EP4363480A1 - Production de mousse dure de polyuréthane ou de polyisocyanurate - Google Patents

Production de mousse dure de polyuréthane ou de polyisocyanurate

Info

Publication number
EP4363480A1
EP4363480A1 EP22733413.3A EP22733413A EP4363480A1 EP 4363480 A1 EP4363480 A1 EP 4363480A1 EP 22733413 A EP22733413 A EP 22733413A EP 4363480 A1 EP4363480 A1 EP 4363480A1
Authority
EP
European Patent Office
Prior art keywords
isocyanate
aromatic
weight
water
emulsifier
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.)
Pending
Application number
EP22733413.3A
Other languages
German (de)
English (en)
Inventor
Martin Glos
Jörg DIENDORF
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.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
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 Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP4363480A1 publication Critical patent/EP4363480A1/fr
Pending legal-status Critical Current

Links

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
    • C08G18/28—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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention is in the field of polyurethanes (PU) and polyisocyanurates (PIR), in particular PU or PIR rigid foams.
  • PU polyurethanes
  • PIR polyisocyanurates
  • PU or PIR rigid foams PU or PIR rigid foams.
  • PU or PIR rigid foams are PU or PIR rigid foams.
  • polyurethane is understood in particular to mean a product obtainable by reaction of polyisocyanates and polyols.
  • other functional groups can also be formed, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and/or uretimines.
  • PU is therefore understood to mean both polyurethane and polyisocyanurate, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretimine groups.
  • Polyimides are not included.
  • polyurethane foam is understood to mean, in particular, foam which is obtained as a reaction product based on polyisocyanates and polyols.
  • other functional groups can also be formed, such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines.
  • Polyisocyanurate foam in particular rigid polyisocyanurate foams, have also been known for a long time and are described in the prior art. They are usually also prepared by reacting polyisocyanates with polyols, preferably polyester-polyols and polyether-polyols, the isocyanate index preferably being 180 or greater. This forms urethane structures, which result from the reaction of isocyanates with compounds with reactive hydrogen atoms, and in addition, the reaction of the isocyanate groups with one another also forms isocyanurate structures or other structures, which result from the reaction of isocyanate groups with other groups, such as polyurethane groups.
  • the focus is in particular on the composition of the polyols or isocyanate-reactive mixture to be used.
  • One or more blowing agents are preferably added to the isocyanate-reactive mixture.
  • Blowing agents are either chemically reactive, such as water or formic acid, or they are physical blowing agents which, due to their boiling point, evaporate during the reaction and thus lead to or contribute to foam expansion.
  • Physical blowing agents are hydrocarbons, halogenated hydrocarbons, etc. This is known as far as is known.
  • the blowing agents in the isocyanate-reactive mixture are often miscible only to a limited extent, so that when the mixture is prepared, the result is not a clear component but a cloudy emulsion, which in turn also entails the problem of phase separation. This means that in many cases the blowing agent separates.
  • the isocyanate-reactive mixture can often contain other components of the overall reaction mixture, in addition to the isocyanate, ie flame retardants, catalysts, any dyes, stabilizers, any cell regulators, etc., such a phase separation is particularly detrimental.
  • US Pat. No. 6,262,136 B1 describes polyol mixtures which contain fluorine-containing blowing agents which are gaseous at atmospheric pressure.
  • phenols or alkyl phenols are used to solubilize the blowing agent in the polyol.
  • the propellants are HFC-134, HCFC-124, HCFC-22.
  • alkyl ethoxylates as emulsifiers for immiscible polyols is described in WO 2018/089768, flexible foams being produced from the reaction mixtures here.
  • DE 3632915 also describes ethoxylated nonylphenols in PU formulations which contain halogenated blowing agents.
  • WO 2020/231603 describes the use of nonionic surfactants to improve the storage stability of polyol mixtures consisting of polyester polyols and hydrocarbons as blowing agents.
  • the surfactants are alkyl ethoxylates or block copolymers based on different alkylene oxides.
  • US Pat. No. 4,595,711 describes the use of nonylphenol alkoxylates in order to facilitate the use of halogenated blowing agents or to improve their solubility/emulsifiability in the polyol mixture.
