WO2018138047A1 - Constituant polyol à phase stable pour la fabrication de pièces moulées en polyuréthane - Google Patents

Constituant polyol à phase stable pour la fabrication de pièces moulées en polyuréthane Download PDF

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Publication number
WO2018138047A1
WO2018138047A1 PCT/EP2018/051432 EP2018051432W WO2018138047A1 WO 2018138047 A1 WO2018138047 A1 WO 2018138047A1 EP 2018051432 W EP2018051432 W EP 2018051432W WO 2018138047 A1 WO2018138047 A1 WO 2018138047A1
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polyol component
phase
koh
isocyanate
hydroxyl number
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German (de)
English (en)
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Melina RUEBBELKE
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BASF SE
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BASF SE
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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
    • C08G18/28—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
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3278—Hydroxyamines containing at least three hydroxy groups
    • C08G18/3284—Hydroxyamines containing at least three hydroxy groups containing four 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
    • C08G18/40—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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having 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
    • C08G18/70—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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2125/00—Compositions for processes using internal mould release agents
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

  • the present invention relates to a phase-stable polyol component for the preparation of polyurethane moldings containing (a) compounds having isocyanate-reactive hydrogen atoms, comprising (a1) at least one amine-initiated propylene oxide having a nominal functionality of 3 to 6 and a hydroxyl number of 400 to 900 mg KOH / g, (a2) at least one alkylene oxide having a nominal functionality of 2 to 4 and a hydroxyl number of 20 to 1200 mg KOH / g and an ethylene oxide content of less than 40%, based on the total weight of alkylene oxide units in component (a2) wherein the alkylene oxides (a1) and (a2) are different, and / or at least trifunctional alcohol having a hydroxyl number greater than 1200 mg KOH / g, (b) internal release agent selected from saturated or unsaturated , aliphatic or cycloaliphatic carboxylic acids with mi at least 8 C-atoms, (c) propellant, containing water
  • the present invention further relates to a process for the preparation of polyurethane molded parts by mixing a polyol component according to the invention with an isocyanate component containing di- and / or polyisocyanate to form a reaction mixture, adding it to a mold and curing it to form the polyurethane molding.
  • polyurethane moldings The production of polyurethane moldings is known. This is usually carried out by reacting a reaction mixture in a mold to the polyurethane molding, wherein the reaction mixture is obtained by mixing the polyol and isocyanate component.
  • Conventional molding tools are made of plastic, such as epoxy resin, aluminum or steel. Since a polyurethane reaction mixture usually has very good adhesive properties mold release agents are used to prevent adhesion to the mold. A distinction is made here between external mold release agents, which are applied directly to the mold surface, and internal mold release agents, which form part of the reaction mixture.
  • DE 4223597 describes a phase-stable polyol component for the production of polyurethane moldings containing a high OH number polyol, a low OH number polyol and a mold release agent mixture containing a mixture of a salt-like release agent and a salt-free release agent.
  • a disadvantage is that the formulation is very complex by the use of two release agents within the polyol mixture. By adding many components, the mixing window described by the various mixing classes 1 to 6 and M1 and M1 1 b to e), limited.
  • the object of the present invention was to provide a phase-stable polyol component for the production of polyurethane molded parts, which allows the preservation of defect-free polyurethane moldings without the constant use of external release agents.
  • the object of the invention is achieved by a phase-stable polyol component for the production of polyurethane moldings containing (a) compounds with isocyanate-reactive hydrogen atoms, comprising (a1) at least one amine-initiated propylene oxide having a nominal functionality of 3 to 6 and a hydroxyl number of 400 to 900 mg KOH / g, (a2) at least one propylene oxide having a nominal functionality of 2 to 4 and a hydroxyl number of 20 to 1200 mg KOH / g and an ethylene oxide content of less than 40%, based on the total weight of alkylene oxide units in component (a2 ), wherein the alkylene oxides (a1) and (a2) are different, and / or a minimum trifunctional alcohol having a hydroxyl number
  • the present invention relates to a process for the preparation of polyurethane moldings by a polyol component according to the invention with an isocyanate component containing di- and / or polyisocyanate, mixed to form a reaction mixture and cured to form the polyurethane molding.
