Procedure for the production of foamed zellularer polymer materials

The invention concerns a procedure for the production of gesehäumter zellularer polymer materials, in which Canadian patent writing NR, 873718 becomes new sehäumbare compositions descriptive, which at least a polymerizable Vinyl more ther, which contains at least two Vinylgmppen per molecule, a sudsy means, acids a catalyst and if necessary at least a connection, like e.g. a mehzweräges phenol and an aliphatic multi-valued alcohol, reactive with the Vinyläther, contains a epoxydiertes material, a Polycarbonsäure, a PP or a Polyearbamat. The composition supplies ge.schäumte zellulare polymer materials, which are superior to the well-known PU regarding the toxicity of the components and the well-known polystyrene foams regarding their suitability for sudsy at place and SteUe. Despite more ibxer numerous useful characteristics to stretch the new foams look rapid and härret rapidly, so that it is difficult, large areas with a gleichrnäßig trained tear-free foam to auszumüllen, to many of the new foams mentioned are missing the resilience, them have brilehige surfaces and are dimension unstable, if they are present in a form with low density. It was determined now the following.: If with the above types of foamable compositions of the Vinyläther first with the component under formation of a Vorpolymeren, reaküven with Vinyläther, one converts, the foams, which are made of this Vorpolymer component under mixture with a sudsy means and satires a catalyst with or without zustauchen Vinylälher and more bzw.oder with Vinyläther reactive connections, possess an längex e Reaktlonszelt forwards to that-to-harden, better resilience, good surface finish, better Hafffestlgkeit and are stable dlmensions=, even if they are present in a form with small density. A goal of the invention is therefore the creation of foamable compositions and foamed zellularer polymer materials, which are also based on polynlerisierburem Vinyläther, which mindestem two Vinylgruppen per molecule contain, in mixture with Vinyläther reactive connections. A further goal of the invention is the production of such foamed zeUutarer polymer materials, which exhibit the favorable characteristics longer reaction tent, good surface finish, good adhesive strength, increased resilience and dimensional stability with forms with low density. The invention concerns from there a procedure for the production of foamed zellularer polymer materials, which is characterized by it, at least dal one 1. a Vorpolymer, which became by conversion by mindestem more polymerisierbarenVinyläther, which at least two Vinylgmppen per molecule contain, with a connection, selected to the group of alcohols, reactive with Vinyläther, mehnqertige phenol, carbonic acids, Polyearbamate and Polyamid%hergestellt, 9 a flüehüges Sehäumungsmittel and 3. one rushes catalyst zusammenmiseht and the mixture lets foam. Vorzugsweisewiß of the Misehung at least one connection from the group, which from a polymerizable Vinylätber, which epoxydierten contains at least two Vinylgmppen per molecule, phenol being DNN gene, aliphatic alcohols, materials, which contain at least a Epoxygmppe per molecule, Polyearbonsänsen, PP, Polycarbamaten and polymerizable B-äthylenisch unge ttigten connections exists, incorporates. It was found that it is favorable to use the components for the production of Vorpelymeren in accordance with the invention in such Verhälmissen that for each molecule of the Vinyläthers at least a reactive group of the connection reactive with Vinyläther is available. The characteristics of the foamed product depended on the equivalent weight of the Vorpelymeren. For example on use of a meb.rwertigen alcohol as connection rigid foam reactive with Vinyläther are received, if the equivalent weight of the Vorpolymeren amounts to less than 270 per Vinyläthergruppe| halbstarm foams, which require a Ofenheizung, are received, if the equivalent weight of the Vorpolymeren 2q0 - 3fi0 proVinyläthergmppe is; one receives flexible foams, which are foamable only in a furnace with 60 to 80°C, if the Äquivalentgewfeht of the Vorpolymeren over aB0 per Vinyläthe.rgmppe besägt. In case of these flexible foams the viscosity of the Vorpolymeren is critical: 18 if the viscosity is too low, escapes the sudsy means, if the viscosity is too high, inferior foams are kept premature. For flexible foams a suitable Viskosi is appropriate for this kind uberetch for the Vo more olymer between 30 and 60 Poises at room temperature the Vorpolymer can 35 - Gew, - % of