  • the object of the present invention was to make it possible to provide isocyanate-reactive mixtures with improved storage stability and to use them for the production of rigid polyurethane or polyisocyanurate foams.
  • the object of the invention which solves the above problem, is a method for producing a PU or PIR rigid foam, comprising bringing at least one isocyanate into contact with an isocyanate-reactive mixture which contains at least one polyol, water and at least one Emulsifier comprises, wherein one or more organic polyisocyanates having two or more isocyanate functions are used as isocyanates, characterized in that the emulsifier comprises at least one alkoxylated aromatic alcohol, wherein the underlying aromatic alcohol has at least 6 and a maximum of 40 carbon atoms and at least has an OH function, and with a maximum of 1/5 of the C atoms of the underlying aromatic alcohol being non-aromatic, and with at least one aromatic unit in the underlying aromatic alcohol having to carry an OH function.
  • the emulsifiers according to the invention are therefore alkoxylates of certain aromatic alcohols.
  • parent aromatic alcohol is meant that upon alkoxylation, it gives rise to the "alkoxylated aromatic alcohol”.
  • the aromatic alcohol is ethoxylated.
  • R 1 is hydrogen, methyl, ethyl or phenyl. It is therefore possible with preference to use ethylene oxide, propylene oxide, butylene oxide or styrene oxide for the alkoxylation n is a number from 2 to 200, preferably from 3 to 150, particularly preferably from 4 to 100.
  • ethoxylates of aromatic alcohols are used.
  • phenol Formula 2
  • the basic starting alcohols are based on aromatic alcohols, such as benzene with one or more OH functions: preferably phenol, pyrocatechol or resorcinol: such as B.
  • At least one aromatic unit in the underlying aromatic alcohol must carry an OH function.
  • the underlying aromatic alcohol can contain 6 to 40 carbon atoms. It can also contain conjugated (polynuclear) aromatic systems (naphthalene) or several aromatic systems can be linked together (bisphenols), with a maximum of 1/5 of the carbon atoms of the underlying aromatic alcohol being non-aromatic.
  • the maximum number of C - atoms in the underlying aromatic alcohol is 40, preferably 35, more preferably 30.
  • the underlying aromatic alcohol preferably contains more than 6 carbon atoms, particularly preferably more than 8.
  • Alkoxylates of mono-alcohols such as tristyrylphenols, naphthols or phenols are preferred. Alkoxylates of naphthols are particularly preferred.
  • the proportion of ethylene oxide in the polyether chain is preferably greater than 80% or greater than 90%, based on the total alkylene oxide. Pure ethoxylates are particularly preferred.
  • alkoxylated aromatic alcohols are based on (i) mononuclear aromatic alcohols with one or more OH functions, preferably phenol, catechol or resorcinol,
  • styrenated phenols preferably 2,4,6-tris(1-phenylethyl)phenol, 2,4-bis(1-phenylethyl)phenol or p-(1-phenylethyl)phenol.
  • the alkoxylated aromatic alcohol used has 4 to 100 alkoxy groups per molecule.
  • the alkoxylated aromatic alcohol used has a calculated HLB value greater than 10, particularly greater than 12, in particular greater than 14.
  • a suitable upper limit is 20.
  • emulsifiers usually consist of a combination of hydrophilic and lipophilic structural elements.
  • hydrophilic-lipophilic balance also known as the HLB value.
  • HLB values usually range from 1 to 20. The higher the proportion of hydrophilic structural elements, the higher the HLB value. This means that different emulsifiers can be compared with one another.
  • ethoxylates by dividing the respective weight percentage of ethylene oxide units by 5.
  • ethoxylates based on fatty alcohols, nonylphenols and also the alcohol ethoxylates according to the invention can be compared with one another according to their HLB value.
