibrompropyl)phosphat, Tris- (1 ,3-dichlorpropyl)phosphat, Tetrakis(2-chlorethyl)ethylendiphosphat, Dimethyl- methanphosphonat, Diethylethanphosphonat, Diethanolaminomethylphosphonsäure- diethylester. Ebenfalls geeignet sind halogen- und/oder phosphorhaltige, flammschützend wirkende Polyole. Die Flammschutzmittel werden bevorzugt in einer Menge von maximal 35 Gew.-%, bevorzugt maximal 20 Gew.-%, bezogen auf die Polyolkomponente, eingesetzt.Weitere Beispiele von gegebenenfalls mitzuverwen- denden oberflächenaktiven Zusatzstoffen und Schaumstabilisatoren sowie Zellreglern, Reaktionsverzögerern, Stabilisatoren, flarnrnhemmenden Substanzen, Farbstof- fen sowie fungistatisch und bakteriostatisch wirksamen Substanzen sowie Einzelheiten über Verwendungs- und Wirkungsweise dieser Zusatzmittel sind in G. Oertel (Hrsg.): "Kunststoff-Handbuch", Band VII, Carl Hanser Verlag, 3. Auflage, München 1993, S.110-115 und DE-OS 27 32 292 beschrieben.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. Further examples of surface-active additives and foam stabilizers to be used, as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances Dye As well as fungistatic and bacteriostatic substances as well as details about the use and mode of action of these additives are in G. Oertel (ed.): "Kunststoff-Handbuch", Volume VII, Carl Hanser Verlag, 3rd edition, Munich 1993, p.110- 115 and DE-OS 27 32 292.
Die Reaktionskomponenten werden üblicherweise nach dem an sich bekannten Ein- stufenverfahren, dem Prepolymerverfahren oder dem Semiprepolymerverfahren zur Umsetzung gebracht, wobei man sich oft maschineller Einrichtungen bedient, z. B. solcher, die in der US-Patentschrift 2 764 565 beschrieben werden. Einzelheiten über Verarbeitungseinrichtungen, die auch erfindungsgemäß infrage kommen, werden inThe 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
R.Vieweg, A. Höchtlen (Hrsg.): „Kunststoff-Handbuch", Band VII, Carl-Hanser- Verlag, München 1966, S. 121-205 beschrieben.R.Vieweg, A. Höchtlen (ed.): "Kunststoff-Handbuch", Volume VII, Carl-Hanser-Verlag, Munich 1966, pp. 121-205.
In einer Ausführungsform der Erfindung wird die Verschäumung in geschlossenen Formen durchgeführt. Dabei wird das Reaktionsgemisch in eine Form eingetragen.In one embodiment of the invention, the foaming is carried out in closed molds. The reaction mixture is introduced into a mold.
Als Formmaterial kommt Metall, z. B. Aluminium oder Kunststoff, z. B. Epoxidharz, in Frage. In der Form schäumt das schaumfähige Reaktionsgemisch auf und bildet den Formkörper. Erfindungsgemäß kann man so vorgehen, dass man in die Form so viel schaumfähiges Reaktionsgemisch einträgt, dass der gebildete Schaumstoff die Form gerade ausfüllt. Man kann aber auch so arbeiten, dass man mehr schaumfähigesMetal, e.g. As aluminum or plastic, e.g. B. epoxy, in question. The foamable reaction mixture foams in the mold and forms the shaped body. According to the invention, 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
Reaktionsgemisch in die Form einträgt, als zur Auffüllung des Forminneren mit Schaumstoff notwendig ist. Im letztgenannten Fall wird somit unter „over-charging" gearbeitet; eine derartige Verfahrensweise ist beispielsweise aus US-PS 3 178 490 und US-PS 3 182 104 bekannt.Enters the reaction mixture into the mold than is necessary to fill the interior of the mold with foam. In the latter case, "over-charging" is used; such a procedure is known, for example, from US Pat. No. 3,178,490 and US Pat. No. 3,182,104.
Bevorzugt wird die Herstellung der erfindungsgemäßen Schaumstoffe so vorgenommen, dass der NCO/OH-Index, d.h. das stöchiometrische Verhältnis zwischen reaktiven Isocyanatgruppen und Hydroxylgruppen multipliziert mit 100, zwischen 65 und 350 beträgt. Besonders bevorzugt beträgt der NCO/OH-Index 70 bis 120. Gegenstand der Erfindung ist auch die Verwendung der erfindungsgemäßen Schaumstoffe als Polstermaterial für z. B. Sitze, Rücken- und Armlehnen sowie Kopfstützen im Automobil, in Schienenfahrzeugen, in Flugzeugen und Wasserfahrzeugen und in Möbeln für private und öffentliche Anwendungen. 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.
BeispieleExamples
In den Beispielen wurden folgende Ausgangskomponenten eingesetzt:The following starting components were used in the examples:
