EP3997161A1 - Method for producing flameproof pur/pir rigid foams - Google Patents

Method for producing flameproof pur/pir rigid foams

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Publication number
EP3997161A1
EP3997161A1 EP20737011.5A EP20737011A EP3997161A1 EP 3997161 A1 EP3997161 A1 EP 3997161A1 EP 20737011 A EP20737011 A EP 20737011A EP 3997161 A1 EP3997161 A1 EP 3997161A1
Authority
EP
European Patent Office
Prior art keywords
polyol
pur
acid
polyol formulation
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20737011.5A
Other languages
German (de)
French (fr)
Inventor
Rolf Albach
Stephan Schleiermacher
Martina Wagner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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 Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3997161A1 publication Critical patent/EP3997161A1/en
Withdrawn legal-status Critical Current

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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
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/10—Water or water-releasing compounds
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2375/06—Polyurethanes from polyesters
    • 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
    • C08J2375/08—Polyurethanes from polyethers
    • 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
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives

Definitions

  • the present invention relates to a polyol formulation for producing flame-retardant polyurethane / polyisocyanurate rigid foams (hereinafter referred to individually or collectively as “PUR / PIR rigid foams”) containing a polyester polyol with an OH number ⁇ 250 mg KOH / g, a functionality of 1.5-2.5 and a content of free glycols with M n ⁇ 150 g / mol of ⁇ 6% by weight, a polyethylene glycol with an average molecular weight of ⁇ 700 g / mol and an average functionality of ⁇ 2.5 and certain polyethylene glycol alkyl phenyl ethers, as well as processes for the production of PUR / PIR rigid foams using this polyol formulation and the PUR / PIR rigid foams thus produced.
  • PUR / PIR rigid foams flame-retardant polyurethane / polyisocyanurate rigid foams
  • PUR / PIR rigid foams refers to those rigid foams that have both urethane and isocyanurate structures.
  • PUR / PIR foams are also flammable, whereby the large surface area per unit of mass in rigid foams intensifies this behavior.
  • PUR / PIR rigid foams are often used as insulation materials, for example as insulation in the construction industry. In many areas of application of PUR / PIR rigid foams, fire protection equipment through added flame retardants is therefore necessary.
  • the fire properties of the polymer backbone can be controlled within certain limits by the selection and composition of the monomers.
  • the presence of isocyanurate structures has a positive effect on fire behavior.
  • the use of high molecular weight polyester building blocks, as in US 2013/184366 A and US 2014/364528 A, is also said to lead to an increase in flame retardancy, but also often hampers the trimerization of isocyanate to isocyanurate structures via a premature increase in the glass transition temperature, which in turn gives the foam strength.
  • a concept for lowering the viscosity could lie in the addition of polyether polyols.
  • PEG polyethylene glycol
  • the object of the present invention is therefore to provide a polyol formulation A containing a high molecular weight polyester polyol for the production of rigid PUR / PIR foams, the rigid PUR / PIR foams having good flame retardancy and good mechanical properties.
  • US 2012/0202903 A describes the use of alkyl ethoxylate alcohols with an average HLB value between 10 and 15 as compatibility promoters for polyol formulations which contain high proportions of water and are used for the production of water-driven polyurethane spray foams.
  • Polyester polyol component which has an OH number of 190-310 mg KOH / g, consisting of
  • Al -2 optionally other polyester polyols which do not fall under the definition of Al-1,
  • A3 further isocyanate-reactive components
  • RI, R2, R3, R4 H, Cl-C4-alkyl
  • R5, R6, R7 H, CI- to C8-alkyl, aryl
  • n 7-20, preferably 10-18, particularly preferably 11-15
  • RI, R3 H, C (CH 3) 2 CR4R5R6
  • R2 C (CH 3) 2 CR4R5R6
  • R4, R5 H or CH 3
  • R6 C2 to C5 alkyl, aryl
  • n 3-8 where the compounds A4 have a molecular weight of less than 1.5 kg / mol and a content of 25-70% ethylene oxide, preferably 40-60% ethylene oxide, and
  • the invention also relates to a method for producing PUR / PIR rigid foams by converting a reaction mixture containing them the polyol formulation A, a polyisocyanate component B, and a blowing agent C, optionally in the presence of a catalytically active component D, the production taking place with an index of 150 to 600, preferably 240-400.
  • component A according to the invention it was possible to provide a formulation which contains high molecular weight polyester building blocks and yet has a low viscosity and can be processed into rigid PUR / PIR foams with a good cell structure.
  • the polyesters produced with component A according to the invention also have good flame retardancy and improved mechanical properties, such as tensile strength, elongation at break, toughness and open-cell structure of the rigid PUR / PIR foams.
  • the polyester polyol component Al-1 is a polyester polyol with an OH number ⁇ 240 mg KOH / g, preferably ⁇ 200 mg KOH / g, a functionality of 1.5-2.5 and a content of free glycols with a molar mass ⁇ 150 g / mol of less than 6% by weight, based on the total mass of Al-1. Due to its molecular weight, such a polyol component usually has a high viscosity for PUR / PIR rigid foam applications, in particular a viscosity of> 5 Pa * s.
  • the proportion of polyester polyols Al-1 in the polyester polyol component Al is preferably> 60% by weight, in particular> 80% by weight and very particularly preferably> 90% by weight.
  • the mass ratio of Al-1 to Al-2 is therefore preferably at least 6: 1, in particular at least 8: 1.
  • Polyester polyols with a low content of free glycols are known per se and their production and use in CFC-based PUR / PIR formulations is disclosed, for example, in US Pat. No. 5,109,301.
  • the polyester polyols of component Al can be, for example, polycondensates of polyhydric alcohols, preferably diols, with 2 to 12 carbon atoms, preferably with 2 to 6 carbon atoms, and polycarboxylic acids, such as di-, tri- or even tetracarboxylic acids, or hydroxycarboxylic acids or lactones, preferably aromatic dicarboxylic acids or mixtures of aromatic and aliphatic dicarboxylic acids are used.
  • the corresponding polycarboxylic anhydrides or corresponding Polycarboxylic acid esters of lower alcohols can be used to produce the polyester. Phthalic anhydride, terephthalic acid and / or isophthalic acid are preferably used.
  • carboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, tetrachlorophthalic acid, itaconic acid, malonic acid, itaconic acid, malonic acid, 2,2-dimethyl-succinic acid, 3,3-methyl-succinic acid, succinic acid , Dodecanedioic acid, endomethylenetetrahydrophthalic acid, dimer fatty acid, trimer fatty acid, citric acid, trimellitic acid, benzoic acid, trimellitic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • carboxylic acids for example dimethyl terephthalate.
  • the carboxylic acids can be used either individually or as a mixture.
  • the carboxylic acids used are preferably adipic acid, sebacic acid and / or succinic acid, particularly preferably adipic acid and / or succinic acid.
  • Hydroxycarboxylic acids which can also be used as reactants in the production of a polyester polyol with terminal hydroxyl groups are, for example, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
  • Suitable lactones include caprolactone, propiolactone, butyrolactone and homologues.
  • Bio-based starting materials and / or their derivatives are particularly suitable for the production of polyester polyols, such as B. castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grape seed oil, black caraway seed oil, pumpkin seed oil, borage seed oil, soybean oil, wheat seed oil, rapeseed oil, sunflower seed oil, peanut oil, apricot kernel oil, avicorn oil, hempseed oil, sandduck oil, almond oil, hempseed oil Hazelnut oil, primrose oil, wild rose oil, safflower oil, walnut oil, fatty acids, hydroxyl-modified and epoxidized fatty acids and fatty acid esters, for example based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, monoleic acid, arachidonic acid and gamma acid , Timnodonic acid,
  • suitable diols are ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, cyclohexanedimethanol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and Isomers, neopentyl glycol or neopentyl glycol hydroxypivalate.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, cyclohexanedimethanol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and Isomers, neopentyl glycol or neopentyl glycol hydroxypivalate.
  • Ethylene glycol 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 .
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate can also be used, glycerol and trimethylolpropane being preferred.
  • Monohydric alkanols can also be used.
  • polyester-polyols which have polyether structures can also be used in the polyester polyol component. These are often referred to as “polyetherester polyols”.
  • Polyetherester polyols that can be used are those compounds containing ether groups, ester groups and OH groups.
  • Organic dicarboxylic acids with up to 12 carbon atoms are suitable for the production of the polyetherester polyols, preferably aliphatic dicarboxylic acids with 4 to 6 carbon atoms or aromatic dicarboxylic acids, which are used individually or in a mixture.
  • Examples are suberic acid, azelaic acid, decanedicarboxylic acid, furandicarboxylic acid, maleic acid, malonic acid, phthalic acid, pimelic acid and sebacic acid, and in particular glutaric acid, fumaric acid, succinic acid, adipic acid, phthalic acid, terephthalic acid and isoterephthalic acid.
  • derivatives of these acids for example their anhydrides and their esters and half esters with low molecular weight, monofunctional alcohols having 1 to 4 carbon atoms, can also be used.
  • bio-based starting materials mentioned above in particular fatty acids or fatty acid derivatives (oleic acid, soybean oil, etc.) is also possible and can have advantages, e.g. with regard to the storage stability of the polyol formulation, dimensional stability, fire behavior and compressive strength of the foams.
  • Polyether polyols obtained by alkoxylating starter molecules such as polyhydric alcohols are used as a further component for the production of the polyether ester polyols.
  • the starter molecules are at least difunctional, but can optionally also contain proportions of higher-functional, in particular trifunctional, starter molecules.
  • Starter molecules are, for example, diols such as 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentenediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-l, 3-propanediol, 2-butene-l, 4-diol and 2-butyne-l, 4-diol, ether diols such as diethylene glycol, triethylene glycol, tetraethylene glycol
  • compounds with more than 2 Zerewitinoff-active hydrogens especially with number-average functionalities from 3 to 8, in particular from 3 to 6, for example 1,1,1-trimethylolpropane, triethanolamine, can also be used as starter molecules for the production of the polyethers , Glycerine, sorbitan and pentaerythritol as well as polyethylene oxide polyols started on triols or tetraoene.
  • Polyetherester polyols can also be prepared by alkoxylation, in particular ethoxylation and / or propoxylation, of reaction products obtained by reacting organic dicarboxylic acids and their derivatives and components with Zerewitinoff-active hydrogens, especially diols and polyols.
  • organic dicarboxylic acids for example, their anhydrides can be used, such as phthalic anhydride.
  • Polyethylene glycols are used as component A2, i. H. Reaction products of a low molecular weight 2-3-functional hydroxy-functional starter molecule with ethylene oxide are used, the ethylene oxide making up> 80% of the molecular weight.
  • the starter molecules are in particular water, ethylene glycol, diethylene glycol, propylene glycol, glycerol and / or trimethylolpropane.
  • the preparation of such polyethylene glycols is known to those skilled in the art and many of these substances are commercially available.
  • Suitable polyethylene glycols are preferably liquid at 298 K and in particular have molecular weights of ⁇ 700 g / mol and an average functionality of ⁇ 2.5, particularly preferably they have an average molecular weight of 200-600 g / mol and very particularly preferably an average functionality of ⁇ 2.12.
  • the further isocyanate-reactive components A3 are, for example, polyols, such as polyether polyols, polycarbonate polyols and polyether-polycarbonate polyols, which do not fall under the definition of components A1 and A2.
  • long-chain polyols in particular polyether polyols, can improve the flowability of the reaction mixture and the emulsifiability of the blowing agent-containing formulation.
  • these can, for example, enable the continuous production of elements with flexible or rigid cover layers.
  • long-chain polyols have functionalities of> 1.2 to ⁇ 3.5 and have a hydroxyl number between 10 and 100 mg KOH / g, preferably between 20 and 50 mg KOH / g, and have more than 70 mol%, preferably more than 80 mol%, in particular more than 90 mol% primary OH groups.
  • the long-chain polyols are preferably polyether polyols with functionalities of> 1.2 to ⁇ 3.5 and a hydroxyl number between 10 and 100 mg KOH / g.
  • medium-chain polyols in particular polyether polyols
  • low molecular weight isocyanate-reactive compounds can improve the adhesion and dimensional stability of the resulting foam.
  • these medium-chain polyols can enable the continuous production of elements with flexible or rigid cover layers.
  • the medium-chain polyols, which are in particular polyether polyols, have functionalities from> 2 to ⁇ 6 and have a hydroxyl number between 300 and 700 mg KOH / g.
  • polyether polyols used are the polyether polyols known to the person skilled in the art and which can be used in polyurethane synthesis and have the features mentioned.
  • Polyether polyols which can be used are, for example, polytetramethylene glycol polyethers, such as are obtainable by polymerizing tetrahydrofuran by means of cationic ring opening.
  • Polyether polyols are obtained by production methods known to those skilled in the art, such as, for example, by anionic polymerization of one or more alkylene oxides having 2 to 4 carbon atoms with alkali hydroxides such as sodium or potassium hydroxide, alkali alcoholates such as sodium methylate, sodium or potassium ethylate or potassium isopropylate, or aminic alkoxylation catalysts , such as dimethylethanolamine (DMEOA), imidazole and / or imidazole derivatives, using at least one starter molecule which contains 2 to 8, preferably 2 to 6, reactive hydrogen atoms bonded.
  • alkali hydroxides such as sodium or potassium hydroxide
  • alkali alcoholates such as sodium methylate, sodium or potassium ethylate or potassium isopropylate
  • aminic alkoxylation catalysts such as dimethylethanolamine (DMEOA), imidazole and / or imidazole derivatives, using at least one starter molecule which contains 2 to 8, preferably 2 to 6,
  • 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, and ethylene oxide is particularly preferred.
  • the alkylene oxides can be converted in combination with CO2.
  • starter molecules 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 N, N'-dialkyl-substituted diamines with 1 to 4 carbon atoms in the alkyl radical such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-tolylenediamine, and 2,2'-, 2,4'- and 4,4'-diaminodiphenylmethane.
  • organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid
  • two or polyhydric alcohols such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, triethanolamine, bisphenols, glycerol, trimethylolpropane, pentaerythritol, sorbitol and Sucrose.
  • Polycarbonate polyols which can be used are polycarbonates containing hydroxyl groups, for example polycarbonate diols. These arise in the reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols.
  • diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2- Methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1,3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenols and lactone-modified diols of the type mentioned above.
  • polyether-polycarbonate diols which are obtainable, for example, by copolymerizing alkylene oxides, such as propylene oxide, with CO 2.
  • polyester and polyether polyols from suitable polymer recyclates via glycolysis.
  • Suitable polyether-polycarbonate polyols and their production are described, for example, in EP 2 910 585 A1, [0024] - [0041]. Examples of polycarbonate polyols and their production can be found, inter alia, in EP 1 359 177 A1.
  • the production of suitable polyetherester polyols is described in WO 2010/043624 A and in EP 1 923 417 A, among others.
  • low molecular weight isocyanate-reactive compounds are used to produce the PUR / PIR rigid foams, e.g. in the function of chain lengthening agents and / or crosslinking agents, these are expediently used in an amount of a maximum of 6% by weight, based on the total weight of the polyol formulation A. for use.
  • Compounds which, due to their structure, fall under the definition of component A3 as well as under one of the definitions of the above-described polyol compounds Al or A2 are counted in quantitative terms as Al or A2 and not with component A3.
  • the mixture of the polyols A1 and A2 preferably has a viscosity of ⁇ 4 Pa * s, in particular a viscosity of 2-4 Pa * s.
  • the mixture of the polyols Al and A2 preferably has an OH number of ⁇ 260 mg KOH / g, in particular ⁇ 230 mg KOH / g
  • the mass ratio of polyester polyols A1 to polyethylene glycols A2 in the polyol formulation is preferably 2-10.
  • the compounds A4 are one or more compounds selected from the group consisting of
  • RI, R2, R3, R4 H, Cl-C4-alkyl
  • R5, R6, R7 H, CI- to C8-alkyl, aryl
  • n 7-20, preferably 10-18, particularly preferably 11-15
  • RI, R3 H, C (CH 3) 2 CR4R5R6
  • R2 C (CH 3) 2 CR4R5R6
  • R4, R5 H or CH 3
  • R6 C2 to C5 alkyl, aryl
  • n 3-8 where the compounds A4 have a molecular weight of less than 1.5 kg / mol and a content of 25-70% ethylene oxide, preferably 40-60% ethylene oxide.
  • the compounds A4 having a molecular weight of less than 1.5 kg / mol and a content of 25-70% ethylene oxide, preferably 40-60% ethylene oxide.
  • Preferred compounds A4 are shown in Table 1 and are those with structure IV (falls under the definition of compounds A4-2), structure V (falls under the definition of compounds A4-1) and structure VI (falls under the definition of compounds A4-3).
  • component A5 In addition to the compounds A4, one or more further additives can optionally also be used as component A5.
  • component A5 are surface-active substances, foam stabilizers, cell regulators, flame retardants, fillers, dyes, pigments, hydrolysis inhibitors, fungistatic and bacteriostatic substances.
  • Suitable surface-active substances are, for example, compounds which serve to support the homogenization of the starting materials and, if necessary, are also suitable for regulating the cell structure of the plastics.
  • emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, e.g. oleic diethylamine, stearic acid diethanolamine, ricinolate diethanolamine, salts of sulfonic acids, e.g.
  • Foam stabilizers such as siloxane oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols different from A4, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and peanut oil, and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • oligomeric acrylates with polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying effect, the cell structure and / or stabilizing the foam.