the foamable compositions in accordance with the invention constitute. The foamable compositions gemäht the invention can also flaming timer, oberfläehenakrlve materials, coloring materials, fillers. Stabilizers, Antioxydantien, Weiehmaeher and Viskositätsregler contain. Polymerize-cash Vinyläther, which is suitable in accordance with the invention for the use in the foamable compositions, is such, in which two or more Vinylgruppen are bound at one Äther-Sauer28 each material atom. They know the general formula from the group of II III R3C = CR1 - O-RIC =CRs I R4 I RaC = RsC = CR1 - 0 -- C I R 2 I CRt - O - C A I R6 I1 exhibit, where n R-S hydrogen, halogen atoms or hydrocarbon remainders represent a whole number of at least 2, g 1 and P'-2 hydrogen or alkyl radicals, R4 and P collected from the group, which consists two Alkylradikalenund a Alkylenradikalode one of two Wassexstoffatomen, substitute-alkyl-radically, selected are meant, hydrogen or alkyl radicals, whereby each substituent g 1 - to represent knows different atoms or radicals, if he arises in the Vinyläthermolektll in different places, and a group of connections with the priority represents n to A. examples of such Vinyl more ther are Divinyläther, Diisopropenyläther, Butandioldivinyläther, alkyl oxide, polyole condensates of the formula. CH2 =CH-O (CH2 CH-O) n--eH =CH2 CHs and n - CH = CHzl 4 t Nr.256479 where n one completely number meant, 3, 4-Dihydro-2H-pyran-2-methyl (3, 4-dihydro-2H-pyran-2-carboxylat) as in the following bemhxieben, 1, 2Äthandioxy-bis (3 ', 4 ' - dihydro-2' H-pyran-9 - carbonyl) the Formeh HC C \ HC o CH/CHz - (3 - O-CHz - CHs - degrees - HC o CH until (3, 4-dihydxo-2H-pyran-2-methyl) sueeinat the formula: /CHs HC CH2 It I HC/CH O - CH2 - O-C-CHz - CHz - C-O-CH2 tl IL o o/CHz Hs “CH [[- HC o CH 1, S-Until (3 “, 4” - dihydro-2' H-pyran-2' - oxT) ethane of the formula: /CI-I2 of /CHs HC CH2 HzC “CH IL I It HC o/CH - O-GH2-CI-Lz-O-HC%.O/cH! ! - To (3 “, 4” - dihydro-2' H-py an-2' - methoxy) ethane of the formula: HC. /CHz. Cycles per second H Hs; /CHs % - CHz O - C - OHzC - HC%. HC o/CH] o CHs CH tl CH 1, 2-Äthandioxy-bis (3 “, 4” - dihydro-5 “- methyl-2” Hpyran-2' - carbonyl) of the formula: /CHz. O Hs (C-CHa - C - O-CHz - CHz - degrees - HC o/CH 1, S-Until (8 ' 4 ' - of dihydro-5' - methyl-2'H-pyran - oxy) äthau the formula: /CHz Hs (/CHz %C H3C - C CHs CH \ \ l II HC o/CH --O-CHz-GHz-O-HC o/CH 1, 1 - to % ' 3 “4, - dihydro-5” - methy1-9., H - pyzan - - methoxy) ethane of the formula: Hs C - C CH2 \ \ l HC o/CH H c/CH2 C - CHs [H21 II - eH2 -- O - C - OH2 C CH [- HC o CHs 3, 4-Dihydro-2H-pyran-2-methyl (3, 4-dihydro-5-methyl-2H-pyran-2, 2-dimethy!) snccinat the formula: /CH2 HC CH2 H c/CH2 c-CH3 II I z I I [HC o/CH - CH2 - degrees [[- CH2 - CHz - C [[- O-CHz - o CH O O CH3 T oluo1-2, 4 - to (3 4 ' - dihydro-2' H - pyran2' - methyl) C arbamat the formula: HC/CH2 CH2 [] I HC%o/C " CHs t.iG/C%C 11 CHz CHII II I - NH - CO - eH2 - HC; O//C; H HC C C I - CH2 - O - C - N II 1 O H of the tri esters” of three moles the 2-Hydroxymethyl-3, 4-dihydro-2H-pyran and a mol of Orthophosphorsänre is derived, and the esters, which are derived from 2-Hydroxymethyl-3, 4-dihydro-2H-pyran and organic more-basic acid such as maleic acid and Adiplnsäure. It was found that the geradkettigen Vlnyl is more ther more reaküonsfäMger than dte verzweigtksttigen or cyelischen Vinyläther. The Vinyl thergruppen in the molecule can directly or different be. It is desirable that the Vinyläther does not simmer during the foaming power reaction. The allphaüschen univalent or multi-valued alcohol components of the Vorpolymeren of the sehäumbasen compositions gemäl3 of the invention cover amyl alcohol, 2-Äthylhexylalkohol, Nonylalkohol, n-Decylalkohol, ethylen glycol, propylene glycol, 1, B-Butylenglykol, Diäthylenglykol, 1,4-Butandiol 1, 5-Pentandtol Neopentylglykol, Glyeerin, 1, 2, 6-Hexantriol, Trimethyloläthan, Trimethylolpropan, castor-oil, Pentaerythrit, sugar alcohols, Znckeralkohol Alkylenoxyd Kondensatiousprodukte and hydroxylhaltige esters and polyester, which will receive acids by condensation from multi-valued alcohols and color mixing. The multi-valued phenol components of the Vorpolymeren cover Resomin, Brenzcatechin, Hydrochinon, 2: 2-Dl-pi-hydroxyphenylpropaß Phloroglncin, polycarbonates with low Moleknlargewieht, which contain phenolic hydroxyl final's groups, Kondensationspmdukte of Phenolen with aldehydes and Ketonen etc. Suitable Polycarbonsäure components of the Vo olymere cover Bernsteinsänre, Glutarsäure, Adipinsäare, Azelains ure, mark in the ure, fumaric