Polyol A: Polypropylenoxid-Polyetherpolyol der rechnerischen Molmasse 630 auf Basis Saccharose/Propylenglykol Polyol B: Polypropylenoxid-Polyetherpolyol der rechnerischen Molmasse 345 auf Basis Ethylendiamin Polyol C: Polypropylenoxid-Polyetherpolyol der rechnerischen Mol- asse 560 auf Basis o-ToluylendiaminPolyol 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. Polypropylenoxid-Polyetherpolyol der rechnerischen Molmasse 1000 aufBasis Propylenglykol Polyol E: Polypropylenoxid-Polyethylenoxid-Polyetherpolyol der rechnerischen Molmasse 6000 auf Basis Trimethylolpropan, in welches 20 Gew-% Styrol/Acrylnitril im GewichtsverhältnisPolyol 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 in situ einpolymerisiert wurden Polyol F: Polyesterpolyol der rechnerischen Molmasse 530 auf Basis60:40 were polymerized in situ based on polyol F: polyester polyol with a calculated molecular weight of 530
Diethylenglykol, Phthalsäureanhydrid und Adipinsäure Polyol G: Polyether-Polyesterpolyol der rechnerischen Molmasse 360, hergestellt durch Addition von Methyloxiran an ein Polyesterpolyol aus Phthalsäureanhydrid, Diethylenglykol und Sorbit Polyol H: Ixol® 251, flammhemmendes Polyol der Hydroxylzahl 330,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,
(Fa. Solvay Fluor und Derivate GmbH, D-30173 Hannover) Tegostab®B-8421: Siloxan-basierender Hartschaumstabilisator (Fa. Th. Goldschmidt AG, Goldschmidtstr. 100, D-45127 Essen)(Solvay Fluor und Derivate GmbH, D-30173 Hanover) Tegostab ® B-8421: Siloxane-based rigid foam stabilizer (Th. Goldschmidt AG, Goldschmidtstr. 100, D-45127 Essen)
Die Bestimmung der Geschlossenzelligkeit erfolgte mit einem Pyknometer (Accupyc 1330, Micromeritics GmbH, D-41238 Mönchengladbach) nach ASTM D 2856. Die Wärmeleitzahlen wurden gemäß DIN 52616 bei 24°C vermessen. Die Brandversuche erfolgten gemäß DIN 4102 (Kleinbrennertest). Beispiel 1 Herstellung eines Stabilisators (Stabilisator A)The closed cell was determined using a pycnometer (Accupyc 1330, Micromeritics GmbH, D-41238 Mönchengladbach) in accordance with ASTM D 2856. The thermal conductivities were measured at 24 ° C. in accordance with DIN 52616. The fire tests were carried out in accordance with DIN 4102 (small burner test). Example 1 Preparation of a Stabilizer (Stabilizer A)
Zu einer auf 90°C temperierten Mischung aus 5 g (2,2,3,3,3-Pentafiuoropropyι)-ac- rylat und 100 g eines difunktionellen Polyoxyalkylenpolyols mit 87 Gew.-% Oxy- propylen- und 13 Gew.-% Oxyethyleneinheiten, dessen Hydroxylgruppen zu 22 % mit Acrylsäure verestert sind, wurden unter Rühren über einen Zeitraum von sechs Stunden hinweg insgesamt 0,1 g Azobisiobuttersäurenitril und 0,2 g Dodecanthiol, gelöst in 10 ml Toluol, zugegeben. Nach Abkühlen erhielt man das Produkt (Stabilisator A) als klare, lagerstabile Flüssigkeit der Viskosität 3210 mPa*s (bei 20°C) mit einem Fluorgehalt von 1 ,9 Gew.-%.To a mixture of 5 g (2,2,3,3,3-pentafiuoropropyl) -acrylicate and 100 g of a difunctional polyoxyalkylene polyol with 87% by weight oxypropylene and 13% by weight at a temperature of 90 ° C. Oxyethylene units, the hydroxyl groups of which were 22% esterified with acrylic acid, were added with stirring over a period of six hours, a total of 0.1 g of azobisiobutyronitrile and 0.2 g of dodecanethiol, dissolved in 10 ml of toluene. After cooling, the product (stabilizer A) was obtained as a clear, storage-stable liquid with a viscosity of 3210 mPa * s (at 20 ° C.) and a fluorine content of 1.9% by weight.
Beispiel 2 Herstellung eines Stabilisators (Stabilisator B)Example 2 Preparation of a Stabilizer (Stabilizer B)
Zu einer auf 90°C temperierten Mischung aus 5 g (2,2,3,3,4,4,4-Heptafluorobutyι)- acrylat und 100 g eines difunktionellen Polyoxyalkylenpolyols mit 87 Gew.-%To a mixture of 5 g (2,2,3,3,4,4,4-heptafluorobutyl) acrylate and 100 g of a difunctional polyoxyalkylene polyol at 87% by weight, heated to 90 ° C.
Oxypropylen- und 13 Gew.-% Oxyethyleneinheiten, dessen Hydroxylgruppen zu 22 % mit Acrylsäure verestert sind, wurden unter Rühren über einen Zeitraum von sechs Stunden hinweg insgesamt 0,1 g Azobisiobuttersäurenitril und 0,2 g Dodecanthiol, gelöst in 10 ml Toluol, zugegeben. Nach Abkühlen erhielt man das Produkt (Stabilisator B) als klare, lagerstabile Flüssigkeit der Viskosität 6320 mPa*s (beiOxypropylene and 13% by weight oxyethylene units, the hydroxyl groups of which are 22% esterified with acrylic acid, were added with stirring over a period of six hours, a total of 0.1 g of azobisiobutyronitrile and 0.2 g of dodecanethiol, dissolved in 10 ml of toluene , After cooling, the product (stabilizer B) was obtained as a clear, storage-stable liquid with a viscosity of 6320 mPa * s (at
