WO2015150304A1 - Procédé de production de mousses dures de polyuréthanne - Google Patents

Procédé de production de mousses dures de polyuréthanne Download PDF

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Publication number
WO2015150304A1
WO2015150304A1 PCT/EP2015/056850 EP2015056850W WO2015150304A1 WO 2015150304 A1 WO2015150304 A1 WO 2015150304A1 EP 2015056850 W EP2015056850 W EP 2015056850W WO 2015150304 A1 WO2015150304 A1 WO 2015150304A1
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WIPO (PCT)
Prior art keywords
component
polyol
acid
cover layer
catalyst
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PCT/EP2015/056850
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German (de)
English (en)
Inventor
Tobias KALUSCHKE
Gunnar Kampf
Original Assignee
Basf Se
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Publication of WO2015150304A1 publication Critical patent/WO2015150304A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
    • B29C44/461—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length dispensing apparatus, e.g. dispensing foaming resin over the whole width of the moving surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • 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

Definitions

  • the present invention relates to a process for the production of rigid polyurethane foams or rigid polyisocyanurate foams comprising the reaction of a component (A) containing at least one polyisocyanate with a polyol component (PK).
  • the polyol component contains at least one polyol, at least one flame retardant, at least one propellant and a composition (ZK) containing as catalyst components a salt of a carboxylic acid (K1), an amine (K2) and another different from the catalyst component (K2) Amine (K3).
  • the present invention relates to methods for producing a composite element, comprising at least one layer of rigid foam a) and at least one cover layer b), wherein a flowable starting material a * ) is provided and applied to the cover layer b) by means of a fixed applicator device c), while the cover layer b) is moved continuously.
  • the present invention relates to a method for producing a composite element, the use of the composition (ZK) as a catalyst for the production of a rigid polyurethane or polyisocyanurate foam, the polyurethane or polyisocyanurate rigid foam obtainable or obtained by a method according to the invention and a composite element obtainable or obtained by a process according to the invention.
  • rigid polyurethane foams by reacting polyisocyanates with relatively high molecular weight compound having at least two reactive hydrogen atoms, in particular polyether polyols from the alkylene oxide or polyester polyols from the polycondensation of alcohols with dicarboxylic acids in the presence of polyurethane catalysts, chain extenders and / or crosslinking agents, blowing agents and Other auxiliaries and additives is known and is described in numerous patent and literature publications.
  • Polyurethane rigid foams or rigid polyisocyanurate foams are frequently used as insulating material and for insulation. The foams are used in particular as composite elements with a cover layer.
  • a polyisocyanurate foam is usually understood as meaning a foam which, in addition to urethane, also contains isocyanurate groups.
  • rigid polyurethane foam can also include rigid polyisocyanurate foam.
  • polyisocyanurate foams often show insufficient adhesion to the metallic cover layers.
  • an adhesion promoter is usually applied between the cover layer and the foam, as described, for example, in WO 99/00559.
  • WO 2005/090432 describes a process for producing rigid polyurethane foams, for the production of which a mixture of a polyester alcohol based on an aromatic carboxylic acid and at least one polyether alcohol based on aromatic amines is used.
  • the use of polyester alcohols is intended to lower the thermal conductivity of the foam and improve the compatibility with the blowing agent.
  • the use of foams produced by this process is preferably carried out in refrigerators.
  • the foam is usually added flame retardants.
  • the addition of flame retardants can change the mechanical properties and the processing properties of the foams.
  • the foam should rise only slightly after the setting time, since otherwise the mechanical values of the components produced therewith will be significantly worsened. Furthermore, it is advantageous, the tensile strength of steel sandwich elements with a PUR
  • Insulating core ie the adhesion of the foam to the top and bottom plate, as well as the stability of the foam core in the tensile test to improve.
  • Known PU rigid foams often show a high brittleness, which is evident in the cutting of the foams either by a strong dust and high sensitivity of the foam, or can lead to poor foam adhesion.
  • known PU rigid foams or their (structural) components are not satisfactory in terms of their property profile from the aforementioned properties in all respects.
  • Object of the present invention was to improve the property profile of the aforementioned properties.
  • a further object of the present invention was to provide a process for the production of suitable rigid polyurethane foams or rigid polyisocyanurate foams and the corresponding composite elements.
  • a further object of the invention was in particular to provide bromine-free, flame-retardant rigid PU foams having improved curing behavior, good-quality, smooth surfaces and low foam rising after the setting time.
  • the object of the invention was also to enable the production of sandwich elements with a bromine-free flame-retardant rigid PU foam core without the use of an adhesion promoter at low processing temperatures, the tensile strength of the steel sandwich element and the foam contact surfaces to both cover layers is good.
  • this object is achieved by a process for the production of rigid polyurethane foams or rigid polyisocyanurate foams comprising the reaction of
  • each R is independently selectable from any other R and represents any organic radical having at least one carbon atom which may also carry heteroatoms;
  • the present invention relates to a method for producing a composite element comprising at least one layer of rigid foam a) and at least one cover layer b), comprising at least the steps
  • (K2) an amine of the general formula (I): (CH 3 ) 2N-CH 2 -CH 2 -X-CH 2 -CH 2 -Y (I) where Y is NR 2 or OH,
  • each R is independently selectable from any other R and represents any organic radical having at least one carbon atom which may also carry heteroatoms;
  • the component (A) containing at least one polyisocyanate and the polyol component (PK) are reacted.
  • the polyol component (PK) contains at least one polyol as component (b1), at least one flame retardant as component (b2), at least one blowing agent as component (b3) and as component (b4) a composition (ZK) containing the catalyst components (K1 ) to (K3).
  • the polyol component may also contain other substances.
  • a component (A) containing at least one polyisocyanate is used.
  • the components (A) contains at least one polyisocyanate, but may also contain two or more polyisocyanates in the context of the present invention.
  • polyisocyanate is understood as meaning an organic compound which contains at least two reactive isocyanate groups per molecule, ie. H. the functionality is at least 2. If the polyisocyanates used or a mixture of several polyisocyanates have no uniform functionality, the number-weighted average of the functionality of the component (A) used is at least 2.
  • Suitable polyisocyanates for component (A) are the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se. Such polyfunctional isocyanates are known per se or can be prepared by methods known per se. The polyfunctional isocyanates can also be used in particular as mixtures, so that component (A) in this case contains various polyfunctional isocyanates. As polyisocyanate eligible Polyfunctional isocyanates have two (hereinafter called diisocyanates) or more than two isocyanate groups per molecule.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical such as 1,12-dodecanediisocyanate, 2-ethyltetramethylene diisocyanate-1, 4,2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate 1,4, and preferably hexamethylene diisocyanate 1, 6;
  • Cycloaliphatic diisocyanates such as cyclohexane-1, 3- and 1, 4-diisocyanate and any mixtures of these isomers, 1 -lsocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- and 2,6-Hexahydrotoluylendiisocyanat and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, 4,4'-
  • MDI 4, 4'-diphenylmethane diisocyanate
  • NDI 1,5-naphthylene diisocyanate
  • TDI 2,4- and / or 2,6-toluene diisocyanate
  • PPDI p-phenylene diisocyanate
  • PPDI tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene - 1, 5-diisocyanate, 2-ethylbutylene-1, 4-diisocyanate, pentamethylene-1, 5-diisocyanate, butylene-1, 4-diisocyanate, 1 -lsocyanato-3,3,5-trimethyl-5-iso-
  • modified polyisocyanates i. Products obtained by chemical reaction of organic polyisocyanates and having at least two reactive isocyanate groups per molecule used. Particular mention may be made of polyisocyanates containing ester, urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione, carbamate and / or urethane groups.