  • emulsifiers can also be used. It corresponds to a preferred embodiment of the invention if at least 2 alkoxylated aromatic alcohols are used, preferably comprising ethoxylated phenol(s) and ethoxylated naphthol(s). If the isocyanate-reactive mixture contains 2 to 30% by mass of water and 1 to 30% by mass of emulsifier and, if any, then less than 3% by mass of nonylphenol ethoxylate, a further preferred embodiment of the invention is present. These percentages by mass relate to the total of all components used that are not organic polyisocyanates. Another preferred embodiment of the invention is also present when the isocyanate-reactive mixture comprises flame retardants.
  • Another preferred embodiment of the invention is also present when the isocyanate-reactive mixture comprises at least one catalyst.
  • the emulsifier according to the invention can therefore preferably be used as an emulsifier-containing preparation.
  • An emulsifier-containing preparation can therefore also contain carrier media or solvents. These include in particular glycols, other alkoxylates and/or oils of synthetic and/or natural origin.
  • the emulsifier-containing preparation can preferably also contain up to 15% water. "Other alkoxylates" means that these alkoxylates do not fall under the definition of the alkoxylated aromatic alcohols according to the invention.
  • all substances suitable as solvents can be used as carrier media.
  • glycols, other alkoxylates and/or oils of synthetic and/or natural origin are preferably used.
  • Protic or aprotic solvents can be used.
  • the emulsifier-containing preparations according to the invention can also be used as part of compositions with various carrier media.
  • Another subject of the invention is an emulsifier-containing preparation, comprising
  • carrier media in amounts of 0 to 80% by weight, preferably 5 to 75% by weight, particularly preferably 10 to 70% by weight, with the proviso that the sum of (b) and (c) > 0 wt% is.
  • Another object of the invention is a composition
  • an isocyanate-reactive mixture which at least one polyol, water and at least one, preferably at least 2 alkoxylated aromatic alcohols according to the invention, as defined above, wherein the isocyanate-reactive mixture contains 2 to 30% by mass of water and 1 to 30% by mass of emulsifier and, if any, then less than 3% by mass of nonylphenol ethoxylates, and optionally , preferably mandatory, contains flame retardants.
  • These percentages by mass relate to the total of all components used that are not organic polyisocyanates.
  • Another object of the invention is a composition for the production of polyurethane or polyisocyanurate rigid foam, comprising an isocyanate component and an isocyanate-reactive mixture, optionally a foam stabilizer, a blowing agent, a catalyst, wherein the composition has at least one emulsifier, which preferably improves the storage stability of the Improved isocyanate-reactive mixture contains, wherein the emulsifier comprises at least one alkoxylated aromatic alcohol, wherein the underlying aromatic alcohol has at least 6 and a maximum of 40 carbon atoms and at least one OH function, and wherein a maximum of 1/5 of the carbon atoms of the underlying aromatic alcohol are not aromatic.
  • PU or PIR rigid foam-based products such as, for example, building insulation can be produced with a particularly high quality and the processes for producing the PU or PIR rigid foams can be made more efficient.
  • Preferred applications are predominantly spray foam, which can be open-cell or closed-cell, preferably open-cell, depending on the application.
  • the emulsification of water is an important task here, particularly in the case of open-cell spray foam, since large amounts of water are usually used as the blowing agent.
  • the total mass fraction of emulsifiers according to the invention in the finished polyurethane foam is from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight.
  • composition according to the invention comprises water and/or blowing agent, optionally at least one flame retardant and/or further additives which can be used advantageously in the production of rigid polyurethane or polyisocyanurate foam.
  • a particularly preferred composition according to the invention contains the following components: a) isocyanate-reactive compounds, in particular polyols, b) at least one polyisocyanate and/or polyisocyanate prepolymer, c) at least one, preferably 2, emulsifiers according to the invention as described above d) catalysts, e) (optional) a foam-stabilizing component on siloxanes or other surfactants, f) one or more blowing agents, g) other (optional) additives such as flame retardants, fillers, etc.
  • Components a), c), d), e), f) and g) can form the constituents of the isocyanate-reactive mixture, which comprises at least one emulsifier according to the invention, as defined above.
  • Another subject of the invention is the use of emulsifiers according to the invention and/or emulsifier-containing preparations, in particular using a composition according to the invention as described above, as an emulsifier for the isocyanate-reactive mixture in the production of rigid polyurethane or polyisocyanurate foams, preferably to improve the storage stability of the isocyanate-reactive mixture and, as a result, its performance properties for the production of rigid polyurethane or polyisocyanurate foams.