acid, Itacousäure, Phthalsäur% Isophthalsäure, Terephthalsäure, Trimellitsäure, Trimesinsäum and Ghlorendsänre (1, 4, 5, 6, 7, 7-Hexach! orobicy 1o [2, 2, 1] -5-heuten-2, 3-dicarbonsäure) and polymerized insatiated fatty acids such as Dimerund rubble-pure and carboxylgmppenhaltige esters and polyesters. For the Vorpolymere suitable Polycarbamat components e.g. cover themselves connections, from organic Polyisocyanaten and Polyolen ableiten° like the Kondeusationsprodukt of Tolylendiisocyanat and 1, 5-Pentandiol of the formula: HO - (C) s. _ _ - 0 - C - l II o H 2 \ NH-C-O (CH2) s-O-C-NH tl IL o o CHs I --NH - C - O - (CH2) 5OH --/flat steel bar o in which n a whole number of at the most 3 is, and the condensation product of diphenylmethan -4,4-diisecyanat with low Molekulaxgewieht and polypropylene glycol with a Molekulargewlcht of 425. As PP the Diarnide, of dimeäsierten linseed oil acids is derived and the formula the H2N is -- - (CH2) 34 II o o exhibit and the PP, which is derived from Isophthalsäure and Pentamethylendiamin, suitably. The Vorpolymer can be manufactured by simple mixture of the components. Accelerate the reaction by warming up in certain FäUen kaunman. It is favorable mostly, one drinks Kakatalysator such as p-Toluolsulfosäum to use hydrochloric acid or sulfuric acid. When flüehüge Schäumungsmlttel is for use with the sehäumbaren compositions in accordance with those identification such means suitably, which are in the other components of the sehäumbaren Zusammensetzuagen solubly or disperglerbar and sufficient volatile, so that they evaporate during the education of the foamed Polymermateäalien. The warmth of the katalyäerten polymerization reaction causes that the Schänmungsrnittel begins to simmer, and the developing steam forms gas bubbles, which see during the Polymefisaüonsreaktion under education of a gesehäumten polyrnerlsierten mass with low density to expand. As Sehäumungsmittel halogenierte hydrocarbons are preferred such as Trlehlormonofluormethan, Diehlortetrafluoiäthan, tri chlorine tri fluorine ethane, Dibromdifluormethan, Diehlorhexafluomyelobutan, Methylenehlortd, Cb.loroform, trichlorethylene, Tetraehlorkohlenstoff and tetrachlorethylene. Those rush catalysts, which are suitable for the activation of the foaming power reaction, cover the strong proton donor acids such as p-Toluolsulfonsäuse and the Lewissäusen such as Bortriftuortd, which be suitable-proves as Ätherate is used. Compositions, which very reaküve Vinyläther to contain, how Butandiot Divinyläther can by p-Toluolsulfosäuse are e.g. catalyzed, but ate catalyst for that Zusammemetzungen, which include-borrowed 3, 4-Dihydro-2H-pyranylverbindungen the 3,4-Dihydro-2H-pyran-2-methyl (3,4-dihydro-2H-pyran-2-eaxboxylat) contains, a Lewissäure preferred. One can adjust the Schaumbildungsreakläon by use of catalyst combinations, e.g. p-Toluolsulfosäure and boron tri fluoride or Bortrifluorld and Trimethoxyboroxin. Others than catalysts suitable Bestaudteile are iron (III) ehlorid, tin (IV) chloride, phosphorus pentachloride, Phosphorsäum, perchloric acid, tri fluorine vinegar äuse, Trichlomssigsäure, Fluoborsäure. Borrsifluorid dihydrate, hydrogen fluoride, Anümenpentafluorid, Hexafluaxphosphorsäure, Bleifluoborat, Antimonfluoborat, sulfuric acid and Silicowolframsäure. Also the solution center! , in which the catalyst is solved, the reactivity of the catalyst affects; Bortrifluoäd Ätherat is less reactive in polypropylene glycol solutions than in xylene solutions. It is günstib the catalyst in quantities of 0, 005 to 2, 0 thread - % of the compositions to use, however these quantity specifications are not restrictivy, there the catalyst quantity depending upon the reaction temperature and the necessary Selääumtmgs Induktionszeit to be adjusted o11. The catalysts used with proceeding in accordance with the invention become as 5 - 50%ige solutions inLösungsmitteln uses, e.g. as solutions in mono ethyl ethers of ethylen glycol, the mono ethyl ether of Diäthylenglykol, Nitromethart, Nitmbenzol, Butyrolaeton, Aeeton, n-butanol more oderDiäthyläther. As flame-retarding means for training into the sehäumbaren Zusammemetzungen tri chlorine ethyl phosphate, 2:2 - ice (3 ', 5 ' - is dibrom-4' hydroxyphenyl) prop.