  • polyisocyanates of component (A) are particularly preferred as polyisocyanates of component (A): i) polyfunctional isocyanates based on tolylene diisocyanate (TDI), in particular 2,4-TDI or 2,6-TDI or mixtures of 2,4- and 2,6- TDI;
  • TDI tolylene diisocyanate
  • polyfunctional isocyanates based on diphenylmethane diisocyanate (MDI), in particular 2,2'-MDI or 2,4'-MDI or 4,4'-MDI or oligomeric MDI, which is also referred to as polyphenylpolymethylene isocyanate, or mixtures from two or three of the aforementioned diphenylmethane diisocyanates, or crude MDI, which in the preparation of MDI is obtained, or mixtures of at least one oligomer of MDI and at least one of the aforementioned low molecular weight MDI derivatives;
  • MDI diphenylmethane diisocyanate
  • 2,2'-MDI or 2,4'-MDI or 4,4'-MDI or oligomeric MDI which is also referred to as polyphenylpolymethylene isocyanate, or mixtures from two or three of the aforementioned diphenylmethane diisocyanates, or crude MDI, which in the preparation of MDI is obtained, or
  • polymeric diphenylmethane diisocyanate As a polyisocyanate is very particularly preferred polymeric diphenylmethane diisocyanate.
  • Polymeric diphenylmethane diisocyanate (hereafter referred to as polymeric MDI) is a mixture of dinuclear MDI and oligomeric condensation products and thus derivatives of diphenylmethane diisocyanate (MDI).
  • the polyisocyanates may preferably also be composed of mixtures of monomeric aromatic diisocyanates and polymeric MDI.
  • the present invention accordingly also relates to a process as described above, wherein component (A) contains at least one polymeric MDI as polyisocyanate.
  • Polymeric MDI contains in addition to binuclear MDI one or more polynuclear condensation products of MDI having a functionality of more than 2, in particular 3 or 4 or 5.
  • Polymeric MDI is known and is often referred to as Polyphenylpolymethylenisocyanat or as oligomeric MDI.
  • Polymeric MDI is usually composed of a mixture of MDI-based isocyanates with different functionality. Typically, polymeric MDI is used in admixture with monomeric MDI.
  • the (average) functionality of a polyisocyanate containing polymeric MDI can vary in the range of about 2.2 to about 5, more preferably 2.3 to 4, especially 2.4 to 3.5.
  • Such a mixture of MDI-based polyfunctional isocyanates with different functionalities is especially the crude MDI, which is obtained in the preparation of MDI as an intermediate.
  • Polyfunctional isocyanates or mixtures of several polyfunctional isocyanates based on MDI are known and are sold, for example, by BASF Polyurethanes GmbH under the name Lupranat®.
  • component (A) is preferably at least two, in particular at least 2.2 and more preferably at least 2.4.
  • the functionality of component (A) is preferably in the range of 2.2 to 4, and more preferably in the range of 2.4 to 3.
  • the content of component (A) in isocyanate groups is preferably in the range from 5 to 10 mmol / g, in particular in the range from 6 to 9 mmol / g, particularly preferably in the range from 7 to 8.5 mmol / g. It is known to the person skilled in the art that the content of isocyanate groups in mmol / g and the so-called equivalent weight in g / equivalent are in a reciprocal ratio. The content of isocyanate groups in mmol / g is calculated from the content in% by weight according to ASTM D-5155-96 A.
  • component (A) consists of at least one polyfunctional isocyanate selected from diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-2,2'-diisocyanate and oligomeric diphenylmetal handiisocyanat.
  • component (A) particularly preferably contains oligomeric diphenylmethane diisocyanate and has a functionality of at least 2.4.
  • the present invention accordingly also relates to a process as described above, wherein component (A) contains oligomeric diphenylmethane diisocyanate and has a functionality of at least 2.4.
  • the viscosity of the component (A) used can vary within a wide range.
  • the component (A) preferably has a viscosity of 100 to 3000 mPa * s, more preferably 100 to 1000 mPa * s, particularly preferably 100 to 600 mPa * s, more particularly 200 to 600 mPa * s, and especially from 400 to 600 mPa * s at 25 ° C, on.
  • component (A) is reacted with the polyol component (PK).
  • the polyol component (PK) as component (b1) contains at least one polyol.
  • Component (b1) may contain one or more polyols in the context of the present invention. Suitable polyols are known in principle to the person skilled in the art, wherein in the context of the present invention the term polyol also includes diols.
  • compounds suitable for the purposes of the present invention are selected from the group consisting of polyethers, polyesters, compounds bearing ester and ether groups, compounds bearing urethane, ester and / or ether groups, and compounds containing urethane Groups, preferably polyesters, polyethers or polycarbonates.
  • component (b1) may also contain mixtures of different polyols.
  • component (b1) comprises at least one polyesterol (b1 1) and at least one polyetherol (b12).
  • polyester polyols in particular polyester polyols (b1 1), may be selected from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aromatic or mixtures of aromatic and aliphatic dicarboxylic acids and polyhydric alcohols, preferably diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, getting produced.
  • Suitable dicarboxylic acids are in particular: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid. phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in admixture. Instead of the free dicarboxylic acids, it is also possible to use the corresponding dicarboxylic acid derivatives, for example dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides.
  • the aromatic dicarboxylic acids used are preferably phthalic acid, phthalic anhydride, terephthalic acid and / or isophthalic acid in a mixture or alone.
  • the aliphatic dicarboxylic acids used are preferably dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, from 20 to 35:35 to 50:20 to 32 parts by weight, and in particular adipic acid.
  • dihydric and polyhydric alcohols in particular diols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 10-decanediol, glycerol, trimethylolpropane and pentaerythritol.
  • ethanediol diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures of at least two of the diols mentioned, in particular mixtures of 1,4-butanediol, 1,5-pentanediol and 1, 6-hexanediol.
  • polyester polyols from lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example co-hydroxycaproic acid.
  • polyester polyols are also bio-based starting materials and / or their derivatives in question, such as.
  • Castor oil polyhydroxy fatty acids, ricinoleic acid, hydroxyl modified oils, grape seed oil, black caraway oil, pumpkin seed oil, borage seed oil, soybean oil, wheat seed oil, rapeseed oil, sunflower seed oil, peanut oil, apricot kernel oil, pistachio nut oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, Hemp oil, hazelnut oil, primrose oil, rosehip oil, thistle oil, walnut oil, fatty acids, hydroxyl-modified fatty acids and fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselinic acid, gadosenic acid, erucic acid, nervonic acid, linole
  • polyester polyols (b1 1) are described below by way of example with reference to the polyester polyols (b1 1 -a) and (b1 1 -b), which can be used individually or in a mixture.
  • polyether esters (b1 1 -a) obtainable by esterification of
  • ß 0 to 30 mol% of one or more fatty acids and / or fatty acid derivatives, ⁇ ) 2 to 70 mol% of one or more aliphatic or cycloaliphatic diols having 2 to 18 C atoms or alkoxylates thereof,
  • component a1) contains at least one compound selected from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET), phthalic acid, phthalic anhydride (PSA) and isophthalic acid.
  • the component a1) particularly preferably contains at least one compound from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET) and phthalic anhydride (PSA).
  • component a1) contains phthalic anhydride, dimethyl terephthalate (DMT), terephthalic acid or mixtures thereof.
  • aromatic dicarboxylic acids or their derivatives of component a1) are particularly preferably selected from the abovementioned aromatic dicarboxylic acids or dicarboxylic acid derivatives and in particular from terephthalic acid and / or dimethyl terephthalate (DMT).
  • Terephthalic acid and / or DMT in component a1) leads to polyether esters (b1 1 -a) with particularly good fire protection properties.
  • aliphatic dicarboxylic acids or derivatives (component a2) to 0 to 30 mol%, preferably 0 to 10 mol% in the dicarboxylic acid composition a).
  • the dicarboxylic acid composition a) contains no aliphatic dicarboxylic acids or derivatives thereof and thus consists of 100 mol% of one or more aromatic dicarboxylic acids or derivatives thereof, the abovementioned being preferred.
  • the component ⁇ ) in amounts of 0.1 to 28 mol%, more preferably 0.5 to 25 mol%, more specifically 1 to 23 mol%, even more specifically 1, 5 to 20 mol%, specifically 2 to 18 mol% and in particular 5 to 15 mol% used.