  • Another subject of the invention is the use of one, preferably at least 2, alkoxylated aromatic alcohols, as defined above, as emulsifiers to improve the storage stability of isocyanate-reactive mixtures comprising polyols, water and optionally flame retardants.
  • Another object of the invention is a polyurethane or polyisocyanurate rigid foam produced by the process according to the invention. It is preferably an open-cell, water-blown spray foam.
  • polyols are particularly suitable as isocyanate-reactive compounds a).
  • Suitable polyols for the purposes of the present invention are all organic substances having two or more isocyanate-reactive groups, preferably OH groups, and preparations thereof.
  • Preferred polyols are all for the production of polyurethane systems, in particular polyurethane coatings, polyurethane elastomers or also foams; commonly used polyether polyols and/or polyester polyols and/or hydroxyl group-containing aliphatic polycarbonates, in particular polyether polycarbonate polyols and/or polyols of natural origin, so-called “natural oil-based polyols” (NOPs).
  • the polyols usually have a functionality of preferably 1.8 to 8 and number-average molecular weights preferably in the range from 500 to 15,000. Usually the polyols with OH numbers preferably in the range from 10 to 1200 mg KOH/g are used.
  • Polyether polyols for example, can be used. These can be prepared by known methods, for example by anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides, alkali metal alcoholates or amines as catalysts and with the addition of at least one starter molecule that preferably contains 2 or 3 reactive hydrogen atoms or by cationic polymerization of alkylene oxides in the presence of Lewis -Acids such as antimony pentachloride or boron trifluoride etherate or by double metal cyanide catalysis. Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical.
  • Examples are tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide; ethylene oxide and 1,2-propylene oxide are preferably used.
  • the alkylene oxides can be used individually, cumulatively, in blocks, alternately one after the other, or as mixtures.
  • compounds with at least 2, preferably 2 to 8, hydroxyl groups or with at least two primary amino groups in the molecule are used as starter molecules.
  • starter molecules examples include water, di-, tri- or tetrahydric alcohols such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, in particular Sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines and melamine, or amines such as aniline, EDA, TDA, MDA and PMDA, particularly preferably TDA and PMDA.
  • the selection of the suitable starter molecule depends on the respective field of application of the resulting polyether polyol in the production of polyurethane
  • Polyester polyols for example, can be used. These are based on esters of polybasic aliphatic or aromatic carboxylic acids, preferably with 2 to 12 carbon atoms. Examples of aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, maleic acid and fumaric acid. Examples of aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
  • polyester polyols are obtained by condensing these polybasic carboxylic acids with polyhydric alcohols, preferably diols or triols having 2 to 12, particularly preferably 2 to 6, carbon atoms, preferably trimethylolpropane and glycerol.
  • polyether polycarbonate polyols can be used. These are polyols containing carbon dioxide bound as a carbonate. Since carbon dioxide is used in many chemical processes Industrially produced in large quantities as a by-product, the use of carbon dioxide as a comonomer in alkylene oxide polymerizations is of particular interest from a commercial point of view. Partial replacement of alkylene oxides in polyols with carbon dioxide has the potential to significantly reduce the cost of polyol production. In addition, the use of CO2 as a comonomer is ecologically very advantageous, since this reaction represents the conversion of a greenhouse gas into a polymer.
  • Suitable alkylene oxides and H-functional starter substances are those which are also used for the preparation of carbonate-free polyether polyols, as described above.
  • NOPs natural oil-based polyols
  • polyurethane foams are of increasing interest in view of the limited long-term availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices and have already been described many times in such applications (WO 2005/033167; US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/116456 and EP 1678232).
  • a number of these polyols from various manufacturers are now available on the market (WO2004/020497, US2006/0229375, WO2009/058367).
  • the basic raw material e.g.
  • soybean oil, palm oil or castor oil and the subsequent processing, polyols with different properties result.
  • Another class of usable polyols are, for example, the so-called packed polyols (polymer polyols).