  • Emulsifiers which, in terms of their structure, fall under the definition of component A4 are also counted in terms of quantity as component A4 and not as component A5.
  • inorganic fillers such as silicate minerals, for example sheet silicates such as. B.
  • metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts such as chalk, huntite, barite and inorganic pigments such as magnetite, goethite, cadmium sulfide and zinc sulfide, as well as glass, among other things, as well as natural and synthetic fibrous minerals such as wollastonite, metal and especially glass fibers of various catches, which can optionally be sized.
  • organic fillers are: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers and cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and carbon fibers.
  • a flame retardant A5 is also preferably used to produce the PUR / PIR rigid foams.
  • Flame retardants are known in principle to those skilled in the art and are described, for example, in “Kunststoffhandbuch”, Volume 7 “Polyurethane”, Chapter 6.1. These can be, for example, halogenated polyesters and polyols, bromine- and chlorine-containing paraffins or phosphorus compounds, such as, for example, the esters of orthophosphoric acid and metaphosphoric acid, which can also contain halogen. Liquid flame retardants at 298 K are preferred.
  • Examples are triethyl phosphate, diethyl ethane phosphonate, cresyl diphenyl phosphate and other triaryl phosphates, dimethyl propane phosphonate, hydroxymethyl phosphonates and tris ( ⁇ -chloroisopropyl) phosphate.
  • Flame retardants selected from the group consisting of tris (chloro-2-propyl) phosphate (TCPP) and triethyl phosphate (TEP) and mixtures thereof are particularly preferred.
  • Flame retardants are preferably used in an amount of 1 to 30% by weight, particularly preferably 5 to 30% by weight, based on the total weight of the isocyanate-reactive composition A) so that a phosphorus content in the foam of 0.4-1, 3 wt .-% is achieved.
  • a phosphorus content in the foam of 0.4-1, 3 wt .-% is achieved.
  • the presence of triethyl phosphate (TEP) in the flame retardant mixture or as the sole flame retardant is particularly advantageous.
  • the polyol formulation furthermore contains A6 a maximum of 2% by weight, preferably a maximum of 2.0% by weight, particularly preferably a maximum of 1.2% by weight of water, based on the total mass of the polyol formulation A.
  • the number average molar mass M n (also: molecular weight) is determined in the context of this invention by gel permeation chromatography according to DIN 55672-1 (March 2007).
  • the OH number (also: hydroxyl number) indicates the OH number in the case of an individually added polyol.
  • Information on the OH number for mixtures relates to the number-average OH number of the mixture, calculated from the OH numbers of the individual components in their respective molar proportions.
  • the OH number indicates the amount of potassium hydroxide in milligrams, which is equivalent to the amount of acetic acid bound during acetylation of one gram of substance.
  • the OH number is determined in accordance with the DIN 53240-1 standard (June 2013).
  • “functionality” denotes the theoretical average functionality calculated from the known starting materials and their proportions (Number of functions that are reactive towards isocyanates or towards polyols in the molecule or averaged over the respective mixture of molecules).
  • the equivalent weight indicates the ratio of the number average molecular mass and the functionality of the isocyanate-reactive component.
  • the equivalent weight data for mixtures are calculated from equivalent weights of the individual components in their respective molar proportions and relate to the number-average equivalent weight of the mixture.
  • blowing agent C can be used as blowing agent C, such as, for example, low-boiling organic compounds such as hydrocarbons, halogenated hydrocarbons, ethers, ketones, carboxylic acid esters or carbonic acid esters.
  • Organic compounds which are inert to isocyanate component B and have boiling points below 100 ° C., preferably below 50 ° C. at atmospheric pressure are particularly suitable. These boiling points have the advantage that the organic compounds evaporate under the influence of the exothermic polyaddition reaction.
  • Examples of such, preferably used organic compounds are 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. B. cyclopentane and / or cyclohexane, ethers, such as. B. furan, dimethyl ether and diethyl ether, ketones, such as. B. acetone and methyl ethyl ketone, carboxylic acid alkyl esters, such as. B.
  • 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. B. cyclopentane and / or cyclo
  • halogenated hydrocarbons such as. B. methylene chloride, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, and heptafluoropropane. It is preferred not to use propellants that are known to have a harmful effect on the earth's ozone layer.
  • propellants that are known to have a harmful effect on the earth's ozone layer.
  • the use of (hydro) fluorinated olefins such as. B. HFO 1233zd (E) (Trans-l-chloro-3,3,3-trifluoro-l-propene) or HFO 1336mzz (Z) (cis-1, 1,1, 4,4,4-
  • Hexafluoro-2-butene or additives such as FA 188 from 3M (l, l, l, 2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) pent-2-en). Mixtures of two or more of the organic compounds mentioned can also be used.
  • the organic compounds can also be used in the form of an emulsion composed of small droplets.
  • blowing agents such as, for example, water, carboxylic acid and mixtures thereof, can also be used as blowing agent C. These react with isocyanate groups to form the propellant gas, as in the case of water, for example, carbon dioxide is formed and in the case of z.
  • formic acid produces carbon dioxide and carbon monoxide.
  • At least one compound selected from the group consisting of formic acid, acetic acid, oxalic acid and ricinoleic acid is preferably used as the carboxylic acid.
  • Water is particularly preferably used as the chemical blowing agent.
  • blowing agents Preferably, no halogenated hydrocarbons are used as blowing agents. At least one compound selected from the group consisting of physical and chemical blowing agents is used as blowing agent C. Only physical blowing agent is preferably used. In a preferred embodiment, the blowing agents C used have an average global warming potential (GWP) of ⁇ 120, preferably a GWP of ⁇ 20.
  • GWP global warming potential
  • catalyst D for the production of PUR / PIR rigid foams compounds are used which accelerate the reaction of the reactive hydrogen atoms, in particular compounds containing hydroxyl groups, with the isocyanate component B, such as. B. tertiary amines or metal salts.
  • the catalyst components can be metered into the reaction mixture or completely or partially in the polyol formulation A.
  • tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N ', N'-
  • Tetramethyldiaminodiethylether bis (dimethylaminopropyl) urea, N-methyl- or N-ethylmorpholine, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N, N, N-tetramethylbutanediamine, N, N, N, N-Tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, bis [2- (dimethylamino) ethyl] ether, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo- (3,3,0) -octane , 1,4-Diaza-bi-cyclo- (2,2,2) -octane (Dabco) and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N
  • the transition metal salts used are, for example, zinc, bismuth, iron, lead or, preferably, tin salts.
  • transition metal salts used are iron (II) chloride, zinc chloride, lead octoate, tin dioctoate, tin diethylhexoate and dibutyltin dilaurate.
  • the transition metal salt is particularly preferably selected from at least one compound from the group consisting of tin dioctoate, tin diethylhexoate and dibutyltin dilaurate.
  • alkali metal salts are alkali alcoholates, such as. B.
  • alkali metal carboxylates such as. B. potassium acetate
  • alkali metal salts of long-chain fatty acids with 10 to 20 carbon atoms and optionally pendant OH groups are preferably used as the alkali metal salt.
  • amidines such as. B. 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine
  • tetraalkylammonium hydroxides such as. B. tetramethylammonium hydroxide
  • alkali hydroxides such as. B. sodium hydroxide
  • tetraalkylammonium or phosphonium carboxylates tetraalkylammonium or phosphonium carboxylates.
  • Mannich bases and salts of phenols are also suitable Catalysts. It is also possible to run the reactions without catalysis. In this case, the catalytic activity of polyols started with amines is used.
  • Catalysts forming isocyanurate groups for example ammonium ions or alkali metal salts, especially ammonium or alkali metal carboxylates, alone or in combination with tertiary amines.
  • the isocyanurate formation leads to particularly flame-retardant PIR rigid foams.
  • the catalyst components can be metered into the reaction mixture or completely or partially in the polyol formulation A.
  • the reactivity of the reaction mixture is usually adapted to the needs by means of the catalyst component.
  • the production of thin plates requires a reaction mixture with a higher reactivity than the production of thicker plates.
  • Typical parameters are the start time and the setting time as a measure of the time at which the reaction mixture begins to react and for the point in time at which a sufficiently stable polymer network is formed.
  • the above-mentioned catalysts can be used alone or in combination with one another.
  • Suitable isocyanate component B are, for. B. polyisocyanates, d. H. Isocyanates with an NCO functionality of at least 2 are possible. Examples of such suitable polyisocyanates are
  • Isocyanate component B is preferably selected from at least one compound from the group consisting of MDI, polymeric MDI and TDI.
  • modified diisocyanates with uretdione, isocyanurate, urethane, carbodiimide, uretonimine, allophanate, biuret, amide, iminooxadiazinedione and / or oxadiazinetrione structure, and unmodified polyisocyanate with more than 2 NCO groups per molecule such as, for example, 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4 ', 4 "-triisocyanate, can also be used.
  • NCO prepolymers can also be used as isocyanate component B.
  • the prepolymers can be prepared by reacting one or more polyisocyanates with one or more polyols, corresponding to the polyols described under the isocyanate-reactive components A1.
  • polymeric MDI types in rigid foam are particularly preferred over monomeric isocyanates.
  • the NCO content of the polyisocyanate component A) is preferably from> 29.0% by weight to ⁇ 33.0% by weight, and preferably has a viscosity at 25 ° C. of> 80 mPas to ⁇ 2900 mPas, particularly preferably of> 95 mPas to ⁇ 850 mPas at 25 ° C.
  • the NCO value (also: NCO content, isocyanate content) is determined using EN ISO 11909: 2007. Unless otherwise stated, the values are at 25 ° C.
  • the viscosity information is the dynamic viscosity at 25 ° C (unless otherwise stated), determined using DIN EN ISO 3219: 1994-10 "Plastics - Polymers / Resins in a liquid, emulsified or dispersed state".
  • the isocyanate index (also called index or isocyanate index) is understood to mean the quotient of the amount of substance [mol] of isocyanate groups actually used and the amount of substance [mol] of isocyanate-reactive groups actually used, multiplied by 100:
  • the index in the reaction mixture is 150 to 600, preferably 240 to 400.
  • This index is particularly preferably in a range from 240 to 400 in which a high proportion of polyisocyanurates (PIR) is present (the foam is called PIR foam or PUR / PIR foam) and leads to a higher flame retardancy of the PUR / PIR foam itself.
  • PIR polyisocyanurates
  • the NCO value (also: NCO content, isocyanate content) is determined using EN ISO 11909 (May 2007). Unless otherwise stated, the values are at 25 ° C.
  • the invention also relates to a PUR / PIR foam which is produced by the method according to the invention.
  • a reaction mixture is produced from components AD by mixing them, which leads to the PUR / PIR foam. Production generally takes place by mixing all the components using conventional high or low pressure mixing heads.
  • the PUR / PIR rigid foams according to the invention are produced according to the one-step process known to those skilled in the art, in which the reaction components are reacted with one another continuously or discontinuously and then either manually or with the aid of mechanical devices in the high-pressure or low-pressure process after discharge onto a conveyor belt or be brought into suitable molds for curing.
  • the PUR / PIR rigid foams according to the invention are preferably used for the production of composite elements.
  • the foaming usually takes place here in a continuous or discontinuous manner against at least one cover layer.
  • the invention accordingly also relates to the use of a rigid PUR / PIR foam according to the invention as an insulation foam and / or as an adhesion promoter in
  • Composite elements comprising a layer comprising a PUR / PIR rigid foam according to the invention and at least one cover layer.
  • the cover layer is at least partially contacted by a layer comprising the PUR / PIR rigid foam according to the invention.
  • Composite elements of the type of interest here are also used as sandwich
  • cover layers can form, for example, metal sheets, plastic sheets or chipboard panels up to 7 mm thick, depending on the intended use of the composite elements.
  • the one or two cover layers can each be a flexible cover layer, for example an aluminum foil, paper, multi-layer cover layers made of paper and aluminum or mineral fleece, and / or a rigid cover layer, for example made of sheet steel or chipboard .
  • OH ethylene oxide ratio of 1: 4.
  • the OH number is 250 mg KOH / g, the viscosity is 0.37 Pa * s at 25 ° C.
  • the flame spread of the PUR / PIR rigid foams was measured by applying flame to the edges with the small burner test according to DIN 4102-1 (March 1998) on a sample measuring 18 cm x 9 cm x 2 cm. The value given is for the maximum vertical flame height in cm.
  • the measurement of the mean heat release rate and its maximum (MARHE), the CO yield and the specific light absorption area SEA as a measure of the smoke gas density was measured according to ISO standard 5660-1: 1990 with a “cone calorimeter”.
  • the test specimens measuring 1 dm x 1 dm x 0.3 dm are irradiated for 20 minutes by a heat radiator with 50 kW / m2.
  • the determined CO yield indicates the average value from two measurements.
  • OH number (hydroxyl number) was determined in accordance with DIN 53240-1 (June 2013).
  • the acid number was determined in accordance with DIN EN ISO 2114 (January 2006).
  • the viscosity was determined on a Physica MCR 501 rheometer from Anton Paar. A cone-plate configuration with a distance of 1 mm was selected (DCP25 measuring system). The polyol (0.1 g) was applied to the rheometer plate and subjected to a shear of 0.01 to 1000 1 / s at 25 ° C. and the viscosity was measured every 10 s for 10 minutes. The viscosity given is averaged over all measuring points.
  • the open-cell content of the PUR / PIR rigid foams was measured with an Accupyk-1330 device on test specimens measuring 5 cm x 3 cm x 3 cm in accordance with DIN EN ISO 4590 (March 2003).
  • the cell structure of the foam was determined by visual inspection.
  • the bulk density was measured in accordance with DIN EN ISO 845 (October 2009).
  • the respective polyol formulations were obtained from a basic polyol component containing
  • the base polyol component also already contains 5 parts by weight of catalyst D-a.
  • the other polyol components according to Table 2 and n-pentane as blowing agent were mixed in a paper cup in addition to the basic polyol component.
  • the isocyanate-reactive mixture obtained was mixed with the isocyanate and the reaction mixture was poured into a paper form (3 ⁇ 3 ⁇ 1 dm 3 ) and reacted completely therein.
  • the exact formulations of the individual experiments are given in the tables below, as are the results of the physical measurements on the samples obtained.
  • Examples 3-5 according to the invention are superior to comparative examples 1 *, 2 *, 6 * and 7 * not according to the invention, inter alia in the combination of the properties of good flame retardancy and cell structure.
  • viscosity of polyol mixture proportion of Al-la in the mixture x ln (viscosity Al-la) + proportion of A2-a in the mixture x ln (viscosity A2-a) + proportion of A2-b in the mixture x is viscosity A2 -b).
  • a viscosity> 5 Pa * s is unfavorable during processing.

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Abstract

The invention relates to a polyol formulation for producing flameproof polyurethane/polyisocyanate rigid foams (referred to individually or jointly in the following as "PUR/PIR rigid foams"), containing a polyester polyol having an OH number ≤ 250 mg KOH/g, a functionality of 1.5 to 2.5 and a free glycol content with Mn < 150 g/mol of < 6 wt.%, a polyethylene glycol with an average molecular weight of < 700 g/mol and an average functionality of < 2.5 and specific polyethyleneglycol alkylphenyl ethers, and to methods for producing PUR/PIR rigid foams using said polyol formulation and to the PUR/PIR rigid foams obtained thereby.

Description

Verfahren zur Herstellung von flammwidrigen PUR-/PIR-Hartschäumen Process for the production of flame-retardant PUR / PIR rigid foams
Die vorliegende Erfindung betrifft eine Polyolformulierung zur Herstellung flammwidriger Polyurethan-/Polyisocyanurat-Hartschäume (im Folgenden einzeln oder gemeinsam auch als „PUR/PIR-Hartschäume“ bezeichnet) enthaltend ein Polyesterpolyol mit einer OH-Zahl < 250 mg KOH/g, einer Funktionalität von 1,5 - 2,5 und einem Gehalt an freien Glykolen mit Mn < 150 g/mol von < 6 Gew.-%, , ein Polyethylenglykol mit einem mittleren Molgewicht von < 700 g/mol und einer mittleren Funktionalität < 2,5 und bestimmte Polyethylenglykol-alkylphenylether, sowie Verfahren zur Herstellung von PUR-/PIR-Hartschäumen unter Verwendung dieser Polyolformulierung und die so hergestellten PUR-/PIR-Hartschäume. The present invention relates to a polyol formulation for producing flame-retardant polyurethane / polyisocyanurate rigid foams (hereinafter referred to individually or collectively as “PUR / PIR rigid foams”) containing a polyester polyol with an OH number <250 mg KOH / g, a functionality of 1.5-2.5 and a content of free glycols with M n <150 g / mol of <6% by weight, a polyethylene glycol with an average molecular weight of <700 g / mol and an average functionality of <2.5 and certain polyethylene glycol alkyl phenyl ethers, as well as processes for the production of PUR / PIR rigid foams using this polyol formulation and the PUR / PIR rigid foams thus produced.
Mit der Bezeichnung„PUR/PIR-Hartschäume“ werden in der vorliegenden Anmeldung solche Hartschäume bezeichnet, die sowohl über Urethan- als auch über Isocyanuratstrukturen verfügen. In the present application, the term “PUR / PIR rigid foams” refers to those rigid foams that have both urethane and isocyanurate structures.
