DE19630281A1 - Preparation of rigid or flexible poly:urethane foams for e.g. insulation, furniture or motor vehicles - Google Patents

Abstract

A method for the preparation of polyurethane foams comprises the reaction of: (A) optionally modified organic di- and/or polyisocyanates; with (B) polyether polyols, prepared by polymerisation of alkylene oxides with starter compounds containing functional hydrogen atoms and optional additional high molecular weight compounds containing at least two reactive hydrogen atoms; and (C) optional low molecular weight chain extenders and/or cross-linking agents ; in the presence of (D) propellents; (E) catalysts; and (F) optional further auxiliary agents and/or additives. (B) are treated with carboxylic acids containing at least four carbon atoms during and/or after the polymerisation reaction between alkylene oxides and H-functional starter compounds.

Description

The invention relates to processes for the production of polyurethane NEN by implementing organic and / or modified orga African di- and / or polyisocyanates with polyether polyols, producible by polymerization of alkylene oxides on H-functio nelle starters, and possibly other higher molecular weight Compounds with at least two reactive hydrogen atoms and other conventional auxiliaries and / or additives.

The production of polyurethane foams by implementing NCO-containing compounds, especially organic polyiso cyanates and / or modified organic polyisocyanates or Prepolymers based on organic isocyanates, with higher functional compounds with at least two reactive water atoms of matter, for example polyoxyalkylene polyamines and / or preferably organic polyhydroxy compounds is common have been described. As polyhydroxy compounds are dependent the desired type of finished polyurethane foam Substance preferably polyether and / or polyesterols under different composition and with different molecular weights used and with the use of the usual additive substances such as chain extenders and / or crosslinking agents, Catalysts, blowing agents and other aids, with the Isocyanates converted to polyurethane foams. To summarize send overview of the production of polyurethane foams z. B. in the plastic manual, volume VII, "Polyurethane", 1st edition, 1966, published by Dr. R. Vieweg and Dr. A. Höchtlen and 2nd edition, 1983, and 3rd edition, 1993, edited by Dr. G. Oertel (Carl Hanser Verlag, Munich) ge give.

As a polyol component, rigid foams become high functional polyols, in particular polyether-based polyols highly functional alcohols, sugar alcohols, saccharides and / or highly functional amines, optionally in a mixture with low functional alcohols and / or amines, and propylene oxide and / or ethylene oxide, for flexible foams 2- and / or 3-functional Polyether and / or polyester polyols based on glycerin and / or Trimethylolpropane and / or glycols and alkylene oxides or ali phatic and / or aromatic dicarboxylic acids used. The Production of the polyether polyols takes place according to a known technology. Depending on the application, the necessary mixed with starter substances, with basic catalyst, ins  special alkali or alkaline earth metal hydroxides, added and at it elevated temperatures and pressures with alkylene oxides, in particular Ethylene and / or propylene oxide, implemented. After synthesis the catalyst by acid neutralization, distillation and fil tration removed. The two anorga are the main acids African acids hydrochloric acid and / or phosphoric acid because of the exact Control of the equivalence point and the technologically simple Removal of any excess acid used.

Common methods, such as. B. in EP-A-59 368 or also DE-A-40 14 484 described go from neutralization under one set of organic or inorganic acids and subsequent Separation of the salts formed, in particular by filtration, out. Even with special cleaning methods using acidic salts, as described in DE-A-38 01 504, the Rohpo finally filtered.

If the neutralization is carried out with carboxylic acids, so obtained partly insoluble, partly soluble salts in the polyetherol, which remain in the polyol. Neutralization is difficult because of the In this case the neutral point must be met very precisely.

DE-A-41 20 432 and WO 93/00378 describe the use of Di hydroxy fatty acids as polyurethane building blocks. It will be carboxy Functional, ionizable polyurethanes, because the Carboxylic acid not under the usual reaction conditions Isocyanates react and the incorporation into the polyurethane alone via the hydroxy functions.

DE-A-42 02 758 describes that certain of the invention Hydroxycarboxylic acids with isocyanates under CO₂ development and React foam formation. The hydroxycarboxylic acids are through Ring opening of epoxidized unsaturated fatty acids with hydroxy compound such as water or alcohol. The production the polyhydroxy fatty acids according to the invention is in DE-A-33 18 596 and EP-A-237 959.

DE-A-42 15 647 and DE-A-42 42 018 describe the production of Substances with amide and urea groups. Carboxylic acids and iso cyanates are in the presence of certain catalysts, namely heteroaromatic amines with substituents with + I and + M effect, implemented.  

EP-A-423 594 describes the production of polyurethane foam fabrics, especially with a dense outer zone, as a propellant salts from organic carboxylic acids, especially lactic acid, and amines can be used.

DE-A-40 41 119 describes the use of multifunctional, non-saponifiable alcohols, available through the ring opening Implementation of epoxidized olefins and epoxidized fatty alcohols low molecular weight diols and triols, as an additive to polyol components.

The present invention was based on the object of a method ren for the production of polyurethane foams based on orga African, in particular aromatic isocyanates and more specifically Polyether polyols with organic acids with no problem Setting the neutral point and avoiding deneutralization steps with formation of homogeneous reaction products and under Avoiding polyol filtration to be cleaned in the presence to show usual auxiliaries and additives.

This object was achieved in that Production of the polyurethane foams while the polyether polyols rend and / or after the alkylene oxide addition to the H function len starting substances of a treatment with carboxylic acids with at least undergo at least 4 carbon atoms.

The invention accordingly relates to a method for the manufacture position of polyurethane foams by implementation of

• a) organic and / or modified organic di- and / or Polyisocyanates with
• b) polyether polyols which can be prepared by polymerizing Alkylene oxides on H-functional starters, as well as given if other higher molecular compounds with at least two reactive hydrogen atoms and optionally
• c) low molecular chain extension and / or crosslinking average

in the presence of

• d) blowing agents,
• e) catalysts and optionally  
• f) further auxiliaries and / or additives,

which is characterized in that the polyether polyols during and / or after the alkylene oxide addition to the H-functional Starting substances of a treatment with carboxylic acids with at least 4 carbon atoms are subjected.

The invention further relates to the use of these Polyurethane foams as rigid polyurethane foams in the cooling and thermal insulation area and in construction as well as flexible poly urethane foams in the furniture and automotive sectors.