  • the component ⁇ ) is preferably used in amounts of from 5 to 60 mol%, preferably from 10 to 55 mol%, particularly preferably from 25 to 45 mol%.
  • the component ⁇ ) is preferably used in amounts of 5 to 70 mol%, preferably 10 to 60 mol%, particularly preferably 15 to 50 mol%.
  • the fatty acid or fatty acid derivative ⁇ ) consists of a fatty acid or fatty acid mixture, one or more glycerol esters of fatty acids, or of fatty acid mixtures and / or one or more fatty acid monoesters, such as biodiesel or methyl esters of fatty acids, especially
  • component ⁇ ) consists of a fatty acid or fatty acid mixture and / or one or more fatty acid monoesters, more specifically component ⁇ ) consists of a fatty acid or fatty acid monoester.
  • acid mixture and / or biodiesel and in particular the component ⁇ ) consists of a fatty acid or fatty acid mixture.
  • the fatty acid or fatty acid derivative ⁇ ) is selected from the group consisting of castor oil, polyhydroxy fatty acids, ricinoleic acid, stearic acid, hydroxyl-modified oils, grape seed oil, black cumin oil, pumpkin seed oil, borage seed oil, soybean oil, wheat seed oil, rapeseed oil, Sunflower seed oil, peanut oil, apricot kernel oil, pistachio nut oil, almond oil, olive oil, macadamia nut oil, avocado oil, sand-thorn oil, sesame oil, hemp oil, hazelnut oil, primrose oil, wild rose oil, thistle oil, walnut oil, animal tallow, such as beef tallow, fatty acids, hydroxyl-modified fatty acids, Biodiesel, methyl esters of fatty acids and fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselinic acid, gadole
  • the fatty acid or fatty acid derivative ⁇ ) is oleic acid, biodiesel, soybean oil, rapeseed oil or tallow, particularly preferably oleic acid, biodiesel, soybean oil, rapeseed oil or beef tallow, specific oleic acid or biodiesel and in particular oleic acid.
  • the fatty acid or the fatty acid derivative improves the blowing agent solubility in the production of rigid polyurethane foams.
  • component ⁇ ) comprises no triglyceride, in particular no oil or fat.
  • the glycerol released from the triglyceride by the esterification or transesterification deteriorates the dimensional stability of the rigid foam, as stated above.
  • preferred fatty acids and fatty acid derivatives are the fatty acids themselves and also alkyl monoesters of fatty acids or alkyl monoesters of fatty acid mixtures, in particular the fatty acids themselves and / or biodiesel.
  • the aliphatic or cycloaliphatic diol ⁇ ) is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-methyl-1 , 3-propanediol and 3-methyl-1, 5-pentanediol and alcoxylates thereof.
  • the aliphatic diol is particularly preferably ⁇ ) monoethylene glycol or diethylene glycol, in particular diethylene glycol.
  • a polyether polyol ⁇ ) having a functionality greater than 2 is used which has been prepared by alkoxylation of a polyol having a functionality greater than or equal to 3.
  • the polyether polyol ⁇ ) has a functionality greater than 2. It preferably has a functionality greater than or equal to 2.7, in particular greater than or equal to 2.9. In general, it has a functionality of less than or equal to 6, preferably less than or equal to 5, more preferably less than or equal to 4.
  • the polyether polyol ⁇ ) is obtainable by reacting a polyol having a functionality of greater than 2 with ethylene oxide and / or propylene oxide, preferably with ethylene oxide.
  • the polyether polyol ⁇ ) is obtainable by alkoxylation of a polyol selected from the group consisting of sorbitol, pentaerythritol, trimethylolpropane, glycerol, polyglycerol and mixtures thereof.
  • the polyether polyol ⁇ ) is obtainable by alkoxylation with ethylene oxide, resulting in rigid polyurethane foams with improved fire protection properties.
  • alkoxylation catalysts such as alkali metal hydroxides such as sodium or potassium hydroxide, or alkali metal such as sodium methylate, sodium or potassium ethylate or Ka - liumisopropylat, or amine alkoxylation catalysts such as dimethylethanolamine (DMEOA), imidazole and imidazole derivatives and mixtures thereof, prepared using at least one starter molecule.
  • alkoxylation catalysts are KOH and amine alk
  • amine alkoxylation catalysts are selected from the group consisting of dimethylethanolamine (DMEOA), imidazole and imidazole derivatives and mixtures thereof, particularly preferably imidazole.
  • the polyether polyol ⁇ ) consists of the reaction product of glycerol with ethylene oxide and / or propylene oxide, preferably with ethylene oxide. This results in a particularly high storage stability of the component (b1 1 -a).
  • the polyether polyol ⁇ ) consists of the reaction product of trimethylolpropane with ethylene oxide and / or propylene oxide, preferably with ethylene oxide. This also results in a particularly high improved storage stability of the component (b1 1 -a).
  • the polyether polyol ⁇ ) has an OH number in the range of 150 to 1250 mg KOH / g, preferably 300 to 950 mg KOH / g, particularly preferably 500 to 800 mg KOH / g.
  • the polyether polyol ⁇ ) consists of the reaction product of trimethylolpropane or glycerol, preferably glycerol, with ethylene oxide, wherein the OH number of the polyether polyol ⁇ ) in the range of 500 to 750 mg KOH / g and KOH or imidazole preferably imidazole is used as the alkoxylation catalyst.
  • the polyether polyol ⁇ ) consists of the reaction product of trimethylolpropane or glycerol, preferably glycerol, with ethylene oxide, wherein the OH number of the polyether polyol ⁇ ) is in the range from 500 to 650 mg KOH / g, imidazole as alkoxylation Catalyst is used, and the aliphatic or cycloaliphatic diol ⁇ ) is diethylene glycol, and the fatty acid or the fatty acid derivative is oleic acid.
  • At least 200 mmol, more preferably at least 400 mmol, more preferably at least 600 mmol, more preferably at least 800 mmol, in particular at least 1000 mmol of the component ⁇ ) are used per kg of polyetherester polyol (b1 1 -a).
  • the polyetherester polyol (b1 1-a) has a number-weighted average functionality of greater than or equal to 2, preferably greater than 2, more preferably greater than 2.2 and especially greater than 2.3, resulting in a higher crosslink density of the polyurethane produced therewith and thus to better mechanical properties of the polyurethane foam.
  • the aliphatic and aromatic polycarboxylic acids and / or derivatives and polyhydric alcohols can be used catalyst-free or preferably in the presence of esterification catalysts, conveniently in an atmosphere of inert gas such as nitrogen in the melt at temperatures of 150 to 280.degree. preferably 180 to 260 ° C optionally under reduced pressure to the desired acid number, which is advantageously less than 10, preferably less than 2, polycondensed.
  • the esterification mixture at the above temperatures to an acid number of 80 to 20, preferably 40 to 20, under normal pressure and then under a pressure of less than 500 mbar, preferably 40 to 400 mbar, polycondensed.
  • Suitable esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts.
  • the polycondensation may also be carried out in the liquid phase in the presence of diluents and / or entraining agents, e.g. Benzene, toluene, xylene or chlorobenzene, be carried out for the azeotropic distillation of the condensation water.
  • the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are advantageously in a molar ratio of 1: 1 to 2.2, preferably 1: 1, 05 to 2.1 and more preferably 1: 1, 1 to 2 , 0 polycondensed.
  • the resulting polyester polyols generally have a number average molecular weight of 300 to 3000, preferably 400 to 1000 and in particular 450 to 800.
  • the component (b1) may also contain further polyetheresterpolyols, for example a polyetheresterpolyol (b1 1 -b).
  • the mass ratio of the polyetheresterpolyols (b1 1 -a) to other polyesterpolyols (b1 1 -b) which differ from (b1 1 -a) is at least 0.1, preferably at least 0.25, particularly preferably at least 0, 5 and in particular at least 0.8.
  • polyester component (b1 1) consists exclusively of polyether ester (b1 1 -a).
  • the proportion of the polyester polyols (b11) according to the invention is at least 10% by weight, preferably at least 20% by weight, particularly preferably at least 25% by weight, based on the polyol component (PK).