-ate trichloroethylene (dibrompropyl) phosphane chlorine final acid and Polyvlnylchlorid with or without antimony oxide been suitable. The Phenolverblndung nnd the ¢hlorendsäure serves both and F1ammverzögerungsrnittel and with Vinyläther reactive Materlalien. Before-pulled as surface-active materials such connections, which belong to the type of silicone, Belsptele are indicated in the Belgian Patentsehriften Nt.582362 and No. 584029, i.e. that they belong to the Siloxun Oxyalkylen Copolymertyp. Into the sehäumbaren compositions in accordance with the invention also or several know niehtzea a erte polymerizable Vinyläther, which contain at least two Vinylgruppen per molecule, or one or more connections, which are trained with the Vinyläthern reactively or eopolymeriäerbar SI, ld. As polymerizable Vinyläther for training into the compositions in accordance with the invention for example the polymerizable Vinyläther specified above is suitable. Connections, which are with the polymerizable Vinyläthern mentioned reactive or copolymerisierbar and were found for training into the compositions in accordance with the invention as particularly suitably, cover phenol connections, aliphatisohe univalent and multi-valued alcohols, epoxydierte materials with at least a Epoxygruppe per molecule, sour connections with at least two groups of carbon acids per molecule, Amidoverbindnngen with at least two Amidogmppen per molecule, Carbamate with mindestem two Carbamatgmppen per molecule and polyme” Islerbare, o - monoäthylenlseh insatiated connections. Belsplele for phenol connections, aliphatic univalent and multi-valued alcohols, Polycarbensäure.n, Amidogruppen with at least two Amidogruppen per molecule and C arbamate with at least two Catbamatgruppen per molecule, which can be trained, are indicated above. Under “epoxydierte materials with mindestem of a Epoxygruppe per molecule” to be trained, are connections know to be understood, at least one group of the formula I I - C - C - o per molecule contain. Examples of such connections are Epiehlo” hyddn, styrene oxide, Diallyläthermonoxyd, Cyelohexenoxyd, Glycidylphenyläther, Glyeidylstearat, Dnpentendioxyd, Vinyleyelohexendioxyd, Polyallylglyeidyläther, Diphenylolpropandiglyeidyläther, epoxydiertes polybutadiene, epoxydiertes styrene Bntadieneopolymere, the resin-like Kondensationslxodukte of Epiehlorohydrin and aliphatisehen or aromatic Polyolen such as Glyeerin or 2, 2-IX-p-hydroxyphenylp” opun etc. Examples of polymeriäerbare A, 13-monoäthylenisch insatiated connections are 3, 4-Dihydro -2H-pyran, 2-Äthoxy-3, 4-dihydro-2H-pyrun, 2-Alkyl-3, 4-dihydro-2H-pyran, 2 - Phenyl3, 4-dihydro-2H-pyrun, 1-Deeen, Vinylstearat, Laurylvinyläther, Dibutylmaleat, Maleinsäureanhydzid, Vinylcyelohexen, Alkylaerylate, Alkylmethacrylate, styrene, etc., then in accordance with the foamable compositions can contain catalyst and Sehänmungsmittel a portion on of the Erirmdung in addition vorgebildetenReaktiomprodukt, urtreagiertexn IXvinyläther and one with this reaktlvenVerblndung. The use of different portions of such materials supply compositions, which lead to the education of gesehäurmer materials with very different self-scolded. In order to receive foamed materials with favourable characteristics, which are suitable fär certain purposes. it is necessary to vary the portions of trained reaction product and of the other active component in accordance with the kind of the trained reaction product and the other active components. The production of the Sohaumstoffe in accordance with the invention with the help of a preceding formation of a Vorpolymers supplies foam materials, which are superior to those, which are won directly from the foaming components without the Zwisohenstufe of the polymer formation. The improved SchaumS0 of materials in accordance with the invention has larger resilience, better Oberfläehenbesohaffenheit, and a longer sound duration with the sudsy. In addition one can use the procedure in accordance with the invention for the production of Sehaumstoffen, which are dimension stable with decreased density. It is to be accepted that the use of Vorpolymeren causes a change of the Reaktiomprozesses with the Sch umungsvorgang. The components of the sehäumbaren compositions can be poured by agitating in a container gerräsehr and afterwards rapidly into a form. Sometimes it is favorable to warm up the composition in the form in order to support the formation of the foam. The scb31umenden Bestandteiie can be mixed also in the container, which is to be filled with the foam, if it permits its form. If mixing the components takes place under agitating, then an additive one is surface-actively “n of material favorable for composition very, in order to receive foam materials with small lines. However an surface-active material is not always substantial. For example the components are mixed with certain sehaumentblndenden