Depending on the type of polyurethane foam required are particularly high molecular weight for flexible polyurethane foams lare polyether polyols and for rigid polyurethane foams special highly branched polyether polyols used. you will be usually by polymerization of alkylene oxides on H radio tional starters. For the production of high molecular weight Ren polyether polyols for flexible polyurethane foams preferably two- and / or three-functional starter substances, such as Ethylene, propylene glycol and / or higher glycols or glycol po lyether and / or glycerin or trimethylolpropane and / or two- and trifunctional amine starters, if appropriate also with a proportion of more functional alcoholic or aminic substances, used individually or in a mixture with Alkylene oxide reacted with the or ganic acids during and / or after the alkylene oxide addition treated and with conventional polyurethane catalysts, propellant agents, foam stabilizers and other auxiliaries and additives converted to polyurethane. For the production of highly branched Polyether polyols for rigid polyurethane foams are preferred wise higher functional alcoholic and / or amine start substances such as higher functional alcohols, sugar alcohols and / or saccharides, optionally together with low-functionality Alcohols and / or with aliphatic or aromatic amines, used, reacted individually or in a mixture with alkylene oxide, with the organic acids to be used according to the invention during and / or treated after the alkylene oxide addition and with the usual auxiliaries and additives to polyurethane implemented. As Alkylene oxides are primarily the lower alkylene oxides ethylene, Propylene and butylene oxide individually in block arrangement and / or in a statistical mixture of two or three alkylene oxides attached. The alkoxylation is preferably carried out at temperatures from 60 to 140 ° C, in particular from 80 to 120 ° C, and unpressurized or especially with slight overpressures from 0.1 to 1.0 MPa below Addition of basic catalysts, especially alkali or  Alkaline earth metal hydroxides, particularly preferably of KOH, or of aminic catalysts performed.

Treatment with the organic to be used according to the invention Acids appear during and / or after the alkylene oxide addition the H-functional starter substances. Preferably he it follows during the alkylene oxide addition and ins especially at the end of the active alkylene oxide metering or during the post-reaction phase and / or after the alkylene oxide addition.

Treatment with organic acids is preferred for the according to the reaction phase at temperatures of 60 up to 140 ° C without pressure, with slight overpressures or under light vacuum.

In addition to salt formation reactions, polycondensation reactions can also occur ions, esterification reactions or etherification reactions ablau fen. In order to strengthen esterification reaction processes in particular, it is possible before and / or during treatment with the carboxylic acids according to the invention special catalysts, such as Ti tan and / or tin compounds, the reaction mixture in quantities add from 2 to 100 ppm of active substance.

For the treatment according to the invention with organic acids Carboxylic acids with at least 4 carbon atoms used. Here for come in particular saturated and unsaturated carboxylic acids, alkyl-branched carboxylic acids, carboxylic acids that contain an oxygen function and / or have a ring in the chain, dimer and / or trimercarboxylic acids and carboxylic acid mixtures in question.

Butter may be mentioned as an example of saturated carboxylic acids acid, valeric acid, caproic acid, enanthic acid, caprylic acid, Pelargonic acid, lauric acid, palmitic acid, stearic acid and Lactic acid, as unsaturated carboxylic acids lauroleic acid, oil acid, elaidic acid, linoleic acid, linolenic acid, isanoic acid and 6-octadecic acid, as alkyl-branched carboxylic acids Isovalerian acid, 10-methyloctadecanoic acid and 2-ethylhexanoic acid, as carbon acids that have an oxygen function ricinoleic acid, ver nolic acid and 4-keto-9,11,13-octadecatrienoic acid, as carboxylic acids, which have a ring in the chain, 13- (2-cyclopentyl) tride canoic acid, as saturated and unsaturated di- and tricarboxylic acids Sebacic acid (octane-1,8-dicarboxylic acid) or longer-chain dimer and trimercarboxylic acids, such as C₃₆ dimer fatty acid, and as carboxylic acid mixtures tall oil fatty acid.  

The carboxylic acids can be used individually or as a mixture with one another are used. It is also a combination of the invention according to the carboxylic acids to be used with those for the catalyst removal from polyetherols commonly used anor ganic or organic acids, such as. B. hydrochloric acid, phosphorus acid or acetic acid, possible.

The carboxylic acids are preferably used in an amount of 0.5 to 10 times that for the neutralization of the basic catalyst necessary stoichiometric amount used. Usually be the ratio of carboxylic acid to polyether polyol is 1 to 5 to 1 to 5000, in particular 1 to 10 to 1 to 1000. Are mixtures of Carboxylic acids used with inorganic acids, so refers the stated ratio to the total acid input. The amount of the organic carboxylic acids according to the invention with at least 4 Carbon atoms is at least 20, preferably min at least 60% by weight, based on the total acid input.

Before treatment with the carboxylic acids according to the invention, ins especially when treated after the alkylene oxide addition Water in amounts of 1 to 10 wt .-% of the raw polyetherol added will. After the treatment, the polyetherol is at 80 to 120 ° C, optionally distilled under vacuum or the alkylene oxide Attachment is completed in the usual way and it is countered distilled if necessary.

The polyether polyols produced in this way are, if appropriate in a combination nation with other higher molecular compounds with at least two reactive hydrogen atoms, with the other components too Polyurethane foams, especially flexible or rigid Polyurethane foams implemented.

The inventive method has the advantage that the Be act with the carboxylic acids of the catalyst is neutralized, the resulting salts homogeneously in the polyol can stay and in polyurethane synthesis as emulsifiers or additive and thus special polyurethane / polyiso cyanurate structures can be produced. Combined is also one Partial esterification of the carboxylic acid according to the invention with existing ones shorter polyether polyol products possible. The result from it allow the polyetheresterols to have special properties in the Processing for better propellant solubility, tax Hydrophobic / hydrophilic character and emulsifying egg properties.  

Those in the treatment of the basic polyetherols with the carbon acidic homogeneous reaction products exist everything from the carboxylates and the carboxylate derivatives, ins especially the carboxylates still carrying free carboxyl groups and which is optionally formed by polycondensation / esterification existing polyester or polyetherester products. The former work by splitting off CO₂ as a blowing agent or as a co-blowing agent and he possible a replacement or a partial replacement of the usual used blowing agents, such as water and / or alkanes. Farther the reaction products act as emulsifiers and help ins especially in the case of polyolic multi-component mixtures, such as between poly ether and polyesterols, as solubilizers. It will Inhomogeneities and segregation in the polyurethane systems and components avoided.