  • SAN, PHD and PIPA polyols can be used.
  • SAN polyols are highly reactive polyols containing a dispersed styrene/acrylonitrile (SAN)-based copolymer.
  • PHD polyols are highly reactive polyols which also contain polyurea in dispersed form.
  • PIPA polyols are highly reactive polyols containing a polyurethane in dispersed form, for example formed by the in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
  • a preferred ratio of isocyanate and polyol expressed as the index of the formulation, ie as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (eg OH groups, NH groups) multiplied by 100, is in the range from 10 to 1000, preferably 40 to 700, particularly preferably 50 to 600, particularly preferably 60 to 550.
  • An index of 100 stands for a molar ratio of the reactive groups of 1 to 1.
  • One or more organic polyisocyanates having two or more isocyanate functions are preferably used as isocyanates b).
  • One or more polyols having two or more isocyanate-reactive groups are preferably used as polyols.
  • Suitable isocyanates b) for the purposes of this invention are all isocyanates which contain at least two isocyanate groups.
  • all aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates known per se can be used.
  • Isocyanates are particularly preferably used in a range from 60 to 200 mol % relative to the sum of the isocyanate-consuming components.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate and preferably hexamethylene - 1,6-diisocyanate (HMDI), cycloaliphatic diisocyanates, such as cyclohexane-1,3- and 1-4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,35-trimethyl-5-isocyanato-rmethylcyclohexane ( Isophorone diisocyanate or IPDI for short), 2,4- and 2,6-hexahydrotoluylene-'diisocyanate and the corresponding isomer mixtures, and preferably aromatic di
  • the organic di- and polyisocyanates can be used individually or in the form of their mixtures.
  • Corresponding “oligomers” of the diisocyanates can also be used (IPDI trimer based on isocyanurate, biurete-urethdione.) It is also possible to use prepolymers based on the isocyanates mentioned above.
  • modified isocyanates which have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups.
  • Particularly suitable organic polyisocyanates that can be used and are therefore particularly preferred in a preferred embodiment of the invention are various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomer mixtures of different composition), 4,4 '-Diphenylmethane diisocyanate (MDI), the so-called “crude MDI” or "polymeric MDI” (contains not only the 4,4'- but also the 2,4'- and 2,2'-isomers of MDI and higher-nuclear products) and/ or the binuclear product referred to as “pure MDI” consisting predominantly of 2,4′- and 4,4′-isomer mixtures or their prepolymers can be
  • Suitable catalysts d) for the purposes of the present invention are all compounds which are able to accelerate the reaction of isocyanates with OH functions, NH functions or other isocyanate-reactive groups and with isocyanates themselves.
  • the usual catalysts known from the prior art can preferably be used here, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and metal salts, preferably those of potassium, tin, iron, zinc or bismuth.
  • mixtures of several components can be used as catalysts.
  • Component e) can be, for example, Si-free surfactants or, for example, organomodified siloxanes.
  • blowing agents f are optional, depending on which foaming process is used. Chemical and physical blowing agents can be used. The choice of propellant depends heavily on the type of system.
  • no HFO is used as blowing agent.
  • Corresponding compounds with suitable boiling points can be used as optional physical blowing agents.
  • chemical blowing agents can optionally be used, which react with NCO groups and release gases, such as water or formic acid.
  • propellants are liquefied CO 2 , nitrogen, air, volatile liquids, for example hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons , preferably HCFC 141b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1233zd(E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
  • hydrocarbons with 3, 4 or 5 carbon atoms preferably cyclo-, iso- and n-pentane
  • fluorocarbons preferably HFC 245fa, HFC 134a and HFC 365m
  • Suitable water contents for the purposes of this invention depend on whether or not one or more blowing agents are used in addition to the water. In the case of purely water-blown foams, the values are preferably from 1 to 30 pphp; if other blowing agents are also used, the amount used is reduced to preferably 0.1 to 5 pphp.
  • polyurethane foams in particular polyurethane foams, such as, for example, crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, Surfactants, biocides, cell-refining additives, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, etc.
