Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/14—Manufacture of cellular products
• • 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
  • C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
  • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
• • 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4804—Two or more polyethers of different physical or chemical nature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08J9/143—Halogen containing compounds
  • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
• • 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
  • C08J9/143—Halogen containing compounds
  • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
  • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L59/00—Thermal insulation in general
  • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
  • F16L59/028—Composition or method of fixing a thermally insulating material
• • 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
  • C08G2101/00—Manufacture of cellular products
• • 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
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
• • 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
  • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
• • 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
  • C08J2203/16—Unsaturated hydrocarbons
  • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/10—Rigid foams
• • 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
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
  • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

• composition suitable for the production of polyurethane foams containing at least one HFO propellant containing at least one HFO propellant
• the present invention relates to compositions suitable for the production of polyurethane foams, the at least one polyol component, at least one blowing agent, a catalyst which catalyzes the formation of a urethane or isocyanurate bond, a silicon-containing foam stabilizer and optionally further additives and optionally an isocyanate Component, characterized in that it contains as blowing agent at least one unsaturated chlorofluorocarbon or fluorocarbon and additionally at least one surfactant TD, which has no silicon atom and an HLB value less than 10, preferably less than 7, more preferably less than 6, the proportion the sum of the surfactants TD in the composition of 0.05 and 20 parts by mass per 100 parts by mass of polyol components, a process for the preparation of polyurethane or Polyisocyanuratschaumstoffen, in particular rigid foams, starting from these Polyolzusammenset tongues, the use of the foams, in particular as insulation materials and the insulating materials themselves.
• a propellant gas In order for a foam to form, a propellant gas is required.
• propellants here are hydrocarbons, (partially) halogenated saturated and unsaturated Kohlenwassen für and C0 2 -generating substances.
• preferred blowing agents are characterized by a low gas phase thermal conductivity and by a low global warming potential (GWP).
• GWP global warming potential
• unsaturated halocarbons so-called HFO propellants, have been identified as particularly effective propellants in the past.
• HFO blowing agents for the production of polyurethane foams is used, for example, in documents
• EP 2154223 A1 EP 2197 935 B1 and US 2009/0305875 A1.
• a trouble-free production process can be ensured by a sufficient storage stability of a pre-formulated A component in large-scale foaming process. For example, for longer Plant downtime, eg during maintenance or over the weekend, a separation of the system in pipes and storage tanks are avoided, which would inevitably lead to severe foam disturbances when restarting the system.
• the object of the present invention was therefore to provide a composition
• a composition comprising at least one polyol component, at least one blowing agent characterized in that it is an unsaturated halogenated hydrocarbon, a catalyst which catalyzes the formation of a urethane or isocyanurate bond, and optionally further additives, wherein the composition is characterized in that it is separation stable for at least three days.
• WO 2007/094780 describes polyol mixtures containing hydrocarbons as blowing agent, wherein an ethoxylate-propoxylate surfactant is added to the mixtures to improve the solubility of the blowing agent in the mixture.
• WO 98/42764 likewise describes polyol mixtures containing hydrocarbons as blowing agent, wherein the mixtures for improving the solubility of the blowing agent in the mixture, a C12-C15 started polyether is added as a surfactant.
• WO 96/12759 also describes polyol blends containing hydrocarbons as propellant, wherein the mixtures to improve the solubility of the propellant in the mixture, a surfactant is added, which has an alkyl radical having at least 5 carbon atoms.
• EP 0767199 A1 describes the use of diethanolamides of fatty acids of natural origin as a surfactant for the preparation of polyol mixtures which contain hydrocarbons as blowing agents.
• EP 1520873 A2 describes mixtures of halohydrocarbon propellants and propellant enhancers having a molecular weight of less than 500 g / mol, the propellant enhancers comprising polyethers or monoalcohols, e.g.
• blowing agent B can be ethanol, propanol, butanol, hexanol, nonanol or decanol.
• the ratio of blowing agent to blowing agent enhancer is reported as 60 to 95 mass% to 40 to 5 mass%.
• the halogenated hydrocarbons used are not HFO propellants. It is not disclosed in this document, whether the propellant used booster lead to a compatibilization of the blowing agent in polyols.
• WO 2013/026813 describes microemulsions of polyols and non-polar organic compounds which are obtained by using at least one halogen-free compound which contains at least one amphiphilic compound selected from nonionic surfactants, polymers and mixtures thereof and at least one compound other than this compound and their use in the production of polyurethanes.
