DE2618280A1 - Catalysts for polyurethane foam - contg. tert. nitrogen atoms and ether gps. - Google Patents

Abstract

(Cyclo)aliphatic cpds. with mol. wt. =200-800 contg. no gps. reactive against NCO and contg. >=2 units (R2)-N-A-O- and additionally >=1 unit -O-A'-N(R")-A"-O-and/or the unit are catalyst, for polyurethane foam. A, A' and A"=methyl-, ethylene-, (iso)propylene- gps., opt. substd. by -NRR',R,R' and R"=a (cyclo)alkyl gp. opt. substd. by 0 and/or N; or R and R' together form a heteroaliphatic ring. In an example the catalyst N,N-bis[2-(2'-dimethyl-amino-ethoxy)-ethyl]-N-methylamine was prepd. The catalyst have a significantly greater activity than known materials and remain active throughout the foaming process. The foams produced have little smell and good hydrolytic stability. They are (semi)flexible or hard and are used for padding materials in the furniture and automobile industries, for heat and cold insulation.

Description

New catalysts for the production of polyurethane

foams It is known that foams containing urethane groups by mixing compounds containing active hydrogen atoms with polyisocyanates in the presence of water, activators, stabilizers and optionally emulsifiers to react. Tertiary amines are preferably used as activators.

The mostly different acceleration of the implementation of each Components through the catalysts is of crucial importance for the Reaction sequence. This is because foam formation is a physico-chemical one Process in which several reactions take place alongside and with one another, whereby the individual Partial processes that lead to the formation of the high molecular structure (urethane reaction) or lead to the development of carbon dioxide (blowing reaction), coordinated with one another must be.

Theoretically, this can be optimally achieved with the help of such catalysts which catalyze either specific urethane or blowing reactions, so that you get the desired ratio with mixtures of such activators the Can set reaction rates, or both partial reactions at the same time and accelerate congruently, so that in certain recipes an optimal foam results. This means that products can be processed without any problems with uniform and good material properties and an often desirable low one specific weight can be achieved. In particular, a flawless Requires pore structure of the foams.

Furthermore, the finished foams must not show any shrinkage, which is particularly useful for hard foams that are used for insulation purposes or as a support material in composite structures use, have a disruptive effect would.

Another important criterion is the least possible odor nuisance through the catalysts.

From DAS 1 030 558, DOS 1 804 361 and the US patent 3,330,782 are catalysts containing ether groups and tertiary nitrogen atoms became known, which partly meet the above requirements very well. However, the insufficient catalytic activity in many cases is unsatisfactory of these compounds, resulting in the use of relatively large amounts of catalyst in the Makes foam recipes required.

In further development of the technical teaching of the above-mentioned publications new compounds have now been discovered, which despite related chemical Structure surprisingly have a significantly greater catalytic effectiveness than the prior art activators.

Decisive for the improved properties of the invention Catalysts are likely to have a tertiary nitrogen atom in the center of the molecule.

The activators according to the invention are aliphatic or cycloaliphatic compounds with a Molecular weight between 200 and 800, preferably between 250 and 500, which are none towards isocyanates contain reactive groups and a) at least 2 tertiary nitrogen atoms in aC-, ß- or X -position (preferably in ß-position) to at least one ether bond and also b) at least one tertiary nitrogen atom and / or one piperazine ring in each α-, ß- or γ-position (preferably in the ß-position) to at least Have 2 ether bonds.

The present invention therefore relates to aliphatic or cycloaliphatic compounds with a molecular weight of 200 to 800, preferably 250 to 500, which have no isocyanate-reactive groups, at least twice the structural unit and additionally at least once the structural unit and / or the structural unit contain, where A, A 'and A "are different or preferably the same and represent a methylene, ethylene, propylene or isopropylene radical (preferably an ethylene radical), which is optionally through may be substituted, R and R 'are different or preferably the same and represent an alkyl or cycloalkyl radical (preferably an ethyl radical) optionally containing oxygen and X or nitrogen as heteroatoms or together form a heteroaliphatic ring and R "optionally an oxygen and' or nitrogen as heteroatoms denotes containing alkyl or cycloalkyl radical.