So wie alle organischen Polymere sind auch PUR-/PIR-Hartschäume brennbar, wobei die große Oberfläche pro Masseneinheit in Hartschäumen dieses Verhalten noch verstärkt. PUR-/PIR- Hartschäume werden häufig als Isolationsmaterialien eingesetzt, beispielsweise als Dämmstoff in der Bauindustrie. In vielen Einsatzgebieten von PUR-/PIR-Hartschäumen ist daher eine Brandschutzausrüstung durch zugesetzte Flammschutzmittel erforderlich. Like all organic polymers, rigid PUR / PIR foams are also flammable, whereby the large surface area per unit of mass in rigid foams intensifies this behavior. PUR / PIR rigid foams are often used as insulation materials, for example as insulation in the construction industry. In many areas of application of PUR / PIR rigid foams, fire protection equipment through added flame retardants is therefore necessary.
Der Zusatz von höheren Mengen an Flammschutzmitteln bringt bekanntermaßen Nachteile mit sich, unter anderem für die mechanischen Eigenschaften der Polymere. Insbesondere Verbindungen, die Halogene enthalten, stehen außerdem wegen potentieller umweltschädlicher oder gesundheitsschädlicher Wirkungen in der Kritik. The addition of larger amounts of flame retardants is known to have disadvantages, including for the mechanical properties of the polymers. In particular, compounds that contain halogens are also subject to criticism because of their potentially harmful effects on the environment or health.
In der Polyurethanchemie lässt sich die Brandeigenschaft des polymeren Grundgerüsts in gewissen Grenzen durch die Auswahl und Zusammensetzung der Monomeren steuern. Positiv auf das Brandverhalten wirkt sich beispielsweise die Anwesenheit von Isocyanuratstrukturen aus. Auch der Einsatz von hochmolekularen Polyesterbausteinen wie in US 2013/184366 A und US 2014/364528 A soll zu einer Erhöhung der Flammwidrigkeit führen, behindert aber auch oft über vorzeitigen Anstieg der Glasübergangstemperatur die Trimerisierung von Isocyanat zu Isocyanuratstrukturen, die dem Schaum ihrerseits Festigkeit geben. In polyurethane chemistry, the fire properties of the polymer backbone can be controlled within certain limits by the selection and composition of the monomers. The presence of isocyanurate structures, for example, has a positive effect on fire behavior. The use of high molecular weight polyester building blocks, as in US 2013/184366 A and US 2014/364528 A, is also said to lead to an increase in flame retardancy, but also often hampers the trimerization of isocyanate to isocyanurate structures via a premature increase in the glass transition temperature, which in turn gives the foam strength.
Die Verarbeitung solcher hochmolekularer und dadurch hoch viskoser Polyolbausteine ist aufwändig und technisch problematisch, wodurch dem Einsatz Grenzen gesetzt sind. The processing of such high molecular weight and therefore highly viscous polyol building blocks is complex and technically problematic, which limits its use.
Ein Konzept zur Erniedrigung der Viskosität könnte in der Beimischung von Polyetherpolyolen hegen. Will man jedoch das industriell gut verfügbare Polyethylenglykol (PEG) verwenden, um die für viele PUR-/PIR-Anwendungen übliche Viskosität der Polyolformulierung von etwa 3500 - 4000 mPa*s einzustellen, weisen die erhaltenen Schäume oft eine mangelhafte Zellstruktur auf, resultierend in schlechten Oberflächen und für die großtechnische Anwendung ungenügenden Eigenschaften. A concept for lowering the viscosity could lie in the addition of polyether polyols. However, if you want to use the industrially readily available polyethylene glycol (PEG) to adjust the polyol formulation viscosity of around 3500 - 4000 mPa * s, which is common for many PUR / PIR applications, the foams obtained often have a deficient cell structure. resulting in poor surfaces and inadequate properties for industrial use.
Die Aufgabe der vorliegenden Erfindung ist es daher, eine Polyolformulierung A enthaltend ein hochmolekulares Polyesterpolyol für die Herstellung von PUR-/PIR-Hartschäumen zur Verfügung zu stellen, wobei die PUR-/PIR-Hartschäume einen guten Flammschutz und gute mechanische Eigenschaften aufweisen. The object of the present invention is therefore to provide a polyol formulation A containing a high molecular weight polyester polyol for the production of rigid PUR / PIR foams, the rigid PUR / PIR foams having good flame retardancy and good mechanical properties.
US 2012/0202903 A beschreibt die Verwendung von Alkylethoxylatalkoholen mit einem durchschnittlichen HLB-Wert zwischen 10 und 15 als Verträglichkeits Vermittler für Polyolformulierungen, welche hohe Anteile an Wasser enthalten und für die Herstellung wassergetriebener Polyurethansprühschäume eingesetzt werden. US 2012/0202903 A describes the use of alkyl ethoxylate alcohols with an average HLB value between 10 and 15 as compatibility promoters for polyol formulations which contain high proportions of water and are used for the production of water-driven polyurethane spray foams.
Diese Aufgabe konnte überraschend gelöst werden durch eine Polyolformulierung A, enthaltend Surprisingly, this object could be achieved by a polyol formulation A containing
Al 35-89 Gew.-%, bezogen auf die Gesamtmasse der Polyolformulierung A, einerAl 35-89 wt .-%, based on the total mass of the polyol formulation A, one
Polyesterpolyolkomponente, welche eine OH-Zahl von 190 - 310 mg KOH/g aufweist, bestehend aus Polyester polyol component, which has an OH number of 190-310 mg KOH / g, consisting of
Al-1 mindestens eines Polyesterpolyols mit einer OH-Zahl < 250 mg KOH/g, einer mittleren Funktionalität von 1,5 - 2,5 und einem Gehalt an freien Glykolen mit Mn < 150 g/mol von < 6 Gew.-%, bezogen auf die Gesamtmasse von Al-1, Al-1 of at least one polyester polyol with an OH number <250 mg KOH / g, an average functionality of 1.5 - 2.5 and a content of free glycols with M n <150 g / mol of <6% by weight , based on the total mass of Al-1,
Al -2 optional weiteren Polyesterpolyolen, welche nicht unter die Definition von Al-1 fallen, Al -2 optionally other polyester polyols which do not fall under the definition of Al-1,
A2 10-40 Gew.-%, bezogen auf die Polyolformulierung A, eines oder mehrererA2 10-40% by weight, based on the polyol formulation A, of one or more
Polyethylenglykole mit einem mittleren Molgewicht von < 700 g/mol und einer mittleren Funktionalität < 2,5; Polyethylene glycols with an average molecular weight of <700 g / mol and an average functionality of <2.5;
A3 weitere isocyanatreaktive Komponenten A3 further isocyanate-reactive components
A4 0,2-5 Gew.-%, bezogen auf die Polyolformulierung A, einer oder mehrerer Verbindungen ausgewählt aus der Gruppe bestehend aus A4 0.2-5% by weight, based on the polyol formulation A, of one or more compounds selected from the group consisting of
A4-1 eines Polyethylenglykol-2,4,6-trialkylphenylethern (Struktur I mit R5, R6, R7 = H, CI - bis C8-Alkyl) und A4-1 of a polyethylene glycol-2,4,6-trialkylphenyl ether (structure I with R5, R6, R7 = H, CI - to C8-alkyl) and
A4-2 Polyethylenglykol-2,4,6-triaralkylphenylethern (Struktur I mit R5, R6 und/oder R7 = Aryl) und A4-3 Polyethylenglykol-alkylphenylethern (Struktur II) A4-2 polyethylene glycol-2,4,6-triaralkylphenyl ethers (structure I with R5, R6 and / or R7 = aryl) and A4-3 polyethylene glycol alkyl phenyl ethers (structure II)
Struktur I Structure i
RI, R2, R3, R4 = H, Cl-C4-Alkyl, RI, R2, R3, R4 = H, Cl-C4-alkyl,
R5, R6, R7 = H, CI- bis C8-Alkyl, Aryl R5, R6, R7 = H, CI- to C8-alkyl, aryl
n = 7-20, bevorzugt 10-18, besonders bevorzugt 11-15 n = 7-20, preferably 10-18, particularly preferably 11-15
Struktur II Structure II
RI, R3 = H, C(CH3)2CR4R5R6 RI, R3 = H, C (CH 3) 2 CR4R5R6
R2 = C(CH3)2CR4R5R6 R2 = C (CH 3) 2 CR4R5R6
R4, R5 = H oder CH3 R4, R5 = H or CH 3
R6 = C2- bis C5-Alkyl, Aryl R6 = C2 to C5 alkyl, aryl
n = 3-8 wobei die Verbindungen A4 ein Molgewicht von unter 1,5 kg/mol und ein Gehalt von 25-70% Ethylenoxid, bevorzugt 40-60% Ethylenoxid aufweisen, und n = 3-8 where the compounds A4 have a molecular weight of less than 1.5 kg / mol and a content of 25-70% ethylene oxide, preferably 40-60% ethylene oxide, and
A5 gegebenenfalls weitere Hilfs- und Zusatzstoffe. A5 other auxiliaries and additives if necessary.
A6 0 - 2 Gew.-%, bezogen auf die Gesamtmasse der Polyolformulierung A, Wasser. A6 0-2% by weight, based on the total mass of the polyol formulation A, water.
Gegenstand der Erfindung ist ebenfalls ein Verfahren zur Herstellung von PUR-/PIR- Hartschäumen durch die Umsetzung eines Reaktionsgemisches enthaltend die Polyolformulierung A, eine Polyisocyanat-Komponente B, und ein Treibmittel C, gegebenfalls in Anwesenheit einer katalytisch aktiven Komponente D, wobei die Herstellung bei einer Kennzahl von 150 bis 600, bevorzugt 240-400, erfolgt. The invention also relates to a method for producing PUR / PIR rigid foams by converting a reaction mixture containing them the polyol formulation A, a polyisocyanate component B, and a blowing agent C, optionally in the presence of a catalytically active component D, the production taking place with an index of 150 to 600, preferably 240-400.
Überraschenderweise konnte mit der erfindungsgemäßen Komponente A eine Formulierung zur Verfügung gestellt werden, welche hochmolekulare Polyesterbausteine enthält und trotzdem über eine niedrige Viskosität verfügt und sich zu PUR-/PIR-Hartschäumen mit guter Zellstruktur verarbeiten lässt. Die mit der erfindungsgemäßen Komponente A hergestellten Polyester weisen außerdem gute Flammwidrigkeiten und mechanische Eigenschaften, wie Zugfestigkeit, Bruchdehnung, Zähigkeit und Offenzelligkeit der PUR-/PIR-Hartschäume verbessert. Surprisingly, with component A according to the invention, it was possible to provide a formulation which contains high molecular weight polyester building blocks and yet has a low viscosity and can be processed into rigid PUR / PIR foams with a good cell structure. The polyesters produced with component A according to the invention also have good flame retardancy and improved mechanical properties, such as tensile strength, elongation at break, toughness and open-cell structure of the rigid PUR / PIR foams.
Bei der Polyesterpolyol - Komponente Al-1 handelt es sich um ein Polyesterpolyol mit einer OH- Zahl < 240 mg KOH/g, bevorzugt < 200 mg KOH/g, einer Funktionalität von 1,5 - 2,5 und einem Gehalt an freien Glykolen mit einer Molmasse < 150 g/mol von unter 6 Gew.-%, bezogen auf die Gesamtmasse von Al-1. Eine solche Polyolkomponente weist üblicherweise aufgrund ihres Molgewichts eine für PUR-/PIR-Hartschauman Wendungen hohe Viskosität auf, insbesondere eine Viskosität von > 5 Pa*s. The polyester polyol component Al-1 is a polyester polyol with an OH number <240 mg KOH / g, preferably <200 mg KOH / g, a functionality of 1.5-2.5 and a content of free glycols with a molar mass <150 g / mol of less than 6% by weight, based on the total mass of Al-1. Due to its molecular weight, such a polyol component usually has a high viscosity for PUR / PIR rigid foam applications, in particular a viscosity of> 5 Pa * s.
Der Anteil von Polyesterpolyolen Al-1 in der Polyesterpolyolkomponente Al ist bevorzugt > 60 Gew.-%, insbesondere > 80 Gew.-% und ganz besonders bevorzugt > 90 Gew.-%. Das Massenverhältnis von Al-1 zu Al-2 beträgt somit bevorzugt mindestens 6:1, insbesondere mindestens 8:1. The proportion of polyester polyols Al-1 in the polyester polyol component Al is preferably> 60% by weight, in particular> 80% by weight and very particularly preferably> 90% by weight. The mass ratio of Al-1 to Al-2 is therefore preferably at least 6: 1, in particular at least 8: 1.
Polyesterpolyole mit einem niedrigen Gehalt an freien Glykolen sind an sich bekannt und ihre Herstellung und Einsatz in FCKW-basierten PUR/PIR-Formulierungen ist z.B. in der US 5,109,301 offenbart. Polyester polyols with a low content of free glycols are known per se and their production and use in CFC-based PUR / PIR formulations is disclosed, for example, in US Pat. No. 5,109,301.
Die Polyesterpolyole der Komponente Al können beispielsweise Polykondensate aus mehrwertigen Alkoholen, vorzugsweise Diolen, mit 2 bis 12 Kohlenstoff atomen, vorzugsweise mit 2 bis 6 Kohlenstoffatomen, und Polycarbonsäuren, wie z.B. Di-, Tri- oder sogar Tetracarbonsäuren, oder Hydroxycarbonsäuren oder Lactonen sein, bevorzugt werden aromatische Dicarbonsäuren oder Gemische aus aromatischen und aliphatischen Dicarbonsäuren verwendet. Anstelle der freien Polycarbonsäuren können auch die entsprechenden Polycarbonsäureanhydride oder entsprechende Polycarbonsäureester von niederen Alkoholen zur Herstellung der Polyester verwendet werden. Bevorzugt verwendet werden Phthalsäureanhydrid, Terephthalsäure und/oder Isophthalsäure. The polyester polyols of component Al can be, for example, polycondensates of polyhydric alcohols, preferably diols, with 2 to 12 carbon atoms, preferably with 2 to 6 carbon atoms, and polycarboxylic acids, such as di-, tri- or even tetracarboxylic acids, or hydroxycarboxylic acids or lactones, preferably aromatic dicarboxylic acids or mixtures of aromatic and aliphatic dicarboxylic acids are used. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding Polycarboxylic acid esters of lower alcohols can be used to produce the polyester. Phthalic anhydride, terephthalic acid and / or isophthalic acid are preferably used.
Als Carbonsäuren kommen insbesondere in Betracht: Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Azelainsäure, Sebazinsäure, Decandicarbonsäure, Tetrahydrophthalsäure, Hexahydrophthalsäure, Cyclohexandicarbonsäure, Tetrachlorphthalsäure, Itaconsäure, Malonsäure, Furandicarbonsäuren, 2-Methylbernsteinsäure, 3,3-Diethylglutarsäure, 2,2-Dimethylbernsteinsäure, Dodekandisäure, Endomethylentetrahydrophthalsäure, Dimerfettsäure, Trimerfettsäure, Zitronensäure, Trimellithsäure, Benzoesäure, Trimellitsäure, Maleinsäure, Fumarsäure, Phthalsäure, Isophthalsäure und Terephthalsäure. Verwendet werden können ebenso Derivate dieser Carbonsäuren, wie beispielsweise Dimethylterephthalat. Die Carbonsäuren können dabei sowohl einzeln als auch im Gemisch verwendet werden. Als Carbonsäuren werden bevorzugt Adipinsäure, Sebacinsäure und/oder Bernsteinsäure, besonders bevorzugt Adipinsäure und/oder Bernsteinsäure, verwendet. Particularly suitable carboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, tetrachlorophthalic acid, itaconic acid, malonic acid, itaconic acid, malonic acid, 2,2-dimethyl-succinic acid, 3,3-methyl-succinic acid, succinic acid , Dodecanedioic acid, endomethylenetetrahydrophthalic acid, dimer fatty acid, trimer fatty acid, citric acid, trimellitic acid, benzoic acid, trimellitic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. It is also possible to use derivatives of these carboxylic acids, for example dimethyl terephthalate. The carboxylic acids can be used either individually or as a mixture. The carboxylic acids used are preferably adipic acid, sebacic acid and / or succinic acid, particularly preferably adipic acid and / or succinic acid.
Hydroxycarbonsäuren, die als Reaktionsteilnehmer bei der Herstellung eines Polyesterpolyols mit endständigen Hydroxylgruppen mitverwendet werden können, sind beispielsweise Hydroxycapronsäure, Hydroxybuttersäure, Hydroxydecansäure, Hydroxystearinsäure und dergleichen. Geeignete Lactone sind unter anderem Caprolacton, Propiolacton, Butyrolacton und Homologe. Hydroxycarboxylic acids which can also be used as reactants in the production of a polyester polyol with terminal hydroxyl groups are, for example, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like. Suitable lactones include caprolactone, propiolactone, butyrolactone and homologues.
