MXPA99000344A - Preparation of compact or cellular polyurethane elastomers and isocyanate prepolimeros suitable for this proposal - Google Patents

Abstract

The present invention relates to: Compact polyurethane elastomers and preferably cellular elastomers are prepared by the reaction of a) polyhydroxyl compounds of relatively high molecular weight and, if desired, b) low molecular weight chain extenders and / or crosslinkers with high molecular weight. ) Phenylene 1,4-diisocyanate (p-PDI) and at least one additional aromatic diisocyanate selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, 3,3'-dimethylbiphenyl diisocyanate, 1,2-diisocyanate -diphenylethane and / or aliphatic diisocyanate, which has from 4 to 12 carbon atoms and / or cycloaliphatic diisocyanate having from 6 to 18 carbon atoms, where the formative components (a), (c) and, if employed (b) react advantageously by means of the prepolymer method, in the presence or absence of d) catalysts, e) expansion agents and additives. Suitable isocyanate prepolymers are described for this purpose

Description

PREPARATION OF COMPLETE OR CELLULAR FOLIURETHANE ELASTOMERÜS AND PRECISION ISOC I MATO ADEQUATE FOR THIS PURPOSE L- presentid mvencLÓn refers to a process for the preparation of the compact polyxuretane humers? preferably cellular, hereinafter referred to as PUs. The preparation of compact or cellular PU elastomers, for example, micracelu 3 ares, has been known for a long time to r > From numerous patent publications and in the 3rd Ixpad Specialist Literature, "Its industrial importance is based on the combination of good mechanical properties with the advantages of 3 economic processing methods. The use of various types of 5 chemical components in various proportions makes it possible to prepare compact or cellular PU elastomers that are physically processable or reticulated which differ widely in terms of their process. its mechanical properties »A general presentation of ls the 0 polyurethane stomers, its properties / applications is provided» pur example, in uns tstoff - Handbueli, volume 7, Pul yuré chañe (Polyurethanes), anger, 1966 edition, edited by Dr R. Vieweg and Dr A "Hoehtlen, 2nd" edition, 1983, edited by Dr G. Oertel, and 3ra. edition, 1993, edited by Prof. G.W. Becl 'ar 5 and Prof. D, Braun, Cari -Hanser-See lag, Munich, Vienna).

Compared to the rubber types that can be used in a similar way, the palxurethane xcrocellulose elastomers have significantly improved master properties and an excellent volume compressibility so that they are used as components of damping systems of vibrations and shocks, paricularly in the aumatrxz industry. For the preparation of the rocellular polyurethane grades, products of the reaction of 1,5-MDT and? Ol? (Ad p3ta de et lengli col.} Which has a molecular weight of 2,000 which react in the form of a prepolymer isocxanate with an aqueous solution that cantxene a sulfonate activator and fatty acid are useful. (t unststof f-Hsndbuch, volume 7, Polyurethane (Polyurethane), anger, edition, pages 270 et seq.) "Since such base formulations provide polyurethane microceiling elastomers having very good damping characteristics - excellent aesthetic and dynamic performance parameters, the prior art presents only a few efforts to replace the 1.5-NDI responsible for the good elastsmeric properties, despite the fact that it is more difficult to handle due to its high melting point, easier to handle and less costly because it causes significant mechanical properties lesser.

The characteristic differences in properties between the compact urethane-polyurethane elastomers in the micellular paliurethane elastomers in particular, based on 1,5-NDI and 4,4 '~ -MDI appear in the Journal of Elastomers and Fias tics ( Journal of Elastomers and Plastics), Volume 21, (1989), pages 100 to 121, Important Disadvantages Provided for a Microcellular Polyurethane Elastomer Based on, 4 '~ MDI are a Significantly Higher Damping Degree with Increased Heat of consolidation material and values means-! ively greater under load rí -x n m. to which it causes finally a faster wear of the material in comparison with elastomers of polxuretanp based on 1,5-ND ?. Despite these known disadvantages, attempts were made to prepare the microcellular polyurethane turners to replace the 1,5-MDI with the 4.4 -MDT with a lower and more economical melting point. However, these attempts have been limited to the use of new initial components, particularly hydro-hydrate compounds. what is relatively high molecular weight, whose use improves certain mechanical properties of the elast? erü £ > Microcellular polyurethane »Document EP-A-0 496 204 (US-A-5 173 518.) describes a process for the preparation of cellular palladium elastomers using polyurethane polycarbonate diules that cpnf ispen from ooli or;; xte trameti lengl i col having an average molecular weight of 150 to 500 in rondensed form as polymorphic compounds of relatively high molecular weight. This improves the mechanical properties, especially the elongation at break, even at relatively low temperatures. However, there is no noticeable difference in the permanent deformation due to static compression according to DIN 53 572 to 70aC, which DO correlate, it is known, with the values of dynamic consolidation. Even when 1, -NDI is used as a polyacyanate, only permanent deformations are obtained by static compression; average. EP-B-0 243 832 (US-ñ-4 798 851), which describes the use of pseudoprepars based on 4,4'-DHT in the absence of water as an expanding agent for the production of molded pol luretano-pal lurea or compact or cellular, elastic polyurethane enseria using a pol icondensado containing hydrophilic a polioKitetrametilengl iCol short chain products and Oth dicarboiíí acid ali ^ attic as compound pol? h? dro :;? the weight of Molecul rr i ed with vamen and high propósi or a compound of ihidras'il pol or containing ester groups can be easily added by pumping for cellular or compact elastomers polyurethane quo have mechanical properties and improved hydraulics. Details of static or dynamic permanent deformation meadows, by means of which they are characterized, have been found. The materials resistant to vibration are not present. DE-A-36 13 961 (US-A-4 647 596) discloses a microcellular polyurethane elastomer based on 4,4 -MDT which, due to a defined composition of the polyhydro compounds of molecular weight re Highly comprised by a polymer co-polymer and tetrahydrofuran, the prolartone has mechanical properties that represent a favorable compromise between static strength and dynamic stability. Despite the use of expensive starting materials for the preparation of pol ihydraxyl compounds, the resulting improvement in performance in terms of the test values "product durability, flexural strength, according to the De Mattia method and the permanent deformation at a compression of 507. " It is only small. For example, the values measured for permanent compression deformation that relate directly to the practically important parameter of dynamic consolidation are only slightly improved by the application of the? = Teachings of the invention. In addition, the test criteria employed, viz. "product durability and flexural strength according to the De Hattia method". they do not seem to be adequate enough for an assessment of the dynamic properties that come close to practice, since in the case of partial improvements in properties they can not satisfactorily show the real differences in properties between polyurethane elastomers based on 4.4 '. ~ MDT and polyurethane elastomers based on 1,5-NDl. Asx, the example based on 1,5-MDI does not present any better level of properties than the examples based on 4,4'-DHT. The preparation in the elastomer stage of paliurethane is also known. According to DE-A-25 47 364 (US-A-4 191 818), a heat-resistant polyurethane elastomer can be prepared by the reaction of a compound d? H? Dro ::? an essentially linear relatively high molecular weight with a deficiency oara diisocyanate to provide an adduct having terminal hidroKilo groups and making roscci anar subsequently this adduct with a symmetric aromatic dusocianato excess and alkanediols or tere * cough cutting di (lquilenglical.} . as understanders of cader \ 3. whether to prepare cellular polyurethane elastomers by this method, it can also be used as understanders chain water, if desired in combination with at candióles / or tereftalatas di (alquxlenglxcol).