  • Polyurethane moldings in the context of the present invention may be solid or foamed moldings of polyurethanes.
  • the density of the polyurethanes according to the invention is preferably greater than 150 g / liter, particularly preferably 150 to 1200 g / liter, more preferably 450 to 950 g / liter and in particular 500 to 700 g / liter.
  • the polyurethanes according to the invention preferably have a non-foamed outer skin, which can be obtained by the shaping process.
  • the hardness of the inventive polyurethane moldings is; depending on the density; preferably at least 30 Shore D, preferably 40 to 95 Shore D and in particular 65 to 90 Shore D, each measured in accordance with DIN ISO 7619.
  • phase-stable polyol component is understood as meaning a single-phase, optically clear liquid which does not separate macroscopically into two or more phases even after several days of storage at room temperature.
  • the phase-stable polyol component is storage stable for 2 weeks, preferably one month, and more preferably at least 6 months, and does not separate macroscopically into two or more phases and does not cloud.
  • a polyol as clear and denotes single-phase, if this has no macroscopic phase boundary surface and this is optically so clear that a 5 cm behind the glass cuvette arranged black writing on a white background with font size Arial 12 pt by a filled with the polyol glass cuvette with a layer thickness of 20 cm cm distance is readable.
  • the described components a1 and a2 are miscible in various proportions with the release agent and the auxiliaries and form a phase-stable polyol component. After mixing with the isocyanate and mold injection, the moldings can be removed after a short time.
  • the compounds having isocyanate-reactive hydrogen atoms per molecule contain at least one amine-started propylene oxide having a nominal functionality of 3 to 6 and a hydroxyl number of 400 mg KOH / g to 900 mg KOH / g, preferably 600 mg KOH / g to 850 mg KOH / g (a1) and at least one propylene oxide having a nominal functionality of 2 to 4 and a hydroxyl value of 20 mg KOH / g to 1200 mg KOH / g, preferably 250 mg KOH / g to 500 mg KOH / g and especially preferably 300 mg KOH / g to 500 mg KOH / g and a content of ethylene oxide groups of less than 40%, preferably less than 20 wt .-% and in particular less than 10 wt .-%, each based on the total weight of alkylene oxide in the Component (a2) and / or a least trifunctional alcohol having a hydroxyl number of greater than
  • alkylene oxides are used as component (a1) and as component (a2), these are not identical and preferably differ at least by the starter molecule.
  • the compounds (a1) and (a2) can be prepared by known processes, for example by anionic polymerization of propylene oxide and optionally ethylenoxide, preferably exclusively propylene oxide, and with the addition of at least one starter molecule with, for example, alkali metal hydroxides or alkali metal alkoxides as catalysts or by cationic polymerization with Lewis acids, such as antimony pentachloride or borofluoride etherate.
  • Lewis acids such as antimony pentachloride or borofluoride etherate.
  • catalysts it is also possible to use multimetal cyanide compounds, so-called DMC catalysts.
  • alkylene oxides ethylene oxide and propylene oxide are used as alkylene oxides, these can be used alternately in succession or as mixtures.
  • the preferred alkylene oxide used is 1, 2-propylene oxide.
  • starter molecules are ethylene glycol, diethylene glycol, propylene glycol,
  • the starter molecules are selected and used in amounts such that the average nominal functionalities are obtained.
  • this invention considers the functionality that results solely by the functionality and the amount of starter molecules. A possible reduction in functionality, for example by side reactions, is disregarded.
  • a diamine, more preferably ethylenediamine and most preferably exclusively ethylenediamine is used for the preparation of the compound (a1) as a starter molecule.
  • the starter molecule of the polyetherols (a2) is preferably a trifunctional alcohol, preferably glycerol and / or trimethylolpropane and more preferably exclusively glycerol.