Catalysts preferred according to the invention are those of the general formula in which Y for one of the remainders or X is a C1-C5-alkyl radical (preferably a methyl radical), a C1-C-acyl radical or a radical represents, A, A 'and have the meaning given above, m, m' and are identical or different and represent an integer from 1 to 3, preferably 1 or 2, and Z, Z 'and Z "are different or preferably identical are and represent an aliphatic or cycloaliphatic radical having at least one tertiary nitrogen atom.

Z, Z 'and Z "preferably represent one of the radicals represent.

The catalysts of the invention are made by reacting chloroalkylene alkylamines with tertiary nitrogen-containing alcoholates or vice versa by reaction of alcoholates of the alkylene alkylamines with tertiary nitrogen-containing alkylaminopolyalkylene chlorides obtained in a manner known per se, as explained in principle in DOS 1 804 361 will.

For example, for the preparation of compounds of the general structural formula given above, chloroalkylene alkylamines of the formulas respectively.

with the alcoholates containing tertiary nitrogen atoms respectively.

bring to reaction, Me for a metal atom, preferably for Well, stands.

In an analogous manner, a third amino ether group can optionally also be used introduce into the catalyst molecule.

Conversely, it is of course also possible to start from the chloroalkylenalkylamines Z-Cl or Z'-Cl (or optionally Z "-Cl) and use these with alcoholates of the formula respectively.

respectively.

realize.

The reactions mentioned take place in inert anhydrous organic Solvents (e.g. optionally halogenated aliphatic or aromatic Hydrocarbons such as benzene, toluene, chlorobenzene or CC14 or ethers) at temperatures between about 0 and 1380, preferably between room temperature and 0 110 C instead of (the higher temperature ranges are required for such connections, which are less reactive due to steric hindrance). The reaction time takes about 10 minutes to 7 hours, usually 2 to 5 hours.

After the end of the reaction, the metal halide formed is suctioned off, the organic solvent evaporated and the catalyst redistilled. links which cannot be distilled without decomposition can also be used directly after the Evaporation of the organic solvent can be used, as in the case of the described Procedure the catalysts of the invention in high yield and purity develop.

The catalysts according to the invention are notable for a surprisingly strong acceleration of the blowing reaction of the foaming process, and for the fact that the foams produced with their help are low in odor and have surprisingly good hydrolytic stability. The compounds according to the invention do not contain an active hydrogen atom and are therefore not incorporated into the polyurethane via main valence bonds and thus remain active during the entire foaming process. Typical examples of the catalysts according to the invention are: preferred preferred preferred preferred The catalysts according to the invention are generally used in amounts of 0.01-5% by weight, but preferably 0.1-1% by weight, based on the foamable reaction mixture.

The present invention also relates to a method for production of polyurethane plastics by reacting compounds with at least two isocyanate-reactive hydrogen atoms and a molecular weight from 400 to 10,000, polyisocyanates and optionally chain extenders, Water and / or organic blowing agents, stabilizers and additives in the presence of catalysts containing tertiary nitrogen atoms and ether groups, which is characterized in that the compounds according to the invention are used as catalysts can be used.

Foams are preferably produced according to the invention, wherein Water is used as a propellant.