Cellular polyurethane elastomers may also be prepared by the process described in document DE-A-2 940 856 (US-A-4 334 033). In accordance with this process, the polyhydroxyl compounds of relatively high molecular weight and, if desired, chain linkers react with an organic dixsacxanata in a ratio between OH and NCQ groups of 1.2; 1 to 2sl. to provide a prepolymer containing hxdranxlo. This is divided into a weight ratio of approximately 80 - 20: 20 - 80 in components (I) and (II); component (I) reacts with 1,5-NDI at a ratio between OH groups and NI-10 groups of ls 2"5-12 to provide an NDT- adduct to the xure which contains CG groups and component (II) is Combined with chain binders, water and additives to form a mixture tank (II). The adduct of NDT-pal luretane and the mixture (III) finally react to provide a compact polyurethane or cellulose ester. This process allows the addition of form components in a manner and minutes and their mixing quickly and intensively. The elastomers of poloxethane are homogeneous and have uniform mechanical properties throughout the molded object. It is an object of the present invention to provide a process for the preparation of compact or preferably microcellular IUrethylene poly elastomers in which expensive, at least partially expensive I + 5 NDI can be replaced by more easily manageable and less expensive organic socianates. or mixtures of dusocyanates. In spite of the concomitant use of other organic dixsacxanata, the mechanical properties of the prepared polyurethane elastomers must be improved or correspond at least essentially to those based on 1,5-NDI. Regardless of the type of polyhydroxy compounds of relatively high molecular weight employed, the polyurethane microcellulose elastomers must have clearly improved static mechanical properties compared to polyurethane elastomers based on 4,4'HD I, particular in terms of values of dynamic consolidation and permanent deformations by compression, in such a way that they can be used, particularly for the production of systems of love, vibration and shock equalization. We have found that this object is achieved by means of a process for the preparation of compact or cellular polyurethane elastomers, preferably microcellular by reaction a) of relatively high molecular weight polyhydroxyl compounds and, if desired, b) low molecular weight chain extenders and / or crosslinkers with c) organic polyacyanates in the presence or absence of d) catalysts, e! expansion agents y, f x? additives, wherein the organic polyisocyanates employed are phenylene 1,4-phenylenediazine (p-PDI) and at least one additional aromatic dusocyanate selected from the group consisting of toluene diisocyanate, dxfenx 1 methane dusocyanate, dusocyanate 3,3-di metí 1 bifen t lo, diisacianata of 1, 2-d? Feni letano, and / or alusic dusarxanalu that has 4 to 12 carbon atoms and / or ifla cycladic dusacianata having 6 to iS atoms of carbon. In accordance with the preparation method used, the polyurethane elastomers are prepared by the prepolymer method, where advantageously a palxadixation product containing urethane * and isocyanate groups is prepared by the compound of relatively high molecular weight polydihydrone (a) - at least one aromatic anaesthoxane selected within the group consisting of toluene dusocyanate f, TDIj, HDT, 3, 3 'dusocyanate - di eti Ibiphenyl (TODI), 1,2-d? phenol ethane dusocyanate (DIBDI), preferably 4,4'-HDI and / or hexamethylene, 1,6-d? socianato (HDI) and / or satiety - 3, 3, 5 ~ tr? met? l-5? soc? anatamet? lc? clahexans (IPDI). This polyadicion product can react with p-PDI, in one step or b little at a time, to convert it into isocyanate groups that contain prepolymer »X-cellular polyurethane urethane elastomers can be prepared from such prepolymers containing isocyanate groups by reaction with water or aqua mixtures and, BL is desired, low molecular weight chain adjuvants or stxculators (b) and / or compounds of relatively high molecular weight (a). The invention also offers prepolymers containing isocyanate groups, having an MCO content of 3.3 to "/" by weight, preferably 3.5 to 9.0% by weight, and prepared by reaction of at least one compound of pol hxdronxlo of relatively high molecular weight (a) a mixture of (a) at least one low molecular weight chain linker and / or re-crosslinker (b) with at least one aromatic dusocyanate selected within the rump consisting of TDI, MDI, TODI, DIBDI , preferably 4.4 -MDI, '// or HDI and / or IPDT to provide a polyadicion product containing urethane groups and isocyanates and having an NCO content of preferably 0.05 to 8% by weight, with higher preferably from 1.2 to 7.5% by weight, and reacting this polyadicon product with p-PDT which can be incorporated into the reaction mixture and reacting with the polyamide product in a step to preferably little by little, the elastomers of microcellular luretan pol nl excellent static and dynamic properties. Due to their specific cushioning characteristics or their long-term use properties, they are used. particularly, in shock and vibration damping systems »Since layer c? da.d of 3 rigid segments comprising urea / or urethane groups in the polyurethane turners based on p-PDT to crystallize is disrupted in a considerable way by the concomitant use of di soc nates that crystallize less easily, for example, the economical 4,4'-MDI with its angular structure, a person skilled in the 3rd mate could have considered that the resulting polyester elastomers had static and dynamic properties inferior to the static and dynamic properties of the elastomers. of polyurethane based on aromatic aromatic dussation. Therefore, it is not foreseeable that icracellular polyurethane elastomers prepared from mixtures of aromatic diisocyanate containing PDT, aliphatic and / or cloali fata co have good mechanical properties virtually comparable with elastomers prepared e. from p-PDI and had clearly improved static mechanical properties, in particular permanent compression deformities and dynamic consolidation values, compared to irreocellular polyurethane elastomers based on 4,4 '~ MDJ. The microcellulous polyurethane elastomers prepared by the process of the present invention are therefore less expensive than polyurethane elastomers based on 1,5-NDT and, because of their good static and mechanical properties, are very useful for the production of polyurethane elastomers. Vibration and shock absorption systems. In addition, the rearrangement mix is simpler in terms of handling and process. t r? As for the subject of the initial materials (a) to (f) for the preparation of the polyurethane, compact, or preferably cellular, for example microcellular, extruders, and in terms of the process of the present invention, the following may be indicated; 15 a) Relatively suitable polyhydryl or high molecular weight compounds preferably have a functionality of 3 to preferably 2 and a molecular weight of 500 to 6,000, preferably from 800 to 3,500 and in particular from 1,000 to 3,300, and preferably comprise polymers containing 0-hydranyla, for example polyacetals, such as polyace; imethylenes and especially insalubles in water, for example polybutanediol formal and pol ihexand formal lol, polyaxyalkylenepolyols, with for example polybutyl 1-ols, polybutyl-laxative IOXI and 1-licole, 5-potyl-butylpolyxopropyl 1 englicox, pol lanxhuti 1 enpol? o "i ro il e olion let l engl icol es, pol i rs >;? T. propí lenpol ipl is pol lomprop lenpol an et il eppol? Ol es and pol ester palíles, such as pal là © s fà © palà © s prepared from organic carbonic acids and / or derived from dicarbomilic acid and dihydric alcohols to tphxdpcos and / od lal quil eng 1 icoles, from hydroni carbon acids! 