machines under pressure and using a Sehäumungsmittels, which is gaseous with the Misehtemperatur, whereby the adjustable pressure is waived, and the “frozen” mixture is then distributed at the time of the use. In such “Einfrier' device is a oberfläehenaktives means avenges substantially. However it is with the usual machines in which the foamable compositions relieved become, before the sudsy begins, which became use of a oberflächenakttven material often desirably, with the Nachaxbeitung of many prescriptions found that the reduction of the quantity supplies material at the time, at soft the blisters straight to burst surface-actively on, if the Polymeflsation is terminated Sohäume, which exhibit the well-known “open” cell structure. The foam materials in accordance with the invention in flexible form can the padding, mattresses etc. are used. In the rigid form they are excellently suitable for purposes fttr lagging and Sehalidämpfung, and zw. either in form of closed cavities or as wrapping covers. The invention is more near described by the following examples, is not eingesehrgnkt however. As VinylIIther becomes in the Beispieien 3,4-Dihydro-2H-pyr at .r2 - methyI “(3,4-dthydrod2H'Pyran-2-carboxylat) the following formula: /CHz /CHz HC CHz H2C CH2 II I II HC o/CH - CH2-OOC-HC O/CH prefers. It can feast dmeh self condensation of the Aeroleindlmeren (2-formyl-3, 4-dihydro-2H-pyran) in presence of approximately 0, 3°10 aluminum isotropic oxide manufactured, whereby the reaction temperature 6 h is held 45°C. A cleaned product can be received by distillation in a piston with 150°C in the vacuum, however satisfying Schaun rstoffe can be won also with the undesttllierten product. B e is pi e 1 1: A Vorpolymer is manufactured as follows: To 448 g 8, 4-Dlhydro-2H-pyran-2-methyi (3, 4-dihydro-2H-pyran-2-earboxyla0, which in a three-neck piston, which waves is provided me Rtlk t, thermometers, funnel and Stiekstoff Einlaßrohr, 62 g ethylen glycol, which contain 0, 06 g p-Toluolsulfosäure, added. The Misehtmg becomes under nitrogen gas and under agitating on 60o (3 heated up. If the temperature begins the exotherms reaction by cooling for instance 800C is held. If the temperature begins to sink, then the cooling bath is removed and the Reaktioasgemiseh still another further hour gerülLrt. The Inframt Absorptionsspektmm of the Reakflonsproduktes did not show absorption point in the HyMroxylbercich. The following mixture is manufactured: Above Vorpolymex 300 g Siloxanoxyalkylencopolymer of the Sflicontyp as oberfläehenaktiver material I, 0 Trlchlor mono fluorine methane 35 cm 3% Bortrlfluorld therat in dichloromethane 22crnq is agitated 18 lake with a meehanisehen RUbxet and poured into a form. After a Induktiomzeit of 48 lake foams the mixture with a Steigzett of 72 seconds under education of a rigid, resilienten foam material with outstanding structure and outstanding Oberfl chenbeschaffenheit. B e i s p i e 1 2: In accordance with example I 4-Dihydro-2H-pyran-2-methyl (3,4-dihydro-2H-pyran-2-carboxylat) becomes using 672 g 3, and 159 g Diäthylenglykol, which contains 0, 1 g p-Toluolsulfosäure, a Vorpolymer produces it the following mixture is manufactured: Above Vorpolymer 300 g Silöxanoxyalkyleneopolymer of the Silieontyp as oberfläehenaktiver material 1, 0 g3 T richlormonofluormeth at 50 cm 20% Bortrlflnoridätherat in polypropylene glycol with the Molekulargewieht 425 5 cm the mixture is agitated 18 lake with a meehanischen Rüber and poured into a form. After a Indukflonszeit of 72 lake foams dieMisehung with one climbing time of 72 lake under education one starts resilaenten to Sehaumstoffes, which is not brittle. Beisp icl 3: In accordance with example 1 4-Dihydro-2H-pyran-2-methyl becomes (3, 4-dihydro-2H-pyran-2-earboxylat) using 672 g 3, and 15ö g 1,4-Pentandiol, which contains 0, 1 g p-Toluolsulfosäure, a Vorpolymer produced. The following mixture is manufactured: Above Vorpolymer 250 g Siloxanoxyalkyleneopolymer of the Silieontyp as oberfläehenaktives means 1, 0gs Triehlormonofluormeth at 45 cm 20% Bomifluoridätherat in Polypropylen3 glycol with the Molekulargewieht 425 4cm the mixture is gertthrt 18 lake with a meehanisehen Rtthrer and poured into a form. After one Induktionszeit of 66 lake foams the mixture with one climbing time of 72 lake., whereby a rigid, resilienter foam material with good structure and good Oberfläehenbesehaffenheit will receive. B e i s p i e I 4: In accordance with example 1 4-Dihydro-2H-pyran-2 becomes - methyl (3,4-dihydro-2H-pyran-2-earboxylat) and 228 g 9 using 896 g 3: 