To produce the polyurethane foams according to the Invention find methods according to the invention, with the exception of the herge provided polyether polyols, the structure known per se components use, to which the following must be carried out in detail ren is.

a) As organic and / or modified organic di- and / or Polyisocyanates (a) come from the known aliphati rule, cycloaliphatic, araliphatic and preferably the aromatic polyvalent isocyanates in question.

Examples include: alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dode candiioscyanate, 2-ethyl-tetramethylene diisocyanate-1,4, 2-Me thylpentamethylene diisocyanate-1,5, tetramethylene diiso cyanate 1,4, and preferably hexamethylene diisocyanate 1,6; cycloaliphatic diisocyanates such as cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- and 2,6-hexahydrotoluenediisocyanate and the corresponding mixtures of isomers, 4,4'-, 2,2'- and 2,4'-di cyclohexylmethane diisocyanate and the corresponding iso mixed mixtures, and preferably aromatic di- and polyiso cyanates such as B. 2,4- and 2,6-tolylene diisocyanate and corresponding mixtures of isomers, 4,4'-, 2,4'- and 2,2'-di phenylmethane diisocyanate and the corresponding isomers mixtures, mixtures of 4,4'- and 2,2'-diphenylmethane diiso cyanates, polyphenylpolymethylene polyisocyanates, mixtures from 2,4'-, 2,4'- and 2,2, -diphenylmethane diisocyanates and Po lyphenylpolymethylene polyisocyanates (raw MDI) and mixtures from raw MDI and tolylene diisocyanates. The organic di  and polyisocyanates can be used individually or in the form of their Mixtures are used.

So-called modified polyvalent iso are also common cyanate, d. H. Products that are organi shear di- and / or polyisocyanates are used. Examples include ester, urea, biuret, Allophanate, carbodiimide, isocyanurate, uretdione and / or Di- and / or polyisocyanates containing urethane groups. in the For example, some are: urethane groups containing organic, preferably aromatic polyiso cyanates with NCO contents of 33.6 to 15% by weight, preferably from 31 to 21% by weight, based on the total weight for example with low molecular weight diols, triplets, dialkyls glycols, trialkylene glycols or polyoxyalkylene glycols Molecular weights up to 6000, especially with molecular weight weight up to 1500, modified 4,4'-diphenylmethane diiso cyanate, modified 4,4'- and 2,4'-diphenylmethane diisocya natural mixtures, modified raw MDI or 2,4- or 2,6-tolylene diisocyanate, being di- or polyoxyalkylene glycols that can be used individually or as mixtures NEN, for example: diethylene, dipropylene glycol, polyoxyethylene, polyoxypropylene and polyoxypropy lenpolyoxyethene glycols, triols and / or tetrols. Suitable are also prepolymers containing NCO groups with an NCO content from 25 to 3.5% by weight, preferably from 21 to 14% by weight, based on the total weight, made from the following described polyester and / or preferably poly ether polyols and 4,4'-diphenylmethane diisocyanate, mixtures from 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-tolylene diisocyanates or crude MDI. Have proven themselves also liquid, carbodiimide groups and / or isocyanurate rings containing polyisocyanates with NCO contents of 33.6 to 15, preferably 31 to 21% by weight, based on the total weight, e.g. B. based on 4,4'-, 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4- and / or 2,6-tolylene diisocyanate.

The modified polyisocyanates can be used together or with unmodified organic polyisocyanates such as B. 2,4'-, 4,4'-diphenylmethane diisocyanate, crude MDI, 2,4- and / or 2,6-tolylene diisocyanate may be mixed.

Organic polyisocyanates have proven particularly useful and are therefore preferably used: mixtures of Toluene diisocyanates and raw MDI or mixtures of modifi graced, organic polyiso containing urethane groups cyanates with an NCO content of 33.6 to 15 wt .-%, ins  special ones based on tolylene diisocyanates, 4,4'-diphenylmethane diisocyanate, diphenylmethane diisocyanate Isomer mixtures or crude MDI and in particular crude MDI with a diphenylmethane diisocyanate isomer content of 30 to 80% by weight, preferably from 30 to 60% by weight, in particular from 30 to 55% by weight.

b) The polyether polyols are those produced according to the invention Polyether polyols as described above are used. There In addition, other higher molecular compounds with min at least two reactive hydrogen atoms in an amount of 20 to 80 wt .-%, preferably 20 to 40 wt .-%, based on the Weight of component (b) can also be used.

As further higher molecular compounds with at least two reactive hydrogen atoms are expediently such with a functionality of 2 to 8, preferably 2 to 6, and a molecular weight of 300 to 8000, preferably of 300 to 3000 used. The use depends on the desired properties of the polyurethane foam to be produced fabric. Have proven themselves. B. polyether polyamines and / or preferably polyols selected from the group of poly ether polyols, polyester polyols, polythioether polyols, poly ester amides, hydroxyl-containing polyacetals and hydroxyl group-containing aliphatic polycarbonates or mixtures from at least two of the polyols mentioned. Preferably on Polyester polyols and / or polyether polyols are used. The hydroxyl number of the polyhydroxyl compounds is usually 150 to 850 mg KOH / g and preferably 200 to 600 mg KOH / g.

Polyethers are used in particular as further polyols polyols by known methods, for example by anionic polymerization with alkali hydroxides, such as. B. Well trium or potassium hydroxide or alkali alcoholates, such as. B. Sodium methylate, sodium or potassium ethylate or potassium iso propylate, as catalysts and with the addition of at least one Starter molecule, the 2 to 8, preferably 2 to 6, reactive Contains hydrogen atoms bound, or by cationic Po lymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate u. a. or bleaching earth, as catalysts one or more alkylene oxides with 2 to 4 carbon atoms Men are produced in the alkylene radical.

Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide. The alkylene  oxides can be used individually, alternately in succession or as Mi be used. Come as starter molecules Examples include: water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalate acid, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'-dialkyl-substituted diamines with 1 to 4 Koh lenstoffatomen in the alkyl radical, such as mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, tri ethylene tetramine, 1,3-propylene diamine, 1,3- or 1,4-butylene diamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylene diamine, Phenylenediamines, 2,3-, 2,4- and 2,6-toluenediamine and 4,4′-, 2,4'- and 2,2'-diamino-diphenylmethane.