1 icos lactones, and also pol ic rbona tos containing hydronxlo. Relatively high molecular weight iodine compounds of relatively high molecular weight that are useful and therefore preferably used are polydihydroni 3 or difunctional compounds having molecular weights of greater than 800 to 3,500, preferably 1,000 to 30, selected within the group consisting of erpolial polies, pal carbonates containing hydra; lio y polioni but i lengl icole »Polyhydranyl compounds of relatively high molecular weight can be used individually or as mixtures. Palióles de pol? On? Suitable Ikylene can be prepared by known methods, for example, from one or more alkanoles having 2 to 4 carbon atoms in the alkoxylene radical by ammonium polymerization using alkali metal hydroxide such as, for example, sodium hydroxide. of potassium, or alternatively to the alkali metal canids such as sodium methoxide, sodium-potassium ethoxide or potassium isoproponide, as catalysts, addition of at least one initiator molecule containing 2 or 3, preferably 2 carbon atoms. hydrogen reactants in linked form, or by cationic polymerization employing leisic acids for example, antimony pentachloride, boron fluoride etherate, etc. , to good bleaching earths as catalysts. Suitable alkylene oxides are, for example, 1,3-propylene oxide, 1, 2-butylene oxide, or 2,3-butylene oxide, preferably ethylene oxide and oxide. of 1,2-t '"< propià ³ n and, particularly, fetrahidrafurano. The alkylene oxides can be used individually, either in succession or as a mixture. Examples of suitable initiator molecules are water, organic carboxylic acids such as, for example, suc-anic acid, Adipic acid, phthalic acid and terephthalic acid, N-monoalkylated and N, H'-dialkylated, nonalkylated, aliphatic and aromatic diamines having from 1 to 4 - Carbon radicals in the alkyl radical, for example txlendxa ma mopo 1 quilada y dí Iquilada, 1, 3-prop? lendi amin, 1,3- 0 butilendiamma or 1, 4-but? 1 ndi mine, 1,2-, 1,3-, 1,4, 1,5- and 1, 6 ™ he? Amet? Lend? mine, to the anolamines such as for example ethanol amine »N-methylantanolamine and N-ei 3 ethanotamine, dialkanol amines such as for example die tanolamxin, H-methyldiethanolamine and N-e ti 3 die tanolamma, and tria 3 canolammas 5 such camo tpetanalamine , and ammonia. Preferably 17 they employ dihydric and / or trxydiphatic alcohols, for example, to candiols having from 2 to 1"* carbon atoms, preferably from 2 to 4 carbon atoms, for example ethanol, 1,2- and 1, -propand ol, 1,4-butanedium, 1,5-pen-diol and 1,1-hexanoyl, glycerol and tri-ethanol propane, as well as dialkyl n-glycols such as diethylolol and dxprop. As paraxyalkylenepolymethylene, it is preferred to use palladium butylalkol (with tetramethylene glycols) which have molecular weights of from 500 to 3, preferably from 650 to 2,300. As polyhydric compounds (a), polyols which can be prepared are also preferably used, such as, for example, from alkaline carbonate acids having 12 carbon atoms, preferably alkaline carbonic acids which they have 4 to 6 carbon atoms, and to aromatic dicarboxylic acids and palcohydric alcohols, preferably alkalies having ds 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and / or dialkyl icoles. Examples of suitable lcandicarbonyl acids are succinic acid, glutaric acid, adipic acid, sufaepic acid, azelaic acid, sebacic acid, and decandi carbonyl ico acid. dxcarboxy acids Suitable aromatic oxides, for example, phthalic acid, isophthalic acid, and terephthalic acid. The alkadicarboxylic acids can be used here either singly or in a mixture with them. Instead of the free dicarboxylic acids, it is also possible to use the corresponding derivatives of dicarboxylic acid such as monoesters of carbom xcos or bxen diesters of alcohols having from 1 to 4 carbon atoms or dicarbonyi anhydrides. It is preferable to use dicarbamic acid mixtures of succinic, glutaric and adipic acid in proportions by weight, for example, of 20-3; 5- 0 s 0-32, and particularly adxopic acid. Examples of dihydric and palihydric alcohols, particularly the candiols or dialkylene glycols, are: ethanediol, dxetxl englxcol, 1,2-propandolol or i, 3-prapandol, di ropilenglical, 1, 4-butandol, 1, -pentandol, 1,6-hexandial, 1, 10-decandial, glyceral and trimethylalprapane. Ethanediol, diethylene glycol, 1,4-butanedixol, , 5-pentandol and 1, fc ~ henand? Al or mixtures of at least two of the mentioned dials, particularly mixtures of 1, 4-butand? Al, 1, pentandol and 1,6-hexand? . It is also possible to use polyester lactone derivatives, for example epsilon-caprol actana, or hydrocarbon acids, for example omega-hydroxycapra acid, to prepare the polyols, the aromatic and / or aliphatic dicarbony acids and preferably Acidic alkalizing agents and / or derivatives can be polycondensated with polyhydric alcohols in the absence of catalysts, preferably in the presence of esterifying cations, advantageously in a mixture of inert gases such as nitrogen, helium, argon, etc. , in the melting at a temperature of 150 to 250 ° C, preferably 180 to 220 ° C, under atmospheric pressure or under reduced pressure at the desired acid number which, preferably is less than 10, with lower preference 2. In accordance with a preferred embodiment, the mixture of polyphenols is polymerized at the temperatures mentioned above until an acid value of z from 80 to 30, preferably from 40 to 30, under atmospheric pressure and subsequently under a pressure of less than 500 mbar, preferably from 50 to 150 mbar. Suitable catalysts for esterification are, for example, catalysts of iron, cadmium, cobalt, lead, zinc, antimony »magnesium, titanium and tin in the form of metals, metal oxides or metal salts. However, the polycondensation can also be carried out in the liquid phase in the presence of diluents / or entrainers such as benzene »toluene, filled with chlorobenzene to remove the condensation water by azeotropic distillation. For the purpose of preparing the polyester polyols, the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are preferably condensed in a molar ratio of 1 s 1 ~ 1.8, preferably 1: 1.05. 1.2. As polyester poly esters, preferably polyalkadeladides are used, such as poly (ethanedialadipate) polys (4,4-butand?; , pal I Cetand? ol-1, 4-hutandiladipatas), poly (t, 6-hexandxol-neopent? lgl icol adipatas) and pol i (1, 6 ~ henand? ol-l, 4-butandxaladxpatos) and polla rolactones . Other pal-olulins are suitable that can be mentioned are pol-carbonates containing hydronyl. Tale palicarnates containing hydroxylam can be prepared, for example, by the reaction of the aforementioned alkanoles, particularly 1, 4-bu to dial and / or 1, 6 / hennand, and / or dialkylene glycols, such as diols. ethylene glycol, dipropyl 1 glycol, and dibutylene glycol 1, dialkyl or diapcarboxycarbons, such as, for example, diphenyl carbonate, phosphenol. As hydrocarbon-containing polycarbonates, preference is given to using polyether-polycarbonate diols which can be prepared by the polysaccharide of al) polybutylglycol having a molecular weight of 150 to 500 or a2 '? mixtures comprising i) at least 10% malar, preferably 50 to 95 molar%, of a polybutylene glycol having a molecular weight of 150 to 5O (al) and ii 5 less than 90 molar%, preferably 5 at 50 mol%, of at least one polyoxyalkylene xlcol which is different from (a, which has a molecular weight of 150 to 2,000, at least one alkylene glycol, at least one linear or branched alkanal having from 2 to 12 carbon atoms and is a cyclic alkanal having 5 to 15 carbon atoms or mixtures thereof with phosgene, diphenyl carbonate or dxalkyl carbonates having alkyl groups (C 1 -C 4), b) For preparing compact polyurethane elastomers or Cellular preference by the process of the present invention, it is also possible to employ ex chain endendures ib) difuncianal is of low molecular weight »crosslinkers (b) of low molecular weight, of piference tpfuncianales or else you are trafuncional or mixtures of e; chain tensioners and crosslinkers in addition to compounds (a) of high molecular weight polyhydroxamine. Such chain binders and crosslinkers (b) are used to modify the mechanical properties, particularly the hardness, of the polyurethane elastomers. Suitable bed chain extenders, for example, alkalies, day 3 quylene glycol and polyalkylene glycols, and ret. Adores, for example, alcohol trxhydrxca or: p tetrahydric and pol xan xa tquil enpol Lales oligom? pcos that have a functionality of 3 4, have usually weights less than 800, preferably 18 to 400 and particularly 60 to 300. As chain entenders, it is used Preference is given to candiols having 2 to 12 carbon atoms, preferably 2, or 6 carbon atoms, for example, etandial, 3-pro? and? al, 2,5-pentanediol, 1, 6-hexand? ol »1, 7-heptapdxal» 1, 8-oc andxal "i, 9-nonand? ol, 1» 10-dec.and? ol and in particular 1, 4-butand? o !. , v di l ui 3 eng licol is that they have ds 4 to 8 carbon atoms »for example diethylene glycol and dipropyl eng 11 col» and also pal laxialquilengicales. However, suitable chain linkers also include branched / or chain-branched alcandials that have 1 to 1 more than 1. carbon atoms, for example, 1,2-propandi a »2-e ti 1 propan -i, 3-dxal» 2,2-d? metx l rapan-1, 3-d? al »2 ~ but? 1-2-et i-lpropan-1, 3-d-ol, but ~ 2- ~ en ~ l, 4 ~ cl Lol and bul -2 ~? Ne-l, 4-d? Ol, diesters of terephthalic acid with glycols having from 2 to 4 carbon atoms, for example, terephthalate of b? s (et? legl? col), or terephthalate of b? s (1,4-butand? al) »hxdrox talquxl enketers of hydroquinone or resorcmal »for example, 1, 4 ~ d? (β-Hydraxyethyl) hydroquinone at 1, 3-d- (R-hydronyethyl) resarmol, to canolae having 2 to 12 carbon atoms, for example, ethanolamine, 2 ™ ammoniapropanol and 3-ammonia-2 , 2-dxmet? Lprupanol, N-al qua Idia amine channel »as for example N ~ met? thdietanol mine and N-ethyldiethanol amin, dxammas (c? clo) al? fetxe: ace having from 2 to 15 carbon atoms, for example, xlendiamxna, 1,2- or 1,3-propyl endia ma, 1 , 4-butyl, and 1,6-hemethylethylenediamine, isophoronediamine, 1,4-c-halohexylenediamine, and 