  • the component (b1) can furthermore also comprise polyethers, for example as polyether polyols (b12).
  • Suitable polyether polyols in particular the polyether polyols (b12), can be prepared by known processes, for example by anionic polymerization of one or more alkylene oxides containing 2 to 4 carbon atoms with alkali hydroxides, such as sodium or potassium hydroxide, alkali metal alkoxides, such as sodium methylate, sodium or potassium ethylate or potassium isopropyl lat, or aminic alkoxylation catalysts such as dimethylethanolamine (DMEOA), imidazole or imidazole derivatives using at least one starter molecule or starter molecule mixture containing on average 2 to 8, preferably 2 to 6 reactive hydrogen atoms bound or by cationic polymerization with Lewis Acids, such as antimony pentachloride, boron fluoride etherate or bleaching earth.
  • alkali hydroxides such as sodium or potassium hydroxide
  • alkali metal alkoxides such as sodium methylate, sodium or potassium ethylate or potassium isopropyl
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1, 3-propylene oxide, 1, 2 or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1, 2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • Preferred alkylene oxides are propylene oxide and ethylene oxide.
  • Suitable starter molecules are, for example: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N, N- and ⁇ , ⁇ '-dialkyl-substituted diamines having 1 to 4 carbon atoms in the alkyl radical , such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 3-propylenediamine, 1, 3 or 1, 4-butylenediamine, 1, 2, 1, 3, 1, 4, 1, 5 and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane.
  • organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and
  • Suitable starter molecules are also: alkanolamines, such as ethanolamine, N-methyl and N-ethylethanolamine, dialkanolamines, such as diethanolamine, N-methyl and N-ethyl diethanolamine, and trialkanolamines, such as triethanolamine, and ammonia.
  • two or more polyhydric alcohols also called “starters”
  • starters such as ethanediol, propanediol-1, 2 and -1, 3, diethylene glycol (DEG), dipropylene glycol, butanediol-1, 4, hexanediol-1, 6, Glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose.
  • starters such as ethanediol, propanediol-1, 2 and -1, 3, diethylene glycol (DEG), dipropylene glycol, butanediol-1, 4, hexanediol-1, 6, Glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose.
  • the polyether polyols in particular the polyether polyols (b12), preferably polyoxypropylene polyols and polyoxyethylene polyols, have a functionality of preferably 2 to 6 and in particular 2 to 5 and number average molecular weights of 150 to 3000, preferably 200 to 2000 and in particular 250 to 1000.
  • polyether polyol (b12) comprises at least one alkoxylated diol, preferably an ethoxylated diol, preferably polyethylene glycol.
  • the polyetherol component (b12) consists of a polyether mixture in which a part of the polyetherol component (b12) was prepared on the basis of propylene oxide (polyetherol component (b12-a)) and the remaining part of the polyetherol component (b12) was prepared based on ethylene oxide (polyetherol component (b12-b)).
  • the present invention accordingly also relates to a process as described above, wherein component (b12) comprises at least one ethoxylated diol as polyetherol.
  • the polyetherol component (b12-a) has an average OH functionality of greater than 3, preferably greater than 3.5, particularly preferably greater
  • the polyetherol component (b12-a) has an average OH functionality of less than 6, preferably less than 5.5, more preferably less
  • the proportion of the polyetherol component (b12-a) in the total amount of the polyetherol component (b12) is greater than 65% by weight, preferably greater than 70% by weight, particularly preferably greater than 75% by weight, in particular greater 80 wt .-% and in particular greater than 85 wt .-%.
  • the polyetherol component (b12-a) is not based on sorbitol.
  • the polyetherol component (b12-a) is based on a polyether prepared from propylene oxide and a starter mixture of sucrose and glycerol or sucrose and DEG, preferably sucrose and glycerol.
  • the polyetherol component (b12-b) is based on a polyetherol based on ethylene oxide having a mean OH functionality of less than or equal to 3, preferably the functionality of the polyetherol component (b12-b) is 2 and the OH number the polyetherol component (b12-b) less than 400 mg KOH / g, preferably less than 300 mg KOH / g, more preferably less than 200 mg KOH / g.
  • the polyetherol component (b12) consists of two polyethers, a polyether (polyetherol component (b12-a)) based on propylene oxide and a starter mixture of sucrose and glycerol having an average OH functionality of greater than 4 and less than 5 and an OH number of greater than 450 mg KOH / g and less than 500 mg KOH / g and a polyethylene glycol having an OH number of less than 200 mg KOH / g (polyetherol component (b12-b)).
  • the proportion of polyether polyols (b12) is from 25 to 55% by weight, preferably from 29 to 45% by weight, more preferably from 31 to 43% by weight, more specifically from 33 to 42% by weight and in particular from 35 to 40 Wt .-%, based on the polyol component (PK).
  • the mass ratio of component (b1 1) to component (b12) is less than 4, preferably less than 2, in particular less than 1.6, more specifically less than 1.4, preferably less than 1.3, particularly preferably less than 1.2 , particularly preferably less than 1, 1 and especially preferably less than 1.
  • the mass ratio of the component (b1 1) to the component (b12) according to the invention is greater than 0.1, in particular greater than 0.2, preferably greater than 0.4, more preferably greater than 0.5, especially preferably greater than 0 , 6 and most preferably greater than 0.8.
  • the present invention accordingly also relates to a process as described above, wherein polyesterol (b1 1) and polyetherol (b12) in a mass ratio of (b1 1) to (b12) in the range of 0.1 to 4 are used.
  • the polyol component (PK) further contains a flame retardant as component (b2).
  • flame retardants (b2) it is generally possible to use the flame retardants known from the prior art.
  • Suitable flame retardants are, for example, brominated esters, brominated ethers (xxol) or brominated alcohols such as dibromoneopentyl alcohol, tribromearopentyl alcohol and PHT-4-diol, and also chlorinated phosphates such as tris- (2-chloroethyl) - phosphate, tris (2-chloropropyl) phosphate (TCPP), tris (1,3-dichloropropyl) phosphate, tricresyl phosphate, tris (2,3-dibromopropyl) phosphate, tetrakis (2-chloroethyl) ethylenediphosphate, dimethylme - thanphosphonate, Diethanolaminomethylphosphonklathylester and commercial
  • DEEP diethyl ethane phosphonate
  • TEP triethyl phosphate
  • DMPP dimethyl propyl phosphonate
  • DPK diphenylcresyl phosphate
  • inorganic or organic flame retardants such as red phosphorus, red phosphorus-containing finishes, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, e.g. Melamine, or mixtures of at least two flame retardants, e.g. Ammonium polyphosphates and melamine, and optionally corn starch or ammonium polyphosphate, melamine, expandable graphite and optionally aromatic polyester for flame retardancy of the rigid polyurethane foams can be used.
  • inorganic or organic flame retardants such as red phosphorus, red phosphorus-containing finishes, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, e.g. Melamine, or mixtures of at least two flame retardants, e.g. Ammonium polyphosphates and
  • Preferred flame retardants do not contain bromine.
  • Particularly preferred flame retardants consist of atoms selected from the group consisting of carbon, hydrogen, phosphorus, nitrogen, oxygen and chlorine, more particularly from the group consisting of carbon, hydrogen, phosphorus and chlorine.
  • Preferred flame retardants have no isocyanate-reactive groups.
  • the flame retardants are liquid at room temperature.
  • Particularly preferred are TCPP, DEEP, TEP, DMPP and DPK, in particular TCPP.
  • the polyol component (PK) according to the invention contains at least one blowing agent.
  • Propellants (b3) used to make the rigid polyurethane foams preferably include water, formic acid and mixtures thereof. These react with isocyanate groups to form carbon dioxide and in the case of formic acid to carbon dioxide and carbon monoxide.
  • physical blowing agents such as low-boiling hydrocarbons can be used.
  • Particularly suitable are liquids which are inert to the polyisocyanates and have boiling points below 100 ° C., preferably below 50 ° C. at atmospheric pressure, so that they evaporate under the influence of the exothermic polyaddition reaction.