The starting components to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates into consideration as they z. B. von W. Siefken in Justus Liebig's Annals of Chemistry, 562, pages 75 to 136, are described, for example ethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1, 1 2-dodecane diisocyanate, Cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, and any Mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, U.S. Patent 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,, 4-phenylene diisocyanate, Perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4, 4 ', 4 "-triisocyanate, Polyphenyl-polymethylene-polyisocyanates, as produced by aniline-formaldehyde condensation and subsequent phosgenation and e.g. in the British Patents 874 430 and 848 671 describe m- and p-isocyanatophenylsulfonyl isocyanates according to the American patent 3 454 606, perchlorinated aryl polyisocyanates, as it is e.g. in the German Auslegeschrift 1 157 601 (American patent specification 3,277,138), polyisocyanates containing carbodiimide groups, such as they in German patent specification 1 092 007 (American patent specification 3 152 162) are described, diisccyanates, as they are in the American patent 3,492,330, allophanate-containing polyoxocyanate such as her e.g. in British patent specification 994 890, Belgian patent specification 761 626 and the published Dutch patent application 7 102 524, Polyisocyanates containing isocyanurate groups, such as those used, for example, in the American Patent specification 3 001 973, in German patents 1 022 789, 1 222 067 and 1 027 394 and in the German Offenlegungsschriften 1 929 034 and 2 004 048 polyisocyanates containing urethane groups, as described in the Belgian patent 752 261 or in US Pat. No. 3,394,164, acylated Polyisocyanates containing urea groups according to German Patent 1 230 778, polyisocyanates containing biuret groups, such as those used in German Patent 1 101 394 (American Patent 3 124 605 and 3 201 372) and in British Patent 889,050 by Telomeri polyisocyanates produced by ionization reactions, such as those used in the American Patent 3 654 106 are described, polyisocyanates containing ester groups, as shown, for example, in British Patents 965,474 and 1,072,956, in American patent 3,567,763 and German patent 1 231 688, reaction products of the above-mentioned isocyanates with acetals according to German Patent 1,072,385, polyisocyanates containing polymeric fatty acid residues according to American patent specification 3,455,883.

It is also possible to use the technical isocyanate production distillation residues containing isocyanate groups, if appropriate dissolved in one or more of the aforementioned polyisocyanates to be used. Further it is possible to use any mixtures of the aforementioned polyisocyanates.

As a rule, those that are technically easily accessible are particularly preferred Polyisocyanates, e.g. the 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene-polyisocyanates, as produced by aniline-formaldehyde condensation and subsequent phosgenation are produced ("crude MDI") and carbodiimide groups, Urethane groups, allophanate groups, isocyanurate groups, urea groups and biuret groups containing polyisocyanates ("modified polyisocyanates").

Starting components to be used according to the invention are also compounds with at least two isocyanate-reactive hydrogen atoms of a molecular weight usually from 400 to 10,000 Compounds containing amino groups, thiol groups or carboxyl groups are preferred Polyhydroxyl compounds, in particular containing two to eight hydroxyl groups Compounds, especially those with a molecular weight of 800 to 10,000, are preferred 1000 to 6000, e.g. at least two, usually 2 to 8, but preferably 2 to 4, polyesters containing hydroxyl groups, polyethers, polythioethers, polyacetals, Polycarbonates and polyester amides, such as those used for the production of homogeneous and cellular polyurethanes are known per se.

The possible hydroxyl group-containing polyesters are e.g. reaction products of polyvalent, preferably divalent and optionally additionally trihydric alcohols with polybasic, preferably dibasic, carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof used to manufacture the polyester. The polycarboxylic acids can be aliphatic, be of a cycloaliphatic, aromatic and / or heterocyclic nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated. As examples of this may be mentioned: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, Phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimers and trimers Fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethyl terephthalate and Terephthalic acid-bis-glycol ester. Come as polyhydric alcohols e.g. ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), Hexanediol (1,6), octanediol (1,8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolene, pentaerythritol, quinitol, mannitol and sorbitol, metiwlglycoside, and more Diet E ¢ lenglycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, giropylene glycol, Polypropylene glycols, dibutylene glycol and polybutylene glycols in question. The polyester may have a proportion of terminal carboxyl groups. Also polyester made from lactones, e.g. £ -caprolactone or hydroxycarboxylic acids, e.g.

w-hydroxycaproic acid can be used.