20°C) mit einem Fluorgehalt von 2,2 Gew.-%.20 ° C) with a fluorine content of 2.2% by weight.
Beispiel 3 Herstellung eines Stabilisators (Stabilisator C)Example 3 Preparation of a Stabilizer (Stabilizer C)
Zu einer auf 90°C temperierten Mischung aus 4,5 g (3,3,4,4,5,5,6,6,7,7,8,8,8-Tri- decafluorooctyl)acrylat und 100 g eines difunktionellen Polyoxyalkylenpolyols mit 70 Gew.-% Oxypropylen- und 30 Gew.-% Oxyethyleneinheiten, dessen Hydroxyl- endgruppen zu 21 % mit Acrylsäure verestert sind, wurden unter Rühren über einen Zeitraum von sechs Stunden hinweg insgesamt 0,1 g Azobisiobuttersäurenitril und 0,2 g Dodecanthiol, gelöst in 10 ml Toluol, zugegeben. Nach Abkühlen erhielt man das Produkt (Stabilisator C) als klare, lagerstabile Flüssigkeit der Viskosität 7900 mPa*s (bei 20°C) mit einem Fluorgehalt von 2,4 Gew.-%.To a mixture of 4.5 g (3,3,4,4,5,5,6,6,7,7,8,8,8-tri-decafluorooctyl) acrylate and 100 g of a difunctional one at a temperature of 90 ° C Polyoxyalkylene polyols containing 70% by weight of oxypropylene and 30% by weight of oxyethylene units, the hydroxyl end groups of which are 21% esterified with acrylic acid, were stirred with a total of 0.1 g of azobisiobutyronitrile and 0.2 g over a period of six hours Dodecanethiol, dissolved in 10 ml of toluene, is added. After cooling, was obtained the product (stabilizer C) as a clear, storage-stable liquid with a viscosity of 7900 mPa * s (at 20 ° C.) with a fluorine content of 2.4% by weight.
Beispiel 4 Herstellung eines Stabilisators (Stabilisator D)Example 4 Preparation of a Stabilizer (Stabilizer D)
Es wurde wie in Beispiel 1 verfahren, außer dass statt Toluol N,N-Dimethylform- amid verwendet wurde. Man erhielt das Produkt (Stabilisator D) als klare, lagerstabile Flüssigkeit der Viskosität 5560 mPa*s (bei 20°C) mit einem Fluorgehalt von 2,3 Gew.-%.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.
Vergleichsbeispiel 1 Herstellung eines Stabilisators (Vergleichsprodukt 1)Comparative Example 1 Preparation of a Stabilizer (Comparative Product 1)
Es wurde wie in Beispiel 1 verfahren, außer dass die Menge (2,2,3,3,3-Pentafluoro- propyl)acrylat 15 g betrug. Man erhielt das Produkt (Vergleichsprodukt 1) als mil- chige, lagerstabile Flüssigkeit der Viskosität 11600 mPa*s (bei 20°C) mit einemThe 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
Fluorgehalt von 5,0 Gew.-%.Fluorine content of 5.0% by weight.
Vergleichsbeispiel 2 Herstellung eines Stabilisators (Vergleichsprodukt 2)Comparative Example 2 Preparation of a Stabilizer (Comparative Product 2)
Es wurde wie in Beispiel 3 verfahren, die Menge an (3,3,4, 4,5,5, 6,6,7,7,8,8,8-Tri- decafluorooctyl)acrylat betrug jedoch 10 g. Man erhielt das Produkt (Vergleichsprodukt 2) als milchige, lagerstabile Flüssigkeit der Viskosität 11600 mPa*s (bei 2Ö°C) mit einem Fluorgehalt von 5,0 Gew.-%.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.
Vergleichsbeispiel 3 Herstellung eines Stabilisators (Vergleichsprodukt 3)Comparative Example 3 Preparation of a Stabilizer (Comparative Product 3)
Es wurde wie in Beispiel 1 verfahren, jedoch wurde die Polymerisierung ohne (2,2,3,3,3-Pentafluoropropyl)acrylat durchgeführt. Man erhielt eine klare Flüssigkeit (Vergleichsprodukt 3) der Viskosität 4660 mPa*s (bei 20°C). Vergleichsbeispiel 4 Herstellung eines Stabilisators (Vergleichsprodukt 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)
Es wurde wie in Beispiel 3 verfahren, jedoch wurde die Polymerisierung ohne (3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)acrylat durchgeführt. Man erhielt eine klare Flüssigkeit (Vergleichsprodukt 4) der Viskosität 7180 mPa*s (bei 20°C).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.
Beispiele 5-8 Herstellung von erfindungsgemäßen PolyurethanhartschäumenExamples 5-8 Production of rigid polyurethane foams according to the invention
Nach der folgenden Rezeptur wurden in Handschaumverfahren PU-Hartschaumstoffe hergestellt (Angaben in Gew.-Teilen):Rigid PU foams were produced according to the following recipe (data in parts by weight):
40 Teile Polyol A40 parts of polyol A.
10 Teile Polyol B10 parts of polyol B