• the nonpolar compounds used may also contain proportionate fluorinated compounds.
• Polyol-based microemulsions containing only halogenated non-polar compounds are not described in this document. Since the solution properties of halogenated hydrocarbons fundamentally differ from those of non-fluorinated hydrocarbons, a transferability of the additives proposed for hydrocarbon-based blowing agents to the present problem is not possible.
• separation-stable compositions of polyol (s), additives and HFO propellants can be provided if a surfactant which has an HLB value of less than 10, preferably less than 7, particularly preferably less than 6, is additionally added to the mixture.
• a surfactant which has an HLB value of less than 10, preferably less than 7, particularly preferably less than 6, is additionally added to the mixture.
• the HLB value is used to select emulsifiers for the production of oil-water emulsions. It was therefore not foreseeable that a such value is also useful for the selection of surfactants for non-water based polyol systems.
• the HLB value of a surfactant can be determined according to Griffin's increment method (WC Griffin, J. Cos. Cosmet.
• the HLB value of a molecule can be composed of individual increments of its molecular building blocks according to Equation 1.
• H h and H ⁇ here are the HLB group numbers of the individual hydrophilic or lipophilic molecular building blocks. Typical values for H h and H ⁇ are listed in Table 1 below. Tab. 1: HLB group numbers of different molecular building blocks (see also Table 3 in R. Sowada and JC McGowan, Surfactants Surfactants Detergents, 1992, 29, 109)
• the present invention therefore relates to compositions suitable for the production of polyurethane foams which contain at least one polyol component, at least one blowing agent, a catalyst which catalyzes the formation of a urethane or isocyanurate bond, a silicon-containing foam stabilizer and optionally further additives and optionally one isocyanate component which are characterized in that they contain as blowing agent at least one unsaturated chlorofluorohydrocarbon or unsaturated fluorohydrocarbon and additionally at least one surfactant TD, which has no silicon atom and an HLB value less than 10, preferably less than 7, particularly preferably less than 6, wherein the Concentration of the surfactant TD in the composition of 0.05 and 20 wt .-% based on the total composition.
• polyurethane or polyisocyanurate foams in particular rigid foams, starting from these polyol compositions, the use of the foams, in particular as insulating materials, and the insulating materials themselves.
• Another object of the present invention are polyurethane foams, which were prepared based on the method described above.
• compositions of the present invention have the advantage that larger amounts of HFO propellant can be incorporated into the compositions without the compositions, even after 72 hours of storage, showing phase separation recognizable to the naked eye.
• compositions according to the invention are those which would otherwise have a negative effect on the compatibility of polyol and blowing agent without resulting in a phase separation mixture can also be used in them.
• polyurethane foam is understood as meaning foam which is obtained as a reaction product based on isocyanates and polyols or compounds with isocyanate-reactive groups.
• PU foam is understood as meaning foam which is obtained as a reaction product based on isocyanates and polyols or compounds with isocyanate-reactive groups.
• further functional groups such as e.g. Allophanates, biurets, ureas or isocyanurates.
• PU foams are therefore understood as meaning both polyurethane foams (PUR foams) and polyisocyanurate foams (PIR foams).
• Preferred polyurethane foams are rigid polyurethane foams.
• Unsaturated halogenated hydrocarbons are also referred to as HFO in the context of the present applications.
• Halohydrocarbons may have one or more identical or different halogens.
• Propellants based on unsaturated halogenated hydrocarbons are accordingly referred to as HFOmaschinem means.
• composition according to the invention suitable for the production of polyurethane foams containing at least one polyol component, at least one blowing agent, a catalyst catalyzing the formation of a urethane or isocyanurate bond, a silicon-containing foam stabilizer and optionally further additives and optionally an isocyanate component is characterized in that it contains at least one unsaturated halogenated hydrocarbon, preferably an unsaturated hydrocarbon, as propellant
• the compositions of the invention preferably have from 0.1 to 15 and preferably from 0.5 to 10 parts by mass of surfactants TD per 100 parts by mass of polyol component.