4'-diamino-dicyryl-methanedi-methane, H-to-alkyl- and N-H-dialkylalkylendia plus such camo N-me ilpr opi lendiamine and N, N-dimethylethylenediin amine and aromatic diammas such as the dimethyl stellate dies metalenbis (4-amna-3-benzoic acid), 1,2-b? s (2-ammofeni 1 uncle) ethane, tp etx 1 eng 1 xcol -di-a-amxnobenzo you, 2,4- and 2,6-tol usndxamxn, 3,5-dxetxl-2,4- and -2,6-toluend? amma, 4, 4'-dxaminod ifenilme taño, 3,3-dichloro-4, 4 '-dxa modifenil etana and 4,4' - diaminadifemlmetanas primary ortho-di-, tp- and / or -tetraalqui 1-sust? Tu? Dos, as for example 3,3-dusopropyl-y, ', 5, 5' -tetraxsopropy 1-4.4 -dxamxnodxfenx l ethane »Examples of reticulators at least tpfunctional is that they are preferably used In the preparation of the open-ended elastomers, polyurethane alcohols are optional and tetrafunctional alcohols are, for example, glycerol, trxmethyl, propane, pentaerxtr, tol and trxhydronxexclohexanes, and tetrahxdranxalquxl, to Iquxlepdxa, such as tetra (2-hi dronieti 1), ethylene diamine, well tetra (2 ~ ha dro iprapil) et lend? am? and also polyaxyalkyl polyols in oligomers which have a functionality of 3 to 4. The chain and reagent binders (b) which are suitable according to the present invention can be used singly in or in the form of mixtures. It is also possible to use mixtures of chain binders and reactors. To adjust the hardness of the PU elastodes, the proportions between the components are (a) and (bi can vary in a relatively wide range) with the hardness rising with the increasing content of chain linkers diffusing and at least cross-linking agents in the PU elastomer »According to the desired hardness, the required quantities of the formative components (a) (b) can be determined in a simple manner in an enpepmental manner. It is advantageous to employ, based on the weight of the pal and hydroxyl compound of relatively high molecular weight (a), from 5 to 50% by weight of a chain linker and / or crosslinker £ b), the cost of which is preferred. 50% by weight for the preparation of rigid paliurethane elastomers »c) According to the present invention» compact polyxurethane and microcellular precursors are prepared using two organic palusaciana, one of which is p-PDI . Different aromatic compounds of p-PDI that are used are dusocxana your of toluene, for example 2,4- and 2,6-TDI thus chromium mixtures with the di-cis-di-cis-ethanes, for example "4'-, 2,2- and preferably 4,4'-MDT and mixtures of at least two of the aforementioned MDI isomers, dusocyanates of 3,3-di and il-bifemlo »for example 3,3-d? metxl-4» 4 -diisocyanatobifeni lo TODI), di-isocyanates of 1,7-dxphenlethena, for example 2,4'-, 2,2- and preferably 4,4 '~ DIfID and mixtures of at least two of the aforementioned DIBDT sesmeri .. Due to its good processability and very good properties Mechanical properties of the elastomers which can be obtained with the use of 4,4 '-MDT are particularly preferably used in combination with p-PDI for the preparation of compact polyurethane grades and preferably microreligres. the p-PDI and aromatic dna socianates selected within the group consisting of TI, MI, TODT and DIBDI can vary over a wide range, for example the proportion between The PDA and the aromatic dices can vary within a range of 1: 0.1 to 1:10, preferably 11: 1 to 1: 9, and especially preferably 1: 1 to 1: 4 »without changing" significantly l a-. aesthetic and dynamic properties, When p-F'Dl and 4 »4'-MDI are used, the preferred combination» the molar ratio between p-PTD /, 4 '-MDI is preferably in the range of 1: 0.1 to 1:10, with even greater preference from L: 0.11 to 1: 9, >; especially from 1: 1 to 1: 4. The aromatic diols can, if required, be individually melted by mixing when mixed and melted together and used as a melt for the preparation of the elastomers of the xuretanus elastomers. fusion of the ot or dusocyanate and melted and dissolved therein In accordance with the last mentioned processing variant, the solid p ~ FDI is usually introduced (melting point: ^ "C) sn a fusion ds 4,4 ' -MDT and it dissolves with the fusion. Instead of the aromatic dusocyanates or the mixture thereof, it is also possible to prepare the elastomers? They are compact polyurethane and preferably cellulose using aliphatic di isocyanates having from 4 to 12 carbon poplars, preferably from 4 to 6 carbon atoms »in the branched chain or bxen preferably linear alkylsin radical and cycloalkyl diisocyanate having from 6 to 18 carbon atoms, preferably from 6 to 10 carbon atoms, in the unsubstituted or substituted alkylcycloalkylene radical. Examples of aliphatic dusocyanates that can be mentioned are 1 »12 ~ d ?? sao? Dodecane ande, 1, 4- 2-ethylene-butane dusocyanate, 1, 5-diasate of 2-methylpentane, butane-1,4-dxxso-xanate and preferably 1,6-d? So-anatene of henametylene (HDI). Examples of suitable cycloalkalic dus- tacianates are: 1,3- and 1,4-dixsocxanatn of cxcl ahexane »2,4- and 2» 2'-dxi soexanata of hexahx rotoluena, 4,4'- »2,4'- "2» 2'-dxcxclahenx dx isocxatin, and preferably i-isoetyanate-3,3, 5-tpmet l ~ 5-? Soc? Ana turne ti 1 riclohennan idnsociana tu isaforona, TPDT). preference is given to modalities in which the organic palxxsaoxanates (e) can be used in the form of a prepoly containing xsoexanate groups, which can be prepared, for example, by the reaction of the dusocyanate fusion which has p-PDI with less one compound (a) of pal i hi roxi 1 or of relatively high relative molecular weight or a mixture of (a) and at least one chain linker of low molecular weight v / or at least one crosslinker (b) to either the reaction in steps of dusocyanate fusion containing p ~ PDI with at least one compound (a) of relatively molecular weight polyhydroxyia elevated and subsequently with at least one chain and / or crosslinker. However, preference is given to preparations containing isocyanate groups and prepared by 1-reaction of a partial amount of the total amount of at least one compound (a) of pol ihi droni 1 or relatively high molecular weight or a partial quantity of the total amount of the mixture of (a) and at least one e; chain tensioner of low molecular weight and / or et icu l adar (b) with the infrias a dusoc aromatic xanata selected within the group consisting of TDI, MD1 »TODI» DIBDI »preferably 4,4 '-MDI / o hDI / or IPD1 to provide a polyaddition product containing urethane crudes, preferably urethane and isocyanate groups, and having an NCO content of from 0.05 to 8.0% by weight, preferably from 1.2 to 7"5% in weight, and by reaction of this addition product with p-PDI to provide the prepolymer containing isociety groups. To prepare the polyurethane products containing urethane and isocyanate groups, the active components (a), if desired (b) and (c), are used with advantage in such quantities that the proportion of equivalence between hydroxyl groups of (a) or (a) and (b) and the issc anata groups of the aromatic dusocyanates TI, MDT, TODI »DIBD1, preferably 4,4 '-MDI? / or HDI and / or IPDI is ls 1 - ^ »of preference 1: 1.01 -4, The polyaddition products that cantxene urethane and isocxanate groups then react with p-PDI in one step or preferably little by little in several steps» preferably »for example, in two steps »to become the prepolymers containing xsaci n groups, can p-PDI being used in a quantity such that the ratio of equivalence between the hxdronxla groups of t, a) to good (a) and (b) and the isocyanate groups of p-F'Dl is 1: 0.02 - 6 , preferably 1: 0.1-5 and paricularly 1: 0.2-3, Co or aforementioned, mixtures of (a) and tb) can be used to prepare the prepolymers which contain isaoiapata groups. However, in accordance with a preferred embodiment, the prepolymers containing isocyanate groups are prepared by the reaction only of relatively high molecular weight polyhydroxy compounds (a) with the polysaccharides preferably preferred. 4.4 -MDI yp-PD [. Particularly suitable polyhydroxy or polyhydroxy compounds for this purpose are polyhydroxy functional compounds having a molecular weight of from 500 to 6,000, preferably greater than SOO to 3,500 and particully from 1,000 to 3,300, which are selected from the group that It consists of polyether polyols, polycarbonates containing hydroxyl, and 10x1 teramethyl alcohols. When 4,4'-HDI and p-PDI are used as aromatic diisocyanates, it has been found that the proportions of equivalence between the hydronyl groups of a) (b), preferably enclusxva in te (a), and the groups NCO of 4,4 '~ MDI and the NCO groups of p-PDI of Is i-6: 0.02-b are useful, The prepolymers having isocyan groups which can be used according to the present invention and which are prepared Preferably, the above-mentioned processing variants preferably have the isocyanate content of 3.3 to 10% by weight, preferably 3.5 to 9% by weight, based on their total weight. ? 