40 Teile Polyol C 10 Teile Polyol D40 parts polyol C 10 parts polyol D
2.0 Teile verschiedener Schaumstabilisatoren (s. Tabelle 1)2.0 parts of different foam stabilizers (see Table 1)
2.1 Teile Wasser2.1 parts of water
0,8 Teile Dimethylcyclohexylamin0.8 parts of dimethylcyclohexylamine
1.2 Teile Pentamethyldiethylentriamin 15,5 Teile Cyclopentan1.2 parts of pentamethyldiethylenetriamine 15.5 parts of cyclopentane
147 Teile rohes Diphenylmethandiisocyanat147 parts of crude diphenylmethane diisocyanate
(Desmodur® 44V20, Bayer AG, D-51368 Leverkusen), NCO/OH-Index 110(Desmodur ® 44V20, Bayer AG, 51368 Leverkusen, Germany), NCO / OH index 110
Alle Komponenten, außer dem Diisocyanat, wurden 60 Sekunden mit 2000 Upm beiAll components except the diisocyanate were run at 2000 rpm for 60 seconds
20°C gerührt, dann wurde das Isocyanat zugegeben und weitere 6 Sekunden bei 1000 Upm gerührt. Die Mischung wurde in eine mit Papier ausgekleidete Holzform der Abmessung 15 x 15 x 10 cm gegossen. Vor der Entnahme ließ man den Schaum ungefähr 15 Minuten aushärten. Die erhaltenen Schäume zeigten die folgenden Eigenschaften:Stirred at 20 ° C., then the isocyanate was added and the mixture was stirred at 1000 rpm for a further 6 seconds. The mixture was poured into a paper-lined wooden mold measuring 15 x 15 x 10 cm. The foam was allowed to cure for about 15 minutes before removal. The foams obtained had the following properties:
Figure imgf000018_0001
Figure imgf000018_0001
Vergleichsbeispiele 5-8 Herstellung von PolyurethanhartschäumenComparative Examples 5-8 Production of rigid polyurethane foams
Die Beispiele 5-8 wurden wiederholt, jedoch wurden als Stabilisatoren die Vergleichsprodukte 1-4 eingesetzt. In allen vier Fällen konnte kein Polyurethanschaum hergestellt werden, weil das aufschäumende Gemisch beim Aufsteigen kollabierte.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.
Beispiel 9 Herstellung eines Schaumstabilisators (Stabilisator E)Example 9 Preparation of a Foam Stabilizer (Stabilizer E)
Zu einer auf 90°C temperierten Mischung aus 4,5 g eines technischen Gemischs von Fluoralkyl-acrylaten, das unter dem Namen Zonyl® TA-N (Fa. DuPont, D-61352 Bad Homburg) kommerziell erhältlich ist, und 100g eines difunktionellen Polyoxy- alkylenpolyols mit 70 Gew.-% Oxypropylen- und 30 Gew.-% Oxyethyleneinheiten, dessen Hydroxylendgruppen zu 21 % mit Acrylsäure verestert sind, wurden unter Rühren über einen Zeitraum von sechs Stunden hinweg insgesamt 0,1 g Azobisiobuttersäurenitril und 0,2 g Dodecanthiol, gelöst in 10 ml Dipropylenglykol, zugegeben. Nach Abkühlen erhielt man das Produkt (Stabilisator E) als leicht trübe, lagerstabile Flüssigkeit der Viskosität 12800 mPa*s (bei 20°C) mit einem Fluorgehalt von 2,7 Gew.-%. Vergleichsbeispiel 9 Herstellung eines Stabilisators (Vergleichsprodukt 5)To a temperature-controlled at 90 ° C mixture of 4.5 of a technical mixture of fluoroalkyl acrylates, sold under the name Zonyl ® TA-N (Fa. DuPont, D-61352 Bad Homburg) g is commercially available, and 100g of a difunctional polyoxy - Alkylene polyols with 70 wt .-% oxypropylene and 30 wt .-% oxyethylene units, the hydroxyl end groups of which 21% are esterified with acrylic acid, were stirred 0.1 g azobisiobutyronitrile and 0.2 g dodecanethiol over a period of six hours , dissolved in 10 ml dipropylene glycol, added. After cooling, the product (stabilizer E) was obtained as a slightly cloudy, storage-stable liquid with a viscosity of 12800 mPa * s (at 20 ° C.) and a fluorine content of 2.7% by weight. Comparative Example 9 Preparation of a Stabilizer (Comparative Product 5)
Es wurde wie in Beispiel 9 verfahren, ausser dass 8 g Zonyl® TA-N (Fa. DuPont) verwendet wurden. Man erhielt eine zweiphasige, trübe Mischung. (Vergleichspro- dukt 5)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)
Beispiele 10-11 Herstellung von erfindungsgemäßen PolyurethanhartschäumenExamples 10-11 Production of rigid polyurethane foams according to the invention
Nach der folgenden Rezeptur wurden in Handschaumverfahren PU-Hartschaumstoffe hergestellt (Angaben in Gew.-Teilen) :Rigid PU foams were produced according to the following recipe (data in parts by weight):
10 Teile Polyol B10 parts of polyol B
10 Teile Polyol F10 parts of polyol F
20 Teile Polyol G 31,5 Teile Polyol H20 parts of polyol G 31.5 parts of polyol H
7,2 Teile Glycerin7.2 parts glycerin