Also the at least two in question according to the invention in the Usually two to eight, preferably two to three, hydroxyl-containing polyethers are of the type known per se and are made, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, e.g. in the presence of BF3, or by agitation of these epoxides, optionally in a mixture or in succession, of starting components with reactive ones Hydrogen atoms such as water, alcohols or amines, e.g. ethylene glycol, propylene glycol- (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia, Ethanolamine, ethylenediamine produced. Sucrose polyethers, such as those found in the German Auslegeschriften 1 176 358 and 1 064 938 come according to the invention in question. In many cases, those polyethers are preferred which are predominantly (up to 90% by weight, based on all existing OH groups in the polyether) have primary OH groups. Also through vinyl polymers modified polyethers, as they are s.B. arise through polymerization of styrene, acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695. German Patent specification 1,152,536) are suitable, as are polybutadienes containing OH groups.

Among the polythioethers are in particular the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, Formaldehyde, aminocarboxylic acids or amino alcohols are listed. Depending on the co-components If the products are polythio mixed ethers, polythioether esters or Polythioether ester amides.

As polyacetals come e.g. those from glycols, such as diethylene glycol, Triethylene glycol, 4,4'-diethoxy-diphenyldimethylmethane, hexanediol and formaldehyde possible connections in question. Also by polymerizing cyclic acetals suitable polyacetals can be produced according to the invention.

Polycarbonates containing hydroxyl groups are those of the known type into consideration, e.g. by reacting diols such as propanediol- (1,3), Butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, e.g. diphenyl carbonateX or phosgene.

The polyester amides and polyamides include, for example, those made of polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent ones saturated and unsaturated k inoalcohols, diamines, polyamines and their mixtures won, predominantly linear londonate.

Also poly hydroxyl compounds already containing urethane or urea groups as well as optionally modified natural polyols, such as castor oil, mineral hydrates, Strength, are usable. Also adducts of alkylene oxides with phenol-formaldehyde resins or urea-formaldehyde resins can be used according to the invention.

Representatives of this invention are in using compounds e.g., in High Polymer Vol. IVI, "Polyurethanes, Chemistry and Technology by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, pages 5-6 and 198-199, as well in the Kunststoff-Handbuch, Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.

Mixtures of the abovementioned compounds can of course be used with at least two isocyanate-reactive? Hydrogen atoms with a molecular weight of 400-10,000, e.g. mixtures of polyethers and polyesters, can be used.

As starting components optionally to be used according to the invention there are also compounds with at least two isocyanate-reactive compounds Hydrogen atoms with a molecular weight of 32-400 are possible. In this case, too This is understood to mean hydroxyl groups and / or amino groups and / or x ol groups and / or compounds containing carboxyl groups, preferably hydroxyl groups and / or compounds containing amino groups, which act as chain extenders or serve as crosslinking agents. These compounds usually have 2 to 8 opposite Isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive Hydrogen atoms. As examples of such Connections are called: ethylene glycol, propylene glycol- (1,2) and - (1,3), butylene glycol- (1,4) and - (2,3), pentanediol (1,5), hexanediol (1,6), octanediol (1,8), neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, hexanetriol- (1,2,6), trimethylolethane, Pentaerythritol, quinitol, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, Polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols with a Molecular weight up to 400, 4,4'-dihydroxydiphenylpropane, di-hydroxymethyl-hydroquinone § Ethanolamine, diethanolamine, triethanolamine, 3-aminopropanol, ethylenediamine, 1 , 3-diaminopropane, 1-mercapto-3-aminopropane, 4-hydroxy- or -amino-phthalic acid, Succinic acid, adipic acid, hydrazine, N, N'-dimethylhydrazine, 4,4'-diaminodiphenylmethane.

In this case too, mixtures of different compounds can be used with at least two hydrogen atoms reactive toward isocyanates a molecular weight of - - 400 can be used.

According to the invention, water and / or volatile organic Substances are used as propellants.