8 To prepare the precursors containing xsoeyanate groups, the compounds (a) pol? H? Clroxx3 or relatively high molecular weight or mixtures of (a) and chain entails of low molecular weight > / or crosslinkers (b) can e ction with the organic paliasoxxatonates (c), as for example, in the form of a mixture of aromatic diisocxanata that can xene p-PDI or preferably in stages, using first at least one aromatic dusocyanate »Selected within the group consisting of TDI, MDI, TODI. DIBDT, preferably 4,4'-HDI and then p-PDI, at a temperature comprised between 80 and 160 ° C, preferably from 90 to 150 * 0. Thus, for example, the total amount or sx is desired. Partial amounts of p-PDI can be dissolved in an aromatic diisocyanate, preferably 4,4-MDI, heated, for example at a temperature of 1103C and the compound of polydihydroxyl (a) and, if desired, chain linkers and / or crosslinkers (b) heated as an example, at a temperature of 125 ° C can be added to the isocyanate mixture. After passing through the minimum reaction temperature, which is customary in the range of 130 to 150 ° C, any remaining partial amount of p-PDI may become clogged and react during the cooling phase "eg, at a temperature comprised in re 90 and 130 ° C »'> Q In accordance with the preferred processing variant, the component (a) to a mixture of i) and i, b) can be heated, for example to 140 ° C and, at this temperature, for example, the aromatic dusocyanate »Preferably the total amount of 4.4-I1D1 heated to 50 * C, can be added. Immediately after the addition of the 4 »4 '~ MDI» all the p-PDI can be incorporated into either partial quantities of p-PDI can be added little by little »/ it has been found that it was helpful to add a partial amount of p-PDI immediately after the addition of 4.4 -HDT and incorporate the partial quantity atra to the other partial quantities in the reaction mixture during the cooling phase, After reaching the theoretically calculated isocyanate content, the reaction ends. This requires constant reaction times within the range of 10 to 200 minutes, preferably 15 to 150 minutes. The lime-containing preparations can be prepared in the presence of catalysts. However, it is also to propagate the prepolymers containing isocyanic groups in the absence of catalysts and to incorporate the latter in the reaction mixture for the preparation of polyurethane elastomers. d) The catalysts (d) used are preferably compounds that strongly accelerate the reaction of the ..H compounds containing the component hxdraxila (as »if desired, (b) with the isocyanate pulses (c), Suitable catalysts are organic metal compounds, preferably organic tin compounds such as tin (II) salts, of carbon acids, organic lees »for example, tin acetate (II), tin octoate (II), tin ethylhexanaate i, 11) and tin laurate (II)) salts of zinc (IV) carbonx acids! organic xcos, for example, diaxethate dxbut xles year »i dilauralo de da butyl tin, maleate de dibuilesilna and diacttato diocti lastaño. The organic metal compounds are used alone or preferably in combination with strongly basic amines. Examples that may be mentioned are amidxins such as 2,3-d? Metal-5, 3,4, 5,6-tetrah? Drop? rimidma »tertiary amines such as for example tpeti lamina» tpbuti lamina, dimeti 1 bencílamina »N -meta Imorfal ma, N-etil morfolma, N ~ eiclohoni Imsrfal ma» N »N, N 'W -tetraalkylalkylenediamines» such as N » N, ', N'-Fetramethylethylepdiamine, N »N» N' »N '- tetramethylbutanedhamine or 0 N, N, W, 14' - tetramethylhenandiamine, pen a etildieti entpa in» bis ídimotí lamxnoeti 1) éte »foxs ( dxmetxlamxnaprapi 1) urea »1» -d? met i Ipiperazin »12-dimethylimidazole »L-azabic i cl or (3" 3 »0) actane and preferably 1,4-d azab? C? Clo (2« 2.2) achane and composed of alkanolamine 5 co or for example tpetanolamxna, triisapropanalamm U-mei ildietanola ipa and N ~ ei Idie anolamma and di metí le tañolamina. Preferably, from 0.003 to 3% by weight, in particular from 0.01 to 1% by weight of the cacifiller or combination of catalysts is used, based on the weight of the forxve components (a), (c) and, if used, (b), e) Compact polyurethane elastomers such as cast polyurethane elastomers can be prepared by the process of the present invention in the absence of moisture and physically active or chemically active blowing agents. However, the process is preferably used for the preparation of cellular polyurethane elastamers, preferably microcellular. For this purpose, aqua co or expansion agent (e) is used. The water reacts with the organic palmeticanatas and preferably with the prepolymers containing isocxanato (a) xn situ groups to form carbon dioxide and xno groups which in turn react with the prepol 2 of isscianato to form urea and couple groups consequently, bed chain linkers. Since the components form xvos (a) and »sx are used, (b) they can, due to their preparation and / or chemical composition» contain water, in some cases there is no need for separate adxption of water to the formatted components ( a) and, if it is used »(b) aa the reaction mixture. 3 However, if water should be added to the formulation of pol lurs year to achieve the desired bulk density, the amount of water added is from a range of 0.001 to 3.0% in psso of preference from 0.01 to 2.0% by weight and particularly from 0.2 to 1.2% in weight, based on the weight of the formatxva components fa) to (c). As agents for expansion (s), it is also possible to use, instead of water or preferably in combination with water, liquids of boiling point or boiling point which are vaporized under the action of the palliative reaction.; and preferably having a boiling point at atmospheric pressure within the range of -40 to 12 [deg.] C., preferably 10 to 90 [deg.] C. "to either co-blowing gases or agents that act physically or as blowing agents. which act chemically »Liquids of the abovementioned type and gases suitable as dispersing agents may be selected, for example, from the group consisting of the metal, such as, for example, propane, n-and iso-butane, n- and iso -pentane and preferably industrial mixtures of pentane, cycloalkyls and cycloalkenes such as clabutane, cyclopentene, cyclahene, and preferably cyclopentane and / or cyclohexyl; dialkylose, as exemplary of ethyl ether; ether or diethyl ether, tert-butyl ether, ether, oleylalkylene ether such as furan, ketones such as acetone, motil ethyl cene, acetals and / or ketones, for example ethyl aldehyde, aldehyde, 1, 3-d? Onol no and tell me ila acetone ketal, carbani esters 11 co-polymer example acetates or ethylene esters »methyl formate, tertiary butyl ester of ethylene-acrylic acid, tertiary alcohols such as for example 5-tertiary-butanol -fluoriferous grains in the troposphere v consequently that they do not damage the ozone layer, for example t < -? f 1 uarams ano, di f luoromethane, di f luorae taño »tetraf luoroethane and heptaf luorae year» chloroal as per axis 2-cl oropropane, and gases such as nitrogen, lf * < mononid carbon and noble gases such as helium »neon and cppton as well as expanding agents that act chemically in a similar way to water» for example, carboxylic acids such as formic acid, acetic acid and prapianic acid »15 Among the liquid quo Inert towards the NCO groups and suitable as expansion agents (e) »ss gives preference to the use of alkanes that have from 4 to 8 atoms of carbon, eiclaalcanas having 4 to 6 carbon atoms or mixtures of al cana / cxclae Icano that have a 0 boiling point of -40 to SO ^ C ba or atmospheric pressure. Special preference is given to the use of (cycle) CS, co or pair and p-n-pentane, iso-pentanes and cxclopsentanu and their industrial ezrlas. Other suitable sxpansion agents are salts that are decayed when heated. For example, bicarbonate of 54 ammonium »ammonium carbamate and / or ammonium salts of organic carbon acids such as, for example, the monaammonium salts of malonic acid, boric acid, formic acid or acetic acid» 5 The most appropriate amount of agents of solid solids »liquids of ba or boiling point and gases that can be used individually or in the form of mixtures» for example, as mixtures of liquids or gases or as gas / liquid mixtures »depends on the density J < "< s achieved and of the amount of water present." The reawake quantities can be easily determined by simple means, and satisfactory results are obtained by using solid amounts of O.5 to 35 parts. by weight »preferably from 2 to 15 parts by weight, liquid amounts of 30 parts by weight, preferably from 3 to 18 parts by weight, and / or gas quantities from 0.01 to 80 parts by weight, preferably from 10 to 35 parts by weight, each case based on the weight of the training components (a) »(c) and, if employ »(b). The gas charge for example with air, carbon dioxide, nitrogen and / or helium can be carried out either through the low molecular chain chain extenders and / or crosslinkers (b) or bain through the polusocyanates. (c) either through (a) and (c) and, if employ »(b).

