CA2095677C - Preparation of resilient elastomers containing bonded urethane groups or urethane and urea groups in the presence of n-perethoxylated polyoxyalkylene-polyamines as a formative component - Google Patents

Abstract

A process for the preparation of resilient, cellular or compact elastomers, preferably elastomer moldings, in particular airbag covers, containing bonded urethane groups or urethane and urea groups comprises reacting a) at least one organic and/or modified organic polyisocyanate with b) at least one relatively high-molecular-weight compound containing at least two hydrogen atoms, c) at least one N-perethoxylated polyaxyalkylene-polyamine and d) low-molecular-weight chain extenders and/or crosslinking agents, in the presence or absence of e) catalysts, f) auxiliaries and g) blowing agents, in a mold.

Description

~~~"~'~l O.Z. 0050/43297 Preparation of resilient elastomers containing bonded urethane groins or urethane and urea rour~s in the presence of N-perethoxylated ~olyoxlralkylene pohyamines as a formative component The present invention relates to a process for the preparation of resilient, cellular or preferably compact elastamers containing bonded urethane groups or urethane and urea groups, preferably elastomer moldings, in particular airbag covers, by reacting organic, modified or unmodified polyisocyanates (a) which are known per se, with relatively high-molecular-weight compounds containing at least two reactive hydrogen atoms (b), at least one I~-perethoxylated polyoxyalkylene-polyamine (c) and at least one low-molecular-weight chain extender and/or crosslinking agent (d), in the presence or absence of catalysts (e), auxiliaries (f) and blowing agents (g), in a mold.
The preparation of elastomers containing bonded urethane groups, urea groups or urethane and urea groups 2U and processes for the production of resilient, compact or cellular moldings from these elastomers by the RII~
(reaction injection molding) method are known from numerous patents and other publications.
According to DE-B-2622951 (US-A-4,218,543), cellular or compact, resilient moldings having a closed surface layer of polyurethane-polyurea elastomers can be produced by the principle of reaction injection molding.
The formulations which are suitable for this purpose essentially comprise organic polyisocyanates, polyols, reactive aromatic diamines or polyamines which are substituted in the o-position to the amino group by alkyl groups, and strong catalysts for the reaction between hydroxyl groups and isocyanate groups. It is essential here that the aromai:ic diamines or polyamines are infinitely miscible with polyols having a molecular weight of from 12000 to 1800 and containing alkyl - 2 ° O.Z, 0050/43297 substituents having 1 to 3 carbon atoms, where at least two of the alkyl substituents have 2 to 3 carbon atoms and each of the o-positions to the amino groups is substituted. Systems of this type have initiation times of down to less than one second; the transition from the liquid phase to the solid phase takes place virtually instantaneously, which results in the liquid reaction mixture as it were solidifying on the walls of the mold.
It is furthermore known that the reactivity of aromatically bonded amino groups toward isocyanates can be greatly reduced by electron-withdrawing substituents.
According to DE-C-12 16 538 (British Patent 981,935), examples of aromatic diamines of this type are 3,3' dichloro-~,~'-diaminodiphenylmethane, 3,3'-dinitro-4,4' diaminodiphenylmethane and 3,3°-dichloro-4,4'-diamino-diphenyl; however, processing of these compounds requires complex and inconvenient equipment due to reservations about the health risk posed by them. Eiowever, the highly electronegative substituents of these compounds reduce the reactivity of the aromatically bonded amino groups so much that full curing in moldings produced by reaction injection molding requires up to 15 minutes and thus becomes uneconomic.
Polyurethane-polyurea formulations having, compared with the systems of DE-B-26 22 951, somewhat reduced reactivity axe obtained, according to EP-A-026 915, if the aromatic diamines used are 3,3',5,5'-tetraalkyl-substituted 4,~'-diaminodiphenyl methanes in which the alkyl radicals are identical or different and are methyl, ethyl, isopropyl, sec- or tert-butyl, it being necessary for at least one of the substituents to be isopropyl or sec-butyl. The tetra-alkyl-substituted diaminodiphenylmethanes described are readily miscible with the polyols in the required amounts at room temperature and have little or no tendency towards crystallization, so that formulations are easy to handle under the usual conditions for conventional 1~IM

-- 3 - O.Z. 0050/43297 systems. However, it has been found that the tetraalkyl-substituted 4,4'-diaminodiphenylmethanes described may not be reactive enough for specific applications.
Polyurethane-polyurea formulation's which are somewhat more reactive than those described in EP-A-026 915 are described in EP-A-069 286. Th.e aromatic diamines used are trialkyl-substituted aneta-phenylene diamines in which two of the alkyl substituents are identical or different, linear or branched alkyl having 1 to 4 carbon atoms, and the third alkyl radical has 4 to 12 carbon atoms or is five- or six-membered cycloalkyl.
Even with a relatively high content of diamines, the formulations have adequate flowability and give moldings having high heat distortian resistance and no progressive fall in the shear modulus curves from 100 to 200°C.
All these processes have the disadvantage that the difference in reactivity between the relatively high-molecular-weight compounds containing at least two primary hydroxyl groups and the aromatic diamines when isocyanate groups are adducted is significant, in spite of steric hindrance of the amino groups, and can only be overcome by using synergistic catalyst combinations of tertiary amines and metal salts, eg. dibutyltin dilaurates, in order to accelerate the hydroxyl-isocyanate polyaddition reaction. However, polyurethane-polyurea elastomers prepared using metal salt catalysts depolymerize at above 150°C, and extended exposure to high temperatures can result in total loss of the mechanical properties of the material.
It is furthermore known to partly or exclusively use polyoxylene-polyamines having molecular weights of from 1100 to 16000 for the preparation of resilient polyurethane-polyurea or polyurea elastomers, for example from EP-A-033 498 (US-A-4,269,945), EP-A-81 701, EP-A-93 861 (US-A-4,396,729), EP-A-92 672, EP-A-93 862 (US-A-4,444,91.0 and US-A-4,433,067), EP-A-93 334 and EP-A-93 336.

- 4 - O.Z. 0050/43297 According to EP-A-81 701 mentioned above as an example, relatively high-molecular-weight polyoxyalkylene-polyamines containing amino groups bonded to aliphatic or aromatic radicals are used. I3owever, aliphatic polyoxyalkylene-polyamines are known to be extremely reactive, so that processing of RIM
formulations based on these compounds can result in considerable problems associated with the machines, in particular in the production of bulky moldings, for ZO example due to short shot times and consequently output of a small amount of material. Somewhat slower to react than aliphatic polyoxyalkylene-polyamines are polyoxyalkylene-polyamines containing aromatically bonded amino groups. These compounds have the disadvantage of an expensive preparation in multistep processes .and, in particular, relatively high viscosities, for example of mare than 20,000 mPas at 25°C, which can cause considerable problems in the processing of formulations containing reinforcing agents.
Furthermore, US Patents 4,048,105, 4,102,833 and 4,374,210 disclose the use of isocyanate group-containing prepolymers and quasiprepolymers having NCO contents of from 9 to 31~ by weight, prepared using unmodified or modified 4,4'-diphenylmethane diisocyanates, in polyurethane systems and the preparation of alkoxylated polyoxyalkylene-polyamines. According to DE-E-1 917 408, DE-A-1 966 059 and DE-A-1 966 058 (CA-A-914,850), poly-oxypropylene-diamines and -triamines can be reacted with ethylene oxide or propylene oxide at from 125 to 170°C, and the resultant polyoxyalkylene-polyamine/alkylene oxide adducts can be further reacted with polyisocyanates to give polyurethane foams. According to US-A-4,465,858 and US-A-4,479,010, alkpxylated polyoxyalkylene-poly-.
amines having a tertiary amino group content of more or less than 90$ are prepared by reacting polyoxyalkylene-polyamines with alkylene oxides at from 75 to 85°C in the presence of from 5 to 15~ by weight of water, based on - C7.Z. 0050143297 the. polyoxyalkylene-polyamine, and then treating a reaction product at from 75 to 135°C. The resultant alkoxylated polyoxyalkylene-polyamines are suitable for the production of flexible polyurethane f~ams, as poly-5 urethane catalysts containing tertiary amino groups, or as crosslinking agents for polyurethane foams, elastomers and adhesives.