• the composition according to the invention preferably comprises at least one compound of the formula (I)
• R is a linear, branched or cyclic, saturated or unsaturated, preferably saturated hydrocarbon radical, having at least 4, preferably from 8 to 30, preferably from 9 to 20 and particularly preferably 9 to 18 carbon atoms
• Particularly preferred surfactants TD are those which have at least one hydrocarbon radical having at least 4 carbon atoms, preferably having at least 8 carbon atoms and particularly preferably having 9 to 18 carbon atoms, and which have an HLB value of less than 10, preferably less than 7, particularly preferably less than 6 ,
• the preparation of corresponding fatty alcohol alkoxylates can be carried out as described in the prior art.
• the surfactants TD are particularly preferably ethoxylates of these amines.
• glycerol mono- and diethers of saturated or unsaturated alcohols such as octanol, nonanol, isononanol, capryl alcohol, lauryl alcohol, tridecanol, isotridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol or isostearyl alcohol are particularly preferred.
• Butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid ), Lignoceric acid (tetracosanoic acid), palmitoleic acid ((Z) - 9-hexadecenoic acid), oleic acid ((Z) -9-hexadecenoic acid), elaidic acid ((E) -9-octadecenoic acid), cis-vaccenic acid ((Z) -1 Octadecenoic acid), linoleic acid ((9Z.12Z) - 9,12-
• Octadecatrienoic acid gamma-linolenic acid ((6Z, 9Z, 12Z) -6,9,12-octadecatrienoic acid), di-homo-gamma-linolenic acid ((8Z, 11Z, 14Z) -8,1 1,14-eicosatrienoic acid )
• Arachidonic acid ((5Z, 8Z, 11Z, 14Z) -5,8,1,14-eicosatetraenoic acid), erucic acid ((Z) -13-docosenoic acid), nervonic acid ((Z) -15-tetracenoic acid), ricinoleic acid, Hydroxystearic acid and undecenylic acid, and mixtures thereof.
• the composition as surfactant TD preferably contains mono- or digylcerides, particularly preferred are mono- and digylcerides of straight-chain saturated or unsaturated fatty acids having up to 30 carbon atoms, such as.
• Octadecatrienoic acid gamma-linolenic acid ((6Z, 9Z, 12Z) -6,9,12-octadecatrienoic acid), di-homo-gamma-linolenic acid ((8Z, 11Z, 14Z) -8,1 1,14-eicosatrienoic acid ), Arachidonic acid ((5Z, 8Z, 11Z, 14Z) -5,8,1,14-eicosatetraenoic acid), erucic acid ((Z) -13-docosenoic acid), nervonic acid ((Z) -15-tetracenoic acid), Rizinolic acid, hydroxystearic acid and undecenylic acid, and mixtures thereof.
• surfactant TD a fatty acid amide of a mono- or dialkanolamine, more preferably diisopropanolamine or diethanolamine.
• the preparation of acid amides can according to the known in the art, such as. In DE 1802500; DE 1802503, DE 1745443, DE 1745459 or US 3578612, carried out. It can be used as raw materials z. B. the corresponding carboxylic acids are used and amide formation take place with dehydration.
• carboxylic esters for example methyl esters, in which case methanol is split off.
• carboxylic esters for example methyl esters, in which case methanol is split off.
• glycerides from the naturally occurring fats and oils, wherein the resulting in the amidation glycerol may remain in the reaction mixture.
• di- and mono-glycerides may still be present in the reaction mixture if the reaction conditions have been selected accordingly.
• carboxylic acid esters are used, appropriate catalysts, such as, for example, alkoxides, are used which allow amidation under relatively mild conditions compared to the abovementioned elimination of water.
• amides When using Of higher-functional amines (DETA, AEEA, TRIS) may also be in the production of amides to form corresponding cyclic amides such as imidazolines or oxazolines.
• a basic catalyst is used in the amidation, it may be advantageous to subsequently neutralize with an appropriate amount of organic or inorganic acid. Suitable compounds are known to the person skilled in the art. Particularly preferred is the neutralization, the amides prepared by basic catalysis, with organic anhydrides of dicarboxylic acids, since these can react with the available OH or NH functions and are thereby connected, and thus later in the finished foam not in the form of free Carboxylic acids can occur as an emission.
• z. B. in the use of alkali alcoholates in the neutralization then formed corresponding esters, so that the free alcohols can not escape from the system.