Examples of organic blowing agents are acetone, ethyl acetate; halogen-substituted Alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, Chlorodifluoromethane, dichlorodifluoromethane, also butane, hexane, heptane or diethyl ether in question. A blowing effect can also be achieved by adding at temperatures above room temperature with the elimination of gases, e.g. compounds that decompose nitrogen, e.g. azo compounds such as azoisobutyronitrile can be achieved. Further examples for propellants and details on the use of propellants are in Plastics Handbook, Volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munchen 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.

It is of course possible, in addition to the compounds according to the invention also to use catalysts known per se. Are particularly suitable in this Relationship Sn (II) compounds, e.g. Sn (II) octoate and diazabicyclo (2,2,2) octane.

According to the invention, surface-active additives such as R gators and foam stabilizers, can also be used.

The sodium salts of castor oil sulfonates, for example, are used as emulsifiers or salts of fatty acids with amines such as oleic diethylamine or stearic acid Diethanolamine in question. Also alkali or ammonium salts of sulfonic acids such as of dodecylbenzenesulphonic acid or dinaphthobylmethanedisulphonic acid or of fatty acids such as e ricinoleic acid or of polymeric fatty acids can be used as surface-active additives can also be used.

hls foam stabilizers come mainly from polyether siloxanes, specifically water-soluble representatives, in question. These connections are generally structured in such a way that that a copolymer of ethylene oxide and propylene oxide with a polydimethylsiloxane radical connected is. Such foam stabilizers are e.g.

in American patents 2,894,748, 2,917,480 and 3 629 308.

According to the invention, reaction retarders, e.g. acid-reacting agents, can also be used Substances such as hydrochloric acid or organic acid halides, as well as cell regulators per se known type such as paraffins or fatty alcohols or dimethylpolysiloxanes and pigments or dyes and flame retardants of the type known per se, e.g. tris-chloroethyl phosphate, Tricresyl phosphate or ammonium phosphate and polyphosphate, and also stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic active substances, fillers such as barium sulfate, kieselguhr, soot or chalk can also be used.

Further examples of optionally also to be used according to the invention surface-active additives and foam stabilizers as well as cell regulators, reaction retarders, Stabilizers, flame retardants, plasticizers, dyes and fillers as well as fungistatic and bacteriostatic substances and details about the use and mode of action of these additives can be found in the plastics manual, Volume V3t, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. described on pages 103 to 113.

According to the invention, the reaction components are made according to what is known per se One-step process, the prepolymer process or the semi-prepolymer process for Implementation brought, whereby one often looks at machine facilities such as those described in U.S. Patent 2,764,565 will. Details about processing devices that are also in question according to the invention come, are in the Kunststoff-Handbuch, Volume VI, edited by Vieweg and Hchtlen, Carl-Hanser-Verlag, Munich 1966, e.g.

described on pages 121 to 205.

According to the invention, foaming is used in foam production often carried out in forms. The reaction mixture is entered into a mold. Metal, e.g. aluminum, or plastic, e.g. htoxy resin, are used as the molding material. in question. The foamable reaction mixture foams up in the mold and forms the Moldings.

The foam molding can be carried out in such a way that the molded part has a cell structure on its surface, but it can also be carried out in such a way that that the molded part has a compact skin and a cellular core. According to the invention one can proceed in this connection in such a way that there is so much foamable in the mold Reaction mixture enters that the foam formed just fills the mold. But you can also work in such a way that you have more foamable lieaktionsverbindungen in enters the shape than necessary to fill the inside of the foil with foam is. In the latter case, "overcharging" is used; such a The procedure is, for example, from American patents 1,178,490 and 3 182 104 known.

In the case of standard foaming, external, known per se Release agents ", such as silicone oils, are also used. However, so-called" internal Release agent ", if necessary in a mixture with external release agents, like they e.g.

from the German Offenlegungsschriften 2 121 670 and 2 307 589 are.

Cold-curing foams can also be produced according to the invention (See British patent specification 1 162 517, German Of.enlesxng, sscilrift 2 155 086).

Of course, foams can also be made by block foaming or by the double conveyor belt process known per se.