Hy selecting suitable relatively high-molecular-weight compounds containing at least two reactive hydrogen atoms, eg. polyether-polyols andJor polyester-polyols, polyoxyalkylene-polyamines containing primary amino groups bonded to aliphatic or aromatic radicals, or, in particular, appropriately substituted aromatic primary diamines as chain extenders and specific catalysts or catalyst systems, attempts have been made to -match the RIM formulations to the given requirements, eg.
volume and geometry of the mold. However, this method has the disadvantage that the starting compounds employed affect not only the reactivity of RIM formulations, but also the mechanical properties of the resultant moldings.
This means that moldings having certain spatial shapes and relatively large dimensions can in soma cases only be produced with impaired mechanical properties, or not at all, since the reaction mixtures have, for example, inadequate flowability or cannot be introduced into the mold in the necessary amounts.
The increasing use of low-density materials in industry means that the mechanical demands made on plastic moldings are often so high that they can only be met, in particular in the case of cellular moldings, if mechanical reinforcing elaareants, known as inserts, are additionally used. This is no less true of processes for the production of resilient, cellular or compact moldings containing urethane groups or urethane and urea groups;
processing of polyurethane°(PU) or polyurethane-polyurea (PU-PH) formulations of this type in the presence of inserts is particularly difficult and, due to the high ~~~~ab"l'~

- 6 - O.Z. 0050/43297 reject rate, is also expensive. Only by using inserts in cellular moldings, eg. airbag covers, can, for example, the rec,~uiredl high flexibility arid high tear strength away from the defined predetermined breaking poiait be ensured.
However, compact moldings, for example PU-PH
elastomer external parts of motor vehicles produced by RIM, also frer~uently exhibit undesired brittieness after demolding and are therefore very fragile. This low-temperature brittleness, which occurs, in particular, in IO moldings made from formulations containing a high proportion of chain extenders and/or crosslinking agents, can in some cases only be reduced or el.uninated by extended storage and/or conditioning. The increased fracture sensitivity of compact moldings of this type for a certain time after demolding likewise causes increased production costs.
It is an object of the present invention to overcome the abovementioned disadvantages, at least in part, but expediently in full, and to develop PU or PU-PH
formulations for the production of compact or cellular moldings which have improved mechanical properties, in particular h9.gh flexibility and simultaneously high tear strength and, in the case of PU-PIi moldings, have reduced or no low--temperature brittleness, ie. have greater flexibility after demolding, with retention of the excellent mechanical properties without the use of inserts.
We have found that, surprisingly, this object is achieved by the additional use of certain polyoxyalkylene-polyamines which have been fully oxyalkylated at the amino groups, in addition to the known relatively high-molecular-weight compounds and low molecular-weight chain extenders and/or crosslinking agents, as 'the compound containing reactive hydrogen atoms.
The present invention accordingly provides a process for the preparation of resilient elastomers 2~9~fi7~

- 7 - 9,Z. 0050/43297 containing bonded urethane groups or urethane and urea groups, by reacting a) at least one organic and/or modified organic polyisocyanate with b) at least one relatively high-molecular-weight compound containing at least two reactive hydrogen atoms, c) at least one oxyalkylated polyoxyalkylene-polyamine and d) low-molecular-weight chain extenders and/or crosslinking agents, in the presence or absence of e) catalysts and/or f) auxiliaries, wherein the oxyalkylated polyoxyalkylene-polyamines (c) used are N-perethoxylated polyoxyalkylene-polyamines.
In a preferred embodiment of the invention, the process is particularly suitable for the production of resilient airbag covers as claimed in claim 9 containing bonded urethane groups or urethane and urea groups.
The process according to the invention expediently uses N-perethoxylated polyoxyalkylene-polyamines prepared from polyoxyalkylene-polyamines containing at least 2, preferably 2 or 3, primary amino groups and having a molecular weight of at least 200, pref$rably from 2~0 to 5850.
The additional use of the N-perethoxylated polyoxyalkylene-polyamines which can be used according to the invention and which can be regarded as relatively high-molecular-weight crosslinking agents with respect to their structure and molecular weight, and which engage in a particular way in the polyisocyanate polyaddition reaction at a certain time due to their specific reactivity, surprisingly gives elastomers having increased tear strength, higher flexibility and lows:.
brittleness. PIE-Pty formulations give, by the RIM method, moldings which no longer have low-temperature ~o~~~~~

- 8 - O.Z. U050/432~7 brittleness, but fully retain their very good mechanical properties. There is no need to use inserts, as are required, for example, for the production of airbag covers for automobiles. The process acao~ding to the invention is therefore preferably used to produce insert-free moldings which, can be used as airbag covers in motor vehicles.
The following applies to the preparation of the N-perethoxylated polyoxyalkylene-polyamines which can be used according to the invention and to the other starting materials which can be used in the process according to the invention for the preparation of the resilient elastomers or elastomer moldings containing bonded urethane groups or urethane and urea groups:
a) Suitable organic polyisocyanates are conven-tional aliphatic, cycloaliphatic and, preferably, aromatic polyisocyanates. Specific examples which may be mentioned are 1,6-hexamethylene diisocyanate, 1-isocyanato-3,5,5-trimethyl-3-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyaanate and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, mixtures of 4,4°-, 2,2'- and 2,4'-dicyclo-hexylmethane diisocyanates and polymethylene-polycyclohexylene polyisocyanates, 2,4- and 2,6-tolylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenyl-m~thane diisocyanate and the corresponding isomer mixtures, mixtures of 4,4'-, and 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenyl-polymethylene polyisocyanates (crude MDT) and mix-tures of crude MDI and tolylene diisocyanates.
Modified polyisocyanates, ie. products obtained by chemical reaction of the above diisocyanates and/or polyisocyanates, are frequently also used.
examples which may be mentioned are diisocyanates - O.Z. 0050143297 and/or polyisocyanates containing ester, urea, biuret, allophanate and, preferably, carbodia.mide, isocyanurate and/or urethane groups. Specific examples are aromatic polyisocyanat'es containing urethane groups and having NCO contents of from 33.6 to 8% by weight, preferably from 31 to 21% by weight, for example 4,4'-diphenylmethane diiso-cyanate or tolylene diisocyanate modified with low-molecular-weight dials, trials, oxyalkylene glycols, dioxyalkylene glycols, polyoxyal~cylene glycols having molecular weights of up to 800, the following being examples of dioxyalkylene glycols or poly-oxyalkylene glycols, which can be employed individually or as mixtures: diethylene glycol, dipropylene glycol, polyoxyethylene glycols, poly-oxypropylene glycols and polyoxypropylene-polyoxy-ethylene glycols. Frepolymers containing NCO groups and having NCO contents of from 25 to 8% by weight, preferably 21 to 14% by weight, are also suitable.

Also suitable are liquid polyisocyanates containing carbodiimide groups and/or isocyanate rings and having NCO contents of from 33.6 to 8% by weight, preferably from 31 to 21% by weight, fax example based on 4,4'-, 2,4'- and/or 2,2-diphenylmethane diisocyanate and/or 2,4- and/or 2,6-tolylene diisocyanate and, preferably, 2,4- and 2,6-tolylene diisocyanate, and the corresponding isomer mixtures, 4,4'-a 2,4'- and 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixtures, for example of 4,4'- and 2,4'-diphenylmethane diisocyanates, crude 1~IDI and mixtureo of tolylene diisocyanates and crude MDI, are also suitable.