21,3 Teile Tris(chlorpropyl)phosρhat21.3 parts of tris (chloropropyl) phosphate
2,0 Teile verschiedener Schaumstabilisatoren (s. Tabelle 2)2.0 parts of different foam stabilizers (see Table 2)
1,8 Teile Wasser 1,1 Teile Dimethylcyclohexylamin1.8 parts water 1.1 parts dimethylcyclohexylamine
10,0 Teile Pentan10.0 parts pentane
138 Teile rohes Diphenylmethandiisocyanat138 parts of crude diphenylmethane diisocyanate
(Desmodur® 44V20, Bayer AG, D-51368 Leverkusen),(Desmodur ® 44V20, Bayer AG, D-51368 Leverkusen),
NCO/OH-Index 115NCO / OH index 115
Alle Komponenten, außer dem Diisocyanat, wurden 60 Sekunden mit 2000 Upm beiAll components except the diisocyanate were run at 2000 rpm for 60 seconds
20°C gerührt, dann wurde das Isocyanat zugegeben und weitere 6 Sekunden beiStirred at 20 ° C, then the isocyanate was added and another 6 seconds
1000 Upm gerührt. Die Mischung wurde in eine mit Papier ausgekleidete Holzform der Abmessung 15 x 15 x 10 cm gegossen. Vor der Entnahme ließ man den Schaum ungefähr 15 Minuten aushärten. Die erhaltenen Schäume zeigten die folgenden Eigenschaften:Stirred 1000 rpm. The mixture was poured into a paper-lined wooden mold measuring 15 x 15 x 10 cm. The foam was allowed to cure for about 15 minutes before removal. The foams obtained had the following properties:
Figure imgf000020_0001
Figure imgf000020_0001
Vergleichsbeispiel 10Comparative Example 10
Es wurde wie in den Beispielen 10-11 verfahren, allerdings wurde anstelle der erfindungsgemäßen Stabilisatoren der Siloxan-Stabilisator Tegostab® B-8421 (Fa. Th. Goldschmidt AG, Essen) in identischer Menge (2,0 Teile) verwendet.The procedure was as in Examples 10-11, but instead of the inventive stabilizers of the siloxane stabilizer Tegostab ® B-8421 (Messrs. Th. Goldschmidt, Essen AG) (2.0 parts) was used in an identical amount.
Der so erhaltene Schaum zeigte die folgenden Eigenschaften:The foam thus obtained showed the following properties:
Figure imgf000020_0002
Figure imgf000020_0002
Beispiel 12 Herstellung von PolyurethanweichschäumenExample 12 Preparation of flexible polyurethane foams
Nach der folgenden Rezeptur wurden in Handschaumverfahren PU- Weichschaumstoffe hergestellt (Angaben in Gew.-Teilen):According to the following recipe, flexible PU foams were produced using the hand foam method (parts by weight):
100 Teile Polyol E,100 parts of polyol E,
2,1 Teile Stabilisator E,2.1 parts stabilizer E,
6,7 Teile Wasser,6.7 parts of water,
0,25 Teile Dabco® BL-11 (Fa. Air Products, NL-3502 Utrecht),0.25 parts Dabco BL-11 ® (Fa. Air Products, NL-3502 Utrecht),
0,57 Teile Dabco® 33 LV (Fa. Air Products, NL-3502 Utrecht), 2,9 Teile Diethanolamin, 87,2 Teile technisches Gemisch aus 80% 2,4-Toluylendiisocyanat und 20%0.57 parts Dabco ® 33 LV (Fa. Air Products, NL-3502 Utrecht), 2.9 parts of diethanolamine, 87.2 parts technical mixture of 80% 2,4-tolylene diisocyanate and 20%
2,6-Toluylendiisocyanat2,6-diisocyanate
(Desmodur® T 80, Bayer AG, D-51368 Leverkusen), NCO/OH-Index 100(Desmodur ® T 80, Bayer AG, 51368 Leverkusen, Germany), NCO / OH index 100
Alle Komponenten, außer dem Diisocyanat, wurden 60 Sekunden mit 2000 Upm bei 20°C gerührt, dann wurde das Isocyanat zugegeben und weitere 8 Sekunden bei 1200 Upm gerührt. Die Mischung wurde in eine Metallform der Abmessung 12 x 20 x 12 cm gegossen. Die Form wurde anschließend verschlossen. Man erhielt nach der üblichen mechanischer Behandlung einen feinzelligen Weichschaumstoff der Rohdichte 42 kg m" , der für Polsterung vorzüglich geeignet ist.All components, except the diisocyanate, were stirred for 60 seconds at 2000 rpm at 20 ° C., then the isocyanate was added and the mixture was stirred for a further 8 seconds at 1200 rpm. The mixture was poured into a 12 x 20 x 12 cm metal mold. The mold was then sealed. After the usual mechanical treatment, a fine-celled soft foam with a bulk density of 42 kg m "was obtained , which is particularly suitable for upholstery.
Vergleichsbeispiel 11 Herstellung von PolyurethanweichschäumenComparative Example 11 Production of flexible polyurethane foams
Beispiel 10 wurde wiederholt unter Verwendung des Vergleichsprodukts 5 alsExample 10 was repeated using Comparative Product 5 as
Schaumstabilisator. Es konnte kein Polyurethanschaumstoff hergestellt werden, da der Schaum beim Aufsteigen kollabierte. Foam stabilizer. No polyurethane foam could be made because the foam collapsed when it got up.