Distribution agents that are used are, as indicated above, chlorofluorocarbaceous hydrocarbons. f) If desired, additives (f) can also be incorporated into the reaction mixture for the preparation of the compact polyurethane elastomers and preferably cellular. Examples that may be mentioned are substances, surfactants, foam stabilizers, cell regulators, reagents, flame retardants, core forming agents, oxidation inhibitors, stabilizers, lubricants and mold release agents, colorants and pigments. Possible surfactants are, for example, compounds which serve to assist the hamogsnexation of the initial materials and which may also be suitable for regulating the structure of the cells. Examples which may be mentioned are those such as, for example, sulphates sodium sulphites. of castor oil or of fatty acids and also of fatty acid amine, eg diethyl amine diethyl amine, diethanolamine stearate of dihatanolamine cinoleate, salts or sulphonic acids, for example alkali metal or ammonium salts of dodecylbenzene acid or dmaphi 1 ethansulphonic acid and pinaleic acid; foam stabilizers such as copal imeras of si loxane-ox Iqui 3 epo and other arganopalisila, anos, to 1 qui ethoxylated ifenoles »fatty alcohols, fine oil, castor oil esters to fine esters cinoleicos» oil ru or Turkish and peanut oil as well as regulators of cells with or paraffins »fatty alcohols and dimethylpal and silonanas. Also suitable for improving the action and ulsifying the structure of the cells and / or their stabilization are oligosaccharides which have radicals of oxyquinone and fluoroalkane as side groups. The surfactants are commonly used in quantities of 0.01 to 5 pyridnes by weight »based on 100 parts by weight of the compounds (a) of polyhydric or relatively high molecular weight. For the purposes of the present inventions, re-lumbering machines, in particular reinforcing fillers, are the usual organic inorganic replenishers, reinforcing agents and weighting agents known per se. Specific examples are: inorganic reagents such as silicous minerals for sheet silicates such as antigort, serpentine, hornblende, amphiboles, teach it, talcum. metal oxides such as »for example, kaolin» aluminum oxides, aluminum silicates »titanium oxides and iron oxides, metal salts such as gis» barite inorganic pigments such as for example cadmium sulphide »zinc sulphide and also glass particles. Examples of suitable organic woodcutters are: black smoke »mel amine» graphite e-panding »ros a» cyan resin open tad enyl as well as graft polymers »Co or reinforcement lumber mills» fiber is preferably used, for example carbon fibers or particularly glass fibers »particularly when a high resistance to thermal distortion is required at very high stiffness. These fibers may be covered with coupling agents and / or pretreators. Suitable glass fibers »which can also be used, for example, in the form of glass fabrics» mats »non-themed articles or preferably fiberglass yarns or fiber glass cut from glass E with alkaline level ba they have a diameter of 5 to 200 μm, preferably 6 to 15 μ, have a gene at an average fiber length of 0.05 ai, preferably 0.1 to 0.5 mm, after their incorporation into the molding compositions. The organic and inorganic fillers can be used individually or as mixtures and are customarily incorporated into the reaction mixture in amounts ds 0.0 to 50% by weight, preferably l 30% by weight, based on the weight of the components (a) to (a) suitable flame retardant substances are, for example, »tpcresyl phosphatase» tp% phosphatase (2-clear), »trisphosphate (2 ~ clearpropyl), tris phosphate (1) , 3- 58 diclarapropyl) »phosphate of tr? s- (2, 3-d Lbromap clothing lo 'f and tetraqui (2-chloroet? 1) et? 3 ene diphosphate Apart from 3 os halgon-substituted phosphates mentioned above» it is also possible to employ inorganic pyrarrstardantus with red phosphide »hydrous aluminum oxide, antimony trioxide» arsenic trioxide »ammonium polyphosphate and calcium sulphate or cyanuric acid derivatives, for example, mixtures of at least two pyrophorous substances with, for example, Use ammonium phosphates and melam and, if desired, expanded starch and / or graphite to make the polysurstane elastomers prepared in accordance with the pyrosistens of the present invention. In general, it has been found useful to employ 5 to 50 parts by weight »preferably from 5 to 25 parts by weight» of said flame retardants in masses by 10 parts by weight cis the formative components (a) to (c), Core forming agents which may employ These are, for example, talcum, cationic fluoride, sodium phenyl phosphite, aluminum oxide, and polyethylene carbonate, finely divided in quantities of up to 5%, based on the total mass of the formative components. a) a (c). Suitable oxidation inhibitors and thermal stabilizers which may be added to the polyurethane elastomers of the present invention, for example, metal halides of group I of the Periodic Table, for example, metal halides of the periodic Table I or I , for example lithium sodium »potassium» lithium, if desired in combination with copper (I) halides, for example chlorides »bromides» or laures »tightly hindered phenols, hydroquinones, and also substituted compounds of these groups and mixtures of they are preferably used in a concentration of up to 1% by weight »based on whether the weight of the training components (a) to (c)" UV stabilizers are vain ressrcinales "salicylates, benzo-riazole is / substituted benzaphenones and also sterically hindered amines generally employed in amounts up to 2.0% by weight, based on the weight of the formative components (a) to (c). Lubricants and mold release agents »which are generally added in the same way in amounts of up to 1% by weight» based on the weight of the formative components (a) to (* "are stearic acid, sstearyl alcohol, stearic esters and stearamides as well as the fatty acid esters of pentaephotol »It is also possible to add organic dyes such as nigrosm» or pigments such as titanium dioxide, cadmium sulphide, cadmium sulphide selenide »phtalaci girls» ultramarine blue or more black smoke »More detailed information about the other auxiliaries and usual additives mentioned above can be found in the literature, for example, in the monograph by JH Saunders and I '.C. Fpsch" High Polymers "(Polymers) volumes) Volume XVI, Palyurethsnes (Pal luretans) »Parts 1 and 2» Interscience Publishers 1962 to 1964 »or in the Ls of f-Hantfbuch, Pol y ure hane Volume VII , Carl-Hanser-Verlag »Munich» Vienna »lera.» 2nd », and 3rd. edition »1966» 1983 and 1993 »In order to prepare the compact or preferably cellular polyurethane elastomers» the compounds (a), from relatively high molecular weight palihxdroxila, if desired molecular weight chain extenders ba and / or crosslinkers (b) and »if desired» the chemically acting blowing agents, preferably water »/ organic polyisocyanates (c) or preferably the pre-polymers containing the associanato groups and prepared from (a) , (fa) and (c) or preferably from ds (a) and (c) and sx ender and / or reticulars (b), mixtures of partial quantities of fa) and (b), mixtures of partial quantities cie ( a), ib) and water preferably mixtures of (b) and water or water can react in the presence or absence of catalysts (d) "physically acting expansion agents (e) and additives (f) in such quantities that 3rd proportion of equivalence in re NCO groups of polyisocyanates (c) or prspul imeras containing xsocxanato groups and the sum of the reactive iudrOyenüb of components (a) and, if it is used (b) and any expansion agent that acts chemically is 0.8 - 1.2: 1, preferably 0.95 - 1.15 s 1 and particularly 1.O0 - 1.05 yes »The compact polyurethane elastomers and preferably cellulose can be prepared by the methods described in the literature, for example, the process of a step to preferably prepaymers, with the help of the known mixing equipment, In order to prepare the compact luretan elastomers, the initial components can mixing homogeneously in the absence of blowing agents (e), usually at a temperature between 80 and 160 * 0, preferably from 110 to 150 * 0, and the reaction mixture can be introduced into an open mold, heated or not heated and left to cure. To form the cellular polyurethane waves, the active components can be mixed in the same way in the presence of an expanding agent, preferably water, and can be placed in the heated or unheated malds »After filling the olde, it closes the molds and the reaction mixture is allowed to foam by compaction "for example" to a compaction harrow from 1.1 to 8, preferably from 1.2 to 6"and par- ticularly from 2 to 4, to form the molded objects. . As soon as the molded objects have sufficient strength they are removed from the mold. The mold removal times depend, among other things, on the temperature of the mold, the geometry of the mold and the reactivity of the reaction mixture. / san generally within a range of 10 to 60 minutes. The compact pallaurethane elastomers prepared by the process of the present invention have, without a filler, a density of 1.0 to L.4 g / cm3, preferably of 1.1 to 1.25 g / cm3, while the products containing re! Woodcutters usually have a density greater than 1.2 g / cm3. The cellular polyurethane turners have densities of 0.2 * 1.1 to 1.1 cm / cm3, preferably 0.35 to 0.80 g / cm3 * The polyurethane elastomers prepared by the process of the present invention are used for the production of molded products, preferably for the construction of machines and for the automotive sector. The cellular polyurethane elastomers are suitable, in particular, for the production of damping elements and springs, for example for vehicles, preferably for motor vehicles, shock absorbers and coating layers.

Comparative Example I a) Preparation of an isocyanate group prepolymer and based on 1,5-NDI 1,000 parts by weight (0.5 mole) of an adipate (1 mole) of poly (and andiol (0.5 mole) ~ 1 »4-bu dial (0.5 mol) having an average molecular weight of 2,000 (calculated from the hadronil index determined as a whole) at 140 ° C and at a temperature were mixed and reacted while they were subjected to vigorous stirring with 240 parts by weight (1.14 mol) of 1.5-WDI solido »This ppororciono a polymer that has an NCO content of 4.32% by weight and a viscosity, at 90 ° C of 2,800 Pa * = (measured using a viscometer "Haaie's gyratupa" by means of which the viscosities were also measured in the following comparative examples and in the examples) b) Production of cellular molded products The crosslinking component comprises ".7 parts by weight of 2.2, 6" 6 '-tetraisapropí Id ifenil-carbodxx ída »2.9 parts by weight of a mixture of ethoxylated aleic acid and ric aleic acid containing an average of 9 units of anethylene, 3.8 parts by weight of the salt of n-alkoxybenzenesulonic acid onaetanolamma containing alkylene radicals (C9 ~ C15), 36.3 parts in weight of the sodium salt of sulfated castor oil, 36.3 parts by weight of water and »03 parts by weight of a mixture of 30% by weight of ethyl acetate tilen triamma and 70% by weight of N ~ met? l ~ N '- (dime til am ome til) piperaca na. 100 parts by weight of the isocyanate prepolymer prepared in accordance with that described in Example 1 were vigorously stirred.