  • the process according to the invention for the production of PU or PIR rigid foams can be carried out by known methods, for example by hand mixing or preferably with the aid of foaming machines. If the process is carried out using foaming machines, high-pressure or low-pressure machines can be used.
  • the process according to the invention can be carried out either batchwise or continuously.
  • a preferred rigid polyurethane or polyisocyanurate foam formulation for the purposes of this invention has a density of 5 to 900 kg/m 3 and preferably has the composition given in Table 1.
  • Table 1 Table 1 :
  • a further object of the invention is a PU or PIR rigid foam obtainable by the process mentioned.
  • PU or PIR rigid foam is an established technical term.
  • the well-known and fundamental difference between flexible foam and rigid foam is that flexible foam shows elastic behavior and the deformation is therefore reversible.
  • Hard foam on the other hand, is permanently deformed.
  • PU or PIR rigid foam is understood to mean, in particular, a foam according to DIN 7726:1982-05, which advantageously has a compressive strength according to DIN 53421:1984-06 and/or DIN EN ISO 604:2003-12 >20 kPa, preferably >80 kPa, preferably >100 kPa, more preferably >150 kPa, particularly preferably >180 kPa.
  • an open-cell rigid foam is produced by the process according to the invention.
  • the foams to be produced according to the invention have densities of preferably 3 kg/m 3 to 300 kg/m 3 , preferably 4 to 250, particularly preferably 5 to 200 kg/m 3 , in particular 7 to 150 kg/m 3 .
  • open-cell foams can be obtained.
  • particularly preferred open-cell PU or PIR rigid foams have densities of ⁇ 25 kg/m 3 , preferably ⁇ 20 kg/m 3 , particularly preferably ⁇ 15 kg/m 3 , in particular ⁇ 10 kg/m 3 . These low foam densities are often desired in spray foams.
  • the determination of the closed cell content and thus the open cell content is preferably carried out according to DIN ISO 4590:2016-12 using a pycnometer.
  • Preferred PU or PIR foams for the purposes of the present invention are open-cell PU or PIR rigid foams.
  • Open-cell PU or PIR rigid foams within the meaning of this invention advantageously have a proportion of closed cells ⁇ 50%, preferably ⁇ 20% and in particular ⁇ 10%, with the determination of the closed-cell content within the meaning of this invention preferably according to DIN ISO 4590:2016- 12 by pycnometer. This means that these foams fall into categories CCC2 or, preferably, CCC1, as defined by DIN 14315-1:2013-04.
  • the PU or PIR rigid foams according to the invention can be used as or for the production of insulating materials, insulating foams, headliners, packaging foams or spray foams.
  • Another object of the invention is the use of the PU or PIR rigid foam as an insulating material in refrigeration technology, in refrigerated furniture, in the construction, automotive, shipbuilding and/or electronics sectors, as a spray foam.
  • Polyether polyol with a molar mass of 6000 g/mol, functionality 3, with primary OH groups.
  • Fyrol TCPP Tris(2-chloroisopropyl)phosphate from ICL POLYCAT® 31 from Evonik Operations GmbH, amine catalyst POLYCAT® 140 from Evonik Operations GmbH, amine catalyst POLYCAT® 142 from Evonik Operations GmbH, amine -Catalyst
  • Emulsifiers are:
  • alkoxylates described here can be prepared by known methods.
  • Emulsifier A (not inventive)
  • Emulsifier B Naphthol-based (inventive): 2-Naphthol with 11 ethylene oxide units per OH function.
  • Emulsifier C (inventive):
  • Emulsifier D (inventive):
  • the isocyanate-reactive compositions according to the invention with the emulsifiers B to E show no phase separation after storage at room temperature for 14 days.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne la production d'une mousse dure de PU ou de PIR, comprenant la mise en contact d'au moins un polyisocyanate organique comprenant au moins deux fonctions isocyanate avec un mélange réactif avec l'isocyanate qui comprend au moins un polyol, de l'eau et au moins un émulsifiant, l'émulsifiant comprenant au moins un alcool aromatique alcoxylé ; l'alcool aromatique sous-jacent comprenant au moins 6 et au plus 40 atomes C et au moins une fonction OH ; et un maximum de 1/5 des atomes C de l'alcool aromatique sous-jacent n'étant pas aromatiques ; et, dans l'alcool aromatique sous-jacent, au moins une unité aromatique devant comprendre une fonction OH.