Other suitable starter molecules are: alkanolamines, such as B. ethanolamine, N-methyl and N-ethylethanolamine, Dialkanolamines such as e.g. B. diethanolamine, N-methyl and N-ethyl-diethanolamine, and trialkanolamines, such as. B. Trietha nolamine, and ammonia. More are preferably used term, especially di- and / or trihydric alcohols, such as Ethanediol, 1,2-propanediol and 1,3, diethylene glycol, dipropy lenglycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethy lolpropane, pentaerythritol, sorbitol and sucrose.

The polyether polyols have a functionality from before preferably 2 to 6 and in particular 2 to 4 and molecular weight weights from 300 to 3000, preferably 300 to 2000 and in particular especially 400 to 2000.

Polymer-modified are also suitable as polyether polyols Polyether polyols, preferably graft polyether polyols, in particular special ones based on styrene and / or acrylonitrile by in situ polymerization of acrylonitrile, styrene or preferably mixtures of styrene and acrylonitrile, e.g. B. in Weight ratio 90:10 to 10:90, preferably 70:30 to 30:70, advantageously in the aforementioned polyether polyols analogous to the information in German patent specifications 11 11,394, 12,22,669 (U.S. 3,304,273, 3,383,351, 3,523,093), 11 52 536 (GB 10 40 452) and 11 52 537 (GB 987 618) be, as well as polyether poly dispersions, which as disperse Phase, usually in an amount of 1 to 50% by weight preferably 2 to 25% by weight, contain: z. B. polyureas, Po lyhydrazide, tertiary amino groups containing bound polyure thane and / or melamine and the z. B. are described in the EP-B-011 752 (US 4 304 708), US-A-4 374 209 and DE-A-32 31 497.  

The polyether polyols can be used individually or in the form of mixtures gene can be used. You can also use the graft po lyether polyols or polyester polyols and the hydroxyl group-containing polyester amides, polyacetals, polycarbonates and / or polyether polyamines are mixed.

Suitable polyester polyols can, for example, from organic Dicarboxylic acids with 2 to 12 carbon atoms, preferred wise aliphatic dicarboxylic acids with 4 to 6 carbon a toms, and polyhydric alcohols, preferably diols, with 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms are made. As dicarboxylic acids come in Examples include: succinic acid, glutaric acid, adipine acid, suberic acid, azelaic acid, sebacic acid, decanedicarbonate acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can both used individually as well as in a mixture with each other. Instead of the free dicarboxylic acids, the corre sponding Chenden dicarboxylic acid derivatives, such as. B. dicarboxylic acid esters of alcohols with 1 to 4 carbon atoms or dicarboxylic acid reanhydrides are used. Preferably used Dicarboxylic acid mixtures of succinic, glutaric and adipic acids in proportions of, for example, 20 to 35: 35 to 50: 20 to 32 parts by weight, and especially adipic acid. Examples of di- and polyhydric alcohols, in particular Diols are: ethanediol, diethylene glycol, 1,2- or 1,3-propane diol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerin and trimethylolpro pan. Ethanediol, diethylene glycol are preferably used kol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or Mi from at least two of the diols mentioned, in particular right mixtures of 1,4-butanediol, 1,5-pentanediol and 1,6-He xandiol. Polyester polyols can also be used from lactones, e.g. B. ε-caprolactone or hydroxycarboxylic acids, e.g. B. ω-hydroxycaproic acid.

To prepare the polyester polyols, the organic, e.g. B. aromatic and preferably aliphatic, polycarbonate acids and / or derivatives and polyhydric alcohols peat-free or preferably in the presence of esterification catalysts analyzers, suitably in an atmosphere of inert gas such as B. nitrogen, carbon monoxide, helium, argon and. a., in the melt at temperatures of 150 to 250 ° C, preferably as 180 to 220 ° C, optionally under reduced pressure up to the desired acid number, which is advantageous is less than 10, preferably less than 2, polycondenses be settled. According to a preferred embodiment, this is  Esterification mixture at the above temperatures up to an acid number of 80 to 30, preferably 40 to 30, under Normal pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar, polycondensed. For example, iron, Cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or Metal salts into consideration. However, the polycondensation can also in the liquid phase in the presence of dilution and / or entraining agents, such as. As benzene, toluene, xylene or Chlorobenzene, for azeotropic distillation of the condensation water.

The organic polyols are used to produce the polyester polyols Polycarboxylic acids and / or derivatives and polyhydric alcohols advantageously in a molar ratio of 1: 1 to 1.8 preferably 1: 1.05 to 1.2, polycondensed.

The polyester polyols obtained preferably have one Functionality from 2 to 4, especially 2 to 3, and a mo molecular weight from 480 to 3000, preferably 600 to 2000 and especially 600 to 1500.

The polyester polyols can be used individually or in the form of Mixtures can be used. They too can, just like the polyether polyols, with the white listed below tere H-functional compounds are mixed.

As polyacetals containing hydroxyl groups such. B. from Glycols, such as diethylene glycol, triethylene glycol, 4,4'-dihy droxyethoxy-diphenyl-dimethylmethane, hexanediol and formaldehyde hyd producible compounds in question. Also through polymer suitable polyacetals produce.

Such polycarbonates come as hydroxyl groups of the type known per se, for example by reacting diols such as 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. B. Diphenyl carbonate, or phosgene can be produced.

The polyester amides include e.g. B. from polyvalent, ge saturated and / or unsaturated carboxylic acids or their An hydride and polyvalent saturated and / or unsaturated Amino alcohols or mixtures of polyhydric alcohols and  Amino alcohols and / or polyamines obtained, mainly li near condensates.

Suitable polyether polyamines can be obtained from the above Polyether polyols are produced by known processes the. The cyanoalkylation of Po may be mentioned by way of example lyoxyalkylene polyols and subsequent hydrogenation of the gebil Detected nitrile (US 3,267,050) or the partially or fully permanent amination of polyoxyalkylene polyols with amines or ammonia in the presence of hydrogen and catalysts (DE 12 15 373).

c) The polyurethane foams can with or without Mitver use of chain extension and / or crosslinking teln (c) are produced. To modify the mechani properties, z. B. the hardness, but can be too set of chain extenders, crosslinking agents or if appropriate, mixtures thereof prove to be advantageous sen. As a chain extender and / or crosslinking agent Diols and / or triols with molecular weights are used less than 400, preferably from 60 to 300. Considerable come for example aliphatic, cycloaliphatic and / or araliphatic diols with 2 to 14, preferably 4 to 10 Carbon atoms such as B. ethylene glycol, 1,3-propanediol, Decanediol-1,10, o-, m-, p-dihydroxycyclohexane, diethylene glycol kol, dipropylene glycol and preferably 1,4-butanediol, hexane diol-1,6 and bis (2-hydroxy-ethyl) hydroquinone, triols, such as 1,2,4-, 1,3,5-trihydroxycyclohexane, glycerin and trimethy lolpropane and low molecular weight hydroxyl-containing polyal kylene oxides based on ethylene and / or 1,2-propylene oxide and the aforementioned diols and / or triols as starter molecules.