  • alkanes such as heptane, hexane, n- and iso-pentane, preferably technical mixtures of n- and iso-pentanes, n- and iso-butane and propane, cycloalkanes, such as cyclopentane and / or cyclohexane, Ethers, such as furan, dimethyl ether and diethyl ether, ketones, such as acetone and methyl ethyl ketone, alkyl carboxylates, such as methyl formate, dimethyl oxalate and ethyl acetate, and halogenated hydrocarbons, such as methylene chloride, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethanes, 1, 1 dichloro-2,2,2-tri
  • low-boiling liquids with one another and / or with other substituted or unsubstituted hydrocarbons.
  • organic carboxylic acids such as formic acid, acetic acid, oxalic acid, ricinoleic acid and carboxyl-containing compounds.
  • no formic acid and no halogenated hydrocarbons are used as the blowing agent.
  • Preferably used are water, all pentane isomers, and mixtures of water and pentane isomers.
  • the blowing agents are either completely or partially dissolved in the polyol component (PK) or are metered in directly before the foaming of the polyol component via a static mixer.
  • PK polyol component
  • water or formic acid are completely or partially dissolved in the polyol component and the physical blowing agent (for example pentane) and optionally the remainder of the chemical blowing agent are metered "online".
  • the amount of blowing agent or of the blowing agent mixture used as component (b3) is from 1 to 30% by weight, preferably from 3 to 15% by weight, particularly preferably from 5 to 10% by weight, based in each case on polyol component (PK) ,
  • water is used as the blowing agent, it is preferably added to the polyol component (PK) in an amount of from 0.2 to 10% by weight, based on the polyol component (PK).
  • the addition of water can be done in combination with the use of the other blowing agents described. Preference is given to using water in combination with pentane.
  • the polyol component further contains a composition (ZK) as component (b4).
  • the composition (ZK) used according to the invention contains the catalyst components (K1) to (K3).
  • a mixture of a salt of a carboxylic acid (component K1) and a mixture of at least two amine PUR catalysts ((K2) and (K3)) is used.
  • Suitable salts of a carboxylic acid as the catalyst component (K1) are known per se to the person skilled in the art.
  • the catalyst components (K1) used are, for example, primarily ammonium or alkali metal carboxylates, preferably alkali metal carboxylate salts, particularly preferably alkali metal formate, alkali metal acetate or alkali metal hexanoate.
  • the salt of a carboxylic acid is preferably a salt of a carboxylic acid having 1 to 12 C atoms, more preferably a salt of a carboxylic acid having 1 to 6 C atoms, particularly preferably a salt of a carboxylic acid selected from the group consisting of formic acid, acetic acid and caproic acid ,
  • the present invention accordingly also relates to a process as described above, wherein the salt of the carboxylic acid is selected from the group consisting of primary ammonium and alkali metal carboxylates.
  • each R can be selected independently of any other R and represents an arbitrarily structured organic radical with at least one C atom which can also carry heteroatoms.
  • X is N-CH 3 or N-CH 2 -CH 2 -N (CH 3 ) 2 or O, more preferably X is N-CH 3 or O, and especially X is N-CH 3.
  • R is an alkyl group having 1 to 12 C-atoms, in particular one to 6 C-atoms, more preferably methyl and ethyl and especially methyl.
  • the present invention accordingly also relates to a process as described above, wherein the catalyst component (K2) is an amine of the general formula (II)
  • each R is independently selectable from any other R and represents an arbitrarily constructed organic radical having at least one carbon atom which can also carry heteroatoms.
  • composition (ZK) includes at least one other amine catalyst (component (K3)) which is different from the component (K2).
  • component (K3) Useful as component (K3) are basic polyurethane catalysts, for example tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine and alkanolamine compounds, such as triethanolamine, triisopropanolamine, N, N ', N "-tris- (dialkylaminoalkyl) hexahydrotriazine, eg N, N ', N "-tris- (dimethylaminopropyl) -s-hexahydrotriazine, and triethylenediamine.
  • tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine and alkanolamine compounds, such as triethanolamine, triisopropanolamine, N, N
  • the present invention accordingly also relates to a process as described above, wherein the catalyst component (K3) is selected from the group consisting of triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine and alkanolamine compounds, N, N ', N " Tris (dialkylaminoalkyl) hexahydrotriazines and triethylenediamine.
  • the catalyst component (K3) is selected from the group consisting of triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine and alkanolamine compounds, N, N ', N " Tris (dialkylaminoalkyl) hexahydrotriazines and triethylenediamine.
  • the composition of the composition (CC) can vary widely.
  • the mass ratio of catalyst components (K2) to (K3) is between 1: 9 and 9: 1, more preferably between 1: 7 and 7: 1, more particularly between 1: 4 and 4: 1 and especially between 1: 2 and 2: 1.
  • the present invention accordingly also relates to a method as described above, wherein the mass ratio of catalyst components (K2) to (K3) is in the range of 1: 9 and 9: 1.
  • the amount of components (K1) to (K3) used can also vary within wide limits.
  • the catalyst component (K1) is preferably used in an amount of at least 0.1% by weight, more preferably at least 0.2% by weight, more specifically at least 0.3% by weight and in particular at least 0.4% by weight. % based on the polyol component (PK) used.
  • the catalyst component (K1) in an amount of not more than 3.0 wt .-%, more preferably at most 2.5 wt .-%, more preferably at most 2.0 wt .-%, and in particular at most 1, 5 wt. -% based on the polyol component (PK) used.
  • the present invention accordingly also relates to a process as described above, wherein the catalyst component (K1) in an amount ranging from 0.1 wt .-% to 3.0 wt .-%, based on the polyol component (PK ) is used.
  • the catalyst component (K2) in an amount of at least 0.1% by weight, more preferably at least 0.2 wt .-%, more specifically at least 0.3 wt .-%, and in particular at least 0.35 wt. -% based on the polyol component (PK) used.
  • the catalyst component (K2) in an amount of at most 4.0 wt .-%, more preferably at most 3.0 wt .-%, more preferably at most 2.0 wt .-%, and in particular at most 1, 5 wt. -% based on the polyol component (PK) used.
  • the present invention accordingly also relates to a process as described above, wherein the catalyst component (K2) in an amount ranging from 0.1 wt .-% to 4.0 wt .-%, based on the polyol component (PK ) is used.
  • the catalyst component (K3) in an amount of at least 0.1% by weight, more preferably at least 0.2 wt .-%, more specifically at least 0.3 wt .-%, and in particular at least 0.35 wt. -% based on the polyol component (PK) used.
  • the catalyst component (K3) in an amount of not more than 5.0 wt .-%, more preferably at most 4.0 wt .-%, more specifically at most 3.0 wt .-%, and especially at most 2.0 wt. -% based on the polyol component (PK) used.
  • the present invention accordingly also relates to a process as described above, wherein the catalyst component (K3) in an amount in the range of 0.1 wt .-% to 5.0 wt .-%, based on the polyol component (PK ) is used.
  • composition (ZK) is particularly suitable as a catalyst for the production of rigid polyurethane foams or rigid polyisocyanurate foams.
  • the present invention also relates to the use of a composition (ZK) comprising the catalyst components (K1) to (K3): (K1) a salt of a carboxylic acid,
  • each R can be selected independently of any other R and represents an arbitrarily structured organic radical having at least one C atom which can also carry heteroatoms;
  • the reaction mixture for producing the rigid polyurethane foams or rigid polyisocyanurate foams may optionally contain further auxiliaries and / or additives Component (b5) of the polyol component (PK) can be added.
  • Component (b5) of the polyol component (PK) can be added.
  • PK polyol component
  • Examples which may be mentioned are surface-active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, hydrolysis protectants, fungistatic and bacteriostatic substances.
  • Suitable surface-active substances are, for example, compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the plastics.