Zur Herstellung der Polyesterpolyole kommen insbesondere auch biobasierte Ausgangsstoffe und/oder deren Derivate in Frage, wie z. B. Rizinusöl, Polyhydroxyfettsäuren, Ricinolsäure, Hydroxyl-modifizierte Öle, Weintraubenkernöl, schwarzem Kümmelöl, Kürbiskernöl, Borretschsamenöl, Sojabohnenöl, Weizensamenöl, Rapsöl, Sonnenblumenkernöl, Erdnussöl, Aprikosenkernöl, Pistazienöl, Mandelöl, Olivenöl, Macadamianussöl, Avocadoöl, Sanddornöl, Sesamöl, Hanföl, Haselnussöl, Primelöl, Wildrosenöl, Distelöl, Walnussöl, Fettsäuren, hydroxylmodifizierte und epoxidierte Fettsäuren und Fettsäureester, beispielsweise basierend auf Myristoleinsäure, Palmitoleinsäure, Ölsäure, Vaccensäure, Petroselinsäure, Gadoleinsäure, Erukasäure, Nervonsäure, Einolsäure, alpha- und gamma-EinoIensäure, Stearidonsäure, Arachidonsäure, Timnodonsäure, Clupanodonsäure und Cervonsäure. Insbesondere bevorzugt sind Ester der Rizinolsäure mit mehrfunktionellen Alkoholen, z.B. Glycerin. Bevorzugt ist auch die Verwendung von Mischungen solcher biobasierten Säuren mit anderen Carbonsäuren, z.B. Phthalsäuren. Bio-based starting materials and / or their derivatives are particularly suitable for the production of polyester polyols, such as B. castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grape seed oil, black caraway seed oil, pumpkin seed oil, borage seed oil, soybean oil, wheat seed oil, rapeseed oil, sunflower seed oil, peanut oil, apricot kernel oil, avicorn oil, hempseed oil, sandduck oil, almond oil, hempseed oil Hazelnut oil, primrose oil, wild rose oil, safflower oil, walnut oil, fatty acids, hydroxyl-modified and epoxidized fatty acids and fatty acid esters, for example based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, monoleic acid, arachidonic acid and gamma acid , Timnodonic acid, clupanodonic acid and cervonic acid. Esters of ricinoleic acid with polyfunctional alcohols, e.g. glycerol, are particularly preferred. The use of mixtures of such bio-based acids with other carboxylic acids, e.g. phthalic acids, is also preferred.
Beispiele für geeignete Diole sind Ethylenglykol, Butylenglykol, Diethylenglykol, Triethylenglykol, Polyalkylenglykole wie Polyethylenglykol, weiterhin 1 ,2-Propandiol, 1,3- Propandiol, Cyclohexandimethanol, 1,3-Butandiol, 1 ,4-Butandiol, 1,6-Hexandiol und Isomere, Neopentylglykol oder Hydroxypivalinsäureneopentylglykolester. Vorzugsweise verwendet werden Ethylenglykol, Diethylenglykol, 1 ,4-Butandiol, 1,5-Pentandiol, 1 ,6-Hexandiol oder Mischungen aus mindestens zwei der genannten Diole, insbesondere Mischungen aus 1 ,4-Butandiol, 1,5- Pentandiol und 1,6-Hexandiol. Examples of suitable diols are ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, cyclohexanedimethanol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and Isomers, neopentyl glycol or neopentyl glycol hydroxypivalate. Preferably used Ethylene glycol, 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 .
Daneben können auch Polyole wie Trimethylolpropan, Glycerin, Erythrit, Pentaerythrit, Trimethylolbenzol oder Trishydroxyethylisocyanurat eingesetzt werden, wobei Glycerin und Trimethylolpropan bevorzugt sind. In addition, polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate can also be used, glycerol and trimethylolpropane being preferred.
Es können zusätzlich auch einwertige Alkanole mit verwendet werden. Monohydric alkanols can also be used.
In der Polyesterpolyolkomponente können auch solche Polyester-Polyole verwendet werden, welche über Polyether-Strukturen verfügen. Diese werden häufig auch als„Polyetheresterpolyole“ bezeichnet. Verwendbare Polyetheresterpolyole sind solche Verbindungen, die Ethergruppen, Estergruppen und OH-Gruppen enthalten. Organische Dicarbonsäuren mit bis zu 12 Kohlenstoffatomen sind zur Herstellung der Polyetheresterpolyole geeignet, vorzugsweise aliphatische Dicarbonsäuren mit 4 bis 6 Kohlenstoffatomen oder aromatische Dicarbonsäuren, die einzeln oder im Gemisch verwendet werden. Beispielhaft seien Korksäure, Azelainsäure, Decandicarbonsäure, Furandicarbonsäure, Maleinsäure, Malonsäure, Phthalsäure, Pimelinsäure und Sebacinsäure sowie insbesondere Glutarsäure, Fumarsäure, Bernsteinsäure, Adipinsäure, Phthalsäure, Terephthalsäure und Isoterephthalsäure genannt. Neben organischen Dicarbonsäuren können auch Derivate dieser Säuren, beispielsweise deren Anhydride sowie deren Ester und Halbester mit niedermolekularen, monofunktionellen Alkoholen mit 1 bis 4 Kohlenstoffatomen eingesetzt werden. Der anteilige Einsatz der oben genannten biobasierten Ausgangsstoffe, insbesondere von Fettsäuren bzw. Fettsäurederivaten (Ölsäure, Sojaöl etc.) ist ebenfalls möglich und kann Vorteile aufweisen, z.B. im Hinblick auf Lagerstabilität der Polyolformulierung, Dimensionsstabilität, Brandverhalten und Druckfestigkeit der Schäume. Those polyester-polyols which have polyether structures can also be used in the polyester polyol component. These are often referred to as “polyetherester polyols”. Polyetherester polyols that can be used are those compounds containing ether groups, ester groups and OH groups. Organic dicarboxylic acids with up to 12 carbon atoms are suitable for the production of the polyetherester polyols, preferably aliphatic dicarboxylic acids with 4 to 6 carbon atoms or aromatic dicarboxylic acids, which are used individually or in a mixture. Examples are suberic acid, azelaic acid, decanedicarboxylic acid, furandicarboxylic acid, maleic acid, malonic acid, phthalic acid, pimelic acid and sebacic acid, and in particular glutaric acid, fumaric acid, succinic acid, adipic acid, phthalic acid, terephthalic acid and isoterephthalic acid. In addition to organic dicarboxylic acids, derivatives of these acids, for example their anhydrides and their esters and half esters with low molecular weight, monofunctional alcohols having 1 to 4 carbon atoms, can also be used. The partial use of the bio-based starting materials mentioned above, in particular fatty acids or fatty acid derivatives (oleic acid, soybean oil, etc.) is also possible and can have advantages, e.g. with regard to the storage stability of the polyol formulation, dimensional stability, fire behavior and compressive strength of the foams.
Als weitere Komponente zur Herstellung der Polyetheresterpolyole werden Polyetherpolyole eingesetzt, die man durch Alkoxylieren von Startermolekülen wie mehrwertigen Alkoholen erhält. Die Startermoleküle sind mindestens difunktionell, können aber gegebenenfalls auch Anteile höherfunktioneller, insbesondere trifunktioneller, Startermoleküle enthalten. Polyether polyols obtained by alkoxylating starter molecules such as polyhydric alcohols are used as a further component for the production of the polyether ester polyols. The starter molecules are at least difunctional, but can optionally also contain proportions of higher-functional, in particular trifunctional, starter molecules.
Startermoleküle sind zum Beispiel Diole wie 1 ,2-Ethandiol, 1,3-Propandiol, 1 ,2-Propandiol, 1 ,4- Butandiol, 1,5-Pentendiol, 1,5-Pentandiol, Neopentylglykol, 1,6- Hexandiol, 1,7-Heptandiol, 1,8- Octandiol, 1,10-Decandiol, 2-Methyl-l,3-propandiol, 2,2-Dimethyl-l,3-propandiol, 3-Methyl-l,5- pentandiol, 2-Butyl-2-ethyl-l,3-propandiol, 2-Buten-l,4-diol und 2-Butin-l,4-diol, Etherdiole wie Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Dibutylenglykol, Tributylenglykol, Tetrabutylenglykol, Dihexylenglykol, Trihexylenglykol, Tetrahexylenglykol und Oligomerengemische von Alkylenglykolen, wie Diethylenglykol. Auch Startermoleküle mit von OH verschiedenen Funktionalitäten können alleine oder in Mischung eingesetzt werden. Starter molecules are, for example, diols such as 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentenediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-l, 3-propanediol, 2-butene-l, 4-diol and 2-butyne-l, 4-diol, ether diols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dibutylene glycol, tributylene glycol, tetrabutylene glycol, dihexylene glycol, Trihexylene glycol, tetrahexylene glycol and Oligomer mixtures of alkylene glycols, such as diethylene glycol. Starter molecules with functionalities other than OH can also be used alone or in a mixture.
Neben den Diolen können als Startermoleküle für die Herstellung der Polyether auch Verbindungen mit mehr als 2 Zerewitinoff-aktiven Wasserstoffen, besonders mit zahlenmittleren Funktionalitäten von 3 bis 8, insbesondere von 3 bis 6 mitverwendet werden, zum Beispiel 1,1,1- Trimethylolpropan, Triethanolamin, Glycerin, Sorbitan und Pentaerythrit sowie auf Triolen oder Tetraoien gestartete Polyethylenoxidpolyole. In addition to the diols, compounds with more than 2 Zerewitinoff-active hydrogens, especially with number-average functionalities from 3 to 8, in particular from 3 to 6, for example 1,1,1-trimethylolpropane, triethanolamine, can also be used as starter molecules for the production of the polyethers , Glycerine, sorbitan and pentaerythritol as well as polyethylene oxide polyols started on triols or tetraoene.
Polyetheresterpolyole können auch durch die Alkoxylierung, insbesondere durch Ethoxylierung und/oder Propoxylierung, von Reaktionsprodukten, die durch die Umsetzung von organischen Dicarbonsäuren und deren Derivaten sowie Komponenten mit Zerewitinoff-aktiven Wasserstoffen, insbesondere Diolen und Polyolen, erhalten werden, hergestellt werden. Als Derivate dieser Säuren können beispielsweise deren Anhydride eingesetzt werden, wie zum Beispiel Phthalsäureanhydrid. Polyetherester polyols can also be prepared by alkoxylation, in particular ethoxylation and / or propoxylation, of reaction products obtained by reacting organic dicarboxylic acids and their derivatives and components with Zerewitinoff-active hydrogens, especially diols and polyols. As derivatives of these acids, for example, their anhydrides can be used, such as phthalic anhydride.
Als Komponente A2 werden Polyethylenglykole, d. h. Umsetzungsprodukte eines niedermolekularen 2-3-funktionellen hydroxyfunktionellen Startermoleküls mit Ethylenoxid eingesetzt, wobei das Ethylenoxid >80% des Molgewichtes ausmacht. Bei den Startermolekülen handelt es sich insbesondere um Wasser, Ethylenglycol, Diethylenglycol, Propylenglycol, Glyzerin und/oder Trimethylolpropan. Die Herstellung solcher Polyethylenglycole ist dem Fachmann bekannt und viele dieser Substanzen sind kommerziell erhältlich. Geeignete Polyethylenglykole sind bevorzugt flüssig bei 298 K und verfügen insbesondere über Molekulargewichte von < 700 g/mol und eine mittlere Funktionalität < 2,5, insbesondere bevorzugt weisen sie ein mittleres Molgewicht von 200-600 g/mol auf und ganz besonders bevorzugt eine mittlere Funktionalität von < 2,12. Polyethylene glycols are used as component A2, i. H. Reaction products of a low molecular weight 2-3-functional hydroxy-functional starter molecule with ethylene oxide are used, the ethylene oxide making up> 80% of the molecular weight. The starter molecules are in particular water, ethylene glycol, diethylene glycol, propylene glycol, glycerol and / or trimethylolpropane. The preparation of such polyethylene glycols is known to those skilled in the art and many of these substances are commercially available. Suitable polyethylene glycols are preferably liquid at 298 K and in particular have molecular weights of <700 g / mol and an average functionality of <2.5, particularly preferably they have an average molecular weight of 200-600 g / mol and very particularly preferably an average functionality of <2.12.
Bei den weiteren isocyanat-reaktiven Komponenten A3 handelt es sich beispielsweise um Polyole, wie Polyetherpolyole, Polycarbonatpolyolen und Polyether-Polycarbonatpolyolen, welche nicht unter die Definition der Komponenten Al und A2 fallen. The further isocyanate-reactive components A3 are, for example, polyols, such as polyether polyols, polycarbonate polyols and polyether-polycarbonate polyols, which do not fall under the definition of components A1 and A2.
Der Zusatz von langkettigen Polyolen, insbesondere Polyetherpolyolen, kann die Verbesserung der Fließfähigkeit des Reaktionsgemisches und die Emulgierfähigkeit der treibmittelhaltigen Formulierung bewirken. Für die Herstellung von Verbundelementen können diese beispielsweise die kontinuierliche Produktion von Elementen mit flexiblen oder starren Deckschichten ermöglichen. The addition of long-chain polyols, in particular polyether polyols, can improve the flowability of the reaction mixture and the emulsifiability of the blowing agent-containing formulation. For the production of composite elements, these can, for example, enable the continuous production of elements with flexible or rigid cover layers.
In einer bevorzugten Ausführungsform weisen langkettige Polyole Funktionalitäten von > 1,2 bis < 3,5 auf und besitzen eine Hydroxylzahl zwischen 10 und 100 mg KOH/g, bevorzugt zwischen 20 und 50 mg KOH/g, und besitzen mehr als 70 mol%, bevorzugt mehr als 80 mol%, insbesondere mehr als 90 mol% primäre OH-Gruppen. Die langkettigen Polyole sind bevorzugt Polyetherpolyole mit Funktionalitäten von >1,2 bis < 3,5 und einer Hydroxylzahl zwischen 10 und 100 mg KOH/g. In a preferred embodiment, long-chain polyols have functionalities of> 1.2 to <3.5 and have a hydroxyl number between 10 and 100 mg KOH / g, preferably between 20 and 50 mg KOH / g, and have more than 70 mol%, preferably more than 80 mol%, in particular more than 90 mol% primary OH groups. The long-chain polyols are preferably polyether polyols with functionalities of> 1.2 to <3.5 and a hydroxyl number between 10 and 100 mg KOH / g.
Der Zusatz von mittelkettigen Polyolen, insbesondere Polyetherpolyolen, und niedermolekularen isocyanat-reaktiven Verbindungen, kann die Verbesserung der Haftung und Dimensionsstabilität des resultierenden Schaumes bewirken. Für die Herstellung von Verbundelementen mit dem erfindungsgemäßen Verfahren können diese mittelkettigen Polyole die kontinuierliche Produktion von Elementen mit flexiblen oder starren Deckschichten ermöglichen. Die mittelkettigen Polyole, bei denen es sich insbesondere um Polyetherpolyole handelt, weisen Funktionalitäten von > 2 bis < 6 auf und besitzen eine Hydroxylzahl zwischen 300 und 700 mg KOH/g. The addition of medium-chain polyols, in particular polyether polyols, and low molecular weight isocyanate-reactive compounds can improve the adhesion and dimensional stability of the resulting foam. For the production of composite elements using the process according to the invention, these medium-chain polyols can enable the continuous production of elements with flexible or rigid cover layers. The medium-chain polyols, which are in particular polyether polyols, have functionalities from> 2 to <6 and have a hydroxyl number between 300 and 700 mg KOH / g.
Bei den verwendeten Polyetherpolyolen handelt es sich um die dem Fachmann bekannten, in der Polyurethansynthese einsetzbaren Polyetherpolyole mit den genannten Merkmalen. The polyether polyols used are the polyether polyols known to the person skilled in the art and which can be used in polyurethane synthesis and have the features mentioned.
Verwendbare Polyetherpolyole sind beispielsweise Polytetramethylenglykolpolyether, wie sie durch Polymerisation von Tetrahydrofuran mittels kationischer Ringöffnung erhältlich sind. Polyether polyols which can be used are, for example, polytetramethylene glycol polyethers, such as are obtainable by polymerizing tetrahydrofuran by means of cationic ring opening.
Polyetherpolyole werden nach dem Fachmann bekannten Herstellungsmethoden erhalten, wie beispielsweise durch anionische Polymerisation von einem oder mehreren Alkylenoxiden mit 2 bis 4 Kohlenstoffatomen mit Alkalihydroxiden, wie Natrium- oder Kaliumhydroxid, Alkalialkoholaten, wie Natriummethylat, Natrium- oder Kaliumethylat oder Kaliumisopropylat, oder aminischen Alkoxylierungs-Katalysatoren, wie Dimethylethanolamin (DMEOA), Imidazol und/oder Imidazolderivate, unter Verwendung mindestens eines Startermoleküls, das 2 bis 8, vorzugsweise 2 bis 6 reaktive Wasserstoffatome gebunden enthält. Polyether polyols are obtained by production methods known to those skilled in the art, such as, for example, by anionic polymerization of one or more alkylene oxides having 2 to 4 carbon atoms with alkali hydroxides such as sodium or potassium hydroxide, alkali alcoholates such as sodium methylate, sodium or potassium ethylate or potassium isopropylate, or aminic alkoxylation catalysts , such as dimethylethanolamine (DMEOA), imidazole and / or imidazole derivatives, using at least one starter molecule which contains 2 to 8, preferably 2 to 6, reactive hydrogen atoms bonded.
Geeignete Alkylenoxide sind beispielsweise Tetrahydrofuran, 1,3 -Propylenoxid, 1,2- bzw. 2,3- Butylenoxid, Styroloxid und vorzugsweise Ethylenoxid und 1 ,2-Propylenoxid. Die Alkylenoxide können einzeln, alternierend nacheinander oder als Mischungen verwendet werden. Bevorzugte Alkylenoxide sind Propylenoxid und Ethylenoxid, besonders bevorzugt ist Ethylenoxid. Die Alkylenoxide können in Kombination mit CO2 umgesetzt werden. 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, and ethylene oxide is particularly preferred. The alkylene oxides can be converted in combination with CO2.