However, the following are used in particular:

(i) carbodiimide- and/or urethane-containing polyiso-cyanates made from 4,4'-diphenylmethane diisocyanate or a mixture of 4,4'- and 2,4'-diphenylmethane diiso-cyanates and having an NCO content of from 33.6 to 8%

- 10 - O.Z, 0050/43297 -by weight, (ii) NGO-containing prepolymers having an NCO content of from 8 to 25~ by weight, based on the prepolymer weight, and prepared by reacting polyoxy-alkylene-polyols having a functionality of from 2 to 4 and having a molecular weight of from 600 t~ 6000 with 4,4'-diphenylmethane diisocyanate or a mixture of 4,4'- and 2,4'-diphenylmethane diisocyanates, and mixtures of (i) and (ii).

As stated above, suitable compounds for the preparation of the NCO-containing prepolymers are polyoxyalkylene-polyols having a functionality of from 2 to 4, preferably of 2 or 3, and having a molecular weight of from 600 to 6000, preferably from 1000 to 4500. Analogous polyoxyalkylene-polyols having molecular weights of at least 200, preferably from approximately 240 to 5850 can be employed, for example, for the preparation of polyoxyalkylene-polyamines, which are themselves suitable starting materials for the preparation of the N-perethoxyl-ated polyoxyalkylene-polyamines which are suitable according to the invention or in combination therewith for the preparation of the elastomers or elastomer moldings containing bonded urethane and urea groups. Polyoxyalkylene-polyols of this type can be prepared from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical and an initiator molecule containing from 2 to 4, preferably 2 or 3, reactive hydrogen atoms in bound form, by canventional processes, for example by anionic polymerization using alkali. metal hydroxides, such as sodium hydroxide or potassium hydroxide, or alkali metal alcoholates, such as sodium methyla~te, sodium ethylate, potassium ~ethylata or potassium isopropylate, as catalysts or by cationic polymerization using ~,ewis acids, such as antimony pentachloride, boron trifluoride etherate inter alia, or bleaching earths as catalysts, 21~~~(i"~~
- 11 - o.z. 0050/43297 - Examples of suitable alkylene oxides are tetra-hydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and, preferably, ethylene oxide and 1,2-propylene oxide. The alkylene oxides may be used individually, one after the other in an alternating manner or as mixtures. Examples of suitable initiator molecules are water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, unsubstituted or N-monosubstituted or N,N- and N,N'-dialkyl-substituted diamines having from 1 to 4 carbon atoms in the alkyl radical, such as unsubstituted or mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylene-tetramine, 1,3-propylenediamine, 1,3- and 1,4-buty-lenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexa-methylene diamine, phenylenediamines, 2,3-, 2,4-, 3,4-and 2,6-talylenediamine and 4,4'-, 2,4'- and 2,2°-diaminodiphenylmethane.
Furthermore, suitable initiator molecules are alkanol~unines, eg. ethanolamine, diethanolamine, N-methyl- and N-ethylethanolamine, N-methyl- and N-ethyldiethanolamine and triethanolamine, and also ammonia. Polyhydric, in particular dihydric and /or trihydric alcohols and dialkylene glycois, such as ethaned3.ol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, glycerol, trimethylolpropane, pentaerythritol, diethylene glycol and dipropylene glycol are preferably used.
The polyoxyalkylene-polyols can be used indi-vidually or in the form of mixtures.
b) The relatively high-molecular-weight compounds b) containing at least two reactive hydrogen atoms can be, for example, those having a functionality of 2 to 4, preferably from 2 to 3, and a molecular weight of from 1200 to 8000, preferably from 1800 to 6000.
Examples of compounds which have proven successful - 12 - O.Z. 0050/43297 -are polyoxyalkylene-polyaznines containing primary and/or secondary amino groups, polyoxyalkylene-polyalda.mines and/or polyketimines and/or preferably polyols, expediently selected from' the group S consisting of polyoxyalkylene-polyols, polyester polyols, polythioether polyols, hydroxyl-containing polyester-amides, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic golycarbonates, or mixtures of at least 2 of said relatively high-molecular-weight compounds containing at least 2 reactive hydrogen atoms. Preference is given to polyoxyalkylene-polyamines containing primary or secondary amino groups, and polyoxyalkylene-polyols.
Suitable polyester-polyols may be prepared, for example, from organic dicarboxylic acids having from 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having from 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols, having from 2 to 12 carbon atoms, preferably from 2 to s carbon atoms. Examples of suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, malefic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids may be used either individually or mixed with one another. The free dicarboxylic acids may also be replaced by the corresponding dicarboxylic acid derivatives, for example dicarboxylates with alcohols having from 1 to 4 carbon atoms or dicarboxylic anhydrides . Preference is given to dicarboxylic acid mixtures comprising succinic acid, glutaric acid and adipic acid in ratios of, for example, from 20 to 35 : 35 to 50 : 20 to 32 parts by weight, and in particular adipic acid. Examples of dihydric and polyhydric alcohols and dialkylene glycols, in particular diols, are ethanediol, diethylene glycol, - 13 - O.Z. 0050143297 .1,2- and 1,3-prapanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glyceral and tramethylolpropane. Pref-erence is given to ethanediol, dieth~,ilene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and mixtures of at least two of said diols, in particular mixtures of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. furthermore, polyester-polyols made from lactones, eg. ~-caprolactone, or hydroxycarboxylic acids, eg. ~-hydroxycaproic acid, may also be employed.

The polyester-polyols may be prepared by polycon-densing the organic, eg. aromatic and preferably aliphatic polycarboxylic acids and/or derivatives thereof and polyhydric alcohols without using a catalyst or preferably in the presence of an ester-ification catalyst, expediently in an inert gas atmosphere, eg, nitrogen, carbon monoxide, helium, argon, inter alia, in the melt at from 150 to 250C, preferably from 180 to 220C, at atmospheric pressure or under reduced pressure until the desired acid number, which is advantageously less than 10, preferably less than 2, is reached. In a preferred embodiment, the esterification mixture is polycondensed at the abovementioned temperatures under atmospheric pressure and subsequently under a pressure of less than 500 mbar, preferably from 50 to 150 mbar, until an acid number of from 80 to 30, preferably from 40 to 30, has been reached. Examples of suitable esterification catalysts are iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts. however, the polycondensation may also be carried out in the liquid phase in the presence of diluents and/or entrainers, eg. benzene, toluene, xylene or chlorobenzene, for removal of the water of 14 - O.Z. x050/43297 -condensation by azeotropic distillation.
The polyester-polyols are advantageously prepared by polycondensing the organic polycarboxylic acids and/or d~rivat.ives thereof with polyhydric alcohols in a molar ratio of from 1:1 to 1:8, preferably fro m 1:1.05 to 1.2.
The polyester-polyols obtained preferably have a functionality of from 2 to 3, in particular from 2 to 2.4, and a molecular weight of from 480 to 3000, preferably from 1200 to 3000 in particular from 1800 to 2500.
However, the polyols used are in particular poly-oxyalkylyene-polyols prepared by the above processes, for example by anionic polymerization using alkali metal hydroxides or alkali metal alkoxides as -catalysts and with addition of at least one initiator molecule containing at least 2 bonded reactive hydrogen atoms, or by cationic polymerization using Lewis acids or bleaching earth as catalysts, from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene moiety.

The polyoxyalkylene-polyols, preferably polyoxypropylene-polyols and polyoxypropylene-polyoxyethylene-polyols, preferably have a functionality of from 2 to 4, in particular from 2 to 3, and molecular weights of from 1200 to 8000, preferably 1800 to 6000, in particular from 2400 to 4800, and suitable polyoxytetramethylene-glycols having a molecular weight of up to approximately 3500.