  • the compound (a1) is obtainable by propoxylating a diamine, preferably ethylenediamine, and the compound (a2) by propoxylating a trifunctional alcohol, preferably glycerol.
  • the compounds having isocyanate-reactive hydrogen atoms (a) may contain other compounds customary in polyurethane chemistry with isocyanate-reactive groups, such as polyols and chain extenders and crosslinkers. These preferably have an average nominal functionality of at least 2.0, preferably 2.5 to 8, more preferably 2.7 to 6 and especially 3.0 to 4.0 and a hydroxyl number of preferably at least 150 mg KOH / g, more preferably 300 to 1000 mg KOH / g. Such are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1 and 3.4.3.
  • These preferably contain only OH groups as isocyanate-reactive groups and are preferably used in amounts of less than 40 wt .-%, more preferably less than 20 wt .-%, more preferably less than 10 wt .-%, even more preferably less than 5 wt. -% and in particular less than 1 wt .-%, based on the total weight of all compounds with isocyanate-reactive groups (a).
  • suitable release agents (b) it is possible to use saturated or unsaturated, aliphatic or cycloaliphatic carboxylic acids having at least 8 carbon atoms.
  • fatty acids are used, in particular natural fatty acids, such as oleic acid, tall oil fatty acid, stearic acid, palm kernel fatty acids, trans fatty acids, ricinoleic acids, linoleic acids. acids, erucic acids or mixtures thereof.
  • the release agent particularly preferably contains an unsaturated fatty acid, of which the oleic acid is particularly preferred as the fatty acid.
  • the releasing agent is fatty acid containing oleic acid, or more preferably exclusively oleic acid, optionally in admixture with a tertiary amine such as 3- (dimethylamino) propylamine, preferably in molar ratio oleic acid to 3- (dimethylamino) propylamine of 1:20 to 10 : 1, more preferably 1: 5 to 2: 1 used.
  • the proportion of release agent is preferably from 1 to 15% by weight, more preferably from 2 to 8% by weight and in particular from 3 to 6% by weight, based in each case on the total weight of components (a) to (e).
  • the proportion of release agent is preferably from 1 to 15% by weight, more preferably from 2 to 8% by weight and in particular from 3 to 6% by weight, based in each case on the total weight of components (a) to (e).
  • only one release agent (b) and no further release agents are used in the polyol component as a release agent (b).
  • water which reacts with isocyanate groups to form carbon dioxide is used as propellant (c) for the process according to the invention.
  • so-called physically acting blowing agents can also be used in admixture with water.
  • Such preferably usable liquids are hydrocarbons, such as pentane, n- and isobutane and propane, ethers, such as dimethyl ether and diethyl ether, ketones, such as acetone and methyl ethyl ketone, ethyl acetate and preferably halogenated hydrocarbons, such as methylene chloride, trichlorofluoromethane, dichlorodifluorene. ormethane, dichloromonofluoromethane, dichlorotetrafluoroethane and 1, 1, 2-trichloro-1, 2,2-trifluoroethane.
  • hydrocarbons such as pentane, n- and isobutane and propane
  • ethers such as dimethyl ether and diethyl ether
  • ketones such as acetone and methyl ethyl ketone
  • ethyl acetate preferably halogenated hydrocarbons, such as methylene chloride,
  • blowing agent and carbon dioxide can be used, which is preferably dissolved as a gas in the starting components.
  • the amount of physical blowing agent required besides water can be easily determined depending on the desired foam density and is about 0 to 50 parts by weight, preferably 0 to 20 parts by weight per 100 parts by weight of the polyhydroxyl compound.
  • water is used as the sole blowing agent (c).
  • Catalysts greatly accelerate the reaction of the polyols (a) and chemical blowing agent (c) with the polyisocyanates.
  • the catalysts (d) preferably contain tertiary amine catalysts. These include compounds having one or more tertiary amino groups. Preferably, at least one of the tertiary amino groups carries at least one aliphatic hydrocarbon radical, preferably having 1 to 10 carbon atoms per radical, more preferably having 1 to 6 carbon atoms per radical.