EP22733413.3A 2021-07-01 2022-06-13 Production de mousse dure de polyuréthane ou de polyisocyanurate Pending EP4363480A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21183094 2021-07-01
PCT/EP2022/065981 WO2023274699A1 (fr) 2021-07-01 2022-06-13 Production de mousse dure de polyuréthane ou de polyisocyanurate

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EP4363480A1 true EP4363480A1 (fr) 2024-05-08

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EP (1) EP4363480A1 (fr)
JP (1) JP2024526111A (fr)
KR (1) KR20240027765A (fr)
CN (1) CN117677648A (fr)
CA (1) CA3224475A1 (fr)
WO (1) WO2023274699A1 (fr)

Family Cites Families (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900424A (en) 1972-07-21 1975-08-19 Nippon Oil Seal Ind Co Ltd Catalyst for copolymerizing epoxy compounds with carbon dioxide
US3953383A (en) 1972-07-21 1976-04-27 Nippon Oil Seal Industry Co., Ltd. Catalytic process for copolymerizing epoxy compounds with carbon dioxide
US4500704A (en) 1983-08-15 1985-02-19 The Dow Chemical Company Carbon dioxide oxirane copolymers prepared using double metal cyanide complexes
US4595711A (en) 1984-06-20 1986-06-17 Stepan Company Aromatic polyester polyols fluorocarbon compatibilized with ethoxylate propoxylate compounds for urethane and isocyanurate foams
DE3632915A1 (de) 1986-09-27 1988-03-31 Bayer Ag Verwendung von mg(oh)(pfeil abwaerts)2(pfeil abwaerts) bei der herstellung von schaumstoffen auf basis von aromatischen isocyanaten
JPS63172737A (ja) 1986-12-31 1988-07-16 ユニオン・カーバイド・コーポレーシヨン ポリシロキサン―ポリオキシアルキレン化合物
US5990187A (en) 1997-03-26 1999-11-23 Th. Goldschmidt Ag Method of preparing polyurethane foam utilizing organofunctionally modified polysiloxanes
US5844010A (en) 1997-03-29 1998-12-01 Th. Goldschmidt Ag Method of preparing polyurethane foam utilizing block copolymers having linked siloxane blocks
DE19905989A1 (de) 1999-02-13 2000-08-17 Bayer Ag Feinzellige, wassergetriebene Polyurethanhartschaumstoffe
US6133329A (en) 1999-03-31 2000-10-17 Oxid L.P. Aromatic polyester polyols made from a natural oil
US6262136B1 (en) 1999-05-26 2001-07-17 Bayer Corporation Storage stable foam-forming system
AU764900B2 (en) 2000-11-28 2003-09-04 Evonik Goldschmidt Gmbh Use of mixtures of organofunctionally modified polysiloxanes with branched alcohols in the production of flexible polyurethane foams
US20020103091A1 (en) 2001-01-29 2002-08-01 Kodali Dharma R. Reactive oil compositions and uses thereof
DE10240186A1 (de) 2002-08-28 2004-03-11 Basf Ag Verfahren zur Herstellung von emissionsarmen Polyurethan-Weichschaumstoffen
MXPA05011487A (es) 2003-04-25 2005-12-15 Dow Global Technologies Inc Polioles a base de aceite vegetal, y poliuretanos preparados a partir de ellos.