Other suitable polyoxyalkylene-polyols are poly-mer-modified polyoxyalkylene-polyole, preferably graft polyoxyalkylens-polyols, in particular those based on styrene and/or acrylonitrile and prepared by in-situ polymerization of acrylonitrile styrene, or preferably mixtures of styrene and acrylonitrile, for example in a weight ratio of from 90 : 10 - 15 - 0,~. 0050/43297 -to 10 . 90, preferably 70 . 30 to 30 . 70, expediently in the abovementioned polyoxyalkylene-polyols, .similar to the methods described in Cterman Patents 11 11 394, 12 22 669 (US-A-3,304,273, 3,383,351, 3,523,093), 11 15 536 (GB-A-1,040,452) and 11 52 537 (GB-A-987,618), and polyoxyalkylene-polyol dispersions Containing, for example, as the disperse phase, usually in an amount of from 1 to 50~C by weight, preferably from 2 to 25~ by weight, poly-areas, polyhydraxides, polyurethanes containing bonded tent-amino grougs and/or melamin, and described, for example, in EP-B-011 752 (US-A-4,304,708), US-A-4,374,209 and DE-A-32 31 497.

Like the polyester-polyols, the polyoxyalkylene polyols can be used individually or in the form of mixtures. Furthermore, they may be mixed with the graft polyoxyalkylene-polyois or polyester-polyols and the hydroxyl-containing polyester-amides, polyacetals, polycarbonates, polyoxyalkylene-polyamines, polyoxyalylene polyaldimines and/or polyoxyalkylene polyketimines.

Examples of suitable hydroxyl-containing polyacetals are the compounds which can be prepared from dihydroxyl compounds, such as diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxydiphenyl-dimethylmethane, hexanediol and formaldehyde.

Suitable polyacetals can also be prepared by poly-merizing cyclic acetals.

Suitable hydroxyl-containing polycarbonates are those of a conventional type, which can be prepared, 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, eg.

diphenyl carbonate, o~ phosgen~.

The polyester-amides include, for example, the predominantly linear condensates obtained from °
16 - 0.~. 0050/43297 . polybasic, saturated and/or unsaturated carboxylic acids or anhydrides thereof and polyhydric saturated and/or unsaturated amino alcohols, or mixtures of polyhydr.ic alcohols and amino alCohols and/or polyamines.
Suitable polyoxyalkylene-polyamines can, as stated above, be prepared from the abovementioned polyoxyalkylene-polyols by known processes. Examgles which may be mentioned are the cyanoalkylation of polyoxyalkylene-polyols and subsequent hydrogenation of the resultant nitrite (US-A-3,267,050), or the partial or complete amination of polyoxyalkylene-polyols by means of amines or ammonia in the presence of hydrogen and catalysts (DE-A-12 15 373).
The preparation of golyoxyalkylene-polyamines containing primary or secondary amino groups is furthermore described in EP-A-81 701 and EP-A-438 695 (CA-A-2,033,444), and that of polyazomethine-contain-ing. eg. polyaidimine- or polyketimine-containing, polyoxyalkylene-polyamines is described in EP-A-438 696 (U'S-A-5,0$4,487).
c) As an additional compound containing reactive hydrogen atoms for the preparation of resilient elastomers or elastomer moldings containing urethane groups or urethane and urea groups, N-perethoxylated polyoxyalkylene-polyamines are used according to the invention. Suitable polyoxyalkylene-polyamines which are fully sthoxylated on the primary amino groups can b~ obtained by known procQSSes, for example by reacting ethylene oxide with polyoxyalkylene-polyamines in the presence of catalysts, preferably basic catalysts, or in particular without using a catalyst, at elevated temperatures and at atmospheric or superatmospheric pressure, the reaction being carried out until all the free -NH-groups have been ethoxylated. The starting materials for the preparation of the I~-perethoxylated - 17 - Q.~. 0050/43297 .polyoxyalkylene-polyamines are expediently polyoxy-alkylene-polyamines containing at least 2 and/or primary amino groups having a molecular weight of at least 20~, preferably from 240 to 5850. In a pre-y ferred embodiment, the N-perethoxylated polyoxy-alkylene-polyamines which can be used according to the invention can be prepared by reacting polyoxy-alkylene-diamines and/or triamines with from 1.0 to 1.2 mol, preferably from 1.05 to 1.15 mol, of ethy-lane oxide per -NH-group in the absence of catalysts at from 90 to 1.20C, preferably from 100 to 120C, and at from 1 to 8 bar, preferably from 4 to 6 bar.

N-perethoxylated polyoxyalkylene-polyamines which have proven particularly successful and are therefore preferred are di[N,N-di(2-hydroxyethyl)amino]-polyoxyalkylenes, tri[N,N-di(2-hydroxyethyl)amino]_ polyoxyalkylenes, or mixtures thereof, having a molecular weight of from 400 to 6000, preferably from 560 to 3200.

In order to produce moldings by the process according to the invention, the N-perethoxylated polyoxyal.kylene-polyamines ( c ) can be employed in any desired amounts. In order to achieve specific mechanical properties, it has proven expedient, for technical reasons associated with processing and on cost grounds, and depending on the formative components (a), (b) and (d), to determine the necessary amounts experimentally by means of simple experimental series. In order to produce resilient moldings having high flexibility and tear strength and very low brittleness, the N-perethoxylated polyoxyalkylen~-polyamines axe expediently used fn an amount of from 1 to 50 parts by weight, preferably from 1 to 25 parts by weight, based on 100 parts by weight of the relatively high-molecular-weight compounds containing at least two reactive hydrogen atoms (b) and the low-molecular-weight chain ~0°~~~~~
18 - O.Z. 0050/43297 . extenders and/or crosslinking agents (d), d) Suitable chain extenders and/or crosslinking agents usually have molecular weights of less than 500. Preferably from 50 to 400. Example~ which can be used are alkanediols having 2 t~ 12 carbon atoms, preferably 2, 4 or 6 carbon atoms, eg, ethanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and preferably 1,4-butanediol, dialkylene glycols having 4 t~ 8 carbon atoms, eg.
diethylene glycol and dipropylene glycol, and difunctional to tetrafunctional polyoxyalkylene-poiyols having a molecular weight of up to 500.
However, other suitable compounds are branched and/or unsaturated alkanediols, usually having not more than 12 carbon atoms, eg. 1,2-gzopanediol, 2-methyl or 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butane-1,4-diol and 2-butyne-1,4-diol, diestezs of terephthalic acid with glycols having 2 to 4 carbon atoms, eg. bis(ethylene glycol) or bis(1,4-.butanediol) terephthalate, hydroxyalkylene ethers of hydroquinone or resorcinol, eg. 1,4-di(~-hydroxyethyl)hydroquinone or 1,3-di(~-hydroxZrethyl)-resorcinol, alkanolamines having 2 to 12 carbon atoms, eg. ethanolamine, 2-aminopropanol and 3-amino-2,2-dimethylpropanol, and N-alkyldialkanolamines, eg.
N-methyl- and N-ethyldiethanolamine.
Examples of higher-functional czosslinking agents which may be mentioned are trifunctional and higher functional alcohols, eg, glycerol, trimethylolpro pane, pentaerythritol and trihydroxycyclohexanes, and trialkanolamines, eg. triethanolamine.
Chain extenders which have proven highly successful and arc then~fore preferred are alkyl substituted aromat:Cc polyamines, preferably having molecular weights of from 122 to 400, in particular primary aromatic diamines which contain, in the - 19 - O.Z. 0050/43297 -ortho-position to the amine groups, at least one alkyl substituent which reduces the reactivity of the amino group due to static hinderance, and which are liquid at room temperature and are partially miscible, but preferably infinitely miscible, under the processing conditions with the relatively high-molecular-weight, at least difunctional compounds (b) and N-perethoxylated polyoxyalkylene-polyamines (c).
Examples of suitable compounds are alkyl-substituted mete-phenylenediamines of the formula z and/or HEN , ~ R1 / ~ RI

where R' and Rz are identical or different and are methyl, ethyl, propyl or isopropyl, and R1 is linear or branched alkyl having 1 to 10, preferably 1 to 6, carbon atoms. Also highly successful are branched alkyl radicals R1 having 4 to 6 carbon atoms in which the branching point is on the C1 carbon atom.