Als Startermoleküle kommen beispielsweise in Betracht: Wasser, organische Dicarbonsäuren, wie Bernsteinsäure, Adipinsäure, Phthalsäure und Terephthalsäure, aliphatische und aromatische, gegebenenfalls N-mono-, N,N- und N,N'-dialkylsubstituierte Diamine mit 1 bis 4 Kohlenstoffatomen im Alkylrest, wie gegebenenfalls mono- und dialkylsubstituiertes Ethylendiamin, Diethylentriamin, Triethylentetramin, 1,3-Propylendiamin, 1,3- bzw. 1,4- Butylendiamin, 1,2-, 1,3-, 1,4-, 1,5- und 1,6-Hexamethylendiamin, Phenylendiamine, 2,3-, 2,4- und 2,6-Toluylendiamin und 2,2'-, 2,4'- und 4,4'-Diaminodiphenylmethan. Vorzugsweise verwendet werden zwei oder mehrwertige Alkohole, wie Ethandiol, 1,2- und 1,3- Propandiol, Diethylenglykol, Dipropylenglykol, 1 ,4-Butandiol, 1,6-Hexandiol, Triethanolamin, Bisphenole, Glycerin, Trimethylolpropan, Pentaerythrit, Sorbit und Saccharose. As starter molecules, 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 N, N'-dialkyl-substituted diamines with 1 to 4 carbon atoms in the alkyl radical such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-tolylenediamine, and 2,2'-, 2,4'- and 4,4'-diaminodiphenylmethane. Preference is given to using two or polyhydric alcohols such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, triethanolamine, bisphenols, glycerol, trimethylolpropane, pentaerythritol, sorbitol and Sucrose.
Verwendbare Polycarbonatpolyole sind Hydroxylgruppen aufweisende Polycarbonate, zum Beispiel Polycarbonatdiole. Diese entstehen in der Reaktion von Kohlensäurederivaten, wie Diphenylcarbonat, Dimethylcarbonat oder Phosgen, mit Polyolen, bevorzugt Diolen. Polycarbonate polyols which can be used are polycarbonates containing hydroxyl groups, for example polycarbonate diols. These arise in the reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols.
Beispiele derartiger Diole sind Ethylenglykol, 1,2- und 1,3-Propandiol, 1,3- und 1 ,4-Butandiol, 1,6- Hexandiol, 1,8-Octandiol, Neopentylglykol, 1,4-Bishydroxymethylcyclohexan, 2-Methyl-l,3- propandiol, 2,2,4-Trimethylpentandiol-l,3, Dipropylenglykol, Polypropylenglykole, Dibutylenglykol, Polybutylenglykole, Bisphenole und lactonmodifizierte Diole der vorstehend genannten Art. Examples of such diols are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2- Methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1,3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenols and lactone-modified diols of the type mentioned above.
Statt oder zusätzlich zu reinen Polycarbonatdiolen können auch Polyether-Polycarbonatdiole eingesetzt werden, welche beispielsweise durch Copolymerisation von Alkylenoxiden, wie zum Beispiel Propylenoxid, mit CO2 erhältlich sind. Instead of or in addition to pure polycarbonate diols, it is also possible to use polyether-polycarbonate diols, which are obtainable, for example, by copolymerizing alkylene oxides, such as propylene oxide, with CO 2.
Herstellungsverfahren der Polyole sind beispielsweise von Ionescu in„Chemistry and Technology of Polyols for Polyurethanes“, Rapra Technology Limited, Shawbury 2005, S.55 ff. (Kap. 4: Oligo- Polyols for Elastic Polyurethanes), S. 263 ff. (Kap. 8: Polyester Polyols for Elastic Polyurethanes) und insbesondere auf S.321 ff. (Kap. 13: Polyether Polyols for Rigid Polyurethane Foams) und S.419 ff. (Kap. 16: Polyester Polyols for Rigid Polyurethane Foams) beschrieben worden. Es ist auch möglich, Polyester- und Polyetherpolyole über Glykolyse von geeigneten Polymer- Rezyklaten zu gewinnen. Geeignete Polyether-Polycarbonatpolyole und ihre Herstellung werden beispielsweise in der EP 2 910 585 Al, [0024] - [0041], beschrieben. Beispiele zu Polycarbonatpolyolen und ihre Herstellung finden sich unter anderem in der EP 1 359 177 Al. Die Herstellung geeigneter Polyetheresterpolyole ist unter anderem in der WO 2010/043624 A und in der EP 1 923 417 A beschrieben. Production processes for the polyols are described, for example, by Ionescu in “Chemistry and Technology of Polyols for Polyurethanes”, Rapra Technology Limited, Shawbury 2005, page 55 ff. (Chapter 4: Oligo- Polyols for Elastic Polyurethanes), page 263 ff. (Ch . 8: Polyester Polyols for Elastic Polyurethanes) and in particular on page 321 ff. (Chapter 13: Polyether Polyols for Rigid Polyurethane Foams) and page 419 ff. (Chapter 16: Polyester Polyols for Rigid Polyurethane Foams). It is also possible to obtain polyester and polyether polyols from suitable polymer recyclates via glycolysis. Suitable polyether-polycarbonate polyols and their production are described, for example, in EP 2 910 585 A1, [0024] - [0041]. Examples of polycarbonate polyols and their production can be found, inter alia, in EP 1 359 177 A1. The production of suitable polyetherester polyols is described in WO 2010/043624 A and in EP 1 923 417 A, among others.
Falls zur Herstellung der PUR/PIR-Hartschäume niedermolekulare isocyanat-reaktiven Verbindungen Anwendung finden, z.B. in der Funktion als Kettenverlängerungs mittel und/oder Vernetzungsmittel, kommen diese zweckmäßigerweise in einer Menge von maximal 6 Gew.-%, bezogen auf das Gesamtgewicht der Polyolformulierung A zum Einsatz. Verbindungen, die aufgrund ihrer Struktur sowohl unter die Definition der Komponente A3 als auch unter eine der Definitionen der oben beschriebenen Polyolverbindungen Al oder A2 fallen, werden mengenmäßig zu der Al oder A2 und nicht zu der Komponente A3 gerechnet. If low molecular weight isocyanate-reactive compounds are used to produce the PUR / PIR rigid foams, e.g. in the function of chain lengthening agents and / or crosslinking agents, these are expediently used in an amount of a maximum of 6% by weight, based on the total weight of the polyol formulation A. for use. Compounds which, due to their structure, fall under the definition of component A3 as well as under one of the definitions of the above-described polyol compounds Al or A2, are counted in quantitative terms as Al or A2 and not with component A3.
Die Mischung der Polyole Al und A2 weist bevorzugt eine Viskosität < 4 Pa*s auf, insbesondere eine Viskosität von 2 - 4 Pa*s. Die Mischung der Polyole Al und A2 weist bevorzugt eine OH-Zahl von < 260 mg KOH/g auf, insbesondere von < 230 mg KOH/g The mixture of the polyols A1 and A2 preferably has a viscosity of <4 Pa * s, in particular a viscosity of 2-4 Pa * s. The mixture of the polyols Al and A2 preferably has an OH number of <260 mg KOH / g, in particular <230 mg KOH / g
Das Massenverhältnis von Polyesterpolyolen Al zu Polyethylenglykolen A2 in der Poylolformulierung beträgt bevorzugt 2-10. The mass ratio of polyester polyols A1 to polyethylene glycols A2 in the polyol formulation is preferably 2-10.
Im Rahmen dieser Anmeldung ist mit der singulären Bezeichnung der Komponenten -„Polyol“, „Polyesterpolyol“ usw. - jeweils die Mischung aller Komponenten gemeint, die unter die entsprechende Definition fallen. In the context of this application, the singular designation of the components - “polyol”, “polyester polyol”, etc. - means the mixture of all components that fall under the corresponding definition.
Bei den Verbindungen A4 handelt es sich um eine oder mehrere Verbindungen ausgewählt aus der Gruppe bestehend aus The compounds A4 are one or more compounds selected from the group consisting of
A4 0,2-5 Gew.-%, bezogen auf die Polyolformulierung A, einer oder mehrerer Verbindungen ausgewählt aus der Gruppe bestehend aus A4 0.2-5% by weight, based on the polyol formulation A, of one or more compounds selected from the group consisting of
A4-1 eines Polyethylenglykol-2,4,6-trialkylphenylethern (Struktur I mit R5, R6, R7 = H, CI - bis C8-Alkyl) und A4-1 of a polyethylene glycol-2,4,6-trialkylphenyl ether (structure I with R5, R6, R7 = H, CI - to C8-alkyl) and
A4-2 Polyethylenglykol-2,4,6-triaralkylphenylethern (Struktur I mit R5, R6 und/oder R7 = Aryl) und A4-2 polyethylene glycol-2,4,6-triaralkylphenyl ethers (structure I with R5, R6 and / or R7 = aryl) and
A4-3 Polyethylenglykol-alkylphenylethern (Struktur II) A4-3 polyethylene glycol alkyl phenyl ethers (structure II)
Struktur I Structure i
RI, R2, R3, R4 = H, Cl-C4-Alkyl, RI, R2, R3, R4 = H, Cl-C4-alkyl,
R5, R6, R7 = H, CI- bis C8-Alkyl, Aryl R5, R6, R7 = H, CI- to C8-alkyl, aryl
n = 7-20, bevorzugt 10-18, besonders bevorzugt 11-15 n = 7-20, preferably 10-18, particularly preferably 11-15
Struktur II Structure II
RI, R3 = H, C(CH3)2CR4R5R6 RI, R3 = H, C (CH 3) 2 CR4R5R6
R2 = C(CH3)2CR4R5R6 R2 = C (CH 3) 2 CR4R5R6
R4, R5 = H oder CH3 R4, R5 = H or CH 3
R6 = C2- bis C5-Alkyl, Aryl R6 = C2 to C5 alkyl, aryl
n = 3-8 wobei die Verbindungen A4 ein Molgewicht von unter 1,5 kg/mol und ein Gehalt von 25-70% Ethylenoxid, bevorzugt 40-60% Ethylenoxid aufweisen. n = 3-8 where the compounds A4 have a molecular weight of less than 1.5 kg / mol and a content of 25-70% ethylene oxide, preferably 40-60% ethylene oxide.
wobei die Verbindungen A4 ein Molgewicht von unter 1,5 kg/mol und ein Gehalt von 25-70% Ethylenoxid, bevorzugt 40-60% Ethylenoxid aufweisen. the compounds A4 having a molecular weight of less than 1.5 kg / mol and a content of 25-70% ethylene oxide, preferably 40-60% ethylene oxide.
Bevorzugte Verbindungen A4 sind in Tabelle 1 gezeigt und sind solche mit der Struktur IV (fällt unter die Definition der Verbindungen A4-2), Struktur V (fällt unter die Definition der Verbindungen A4-1) und Struktur VI (fällt unter die Definition der Verbindungen A4-3). Preferred compounds A4 are shown in Table 1 and are those with structure IV (falls under the definition of compounds A4-2), structure V (falls under the definition of compounds A4-1) and structure VI (falls under the definition of compounds A4-3).
abelle 1 abelle 1
Gegebenenfalls können neben den Verbindungen A4 auch noch ein oder mehrere weitere Additive als Komponente A5 eingesetzt werden. Beispiele für die Komponente A5 sind oberflächenaktive Substanzen, Schaumstabilisatoren, Zellregler, Flammschutzmittel, Füllstoffe, Farbstoffe, Pigmente, Hydrolyseschutzmittel, fungistatische und bakteriostatisch wirkende Substanzen. In addition to the compounds A4, one or more further additives can optionally also be used as component A5. Examples of component A5 are surface-active substances, foam stabilizers, cell regulators, flame retardants, fillers, dyes, pigments, hydrolysis inhibitors, fungistatic and bacteriostatic substances.
Als oberflächenaktive Substanzen kommen z.B. Verbindungen in Betracht, welche zur Unterstützung der Homogenisierung der Ausgangsstoffe dienen und gegebenenfalls auch geeignet sind, die Zellstruktur der Kunststoffe zu regulieren. Genannt seien beispielsweise Emulgatoren, wie die Natriumsalze von Ricinusölsulfaten oder von Fettsäuren sowie Salze von Fettsäuren mit Aminen, z.B. ölsaures Diethylamin, stearinsaures Diethanolamin, ricinolsaures Diethanolamin, Salze von Sulfonsäuren, z.B. Alkali- oder Ammoniumsalze von Dodecylbenzol- oder Dinaphthylmethandisulfonsäure und Ricinolsäure; Schaumstabilisatoren, wie Siloxanoxalkylen- Mischpolymerisate und andere Organopolysiloxane, oxethylierte Alkylphenole unterschiedlich von A4, oxethylierte Fettalkohole, Paraffinöle, Rizinusöl- bzw. Ricinolsäureester, Türkischrotöl und Erdnussöl, und Zellregler, wie Paraffine, Fettalkohole und Dimethylpolysiloxane. Zur Verbesserung der Emulgierwirkung, der Zellstruktur und/oder Stabilisierung des Schaumes eignen sich ferner die oben beschriebenen oligomeren Acrylate mit Polyoxyalkylen- und Fluoralkanresten als Seitengruppen. Emulgatoren, welche in ihrer Struktur unter die Definition der Komponente A4 fallen, werden mengenmäßig auch zu der Komponente A4 und nicht zu der Komponente A5 gerechnet. Suitable surface-active substances are, for example, compounds which serve to support the homogenization of the starting materials and, if necessary, are also suitable for regulating the cell structure of the plastics. Examples include emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, e.g. oleic diethylamine, stearic acid diethanolamine, ricinolate diethanolamine, salts of sulfonic acids, e.g. alkali or ammonium salts of dodecylbenzylbenzyl benzene or dinaphonic acid; Foam stabilizers such as siloxane oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols different from A4, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and peanut oil, and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes. The above-described oligomeric acrylates with polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying effect, the cell structure and / or stabilizing the foam. Emulsifiers which, in terms of their structure, fall under the definition of component A4 are also counted in terms of quantity as component A4 and not as component A5.
Als Füllstoffe, insbesondere verstärkend wirkende Füllstoffe, sind die an sich bekannten, üblichen organischen und anorganischen Füllstoffe, Verstärkungsmittel, Beschwerungsmittel, Mittel zur Verbesserung des Abriebverhaltens in Anstrichfarben, Beschichtungsmittel usw. zu nennen. Im Einzelnen seien beispielhaft genannt: anorganische Füllstoffe wie silikatische Mineralien, beispielsweise Schichtsilikate wie z. B. Antigorit, Serpentin, Sepiolit, Hornblenden, Amphibole, Chrisotil, Montmorillonit und Talkum, Metalloxide, wie Kaolin, Aluminiumoxide, Titanoxide und Eisenoxide, Metallsalze, wie Kreide, Huntit, Schwerspat und anorganische Pigmente, wie Magnetit, Goethit, Cadmiumsulfid und Zinksulfid, sowie Glas u.a. sowie natürliche und synthetische faserförmige Mineralien wie Wollastonit, Metall- und insbesondere Glasfasern verschiedener Fänge, die gegebenenfalls geschlichtet sein können. Als organische Füllstoffe kommen beispielsweise in Betracht: Kohle, Melamin, Kolophonium, Cyclopentadienylharze und Pfropfpolymerisate sowie Cellulosefasern, Polyamid-, Polyacrylnitril-, Polyurethan-, Polyesterfasern auf der Grundlage von aromatischen und/oder aliphatischen Dicarbonsäureestern und Kohlenstofffasern. Zur Herstellung der PUR-/PIR -Hartschäume wird bevorzugt auch ein Flammschutzmittel A5 eingesetzt. The usual organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating agents, etc., known per se, are to be mentioned as fillers, in particular reinforcing fillers. The following may be mentioned in detail: inorganic fillers such as silicate minerals, for example sheet silicates such as. B. antigorite, serpentine, sepiolite, hornblende, amphibole, chrismotile, montmorillonite and talc, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts such as chalk, huntite, barite and inorganic pigments such as magnetite, goethite, cadmium sulfide and zinc sulfide, as well as glass, among other things, as well as natural and synthetic fibrous minerals such as wollastonite, metal and especially glass fibers of various catches, which can optionally be sized. Examples of organic fillers are: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers and cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and carbon fibers. A flame retardant A5 is also preferably used to produce the PUR / PIR rigid foams.