US8133930B2 (en) 2003-04-25 2012-03-13 Dow Global Technologies Llc Polyurethane foams made from hydroxymethyl-containing polyester polyols
US8293808B2 (en) 2003-09-30 2012-10-23 Cargill, Incorporated Flexible polyurethane foams prepared using modified vegetable oil-based polyols
ATE316545T1 (de) 2003-10-04 2006-02-15 Goldschmidt Gmbh Verfahren zur herstellung von organischen siliciumverbindungen
DE102004011559A1 (de) 2004-03-08 2005-09-29 Rathor Ag Phasenstabile Polyurethanprepolymere
JPWO2006035941A1 (ja) * 2004-09-30 2008-05-15 東邦化学工業株式会社 硬質ポリウレタンフォームの製造方法
CA2599983A1 (fr) 2005-03-03 2006-09-08 South Dakota Soybean Processors, Llc Nouveaux polyols issus d'une huile vegetale au moyen d'un procede d'oxydation
US20060229375A1 (en) 2005-04-06 2006-10-12 Yu-Ling Hsiao Polyurethane foams made with alkoxylated vegetable oil hydroxylate
US20060235100A1 (en) 2005-04-13 2006-10-19 Kaushiva Bryan D Polyurethane foams made with vegetable oil hydroxylate, polymer polyol and aliphatic polyhydroxy alcohol
EP1888666B1 (fr) 2005-04-25 2017-06-21 Cargill, Incorporated Mousses de polyurethane comprenant des polyols oligomeriques
US9856355B2 (en) 2005-09-27 2018-01-02 Evonik Degussa Gmbh Silanol-functionalized compounds for the preparation of polyurethane foams
DE102006030531A1 (de) 2006-07-01 2008-01-03 Goldschmidt Gmbh Siliconstabilisatoren für flammgeschützte Polyurethan- bzw. Polyisocyanurat-Hartschaumstoffe
ES2366931T3 (es) 2006-11-15 2011-10-26 Basf Se Procedimiento para la obtención de espumas blandas de poliuretano.
WO2009058367A1 (fr) 2007-11-01 2009-05-07 Cargill, Incorporated Polyols de polyester dérivés d'huile naturelle et polyuréthanes obtenus à partir de ceux-ci
GB0807607D0 (en) 2008-04-25 2008-06-04 Imp Innovations Ltd Catalyst
PL2337809T5 (pl) 2008-09-08 2024-03-04 Saudi Aramco Technologies Company Kompozycje poliwęglanowego poliolu i sposoby
DE102009028061A1 (de) 2009-07-29 2011-02-10 Evonik Goldschmidt Gmbh Verfahren zur Herstellung von Polyurethanschaum
WO2011163133A1 (fr) 2010-06-20 2011-12-29 Novomer, Inc. Polycarbonates aliphatiques
US9290604B2 (en) 2010-08-13 2016-03-22 Air Products And Chemicals, Inc. NPE-free emulsifiers for water-blown polyurethane spray foam
JP2014529589A (ja) 2011-08-08 2014-11-13 ノボマー， インコーポレイテッド ポリマー合成のための触媒および方法
CN103044687B (zh) 2012-12-21 2015-03-11 江苏美思德化学股份有限公司 一种含氟有机硅聚醚共聚物及其制备方法
CN103055759A (zh) 2012-12-21 2013-04-24 南京美思德新材料有限公司 一种兼有稳泡和开孔性能的聚氨酯泡沫有机硅表面活性剂
CN103657518B (zh) 2013-12-16 2015-11-04 南京美思德新材料有限公司 一种非离子有机硅表面活性剂及其制备方法
CN103665385B (zh) 2013-12-16 2016-03-02 江苏美思德化学股份有限公司 一种含烯酸酯有机硅聚醚共聚物及其制备方法
WO2016180757A1 (fr) * 2015-05-11 2016-11-17 Covestro Deutschland Ag Mousses rigides pur/pir composées de polyéthers à base d'isopropylidènediphénol
WO2018089768A1 (fr) 2016-11-11 2018-05-17 Evonik Degussa Gmbh Émulsifiants destinés à une mousse à base de polyuréthanne
JP2022533617A (ja) 2019-05-16 2022-07-25 ダウ グローバル テクノロジーズ エルエルシー テレフタル酸エステルポリオールおよび炭化水素発泡剤の相溶化ブレンド
EP3819332B1 (fr) * 2019-11-06 2022-07-06 Basf Se Procédé de production de mousses de polyuréthane rigides

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CA3224475A1 (fr) 2023-01-05
KR20240027765A (ko) 2024-03-04
WO2023274699A1 (fr) 2023-01-05
CN117677648A (zh) 2024-03-08

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