2-Di-p-hydroxyphenylpropan, which contains 0.12 g p-Toluolsulfosäure, a Vorpolymer produces. The following mixture is manufactured: Above Vorpolymer 250 g Siloxanoxyalkylencopolymer of the Silieontyp as oberfläehenaktive means 1, 0 g Trichl mono fluorine methane 40 cms 20% Bortrifluoridätherat in Polypropylen3 glycol with the Molekulargewieht 425 4 cm the mixture is agitated 18 lake with a mecahanisehen agitator and poured into a form. After one Induktionszeit of 18 lake foams the mixture with one climbing time of 24 lake. In such a way manufactured rigid foam material showed a gegentlber Sehaumstoffen, which were won from the same Vinyläther and the same phenol components, however without production of the Vorpolymers, improved resilience and Oberflächenbesehaffenheit. B e i s p i e 1 5: In accordance with example 1 4-Dihydro-2H-pyran-2-melhyl (3, 4-dihydro-2H-pyran-2-earboxylat) becomes using 900 g 3, and 880 g Polypmpylenglykol with a Molekulargewieht of 425 and a Hydroxylzahl of 255, 0 (Niax Dlol PPG 42ö) the p-Toluolsulfosäure, 4.5 a Vorpolymer contains of 0, 5 g produced. The following mixture is manufactured. Above V of polymere 75 g Siloxanoxyalkyleneopolymer of the Silieontyp as surface-active means 1, 0 gs Trichlormonofluorom ethun 90 cm 20% Bortrifluortd therat in polypropylene glycol with the molecular weight 425 2 cm the mixture is agitated 18 seconds with a mechanical agitator and poured into a form. The form with the mixture wiß into a furnace with 66°C posed. After 1 h a good flexible foam material was received. With s pi e 1 6: In accordance with example! becomes using 34! g 3, 4-Dihydro-2H-pyran-2-methyl (3,4-dihydro-2H-pytan-2-eatboxylat) and 500 g of a Polyglykols with the molecular weight 1000 and the Hydroxylzahl! 70,4 (Niaz Tfiol LG-168), which 0, 5 g p-Toluolsulfosättte enthälr a Vorpolymer produces, the following mixture one manufactures: I0 16 above Vorpolymer 15 g Vorpolymer of example 5 60 g Siloxanoxyalkylencopolymer of the type of silicone as surface-active means I, 0 g3 tri chlorine mono fluorine methane 9,0 cm 20% Borttifluoddätherat in Polypropylenglyko! with the Molekulazgewicht 425 2 cm3 thyI (8, 4-dihydro-2H-pyran-2-carboxylat), solved, a Vorpolymer is produced for 500 g castor-oil 8 cms Äthylaeetat. The following mixture is manufactured: The mixture becomes! 8 lake with a Rtihrer agitated and into a form poured. The form with the mixture is placed into a furnace with 60°C. After 1 h a good flexible foam material became erhalten° with s p i e 1 7: In accordance with example 1 4-Dihydro-2H-pyran-9 becomes. using 886 g 8, - meund 0.35 g p-Toluolsulfosättte, those into above Vorpolymer 15 g Vorpolymer of the example 5 60 g Siloxanoxyalkylencopolymer of the type of silicone as surface-active means I, 0 g3 Tächlormonofluormethan 20 cm 20% Borlzifluoridätherat in polypropylene glycol with the Molekulazgewicht 425 2 cms the mixture 18 lake with a meehanisehen Rüt he is agitated and poured into a form. The form with the mixture becomes into a furnace with 60o (3 placed. After I h a very well flexible foam material was received, to B e i s p i e 1 8: Using equipment in accordance with example 1 a Vorpolymer is manufactured. 66 g Glutarsäure become with 29.4 g 8, 4-Dihydto-9.H-p an-2-methyl (8, 4-dihydro-2H-pyran -2-earboxylat) 8 h in a nitrogen atmosphere with 70 - %°C considered. The sour one solves sees in approximately 1 h completely. The product has an acid number of 28, 7. The following mixture is manufactured. Above Vorpolymer 25 g Siloxanoxyalkylencopolyrrmr of the Sflikoatyp as obefflächenaktives means O, I g Triehlor mono fluorine methane 5 cm3 10% Bortrifluorldätherat in polypropylene glycol with the Molekulatgewieht 425 0, 25 cms the mixture is gerllhrt 18 seconds with a mechanical agitator and poured into a form. The mixture foams to rigid foam material with after a Induktäonszeit of 7 lake and supplies one seh resitierten. B e i s p i e 1 9: Dmeh heating up of 20 g 3, 4-Dihydro-9.H-pyran-9. - methyl (8, 4-dihydro-2H-pyran -9. - catboxylat) when 100°C and engaging in 6 g Cholansäure (! , 4, 5, 6, 7, 7-Hexaehlorobicyclo [2° 2,1] - hepten-2,3-diearbonsäure is manufactured a Vorpolymer. The solid separates allmäh! I and the viscosity of the mixture rises, wodmeh progressing the reaction is indicated. After min tird the solution of meaning quantity of unresolved material abdekantiert. So 9,1, 5 g material will receive. The following mixture is manufactured: Above Verpelymer 21, 5 g Siloxanoxyalkylencopolymer of the type of silicone as surface-active means 0, 25 g Trichlermenofluo” methane 2, 0 g 20qo Bortfifluoridätherat in polypropylene glycol with the Molekulargewieht 209,5 I, 0 g the mixture is agitated 5 seconds with a mechanical agitator and poured into a form. Within! 