Flammschutzmittel sind dem Fachmann im Prinzip bekannt und beispielsweise in „Kunststoffhandbuch“, Band 7 „Polyurethane“, Kapitel 6.1 beschrieben. Dies können beispielsweise halogenierte Polyester und Polyole, brom- und chlorhaltige Paraffine oder Phos phorverbindungen, wie zum Beispiel die Ester der Orthophosphorsäure und der Metaphosphor säure, die ebenfalls Halogen enthalten können, sein. Bevorzugt werden bei 298 K flüssige Flammschutzmittel gewählt. Beispiele sind Triethylphosphat, Diethylethanphosphonat, Kresyldiphenylphosphat und andere Triarylphosphate, Dimethylpropanphosphonat, Hydroxymethylphosphonate und Tris(ß-chlorisopropyl)phosphat. Besonders bevorzugt sind Flammschutzmittel ausgewählt aus der Gruppe bestehend aus Tris(chloro-2-propyl)-phosphat (TCPP) und Triethylphosphat (TEP) und Mischungen daraus. Bevorzugt werden Flammschutzmittel in einer Menge von 1 bis 30 Gew.-%, besonders bevorzugt 5 bis 30 Gew.- %, bezogen auf das Gesamtgewicht der Isocyanat-reaktiven Zusammensetzung A) eingesetzt so dass ein Phosphorgehalt im Schaumstoff von 0,4-1, 3 Gew.-% erreicht wird. Um bestimmte Eigenschaftsprofile (Viskosität, Sprödigkeit, Brennbarkeit, Halogengehalt etc.) zu erzielen, kann es auch günstig sein, unterschiedliche Flammschutzmittel miteinander zu kombinieren. In bestimmten Ausführungsformen ist die Anwesenheit von Triethylphosphat (TEP) im Flammschutzmittelgemisch oder als alleiniges Flammschutzmittel besonders vorteilhaft. Flame retardants are known in principle to those skilled in the art and are described, for example, in “Kunststoffhandbuch”, Volume 7 “Polyurethane”, Chapter 6.1. These can be, for example, halogenated polyesters and polyols, bromine- and chlorine-containing paraffins or phosphorus compounds, such as, for example, the esters of orthophosphoric acid and metaphosphoric acid, which can also contain halogen. Liquid flame retardants at 298 K are preferred. Examples are triethyl phosphate, diethyl ethane phosphonate, cresyl diphenyl phosphate and other triaryl phosphates, dimethyl propane phosphonate, hydroxymethyl phosphonates and tris (β-chloroisopropyl) phosphate. Flame retardants selected from the group consisting of tris (chloro-2-propyl) phosphate (TCPP) and triethyl phosphate (TEP) and mixtures thereof are particularly preferred. Flame retardants are preferably used in an amount of 1 to 30% by weight, particularly preferably 5 to 30% by weight, based on the total weight of the isocyanate-reactive composition A) so that a phosphorus content in the foam of 0.4-1, 3 wt .-% is achieved. In order to achieve certain property profiles (viscosity, brittleness, flammability, halogen content, etc.), it can also be beneficial to combine different flame retardants with one another. In certain embodiments, the presence of triethyl phosphate (TEP) in the flame retardant mixture or as the sole flame retardant is particularly advantageous.
Die Polyolformulierung enthält weiterhin A6 maximal 2 Gew.-%, bevorzugt maximal 2,0 Gew.-%, insbesondere bevorzugt maximal 1,2 Gew.-% Wasser, bezogen auf die Gesamtmasse der Polyolformulierung A. The polyol formulation furthermore contains A6 a maximum of 2% by weight, preferably a maximum of 2.0% by weight, particularly preferably a maximum of 1.2% by weight of water, based on the total mass of the polyol formulation A.
Die zahlenmittlere Molmasse Mn (auch: Molekulargewicht) wird im Rahmen dieser Erfindung durch Gelpermeationschromatographie nach DIN 55672-1 (August 2007) bestimmt. The number average molar mass M n (also: molecular weight) is determined in the context of this invention by gel permeation chromatography according to DIN 55672-1 (August 2007).
Die OH-Zahl (auch: Hydroxylzahl) gibt im Falle eines einzelnen zugesetzten Polyols dessen OH- Zahl an. Angaben der OH-Zahl für Mischungen beziehen sich auf die zahlenmittlere OH-Zahl der Mischung, berechnet aus den OH-Zahlen der einzelnen Komponenten in ihren jeweiligen molaren Anteilen. Die OH-Zahl gibt die Menge an Kaliumhydroxid in Milligramm an, welche der bei einer Acetylierung von einem Gramm Substanz gebundenen Menge Essigsäure gleichwertig ist. Die OH- Zahl wird im Rahmen der vorliegenden Erfindung nach der Norm DIN 53240-1 (Juni 2013) bestimmt. The OH number (also: hydroxyl number) indicates the OH number in the case of an individually added polyol. Information on the OH number for mixtures relates to the number-average OH number of the mixture, calculated from the OH numbers of the individual components in their respective molar proportions. The OH number indicates the amount of potassium hydroxide in milligrams, which is equivalent to the amount of acetic acid bound during acetylation of one gram of substance. In the context of the present invention, the OH number is determined in accordance with the DIN 53240-1 standard (June 2013).
„Funktionalität“ bezeichnet im Rahmen der vorliegenden Erfindung die theoretische, aus den bekannten Einsatzstoffen und deren Mengenverhältnissen berechnete mittlere Funktionalität (Anzahl an gegenüber Isocyanaten bzw. gegenüber Polyolen reaktiven Funktionen im Molekül bzw. gemittelt über die jeweilige Mischung der Moleküle). In the context of the present invention, “functionality” denotes the theoretical average functionality calculated from the known starting materials and their proportions (Number of functions that are reactive towards isocyanates or towards polyols in the molecule or averaged over the respective mixture of molecules).
Das Äquivalentgewicht gibt das Verhältnis der zahlenmittleren Molekularmasse und der Funktionalität der Isocyanat-reaktiven Komponente an. Die Angaben des Äquivalentgewichts für Mischungen berechnen sich aus Äquivalentgewichten der einzelnen Komponenten in ihren jeweiligen molaren Anteilen und beziehen sich auf das zahlenmittlere Äquivalentgewicht der Mischung. The equivalent weight indicates the ratio of the number average molecular mass and the functionality of the isocyanate-reactive component. The equivalent weight data for mixtures are calculated from equivalent weights of the individual components in their respective molar proportions and relate to the number-average equivalent weight of the mixture.
Als Treibmittel C kann physikalisches Treibmittel eingesetzt werden, wie beispielsweise niedrig siedende organische Verbindungen, wie z.B. Kohlenwasserstoffe, halogenierte Kohlenwasserstoffe, Ether, Ketone, Carbonsäureester oder Kohlensäureester. Geeignet sind insbesondere organische Verbindungen, welche gegenüber der Isocyanatkomponente B inert sind und Siedepunkte unter 100 °C, vorzugsweise unter 50 °C bei Atmosphärendruck aufweisen. Diese Siedepunkte haben den Vorteil, dass die organischen Verbindungen unter dem Einfluss der exothermen Polyadditionsreaktion verdampfen. Beispiele solcher, vorzugsweise verwendeten organischen Verbindungen sind Alkane, wie Heptan, Hexan, n- und iso-Pentan, vorzugsweise technische Gemische aus n- und iso-Pentanen, n- und iso-Butan und Propan, Cycloalkane, wie z. B. Cyclopentan und/oder Cyclohexan, Ether, wie z. B. Furan, Dimethylether und Diethylether, Ketone, wie z. B. Aceton und Methylethylketon, Carbonsäurealkylester, wie z. B. Methylformiat, Dimethyloxalat und Ethylacetat und halogenierte Kohlenwasserstoffe, wie z. B. Methylenchlorid, Difluormethan, Trifluormethan, Difluorethan, Tetrafluorethan, und Heptafluorpropan. Bevorzugt werden keine Treibmittel eingesetzt, für die eine für die Ozonschicht der Erde schädliche Wirkung bekannt ist. Auch bevorzugt ist der Einsatz von (hydro)fluorierten Olefinen, wie z. B. HFO 1233zd(E) (Trans-l-chlor-3,3,3-trifluor-l-propen) oder HFO 1336mzz(Z) (cis-1, 1,1, 4,4,4-Physical blowing agents can be used as blowing agent C, such as, for example, low-boiling organic compounds such as hydrocarbons, halogenated hydrocarbons, ethers, ketones, carboxylic acid esters or carbonic acid esters. Organic compounds which are inert to isocyanate component B and have boiling points below 100 ° C., preferably below 50 ° C. at atmospheric pressure are particularly suitable. These boiling points have the advantage that the organic compounds evaporate under the influence of the exothermic polyaddition reaction. Examples of such, preferably used organic compounds are 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. B. cyclopentane and / or cyclohexane, ethers, such as. B. furan, dimethyl ether and diethyl ether, ketones, such as. B. acetone and methyl ethyl ketone, carboxylic acid alkyl esters, such as. B. methyl formate, dimethyl oxalate and ethyl acetate and halogenated hydrocarbons, such as. B. methylene chloride, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, and heptafluoropropane. It is preferred not to use propellants that are known to have a harmful effect on the earth's ozone layer. The use of (hydro) fluorinated olefins, such as. B. HFO 1233zd (E) (Trans-l-chloro-3,3,3-trifluoro-l-propene) or HFO 1336mzz (Z) (cis-1, 1,1, 4,4,4-
Hexafluor-2-buten) oder Additive wie FA 188 von 3M (l,l,l,2,3,4,5,5,5-Nonafluor-4- (trifluormethyl)pent-2-en). Auch Gemische zweier oder mehrerer der genannten organischen Verbindungen können verwendet werden. Die organischen Verbindungen können dabei auch in Form einer Emulsion aus kleinen Tröpfchen eingesetzt werden. Hexafluoro-2-butene) or additives such as FA 188 from 3M (l, l, l, 2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) pent-2-en). Mixtures of two or more of the organic compounds mentioned can also be used. The organic compounds can also be used in the form of an emulsion composed of small droplets.
Als Treibmittel C kann auch chemisches Treibmittel, wie beispielsweise Wasser, Carbonsäure und deren Gemische, verwendet werden. Diese reagieren mit Isocyanatgruppen unter Bildung des Treibgases, wie beispielsweise im Falle von Wasser entsteht dabei Kohlendioxid und im Falle von z. B. Ameisensäure entsteht dabei Kohlendioxid und Kohlenstoffmonoxid. Als Carbonsäure wird bevorzugt mindestens eine Verbindung, ausgewählt aus der Gruppe bestehend aus Ameisensäure, Essigsäure, Oxalsäure und Ricinolsäure, eingesetzt. Als chemisches Treibmittel wird besonders bevorzugt Wasser eingesetzt. Chemical blowing agents, such as, for example, water, carboxylic acid and mixtures thereof, can also be used as blowing agent C. These react with isocyanate groups to form the propellant gas, as in the case of water, for example, carbon dioxide is formed and in the case of z. B. formic acid produces carbon dioxide and carbon monoxide. At least one compound selected from the group consisting of formic acid, acetic acid, oxalic acid and ricinoleic acid is preferably used as the carboxylic acid. Water is particularly preferably used as the chemical blowing agent.
Vorzugsweise werden keine halogenierten Kohlenwasserstoffe als Treibmittel verwendet. Als Treibmittel C wird mindestens eine Verbindung, ausgewählt aus der Gruppe bestehend aus physikalischen und chemischen Treibmittel, eingesetzt. Bevorzugt wird nur physikalisches Treibmittel eingesetzt. In einer bevorzugten Ausführungsform weisen die eingesetzten Treibmittel C ein mittleres global warming potential (GWP) von < 120, bevorzugt ein GWP von < 20 auf. Preferably, no halogenated hydrocarbons are used as blowing agents. At least one compound selected from the group consisting of physical and chemical blowing agents is used as blowing agent C. Only physical blowing agent is preferably used. In a preferred embodiment, the blowing agents C used have an average global warming potential (GWP) of <120, preferably a GWP of <20.
Als Katalysator D zur Herstellung der PUR-/PIR-Hartschäume werden Verbindungen verwendet, welche die Reaktion der reaktiven Wasserstoffatome, insbesondere Hydroxylgruppen enthaltenden Verbindungen mit der Isocyanatkomponente B beschleunigen, wie z. B. tertiäre Amine oder Metallsalze. Die Katalysatorkomponenten können dem Reaktionsgemisch zudosiert oder auch ganz oder teilweise in der Polyolformulierung A vorgelegt werden. As a catalyst D for the production of PUR / PIR rigid foams, compounds are used which accelerate the reaction of the reactive hydrogen atoms, in particular compounds containing hydroxyl groups, with the isocyanate component B, such as. B. tertiary amines or metal salts. The catalyst components can be metered into the reaction mixture or completely or partially in the polyol formulation A.
Verwendet werden beispielsweise tertiäre Amine, wie Triethylamin, Tributylamin, Dimethylbenzylamin, Dicyclohexylmethylamin, Dimethylcyclohexylamin, N, N ,N', N'-For example, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N ', N'-
Tetramethyldiaminodiethylether, Bis-(dimethylaminopropyl)-harnstoff, N-Methyl- bzw. N- Ethylmorpholin, N-Cyclohexylmorpholin, N,N,N',N'-Tetramethylethylendiamin, N,N,N,N- Tetramethylbutandiamin, N, N, N, N-Tetramethylhexandiamin-1,6, Pentamethyldiethylentriamin, Bis[2-(dimethylamino)ethyl]ether, Dimethylpiperazin, N-Dimethylaminoethylpiperidin, 1,2- Dimethyl-imidazol, l-Azabicyclo-(3,3,0)-octan, l,4-Diaza-bi-cyclo-(2,2,2)-octan (Dabco) und Alkanolaminverbindungen, wie Triethanolamin, Triisopropanolamin, N-Methyl- und N- Ethyldiethanolamin, Dimethylaminoethanol, 2-(N,N-Dimethylaminoethoxy)ethanol, N,N',N"-Tris- (dialkylaminoalkyl)hexahydrotriazin, z.B. N,N',N"-Tris-(dimethylaminopropyl)hexahydrotriazin und Triethylendiamin. Tetramethyldiaminodiethylether, bis (dimethylaminopropyl) urea, N-methyl- or N-ethylmorpholine, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N, N-tetramethylbutanediamine, N, N, N, N-Tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, bis [2- (dimethylamino) ethyl] ether, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo- (3,3,0) -octane , 1,4-Diaza-bi-cyclo- (2,2,2) -octane (Dabco) and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine, dimethylaminoethanol, 2- (N, N-dimethylaminoethoxy ) ethanol, N, N ', N "-Tris- (dialkylaminoalkyl) hexahydrotriazine, for example N, N', N" -Tris- (dimethylaminopropyl) hexahydrotriazine and triethylenediamine.
Es können auch Metallsalze wie z. B. Alkali- oder Übergangsmetallsalze eingesetzt werden. Als Übergangsmetallsalze werden beispielsweise Zink-, Wismut-, Eisen-, Blei- oder bevorzugt Zinnsalze eingesetzt. Beispiele für eingesetzte Übergangsmetallsalze sind Eisen(II)-chlorid, Zinkchlorid, Bleioctoat, Zinndioctoat, Zinndiethylhexoat und Dibutylzinndilaurat. Besonders bevorzugt ist das Übergangsmetallsalz ausgewählt aus mindestens einer Verbindung aus der Gruppe bestehend aus Zinndioctoat, Zinndiethylhexoat und Dibutylzinndilaurat. Beispiele für Alkalimetallsalze sind Alkalialkoholate, wie z. B. Natriummethylat und Kaliumisopropylat, Alkalicarboxylate, wie z. B. Kaliumacetat, sowie Alkalimetallsalze von langkettigen Fettsäuren mit 10 bis 20 C-Atomen und gegebenenfalls seitenständigen OH-Gruppen. Bevorzugt als Alkalimetallsalz werden ein oder mehrere Alkalicarboxylate eingesetzt. It can also be metal salts such. B. alkali or transition metal salts can be used. The transition metal salts used are, for example, zinc, bismuth, iron, lead or, preferably, tin salts. Examples of transition metal salts used are iron (II) chloride, zinc chloride, lead octoate, tin dioctoate, tin diethylhexoate and dibutyltin dilaurate. The transition metal salt is particularly preferably selected from at least one compound from the group consisting of tin dioctoate, tin diethylhexoate and dibutyltin dilaurate. Examples of alkali metal salts are alkali alcoholates, such as. B. sodium methylate and potassium isopropylate, alkali metal carboxylates, such as. B. potassium acetate, and alkali metal salts of long-chain fatty acids with 10 to 20 carbon atoms and optionally pendant OH groups. One or more alkali metal carboxylates are preferably used as the alkali metal salt.
Als Katalysator D kommen ferner in Betracht: Amidine, wie z. B. 2,3-Dimethyl-3,4,5,6- tetrahydropyrimidin, Tetraalkylammoniumhydroxide, wie z. B. Tetramethylammonium-hydroxid, Alkalihydroxide, wie z. B. Natriumhydroxid, und Tetraalkylammonium- oder Phosphoniumcarboxylate. Darüber hinaus sind Mannichbasen und Salze von Phenolen geeignete Katalysatoren. Es besteht auch die Möglichkeit, die Reaktionen ohne Katalyse ablaufen zu lassen. In diesem Fall wird die katalytische Aktivität von mit Aminen gestarteten Polyolen ausgenutzt. Also suitable as catalyst D are: amidines, such as. B. 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammonium hydroxides, such as. B. tetramethylammonium hydroxide, alkali hydroxides, such as. B. sodium hydroxide, and tetraalkylammonium or phosphonium carboxylates. Mannich bases and salts of phenols are also suitable Catalysts. It is also possible to run the reactions without catalysis. In this case, the catalytic activity of polyols started with amines is used.
Wird beim Verschäumen ein größerer Polyisocyanatüberschuss verwendet, kommen als Katalysatoren für die Trimerisierungsreaktion der überschüssigen NCO-Gruppen untereinander ferner in Betracht: Isocyanuratgruppen bildende Katalysatoren, beispielsweise Ammoniumionen oder Alkalimetallsalze, speziell Ammonium- oder Alkalimetallcarboxylate, alleine oder in Kombination mit tertiären Aminen. Die Isocyanurat-Bildung führt zu besonders flammwidrigen PIR-Hartschäumen. If a larger excess of polyisocyanate is used during foaming, the following are also possible catalysts for the trimerization reaction of the excess NCO groups with one another: Catalysts forming isocyanurate groups, for example ammonium ions or alkali metal salts, especially ammonium or alkali metal carboxylates, alone or in combination with tertiary amines. The isocyanurate formation leads to particularly flame-retardant PIR rigid foams.