If chain ver. For the production of the polyurethane foams extenders, crosslinking agents or mixtures thereof find application, these are expediently come in a quantity from 0 to 20% by weight, preferably from 2 to 8% by weight on the weight of component (b).

d) To blowing agents used to manufacture the polyurethane foams are used, preferably include water, the re with isocyanate groups to form carbon dioxide acts, and / or physically acting blowing agents. Suitable are liquids which are compared to the organic ones modified polyisocyanates are inert and boil points below 100 ° C, preferably below 50 ° C, especially between have -50 ° C and 30 ° C at atmospheric pressure, so that it under the influence of the exothermic polyaddition reaction  evaporate. Examples of such, preferably usable Liquids are alkanes such as heptane, hexane, n- and iso-pen tan, preferably technical mixtures of n- and iso-penta nen, n- and iso-butane and propane, cycloalkanes, such as cyclopen tan and / or cyclohexane, ethers such as furan, dimethyl ether and Diethyl ether, ketones such as acetone and methyl ethyl ketone, Car alkyl acid esters, such as methyl formate, dimethyl oxalate and Ethyl acetate and halogenated hydrocarbons, such as Methylene chloride, dichloromonofluoromethane, difluoromethane, tri fluoromethane, difluoroethane, tetrafluoroethane, chlorodifluor ethane, 1,1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2- fluoroethane and heptafluoropropane. Mixtures of this cute Rigid liquids with each other and / or with others substituted or unsubstituted hydrocarbons be used. Organic carbon are also suitable acids, such as B. formic acid, acetic acid, oxalic acid, Rici nolic acid and compounds containing carboxyl groups.

Water, chlorodifluoromethane, Chlorodifluoroethanes, dichlorofluoroethanes, pentane mixtures, Cyclohexane and mixtures of at least two of these propellants medium, e.g. B. mixtures of water and cyclohexane, mixtures from chlorodifluoromethane and 1-chloro-2,2-difluoroethane and counter also water.

These blowing agents are usually added to component (b) set. However, you can use the isocyanate component (a) or as a combination of both component (b) and iso cyanate component (a) or premixes of these components be added with the other structural components.

The amount of blowing agent or blowing agents used mixture is 1 to 25 wt .-%, preferably 5 to 15% by weight, based in each case on the polyol component (b).

If water serves as a blowing agent, it is preferably the Build-up component (b) in an amount of 0.5 to 5 wt .-%, be pulled on the build component (b) added. The Wasserzu set can be used in combination with the other written propellants.

Since in the treatment of the polyetherols according to the invention reaction products formed with the carboxylic acids Elimination of CO₂ can also act as a blowing agent the use of the above Reduce blowing agents.  

e) As catalysts (e) for the production of the polyurethane foam Substances are used in particular, which the Reaction of reactive hydrogen atoms, especially hydro xyl groups containing compounds of component (b) and optionally (c) with the organic, optionally modes accelerate the infected polyisocyanates (a).

Basic polyurethane is expediently used catalysts, for example tertiary amines, such as triethyl amine, tributylamine, dimethylbenzylamine, dicyclohexylmethyl amine, dimethylcyclohexylamine, N, N, N ′, N′-tetramethyl-diamino diethyl ether, bis (dimethylaminopropyl) urea, N-methyl or N-ethylmorpholine, N-cyclohexylmorpholine, N, N, N ′, N′- Tetramethylethylenediamine, N, N, N ′, N′-tetramethylbutanediamine, N, N, N ', N'-tetramethylhexanediamine-1,6, pentamethyldiethylene triamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo (2,2,0) octane, 1,4-diaza bicyclo (2,2,2) octane (Dabco) and alkanolamine compounds such as Triethanolamine, triisopropanolamine, N-methyl and N-ethyl diethanolamine, dimethylaminoethanol, 2- (N, N-dimethylamino ethoxy) ethanol, N, N ′, N ′ ′ - tris (dialkylaminoalkyl) hexahydrotri azine, e.g. B. N, N ', N' '- tris- (dimethylaminopropyl) -s-hexahydro triazine, and triethylenediamine. However, Me are also suitable tall salts such as ferric chloride, zinc chloride, lead octoate and preferably tin salts such as tin dioctoate, tin diethylhexoate and dibutyltin dilaurate and in particular mixtures of tertiary amines and organic tin salts.

Other suitable catalysts are: amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, alkali hydroxides, such as sodium hydroxide and alkali alcoholates, such as sodium methylate and potassium isopropylate, and alkali salts of long-chain Fatty acids with 10 to 20 carbon atoms and optionally sides permanent OH groups. Preferably 0.001 to 5% by weight, in particular 0.05 to 2% by weight, of catalyst or Catalyst combination, based on the weight of the components te (b).

f) The reaction mixture for producing the polyurethane foam if necessary, substances can also be used for additional aids and / or additives (f) are incorporated. May be mentioned at for example surface-active substances, foam stabilizer Ren, cell regulator, fillers, dyes, pigments, flame Protective, hydrolysis, fungistatic and bak teriostatic substances.  

As surface-active substances such. B. Connections in Consider which to support the homogenization of the Serve as starting materials and are also suitable if necessary, regulate the cell structure of plastics. Be mentioned for example emulsifiers, such as the sodium salts of Ricinus oil sulfates or of fatty acids and salts of fatty acids with Amines, e.g. B. oleic acid diethylamine, stearic acid diethanola min, ricinoleic acid diethanolamine, salts of sulfonic acids, e.g. B. alkali or ammonium salts of dodecylbenzene or di naphthylmethane disulfonic acid and ricinoleic acid; Foam stabilizer catalysts, such as siloxane-oxalkylene copolymers and others Organopolysiloxanes, ethoxylated alkylphenols, ethoxylated Fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and peanut oil, and cell regulators such as paraffins, Fatty alcohols and dimethylpolysiloxanes. To improve the Emulsifying effect, the cell structure and / or stabilization of the The oligomers described above are also suitable for foam Acrylates with polyoxyalkylene and fluoroalkane residues as sides groups. The surface-active substances are becoming more common in amounts of 0.01 to 5% by weight, based on 100% by weight component (b) applied.