Specific examples of Rl radicals are methyl, ethyl, isopropyl, 1-methyloctyl, 2-ethyloctyl, 1-methyl-hexyl, 1,1-dimethylpentyl, 1,3,3-tri.nnethylhexyl, 1-ethylpentyl, 2-ethylpentyl, cyclohexyl, 1-methyl-n-propyl, tart-butyl, 1-ethyl-n-propyl, 1-methyl-n-butyl and i,l-dimethyl-n-propyl.
Specific examples of alkyl-substituted m-phenyl enediamines area 2,4-dimethyl-6-cyclohexyl-, 2-cyclo hexyl-4,6-diethyl-, 2-chyclohexyl-2,6-isopropyl--, 2,4-dimethyl-6-(1-ethyl-n-propyl)-, 2,4-dimethyl-6 (1,1-dimethyl-n-propyl)- and 2-(1-methyl-n-butyl) 4,6-dimethyl-1,3-phenylenediamine. Preference is given to 1-methyl-3,S-diethyl-2,4- and/or -2,6-ghenylenediamines, 2,4-dimethyl-6-tent-butyl-, 2,4-~~~~7~
- 20 -- O.Z. 0050/43297 dimethyl-6-isooctyl- arid 2,4-dimethyl-5-cyclohexyl-1,3-phenylenediamine.
Also suitable are 3,3'-di- and/or 3,3',5.5'-tetra n-alkyl-substituted4,4'-diaminodiphenyimethanes,eg.
3,3'-dimethyl-, 3,3'-diethyl-, 3,3'-di-n-propyl-, 3,3',5,5'-tetramethyl-, 3,3',5,5'-tetraethyl- and 3,3',5,5°-tetra-n-propyl-4,4'-diaminodiphenylmethane.
Preferred alkyl-substituted4,4'-diaminodiphenyl-methanes are those of the formula H2N ~ ~ CHZ ~ ~ NHZ
Ra ~R7 where R°, R5, R6 and R' are identical ar different and are methyl, ethyl, propyl, isopropyl, sec-butyl or tert-butyl, but where at least one of the radicals must be isopropyl or sec-butyl. ~°he 4,4'-diaminodi-phenylmethanes may also be used as a mixture with isomers of the formula HzN RS R6 HzN RS
and/or R4 ~ ~ CH2 ~ ~ ~z R4 ~ ~ CHZ l ~ R6 R7 R~ NH2 where R', R°, R6 and R' are as defined above.
Specific examples are: 3,3',5-trimethyl-5'-iso-propyl-, 3,3',5-triethyl-5'-isopropyl-, 3,3',5-trimethyl-5'-sic-butyl-, 3,3°,5-triethyl-5'-sec -butyl-, 3,3'-dim~ethyl-5,5'-diisopropyl-, 3,3'-diethyl-5,S'-diisopropyl-, 3,3'-dimethyl-5,5'-di-sec-butyl-, 3,3'-diethyl-5,5'-di-sec-butyl-, -3,5-di-- 21 - 0.~. 0050/43297 -methyl-3',5'-diisopropyl-, 3,5-diethyl-3,5'-di-isopropyl-, 3,5'-dimethyl-3',5-di-sec-butyl-, 3,5-diethyl-3',5'-di-sec-butyl-, 3-methyl-3'-5,5-tri-isopropyl-, 3-ethyl-3',5,5'-triisopropy~-, 3-methyl-3'-ethyl-5,5'-diisopropyl-, 3-methyl-3',5,5'-tri-sec-butyl-, 3-ethyl-3',5,5'-tri-sec-butyl-, 3,3'-di-isopropyl-5,5-di-sec-butyl-, 3,5-diisopropyl-3',5'-di-sec-butyl-, 3-ethyl-5-sec-butyl-3',5'-diisopropyl-3-methyl-5-tart-butyl-3',5-diisopropyl-, 3-ethyl-5-sec-butyl-3'-methyl-5'-tart-butyl-, 3,3'-5,5'-tetraisopropyl- and 3,3',5,5'-tetra-sec-butyl-4,4'-diamino-diphenylmethane. Preference is given to 3,5-dimethyl-3',5'-diisopropyl- and 3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane. The Z5 diaminodiphenylmethanes can b2 employed individually -or in the form of mixtures.

In order to prepare therefrom elastomers and resilient moldings containing bonded urethane and urea groups, it is expedient to use the following, which are readily available industrially: 1,3,5-triethyl-2,4-phenylenediamine, 1-methyl-3,5-diethyl-2,4-phenylenediamine, mixtures of 1-methyl-3,5-diethyl-2,4- and -2,6-phenylenediamines, known as DETDA, mixtures of 3,3'-di- or 3,3',5,5'-tetraalkyl-substituted 4,4'-diaminodiphenylmethane isomers having 1 to 4 carbon atoms in the alkyl moiety, in particular 3,3',5,5'-tetraalkyl-substituted 4,4'-diaminodiphenylmethanes containing bonded methyl, ethyl and isopropyl radicals, and mixtures of the said tetraalkyl-substituted 4,4'-diaminodiphenyl-methanes and DETDA.

In order to achieve specific mechanical properties, it may also be expedient to use the alkyl-substituted aromatic polyamines as a mixture with the abovementioned low-molecular-weight polyhydric alcohols, preferably dihydric and/or trihydric alcohols, or dialkylene glycols.

2~~~~°~7 - 22 - O.Z, 0050/43297 The low-molecular-weight chain extenders and/or crosslinking agents are thus selected, in particular, from the group consisting of law-molecular--weight difunctional and/or trifunctional' alcohols, difunctional to tetrafunctional polyoxyalkylene-polyols having a molecular weight of up to 500, and alkyl-substituted aromatic diamines, or mixtures of at least two of said chain extenders and/or cross-linking agents.
zn order to prepare the resilient elastomers containing bonded urethane groups or urethane and urea groups, the organic polyisocyanates and/or modified organic polyisocyanate mixtures (a), relatively high-molecular-weight compounds containing at least two reacta.ve hydrogen atoms (b), N-pere-thoxylated polyoxyalkylene-polyamines (c) and low-molecular-weight chain extenders and/or crosslinking agents (d) are advantageously reacted in such amounts that the ratia between number of equivalents of RICO
groups in component (a) and the total number of reactive hydrogen atoms in components (b) to (d) is from 0.85 to 1.25:1, preferably from 0.95 to 1.15:1, in particular from 0.98 to 1.05:1, and the ratio between the number of reactive hydrogen atoms in components (b) and (d) is expediently in the range from 1:2 to 1:15, preferably from 1:2.9 to 1:10.
e) The elastomers containing bonded urethane and urea groups and the moldings produced therefrom are preferably prepared in the absence of catalysts, while the formation of the elastomers containing urethane groups and the moldings produced therefrom is expediently carried out in the presence of cata-lysts.
The catalysts, where used, are, in particular, highly basic amines. In order to produce heat-resist ant moldings which can be painted on-line, it is expedient to completely omit synergistic - 23 - ~.~. 0050J432~7 -organometallic compounds, eg. organotin compounds.
Specific examples of suitable catalysts are: ami-dines,eg,2,3_dimethyl-3,4,5,5-tetxahydropyrimidine, and tertiary amines, eg. triethylamirie, tributyl-amine, dimethylbenzylamine, N-methyl-, N-ethyl- and N-cyclohexylmorpholine, N,N,N',N'-tetramethylethyl-enediamine, N,N,N°,N°-tetramethylbutanediamine, N,N,N',N " ,N " -pentamethyldisthylenetriamine, N,N,N',N'-tetramethyldiaminoethyl ether, N,N,N',N'-tetramethyl-4,4°-diaminodicyclohexylmethane, bis-(diznethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane and preferably 1,4-diazabicyclo[2.2.2]octane.