Die Katalysatorkomponenten können dem Reaktionsgemisch zudosiert oder auch ganz oder teilweise in der Polyolformulierung A vorgelegt werden. The catalyst components can be metered into the reaction mixture or completely or partially in the polyol formulation A.
Die Reaktivität des Reaktionsgemisches wird i.d.R. mittels der Katalysatorkomponente auf die Bedürfnisse angepasst. So verlangt die Herstellung von dünnen Platten ein Reaktionsgemisch mit einer höheren Reaktivität als die Herstellung von dickeren Platten. Typische Parameter sind die Startzeit und die Abbindezeit als Maß für die Zeit, zu der das Reaktionsgemisch zu reagieren beginnt, und für den Zeitpunkt, an dem ein hinreichend stabiles Polymernetzwerk gebildet ist. The reactivity of the reaction mixture is usually adapted to the needs by means of the catalyst component. The production of thin plates requires a reaction mixture with a higher reactivity than the production of thicker plates. Typical parameters are the start time and the setting time as a measure of the time at which the reaction mixture begins to react and for the point in time at which a sufficiently stable polymer network is formed.
Die oben genannten Katalysatoren können alleine oder in Kombination miteinander eingesetzt werden. The above-mentioned catalysts can be used alone or in combination with one another.
Als geeignete Isocyanatkomponente B kommen z. B. Polyisocyanate, d. h. Isocyanate mit einer NCO-Funktionalität von mindestens 2, in Frage. Beispiele solcher geeigneten Polyisocyanate sindSuitable isocyanate component B are, for. B. polyisocyanates, d. H. Isocyanates with an NCO functionality of at least 2 are possible. Examples of such suitable polyisocyanates are
1.4-Butylendiisocyanat, 1,5-Pentandiisocyanat, 1,6-Hexamethylendiisocyanat (HDI), Isophorondiisocyanat (IPDI), 2,2,4- und/oder 2,4,4-Trimethylhexamethylendiisocyanat, die isomeren Bis(4,4'- isocyanatocyclohexyl)methane oder deren Mischungen beliebigen Isomerengehalts, 1 ,4-Cyclohexylendiisocyanat, 1 ,4-Phenylendiisocyanat, 2,4- und/oder 2,6- Toluylendiisocyanat (TDI), 1,5-Naphthylendiisocyanat, 2,2'- und/oder 2,4'- und/oder 4,4'- Diphenylmethandiisocyanat (MDI) und/oder höhere Homologe (polymeres MDI), 1,3- und/oder1,4-butylene diisocyanate, 1,5-pentane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'- isocyanatocyclohexyl) methanes or mixtures thereof with any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and / or higher homologues (polymeric MDI), 1,3- and / or
1.4-Bis-(2-isocyanato-prop-2-yl)-benzol (TMXDI), l,3-Bis-(isocyanatomethyl)benzol (XDI), sowie Alkyl-2,6-diisocyanatohexanoate (Fysindiisocyanate) mit CI- bis C6-Alkylgruppen. Bevorzugt wird die Isocyanatkomponente B ausgewählt aus mindestens einer Verbindung aus der Gruppe bestehend aus MDI, polymeres MDI und TDI. 1,4-bis- (2-isocyanato-prop-2-yl) -benzene (TMXDI), 1,3-bis- (isocyanatomethyl) benzene (XDI), as well as alkyl-2,6-diisocyanatohexanoate (fysine diisocyanate) with CI- bis C6 alkyl groups. Isocyanate component B is preferably selected from at least one compound from the group consisting of MDI, polymeric MDI and TDI.
Neben den vorstehend genannten Polyisocyanaten können anteilig auch modifizierte Diisocyanate mit Uretdion-, Isocyanurat-, Urethan-, Carbodiimid-, Uretonimin-, Allophanat-, Biuret-, Amid-, Iminooxadiazindion- und/oder Oxadiazintrionstruktur sowie nicht-modifiziertes Polyisocyanat mit mehr als 2 NCO-Gruppen pro Molekül wie zum Beispiel 4-Isocyanatomethyl-l,8-octandiisocyanat (Nonantriisocyanat) oder Triphenylmethan-4,4',4"-triisocyanat, mit eingesetzt werden. Statt oder zusätzlich zu den oben genannten Polyisocyanaten können auch geeignete NCO- Präpolymere als Isocyanatkomponente B eingesetzt werden. Die Präpolymere sind herstellbar durch Umsetzung eines oder mehrerer Polyisocyanate mit einem oder mehreren Polyolen, entsprechend den unter den Isocyanat-reaktiven Komponenten Al beschriebenen Polyolen. In addition to the above-mentioned polyisocyanates, modified diisocyanates with uretdione, isocyanurate, urethane, carbodiimide, uretonimine, allophanate, biuret, amide, iminooxadiazinedione and / or oxadiazinetrione structure, and unmodified polyisocyanate with more than 2 NCO groups per molecule such as, for example, 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4 ', 4 "-triisocyanate, can also be used. Instead of or in addition to the abovementioned polyisocyanates, suitable NCO prepolymers can also be used as isocyanate component B. The prepolymers can be prepared by reacting one or more polyisocyanates with one or more polyols, corresponding to the polyols described under the isocyanate-reactive components A1.
Für den Einsatz als Polyisocyanat-Komponente sind polymere MDI-Typen im Hartschaum gegenüber monomeren Isocyanaten besonders bevorzugt. For use as a polyisocyanate component, polymeric MDI types in rigid foam are particularly preferred over monomeric isocyanates.
Der NCO-Gehalt der Polyisocyanatkomponente A) beträgt bevorzugt von > 29,0 Gew.-% bis < 33,0 Gew.%, und weist bevorzugt eine Viskosität bei 25 °C von > 80 mPas bis < 2900 mPas, besonders bevorzugt von > 95 mPas bis < 850 mPas bei 25°C auf. The NCO content of the polyisocyanate component A) is preferably from> 29.0% by weight to <33.0% by weight, and preferably has a viscosity at 25 ° C. of> 80 mPas to <2900 mPas, particularly preferably of> 95 mPas to <850 mPas at 25 ° C.
Der NCO-Wert (auch: NCO-Gehalt, Isocyanatgehalt) wird bestimmt mittels EN ISO 11909:2007. Falls nicht anders angegeben, handelt es sich um die Werte bei 25°C. The NCO value (also: NCO content, isocyanate content) is determined using EN ISO 11909: 2007. Unless otherwise stated, the values are at 25 ° C.
Bei Angaben zur Viskosität handelt es sich um die dynamische Viskosität bei 25°C (falls nicht anders angegeben), bestimmt mittels DIN EN ISO 3219:1994-10„Kunststoffe - Polymere/Harze in flüssigem, emulgiertem oder dispergiertem Zustand“. The viscosity information is the dynamic viscosity at 25 ° C (unless otherwise stated), determined using DIN EN ISO 3219: 1994-10 "Plastics - Polymers / Resins in a liquid, emulsified or dispersed state".
Unter der Isocyanat-Kennzahl (auch Kennzahl oder Isocyanat-Index genannt) wird der Quotient aus der tatsächlich eingesetzten Stoffmenge [Mol] an Isocyanat-Gruppen und der tatsächlich eingesetzten Stoffmenge [Mol] an Isocyanat-reaktiven Gruppen, multipliziert mit 100, verstanden: The isocyanate index (also called index or isocyanate index) is understood to mean the quotient of the amount of substance [mol] of isocyanate groups actually used and the amount of substance [mol] of isocyanate-reactive groups actually used, multiplied by 100:
Kennzahl = (Mole Isocyanat-Gruppen / Mole Isocyanat-reaktive Gruppen) * 100 Index = (moles of isocyanate groups / moles of isocyanate-reactive groups) * 100
Erfindungsgemäß beträgt die Kennzahl (Index) im Reaktionsgemisch 150 bis 600, bevorzugt 240 bis 400. Diese Kennzahl hegt besonders bevorzugt in einem Bereich von 240 bis 400 in dem ein hoher Anteil an Polyisocyanuraten (PIR) vorliegt (der Schaumstoff wird als PIR-Schaumstoff oder PUR-/PIR-Schaumstoff bezeichnet) und zu einer höheren Flammwidrigkeit des PUR-/PIR- Schaumstoffs selbst führt. According to the invention, the index in the reaction mixture is 150 to 600, preferably 240 to 400. This index is particularly preferably in a range from 240 to 400 in which a high proportion of polyisocyanurates (PIR) is present (the foam is called PIR foam or PUR / PIR foam) and leads to a higher flame retardancy of the PUR / PIR foam itself.
Der NCO-Wert (auch: NCO-Gehalt, Isocyanatgehalt) wird bestimmt mittels EN ISO 11909 (Mai 2007). Falls nicht anders angegeben, handelt es sich um die Werte bei 25°C. The NCO value (also: NCO content, isocyanate content) is determined using EN ISO 11909 (May 2007). Unless otherwise stated, the values are at 25 ° C.
Die Erfindung betrifft ebenfalls einen PUR-/PIR-Schaumstoff, der durch das erfmdungsgemäße Verfahren hergesteht ist. The invention also relates to a PUR / PIR foam which is produced by the method according to the invention.
Aus den Komponenten A - D wird durch Mischung ein Reaktionsgemisch erzeugt, welche zu dem PUR/PIR-Schaumstoff führt. Die Herstellung erfolgt im Allgemeinen über Vermischung aller Komponenten über übliche Hoch- oder Niederdruckmischköpfe. Die Herstellung der erfindungsgemäßen PUR-/PIR-Hartschäume erfolgt nach dem Fachmann bekannten Einstufenverfahren, bei dem die Reaktionskomponenten kontinuierlich oder diskontinuierlich miteinander zur Reaktion gebracht werden und dann anschließend entweder manuell oder durch Zuhilfenahme maschineller Einrichtungen im Hochdruck- oder Niederdruckverfahren nach Austrag auf ein Transportband oder in geeignete Formen zur Aushärtung gebracht werden. A reaction mixture is produced from components AD by mixing them, which leads to the PUR / PIR foam. Production generally takes place by mixing all the components using conventional high or low pressure mixing heads. The PUR / PIR rigid foams according to the invention are produced according to the one-step process known to those skilled in the art, in which the reaction components are reacted with one another continuously or discontinuously and then either manually or with the aid of mechanical devices in the high-pressure or low-pressure process after discharge onto a conveyor belt or be brought into suitable molds for curing.
Die erfindungsgemäßen PUR-/PIR-Hartschäume finden bevorzugt zur Herstellung von Verbundelementen Verwendung. Üblicherweise findet hier die Verschäumung in kontinuierlicher oder diskontinuierlicher Weise gegen mindestens eine Deckschicht statt. Ein weiterer Gegenstand der Erfindung ist demzufolge die Verwendung eines erfindungsgemäßen PUR-/PIR-Hartschaumes als Isolationsschaumstoff und/oder als Haftvermittler inThe PUR / PIR rigid foams according to the invention are preferably used for the production of composite elements. The foaming usually takes place here in a continuous or discontinuous manner against at least one cover layer. The invention accordingly also relates to the use of a rigid PUR / PIR foam according to the invention as an insulation foam and / or as an adhesion promoter in
Verbundelementen, wobei die Verbundelemente eine einen erfindungsgemäßen PUR-/PIR- Hartschaum umfassende Schicht und mindestens eine Deckschicht umfassen. Die Deckschicht wird hierbei zumindest teilweise von einer den erfindungsgemäßen PUR-/PIR-Hartschaum umfassenden Schicht kontaktiert. Verbundelemente der hier interessierenden Art werden auch als Sandwich-Composite elements, the composite elements comprising a layer comprising a PUR / PIR rigid foam according to the invention and at least one cover layer. The cover layer is at least partially contacted by a layer comprising the PUR / PIR rigid foam according to the invention. Composite elements of the type of interest here are also used as sandwich
Elemente oder Dämmplatten bezeichnet und dienen in der Regel als Bauelemente für den Schallschutz, die Dämmung, zum Hallenbau oder für den Fassadenbau. Die Deckschichten können dabei z.B. Metallbahnen, Kunststoffbahnen oder bis zu 7 mm starke Spanplatten bilden, abhängig vom Einsatzzweck der Verbundelemente. Bei den einen oder zwei Deckschichten kann es sich jeweils um eine flexible Deckschicht, z.B. um eine Aluminium-Folie, Papier, Multischicht- Deckschichten aus Papier und Aluminium oder aus Mineralvließ, und/oder um eine starre Deckschicht, z.B. aus Stahlblech oder Spanplatten, handeln. Elements or insulation boards are called and usually serve as structural elements for soundproofing, insulation, hall construction or facade construction. The cover layers can form, for example, metal sheets, plastic sheets or chipboard panels up to 7 mm thick, depending on the intended use of the composite elements. The one or two cover layers can each be a flexible cover layer, for example an aluminum foil, paper, multi-layer cover layers made of paper and aluminum or mineral fleece, and / or a rigid cover layer, for example made of sheet steel or chipboard .
Beispiele Examples
Einsatzstoffe: Input materials:
Al-l-a Aromatisch / aliphatischer Polyester, f = 2, enthält 1,5 Gew.-% freies Ethylenglykol, Al-l-a aromatic / aliphatic polyester, f = 2, contains 1.5% by weight of free ethylene glycol,
2,4 Gew.-% freies Diethylenglykol (nach Monte-Carlo-Berechnung), OH-Zahl 195 mg KOH/g, Säurezahl 0,55 mg KOH/g. 2.4% by weight of free diethylene glycol (according to Monte Carlo calculation), OH number 195 mg KOH / g, acid number 0.55 mg KOH / g.
A2-a Polyethylenglykol PEG 400, Viskosität 0,12 Pa*s (25°C) A2-a polyethylene glycol PEG 400, viscosity 0.12 Pa * s (25 ° C)
A2-b Umsetzungsprodukt aus Trimethylolpropan und Ethylenoxid im molaren A2-b reaction product of trimethylolpropane and ethylene oxide in the molar
Verhältnis OH: Ethylenoxid von 1:4. Die OH-Zahl beträgt 250 mg KOH/g, die Viskosität beträgt 0,37 Pa*s bei 25°C. OH: ethylene oxide ratio of 1: 4. The OH number is 250 mg KOH / g, the viscosity is 0.37 Pa * s at 25 ° C.
A3-a Umsetzungsprodukt aus Phthalsäureanhydrid und Diethylenglycol im molaren A3-a Reaction product of phthalic anhydride and diethylene glycol in the molar
Verhältnis 1:1 Ratio 1: 1
A4-l-a Polyethylenglycolmono(2,4,6-tri-sec-butylphenyl)ether (Struktur I mit n = 11, A4-l-a polyethylene glycol mono (2,4,6-tri-sec-butylphenyl) ether (structure I with n = 11,
R1=R2=R3 = CH3, R4 = H, R5=R6=R7 = C2H5; 67 Gew.-% Ethylenoxid; HLB = 13) R1 = R2 = R3 = CH3, R4 = H, R5 = R6 = R7 = C 2 H 5; 67 wt% ethylene oxide; HLB = 13)
A4-2-a Polyethylene glycol 2,4,6-tristyrylphenyl ether (n = 10, R1=R2=R3 = CH , R4 = H, A4-2-a Polyethylene glycol 2,4,6-tristyrylphenyl ether (n = 10, R1 = R2 = R3 = CH, R4 = H,
R5=R6=R7 = C6H5;54 Gew.-% Ethylenoxid; HLB = 10) R5 = R6 = R7 = C 6 H 5 ; 54% by weight ethylene oxide; HLB = 10)
A4-2-b Polyethylene glycol 2,4,6-tristyrylphenyl ether (n = 16, R1=R2=R3 = CH;, R4 = H, A4-2-b Polyethylene glycol 2,4,6-tristyrylphenyl ether (n = 16, R1 = R2 = R3 = CH ;, R4 = H,
R5=R6=R7 = C6H5, 65 Gew.-% Ethylenoxid; HLB = 13) R5 = R6 = R7 = C 6 H 5 , 65 wt% ethylene oxide; HLB = 13)
A4-2-C Polyethylene glycol 2,4,6-tristyrylphenyl ether (n = 29, R1=R2=R3 = CH;, R4 = H, A4-2-C Polyethylene glycol 2,4,6-tristyrylphenyl ether (n = 29, R1 = R2 = R3 = CH ;, R4 = H,
R5=R6=R7 = C6H577 Gew.-% Ethylenoxid; HLB = 15) R5 = R6 = R7 = C 6 H 5 77% by weight ethylene oxide; HLB = 15)
A4-2-d Polyethylene glycol 2,4,6-tristyrylphenyl ether (n = 60, R1=R2=R3 = CH;, R4 = H, A4-2-d Polyethylene glycol 2,4,6-tristyrylphenyl ether (n = 60, R1 = R2 = R3 = CH ;, R4 = H,
R5=R6=R7 = C6H5, 87 Gew.-% Ethylenoxid; HLB = 17) R5 = R6 = R7 = C 6 H 5 , 87 wt% ethylene oxide; HLB = 17)
A5-a Polyether-modifiziertes Oligodimethylsiloxan A5-a polyether modified oligodimethylsiloxane
A5-b Mischung aus Levagard® PP und Levagard® TEP im Gewichtsverhältnis 4:1 (beide A5-b Mixture of Levagard® PP and Levagard® TEP in a weight ratio of 4: 1 (both
Lanxess AG) Lanxess AG)
B-a polymeres MDI mit einer Viskosität von 700 mPas bei 25°C und einem NCO-Gehalt von 31,5 Gew.-% (Desmodur® 44V70L, Covestro Deutschland AG) C-a n-Pentan Ba polymeric MDI with a viscosity of 700 mPas at 25 ° C and an NCO content of 31.5% by weight (Desmodur ® 44V70L, Covestro Deutschland AG) Ca n-pentane
D-a 25 Gew .-% Kaliumacetat in Diethylenglycol D-a 25 wt% potassium acetate in diethylene glycol
Herstellung und Prüfung der PUR-/PIR-Hartschäume Manufacture and testing of PUR / PIR rigid foams
Die Flammenausbreitung der PUR-/PIR-Hartschäume wurde durch Kantenbeflammung mit dem Kleinbrennertest gemäß DIN 4102-1 (Mai 1998) an einer 18 cm x 9 cm x 2 cm großen Probe gemessen. Angegeben ist der Wert für die maximale vertikale Flammhöhe in cm. The flame spread of the PUR / PIR rigid foams was measured by applying flame to the edges with the small burner test according to DIN 4102-1 (May 1998) on a sample measuring 18 cm x 9 cm x 2 cm. The value given is for the maximum vertical flame height in cm.