As fillers, in particular reinforcing fillers, are the usual organic and anorga known per se African fillers, reinforcing agents, weighting agents, Means to improve the abrasion behavior in paint ben to understand coating agents, etc. In particular Examples include: inorganic fillers such as silica minerals, for example layered silicates such as antigo rit, serpentine, hornblende, amphibole, chrisotile and talc, Metal oxides such as kaolin, aluminum oxides, titanium oxides and egg senoxides, metal salts such as chalk, heavy spar and inorganic pigments such as cadmium sulfide and zinc sulfide, and glass u. a .. Kaolin (China Clay), aluminum are preferably used minium silicate and coprecipitates made from barium sulfate and aluminum silicate as well as natural and synthetic fibrous Mi minerals such as wollastonite, metal and especially glass fibers of different lengths, which may be mediated can. Organic fillers come in, for example Consideration: coal, melamine, rosin, cyclopentadienyl resins and graft polymers and cellulose fibers, polyamide, Po lyacrylonitrile, polyurethane, polyester fibers on the bottom location of aromatic and / or aliphatic dicarboxylic acid esters and especially carbon fibers.  

The inorganic and organic fillers can be used individually or used as mixtures and are the reaction mixture advantageously in amounts of 0.5 to 50% by weight, preferably 1 to 40% by weight, based on the weight of the com components (a) to (c), but the content of Mats, fleeces and fabrics made of natural and synthetic Fibers can reach values of up to 80% by weight.

Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloroprop pyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris (2,3-di bromopropyl) phosphate, tetrakis (2-chloroethyl) ethylenediphos phate, dimethylmethanephosphonate, diethanolaminomethylphosphon acid diethyl ester and commercially available halogen-containing flame protective polyols.

In addition to the halogen-substituted phosphates already mentioned inorganic or organic flame retardants, such as red phosphorus, aluminum oxide hydrate, antimony trioxide, Ar senoxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, such as. B. melamine, or mixtures from at least two flame retardants, such as. B. ammonium po lyphosphates and melamine and optionally corn starch or Ammonium polyphosphate, melamine and expandable graphite and / or also aromatic polyester to flame retard the bottom lyisocyanate polyaddition products are used. Generally mine has proven to be expedient, 5 to 50 wt .-%, preferably 5 to 25% by weight of said flame retardant tel, based on component (b).

Details of the other usual above mentioned Auxiliaries and additives are in the specialist literature, for example se of the monograph by J.H. Saunders and K.C. Fresh "high Polymers "Volume XVI, Polyurethanes, Parts 1 and 2, Publisher In terscience Publishers 1962 or 1964, or the plastic Manual, Polyurethane, Volume VII, Hanser-Verlag, Munich, Vienna, 1st and 2nd editions, 1966 and 1983.

For the production of the polyurethane foams according to the invention the organic and / or modified organic poly isocyanates (a), higher molecular weight compounds with at least two reactive hydrogen atoms (b) and optionally chain extender Gerungs- and / or crosslinking agent (c) in such amounts to Um brought that the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of the reactive hydrogen atoms components (b) and optionally (c) 0.85 to 1.25: 1, preferably 0.95 to 1.15: 1 and in particular 1 to 1.05: 1,  is. If the rigid polyurethane foams at least partially se isocyanurate groups bound, is usually a Ratio of NCO groups of the polyisocyanates (a) to the sum of the reactive hydrogen atoms of component (b) and optionally (c) from 1.5 to 60: 1, preferably 1.5 to 8: 1.

The polyurethane foams are advantageously after one shot process, for example with the help of high pressure or Low pressure technology in open or closed molds, for example, metallic molds. Common is also the continuous application of the reaction mixture suitable belt lines for the production of panels.

It has proven to be particularly advantageous after the two-com to work on component processes and the structural components (b), (d), (e) and optionally (c) and (f) in component (A) some and as component (B) the organic and / or modifi graced organic polyisocyanates (a) or mixtures of the mentioned polyisocyanates and optionally blowing agent (d) use.

The output components are dependent on the application at a temperature of 0 to 100 ° C, preferably from 20 to 60 ° C, mixed and raised in the open or, if necessary, under pressure into the closed mold or at a continuous workstation on a belt that the Reak absorbing mass, applied. The mixing can, as be has already been demonstrated, mechanically using a stirrer or a Stirring screw. The mold temperature be appropriately carries 20 to 110 ° C, preferably 30 to 60 ° C and especially 45 to 50 ° C.

According to the inventive method, depending on all common polyurethane foams, ins special but hard and flexible polyurethane foams, herge be put.

The polyures produced by the process according to the invention rigid foams usually have a density of 0.02 to 0.30 g / cm³, preferably from 0.025 to 0.24 g / cm³ and esp special from 0.03 to 0.1 g / cm³. They are particularly suitable as Insulation material in the construction and refrigeration sector, e.g. B. as Zwi layer for sandwich elements or for foaming cooling cabinet and freezer cabinets.  

The polyures produced by the process according to the invention than soft foams usually have a density of 15 to 100 kg / m³ and are used particularly in furniture and automobiles area used.

The invention is illustrated in the following exemplary embodiments ago explained.

Example 1 (comparison)

In a 2 l reaction flask with stirrer, thermometer and De Stillationseinrichtung were 1260 g of an alkaline poly etherols, made from sucrose, glycerin and water as hy starter mixture containing droxyl groups and propylene oxide under Use of 48% aqueous potassium hydroxide solution as anionic kata lysator, filled. The reaction product containing Potassium of 890 ppm and a pH of 11.5 became the neutral sation of the alkaline components at room temperature with 1.1 ml Phosphoric acid and 5% by weight of water, based on the polyetherol, added and at a temperature of 90 ° C over a period of Stirred for 2 hours. Then the water from the poly etherol by distillation at a temperature of 120 ° C and a pressure from 4 mbar over a period of 8 hours. The emerged NEN salts were separated by pressure filtration. The be heatable pressure filter was at a temperature of 105 ° C and operated at a pressure of 3 mbar. A polyetherol was also formed following specification:

Hydroxyl number = 408 mg KOH / g
Acid number = 0.04 mg KOH / g
pH = 7.8
Viscosity at 25 ° C = 5750 mPas
Potassium content = 9 ppm
Water content = 0.08% by weight.