  • emulsifiers such as the sodium salts of castor sulfinates or of fatty acids and salts of fatty acids with amines, for example diethylamine, diethanolamine stearate, ricinoleic diethanolamine, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic acid and ricinoleic acid;
  • Foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, turkey red oil and peanut oil, and cell regulators, such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • the above-described oligomeric acrylates having polyoxyalkylene and fluoroalkane radicals as side groups are also suitable.
  • the surface-active substances are usually used in amounts of 0.01 to 10 parts by weight, based (ie, calculated) per 100 parts by weight of component (b1) applied.
  • Fillers, in particular reinforcing fillers are the conventional, customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating compositions, etc.
  • inorganic fillers such as silicate minerals, for example phyllosilicates such as antigorite, serpentine, hornblende, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminas, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide and zinc sulfide, as well as glass and others.
  • silicate minerals for example phyllosilicates such as antigorite, serpentine, hornblende, amphiboles, chrysotile and talc
  • metal oxides such as kaolin, aluminas, titanium oxides and iron oxides
  • metal salts such as chalk
  • barite and inorganic pigments such as cadmium sulfide and zinc sulfide, as well as glass and others.
  • kaolin China Clay
  • aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as wollastonite, metal fibers and, in particular, glass fibers of various lengths, which may be optionally sized.
  • Suitable organic fillers are, for example: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and in particular carbon fibers.
  • the inorganic and organic fillers can be used individually or as mixtures and are advantageously added to the reaction mixture in amounts of 0.5 to 50% by weight, preferably 1 to 40% by weight, based on the weight of the sum of the components (A). and (PK), but the content of mats, nonwovens and woven fabrics of natural and synthetic fibers can reach values of up to 80% by weight, based on the weight of the sum of components (A) and (PK) ,
  • Further details of the above-mentioned other customary auxiliaries and additives are the specialist literature, for example the monograph by JH Saunders and KC Frisch "High Polymers” Volume XVI, Polyurethanes, Part 1 and 2, published by Interscience Publishers 1962 and 1964, or the plastic Handbook, Polyurethane, Volume VII, Hanser Verlag, Kunststoff, Vienna, 1st and 2nd Edition, 1966 and 1983 refer to.
  • the present invention also relates to the polyol component as such.
  • a further subject of the present invention is a polyol component (PK * ) comprising:
  • blowing agent (b3) 1 to 30% by weight of blowing agent (b3)
  • composition (CC) or component (b4) 0.5 to 10 wt .-% composition (CC) or component (b4), and
  • auxiliaries and additives each as defined above and in each case based on the total weight of the polyol component (PK), wherein the weight. % to 100 wt .-%, wherein the mass ratio of the component (b1 1) to component (b12) is less than 1.6.
  • the polyol component particularly preferably contains
  • blowing agent (b3) From 3 to 15% by weight of blowing agent (b3),
  • composition (CC) or component (B4) 0.5 to 10% by weight of composition (CC) or component (B4)
  • the present invention also relates to a rigid polyurethane foam or polyisocyanurate rigid foam, obtainable or obtained by a process according to the invention as described above
  • the polyisocyanates (A) and the polyol component (PK) are mixed in such amounts that during the reaction the molar ratio of NCO groups of the polyisocyanates (A) to the sum of the reactive hydrogen atoms of the polyol components (PK), 1 to 3.5: 1, preferably 1 to 2.5: 1, preferably 1, 1 to 2.1: 1, more preferably 1.2 to 2.0: 1, in particular 1.3 to 1, 9: 1, more specifically 1, 4 to 1, 8: 1 and in particular 1, 4 to 1, 7: 1.
  • the rigid polyurethane foams according to the invention and the rigid polyisocyanurate foams are particularly suitable for the production of sandwich elements or composite elements.
  • the present invention also relates to the use of a rigid polyurethane foam or polyisocyanurate rigid foam, obtainable or obtained by a process according to the invention as described above or a rigid polyurethane foam or rigid polyisocyanurate foam as described above for the production of composite elements.
  • the present invention also relates to a method for producing a composite element comprising at least one layer of rigid foam a) and at least one cover layer b), comprising at least the steps of (i) providing a flowable starting material a * ) and
  • (K2) an amine of the general formula (I): (CH 3 ) 2N-CH 2 -CH 2 -X-CH 2 -CH 2 -Y (I) where Y is NR 2 or OH,
  • each R is independently selectable from any other R and represents any organic radical having at least one carbon atom which may also carry heteroatoms; (K3) comprises another amine other than the catalyst component (K2).
  • the application of the liquid polyurethane reaction mixture (shortly after the mixing of the components (A) and (PK)) by means of a fixed applicator device.
  • This fixed application device is particularly preferably formed from at least one tube c), which is essentially parallel to the cover layer b) and fixed, provided with openings f).
  • the tube provided with outlet openings is mounted substantially at right angles to the direction of movement of the cover layer b).
  • the present invention accordingly relates to a method for producing composite elements as described above, wherein the fixed applicator c) of at least one fixed parallel to the cover layer b) and perpendicular to the direction of movement of the cover layer b) provided with openings f) provided Tube c) exists.
  • the at least one tube is particularly preferably mounted parallel to the cover layer b) and at right angles to the direction of movement of the cover layer b).
  • the at least one tube c) is fixed in the context of the method according to the invention, d. H. the angle between the
  • the longitudinal axis of the tube or tubes and the direction of movement of the cover layer is constant substantially at right angles or at right angles.
  • a tube or, preferably, a plurality of tubes arranged side by side in the longitudinal direction can be used as the application device.
  • the application device is known from the prior art and is described, for example, in WO 2009/077490.
  • the application device is also referred to below as a casting rake.
  • at least two tubes c) provided with openings f) are arranged in particular so as to form a straight line.
  • 2 to 4 more preferably 2 to 3 and in particular 2 tubes c) are used as application device (casting rake).
  • the casting bar according to the invention has, as described, a tube-like shape, with holes at the bottom, distributed over the entire length, and the supply of the reaction mixture either at one end of the tubes c) or preferably sitting in the middle.
  • the supply is preferably made in all tubes c) in the same way.
  • the tubes c) or the longitudinally juxtaposed tubes c) together may have a length which is equal to the width of the cover layer b).
  • the length of the tube or the longitudinally juxtaposed tubes c) is ringer than the width of the cover layer b) to ensure that the reaction mixture is not partially applied next to the cover layer b).
  • the casting rake is arranged centrally above the cover layer b).
  • the casting bar covers at least 70% of the width of the cover layer b). With a width of the cover layer b) of 1, 2 m, as is customary in sandwich elements, in this case, a width of 25 cm would not be covered by the casting bar on each side.
  • the casting bar preferably covers at least 70%, particularly preferably at least 80%, and in particular at least 95%, of the width of the covering layer b).
  • the casting bar is preferably mounted at a height to the cover layer b) of 5 to 30 cm, preferably 10 to 30 cm, and in particular 15 to 25 cm.
  • the number of openings f) along the tube c) or along each tube c) is at least 2, preferably at least 6, more preferably 10 to 50, and especially 20 to 40, depending on the length of the tube c). Preferably, the number of holes an even number.
  • the diameters of the openings f) are in the range of 0.5 to 10 mm, preferably 1, 0 mm to 4 mm.
  • the distances of the openings f) from each other are preferably from 5 to 200 mm, more preferably 5 to 60 mm, and especially 10 to 30 mm.
  • the distance and the diameter over the entire length of the tube c) is the same.
  • the pipe c) or each pipe has an inner diameter of 0.2 to 5 cm, preferably 0.3 to 2.5 cm and in particular 0.2 to 2 cm.
  • the length of the openings f) is to be understood as the distance which the mixture a * ) must travel from the inside of the pipe c) to the exit from the pipe c). This can be done in different ways.
  • the inner diameter of the tube c) can be changed. This is not preferred because such components are difficult to manufacture and clean.
  • the length of the openings f) is changed by one or more components are mounted on the underside of the tube c), that the length of the holes varies in the desired manner. By this measure, in fact, the wall thickness of the tube c) is changed.
  • the hole lengths viewed from the point of supply of the starting material for the isocyanate-based rigid foam a * ) to the end, do not decrease linearly but exponentially.