  • the tertiary amino groups carry two radicals independently of one another selected from methyl and ethyl radical and a
  • suitable amines are amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylbutanediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylhexanediamine, bis (2-dimethylamino) ethyl) methylamine, tetramethyl-diaminoethyl ether, bis (dimethylaminopropyl) -urea, dimethylpiperaz
  • the catalysts (d) contain at least one amine catalyst having at least two tertiary amino groups, each carry two radicals independently selected from methyl and ethyl radical (d1), and a tertiary amine catalyst having a ring structure (d2), for example, 1, 2-dimethyimidazole or 1, 4-diaza-bicyclo- (2,2 , 2) octane.
  • the catalyst (d) contains bis (2-dimethylaminoethyl) methylamine and 1,4-diazabicyclo (2,2,2) octane, more preferably bis (2-dimethylaminoethyl) methylamine and 1-methylimidazole. If catalysts (d1) and (d2) are used, the weight ratio of (d1) to (d2) is preferably from 1:30 to 1: 2, more preferably from 1:20 to 1: 5.
  • organic metal compounds preferably organotin compounds, such as stannous salts of organic carboxylic acids, e.g. Stannous acetate, stannous octoate, stannous ethylhexanoate and stannous laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g.
  • organotin compounds such as stannous salts of organic carboxylic acids, e.g. Stannous acetate, stannous octoate, stannous ethylhexanoate and stannous laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g.
  • bismuth carboxylates such as bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate, or mixtures thereof, but preferably no Metal catalyst used.
  • the proportion of the catalyst (e), based on the total weight of the components (a) to (d), is preferably 0.4 to 2 wt .-%, and in particular 0.6 to 1, 6 wt. -%.
  • reaction mixture may contain auxiliaries and additives (e).
  • auxiliaries and additives include customary additives in polyurethane production, such as emulsifiers, fillers, flame retardants, stabilizers, dyes, pigments, hydrolysis stabilizers and also fungistatic and bacteriostatic substances.
  • customary additives in polyurethane production such as emulsifiers, fillers, flame retardants, stabilizers, dyes, pigments, hydrolysis stabilizers and also fungistatic and bacteriostatic substances.
  • Such substances are known and described for example in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, chapter 3.4.4 and 3.4.6 to 3.4.1 1.
  • Nonionic surfactants such as fatty alcohol ethoxylates, oxo alcohol ethoxylates, guerbet alcohol ethoxylates, alkylphenol ethoxylates, ethoxylated oleylamine, ethoxylated coconut fatty amine, ethoxylated tallow fatty amine, ethoxylated oleic acid amide, EO / PO block polymers, PIB derivatives and oleic acid amides, are preferably used.
  • the emulsifier used is an alkoxyethylene glycol ether of the general formula RO (CH 2 -CH 2 -O) x H, where R is a linear or branched or cyclic alkyl radical having 5 to 20 carbon atoms and x is an integer from 3 to 15. Particularly preferably, R is a decyl radical and x is 7.
  • no emulsifier (f) is used.
  • Fillers in particular reinforcing fillers, are the known conventional organic and inorganic fillers, reinforcing agents, etc. Specific examples are: inorganic fillers such as silicate minerals, for example quartz flour, phyllosilicates, such as antigorite, serpentine, hornblende, amphibole, chrysotile, and talc; Metal oxides such as kaolin, aluminas, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide, zinc sulfide and glass and others.
  • inorganic fillers such as silicate minerals, for example quartz flour, phyllosilicates, such as antigorite, serpentine, hornblende, amphibole, chrysotile, and talc
  • Metal oxides such as kaolin, aluminas, titanium oxides and iron oxides, metal salts such as chalk,
  • kaolin China Clay
  • quartz flours aluminum silicate and coprecipitates of barium sulfate and aluminum silicate
  • natural and synthetic fibrous minerals such as wollastonite, metal fibers and glass fibers of various lengths, which may optionally be sized.
