SE188011C1

SE188011C1 -

Info

Publication number: SE188011C1
Authority: SE
Publication date: 1963-01-01

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Uppfinnare: J F Wood och G Woods Prioritet begtird frem den 9 oktober 1959 och den 28 september 1960 (Storbritarznien) Foreliggande uppfinning avser framstallning av polymera material, narmare bestamt polyuretanmaterial, framstallda genom skumbildning. Inventors: J F Wood and G Woods Priority set forth October 9, 1959 and September 28, 1960 (Great Britain).

Det liar foreslagits aft framstalla polymera material genom samverkan mellan organiska polyisocyanater och hydroxylgrupper innehallande amnen, t. ex. polyestrar, polyesteramider och polyetrar. Det har ocksa fOreslagits att modifiera denna reaktion, t. ex. genom lampligt val av utgangsmaterial eller genom tillsats av vatten, i avsikt att framstalla blasta, cellulara material. - For att kontrollera eller modifiera strukturen av pa detta satt genom skumbildning erhallna cellprodukter, ar det i allmanhet nodvandigt aft inblanda ytterligare komponenter eller tillsatsmedel. De tillsatsmedel, som hittills foreslagits inkludera silikonoljor, eller polysiloxaner, vilka kunna hjalpa till da det galler att fa fram en jamn och likformig porstruktur och eliminera felaktigheter i form av grova, fasta partier i skummet, saval pa ytan som inuti materialet. Den mangd silikon som erfordras är emellertid liten och mycket kritisk, och am man inte uppnar en likformig fordelning vid inblandningen, kan skumprodukten delvis sjunka samman inuti eller to.m. falla samman helt och hallet. It has been proposed to produce polymeric materials by the interaction of organic polyisocyanates and hydroxyl groups containing the substances, e.g. polyesters, polyesteramides and polyethers. It has also been suggested to modify this reaction, e.g. by appropriate choice of starting material or by the addition of water, with a view to producing blasted, cellular materials. In order to control or modify the structure of cell products thus obtained by foaming, it is generally necessary to add additional components or additives. The additives proposed so far include silicone oils, or polysiloxanes, which can help to achieve a smooth and uniform pore structure and eliminate imperfections in the form of coarse, solid portions in the foam, both on the surface and inside the material. However, the amount of silicone required is small and very critical, and if a uniform distribution is not achieved with the admixture, the foam product may partially collapse inside or even. collapse completely and the hall.

De vanligen anvanda blandningsmetoderna pa detta omrade och de fysikaliska egenskaperna for de vanliga silikonerna aro i allmanhet jute Iampade for framstallning av en tillraddigt tillforlitlig och homogen blandning av komponenterna, for att anvandningen av silikonoljor fiir detta andamal skall kunna betraktas som andamalsenlig och acceptabel ur kommersiell synpunkt. The commonly used blending methods in this field and the physical properties of the common silicones are generally used to produce a reasonably reliable and homogeneous mixture of the components, so that the use of silicone oils for this purpose can be considered commercially acceptable and acceptable from a commercial point of view. .

Si t. ex. aro de vanliga silikonoljoma, sasom dimetylpolysiloxan, i det narmaste olosliga i de hydroxylgrupper innehallande polymererna och polyisocyanaterna, Iran vilka polyuretanskumprodukter framstallas, och kunna dad& avsatta sig eller clispergeras olikformigt; vattenemulsioner av de vanliga silikonoljorna kunna anvandas, men dessa aro i allmanhet instabila i narvaro av storre mangder av sadana tertiara aminer, som vanligtxis anvandas som katalysatorer och kunna pa sa satt i regel late blandas med de aktivatorblandningar som anvandas vid utbildning av polyuretanskum. Olosligheten for de vanliga silikonoljorna och den lilla mane som anvandes gOr det svart att exakt tillfora den erforderliga mangden silikonolja till den skumbildande blandningen. Si t. Ex. are the common silicone oils, such as dimethylpolysiloxane, almost insoluble in the hydroxyl groups containing the polymers and polyisocyanates, Iran, which polyurethane foam products are prepared, and can be deposited or cleaved non-uniformly; water emulsions of the usual silicone oils can be used, but these are generally unstable in the presence of large amounts of such tertiary amines, which are usually used as catalysts and can thus usually be mixed with the activator mixtures used in polyurethane foam formation. The insolubility of the usual silicone oils and the small mane used made it difficult to add exactly the required amount of silicone oil to the foam-forming mixture.