  • the extension of the openings f) takes place in such a way that the length decreases from the supply of the mixture a * ) to the ends of the tube c). That is, when feeding the mixture a * ) in the middle of the pipe c), the length of the openings f) decreases toward the edges.
  • feeding the mixture a * ) at the edge of the tube c) takes the length of the openings f) decreases from the side in which the feed takes place to the other side.
  • the casting rake which preferably consists of plastic, can consist of a single component, i. H. be made in one piece.
  • the length of the openings varies according to the previous embodiments, in that the openings are adapted by tubular extensions in the length at the bottom of the tube.
  • the length of the openings f) is preferably to be chosen such that the ratio of the length of the openings f) from the edge to the center for each tube c) is from 1, 1 to 10. Particularly preferably, the ratio is from 2.5 to 10, in particular from 5 to 10.
  • each of the tubes c) provided with openings f) is connected to a mixing device for mixing the components of the flowable raw material for the isocyanate-based rigid foam a * ). This is usually done by means of an intermediate feeder d) and e). This is designed as a tube, in the case of using multiple tubes c) each is connected to the feeder. This can be done by a pipe from which in turn connecting pipes go out to the pipes c).
  • the diameter of the feeds d) is preferably constant. It is preferably 4 to 30 mm, more preferably 6 to 22 mm.
  • the process according to the invention is preferably designed such that the amount of flowable starting material applied to the outer layer b) for the isocyanate-based rigid foam a * ) is from 2 kg / min to 100 kg / min, preferably from 8 kg / min to 60 kg / min , is.
  • the viscosity of the flowable starting material for the isocyanate-based rigid foam a * ) is preferably at 25 ° C. of from 100 mPa * s to 4000 mPa * s, more preferably from 100 mPa * s to 3500 mPa * s, in particular from 200 to 2000 mPa * s.
  • the present invention accordingly relates to a method for producing a composite element as described above, wherein the viscosity of the liquid starting material for the rigid foam a * ) at 25 ° C in the range of 100 mPa * s to 3500 mPa * s.
  • the starting time of the systems used for the process according to the invention is preferably below 15 s, preferably below 12 s, more preferably below 10 s and in particular below 8 s at a setting time of the system of 20 to 60 s.
  • Start time is the time between the mixing of the polyol and isocyanate components and the start of the urethane reaction. Under the setting time, the time from the mixing of the starting components of the foams to the time stood where the reaction product is no longer flowable.
  • the setting time is adjusted depending on the produced element thickness as well as double belt speed.
  • the rigid foams of the invention are preferably produced on continuously operating double-belt systems.
  • the polyol and the isocyanate component are metered with a high-pressure machine and mixed in a mixing head.
  • the polyol mixture can be previously metered with separate pumps catalysts and / or propellant, i. the components of the polyol component (PK) are mixed only shortly before the reaction.
  • the reaction mixture is applied continuously to the lower cover layer.
  • the lower cover layer with the reaction mixture and the upper cover layer enter the double belt.
  • the reaction mixture foams and hardens.
  • the endless strand is cut to the desired dimensions. In this way, sandwich elements with metallic cover layers or insulation elements with flexible cover layers can be produced.
  • the starting components are mixed in the context of the present invention, for example at a temperature of 15 to 90 ° C, preferably from 20 to 60 ° C, in particular from 20 to 45 ° C.
  • the reaction mixture can be poured into closed support tools with high or low pressure metering machines. According to this technology, e.g. discontinuous sandwich elements made.
  • the present invention also relates to a composite member obtainable or obtained by a method as described above.
  • Preferred layers of rigid polyurethane foam have a density of 0.02 to 0.75 g / cm 3 , preferably from 0.025 to 0.24 g / cm 3 and in particular from 0.03 to 0.1 g / cm 3 . They are particularly suitable as insulating material in the construction and refrigeration furniture sector, for example as described for composite elements or for foaming refrigerator anddetruhenge- housing.
  • the rigid foams produced by the process according to the invention have good surfaces with few defects, good adhesion, and good hardening.
  • the polyol component (PK) has good storage stability at 20 ° C. or 5 ° C. over several months.
  • a polyol component (PK) comprising (b1) at least one polyol
  • each R is independently selectable from any other R and represents any organic radical having at least one carbon atom which may also carry heteroatoms;
  • each R is independently selectable from any other R and represents an arbitrarily constructed organic radical having at least one carbon atom which can also carry heteroatoms.
  • the catalyst component (K3) is selected from the group consisting of triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine and alkanolamine compounds, N, N ', N "-tris- (dialkylaminoalkyl ) hexahydrotriazines and triethylenediamine.
  • component (b1) comprises at least one polyesterol (b1 1) and at least one polyetherol (b12).
  • polyesterol (b1 1) and polyetherol (b12) are used in a mass ratio of (b1 1) to (b12) in the range of 0.1 to 4.
  • component (b12) comprises at least one ethoxylated diol as the polyetherol.
  • a process for producing a composite element comprising at least one layer of rigid foam a) and at least one cover layer b), comprising at least the steps
  • the starting material a * at least one component (A) comprising at least one polyisocyanate, and a polyol component Containing (PK)
  • each R is independently selectable from any other R and represents any organic radical having at least one carbon atom which may also carry heteroatoms;
  • (K3) comprises another amine other than the catalyst component (K2).
  • X NR or O is and each R can be selected independently of any other R and represents an arbitrarily structured organic radical having at least one C atom which can also carry heteroatoms; (K3) another amine other than the catalyst component (K2), as a catalyst for the reaction of at least one polyisocyanate with at least one polyol. 14.
  • Hard foam according to embodiment 14 for the production of composite elements are hard foam according to embodiment 14 for the production of composite elements.
  • a process for producing a composite element comprising at least one layer of rigid foam a) and at least one cover layer b), comprising at least the steps of (i) providing a flowable starting material a * ) and
  • composition (b3) at least one propellant, a composition (CC) containing the catalyst components (K1) to (K3):
  • each R is independently selectable from any other R and represents any organic radical having at least one carbon atom which may also carry heteroatoms;
  • (K3) comprises another amine other than the catalyst component (K2).
  • the fixed applicator c) consists of at least one parallel to the cover layer b) and at right angles to the direction of movement of the cover layer b), provided with openings f), fixed tube c). 19. Method according to one of the embodiments 17 or 18, wherein the application device covers at least 70% of the width of the cover layer b).
  • catalyst component (K3) is selected from the group consisting of triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine and alkanolamine compounds, N, N ', N "-tris- (dialkylaminoalkyl ) hexahydrotriazines and triethylenediamine.
  • Polyol component (PK) is used.
  • component (b1) comprises at least one polyesterol (b1 1) and at least one polyetherol (b12).
  • Polyesterol 1 esterification product of terephthalic acid (32.5 mol%), oleic acid (9.0
  • the polyesterol has a hydroxyl functionality of 2.9 and a hydroxyl number of 247 mg KOH / g.
  • Polyetherol 1 Polyetherol with an OHN of 490 mg KOH / g prepared by polyaddition of propylene oxide to a sucrose / glycerol mixture as starter molecule and an average functionality of 4.3
  • Polyetherol 2 Polyetherol of ethoxylated ethylene glycol with a hydroxy functionality of 2 and a hydroxyl number of 190 mg KOH / g
  • Catalyst system 2 (according to the invention): a mixture of 50% by weight of pentamethyldiethylenetriamine (PMDETA) and 50% by weight of dimethylcyclohexylamine (DMCHA)
  • the hardening was determined with the bolt test. This was 2.5; 3; 4; 5; 6 and 7 minutes after mixing the components of the polyurethane foam in a polystyrene cup a steel bolt with a spherical cap of 10 mm radius with a
  • the time was determined at which the surface of the rigid foam had visible fracture zones during the bolt test (breakage in the bolt test). Further, the brittleness immediately after the foaming by the suds was subjectively determined (brittleness subjectively) and evaluated according to a score of 1 to 6. 1 means that the foam is hardly brittle, 6 means that the foam has a high brittleness. Assessment of the surface quality of the foams (hand foaming)
  • the evaluation of the surface quality of the foams was qualitative, in which the foam mushrooms produced in the laboratory were visually assessed.