The polyol component, consisting of:

40 parts by weight of the polyol described in Example 1,
27 parts by weight of a polyol based on sucrose / glycerol / propylene oxide, OH number 440 mg KOH / g,
13 parts by weight of a polyol based on amine / ethylene oxide / propylene oxide, OH number 110 mg KOH / g,
4 parts by weight of a polyol based on propylene glycol / propylene oxide, OH number 250 mg KOH / g,
2 parts by weight of silicone stabilizer SR 321 (company OSi Special ties),
2 parts by weight of dimethylcyclohexylamine,
2 parts by weight of water and
10 parts by weight of cyclopentane,

was with 120 parts by weight of MDI crude product, NCO content 31.5% by mass, intensive in a beaker with a volume of 1 l mixed.

With the help of a universal testing machine, a bolt was removed after 3 minutes with a diameter of 20 mm pressed into the foam. The one penetration depth was 10 mm (bolt test). This test is suitable to precisely determine the curing process at certain times.

In the bolt test, a result of 15 N was determined after 3 minutes.

Example 2

In a 1.5 l reaction flask with stirrer, thermometer and De 840 g of an alkaline poly etherols, produced analogously to Example 1, with a pH of 11.5 and a content of 890 ppm of potassium for neutralization 11.4 g of stearic acid and 2% by weight of water, based on the poly etherol, added and ge over a period of 2 hours at 130 ° C. stirs. In a subsequent distillation, the rest water at a temperature of 130 ° C and a vacuum of 10 mbar away. After a period of 60 minutes the product showed one Water content of 0.10% by weight.

The clear product had the following characteristics:

Hydroxyl number = 408 mg KOH / g
Acid number = 0.07 mg KOH / g
pH = 8.1
Viscosity at 25 ° C = 5710 mPas
Potassium content = 86 ppm
Water content = 0.16% by weight.

A foam was produced as in Example 1, wherein but 40 parts by weight of the polyol described in Example 2 were set.

In the bolt test, a result of 19 N was determined after 3 minutes.

Example 3 (comparison)

2500 g of an alkaline polyetherol made from toluene diamine, ethylene oxide and propylene oxide using 48% aqueous potassium hydroxide solution as an anionic catalyst, with  a potassium content of 407 ppm and a pH of 12.4 were placed in a 4 l reaction flask equipped with a stirrer, Thermometer and distillation device transferred. The product was based on 1.0 ml of phosphoric acid and 5 wt .-% water the polyetherol, and added over a period of 2 hours stirred at a temperature of 110 ° C. By a subsequent Distillation at a temperature of 130 ° C and a maximum The reaction became pressure of 6 mbar in a period of 8 hours water removed from the polyetherol. The potassium salts formed were then separated in a filtration step. The product was at a temperature of 110 ° C over a pressure filter passed with filter cloth at a pressure of 2.5 bar. The Polyetherol cleaned in this way had the following characteristic values:

Hydroxyl number = 394 mg KOH / g
Acid number = 0.01 mg KOH / g
pH = 9.0
Viscosity at 25 ° C = 14500 mPas
Potassium content = 12 ppm
Water content = 0.05% by weight

The polyol component, consisting of:

30 parts by weight of the polyol described in Example 3,
17 parts by weight of a polyol based on a Mannich condensate / propylene oxide, OH number 550 mg KOH / g,
18 parts by weight of a polyol based on sucrose / propylene oxide, OH number 490 mg KOH / g,
15 parts by weight of a polyol based on amine / ethylene oxide / propylene oxide, OH number 110 mg KOH / g,
4 parts by weight of a polyol based on propylene glycol / propylene oxide, OH number 250 mg KOH / g,
2 parts by weight of silicone stabilizer SR 321 (company OSi Special ties),
52 parts by weight of dimethylcyclohexylamine,
2 parts by weight of water and
10 parts by weight of cyclopentane,

was with 140 parts by weight of MDI crude product, NCO content 31.5% by mass, intensive in a beaker with a volume of 1 l mixed.

In the bolt test, a result of 20 N was determined after 3 minutes.  

Example 4

In a 4 l reaction flask equipped with a thermometer, Stirrer and distillation head were 3000 g of an alkaline Polyetherols, produced analogously to Example 3, with a pH of 12.4 and a potassium content of 407 ppm and presented with 0.236 g lactic acid and 2 wt .-% water, based on the poly etherol, added. The mixture was at a temperature of 90 ° C stirred over a period of 60 minutes. In one itself closing distillation was at a temperature of 120 ° C and a maximum vacuum of 4 mbar over a period of 5 hours the polyetherol is dried to a water content of 0.07% by weight. The clear polyetherol thus neutralized had the Characteristic values:

Hydroxyl number = 394 mg KOH / g
Acid number = undetectable
pH = 9.5
Viscosity at 25 ° C = 14395 mPas
Potassium content = 284 ppm
Water content = 0.075% by weight.

A foam was produced as in Example 1, wherein but 30 parts by weight of the polyol described in Example 4 were set.

In the bolt test, a result of 25 N was determined after 3 minutes.

Example 5 (comparison)

In a 2 l reaction flask equipped with a stirrer, Thermome ter and distillation head, 1700 g of an alkaline Polyetherols from glycerin and propylene oxide, using 48% aqueous potassium hydroxide solution as an anionic catalyst gate manufactured, filled. The reaction product contained 930 ppm alkali in the form of potassium and had a pH of 12.1. At a temperature of 80 ° C were used for neutralization 1.79 g acetic acid and 2 wt .-% water, based on the poly etherol, added and stirred for 2 hours. A distillation of the Water in the polyetherol followed. This was done the reaction product heated to 120 ° C and under vacuum, the was slowly increased to a value of 8 mbar, over a Distilled from 8 hours to a water content of 0.0091% by weight. Then the resulting potassium acetate salt in a heatable pressure filter over a filter cloth and  filtered at a pressure of 2 bar. The resulting reaction product had the following specification:

Hydroxyl number = 402 mg KOH / g
5 acid number = 0.17 mg KOH / g
pH = 6.6
Viscosity at 25 ° C = 368 mPas
Potassium content = 216 ppm
Water content = 0.011% by weight.