Comparative Example and heated to 90 ° C with 2.4 parts by weight of the crosslinking component during approx. irrationally 8 seconds The reaction mixture was then introduced into a metal mold, which can be closed at 8 ° C. The mold was closed and the mixing of the reaction was allowed. After 25 minutes, the malcelled microcellular object was removed from the mold and heated to 11 C for 16 hours for additional thermal curing. Comparative Example II a) Pipera tion of a prepoly era containing isocyanate groups and based on 4,4 '-MDI The procedure of Comparative Example was repeated' but employing 380 parts by weight (1.52 mol, of 4.4 -MDt heated to 50 ° C instead of the i »5-NDI, this provided a prepsl number that has a content of NCO of 6.19% by weight and a viscosity at a temperature ds 9 * C of 1,600 mPa * s (was carried out by measurement using a vi = rotating meter). b) Production of a cell test plate 300 parts by weight of the prepolymer in accordance with those described in Comparative Example 1 and 3.42 parts by weight of the crosslinker component in accordance with that described in Comparative Example Ib were reacted in accordance with what is described in Comparative Example I and the melt reaction mixture molded to form test plates. The reaction mixture could not be processed in test springs for dynamic testing. Comparative Example TTI a) Preparation of a preparation containing isocyanate groups and based on 4,4'-MDI A mixture of 1,000 parts by weight of the adipate ds pal i (booth? Al-1?? -butand? Al) described in Comparative Example I and 3 parts by weight of tp etx 3 ol propane reacted with 380 par ss by weight (1.52 mol) of 4.4-Mdi cal at 50 ° C according to that described in the Comparative Example II »This provided a prepolymer having an NCO content of 5.80% by weight and a viscosity at? 0 ° C of 1,750 mF'a * s (the measurement was performed using a rotary viscometer). b) Production of cellular molded objects Molded objects will be produced by a method similar to the method described in Comparative Example I from 100 parts by weight of lime preparatory in accordance with that described in Comparative Example Illa and 3.1 parts by weight of crosslinker component in accordance with that described in Comparative Example Tb. Comparative Example IV a) Preparation of a prepolx was containing isocyanate groups and based on p-PDI A 1000 weightless (0.5 mole) of an adduct (1 mole) of poly (ethanol xol (0.5 mole) ™ was heated. 1, 4-butanedxol (0.5 mol)) having an average molecular weight of 2000 (calculated from the hydraxi index as determined experimentally) at a temperature of 100 ° C and at this temperature were added and reacted with stirring vigorous 183 parts by weight (1.14 mol) of solid p ~ FDi. This provided a polymer having a content of NCO ds 4.40% by weight and a viscosity at 8 3C of 2900 mPas (the measurement was made using a rotating viscometer), b Production of cellular smeared objects Molded objects were produced by a method similar to the method described in Comparative Example I from 100 parts by weight of the prepol in accordance with that described in Comparative Example IVa and 2.43 parts by weight of the crosslinker component according to that described in Comparative Example Ib. but the isocyanate preputer from comparative example IVa was heated to S0 ° C. The molded objects were removed from the mold only t ~ 7 after 60 minutes and were heated at a temperature of 110 ° C for 16 hours for additional thermal cure. Example 1 a) Preparation of a prepolymer that can isocyanate groups and based on 4.4,4 MI p-FDT 1 0 pair is warmed by weight (0.5 mol) of an adipate (1 bad) of pal i (etandial (.5 mol) -1 »~ butandol (0.5 mol)) having an average weight of 2000 (calculated on the basis of the hydrolyses determined from the experiment) at a temperature of 130 ° C and , under vigorous stirring "174 parts by weight (0.696 mol) of 4.4 '-HDT heated to 50 ° C and immediately after 55.75 parts in weight (0.348 mal) of solid p-PDI were added. This gave rise after a reaction time of approximately 15 minutes to a polyurethane product containing urethane, isocyanate groups and having an NCO content of 3.7% in psso. This process of pol lation reacted to a temper ds 97 ° C with an additional 55.75 parts (0.348 mol) of solid p-PDI and cooled to S0 ° C for a period of about 30 minutes under agitation. This gave a prepolymer with an NCO content of 5.77% and a viscosity at S ^ C ds 3000 mPas (the measurement was made using a rotary vxscometer) «b) Production of cellular molded parts 100 parts by weight of isocyanate prepolymer based on 4.4 -MDI / p- DT and heated to 80 ° C, prepared in accordance with that described in the Example, the mixture was mixed with vigor-ose stirring, with 3.21 parts by weight of the crosslinker component, prepared in accordance with that described in Comparative Example Ib. After a stirring time of about 8 seconds, the reaction mixture was introduced into a metal mold which was closed heated to 80 ° C. The mold was closed and curing of the reaction mixture was allowed. After 60 minutes »the molded product was removed from the mold and heated at 110 ° C for 16 hours for additional thermal curing. Example 2 a) Preparation of a prepolymer containing isocyanate groups and based on 4,4 '-MDI / p-PDI The procedure of Example 1 was repeated but the 1000 parts by weight (0.5 mole) of the adipata de po3 i (etandiol -i »4-butandial) was mixed with 174 parts by weight (0.696 mol) of 4» 4'-HDI and immediately afterwards with 111.5 parts by weight (0.696 mol) of p-PDI »A reaction time of Approximately 60 minutes in a temperature range of 130-90 ° C provided a prepolymer with an NCO content of 5.70% in psso and a viscosity at 80 ° C of 3000 mPas (measured using a rotating viscometer). b) Production of cellular molded products The cellular molded products were produced by a method similar to that described in Example Ib employing the prepol polymer in accordance with that described in Example 2a. The static and dynamic mechanical properties of the elastomers of paliurstane microcelu The elongations were measured in more cellular molded parts produced in accordance with that described in Comparative Examples Ib to IVb v in Examples 1 and 2 »ta = measured static mechanical properties were the tensile strength in accordance with DIN 53 571» the elongation to break in accordance with DIN 53 571 »the resistance to tear propagation in accordance with D3N 53 515 and the permanent deformation for compression at 80 * C by a modification of DIN 53 572 using spacers of 18 mm high and samples of proof that they have a base area of 40: 40 mm \ a height of 30 ± 1 mm »The permanent deformation by compression ón (CS) was calculated according to the Ha - H2 equation Ho - Hl where Ho is the original height of the test sample in mm, Hl is the height of B test sample in the state of "ñO formed in mm / H2 ss the all ¡"? ra d« = > the test sample after the release of pressure in mm »The mechanical dynamic properties of erminadas are the increase of displacement (DI) b or the action of the maximum force and the consolidation (CON) (Figure), The molded object for the measurement of consolidation was a us! What is the cylindrical test that has 3 constrictions of segments? a height of 100 m »a diameter e terna of 50 mm and an internal diameter of 10 mm. After pressing the spring in 100,000 load cycles at a force of 6 lN and a frequency of 1.2 Hz, the NOC was measured as the difference between the initial and final values of the test spring height and was given as a percentage. Consolidation is a measurement of the permanent deformation of the cellular polyurethane elastomer during the long-term vibration test. The smaller the consolidation, the greater the dynamic performance capacity of the material. The HR height to determine the consolidation after the dynamic test is determined after the registration of the spring characteristic curve: H0 is the initial height: the molded object is precompounded 3 times under maximum force (maximum force according to the characteristic curves), then the characteristic curve is recorded in a fourth sky as the compression speed of V = 50 mm / min.