  • the sandwich panels produced in the double-band method were examined in cross-section a few millimeters below the top layer in the double-band method, qualitatively for gas inclusions in the foam (gas inclusions in the foam ⁇ 5 mm below the upper cover layer).
  • the determination of the tensile strength over the entire sandwich element was carried out in accordance with DIN EN 1607.
  • the test specimens used were cuboids measuring 100 mm ⁇ 100 mm ⁇ sandwich thickness.
  • the test specimens were always removed at identical points from the sandwich element center.
  • the values given in the table are averages of a triple determination.
  • the isocyanates and the isocyanate-reactive components were foamed together with the blowing agents, catalysts and all other additives at a constant mixing ratio of polyol component to isocyanate of 100: 200.
  • polyesterol 1 40 parts by weight of polyesterol 1;
  • TCPP flame retardant trischloroisopropyl phosphate
  • catalyst system 1, 2 or 3 for setting the setting times isocyanate isocyanate
  • Lupranat® M50 polymeric methylene diphenyl diisocyanate (PMDI), having a viscosity of about 500 mPa * s at 25 ° C. from BASF SE
  • the components were thoroughly mixed by means of a laboratory stirrer.
  • the bulk density was adjusted at constant pentane content of 5.5 parts by varying the water content to 39 +/- 1 g / L.
  • the setting time was further adjusted to 45 +/- 1 s by varying the proportion of the catalyst system 1, 2 or 3.
  • the above-described polyol component with the three catalyst systems on the double belt was made into 170 mm thick sandwich elements.
  • the upper cover layer used was a 50 ⁇ m epoxy-coated talcum-coated aluminum foil from Amcor®.
  • the lower cover layer used was lightly-lined, coil-coated aluminum sheets from Aluform® in the thickness of 0.7 mm.
  • the processing was carried out at sheet temperatures of 37 ° C and a double belt temperature of 50 ° C by means of a fixed applicator.
  • As the applicator two juxtaposed, fixed tubes with a length of 560 mm were used, which were mounted parallel to the cover layer at a distance of 90 mm and perpendicular to the direction of movement of the cover layer and provided with 14 openings.
  • the supply of the flowable starting material took place in the middle of the tubes and the length of the openings of the tube decreased from the middle of the tube to the ends thereof.
  • Table 1 Comparison of the differently catalyzed rigid foams with respect to the hardening, the brittleness and the surface quality.
  • the catalyst elements catalyzed with catalyst system 3 show increased gas inclusions a few millimeters below the top layer in the double-belt process. Both the sandwich elements produced with catalyst system 1 and, surprisingly, with catalyst system 2 hardly show gas inclusions below the upper cover layer.
  • the sandwich elements produced with catalyst system 1 break due to the higher foam brittleness between the foam and the lower cover layer (adhesion breakage) and lead to poor tensile strength values.
  • Sandwich elements made with catalyst system 3 break within the gas confinement zone a few millimeters below the top cover and also result in poor levels of tensile strength.
  • sandwich panels made with catalyst system 2 show the best tensile strength values and, in the tensile test, cause cracks within the foam (cohesive failure).

Abstract

La présente invention concerne un procédé de production de mousses dures de polyuréthanne ou de mousses dures de polyisocyanurate, comprenant la mise en réaction d'un composant (A) contenant au moins un polyisocyanate avec un composant polyol (PK). Le composant polyol contient au moins un polyol, au moins un agent ignifuge, au moins un agent moussant et une composition (ZK) contenant comme composants de catalyseur un sel d'un acide carboxylique (K1), une amine (K2) et une autre amine (K3) différente du composant catalyseur (K2). En particulier, la présente invention concerne des procédés de production d'un élément composite comprenant au moins une couche de mousse rigide dure a) et au moins une couche de revêtement b), un matériau de départ fluide a*) étant produit et appliqué sur la couche de revêtement b) au moyen d'un applicateur fixe c) tandis que la couche de revêtement b) est déplacée en continu. En outre, la présente invention concerne un procédé de production d'un élément composite, l'utilisation de la composition (ZK) comme catalyseur pour la production d'une mousse dure de polyuréthane ou de polyisocyanurate, la mousse dure de polyuréthanne ou de polyisocyanurate étant ou pouvant être obtenue selon un procédé de l'invention, ainsi qu'un élément composite obtenu ou pouvant être obtenu par un procédé de l'invention.
PCT/EP2015/056850 2014-04-03 2015-03-30 Procédé de production de mousses dures de polyuréthanne WO2015150304A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018138048A1 (fr) * 2017-01-25 2018-08-02 Basf Se Formulation de polyuréthane souple à froid
EP3482904A1 (fr) 2017-11-14 2019-05-15 Covestro Deutschland AG Dispositif variable et procédé d'application d'un mélange de réaction expansible à une couche de revêtement en mouvement
US20210324251A1 (en) * 2018-07-23 2021-10-21 Dow Global Technologies Llc A foam composition and a foam composite made therefrom

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000559A1 (fr) 1997-06-26 1999-01-07 Altenberg Milton J Panneaux sandwich metalliques
WO2005090432A1 (fr) 2004-03-15 2005-09-29 Huntsman International Llc Procédé pour fabriquer des mousses de polyuréthane rigides
WO2009077490A2 (fr) 2007-12-17 2009-06-25 Basf Se Procédé de fabrication d'éléments composites à partir de mousses à base d'isocyanate
WO2013010988A1 (fr) * 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Mousse rigide pur/pir pulvérisable, moussée à l'eau
WO2013023965A1 (fr) * 2011-08-12 2013-02-21 Bayer Intellectual Property Gmbh Dispositif servant à l'application de mélanges réactionnels moussants

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000559A1 (fr) 1997-06-26 1999-01-07 Altenberg Milton J Panneaux sandwich metalliques
WO2005090432A1 (fr) 2004-03-15 2005-09-29 Huntsman International Llc Procédé pour fabriquer des mousses de polyuréthane rigides
WO2009077490A2 (fr) 2007-12-17 2009-06-25 Basf Se Procédé de fabrication d'éléments composites à partir de mousses à base d'isocyanate
WO2013010988A1 (fr) * 2011-07-18 2013-01-24 Bayer Intellectual Property Gmbh Mousse rigide pur/pir pulvérisable, moussée à l'eau
WO2013023965A1 (fr) * 2011-08-12 2013-02-21 Bayer Intellectual Property Gmbh Dispositif servant à l'application de mélanges réactionnels moussants

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Kunststoffhandbuch", vol. VII, 1966, CARL HANSER VERLAG
"Kunststoff-Handbuch, Polyurethane", vol. VII, HANSER-VERLAG
J.H. SAUNDERS; K.C. FRISCH: "High Polymers", vol. XVI, 1962, VERLAG INTERSCIENCE PUBLISHERS

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018138048A1 (fr) * 2017-01-25 2018-08-02 Basf Se Formulation de polyuréthane souple à froid
CN110234674A (zh) * 2017-01-25 2019-09-13 巴斯夫欧洲公司 冷柔聚氨酯制剂
US11091652B2 (en) 2017-01-25 2021-08-17 Basf Se Cold flexible polyurethane formulation
CN110234674B (zh) * 2017-01-25 2021-11-16 巴斯夫欧洲公司 冷柔聚氨酯制剂
EP3482904A1 (fr) 2017-11-14 2019-05-15 Covestro Deutschland AG Dispositif variable et procédé d'application d'un mélange de réaction expansible à une couche de revêtement en mouvement
WO2019096733A1 (fr) 2017-11-14 2019-05-23 Covestro Deutschland Ag Dispositif variable et procédé destiné à appliquer un mélange réactionnel expansible sur une couche de recouvrement en mouvement
US20210324251A1 (en) * 2018-07-23 2021-10-21 Dow Global Technologies Llc A foam composition and a foam composite made therefrom

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