Other suitable catalysts area tris(dialkylamino alkyl)-s-hexahydrotriazines, in particular tris(N,N
dimethylaminopropyl)-s-hexahydrotriazine, tetraalkyl ammonium hydroxides, eg. tetramethylammonium hydroxide, alkali metal hydroxides, eg. sodium hydroxide, and alkali metal alkoxides, eg. sodium methoxide and potassium isoprogropoxide, and alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms, with or without lateral Oki groups. It is usual to use from 0.001 to 5% by weight, preferably from 0.05 to 2% by weight of catalysts, based on the weight of the components (b) to (d).
f) Specific examples of suitable auxiliaries (f) are surfactants, foam stabilizers, cell regulators, fillers, flameproofing agents, external and/or internal release agents, dyes, pigments, hydrolysis-protection agents, and fung.ista~t.ic and bacteriostatic substances.
Suitable surfactants are compounds which are used to support homogenization of the starting materials and may also be suitable for regulating the cell structure. Specific examples are emulsifiers, such as the sodium salts of castor oil sulfates or of fatty acids, and salts of fatty acids with amines, eg.

- 24 .~ O.Z. 0050/43297 diethylamine oleate, diethanolamine stearate and diethanolamine ricinoleate, salts of sulfonic acids, eg. alkali metal or ammonium salts of dadecylbenzene-or dinaphthylmethanedisulfonic acid and ricinoleic acid; foam stabilizers, such as siloxane-oxaalkylene copolymers and other organopolysiloxanes, oxyethyl-ated alkylphenols, oxyethylated tatty alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, turkey red oil and groundnut oil, and cell regulators, such as paraffins, fatty alcohols and di-methylpolysiloxanes. the surfactants are usually used in amounts of from 0.01 to 5 parts by weight, based on 100 parts by weight of components (b) to (d).

For the purposes of the present invention, fillers, are conventional organic and inorganic fillers. Specific examples are inorganic fillers, such as silicate minerals, for example phyilosili--cates, such as antigorite, serpentine, hornblendes, amphiboles, chrysotile, talc and zeolites, metal oxides, such as kaolin, alumina, titanium oxides and iron oxides, metal salts, such as chalk and barytes, and inorganic pigments, such as cadmium sulfide and zinc sulfide. Preference is given to kaolin (china clay) , a:Luminum silicate and coprecipitates of barium 2S sulfate and aluminum silicate, and natural and synthetic fibrous minerals, such as wollastonite or glass fibers of various lengths, which may be sized.

Examples of suitable organic f~.llers are carbon black, melamine, collophony, cyclopentadienyl resins and graft polymers based on styrene-acrylonitrile , which are prepared by in-situ polymerization of acrylo-n.itrile/styrene mixtures in polyoxyalkylene-polyols in a similar manner to those given in German Patents 11 11 394, 12 22 669 (US 3,304,273, 3,383,351, and 3 , 52.3, 093 ) , 11 52 536 ( GH 1, 040, 452 ) and (GB 987,618) and then aminated if desired, and also filler-polyoxyalkylene-polyols or polyamines in which - 25 - o.Z. 0050143297 aqueous polymer dispersions are converted into polyoxyal.kylene-polyol or polyamine dispersions. The inorganic and organic fillers can be used individually or as mixtures.

The inorganic and/or organic fillers can advantageously be incorporated into the reaction mixture in amounts of from 0.5 to 35~ by weight, preferably from 3 to 20~ by weight, based on the weight of components (a) to (d).

Examples of suitable flameproofing agents are tricresyl phosphate, tris-2-chloroethyl phosphate, trischloropropyl phosphate and tris-2,3-dibromopropyl phosphate.

In addition to the abovementioned halo-sub-stituted phosphates, it is also possible to use inorganic flameproofing agents, eg. aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, or melamine, expandable graphite or mixtures thereof, for example mixtures of melamine, expandable graphite and/or ammonium polyphosphate, for flameproofing the moldings. In general, it has proved expedient to use from 5 t,o 50 parts by weight, preferably from 5 to 25 parts by weight, of the flameproofing agents mentioned per 100 parts by weight of components (b) to (d).

Further details on the other conventional aux-iliaries mentioned above can be obtained from the literature, for example from the monograph by ~'.H.

Saunders and K.C. Frisch, High Polymers, Volume XVI, Polyurethanes, Parts 1 and 2, Interscience Pub-lishers, 1962 and 1964 respectively, or Kunststoff-Handbuch, Polyurethane, Volume VIT, Hanser-Verlag, Munich, Vienna, 1st and 2nd Editions, 1966 and 1983.

g) In order to produce resilient moldings based on the novel elastomers containing urethane groups or - 26 - O.Z. 0050/43297 -urethane and urea groups, blowing agents (g) may be introduced into the reaction mixture comprising components (a) to (d) and possibly catalysts (e) and/or auxiliaries (f), in order to produce cellular moldings.
An example of a suitable blowing agent for the production of cellular moldings is water, which reacts with isocyanate groups to form carbon dioxide) The amount of water which can expediently be used is from 0.01 to 5~ by weight, preferably from 0.1 to 1.0~ by weight, in particular from 0.2 to 0.4~ by weight, based on the weight of components (b) to (d).

Other blowing agents which can be used are low-boiling liquids which evaporate during the exothermic polyaddition reaction. Suitable liquids are those which are inert toward the organic polyisocyanate and have a boiling point of less than 100C. examples of preferred liquids of this type are halogenated, preferably fluorinated, hydrocarbons, such as methylene chloride and dichloromonofluoromethane , perfluorinated or partially fluorinated hydrocarbons, such as trifluoromethane, difluoromethane, difluoroethane, tetrafluoroethane and hepta-fluoropropane, hydrocarbons, such as n- and iso-butane, n- and iso-pentane and technical-grade mix-tures of these hydrocarbons, propane, propylene, hexane, heptane, cyclobutane, cyclopentane, cyclo-hexane, dialkyl ethers, such as dimethyl ether, diethyl ether and furan, carboxylic acid esters, such as methyl formats and ethyl formats, ketones, such as acetone, and/or fluorinated and/or perfluorinated tertiary alkylamines, such as perfluorodimethyliso-propylamine. Mixtures of these low-boiling liquids with one another and/or with other substituted or unsubstituted hydrocarbons can also be used.

The most expedient amount of low-boiling liquid 27 ° ~.Z. 0050/43297 -for the production of resilient, cellular moldings of this type from elastomers containing bonded urethane groups or urethane and urea groups depends on the desired density and, where appropriate, on the presence of water. In general, amounts of from 1 to 15~ by weiglxt, preferably from 2 to 11~ by weight, based on the weight of components (b) to (d) give satisfactory results.
The resilient, compact moldings based on the elastomers according to the invention containing urethane and urea groups are expediently produced by the orie-shot process using the low-pressure method or in particular by reaction injection molding (RIM) in open or preferably closed molds. Cellular moldings are produced by carrying out the reaction, in particular, with compaction in a closed mold. Reaction injection molding is described, for example, by H. Piechota and H. Rbhr in Integral-.
schaumstoffe, Carl ~Ianser-verlag, Munich, Vienna, 1975;
D.J. Prepelka and J.L. Wharton in Journal of Cellular Plastics, March/Apr_il 1975, pages 87 to 98, and U. ICnipp in Journal of Cellular Plastics, March/April 1973, pages 76-84.
If a mixing chamber having several teed nozzles is used, the starting components can be fed in individually and mixed vigorously in the mixing chamber. It has proven particularly advantageous to use the two-component method, combining formative components (b) to (d) and, if used, (e) to (g) in component (A) and using, as component (B), organic polyisocyanates or modified polyisocyanate mixtures. It is advantageous her~, for example, that components (A) and (B) can be stored separately and transported using a minimum of space and merely need to be mixed in the appropriate amounts during processing.