Example 6

In a 1.5 l laboratory flask with stirrer, thermometer and distilla tion device were 1050 g of an alkaline polyetherol for Soft foam applications based on glycerin and monoethylene glycol as a starter mixture, reacted with propylene oxide and then with a propylene oxide / ethylene oxide mixture and using of 47% aqueous potassium hydroxide solution as a catalyst. The Reaction mixture with a pH of 10.9 and a potassium ge was 940 ppm with 2 wt .-% water, based on the poly etherol, and 8.5 g of ricinoleic acid and at 100 ° C over a Stirred for 2 hours. Then the product was at a temperature of 130 ° C and a maximum pressure of 6 mbar above dried by distillation for a period of 4 hours. The product pointed the following parameters:

Hydroxyl number = 51.5 mg KOH / g
Acid number = 0.406 mg KOH / g
pH = 8.5
Viscosity at 25 ° C = 652 mPas
Potassium content = 256 ppm
Water content = 0.41% by weight.

The polyol component, consisting of:

94 parts by weight of the polyetherol described in Example 6,
2 parts by weight of a polyetherol based on glycerol / propylene oxide / ethylene oxide, OH number = 41 mg KOH / g,
30 parts by weight of a polyetherol based on ethylenediamine / propylene oxide, OH number = 465 mg KOH / g,
2.5 parts by weight of diethanolamine,
1.2 parts by weight of Dabco,
0.3 part by weight of dimethylaminopropylamine,
1.5 parts by weight of silicone stabilizer B 8631 (from Goldschmidt) and
2.9 parts by weight of water,

was with

100 parts by weight of a prepolymer made from polymer MDI, 4,4'-monomer MDI, a polyetherol based Glycerin / propylene oxide / ethylene oxide, OH number = 41 mg KOH / g, and a polyetherol Based on propylene glycol / propylene oxide, OH number = 56 mg KOH / g,

intensively mixed in the cup and brought to implementation. The ent standing polyurethane foam was highly elastic, had in use good long-term use properties in the furniture sector and offered one excellent seating comfort.

Example 7

2700 g of an alkaline polyetherol for soft foam applications based on glycerin, propylene oxide and ethylene oxide with a OH number of 43 g KOH / g, a pH of 10.9 and a potassium ge hold of 1070 ppm were equipped in a 4 l laboratory glass flask tet with stirrer, thermometer and distillation attachment, presented and with 12 ml of 2-ethylcaproic acid and 2% by weight of water, based on the polyetherol for three hours at a temperature of 130 ° C touched. A distillery closed to dry the polyetherol lation at a temperature of 130 ° C and a maximum pressure from 5 mbar over a period of 6 hours to a water content from 0.085% by weight. In a heatable pressure filter with filter The polyetherol was then clothed at a temperature of Filtered 110 ° C and a pressure of 3 bar. The resulting Re Promotional product had the following characteristics:

Hydroxyl number = 38.7 mg KOH / g
Acid number = 0.22 mg KOH / g
pH = 7.9
Viscosity at 25 ° C = 607 mPa · s
Potassium content = 94 ppm
Water content = 0.096% by weight

The polyol component, consisting of:

90 parts by weight of the polyetherol described in Example 7,
3 parts by weight of a polyetherol based on glycerol / propylene oxide / ethylene oxide, OH number = 41 mg KOH / g,
3 parts by weight of glycerin,
20 parts by weight of a polyetherol based on ethylenediamine / propylene oxide, OH number = 465 mg KOH / g,
1.0 part by weight of silicone stabilizer B 4690 (Goldschmidt),
1.0 part by weight of Dabco Lupragen N 201,
0.4 parts by weight of dimethylaminopropylamine and
3.1 parts by weight of water,

was with

100 parts by weight of polymer MDI, NCO content = 31.5%,

mixed intensively in a beaker and brought to implementation. The resulting flexible polyurethane foam was used for the production heavy duty molded foams for car upholstery excellent seating comfort with good long-term use properties suitable.

The polyurethane foams produced according to the invention showed a lot good physical-mechanical parameters.

Claims (17)

1. Process for the production of polyurethane foams by implementation of

• a) organic and / or modified organic di- and / or polyisocyanates with
• b) polyether polyols, which can be prepared by polymerizing alkylene oxides on H-functional starters, and, if appropriate, other higher molecular weight compounds with at least two reactive hydrogen atoms and, if appropriate
• c) low molecular chain extenders and / or crosslinking agents

in the presence of

• d) blowing agents,
• e) catalysts and optionally
• f) further auxiliaries and / or additives,

characterized in that the polyether polyols are subjected to a treatment with carboxylic acids having at least 4 carbon atoms during and / or after the alkylene oxide addition to the H-functional starting substances. 2. The method according to claim 1, characterized in that the Carboxylic acids are saturated carboxylic acids. 3. The method according to claim 1, characterized in that the Carboxylic acids are unsaturated carboxylic acids. 4. The method according to claim 1, characterized in that the Carboxylic acids are alkyl branched carboxylic acids. 5. The method according to claim 1, characterized in that the Carboxylic acids have an oxygen function.   6. The method according to claim 1, characterized in that the Carboxylic acids have a ring in the chain. 7. The method according to claim 1, characterized in that the Carboxylic acids are dimeric and / or trimercarboxylic acids. 8. The method according to claim 1, characterized in that the Carboxylic acids are carboxylic acid mixtures. 9. The method according to any one of claims 1 to 8, characterized records that the carboxylic acids are used individually or in a mixture be set. 10. The method according to any one of claims 1 to 9, characterized records that the carboxylic acids in an amount of 0.5 to 10 times that for the neutralization of the basic catalyst tors necessary stoichiometric amount can be used. 11. The method according to any one of claims 1 to 10, characterized records that the treatment of the polyether polyols with the Carboxylic acids at temperatures from 60 to 180 ° C. 12. The method according to any one of claims 1 to 11, characterized records that before and / or during the treatment of the poly ether polyols with the carboxylic acids polycondensation toren in an amount of 1 to 100 ppm metallic action substance, based on the polyetherol, are added. 13. The method according to any one of claims 1 to 12, characterized records that as a polycondensation catalyst titanium and / or tin compounds can be used. 14. Use of the manufactured according to one of claims 1 to 13 ten rigid polyurethane foams in the cooling and Thermal insulation area and in construction. 15. Use of the manufactured according to one of claims 1 to 13 ten polyurethanes as flexible polyurethane foams in furniture and automotive.