• Preferred organic anhydrides are cyclic anhydrides such as succinic anhydride, maleic anhydride, alkyl succinic anhydrides such as dodecyl succinic anhydride or polyisobutylene succinic anhydride, adducts of maleic anhydride to corresponding polyolefins such as polybutadienes, copolymers of maleic anhydride and olefins, styrene-maleic anhydride copolymers, vinyl ether-maleic anhydride copolymers , and generally copolymers containing maleic anhydride as a monomer, phthalic anhydride, Benzophenontetracarboxyldianhydrid,
• alkyl radicals of the monocarboxylic acids are, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, and the like, preferably 2-ethylhexanoic acid, nonanoic acid, isononanoic acid.
• alkenyl groups include, for example, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the like.
• aromatic acids are, for.
• aryl and alkylaryl (alkylaryl is defined as an aryl-substituted alkyl or arylalkyl group) such as: phenyl, alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl , Propyl-2-phenylethyl, salicyl and the like.
• Aromatic dicarboxylic acids may, for. As: isophthalic acid, terephthalic acid or phthalic acid.
• aliphatic dicarboxylic acids which may be used are: succinic acid, malonic acid, adipic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, tartaric acid, malic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid.
• trimesic acid trimesic acid, pyromellitic acid, Benzophenontetracarbonklare
• Preferred acids are straight-chain saturated or unsaturated fatty acids having up to 40 carbon atoms, such as. Butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid ), Lignoceric acid (tetracosanic acid), palmitoleic acid ((Z) -9-hexadecenoic acid), oleic acid ((Z) -9-hexadecenoic acid), elaidic acid ((E) -9-octadecenoic acid), cis-vaccenic acid ((Z) -11 Octade
• Sources of Suitable Fatty Acids or Fatty Acid Esters Especially glycerides can be vegetable or animal fat, oils or waxes.
• vegetable or animal fat, oils or waxes there may be used: lard, beef tallow, goose fat, duck fat, chicken fat, horse fat, whale oil, fish oil, palm oil, olive oil, avocado oil, seed kernel oil, coconut oil, palm kernel oil, cocoa butter, cottonseed oil, pumpkin seed oil, corn oil, sunflower oil, wheat germ oil, grapeseed oil, sesame oil, linseed oil , Soybean oil, peanut oil, lupine oil, rapeseed oil, mustard oil, castor oil, jatropa oil, walnut oil, jojoba oil, lecithin eg based on soybean oilseed rape or sunflower oil, bone oil, claw oil, lanolin, emu oil, deer tallow, marmot oil, mink oil, borage oil, thistle oil, hemp oil, pumpkin oil, evening primrose oil, tall
• suitable hydroxylamine having at least one OH function are, for example: diethanolamine, monoethanolamine, diisopropanolamine, isopropanolamine, diglycolamine (2- (2-aminoethoxy) ethanol), 3-amino 1 -propanol and polyetheramines such as polyetheramine D 2000 (BASF), polyetheramine D 230 (BASF), polyetheramine T 403 (BASF), polyetheramine T 5000 (BASF) or also corresponding Jeffamine types from Huntsman.
• the amidation is carried out with a deficiency of amine, so that as little or no free amine as possible is present in the end product. Since amines generally have no beneficial toxicological properties due to their irritating or corrosive action, minimizing amine levels is desirable and advantageous.
• the Armin contents in the blend used according to the invention, in particular the proportions of compounds carrying primary and secondary amine groups, are preferably less than 5% by weight, more preferably less than 3% by weight, particularly preferably less than 1% by weight, based on the sum of amines and amides.
• the composition according to the invention contains one or more polyols.
• the polyol component is preferably different from the surfactants TD present in the composition.
• Suitable polyols for the purposes of this invention are all organic substances having a plurality of isocyanate-reactive groups and their preparations.
• Preferred polyols are all polyether polyols and polyester polyols commonly used to make polyurethane foams.
• Polyether polyols are obtained by reacting polyhydric alcohols or amines with alkylene oxides.
• Polyester polyols are based on esters of polybasic carboxylic acids (usually phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols).
• corresponding polyols are used, such as for example, described in: US 2007/0072951 A1, WO 2007/1 1 1828 A2, US 2007/0238800, US 6359022 B1 or WO 96 12759 A2.
• preferably usable vegetable oil-based polyols are described in various patents, for example in WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/1 16456 and EP 1 678 232.
• composition of the invention preferably contains at least one physical blowing agent, i. a volatile (boiling temperature less than 100 ° C, preferably less than 70 ° C) liquid or a gas based on an unsaturated halogenated hydrocarbon, preferably unsaturated fluorohydrocarbon and / or chlorofluorohydrocarbon.