The amount of reaction mixture introduced into the mold is such that the moldings obtained, which may be cellular, have a density of from 250 to 1400 kg/m', the compact moldings preferably having a density of from 1000 - 28 - O.Z. 0050/43297 to 1400 kg/m', in particular from 1000 to 1200 kg/m', and the cellular and microcellular moldings preferably having a density of from 400 to 1100 kg/rn', for example from 450 to 750 kg/m', in particular from 550 to 6'SO kg/m', for shoe soles, and from 700 to 1200 kg/m', in particular from 950 to 1150 kg/m', for panelling elements. The starting components are introduced into the mold at from to 80°C, preferably from 30 to 65°C. The mold temper-ature is expediently from 20 to 110°C, preferably from 35 10 to 95°C and in particular from 35 to 75°C. The degree of compaction for the production of microcellular or cellu-lar moldings is from 1.1 to 8, preferably from 2 to 6.
In order to improve demolding of the elastomer moldings produced by the novel process, it has proven 15 advantageous to coat the internal surfaces of the mold, at least at the beginning of a production run, with conventional external mold-release agents, for example based on wax or silicone, or, in particular, with. aqueous soap solutions. However, internal mold-release agents, as described, for example, in EP-A-153 649, EP-A-180 749 (AU 85/47,498), EP-A-173 888 (US 4,519,965), WO 84/03,288 (EP-A-119 47:L) and WO 86/01,215, have proven particularly successful and are therefore preferred. The mold dwell times are on average from 3 to 60 seconds, depending on the size and geometry of the molding.
The compact moldings obtainable by the process according to the invention are preferably used in the automotive and aircraft industries, for example as bumper covers and in particular as airbag covers, bump strips, body parts, eg. rain gutters, mudguards, spoilers, wheel arch extensions and for other industrial housing parts and rollers. Cellular moldings are suitable for shoe soles, armrests, headrests, sun visors, safety covers in vehicle cabins, and as motorcycle, tractor and bicycle saddles, seat cushions and top layers in composite elements.

- 2~ - 0.2. 0050/43297 ExAMPLES
Preparation of N,N,N~-.P1~_tetra(2-hydroxyethyl)_ polyoxypropylene-diamine mixtures 3560 g (8.9 mol) of a polyoxypropylene-~diamine having the structure HEN- CH - CH2 ~ OCH~ --- CH ~ NHS
n and a mean molecular weight of 400 (,Teffamine~ D 400 from Texaco AG) was treated for one hour in a 10 1 autoclave at 105°C under reduced pressure (1.33 mbar) in order to remove the volatile constituents. The autoclave was then filled with nitrogen to an absolute pressure of 3 bar, and 1722 g (39.14 mol) of ethylene oxide were metered in over a period of 4 hours at 105°C. After a reaction time of 10 hours at 105°C, all the unreacted ethylene oxide was remaved by distillation under reduced pressure at 33 mbar for 30 minutes and then at 1.33 mbar for 60 minutes.
The N-perethoxylated polyoxypropylene-diamine prepared in this way had a hydroxyl number of 344, a viscosity of 1110 mPas at 25°C (by the Ubbelohde method), a residual water content of 0.015 by weight and a pH of 11.7.

The procedure was similar to that in Example 1, but 5260 g (2.63 mol) of a polyoxypropylene.~diamine having a mean molecular weight of 2000 (,7effamine~ D 2000 from Texaco AG) and 509 g (11.568 mot) of ethyleize oxide, which were metered in over a period of 2 hours at 105°C, were used.
This gave an N~~perethoxylated polyoxypropylene diamine having an hydroxyl number of I01, a viscosity of 720 mPas at 25°C (by the Ubbelohde method), a residual ~~~a~'~~
° 30 - O.Z. 0050/43297 water content of 0.07 by weight and a pH of 11.7.
Production of moldings containing bonded urethane and urea groups Polyoxyalkylene-polyamine component (A):
Mixture of 66.5 parts by weight of polyoxypropylene-diamine (,Teffamine~ D 2000 ) , 3.0 parts by weight of N-perethoxylated polyoxypropylene diamine prepared as described in Example 1, 30.0 parts by weight of a mixture of 1-methyl-3,5-diethyl-2,4-phenylenediamine and -2,6-phenyl-enediamine in a weight ratio of 80:20 (DETDA1 and 0.5 part by weight of oleic acid.
Isocyanate component (Component B):
An NCO-containing prepolymer, having an NCO
cantent of 20~ by weight, prepared by reacting a carbodiimide group-containing 4,4'-diphenylmethane diisocyanate having an NCO content of 29.5 by weight and a dipropylene glycol-initiated polyoxypropylene-diol having an hydroxyl number of 56.
The polyoxyalkylene-polyamine (A) and the isocyanate (B) components were mixed in an A:B mixing ratio of 100:97.7 parts by weight in a Puromat~ 30 high pressure metering unit from Elastogran Polyurethane GmbH, Machine Construction Division, and irr~ected into a metallic mold having the internal dimensions 400 x 200 x 2 mm which was held at 90°C. Component A was at 65°C and B was at 50°C.
After a mold dwell time of 20 seconds, the molding was removed. No low-temperature brittleness, ie. fracture of the test sheet, was observed up to 30 minutes after demolding. The test was then terminated.

- 31 - O.Z. 0050/43297 Comparative Example I
Polyoxyalkylene-polyamine component (A):
Mixture of 69.5 parts by weight of polyoxypropyle'ne-diamine (Jeffamine~ D 2000), 30.0 parts by weight of a mixture of 1-methyl 3,5-diethyl-2,4-phenylenediamine and -2,6-phenylenediamine in a ratio by weight of 80:20 (DETDA) and 0.5 part by weight of an oleic acid.
Isocyanate component (E): as in Example 3 The procedure was similar to that of Example 3, but a mixing ratio between the polyoxyalkylene-polyamine component (A) and isocyanate component (E) of 100:94.2 parts by weight was used. Low-temperature brittleness occurred after only 10 minutes after the molding had been removed, causing the test sheet to break.
2 0 E~~AMPLE 4 Polyoxyalkylene-polyamine component (A):
Mixture of 43.5 parts by weight of N,N°-dibenzylpolyoxypropylene diamine having a molecular weight of approximately 2180 (prepared as described in EP-A-4389 695, Example 1) 20.0 parts by weight of N-perethoxylated polyoxypropyl-ene-diamine, prepared as described in Example 2, 30.0 parts by weight of a mixture of 1-methyl-3,5-diethyl-2,4-phenylenediamine and -2,6-phenylenediamine in a weight ratio of 80:20 (DETDA), 2~~~6'~'~
- 32 - 0.2. 0050/43297 4.1 parts by weight of N,N'-polyoxypropylene-dicyclopentylimine having a molecular weight of from 350 to 700, 1.9 parts by weight of zinc stearate and 0.5 parts by weight of oleic acid.
Isocyanate comgonent (B): as described in Example 3.
First, ground glass fibers as filler were added to polyoxyalkylene-polyamine component (A) in such an amount that the glass fiher content in the molding produced was 20~ by weight.
The glass fiber-containing polyoxyalkylene-polyamine (A) and isocyanate (B) components were mixed in a A:B mixing ratio of 100:66.9 parts by weight in a Puromat~ 30 high-pressure metering unit and in~ecaed into a metallic mold having the internal dimensions 400 x 200 x 2 mm kept at 65°C. Component A was at 65°C
and component B was at 50°C.
After a mold dwell time of 20 seconds, the molding was removed. No low-temperature brittleness, ie.
fracture of the test sheet, was observed up to 30 minutes after demolding. The remainder of the test was then terminated.