Claims

Patentansprüche claims
1. Stabilisatoren für Polyurethangruppen enthaltende Schaumstoffe mit einem Fluorgehalt von 0,1 bis 4,5 Gew.-%, erhältlich durch Copolymerisierung eines Doppelbindungen aufweisenden Poly(oxyalkylen)polyols mit mindestens 10 Gew.-% Polyoxyethylenemheiten und eines Fluoratome enthaltenden Acrylats.1. Stabilizers for foams containing polyurethane groups with a fluorine content of 0.1 to 4.5% by weight, obtainable by copolymerizing a poly (oxyalkylene) polyol containing double bonds with at least 10% by weight of polyoxyethylene units and an acrylate containing fluorine atoms.
2. Eine Formulierung, enthaltend2. A wording containing
a) mindestens eine Verbindung mit mindestens zwei gegenüber Isocyanatgruppen reaktiven Gruppen sowie gegebenenfalls Wasser, Katalysatoren und weitere Hilfsmittel und b) 0,1 bis 5 Gew.-% eines Stabilisators gemäß Anspruch 1, bezogen auf die Gesamtmenge an Verbindungen mit mindestens zwei gegenübera) at least one compound with at least two groups reactive toward isocyanate groups and optionally water, catalysts and other auxiliaries and b) 0.1 to 5% by weight of a stabilizer according to claim 1, based on the total amount of compounds with at least two groups
Isocyanatgruppen reaktiven Gruppen.Isocyanate groups reactive groups.
3. Eine Formulierung, enthaltend3. A wording containing
a) mindestens ein organisches Polyisocyanat und b) 0,1 bis 5 Gew.-% mindestens eines Stabilisators gemäß Anspruch 1.a) at least one organic polyisocyanate and b) 0.1 to 5% by weight of at least one stabilizer according to claim 1.
4. Polyurethangruppen enthaltender Schaumstoff, der mindestens einen Stabilisator gemäß Anspruch 1 enthält.4. Foam containing polyurethane groups, which contains at least one stabilizer according to claim 1.
5. Verfahren zur Herstellung von Polyurethangruppen enthaltenden Schaumstoffen aus mindestens difunktionellen Polyisocyanaten, Verbindungen mit mindestens zwei gegenüber Isocyanaten reaktionsfähigen Wasserstoffatomen, Treibmitteln und Schaumstabilisatoren sowie gegebenenfalls Katalysatoren und anderen Additiven, bei dem mindestens ein Stabilisator gemäß Anspruch5. A process for the preparation of foams containing polyurethane groups from at least difunctional polyisocyanates, compounds with at least two isocyanate-reactive hydrogen atoms, blowing agents and foam stabilizers and optionally catalysts and other additives, in which at least one stabilizer according to claim
1 als Schaumstabilisator eingesetzt wird. 1 is used as a foam stabilizer.
PCT/EP2001/004633 2000-05-08 2001-04-25 Stabilizers for polyurethane foams WO2001085822A1 (en)