• unsaturated halogenated hydrocarbon preferably unsaturated fluorohydrocarbon and / or chlorofluorohydrocarbon.
• Halohydrocarbons are trans-1,3,3,3-tetrafluoro-1-propene (HFO-1234zeE), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), cis-1, 1, 1, 4,4,4-hexafluoro-2-butene (HFO-1336mzzZ), trans-1, 1, 1, 4,4,4-hexafluoro-2-butene (HFO-1336mzzE) and trans-1-chloro-3, 3,3-trifluoro-1-propene (HFO-1233zd-E).
• the HFO propellant may optionally be combined with other physical co-propellants, which are preferably not hydrocarbons.
• Preferred co-blowing agents are, for example, saturated or unsaturated fluorohydrocarbons, more preferably 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,3,3,3-pentafluoropropane (HFC-245fa), 1,1,1 , 3,3-pentafluorobutane (HFC-365mfc), 1,1,1,3,3,3,3-heptafluoropropane (HFC-227ea) 1,1-difluoroethane (HFC-152a), saturated chlorofluorocarbons, more preferably 1, 1-dichloro-1-fluoroethane (HCFC-141 b), oxygen-containing compounds, more preferably methyl formate or dimethoxymethane, or chlorinated hydrocarbons, more preferably 1, 2-dichloroethane, or mixtures of these blowing agents.
• HFC-134a 1,1,1,2-tetrafluoroethane
• HFC-245fa 1,
• compositions according to the invention have as physical blowing agents no hydrocarbons, such as. As n-pentane, isopentane or cyclopentane.
• the preferred levels of physical blowing agent are dictated by the desired density of the foam to be produced and are typically in the range of 5 to 40 parts by mass, based on 100 parts by mass of polyol.
• physical blowing agents and chemical blowing agents may be included, which react with isocyanates to gas evolution, such as water or formic acid.
• the composition according to the invention contains at least one silicon-containing foam stabilizer, which is different from the surfactants TD.
• Preferred silicon-containing foam stabilizers are organic polyether siloxanes, such as. B. polyether-polydimethylsiloxane copolymers.
• Typical use amounts of silicon-containing foam stabilizers are 0.5 to 5 parts by mass per 100 parts by mass of polyol, preferably 1 to 3 parts by mass per 100 parts by mass of polyol.
• Suitable silicon-containing Schaumstabilisatorn be z.
• the preparation of the siloxanes can be carried out as described in the prior art. Particularly suitable examples for the preparation are, for. In US 4,147,847, EP 0493836 and US 4,855,379.
• compositions according to the invention may contain further components, such as further foam stabilizers, catalysts, crosslinkers, flame retardants, fillers, dyes, antioxidants and thickener / rheology additives. These further components are preferably not surfactants TD or different from these.
• the composition according to the invention preferably comprises one or more catalysts for the catalyst isocyanate-polyol and / or isocyanate-water and / or isocyanate-trimerization.
• Suitable catalysts for the purposes of this invention are preferably catalysts which catalyze the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) and / or the di- or trimerization of the isocyanate.
• Suitable catalysts are the amines triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1, 2-dimethylimidazole, N-ethylmorpholine, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, dimethylaminoethanol , Dimethylaminoethoxyethanol and Bis (dimethylaminoethyl) ether, tin compounds such as dibutyltin dilaurate and potassium salts such as potassium acetate and potassium 2-ethylhexanoate.
• Suitable catalysts are mentioned, for example, in EP 1985642, EP 1985644, EP 1977825, US 2008/0234402, EP 0656382 B1, US 2007/0282026 A1 and the
• a flame retardant composition of the invention may comprise all known and suitable for the production of polyurethane foams flame retardants.
• Suitable flame retardants in the context of this invention are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. Triethyl phosphate (TEP), halogenated phosphates, e.g. Tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. Dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus.
• halogenated compounds for example halogenated polyols, and solids, such as expandable graphite and melamine, are suitable as flame retardants.
• additives may be included in the composition optionally also known in the art further components, such as. Polyethers, nonylphenol ethoxylates or nonionic surfactants, all of which are not surfactants as defined for the TD surfactants.
• compositions of the invention may, for. B are used for the production of polyurethane foams, in particular rigid polyurethane foams.