Comparative Example II
Polyoxyalkylene-polyamine component (A):
Mixture of 63.5 parts by weight of N,N'-dibenzylpolyoxypropylene--diamine having a molecular weight of approximately 2180 (prepared as described in EP-A-438 695, Example 1) 30.0 parts by weight of a mixture of 1-methyl-3,5-diethyl-2,4-phenylenediamine and -2,6-phenylenediamine in a weight ratio of 80:20 (DETDA), 4.1 parts by weight of N, N' -polyoxypropylene-dicyclopentylimine having a 20~~~'~~~
- 33 _ o.Z. 0050/43297 _ molecular weight of from 350 to 700, 1.9 parts by weight of zinc stearate and 0.5 parts by weight of oleic acid. , Isocyanate component (B): as described in Example 3.
The procedure was similar to that of Example 4, but a mixing ratio between the polyoxyalkylene-polyamine (A) and isocyanate (B) components of 100:64.6 parts by weight was used. Low-temperature brittleness occurred after only one minute after the molding had been demolded, causing the test sheet to break.
The N,N'-polyoxypropylene-dicyclopentylimine used in Example 4 and Comparative Example II was prepared as follows:
520 g of polyoxypropylene-diamine having a mean molecular weight of 230 (Jeffamin~T~ 230 from Texaco AG) were mixed at room temperature with 675 g of a solution comprising 425 g of cyclopentanone and 250 g of toluene, and the resultant reaction mixture was heated under reflux on a water separator until water no longer separated out (after about 9 hours). The toluene and excess cyclopentanone were then removed by distillation under reduced pressure at from 100 to 120°C, leaving, as residue, 810 g of polyoxypropylene-dicyclopentylimine, which was used without further purification.

The production of an airbag cover Component A: mixture of 40.2 parts by weight of a glycerol-initiated polyoxy propylene (86~ by weight)-polyoxy ethylene (14~ by weight)-polyol having a hydroxyl number of 26, 37.5 parts by weight of a tra.msthylolpropane-initiated po:lyoxypropylene (BO~k by weight) polyoxyethylene (20~ by weight) polyol having a hydroxyl number of - 34 - O.Z. 0050143297 27, 5.0 parts by weight of a N-perethoxylated polyoxy-propylene-diamine prepared as described in Example~2, 5.0 parts by weight of ethylene glycol, 5.0 parts by weight of polyoxytetramethylene glycol having a hydroxyl number of approximately 112, 0.5 Bart by weight of a 33~ strength by weight solution of diazabicyclooctane in ethylene glycol, 1.8 parts by weight of diazabicyclooctane-based catalyst (DABCO~ 8154 from Air Products) and 5.0 parts by weight of black paste (carbon black).
Component B:
NCO-containing prepolymer having an NCO content of 26$ by weight, prepared by reacting 4,4'-diphenylmethane diisocyanate and a carbodiimide group containing 4,4'-diphenylmethane diisocyanate having an NCO content of 29.5~c by weight with trioxypropylene glycol.
Components A and B were mixed in a mixing ratio of 100:41 parts by weight in a Puromat~ 30 high-pressure metering unit, and the mixture was injected into a metallic mold (airbag cover from Chrysler AG, internal dimensions 260 x 175 x 50 mm) kept at 50°C. Companent A
was at 40°C and component B was at 30°C. After 100 seconds, the polyurethane molding was removed. After storage for 48 hours, the molding was clamped in a holder device for penetration testing, and a stamp measuring 120 x 20 mm and weighing 20.8 kg was allowed to act on the molding at a speed of 16 km/h at -40°C, 25°C and 80°C. The polyurethane molding was penetrated and only broke, as desired, at the predetermined breaking point.

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- 35 - O.Z. 0050/4327 COMPARISON E~CAMphE III
The production of an airbag cover Component A: mixture of 45.2 parts by weight of a glycerol-initiated polyoxy propylene (86~ by weight)-.polyoxy ethylene (14~ by weight)-polyol having a hydroxyl number of 26, 37.5 parts by weight of a trimethylolpropane-initiated polyoxypropylene (80~ by weight)_ polyoxyethylene (20~ by weight) polyol having a hydroxyl number of 27, 5.0 parts by weight of ethylene glycol, 5.0 parts by weight of polyoxytetramethylene glycol having a hydroxyl number of approximately 112, 0.5 part by weight of a 33~ strength by weight solution of diazabicyclooctane in ethylene glycol, 1.8 parts by weight of diazabicyclooctane-based catalyst (OABCO~ 8154 from Air Products) and 5.0 parts by weight of black paste (carbon black).
Component B: as described in Example 5 The airbag cover was produced as described in Example 5, but using an A:B mixing ratio of 100:40 parts by weight.
A polyurethane molding was obtained which did not pass the penetration test described in Example 5 since it broke at a random point.

Claims (10)

1. A process for the preparation of resilient elastomers containing bonded urethane groups or urethane and urea groups, by reacting a) at least one organic and/or modified organic polyisocyanate with b) at least one relatively high-molecular-weight compound containing at least two reactive hydrogen atoms, c) at least one oxyalkylated polyoxyalkylene-polyamine and d) low-molecular-weight chain extenders and/or crosslinking agents, in the presence ar absence of e) catalysts and/or f) auxiliaries, wherein the oxyalkylated polyalkylene-polyamines (c) used are N-perethoxylated polyoxyalkylene-polyamines.

2. A process as claimed in claim 1, wherein the axyalkylated polyoxylene-polyamines (c) used are di- and/or tri-[N,N-di-(2-hydroxyethyl)amino]polyoxyalkylenes having a molecular weight of from 400 to 6000.

3. A process as claimed in claim 1, wherein the oxyalkylated polyoxyalkylene-polyamines (c) used are N-perethoxylated polyoxyalkylene-polyamines prepared by reacting polyoxyalkylene diamines and/or triamines containing primary amino groups with from 1.0 to 1.2 mol of ethylene oxide per -NH-function, in the absence of catalysts and from 90 to 120°C and at from 1 to 8 bar.

4. A process as claimed in claim 1, wherein the N-perethoxylated polyoxyalkylene-polyamines (c) are used in an amount of from 1 to 50 parts by weight, based on 100 parts by weight of the relatively high-molecular-weight compounds containing at least two reactive hydrogen atoms (b) and low-molecular-weight chain extenders and/or crosslinking agents (d).

5. A process as claimed in claim 1, wherein the relatively high-molecular-weight compounds containing at least two reactive hydrogen atoms (b) have a functionality of from 2 to 4 and a molecular weight of from 1200 to 8000 and are selected from the group consisting of the polyols, polyoxyalkylene-polyamines containing primary and/or secondary amino groups, and polyoxyalkylene-polyaldimines and/or polyketimines, or mixtures thereof.

6. A process as claimed in claim 1, wherein the low-molecular-weight chain extenders and/or crosslinking agents are selected from the group consisting of low-molecular-weight difunctional and/or trifunctional alcohols, difunctional to tetrafunctional polyoxyalkylene-polyols having a molecular weight of up to 500, and alkyl-substituted aromatic diamines, or mixtures thereof.

7. A process as claimed in claim 1, wherein moldings are produced in a closed mold by the one-shot RIM method.

8. A process for the production of cellular, resilient elastomers containing bonded urethane groups or urethane and urea groups as claimed in claim 1, wherein the reaction is carried out in a closed mold by the RIM
method with compaction in the presence of g) blowing agents.

9. A process for the production of resilient airbag covers containing bonded urethane groups or urethane and urea groups, by reacting a) at least one organic and/or modified organic polyisocyanate with b) at least one relatively high-molecular-weight compound containing at least two reactive hydrogen atoms, c) at least one oxyalkylated polyoxyalkylene-polyamine and d) low-molecular-weight chain extenders and/or crosslinking agents, in the presence or absence of e) catalysts and/or f) auxiliaries, in a closed mold, wherein the oxyalkylated polyoxyalkylene-polyamines (c) used are N-perethoxylated polyoxyalkylene-polyamines.

10. A process as claimed in claim 9, wherein the oxyalkylated polyoxyalylene-polyamines (c) used are di-and/or tri[N,N-di(2-hydroxyethyl)amino}polyoxyalkylenes having a molecular weight of from 400 to 6000.