The process products represent flexible, semi-flexible or waiting urethane groups having foams. You will find the per se known use for such Products, e.g.

as mattresses and upholstery material in the furniture and automotive industries, Werner for the production of protective pads, as used in the automotive industry and finally as Danish means and means for heat and cold insulation, e.g.

in the construction sector or in the refrigerated cabinet industry.

The following examples explain the process according to the invention, without limiting it. Unless otherwise stated, quantities are given as parts by weight or percentages by weight.

Example 1 N, N-BisLa- (2'-dimethylamino-ätho.Yy) -äthylL7-N-methylamine To a solution, heated to 90 ° C., of 221.8 g (2 moles) of 2-dimethylamine sodium ethylate a solution of 156 g (1 mol) is added dropwise to 2 l of toluene over the course of one hour N-methyl-2,2'-dichlorodiethylamine in 1 l of toluene (shown according to J. T. Abrams et al., J. Soc. chem. Ind. 68, 282 (1949)) 1a leaves on after increasing the temperature 110 ° C the reaction mixture for five hours at this temperature.

Then the brown solution is allowed to cool, the table salt is suctioned off, draws off the toluene at 700C in a water jet pump vacuum and distills the remaining brown liquid twice with the aid of a 60 cm long mirror column (vacuum jacketed).

Yield: 139 g (53.4 96 of theory) b.p .: 1100C / 0.1 Torr. The structure is secured by NMR data.

Example 2 N, N-bis- [2- (2 ', 2 "- bis-dimethylamino) -isopropoxy-ethyl] -N-methylamine To a heated to 900C solution of 336 g (2 moles) of the sodium salt of 1,3-bis-dimethylamino-propanol- (2) in 3 l of toluene, a solution of 156 g (1 mol) is added dropwise over the course of one hour N-methyl-2,2'edichloro-diethyl-amine in 1 l of toluene (shown according to J.T. Abrams et al., J. Soc. chem.

Ind. 68, 282 (1949)) and leaves after increasing the temperature to 110.degree the reaction mixture for five hours at this temperature.

The brown solution is then cooled, the table salt is filtered off with suction and removed the toluene at 700C in a water jet pump vacuum and the remaining is distilled brown liquid twice with the aid of a 60 cm long mirror column (vacuum-jacketed) Yield: 159.5 g (42.5% of theory) b.p .: 1320C / 0.1 Torr Example 3 Tris- (3-oxa-5-dimethylamino-pentyl) -amine in 500 ml of 2-dimethylamino-ethanol 18.5 g (0.8 mol) of sodium entered in small portions and, with heating, a brought about complete dissolution. The excess 2-dimethylamino-ethanol is then drawn off and gives 2 liters of absolute toluene to the alcoholate at room temperature. Then warmed up one to 900C and, after the alcoholate has dissolved, 44.2 in portions g (0.183 mol) of trichlorotriäthylamine hydrochloride and then allowed to stir react for another six hours. After cooling, the excreted is sucked Table salt from the brown-black liquid, removed in a water jet pump vacuum the toluene and newly formed 2-dimethylamino-ethanol and fractionates the brown Liquid using a vacuum jacketed 60 cm long silver mirror column.

Yield: 29.7 g (44.5% of theory, based on trichlorotriethylamine hydrochloride).

The structure is confirmed by NMR data.

EXAMPLE 4 Polyurethane foam with a catalyst according to Example 1 100 Parts by weight of a polypropylene glycol started on trimethylolpropane, the was modified with ethylene oxide so that terminal 80% primary hydroxyl groups at an OH number of 28 the result is 3.2 parts by weight of water, 0.1 part by weight of diazabicyclo-2,2,2-octane, 1.0 part by weight of the siloxane 1 from DOS 2 221 811, 0.3 part by weight of the catalyst according to Example 1 and 39.0 parts by weight of the polyisocyanate described below are made to react.