• the compositions of the invention can be used in a process according to the invention for the production of polyurethane or Polyisocyanuratschaumstoffen (polyurethane foams), in particular for the production of rigid polyurethane foams, which are characterized in that a composition according to the invention is implemented.
• the isocyanate component all isocyanate compounds suitable for producing polyurethane foams, in particular polyurethane foams or polyisocyanurate rigid foams, can be used.
• the isocyanate component comprises one or more organic isocyanates having two or more isocyanate functions.
• Suitable isocyanates in the context of this invention are, for. B. all polyfunctional organic isocyanates, such as 4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI).
• polymeric MDI ("crudeMDI) of MDI and higher condensed analogues having an average functionality of 2 to 4.
• suitable isocyanates are described in EP 1 712 578 A1, EP 1 161 474, WO 058383 A1, US 2007/0072951 A1, EP 1 678 232 A2 and WO 2005/085310.
• the ratio of isocyanate to polyol is preferably in the range from 40 to 500, preferably 100 to 350.
• the index describes the ratio of actually used isocyanate to calculated isocyanate (for a stoichiometric reaction with polyol).
• An index of 100 indicates a molar ratio of the reactive groups of 1 to 1.
• the process according to the invention for producing polyurethane foams can be carried out by the known methods, for example by hand mixing or preferably by means of foaming machines. If the process is carried out by means of foaming machines, high-pressure or low-pressure machines can be used.
• the process according to the invention can be carried out both batchwise and continuously.
• a preferred polyurethane or polyisocyanurate rigid foam formulation according to this invention would give a density of 20 to 150 kg / m 3 and preferably has the composition mentioned in Table 2.
• Table 2 Composition of a polyurethane or polyisocyanurate hard foam formulation
• Polyurethane foams according to the invention are also distinguished by the fact that they are obtainable by the process according to the invention.
• Preferred polyurethane foams according to the invention in particular rigid polyurethane foams prepared by using the composition according to the invention, have a thermal conductivity of less than 21 mW / nVK, preferably less than 20 mW / nVK measured in fresh (ie cured for 24 h at room temperature) at 23 ° C ( Determined by means of a 2-plate heat conductivity measuring device "Lambda Control" from Hesto.
• polyurethane foams according to the invention can be used as or for the production of insulating materials, preferably insulating boards, refrigerators, insulating foams or spray foams.
• Cooling apparatuses according to the invention are distinguished by the fact that they have as insulating material a polyurethane foam according to the invention (polyurethane or polyisocyanurate foam), in particular rigid polyurethane foam.
• a foamable A component 72.0 parts by weight (GT) of a polyol A (containing an aliphatic polyether polyol and an MDA-initiated polyether polyol, 2.3 parts by weight of water, and a mixture of amine catalysts DMCHA and PMDETA) was 24 , 5 parts of the HFO propellant Trans-1 -Chloro-3,3,3-trifluoro-1-propene (HFO-1233zd-E) available under the trade name Solsitce LBA (Honeywell) mixed. In addition, this mixture was added 4 parts of various polyether-based foam stabilizers, available as TEGOSTAB ® Bxxxx types at Evonik Industries AG. The exact composition of this mixture is summarized in Table 3.
• Table 4 Composition of surfactant-containing foamable A components based on the polyol A and the HFO propellant 1233zd-E

Landscapes

• Chemical & Material Sciences (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• General Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=52130228

Family Applications (1)

Country Status (9)

Families Citing this family (26)

Family Cites Families (108)

• 2013
  • 2013-12-19 DE DE102013226575.1A patent/DE102013226575B4/de active Active
• 2014
  • 2014-12-05 WO PCT/EP2014/076712 patent/WO2015091021A1/de active Application Filing
  • 2014-12-05 BR BR112016014329A patent/BR112016014329A2/pt not_active Application Discontinuation
  • 2014-12-05 EP EP14815274.7A patent/EP3083786A1/de not_active Ceased
  • 2014-12-05 CN CN201480069227.XA patent/CN105873993B/zh active Active
  • 2014-12-05 US US15/103,015 patent/US10023679B2/en active Active
  • 2014-12-05 KR KR1020167018751A patent/KR102254280B1/ko active IP Right Grant
  • 2014-12-05 JP JP2016535696A patent/JP6513090B2/ja active Active
  • 2014-12-05 MX MX2016008097A patent/MX2016008097A/es unknown

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events