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
DE10022370.2 2000-05-08
DE10022370A DE10022370A1 (en) 2000-05-08 2000-05-08 Stabilizer for polyurethane foam, for use as e.g. padding material in cars and furniture, is obtained by copolymerizing a special double bond-containing polyether-polyol with a fluoro-acrylate compound

Publications (1)

Publication Number Publication Date
WO2001085822A1 true WO2001085822A1 (en) 2001-11-15

Family

ID=7641190

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/004633 WO2001085822A1 (en) 2000-05-08 2001-04-25 Stabilizers for polyurethane foams

Country Status (3)

Country Link
AU (1) AU2001267370A1 (en)
DE (1) DE10022370A1 (en)
WO (1) WO2001085822A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1688448A1 (en) * 2003-11-26 2006-08-09 Asahi Glass Company Ltd. Flexible polyurethane foam, process for producing the same, and automotive sheet employing the same
EP1790682A1 (en) * 2005-11-25 2007-05-30 Goldschmidt GmbH Grafted polyether copolymers and their use as stablizers in polyurethane foams
EP1884529A1 (en) * 2005-05-25 2008-02-06 Asahi Glass Company, Limited Flexible polyurethane foam, process for producing the same, and automotive seat employing the flexible polyurethane foam
EP2028223A1 (en) * 2007-08-23 2009-02-25 Bayer MaterialScience AG EO/PO block copolymers as stabilisers for PUR foams
EP2085413A1 (en) * 2006-11-20 2009-08-05 Asahi Glass Company, Limited Method for producing polymer-dispersed polyol
EP2085414A1 (en) * 2006-11-20 2009-08-05 Asahi Glass Company, Limited Method for producing hard polyurethane foam
EP2284207A1 (en) * 2008-05-30 2011-02-16 Asahi Glass Company, Limited Hard foam synthetic resin and process for producing the same
CN112341596A (en) * 2020-10-28 2021-02-09 山东一诺威聚氨酯股份有限公司 Prefabricated polyurethane foaming elastomer material, preparation method thereof, constructed court and construction method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3092837B1 (en) * 2019-02-18 2021-08-27 Gaztransport Et Technigaz METHACRYLATE COPOLYMERS, AND THEIR USES FOR THE PREPARATION OF POLYURETHANE FOAM

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4356273A (en) * 1979-04-30 1982-10-26 Minnesota Mining And Manufacturing Company Fluorochemical foam stabilizer and foamed polyurethanes made therewith
EP0124111A2 (en) * 1983-05-02 1984-11-07 Sloss Industries Corporation Unsaturated polyoxyalkylene adduct/fumarate diester reaction product for cellular foam stabilization
DE3824355A1 (en) * 1988-07-19 1990-01-25 Basf Ag Polyurethane foams produced in the presence of oligomers containing fluoroaliphatic side groups, production thereof, and use of the oligomers containing fluoroaliphatic side groups as surface-active auxiliary
US5350795A (en) * 1991-07-10 1994-09-27 Minnesota Mining And Manufacturing Company Aqueous oil and water repellent compositions which cure at ambient temperature

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4356273A (en) * 1979-04-30 1982-10-26 Minnesota Mining And Manufacturing Company Fluorochemical foam stabilizer and foamed polyurethanes made therewith
EP0124111A2 (en) * 1983-05-02 1984-11-07 Sloss Industries Corporation Unsaturated polyoxyalkylene adduct/fumarate diester reaction product for cellular foam stabilization
DE3824355A1 (en) * 1988-07-19 1990-01-25 Basf Ag Polyurethane foams produced in the presence of oligomers containing fluoroaliphatic side groups, production thereof, and use of the oligomers containing fluoroaliphatic side groups as surface-active auxiliary
US5350795A (en) * 1991-07-10 1994-09-27 Minnesota Mining And Manufacturing Company Aqueous oil and water repellent compositions which cure at ambient temperature