Det liar nu visat sig, aven om det dr sa, att de vanliga silikonoljorna, namligen dimetylpolysiloxanerna, aro praktiskt taget olosliga i den hydroxylgrupper innehallande polymererna och polyisocyanaterna, fran vilka polyuretanskumprodukter framstallas, att metyl-fenylpolysiloxaner ha myeket storre loslighet. Pa sa satt undanrojas eller reduceras till ett minimum de nackdelar som aro fiirbundna med anvandningen av de vanliga silikonoljorna, genom anvandning av metyl-fenylpolysiloxaner, vilka salunda aro av ovantat varde som tillsatsmedel dâ det galler framstallning av polyuretanskumprodukter. It has now been found, even though it has been said, that the common silicone oils, namely the dimethylpolysiloxanes, are practically insoluble in the hydroxyl groups containing the polymers and polyisocyanates from which polyurethane foam products are prepared, that methylphenylpolysiloxanes have much greater solubility. In this way, the disadvantages associated with the use of the usual silicone oils are eliminated or reduced to a minimum by the use of methylphenylpolysiloxanes, which are therefore of unexpected value as additives in the production of polyurethane foam products.

I enlighet med uppfinningen astadkommes shlunda eft forbattrat forfarande for framstallning av cellpolyuretanmaterial genom skumbildning genom samverkan mellan organiska polyisocyanat och hydroxylgrupper innehallande polymerer, som kannetecknas av, att reaktionen genomf Ores narvaro av en metyl-fenylpolysiloxan. According to the invention, there is thus provided an improved process for the preparation of cellular polyurethane materials by foaming by the interaction of organic polyisocyanates and hydroxyl groups containing polymers, which are characterized in that the reaction is carried out in the presence of a methylphenylpolysiloxane.

De rnetyl-fenylpolysiloxaner som komma till anvandning vid sattet enligt uppfinningen kunna framstallas enligt for framstallning av polysil- 2— 18801t oxaner kanda forfaranden, t. ex. genom polymerisation av metyl-fenylklorsilaner eller genom polymerisation av blandning av -metylklorsilaner och fenylklorsilaner. The methylphenylpolysiloxanes which will be used in the process according to the invention can be prepared according to processes known for the preparation of polysiloxanes, e.g. by polymerization of methylphenylchlorosilanes or by polymerization of a mixture of -methylchlorosilanes and phenylchlorosilanes.

De metyl-fenylpolysiloxaner som komma till anvandning vid sattet enligt uppfinningen kunna vara sadana, i vilka fOrhallandet mellan antalet metyl- och fenylgrupper ligger mellan 101 och 1:1. Forhallandet mellan -antalet metylgrupper och antalet fenylgrupper upper foretradesvis- till 10:1-2:1. The methylphenylpolysiloxanes used in the process according to the invention may be those in which the ratio between the number of methyl and phenyl groups is between 101 and 1: 1. The ratio between -the number of methyl groups and the number of phenyl groups upper is preferably- to 10: 1-2: 1.

Det är att foredraga, att de metyl-fenylpolysiloxaner som anvandas vid sattet enligt uppfinningen inte innehalla isocyanatreaktiva grupper. Anvandningen av polysiloxaner, innehallande isocyanatreaktiva grupper, ar i allnianhet inindre onskvard, eftersom anvandningen av sacrana foreningar leder till stone forbrukning av isocyanat. Anvandnidgen av isocyanatreaktiva som endast innehalla en isocyanatreaktiv grupp per molekyl Er i manga fall foga tilldragande, eftersom sadana foreningar bilda oreaktiva slutgrupper och darigenom forhindra fortsatt tillvaxt av polyeter-isocyanatkedjan, -varigenom sadana skumprodukter i konsekvens harav uppvisa samre mekaniska egenskaper an de som framstallts med anvandning av icke-isocyanatreaktiva polysiloxaner. It is preferred that the methylphenylpolysiloxanes used in the kit of the invention do not contain isocyanate-reactive groups. The use of polysiloxanes, containing isocyanate-reactive groups, is generally undesirable, since the use of sacrane compounds leads to stone consumption of isocyanate. The use of isocyanate-reactive products which contain only one isocyanate-reactive group per molecule is in many cases attractive, since such compounds form unreactive end groups and thereby prevent further growth of the polyether-isocyanate chain, whereby such foam products consistently exhibit the same mechanical properties. use of non-isocyanate-reactive polysiloxanes.