After 10 minutes, Hl, viz. the component temperature after the reqastro of the characteristic curve. It is determined. Only then does the dynamic test begin. HR = Final height after the dynamic test measured after storage for 24 hours at a temperature of 23 ° C / 50% relative atmospheric humidity after the end of the dynamic test. However, the reference point (= initial height) used to determine the permanent consolidation after the dynamic test is H. the height of the spring in the completely "new" state, without any compression: HO HR WITH x 100 (%) HO The dynamic test is carried out without additional cooling in a room with air conditioning at a temperature of 23 * 0 and at a relative atmospheric humidity of 50%. The mechanical properties measured in the test samples are summarized in the following table. Table Aesthetic and dynamic mechanical properties of cellular polyurethane elastomers prepared in accordance with 3o described in Comparative Examples I to IV and in Examples 1 and 2 Example I TI III IV E, Comparative NDI MD dusocyte base? MDI p-PDI Isocyanate prepolymer NCO content (%) 4.32 6.19 5.8 4. 0 Viscosity at G > OC (mPa «s) 2800 3600 1750 2900 (8o * C) Systatic mechanical properties Permanent compression deformation (8 * 0,%) 20 43 20 37 Tensile strength 3.6 4.5 4.3 4.1 (N / mm2) Elongation (%) 350 510 460 630 Resistance to propagation 16.2 19.9 17.4 17.5 tearing (N / 'mm) Dynamic mechanical properties Consolidation (%) 8 - 16-18 6.2-7.2 Movement increment 3.4-2.1 - 5.0-5.7 1.8-2.1 (mm) Example 1 2"Comparative Basis of HD1 / p-PDI MDI / PDI PDI PDI PDI Isocyanate Prepolymer Content of NCO (%) 5.77 5.70 Viscosity at 9GaC (mPa * s) 3000 3? 00 (80 ' Cj (80 ° C) Static mechanical properties Permanent deformation by compression (8 ßC,%) 20 22 Tensile strength 4.5 4.6 (N / mm2) Elongation (%) 600 610 Resistance to propagation 17.5 17"3 tearing (N / mm) l Dynamic mechanical forces Consolidation (%) 12 11» 7 Movement increment 3.0 2.9 (mm) fifteen 0

Claims (12)

1. CLAIMS 1. A process for the preparation of oalxuretan elastomers by reaction a) of ifudranyl pal compounds having a functionality of 2 to 3 and a molecular weight of 800 to 6000 »and» if desired »b) chain linkers and / or reticuladpres which have a molecular weight of up to 80O with c) organic polyisocyanates in the presence or absence of d) catalysts »e) aqen is enpansión that have water and» f) additives »where organic polyisocyanates employed are 1,4-dusciacyanate (p-PDI) of phenylene and at least one additional aromatic dusopanate selected from the group consisting of toluene dusacianate »diphenylmetharyl dusocyanate» 3,3-di-ethylacetate di-ethynyl phene » diisocyanate of aliphatic diisocyanate having 4 to 12 carbon atoms and / or cycloaliphatic diisocyanate having from 6 to 38 carbon atoms, and of aromatic additional dusacyanate. / or aliphatic and / or cycloaliphatic co and rom rapporteur a) or a mixture of components a) and b) in an equivalence relation between the hydronyl groups of a) or in a) and b) of 1: 1-6, the preparation of a polyunsaturated product containing urethane and isocianatu groups, convir store this product with dixsociana your cie 1,4-fen? lo in? na proportion of equivalence entre e groups hi? ilo a) or a) and b) of 1: 0. 2 to 6 in a prepol i Either containing isocxanate groups and by reacting this prepolymer with the subtraction of a) and / or water to provide the polyurethane elastomer.
2. 2. A process according to claim 1"wherein the polyhydroxy compounds at San diffuse them". they have a molecular weight of 800 to 3,500 and are selected within the rump consisting of terpolial pads, poly carbonates that contain hydraxxlo and polionibu tilenglical es.
3. 3. A process according to claim 1 to claim 2, wherein the chain linkers have a molecular weight of 800 and are selected from the group consisting of alkanediols, dialkylene glycol and polyalkylene glycol. and the crosslinkers have a molecular weight of up to 800 and are selected from the group consisting of alcohols tphidic to tetrahydric and alkylaminoleanthiols which have a functionality of from 3 to 4 *
4. 4. A process of compliance with any of the claims 1 to Z ^ where the organic member polynucleotides (c) employed are a fluid mixture of phenylene-4-dimethacrylate (p ~ F'DI) and at least one additional solvent. selected within the group consisting of toluene dusocyanate. dn sacianata de da fsni Imstano »diisocyanate of 3,3-dimeti Ibifsni 3 or» dusocyanate of 1, 2-d? pheni letanu »and / or 1, 6-d ?? sac? ana or of hsxame tileno y / oi - isaciana fo-3 »3» 5-tpmeti 1 ~ 5 ~? sac? anatamet? l ci cl ohenano.
5. 5. A process according to any one of claims 1 to 3. wherein the organic polusocyanates (c) are used in the form of a prepolymer containing isocyanate groups and prepared by the reaction of the pal ihydroxyl compound (a). ) or a mixture of (a) and a chain and / or crosslinker (b? can an aromatic dusatianate selected within the group q? e consists of toluene dusocyanate, diphenyl ethane diisocyanate, 3,3 '-dimstilbifsnil diisapanata or »diisocisnatp of 1,2-diphenylethane, and / or 1» 6-d ?? soc? an to hexmetitena and / or 1-? so-c? anata-3,3, 5? t ime? l-1 5- Scyanatomethylcycline ohenan in an equivalence ratio between the hydroxyl groups of (a) or bisn (a) and (b) and the isocyanate groups of the organic diisocyanates of 1: 1-6 to provide a product of palliation. containing urethane and isocyanate groups and by reacting this polyaddition product with 1 »4-d ?? soe? anata of faith ilena (p ~ PD!) in a ratio The equivalence between the hydranyla groups of a) or well (a) and (b) and the isocyanate groups of 1, 4 ~ d-phenyl snoate (p-PDI) of 1 s 0.02 - 6 to convert them to the prepolymer containing the asacianata groups.
6. 6 »A process of compliance with any of claims 1 to 3wherein the organic polyacyanates (c) are used in the form of a preparator containing 5 isacienate groups and are prepared by reaction of the polyhydranyl compound (a) to a mixture ds (a) and a chain linker and / a crosslinker (b) with 4,4 - dusocian your of di femlmetanu in a proportion of equivalence in te hydroxyl groups and groups The isocyanate of 1; * i-6 is used to provide a polyurethane product which contains urethane and isucyanate groups by reacting this polyaddition product with 1,4-p-phenylacetate. PDI) in an equivalence relation between hydroxy groups of (a; or (a) and (b) 15 and the isocyanate groups ds 1, 4-d ?? soc? Anato of phenylene s, p-PDI) of 1: 0.02 - 6 to convert it into the prepolymer containing the isacyanate groups.
7. 7. A process for the preparation of cellular polyurethane standards in accordance with that claimed in any of claims 1 to 6"wherein the blowing agent (d) is selected within the rump consisting of ranges having 4 to 8 carbon atoms, cycloalkapes having 4 to 6 carbon atoms and water.
8. 8. A process for the preparation of the cellular polyurethane turners according to claim as claimed in any of claims i to 7, wherein the turners have a density of 0.2 to 1.1 g / l.
9. 9. A prepaymer containing isocyanate groups, having an NCO content of 3.3 to 10% by weight, prepared by the reaction of at least one polyhydroxy compound (a) or a mixture of (a) ) and a chain entendedor tle / or crosslinker (b) with at least one selected dusacianata arom tico within the croup q? and consists of toluene dusacianato "difeni diisocianata of 1 mess" "Tell me iin TII 3.3 t il bi feni lo »diasaciapato ds 1,2- diffémle taño» y / oi »6-d ?? sac? anato hexamsti leño and / or 1-? soc? anato-3,3, 5-tr? me til -5- They also used cyclohexane to provide a polyaddition product containing urea and isacyanate groups and having an NCO content of 0.05 to 8% by weight, and by reacting this pallidose product with 1 to 4% by weight. ~ d? Soc? anato de fsnileno! p ~ PDI) to provide the prepol containing isocyanate groups.
10. 10. A prepaymer containing isocyanate groups according to claim 9, wherein the ratio of equivalence between the hydranylation groups of (a) to either (a) and ib) and the NCO groups of the aromatic dussaccharides selected within the group consisting of dusoc janato toluene dusocianato d ifeni Imetano »diasocianalu 3.35 '-dimetilbifenilo, dusocianato i, 2 ~ d? phenylethane' and / or 1,6-d ?? soc? anata henametilena and / or 1- isacian ta- 3,3, 5-tpmeti 1 -1, 5-? sac? ana to eti 3 cyclone ahenane and NCO groups of 1,4-cl ii sociana ta de fepilepo (p ~ PDT) is 1: 1 - 6 : 0. 2 - 6 ,.
11. 11. A preparation was that it contains isocyanate groups, which has an NCO content of 3.3 to 10% in pe = > u, and is prepared by the reaction of at least one pal ihydronyl compound or (a) to a mixture of (a) and a chain extender and 'binder (b) with 4,4' -isocyanate of difsm 1. methane to provide a polymerization product containing urethane and isacyanate groups and having an NCO content of 0.05 to R in weight, and by reacting this polymerization reaction with i »4-d Soc? annatto of filled phen (p-PDI) pair provide the pre-polymer containing isocyanate groups.
12. 12. An americ prepoly containing isocyanate groups, having an NCO content of 3.3 to 10% by weight v prepared by the reaction of a hydroxyl and diammonium compound having a molecular weight of more than 800 to 3. "fifty? and dentra selected from croup consisting of pal lestsrpolioles, pol icarbanatos containing hidraniio v pal lonitetrßmetilenglicoles with 4,4' -dusacianata of diísnilmetano to provide a polyaddition product containing urethane and isacianata that groups and by reacting this product with paliadición 1,4-fsnilsno dusocyanate (p-PDI) to provide the prepolymer containing the isocyanate groups. 13 »A prepolymer containing 6t 'isacianata groups according to claim 11 or cor! claim 12, wherein the ratio of equivalence between the hydroxyl groups of (a) or (a) and (b) with the NCO groups of the 4,4-dusocyan di to di methane with the NCO groups of the ~ d? isoenzyne of phen i lena (p-PDI) is 1 i 1 - 6 s 0.03 - 6. OR 5 0