  • Suitable organic fillers are, for example: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and in particular carbonic acids.
  • the fillers used are preferably those having an average particle diameter of from 0.1 to 500, more preferably from 1 to 100 and in particular from 1 to 10 ⁇ m.
  • the term "diameter" for non-spherical particles means their extent along the shortest spatial axis.
  • Glass fibers and quartz flours are preferably used as fillers.
  • fabric mats, such as glass fiber mats or natural fiber mats can be used as fillers.
  • the inorganic and organic fillers can be used individually or as mixtures and are advantageously used in amounts of 0.5 to 30% by weight, particularly preferably 10 to 20% by weight, based on the weight of the total reaction mixture.
  • Stabilizers are substances which promote the formation of a regular cell structure during foaming.
  • silicone-containing foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes.
  • Foam stabilizers are preferably used in an amount of 0.1 to 4, more preferably 1 to 3 wt .-%, based on the total weight of components (a) to (e).
  • flame retardants the flame retardants known from the prior art can generally be used.
  • Suitable flame retardants are, for example, brominated ethers (IXol B 251), brominated alcohols, such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol, and also chlorinated phosphates, for example, tris (2-chloroethyl) phosphate, tris (2 -chloroisopropyl) phosphate (TCPP), tris (1,3-dichloroisopropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis (2-chloroethyl) ethylenediphosphate, or mixtures thereof.
  • brominated ethers IXol B 251
  • brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol
  • chlorinated phosphates for example, tris (2-chloroethyl
  • inorganic flameproofing agents such as red phosphorus, red phosphorus-containing finishes, expandable graphite, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives such as melamine, or mixtures of at least two flame retardants such as ammonium polyphosphates and melamine and, if appropriate, starch, for flameproofing the rigid polyurethane foams produced according to the invention.
  • inorganic flameproofing agents such as red phosphorus, red phosphorus-containing finishes, expandable graphite, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives such as melamine, or mixtures of at least two flame retardants such as ammonium polyphosphates and melamine and, if appropriate, starch, for flameproofing the rigid polyurethane foams produced according to the invention.
  • DEEP Diethyl ethane phosphonate
  • TEP triethyl phosphate
  • DMPP dimethyl propyl phosphonate
  • DPK diphenyl cresyl phosphate
  • the flame retardants are used in the context of the present invention preferably in an amount of 0 to 60 wt .-% and particularly preferably from 5 to 50 wt .-%, based on the total weight of components (a) to (e).
  • halogen-free and halogenated flame retardants are used.
  • the polyol component according to the invention is mixed with an isocyanate component containing polyisocyanates to form a reaction mixture and the reaction mixture is introduced into a mold and cured to give the polyurethane molding.
  • the polyisocyanates used for the preparation of the polyurethane moldings according to the invention include the known from the prior art aliphatic, cycloaliphatic and aromatic di- or polyfunctional isocyanates and any mixtures thereof.
  • Examples are 4,4 '-Metandiphenyldiisocyanat, 2,4' -Metandiphenyldiisocyanat, the mixtures of monomeric Metandiphenyldiisocyanaten and higher-nuclear homologues of Metandiphe- nyldiisocyanats (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,4- or 2,6-toluene diisocyanate (TDI) or mixtures of said isocyanates.
  • the preferred MDI mixtures used may contain up to about 20% by weight of allophanate- or uretonimine-modified polyisocyanates.
  • the proportion of higher nuclear homologs of MDI is preferably 2 to 30 wt .-%, preferably 4 to 20 wt .-% and in particular 5 to 15 wt .-%, each based on the total amount of MDI used in the isocyanate component.
  • polyisocyanates can also be used in the form of their prepolymers.
  • These polyisocyanate prepolymers are obtainable by reacting polyisocyanates (a-1) described above, for example at temperatures of 30 to 100 ° C., preferably at about 80 ° C., with polyols to form the prepolymer.
  • Polyols are known to the person skilled in the art and are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1.
  • the polyols used are preferably the polyols described under (a).
  • the isocyanate component is preferably added as a release agent, for example 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 4 to 12 wt .-%, each based on the total weight of release agent and isocyanate.
  • the release agent in the isocyanate component is oleic acid or an ester of oleic acid which may contain isocyanate-reactive groups such as OH groups.
  • the starting components a) to f) and the isocyanate component are preferably mixed at a temperature of from 15 to 90.degree. C., more preferably from 25 to 55.degree.
  • the proportions of the polyol component and the isocyanate component are chosen so that the equivalence ratio of NCO groups of the isocyanate component to the sum of the reactive hydrogen atoms of the polyol preferably 0.9 to 1, 8: 1, more preferably 0.95 to 1, 4: 1 and especially 1 to 1, 2.
  • the isocyanate index is 100 at a ratio of 1: 1.
  • the preparation of the polyurethane moldings in a mold for example made of plastic, aluminum or steel, particularly preferably in a closed mold.
  • a closed mold while a closable mold, for example, with a lid called.
  • the reaction mixture is optionally introduced under elevated pressure into the mold.
  • the mixing can be carried out mechanically by means of a stirrer or a stirring screw or under high pressure in the so-called countercurrent injection method.
  • the mold temperature is expediently 20 to 160 ° C, preferably 30 to 120 ° C, particularly preferably 40 to 70 ° C.
  • the mixture of components a) to h) at reaction conversions of less than 90%, based on the isocyanate groups is referred to as the reaction mixture.
  • the polyol component according to the invention is stable on storage at room temperature for at least 2 weeks, preferably one month and in particular at least 6 months, and does not segregate. This allows the customer to reduce another step; namely, the stirring of the component before and during processing. This eliminates an important source of error in the production of polyurethane components.
  • the liquid is single-phase and clear, which makes the production of defect-free polyurethane molded parts easier.
  • the miscibility with the isocyanate component is also improved, as a result of which the reaction can proceed rapidly and more completely and also demolding times can be shortened.
  • improved mechanical properties such as a higher Shore D hardness, are to be expected.
  • the component compared to other release agents has a different surface tension, which provides an additional advantage in subsequent painting.
  • PolyoM ethylenediamine started propylene glycol with a hydroxyl number of 750 mg
  • Polyol 2 Glycerol-initiated propylene glycol having a hydroxyl number of 400 mg KOH / g
  • Polyol 3 Glycerol-initiated propylene / ethylene glycol having a hydroxyl number of 27 mg KOH / g and an ethylene oxide content, based on the total weight of alkylene oxide, of about 20% by weight. %
  • Release agent 2 oleic acid esters of oleic acid, adipic acid and pentaerythritol
  • Release agent 3 half ester of polyisobuccinic anhydride
  • Catalyst 2 methyl bis-2-dimethylaminoethylamine (PM-DETA)
  • the polyol component as described in Example 1, can be stored at room temperature for at least 6 months without these being demixed.
  • the liquid remains single-phase and clear.
  • a polyol mixture with 2 types of release agent (Comparative Example 2) or a particular type of release agent (Comparative Example 1) is not phase stable for more than 24 hours or stored without turbidity.