The polyisocyanate was prepared in the following way: To a mixture of 225 parts of a mixture of 80% 2,4- and 20% 2,6-tolylene diisocyanate and 274 parts of 4,4'-diphenylmethane diisocyanate become 20 parts of 1,2-propylene glycol at 60.degree added and brought to reaction for 30 minutes. After adding 1 part ß-Phenyläthyläthylenimin is heated to 1300C. The one taking place at this temperature Trimerization occurs after 2 1/2 hours when the reaction mixture has an NCO content stopped from 26.5 wt .-% by adding 1 part of p-toluenesulfonic acid methyl ester.

After dilution with a further 624 parts of the above mixture of 2.4 and 2,6-tolylene diisocyanate, a polyisocyanate solution is obtained which is 38.4 Contains wt .-% NCO, a viscosity at 25 0C of 24 cP and a refractive index 50 has 1.5738.

A foam with the following mechanical properties is obtained: Density DIN 53420 (kg / m3) 35 Tensile test DIN 53571 (KPa) 132 Elongation at break DIN 53571 (%) 183 Compression test DIN 53577 (KPa) 1.6 Example 5 50 parts by weight a started on trimethylolpropane polypropylene glycol, which with ethylene oxide was modified so that terminal 80% primary hydroxyl groups with an OH number of 28 result and 50 parts by weight of a polypropylene glycol started on trimethylolpropane, which was modified with ethylene oxide so that terminal 70% primary hydroxyl groups result, and which also with acrylonitrile and styrene in a ratio of 60:40 was grafted and had an OH number of 28, 2.7 parts by weight of water, 0.15 part by weight Diazabicyclo-2,2,2-octane, 0.08 part by weight of the catalyst according to Example 2, 1.0 Parts by weight of the siloxane 1 from DOS 2 221 811, 0.1 part by weight of a polyether polysiloxane, which under the trade name Tegostab B 2909 from Th. Goldschmidt AG, Essen, FRG is sold, 27.2 parts by weight of a toluene diisocyanate mixture (2.4 and 2,6-isomer in a weight ratio of 80:20) and 6.8 parts by weight of a polyphenyl-polymethylene-polyisocyanate, which is obtained by aniline-formaldehyde condensation and subsequent phosgenation are reacted in a mold.

A molded foam with the following mechanical properties is obtained: Density DIN 53420 (kg / m3) 43 Tensile test DIN 53571 (KPa) 141 Elongation at break DIN 53571 (5 ') 158 compression test DIN 53577 (KPa) 3.18

Claims (7)

Claims 1. Pliphatic or cycloaliphatic compounds with a molecular weight of 200 to 800, which have no isocyanate-reactive groups, at least twice the structural unit and additionally at least once the structural unit and / or the structural unit contain, where A, A 'and A "are different or the same and represent a methylene, ethylene, propylene or isopropylene radical, which is optionally through may be substituted, R and R 'are different or identical and represent an alkyl or cycloalkyl radical optionally containing oxygen and / or nitrogen as heteroatoms or together form a heteroaliphatic ring and denote an alkyl or cycloalkyl radical optionally containing oxygen and / or nitrogen as heteroatoms . 2. Compound according to claim 1 of the general formula in which Y for one of the remainders or X is a C1-C5-alkyl radical, a C1-C5-acyl radical or a radical represents, A, A 'and A "have the meaning given above, m, m' and are identical or different and represent an integer from 1 to 3, and Z, Z 'and Z" are different or identical and for at least one an aliphatic or cycloaliphatic radical containing a tertiary nitrogen atom. 3. Compounds according to claim 2, characterized in that Z, Z 'and Z "are one of the radicals represent. 4. Compound of Formula 5. Compound of formula 6. Compound of Formula 7. Process for the production of polyurethane plastics by converting compounds with at least two hydrogen atoms reactive with isocyanates and a molecular weight of 400 to 10,000, polyisocyanates and optionally Chain extenders, water and / or organic blowing agents, stabilizers and additives in the presence of catalysts containing tertiary nitrogen atoms and Have ether groups, characterized in that compounds are used as catalysts according to claim 1 to 6 are used.