0 seconds the sudsy and it take place develop a ldeinzelliger foam of good appearance i0 the foam were “deleting” in accordance with ASTM 1652-59-T. Example 10: A Vorpolymer is manufactured as follows: 31,5 g (0.25 mol) of wasseffreies Phlotoglucin are solved in 180 g (0.025 mol) 3,4-Dihydro-2H-pyran-2methyl (3,4-dihydro-2H-pyran-2-carboxylat) under agitating and warming up. The mixture becomes during the ttopfenweisen Tusatzes of 0, 12 eß 2 a oigen solution of p-Toluolsulfosäure in ethyl close! ykol with 60oC held. The Reaktiensgemisch is then diluted thicker and with 90 g 3, 4-Dihydro-2H-pyran-2-methyl (3, 4-dihydro-2H-pyran-2-earobxylat) under education of a heavily flowing liquid. The following two mixtures are manufactured: Mixture A: Above Vorpelymer! 7, 5 g 3, 4 - Dihydro-2H - pyran -2mcthyl (3, 4-dihydro-2H-pyran-2-carboxylat) 7, 5 g Siloxanoxyalkyleneopolymer of the type of silicone ms surface-active means 0, I g Triehlormonofluor methane 5 g mixture B: 10°/0 Bortrifluoridätherat in Polypmpylenglykol with the Molekulargewieht 425,0.3 g mixture A is thoroughly geruft and added then mixture B. Agitating is continued far lake. After one Induktionszeit of 40 seconds the mixture with one climbing time of seconds foams. In such a way manufactured foam material had a fine, even condition and become under education glatzen, yields surface air-hardened. The Kemdichte cheated 20, 82 kg/m3. B e i s p i e 1! ! • a Vorpolymer is manufactured as follows: 55 g (0, 5 mol) Resorein are solved in 246 g (1, 1 mol) 3,4-Dihydro-2H-pyran-2-methyl (3, 4-dthydre-2H-pyran-2-carboxylat) under warming up and agitating. This mixture is held for a 20°] oigen solution during the tmpfenweisen Zusarzes of 2 cma by p-Toluolsulfosäum in ethylen glycol with 60°C. The temperature of the reaction mixture rises rapidly to 76°C. The reaction mixture is cooled down under education of a heavyflowing mixture. The following two mixtures are manufactured: Mixture A: Above Vorpolymer 25 g Siloxanoxyalkylencopolymer of the type of silicone as surface-active means 0, l g tri chlorine mono fluorine methane 5 g mixture B: o Borttifluoridätherat in polypropylene glycol with the molecular weight 425,0.4 g mixture A is thoroughly agitated and added then mixture B. Agitating is continued further 5 seconds. After one Induktionszeit of 25 lake foams the mixture with one climbing time of 29 seconds. The manufactured was white and had an even condition with a density of 27, 23 kg/ms. B e i s p i e 1! 2 • the following polymer is manufactured: 55 g (0, 5 mol) Hydroehinon become in 246 g (1, 1 mol) 3, 4-Dihy& o-2H-pyran-2-methyl (3, 4-dihydro-2H-pyran-2-earboxylat under consider - 11 Nr.2564q9 men and agitating solved. This mixture is held during the drip-wise additive of 3 cm3 of a 2O) bigen solution of p-Toluolsulfosäure in Ättqlengiykol with 60°C. The temperature of the Reaküonsmisehung rises rapidly to q! °C. The reaction mixture is cooled under education of a viscous resin. The following two mixtures are manufactured: Mixture A. Above Vorpolymer 16, 65 g 3, 4-Dihydro-2H-pyran-2-me yI (3, 4dihydro-2H-pyran-2-carboxylat) 8, 35 g Siloxauoxyalkylencopolymer of the type of silicone as oberfläehenakt2ves means 0, I g T ächlormonofluor meth at 5 g mixture B: 10°7o Bortzifluoridätherat in polypropylene glycol with the Molekulargewieht 425 0, 4 g mixture A is agitated gtündlida and added then mixture B. The Rähmn is continued further 5 lake, after one Induktionszeit of 95 seconds foams the mixture with a Stelgzeit of 50 seconds. The manufactured foam material had a soft even condition and a Kemdlchte of 28° 83 kg/ms. After 10 seconds of continuous hardening in a furnace with 60o (3 the foam material exhibited a smooth tough surface. Example 13: A Carbamat is manufactured as follows: 2 mole methanol becomes from a dropping funnel slowly an agitated mixture of 168 g Hexamethylendiisocyanat and 0, 06 cms N-Äthylmorpholin zugesetzto during the reaction rises the temperature to 150°C. The product becomes firm with for instance 90°. One from benzene recrystallized sample had a fusion point of 110oc. A Vorpolymer is manufactured as follows: The above Carbarnat 46 g 3, 4-Dihydro-2H-pyran-2-melhyl (3, 4-dihydro -2H-pyr an-2-carboxylat) 134 g benzene 100 cms p-Toluolsulphonsäure O, 3 g under Rtlcldlußkühlung 5 h are heated up. The solvent is then removed by distillation under decreased pressure. The product is considerable one viscose rayon light brown liquid. The following mixture is manufactured: Above Vorpolymer 25 g Siloxanoxyalkyleneopolymer of the type of silicone as surface-active means O, I g Trichlormonofluormeth at 5 cms Bortrifluoridätherat in polypropylene glycol with the molecular weight 425 (1: 1,5 volume ratio) 1, 5 cm3 the mixture 30 lake is agitated and poured into a form. Then it is hardened 10 min with q0°C in a furnace and foams after a Induküonszeit of 2 me under education einesgatenresilfenten Sehaumstoffes. Example! 