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KRUPERS M J ET AL: "Formation of rigid polyurethane foams with semi-fluorinated diblock copolymeric surfactants", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 39, no. 10, 1 May 1998 (1998-05-01), pages 2049 - 2053, XP004108253, ISSN: 0032-3861 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1688448A1 (en) * 2003-11-26 2006-08-09 Asahi Glass Company Ltd. Flexible polyurethane foam, process for producing the same, and automotive sheet employing the same
EP1688448A4 (en) * 2003-11-26 2009-02-18 Asahi Glass Co Ltd Flexible polyurethane foam, process for producing the same, and automotive sheet employing the same
EP1884529A1 (en) * 2005-05-25 2008-02-06 Asahi Glass Company, Limited Flexible polyurethane foam, process for producing the same, and automotive seat employing the flexible polyurethane foam
EP1884529A4 (en) * 2005-05-25 2011-10-12 Asahi Glass Co Ltd Flexible polyurethane foam, process for producing the same, and automotive seat employing the flexible polyurethane foam
EP1790682A1 (en) * 2005-11-25 2007-05-30 Goldschmidt GmbH Grafted polyether copolymers and their use as stablizers in polyurethane foams
EP2085413A1 (en) * 2006-11-20 2009-08-05 Asahi Glass Company, Limited Method for producing polymer-dispersed polyol
EP2085414A1 (en) * 2006-11-20 2009-08-05 Asahi Glass Company, Limited Method for producing hard polyurethane foam
EP2085413A4 (en) * 2006-11-20 2012-11-07 Asahi Glass Co Ltd Method for producing polymer-dispersed polyol
EP2085414A4 (en) * 2006-11-20 2012-11-07 Asahi Glass Co Ltd Method for producing hard polyurethane foam
WO2009024266A1 (en) * 2007-08-23 2009-02-26 Bayer Materialscience Ag Eo/po block polymers as stabilizers for pur foams
EP2028223A1 (en) * 2007-08-23 2009-02-25 Bayer MaterialScience AG EO/PO block copolymers as stabilisers for PUR foams
EP2284207A1 (en) * 2008-05-30 2011-02-16 Asahi Glass Company, Limited Hard foam synthetic resin and process for producing the same
EP2284207A4 (en) * 2008-05-30 2011-06-15 Asahi Glass Co Ltd Hard foam synthetic resin and process for producing the same
CN112341596A (en) * 2020-10-28 2021-02-09 山东一诺威聚氨酯股份有限公司 Prefabricated polyurethane foaming elastomer material, preparation method thereof, constructed court and construction method thereof
CN112341596B (en) * 2020-10-28 2022-04-19 山东一诺威聚氨酯股份有限公司 Prefabricated polyurethane foaming elastomer material, preparation method thereof, constructed court and construction method thereof

Also Published As

Publication number Publication date
DE10022370A1 (en) 2001-11-15
AU2001267370A1 (en) 2001-11-20

Similar Documents

Publication Publication Date Title
EP1873209B1 (en) Siliconstabilizers for flame retardant polyurethane- resp. polyioscyanurate rigid foams
EP1799736B1 (en) Method for producing rigid polyurethane foams
EP3010951B1 (en) Isocyanate/siloxane polyether composition
EP1175459B1 (en) Compressed, rigid polyurethane foams
EP2820057B1 (en) Polyether ester polyols and use of same for producing polyurethane solid foam materials
DE102009029363A1 (en) Lecithin-containing composition suitable for the production of rigid polyurethane foams
EP3036267B1 (en) Improved rigid polyurethane and polyisocyanurate foams based on fatty acid modified polyether polyols
EP0904309B1 (en) Process for producing hard polyurethane foams with low heat conductivity
EP2820059B1 (en) Polyurethane solid foam materials
EP2855551B1 (en) Method for manufacturing rigid polyurethane foams
EP2804886A1 (en) Method for producing rigid polyurethane foams
WO2014048777A1 (en) Rigid polyurethane and polyisocyanurate foams based on fatty acid-modified polyether polyols
EP1173495B1 (en) Open-cell rigid polyurethane foams
WO2001085822A1 (en) Stabilizers for polyurethane foams
US6590007B2 (en) Flame-resistant hr cold-moulded foam with reduced fume density and toxicity
US20140094531A1 (en) Rigid polyurethane and polyisocyanurate foams based on fatty acid modified polyetherpolyols
WO2013174745A1 (en) Method for producing flame-protected polyurethane foams having low bulk densities
WO2002040568A1 (en) Activators for the production of polyurethane foamed materials
WO2023237420A1 (en) Polyether-siloxane block copolymers for producing polyurethane foams
EP3608347A1 (en) Soft foam having halogen-free flame protection
KR20230154451A (en) Polyurethane foam composition for potting products and uses thereof
EP3428212A1 (en) Flexible foam having halogen-free flame protection

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP