WO2005123806A1 - Verfahren zur herstellung von polyetheralkoholen und polyurethanen - Google Patents
Verfahren zur herstellung von polyetheralkoholen und polyurethanen Download PDFInfo
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- WO2005123806A1 WO2005123806A1 PCT/EP2005/006197 EP2005006197W WO2005123806A1 WO 2005123806 A1 WO2005123806 A1 WO 2005123806A1 EP 2005006197 W EP2005006197 W EP 2005006197W WO 2005123806 A1 WO2005123806 A1 WO 2005123806A1
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- polyether
- compounds
- alkoxylation
- polyurethanes
- polyether alcohols
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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
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- 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
-
- 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
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
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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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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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
- 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 invention relates to processes for the preparation of polyether alcohols, preferably with a functionality compared to isocyanates of 1.7 to 6, particularly preferably 1.7 to 4, particularly preferably 1.7 to 3, in particular 2 to 3, preferably with a hydroxyl number between 10 mg KOH / g and 500 mg KOH / g, particularly preferably between 10 mg KOH / g and 100 mg KOH / g, particularly preferably between 10 mg KOH / g and 60 mg KOH / g, in particular between 25 mg KOH / g and 35 mg KOH / g, preferably by alkoxylation of starter substances, preferably alcohols or amines, particularly preferably alcohols, preferably having 2 to 6, particularly preferably 2 to 4, in particular 2 or 3 hydroxyl groups, the alkoxylation being carried out in the presence of layered silicates, and in such a way Available polyether alcohols, in particular polyether alcohols containing exfoliated layered silicates.
- the invention further relates to processes for the production of polyurethanes, for example compact or cellular, crosslinked or thermoplastic polyurethanes, e.g. Polyurethane soft, semi-rigid or rigid foams by reacting (a) polyisocyanates with (b) compounds with hydrogen atoms reactive towards isocyanate groups, the polyether alcohols according to the invention being used as (b) compounds with hydrogen atoms reactive towards isocyanate groups, and polyurethanes obtainable in this way, in particular flexible polyurethane foams ,
- polyurethanes for example compact or cellular, crosslinked or thermoplastic polyurethanes, e.g. Polyurethane soft, semi-rigid or rigid foams by reacting (a) polyisocyanates with (b) compounds with hydrogen atoms reactive towards isocyanate groups, the polyether alcohols according to the invention being used as (b) compounds with hydrogen atoms reactive towards isocyanate groups, and polyurethanes obtainable in this way, in particular flexible
- EP-A-1209189 describes the use of nanocomposites in PUR foams.
- the clays serve as a nucleating agent and gas barrier, resulting in an improvement in thermal conductivity.
- the layered silicates are not exfoliated.
- DE-A-10032334 describes the incorporation of silicate-containing nanofillers without disadvantages on the bulk density. It is disclosed that expanded sheet silicates are delaminated during PUR foam production and are preferably installed in the cell webs. Cloisite 30 A was used as layered silicate, Cloisite 30 A is incorporated by stirring into the A component and immediate foaming with the isocyanate. A disadvantage of the fillers disclosed here is that they settle very quickly in the A component, which results in the A component having a low storage stability.
- WO 03/059817 describes a nanodispersion which contains a layered silicate and a compound which is embedded in the layered silicate and is produced by intensive mixing of the layered silicates with polyols. This document makes it clear referred to the problems of introducing the layered silicates into the polyols and of exfoliating the layered silicates. According to WO 03/059817, only layered silicates with hydrophilic end groups that are organically modified with quaternary ammonium compounds are suitable, and they must also be incorporated and dispersed in the polyols in an additional step.
- a disadvantage of the known technical teachings is the only low content of exfoliated layered silicate in polyols due to the increase in viscosity and the low degree of exfoliation that is achieved, as well as a complex dispersion step, as a result of which advantages due to the use of the nanoparticles can only be insufficiently exploited.
- Sub-layer silicates which are known from the prior art silicate structure with • two-dimensional layers of SiO 4 tetrahedra be understood (as a sheet or phyllosilicates known in the art).
- suitable layered silicates are preferably naturally occurring clay minerals, montmorillonite, bentonite, mica, kaolinite, boehmite, smectite, hectorite, vermiculite or mixtures thereof. Examples are mentioned in the publication "Dispersions and Emulsions", Lagaly, Schulz, Zimehl, Steinkopf Verlag Darmstadt. Bentonite, montmorillonites, including those which can be obtained from Südchemie, for example, and / or Southern Clay are preferably used.
- the hydroxyalkyl chains grow between the layers of the layered silicates and these layers are separated, that is to say to the desired exfoliation.
- the main advantage of this method according to the invention lies in the favorable combination of two method steps: with the Production of the polyether alcohols, the layered silicate is exfoliated in parallel in one process step, ie delaminated.
- exfoliated sheet silicates are used, which do not have to be stirred in, dispersed or delaminated by high shear energy or delaminated during foaming.
- polyether alcohols also referred to below as polyetherols
- alkoxylation for example after anionic polymerization
- the process according to the invention is preferably carried out in such a way that the layered silicate is taken up (mixed) in the starter substance or substances and then alkylene oxide is metered in. It is preferred to mix the layered silicates well with the starter substance (s) and bring them to the desired starting temperature for the alkoxylation reaction.
- the inclusion of the layered silicates is carried out in the low molecular weight starter substances preferably at temperatures of 80 to 150 C C and sufficient mixing effect in a homogeneous manner and leads to a uniform distribution in the starting mixture.
- the homogeneity of the mixtures is largely retained during the reaction with alkylene oxides to give higher molecular weight products, since the starter mixture with the layered silicate incorporated therein is subject to a controlled addition of alkylene oxides.
- the continuous increase in chain lengths or molecular weights maintains the homogeneous distribution. This homogeneous distribution is generally difficult to achieve when remixing in the fully reacted polyetherol.
- Well-known compounds which preferably have hydroxyl and / or amino groups to which alkylene oxides can be added can be used as starter substances.
- the use of, for example, mono-, di- or polyaccharides and other highly functional compounds for the synthesis of highly functional polyetherols is a known and often described method for the production of polyetherols, in particular for those which are intended for use in PUR Rigid foams are provided.
- Alkoxylations of sucrose in a mixture with liquid costartem such as diols, triols or amines are common. Depending on the proportion of this costarter, more or less high functionality of the polyether is obtained.
- trifunctional, hydroxyl-containing starter substances are preferably used, also in a mixture with glycols, such as mono-, di- or triethylene glycols or propylene glycols, or also tetrols, such as pentaerythritol and diglycerol.
- the following compounds can be used as starter substances: water, alkanolamines, dialkanolamines, dihydric and / or polyhydric alcohols, such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, pentaerythritol, sorbitol and / or sucrose.
- water alkanolamines, dialkanolamines, dihydric and / or polyhydric alcohols, such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, pentaerythritol, sorbitol and / or sucrose.
- At least one of the following compounds is preferably used as starting substances: glycerol, trimethylolpropane, diethylene glycol, monoethylene glycol, propylene glycol, triethylene glycol, N, N '- bis (3- Aminopropyl) ethylenediamine, vicinal toluenediamines, ethylenediamine, sucrose, sorbitol, preferably, glycerol, trimethylolpropane, mono-, di- and / or triethylglycol, mono-, di- and / or tripropylene glycol.
- alkylene oxides which can be used to prepare the alkoxylated amines
- generally known alkylene oxides can be used, for example ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, the alkylene oxides being added to the amines individually, in a mixture with one another or in blocks can be added.
- the amines can only be reacted only with ethylene oxide, only with propylene oxide, with a mixture of ethylene oxide and propylene oxide or only with propylene oxide and then with ethylene oxide, in the latter case the reactivity of the alkoxylated amines towards isocyanates due to the high proportion of primary hydroxyl groups is increased.
- the production of polyols after the anionic polymerization can be carried out by generally known double metal cyanide (DMC) catalysis or by the known basic catalysis with metal hydroxides or tertiary amines.
- the type of catalysis influences the property profile of the polyols.
- the catalytic addition of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide, takes place at the active centers of the starters or starter mixtures.
- alkyl oxides can be dosed and arranged in succession and / or in a mixture or in parallel.
- the amount and type of alkylene oxides essentially determine the polyol properties and are largely incorporated into the property profile of the PUR foam.
- the alkoxylation is preferably catalyzed by means of alkali metal hydroxides, preferably potassium hydroxide.
- the catalysts can be used in generally known amounts and, if appropriate, can also be metered in during the al
- the addition of the alkylene oxides to the starting substances can be carried out by generally known methods.
- the starting substances can be mixed with the alkylene oxide at a temperature of, for example, 70 to 160, preferably 80 to 150 ° C.
- the alkylene oxides can preferably be added such that the reaction temperature is within a range from 70 to 160, preferably 80 to 150 ° C.
- the reaction times usually depend on the temperature profile of the reaction mixture and are therefore dependent, inter alia, on the batch size, the reactor type and the cooling devices.
- the reaction can be carried out at pressures between 0.1 MPa and 1 MPa, preferably between 0.1 MPa and 0.7 MPa.
- the polyether polyalcohols produced according to the invention can be purified in a known manner, for example by reacting the reaction mixture with mineral acids, such as for example hydrochloric acid, sulfuric acid and / or preferably phosphoric acid, almost neutralized to a pH of usually 6 to 8 with organic acids or with carbon dioxide, the water is removed from the polyether polyalcohol by conventional vacuum distillation and the salts are filtered off.
- mineral acids such as for example hydrochloric acid, sulfuric acid and / or preferably phosphoric acid
- the amines are usually distilled off and partially reused or remain in the polyol in order to continue the catalysis in the PUR system.
- Catalysis with metal hydroxides produces metal alcoholates, which are usually hydrolyzed with water and neutralized with acids.
- mineral acids such as sulfuric, phosphoric and hydrochloric acid, as well as carbon dioxide leads to the formation of salts which can be separated off by filtration.
- Organic acids are preferably used to adjust the pH of the reaction product of the alkoxylation to a value greater than 6, particularly preferably between 7 and 8.
- the organic acid used in this neutralization step is preferably generally known organic acids, particularly preferably ethylhexanoic acid, lactic acid, formic acid, acetic acid and / or oxalic acid, in particular acetic acid.
- the organic acid, in particular acetic acid, used in this preferred embodiment to neutralize the KOH offers the advantage that in this case a soluble salt, in particular the potassium acetate, is obtained. The filtration step and thus the undesirable possibility of separating the layered silicates is eliminated.
- the polyether alcohol preferably contains the layered silicate (s) in an amount between 0.5 and 5% by weight, based on the total weight of the polyether alcohol.
- Another object of the present invention was to provide a method for
- soft foams for example soft integral foams, with improved properties, preferably improved elasticity, in particular with improved elongation at break.
- polyurethanes for example compact or cellular, cross-linked or thermoplastic poly Urethanes, for example flexible polyurethane, semi-rigid or rigid foams, preferably flexible polyurethane foams, are reacted by reacting (a) polyisocyanates with (b) compounds with hydrogen atoms reactive toward isocyanate groups, preferably in the presence of blowing agents, in which as (b) Compounds with hydrogen atoms reactive towards isocyanate groups use the polyether alcohols according to the invention.
- polyurethanes for example compact or cellular, cross-linked or thermoplastic poly Urethanes, for example flexible polyurethane, semi-rigid or rigid foams, preferably flexible polyurethane foams
- polyisocyanate polyaddition products for example polyurethanes, which may contain urea and / or isocyanurate structures
- polyisocyanates by reacting (a) polyisocyanates with (b) compounds reactive toward isocyanates, optionally in the presence of (c) chain extenders and / or crosslinking agents, (i.e. ) Catalysts which accelerate the reaction of the isocyanate-reactive substances with isocyanates and, if appropriate, (e) blowing agents and / or (f) additives are generally known, the production of the preferred flexible foams preferably being carried out in the presence of blowing agents (e).
- the PU foams and in particular the flexible PU foams by the process according to the invention, with the exception of the polyol component (b) according to the invention, the known structural components (a) to (d), blowing agents (e) and optionally additives (f) use to which the following can be carried out.
- 2,4- and / or 2,6-tolylene diisocyanate (TDI) and / or 4,4'-, 2,2'- and / or 2,4'-diphenylmethane diisocyanate (MDI) can preferably be used as isocyanates (a) , particularly preferably 2,4- and / or 2,6-tolylene diisocyanate, it being possible for the isocyanates to be used in modified form.
- the isocyanates (a) can have ester, urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione and / or urethane groups.
- generally known compounds, preferably diisocyanates are suitable as isocyanates, e.g. generally known aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyvalent isocyanates can be used.
- the compounds (b) which are reactive towards isocyanates are the polyether alcohols described at the outset, containing the delaminated layered silicates.
- other polyols selected from the group of polyether polyols, polyester polyols, polythioether polyols, hydroxyl group-containing polyester amides, hydroxyl group-containing polyacetals, hydroxyl group-containing aliphatic polycarbonates and polymer-modified polyether polyols or mixtures of at least two of the polyols mentioned can optionally be used are used.
- the polyurethane foams can be produced with or without the use of chain extenders and / or crosslinking agents (c).
- chain extenders preferably diols and / or triols, with molecular weights preferably less than 499 g / mol, preferably from 60 to 300 g / mol, are used as chain extenders and / or crosslinking agents.
- Suitable chain extenders are, for example, aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14 carbon atoms, such as, for example, ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably ethylene glycol, butanediol-1, 3, butanediol-1, 4, hexanediol-1, 6 and bis- (2-hydroxyethyl) -hydroquinone and as crosslinking agents, triols, such as 1,2,4-, 1,3,5 -Trihydroxycyclohexane, trimethylolethane, glycerin and trimethylolpropane.
- the compounds of component (c) are also used, they can be used in the form of mixtures or individually and are advantageously used in amounts of 1 to 40 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight. Parts of the higher molecular weight polyhydroxyl compounds (b) applied.
- Suitable catalysts (d) are generally customary compounds, for example organic amines, for example triethylamine, triethylene diamine, tributylamine, dimethylbenzylamine, N, N, N ', N'-tetramethylethylene diamine, N, N, N', N'-tetramethylbutane diamine , N, N, N ', N'-tetramethylhexane-1,6-diamine, dimethylcyclohexylamine, pentamethyldipropylenetriamine, pentamethyldiethylenetriamine, 3-methyl-6-dimethylamino-3-azapentol, dimethylaminopropylamine, 1,3-bisdimethylaminobutane, bis ( 2-dimethylaminoethyl) ether, N-ethylmorpholine, N-methylmorpholine, N-cyclohexylmorpholine, 2-dimethylamino-ethoxy-ethanol, dimethylethanolamine,
- organic metal compounds can be used as catalysts for this purpose, preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, e.g. Tin (II) acetate, Tin (II) octoate, Tin (II) ethylhexoate and Tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate.
- Tertiary aliphatic and / or cycloaliphatic amines can preferably be used, particularly preferably triethylenediamine.
- Water is preferably used as the blowing agent (s), which reacts with the organic, optionally modified polyisocyanates (a) to form carbon dioxide and urea groups, thereby influencing the compressive strength of the end products. enced.
- the water is usually used in amounts of 0.05 to 6% by weight, preferably 0.1 to 5% by weight, based on the weight of the structural components (a) to (c).
- Low-boiling liquids which evaporate under the influence of the exothermic polyaddition reaction and advantageously have a boiling point under normal pressure in the range from -40 to 90 ° C., preferably from 10 to 50, can also be used as blowing agent (d) instead of water or preferably in combination with water ° C, or gases are used.
- the liquids of the above-mentioned type and gases suitable as blowing agents can be selected, for example, from the group of alkanes and alkenes such as, for example, propane, n- and isobutane, n- and isopentane and preferably technical pentane mixtures, cycloalkanes such as cyclobutane, Cyclopentane, cyclohexane and preferably cyclopentane and / or cyclohexane, dialkyl ethers, such as, for example, dimethyl ether, methyl ethyl ether and diethyl ether, cycloalkylene ethers, such as, for example, furan, ketones, such as, for example, acetone, methyl ethyl ketone, carboxylic acid esters, such as ethyl acetate and methyl formate, carboxylic acids such as formic acid, acetic acid and propionic acid Fluoroalkane
- low-boiling liquid and gases which can be used individually as liquid or gas mixtures or as gas-liquid mixtures, depends on the density that you want to achieve and the amount of water used.
- the required quantities can easily be determined by simple manual tests. Satisfactory results usually provide amounts of liquid from 0.5 to 20 parts by weight, preferably from 2 to 10 parts by weight and gas amounts from 0.01 to 30 parts by weight, preferably from 2 to 20 parts by weight, based on each per 100 parts by weight of component (b) and optionally (c).
- Water, alkanes with 3 to 7 carbon atoms, cycloalkanes with 4 to 7 carbon atoms or mixtures containing at least two of the compounds mentioned as preferred blowing agents are preferably used as blowing agent (s).
- Additives (f) can optionally be used to produce the polyisocyanate polyadducts, in particular the flexible polyurethane foams, by the process according to the invention.
- additives are: surface-active substances, foam stabilizers, cell regulators, lubricants, fillers, dyes, pigments, flame retardants, hydrolysis protection agents, fungistatic and bacteriostatic substances.
- foams can be reacted in amounts such that the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of the reactive hydrogen atoms of components (b) and optionally (c) is 0.70 to 1.50: 1, preferably 0.85 to 1.15: 1 and in particular 0.9 to 1.1: 1.
- the foams can be prepared by the prepolymer or preferably by the one-shot process with the aid of the low-pressure technique or the high-pressure technique in open or closed, suitably temperature-controlled molds, for example metallic molds, for example made of aluminum, cast iron or steel, or molds made of fiber-reinforced polyester - Or epoxy molding compounds are produced.
- the starting components are usually mixed at a temperature of from 15 to 80 ° C., preferably from 25 to 55 ° C., and can be introduced without pressure into an open mold or, if appropriate, into a closed mold under increased pressure.
- the mixing can be carried out mechanically by means of a stirrer or back screw or under high pressure in the so-called counter-current injection process.
- the mold temperature is advantageously 20 to 120 ° C, preferably 30 to 80 ° C and in particular 45 to 60 ° C.
- Polyurethane flexible foam molded articles produced with compression the degrees of compression are usually in the range from 1.1 to 8.3, preferably from 2 to 7 and in particular from 2.4 to 4.5.
- the amount of the reaction mixture introduced into the mold is advantageously such that the moldings obtained have a total density of 0.01 to 0.9 g / cm 3 , preferably 0.03 to 0.7 g / cm 3 .
- the flexible polyurethane foams can also be produced using the block foam process.
- the block foams usually have densities of 0.02 to 0.06 g / cm 3 .
- the block foams and flexible polyurethane foam moldings produced by the process according to the invention are used, for example, in the motor vehicle industry, e.g. as armrests, headrests and safety cladding in the interior of a motor vehicle, as well as a bicycle or motorcycle saddle, shoe soles and as an inner shoe for ski boots. They are also suitable as upholstery materials in the furniture and automotive industries.
- the product is homogeneous.
- a polyurethane foam was produced by hand foaming from 100 parts by weight of A component and 42.9 parts of B component.
- the reaction mixture was stirred with a disk stirrer from Vollrath at a speed of approximately 1800 revolutions per minute.
- Polyol A from the basic formulation was replaced by the polyether alcohol according to the invention with 1.12% exfoliated layered silicate.
- the foam obtained with the layered silicate has a density of 40 + 2 g / l with 91% an improved elongation at break compared to 79% elongation at break (measured according to DIN EN ISO 1798) of the foam without layered silicate.
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- Polymers & Plastics (AREA)
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Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05750175A EP1761584A1 (de) | 2004-06-16 | 2005-06-09 | Verfahren zur herstellung von polyetheralkoholen und polyurethanen |
US11/628,465 US20080064779A1 (en) | 2004-06-16 | 2005-06-09 | Method For Producing Polyether Alcohols And Polyurethanes |
MXPA06013567A MXPA06013567A (es) | 2004-06-16 | 2005-06-09 | Metodo para producir alcoholes de polieter y poliuretanos. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102004028769A DE102004028769A1 (de) | 2004-06-16 | 2004-06-16 | Verfahren zur Herstellung von Polyetheralkoholen und Polyurethanen |
DE102004028769.4 | 2004-06-16 |
Publications (1)
Publication Number | Publication Date |
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WO2005123806A1 true WO2005123806A1 (de) | 2005-12-29 |
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PCT/EP2005/006197 WO2005123806A1 (de) | 2004-06-16 | 2005-06-09 | Verfahren zur herstellung von polyetheralkoholen und polyurethanen |
Country Status (7)
Country | Link |
---|---|
US (1) | US20080064779A1 (de) |
EP (1) | EP1761584A1 (de) |
KR (1) | KR20070020277A (de) |
CN (1) | CN1968990A (de) |
DE (1) | DE102004028769A1 (de) |
MX (1) | MXPA06013567A (de) |
WO (1) | WO2005123806A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011107367A1 (de) * | 2010-03-02 | 2011-09-09 | Basf Se | Verfahren zur herstellung von polyetheralkoholen |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200942558A (en) * | 2008-04-09 | 2009-10-16 | jin-bing Zhang | Method of preparing MDI (Methylene Diphenyl di-Isocyanate) polyurethane polymer |
EP2406182B1 (de) * | 2009-03-13 | 2017-05-10 | Basf Se | Verfahren zur herstellung von silica-haltigen dispersionen enthaltend polyetherole oder polyetheramine |
US20110218324A1 (en) * | 2010-03-02 | 2011-09-08 | Basf Se | Preparing polyether alcohols |
EP2722144A1 (de) * | 2012-10-19 | 2014-04-23 | Bayer MaterialScience AG | Reaktionssystem zur Herstellung von PUR- und PIR Hartschaumstoffen enthaltend Schichtsilikate |
DE102015000393A1 (de) | 2014-01-21 | 2015-07-23 | Frank Becher | Verfahren zur Herstellung von geschlossen-porigen Erzeugnissen mit hohlen Zellen, mittels dessen der Druck in den Zellen kontrolliert während des Aufschäumens erhöht oder reduziert werden kann, sowie Erzeugnisse, die nach diesem Verfahren hergestellt werden |
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US4251427A (en) * | 1978-09-30 | 1981-02-17 | Bayer Aktiengesellschaft | Coating compositions from polyurethanes containing a molecular sieve of the sodium aluminum silicate type |
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US4521548A (en) * | 1983-04-12 | 1985-06-04 | The Dow Chemical Company | Preparation of polyether polyols |
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-
2004
- 2004-06-16 DE DE102004028769A patent/DE102004028769A1/de not_active Withdrawn
-
2005
- 2005-06-09 CN CNA2005800196548A patent/CN1968990A/zh active Pending
- 2005-06-09 US US11/628,465 patent/US20080064779A1/en not_active Abandoned
- 2005-06-09 MX MXPA06013567A patent/MXPA06013567A/es unknown
- 2005-06-09 EP EP05750175A patent/EP1761584A1/de not_active Withdrawn
- 2005-06-09 WO PCT/EP2005/006197 patent/WO2005123806A1/de not_active Application Discontinuation
- 2005-06-09 KR KR1020067025587A patent/KR20070020277A/ko not_active Application Discontinuation
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US5969166A (en) * | 1904-12-09 | 1999-10-19 | Hoechst Aktiengesellschaft | Epoxides produced by the oxidation of olefins with air or oxygen |
US4251427A (en) * | 1978-09-30 | 1981-02-17 | Bayer Aktiengesellschaft | Coating compositions from polyurethanes containing a molecular sieve of the sodium aluminum silicate type |
US4215004A (en) * | 1979-03-28 | 1980-07-29 | Chemed Corporation | Slurried laundry detergent |
US4526906A (en) * | 1983-09-06 | 1985-07-02 | Wegner Development Company | Non-burning, non-dripping instant set microcellular polyurethanes |
EP0323209A2 (de) * | 1987-12-30 | 1989-07-05 | Unilever Plc | Reinigungsmittel |
EP0431728A1 (de) * | 1989-09-25 | 1991-06-12 | Texaco Chemical Company | Sprüh-Polyharnstoffelastomere mit verbesserter Abriebfestigkeit |
US5728745A (en) * | 1995-06-15 | 1998-03-17 | Arco Chemical Technology, L.P. | Polyurethane elastomers having improved green strength and demold time, and polyoxyalkylene polyols suitable for their preparation |
EP0778302A1 (de) * | 1995-12-07 | 1997-06-11 | Shell Internationale Researchmaatschappij B.V. | Polyetherpolyd zur Herstellung von starren Polyurethanschäumen |
WO1999052883A1 (en) * | 1998-04-15 | 1999-10-21 | The Dow Chemical Company | Process for the direct oxidation of olefins to olefin oxides |
WO1999055765A1 (en) * | 1998-04-27 | 1999-11-04 | The Dow Chemical Company | High molecular weight polyols, process for preparation and use thereof |
US6538043B1 (en) * | 1998-09-10 | 2003-03-25 | Shell Oil Company | Co-initiated polyether polyol and process for its preparation |
DE10032334A1 (de) * | 2000-07-04 | 2002-01-17 | Basf Ag | Schaumstoffe auf der Basis von Polyisocyanat-Polyadditionsprodukten |
WO2003059817A2 (en) * | 2002-01-21 | 2003-07-24 | Huntsman International Llc | Nano composite materials with enhanced properties |
DE10244283A1 (de) * | 2002-09-23 | 2004-04-01 | Basf Ag | Verfahren zur Herstellung von Polyetheralkoholen |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011107367A1 (de) * | 2010-03-02 | 2011-09-09 | Basf Se | Verfahren zur herstellung von polyetheralkoholen |
Also Published As
Publication number | Publication date |
---|---|
EP1761584A1 (de) | 2007-03-14 |
MXPA06013567A (es) | 2007-03-15 |
US20080064779A1 (en) | 2008-03-13 |
CN1968990A (zh) | 2007-05-23 |
DE102004028769A1 (de) | 2005-12-29 |
KR20070020277A (ko) | 2007-02-20 |
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