4. A PP is manufactured as follows: 300 g tzimerisierte I inölsauren become in presence of a small quantity xylene under RüekfIußktlhlung with 190 - 210° (3 warmed up. Into the solution a sehwaeher ammonia gas flow is introduced. In two days distill altogether! 7 cms water over. Then the xylene under decreased pressure is abdestilliert. The PP product contained 4, 48% nitrogen. By 3-ständiges heating up under Rüekflußkühlung of 177 g of the above PP product, 115 g 3o4-Dihydro-2H-pyran-2-methyl (3, 4-dihydro-2H-pyran-2-earboxylat), 100 em3 benzene and 3 em3 with Chlarwasserstoff satisfied ethyl ether is manufactured a Vorpolymer. The Benzo! intestine under decreased pressure is abdestilliert. The product has a light brown color. The following mixture is manufactured: Above Vorpelymer 12, 5 g 3, 4-Dihydto-2I I-pyran-2 - methyl (3, 4-dihydro-2H-pyran-2-carboxylat) 12, 5 g SI! more oxanoxyalkylencopoiymer of the type of silicone than surface-active means O, I g Trichlormonofluormcthan 5 em3 I3ortrifIuoridätherat in Polypropyienglykol with the molecular weight 425 (1: 1, 5 volume ratio) 3 ema/iisehung 30 lake with a meehanisehen agitator is agitated and poured into a form. The mixture foams 44 second after the additive of the catalyst and supplies after one climbing time of 11 second a rigid foam material with good resilience. GODFATHER NT ANSPRÜH HE: i. Procedure for ago telltmg the foamed zellularer Polymermaterlalien, draws, daßInan thereby gekenn - 1. at least a Vorpolymer, which was made by conversion by at least a polymerizable Vinyläthet, which contains at least two Vinylgruppen per molecule, with a connection reactive with Vinyläther of the group of alcohols, multi-valued phenol, Catbonsäuren, Polycarbamate and PP, 2. a flüchüges Schänmungsmlttel and 3. acids a catalyst zusammenmiseht and the mixture foam to Iäßt. 2. Procedures after requirement 1, thereby characterized that one the Misehungmindestens a connection from the group, which from polymerizable Vinyläther, which epoxydierten contains at least two Vinylgruppen per Moiekül, phenol connections, aliphafisehen alcohols, materials, which contain at least a Epoxygruppe per molecule, Polyearbonsäuren, PP, Polycarbamaten and polymerizable A, - äthyleniseh exists insatiated connections, incorporates. 3. Procedure according to requirement 1 or 2, by characterized that one manufactures a polymer material, which contains 35 - 98 thread - % Vorpolymer. 4. Procedure nadelt one the Ansprfiche 1 to 3, by characterized that one adds as Vorpotymer a reaction product of a Vinyläthers, which contains at least two Vinylgruppen per molecule and to a connection, which contains a group reactive with Vinyläther in sufficient quantity, so that at least a group per Moekül Vinyläther, reactive with Vinyläther, is present. Procedure after one the Ansprtlehe 1bis4, thereby characterized, that-that-polymerizable Vinyläther two 3, 4-DLhydro-2H-pyranyl-Gmppen contains. 6. Procedure according to requirement 5, by characterized that one uses as polymeriäerbaren Vinyläther 3.4-Dihydro-2H-pyran-2-methyl (3, 4-dihydro-2H-pyran-2-earboxylat). 7. Procedure after one the speech 1bis 6, by characterized that one as Vorpolymer the reaction product of 3, 4-Dihydro-2H-pyran-2-methy! - (3, 4-dihydro-2H-pyran-2-earboxylaß with a connection from the group ethylen glycol, Diäthylenglykol, 1, 5-Pentandiol, 2, 2-Di - pi-hydroxyphenylpropan, polypropylene glycol with a Molekulargewieht of 425, RieinusöI, GIutarsäure, chlorine final acid, PhlorogIucin, Resorein, Hydroehinon, Dimethylhexamerhylendicarbamat and the amide of trimerisierten Lelnölsäuren uses. d. Procedure after one of the requirements 1 to 7, by characterized that one uses catalyst boron tri fluoride as acids. 9. Procedure after one of the requirements l to 8, by it characterized, that one one mixture uses, which contains an surface-active material. Procedure nachAnsprueh 9, by characterized that one uses a silicone of the Siloxan Oxyalkylentyp as oberfläehemaktiven material. Pressure. Ing.E.Voytjeeh, Vienna