  • the polyol component (Example 1) from Table 1 was containing an isocyanate component containing about 90 wt .-% of polymeric diphenylmethane diisocyanate and about 10 wt .-% of a release agent based on an oleic acid ester, with an isocyanate index of 1 10 in one on 65 ° C tempered aluminum plate form given (500mmx400mmx10mm) and converted to a polyurethane molded body with a density of 600 g / liter. This was already removed after 2 minutes and 30 seconds and shows the following mechanical properties: Table 2

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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

La présente invention concerne un constituant polyol à phase stable pour la fabrication d'objets moulés en polyuréthane, contenant (a) des composés comportant des atomes d'hydrogène réactifs vis-à-vis des isocyanates, comprenant (a1) au moins un oxyde de propylène amorcé par une amine, présentant une fonctionnalité nominale de 3 à 6 et un indice d'hydroxyle de 400 à 900 mg KOH/g, (a2) au moins un oxyde d'alkylène présentant une fonctionnalité nominale de 2 à 4 et un indice d'hydroxyle de 20 à 1200 mg KOH/g et une teneur en groupes oxyde d'éthylène inférieure à 40 %, par rapport au poids total des motifs oxyde d'alkylène se trouvant dans le constituant (a2), les oxydes d'alkylène (a1) et (a2) étant différents, et/ou un alcool au moins trifonctionnel, présentant un indice d'hydroxyle supérieur à 1200 mg KOH/g, (b) des agents de démoulage internes choisis parmi les acides carboxyliques saturés ou insaturés, aliphatiques ou cycloaliphatiques, présentant au moins 8 atomes de carbone, ainsi que les sels de ces derniers, (c) des agents porogènes contenant de l'eau, (d) au moins un catalyseur à base d'amine tertiaire, ainsi que (e) éventuellement d'autres additifs et auxiliaires. La présente invention concerne en outre un procédé de fabrication d'objets moulés en polyuréthane, dans lequel on mélange un constituant polyol selon l'invention à un constituant isocyanate contenant un di- et/ou un polyisocyanate pour obtenir un mélange réactionnel, on l'introduit dans un moule, et on le durcit pour obtenir une pièce moulée en polyuréthane.
PCT/EP2018/051432 2017-01-24 2018-01-22 Constituant polyol à phase stable pour la fabrication de pièces moulées en polyuréthane Ceased WO2018138047A1 (fr)

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CN112752780A (zh) * 2018-10-08 2021-05-04 陶氏环球技术有限责任公司 配制的多元醇组合物
CN113165223A (zh) * 2018-11-23 2021-07-23 巴斯夫涂料有限公司 涂覆部件的注射模塑的自动化方法
CN115746618A (zh) * 2022-11-23 2023-03-07 黎明化工研究设计院有限责任公司 一种内脱模剂、自脱模的双组分自修复透明聚氨酯涂层及其制备方法
CN119735780A (zh) * 2025-01-02 2025-04-01 万华化学（北京）有限公司 一种聚氨酯表皮材料及其制备方法

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EP0490342A2 (fr) * 1990-12-11 1992-06-17 The Dow Chemical Company Agents de démoulage internes compatibilisés, pour l'élaboration d'articles polymériques moussés ou renforcés de fibres
DE4223597A1 (de) 1992-07-17 1994-01-20 Bayer Ag Lagerstabile, Formtrennmittel enthaltende Polyolgemische

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112752780A (zh) * 2018-10-08 2021-05-04 陶氏环球技术有限责任公司 配制的多元醇组合物
CN112752780B (zh) * 2018-10-08 2023-03-31 陶氏环球技术有限责任公司 配制的多元醇组合物
US11932722B2 (en) 2018-10-08 2024-03-19 Dow Global Technologies Llc Formulated polyol compositions
CN113165223A (zh) * 2018-11-23 2021-07-23 巴斯夫涂料有限公司 涂覆部件的注射模塑的自动化方法
CN113165223B (zh) * 2018-11-23 2024-03-05 巴斯夫涂料有限公司 涂覆部件的注射模塑的自动化方法
CN115746618A (zh) * 2022-11-23 2023-03-07 黎明化工研究设计院有限责任公司 一种内脱模剂、自脱模的双组分自修复透明聚氨酯涂层及其制备方法
CN115746618B (zh) * 2022-11-23 2024-04-05 黎明化工研究设计院有限责任公司 一种内脱模剂、自脱模的双组分自修复透明聚氨酯涂层及其制备方法
CN119735780A (zh) * 2025-01-02 2025-04-01 万华化学（北京）有限公司 一种聚氨酯表皮材料及其制备方法

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