Die Messung der mittleren Wärmefreisetzungsrate und ihres Maximums (MARHE), der CO- Ausbeute und der spezifischen Lichtabsorptionsfläche SEA als Maß für die Rauchgasdichte wurde nach der ISO-Norm 5660-1:1990 mit einem„Cone Calorimeter“ gemessen. Die Probenkörper von 1 dm x 1 dm x 0,3 dm werden dabei 20 min lang durch einen Wärmestrahler mit 50 kW/m2 bestrahlt. Die ermittelte CO-Ausbeute gibt dabei den Durchschnittswert aus zwei Messungen an. The measurement of the mean heat release rate and its maximum (MARHE), the CO yield and the specific light absorption area SEA as a measure of the smoke gas density was measured according to ISO standard 5660-1: 1990 with a “cone calorimeter”. The test specimens measuring 1 dm x 1 dm x 0.3 dm are irradiated for 20 minutes by a heat radiator with 50 kW / m2. The determined CO yield indicates the average value from two measurements.
Die OH-Zahl (Hydroxylzahl) wurde gemäß DIN 53240-1 (Juni 2013) bestimmt. The OH number (hydroxyl number) was determined in accordance with DIN 53240-1 (June 2013).
Die Bestimmung der Säurezahl wurde gemäß DIN EN ISO 2114 (November 2006) durchgeführt. The acid number was determined in accordance with DIN EN ISO 2114 (November 2006).
Die Bestimmung der Viskosität erfolgte auf einem Physica MCR 501 Rheometer der Fa. Anton Paar. Es wurde eine Kegel-Platte-Konfiguration mit einem Abstand von 1 mm gewählt (Messsystem DCP25). Das Polyol (0,1 g) wurde auf der Rheometerplatte aufgebracht und bei 25 °C einer Scherung von 0,01 bis 1000 1/s unterworfen und für 10 min alle 10 s die Viskosität gemessen. Angegeben ist die über alle Messpunkte gemittelte Viskosität. The viscosity was determined on a Physica MCR 501 rheometer from Anton Paar. A cone-plate configuration with a distance of 1 mm was selected (DCP25 measuring system). The polyol (0.1 g) was applied to the rheometer plate and subjected to a shear of 0.01 to 1000 1 / s at 25 ° C. and the viscosity was measured every 10 s for 10 minutes. The viscosity given is averaged over all measuring points.
Die Offenzelligkeit der PUR-/PIR-Hartschäume wurde mit einem Accupyk-1330-Gerät an Probenkörpern mit den Maßen 5 cm x 3 cm x 3 cm nach DIN EN ISO 4590 (August 2003) gemessen. The open-cell content of the PUR / PIR rigid foams was measured with an Accupyk-1330 device on test specimens measuring 5 cm x 3 cm x 3 cm in accordance with DIN EN ISO 4590 (August 2003).
Druckfestigkeit in Steigrichtung wurde gemessen gemäß DIN ISO 826 (Mai 2013) Compressive strength in the direction of rise was measured according to DIN ISO 826 (May 2013)
Die Zellstruktur des Schaumstoffes wurde durch optische Begutachtung ermittelt. The cell structure of the foam was determined by visual inspection.
Die Messung der Rohdichte wurde nach der DIN EN ISO 845 (Oktober 2009) durchgeführt. The bulk density was measured in accordance with DIN EN ISO 845 (October 2009).
Durch Zugversuche gemäß DIN 53430 (September 1975) wurde an Zugstäben (gefräst nach DIN 53430 5.1) die Zugfestigkeit (öFmax), die Bruchdehnung (sBmch) und ein Maß für die ZähigkeitTensile tests according to DIN 53430 (September 1975) were used to determine the tensile strength (ö Fmax ), the elongation at break (s Bmch ) and a measure of the toughness on tensile rods (milled according to DIN 53430 5.1)
(öFmax* eBruch/2) bestimmt. Formulierungen (öFmax * e B ruch / 2) determined. Formulations
Die jeweiligen Polyolformulierungen wurden erhalten aus einer Basis - Polyolkomponente, enthaltend The respective polyol formulations were obtained from a basic polyol component containing
46 Gewichtsteile Al-l-a 46 parts by weight of Al-l-a
5 Gewichtsteile A2-b 5 parts by weight A2-b
2 Gewichtsteile A3-a 2 parts by weight A3-a
4 Gewichtsteile A5-a 4 parts by weight A5-a
25 Gewichtsteile A5-b. 25 parts by weight A5-b.
Die Basis - Polyolkomponente enthält weiterhin bereits 5 Gewichtsteile des Katalysators D-a. The base polyol component also already contains 5 parts by weight of catalyst D-a.
Zu der Basis-Polyolkomponente wurden zur Herstellung der unterschiedlichen PUR-PIR - Schäume jeweils noch die weiteren Polyolkomponenten gemäß Tabelle 2 und n-Pentan als Treibmittel in einem Pappbecher verrührt. To produce the different PUR-PIR foams, the other polyol components according to Table 2 and n-pentane as blowing agent were mixed in a paper cup in addition to the basic polyol component.
PUR-/PIR-Schäume PUR / PIR foams
Die erhaltene isocyanatreaktive Mischung wurde mit dem Isocyanat vermischt und das Reaktionsgemisch in eine Papierform (3 x 3 x 1 dm3) gegossen und darin ausreagiert. Die genauen Rezepturen der einzelnen Versuche sind in den nachfolgenden Tabellen wiedergegeben, ebenfalls die Ergebnisse der physikalischen Messungen an den erhaltenen Proben. The isocyanate-reactive mixture obtained was mixed with the isocyanate and the reaction mixture was poured into a paper form (3 × 3 × 1 dm 3 ) and reacted completely therein. The exact formulations of the individual experiments are given in the tables below, as are the results of the physical measurements on the samples obtained.
Die Reaktionsparameter sowie die Schaumeigenschaften sind in Tabelle 4 wiedergegeben. The reaction parameters and the foam properties are shown in Table 4.
Die erfindungsgemäßen Beispiele 3-5 sind den nicht erfindungsgemäßen Vergleichsbeispielen 1*, 2*, 6* und 7* unter anderem in der Kombination der Eigenschaften gute Flammwidrigkeit und Zellstruktur überlegen. Examples 3-5 according to the invention are superior to comparative examples 1 *, 2 *, 6 * and 7 * not according to the invention, inter alia in the combination of the properties of good flame retardancy and cell structure.
belle 2. belle 2.
erechnet nach ln(Viskosität Polyolmischung) = Anteil Al-l-a an der Mischung x ln(Viskosität Al-l-a) + Anteil A2-a an der Mischung x ln(Viskosität A2-a) + Anteil A2-b an der Mischung x iskosität A2-b). Eine Viskosität > 5 Pa*s ist ungünstig bei der Verarbeitung. calculated according to ln (viscosity of polyol mixture) = proportion of Al-la in the mixture x ln (viscosity Al-la) + proportion of A2-a in the mixture x ln (viscosity A2-a) + proportion of A2-b in the mixture x is viscosity A2 -b). A viscosity> 5 Pa * s is unfavorable during processing.
lle 4. lle 4.

Claims

Patentansprüche Claims
1. Polyolformulierung A, enthaltend 1. Polyol formulation A containing
Al 35-89 Gew .-%, bezogen auf die Gesamtmasse der Polyolformulierung A, einer Polyesterpolyolkomponente, welche eine OH-Zahl von 190 - 310 mg KOH/g aufweist, bestehend aus Al 35-89% by weight, based on the total mass of the polyol formulation A, of a polyester polyol component which has an OH number of 190-310 mg KOH / g, consisting of
Al-1 mindestens ein Polyesterpolyol mit einer OH-Zahl < 250 mg KOH/g, einer Funktionalität von 1,5 - 2,5 und einem Gehalt an freien Glykolen mit Mn < 150 g/mol von < 6 Gew.-%, bezogen auf die Gesamtmasse von Al-1, Al-1 at least one polyester polyol with an OH number <250 mg KOH / g, a functionality of 1.5-2.5 and a content of free glycols with M n <150 g / mol of <6% by weight, based on the total mass of Al-1,
Al -2 optional weiteren Polyesterpolyolen, welche nicht unter die Definition von Al- 1 fallen, Al -2 optionally other polyester polyols which do not fall under the definition of Al- 1,
A2 10-40 Gew.-%, bezogen auf die Polyolformulierung A, eines oder mehrerer Polyethylenglykole mit einem zahlenmittleren Molgewicht Mn von < 700 g/mol und einer mittleren Funktionalität von < 2,5; A2 10-40% by weight, based on polyol formulation A, of one or more polyethylene glycols with a number-average molecular weight M n of <700 g / mol and an average functionality of <2.5;
A3 optional weitere isocyanatreaktive Komponenten A3 optionally further isocyanate-reactive components
A4 0,2-5 Gew.-%, bezogen auf die Polyolformulierung A, einer oder mehrerer Verbindungen ausgewählt aus der Gruppe bestehend aus A4 0.2-5% by weight, based on the polyol formulation A, of one or more compounds selected from the group consisting of
A4-1 eines Polyethylenglykol-2,4,6-trialkylphenylethern (Struktur I mit R5, R6, R7 = H, CI - bis C8 -Alkyl) und A4-1 of a polyethylene glycol-2,4,6-trialkylphenyl ether (structure I with R5, R6, R7 = H, CI - to C8 -alkyl) and
A4-2 Polyethylenglykol-2,4,6-triaralkylphenylethern (Struktur I mit R5, R6 und/oder R7 = Aryl) und A4-2 polyethylene glycol-2,4,6-triaralkylphenyl ethers (structure I with R5, R6 and / or R7 = aryl) and
A4-3 Polyethylenglykol-alkylphenylethern (Struktur II) RI, R2, R3, R4 = H, C1-C4- Alkyl, A4-3 polyethylene glycol alkyl phenyl ethers (structure II) RI, R2, R3, R4 = H, C1-C4- alkyl,
R5, R6, R7 = H, CI- bis C8-Alkyl, Aryl R5, R6, R7 = H, CI- to C8-alkyl, aryl
n = 7-20, bevorzugt 10-18, besonders bevorzugt 11-15 n = 7-20, preferably 10-18, particularly preferably 11-15
Struktur II Structure II
R1, R3 = H, C(CH3)2CR4R5R6 R1, R3 = H, C (CH 3) 2 CR4R5R6
R2 = C(CH3)2CR4R5R6 R2 = C (CH 3) 2 CR4R5R6
R4, R5 = H oder CH3 R4, R5 = H or CH 3
R6 = C2- bis C5-Alkyl, Aryl R6 = C2 to C5 alkyl, aryl
n = 3-8 wobei die Verbindungen A4 ein zahlenmittleres Molekulargewicht Mn von unter 1,5 kg/mol und ein Gehalt von 25-70% Ethylenoxid, bevorzugt 40-60% Ethylenoxid aufweisen, und n = 3-8 where the compounds A4 have a number average molecular weight M n of less than 1.5 kg / mol and a content of 25-70% ethylene oxide, preferably 40-60% ethylene oxide, and
A5 gegebenenfalls weitere Hilfs- und Zusatzstoffe. A5 other auxiliaries and additives if necessary.
A6 0 - 2 Gew.-% Wasser, bezogen auf die Gesamtmasse der Polyolformulierung A [Mn - Werte bestimmt nach DIN 55672-1 (August 2007)]. A6 0-2% by weight of water, based on the total mass of the polyol formulation A [M n values determined according to DIN 55672-1 (August 2007)].
2. Polyolformulierung A gemäß Anspruch 1, wobei die Polyolkomponente Al-1 eine dynamische Viskosität (25°C, bestimmt mittels DIN EN ISO 3219:1994-10) von > 5 Pa*s aufweist. 2. Polyol formulation A according to claim 1, wherein the polyol component Al-1 has a dynamic viscosity (25 ° C, determined by means of DIN EN ISO 3219: 1994-10) of> 5 Pa * s.
3. Polyolformulierung gemäß Anspruch 1 oder 2, wobei das Massenverhältnis von Al-1 zu Al -2 mindestens 6:1, insbesondere mindestens 8:1 beträgt. 3. Polyol formulation according to claim 1 or 2, wherein the mass ratio of Al-1 to Al -2 is at least 6: 1, in particular at least 8: 1.
4. Polyolformulierung gemäß einem der vorangehenden Ansprüche, wobei die Polyolkomponente A2 ein Mn von 200-600 g/mol aufweist. 4. Polyol formulation according to one of the preceding claims, wherein the polyol component A2 has an M n of 200-600 g / mol.
5. Polyolformulierung A gemäß einem der vorangehenden Ansprüche, wobei die5. Polyol formulation A according to any one of the preceding claims, wherein the
Polyolkomponente A2 eine mittlere Funktionalität von < 2,12 aufweist. Polyol component A2 has an average functionality of <2.12.
6. Polyolformulierung A gemäß einem der Ansprüche 1-3, wobei die Polyolkomponente A2 eine mittlere Funktionalität von < 2,12 und ein Mn von 200-600 g/mol aufweist. 6. Polyol formulation A according to any one of claims 1-3, wherein the polyol component A2 has an average functionality of <2.12 and an M n of 200-600 g / mol.
7. Polyolformulierung A gemäß einem der vorangehenden Ansprüche, wobei die7. Polyol formulation A according to any one of the preceding claims, wherein the
Polyolkomponente A5 ein Flammschutzmittel umfasst. Polyol component A5 comprises a flame retardant.
8. Polyolformulierung A gemäß einem der vorangehenden Ansprüche, wobei die Mischung der Polyole Al und A2 eine dynamische Viskosität (25°C, bestimmt mittels DIN EN ISO 3219: 1994-10) von < 4 Pa*s aufweist, insbesondere eine Viskosität von 2 - 4 Pa*s. 8. Polyol formulation A according to one of the preceding claims, wherein the mixture of polyols Al and A2 has a dynamic viscosity (25 ° C, determined by means of DIN EN ISO 3219: 1994-10) of <4 Pa * s, in particular a viscosity of 2 - 4 Pa * s.
9. Verwendung einer Polyolformulierung gemäß einem der vorangehenden Ansprüche zur Herstellung von PUR-/PIR-Hartschaumstoffen. 9. Use of a polyol formulation according to one of the preceding claims for the production of rigid PUR / PIR foams.
10. Reaktionsgemisch zur Herstellung von PUR-/PIR-Hartschaumstoffen umfassend eine Polyolformulierung A gemäß einem oder mehreren der vorangehenden Ansprüche 1 - 8, eine Polyisocyanat-Komponente B, ein Treibmittel C, gegebenenfalls eine katalytisch aktive Komponente D, welche eine Isocyanat-Kennzahl von 150 bis 600 aufweist. 10. Reaction mixture for the production of rigid PUR / PIR foams comprising a polyol formulation A according to one or more of the preceding claims 1-8, a polyisocyanate component B, a blowing agent C, optionally a catalytically active component D, which has an isocyanate number of 150 to 600.
11. Reaktionsgemisch gemäß Anspruch 8, wobei die Polyisocyanat-Komponente B aus mindestens einer Verbindung aus der Gruppe bestehend aus MDI, polymeres MDI und TDI ausgewählt wird, insbesondere polymeres MDI. 11. The reaction mixture according to claim 8, wherein the polyisocyanate component B is selected from at least one compound from the group consisting of MDI, polymeric MDI and TDI, in particular polymeric MDI.
12. Verfahren zur Herstellung von PUR-/PIR-Hartschaumstoff umfassend die Umsetzung des Reaktionsgemisches gemäß Anspruch 10 oder 11. 12. A method for the production of PUR / PIR rigid foam comprising the implementation of the reaction mixture according to claim 10 or 11.
13. PUR-/PIR-Hartschaumstoff, erhältlich nach dem Verfahren gemäß Anspruch 12. 13. PUR / PIR rigid foam, obtainable by the method according to claim 12.
14. Verwendung von PUR-/PIR-Hartschäumen nach Anspruch 12 zur Herstellung eines Isolationsmaterials und/oder von Verbundelementen. 14. Use of PUR / PIR rigid foams according to claim 12 for the production of an insulation material and / or composite elements.
EP20737011.5A 2019-07-12 2020-07-06 Method for producing flameproof pur/pir rigid foams Withdrawn EP3997161A1 (en)

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US2764565A (en) 1951-12-24 1956-09-25 Bayer Ag Process and apparatus for the manufacture of polyurethane plastics
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