Den anvanda mangden metyl-fenylpolysiloxan kan uppga till 0,005-5 %, foretradesvis 0,021 %, beraknat pa hela reaktionsblandningens vikt. The amount of methylphenylpolysiloxane used may be 0.005-5%, preferably 0.021%, based on the weight of the whole reaction mixture.

Denna mangd metyl-fenylpolysiloxan kan med latthet inblandas, genom blandning av den hydroxylgrupper innehallande polymeren, eller reaktionsprodukten haray, med ett molart Over. skott av polyisoeyanatet, i och for framstallning av en fOrradsblandning, som sedan kart blandas med mera hydroxylgrupper innehallande polymer, . eller en polyisocyanatreaktionsprodukt darav och eventuellt andra onskade komponenter i Adana mangdfOrhallanden, att den onskade koncentrationen av polysiloxan i den slutliga blandningen erhalles. Det dr i allmanhet lampligt att framstalla en forradsblandning, som innehaller e:a 5-30 viktprocent av metyl-fenylpolysiloxanen. . De utgangsmaterial som komma till anvandning vid sattet enligt uppfinningen aro de som redan till fullo finnas beskrivna i samband med redan kanda fOrfaranden. This amount of methyl-phenylpolysiloxane can be readily mixed, by mixing the hydroxyl group-containing polymer, or the reaction product haray, with a molar Over. shot of the polyisoyanate, in order to prepare a stock mixture, which is then blended with more hydroxyl groups containing polymer,. or a polyisocyanate reaction product thereof and any other desired components of the Adana composition, to obtain the desired concentration of polysiloxane in the final mixture. It is generally convenient to prepare a stock mixture containing from 5 to 30% by weight of the methylphenylpolysiloxane. . The starting materials which will be used in the method according to the invention are those which have already been fully described in connection with already known processes.

Lampliga polyisocyanat omfatta hexametylendiisoeyanat, tolylendiisocyanat, difenylmetan-4,4'- diisocyanat, 3-mety1-4,4'-diisoeyanatdifenylmetan, m- och p-fenylendlisocyanat, klorfenylen-2,4- - diisocyanat och dicyklohexylmetandiisocyanat. Triisocyanat som kunna anvandas omfatta 2,4,6- triisocyanattoluen och 2,4,4'-triisocyanatdifenyl- eter. Andra polyisocyanat som kunna anvandas omfatta polymerer av tolylen-2,4-diisocyanat och _ polyisocyanatkompositioner, som innehalla en huvuddel .av ett diarylmetandiisoeyanat och minst 5 viktprocent polyisocyanat med hogre funktionalitet an 2, framstallda -L. ex. genom fos...genering av sadana polyanainkompositioner som erhallits genom kondensation av formaldehyd med aromatiska aminer. Blandningar av polyisocyanat kunna likasa anvandas. Suitable polyisocyanates include hexamethylene diisoeyanate, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyl-4,4'-diisoeyanate diphenylmethane, m- and p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate and dicocyanate. Triisocyanates that can be used include 2,4,6-triisocyanate toluene and 2,4,4'-triisocyanate diphenyl ether. Other polyisocyanates which may be used include polymers of tolylene-2,4-diisocyanate and polyisocyanate compositions which contain a major proportion of a diarylmethane diisocyanate and at least 5% by weight of polyisocyanate having a higher functionality than 2, prepared -L. ex. by phos ... generation of such polyanainic compositions obtained by condensation of formaldehyde with aromatic amines. Mixtures of polyisocyanate can also be used.

Den hydroxylgrupper innehallande polymeren kan t. ex. vara en polyester, polyesteramid eller polyeter. Sattet enligt uppfinningen Or emellertid sarskilt lampligt vid framstallning av skumprodukter frail polyetrar. Metyl-fenylpolysiloxanerna ha visat sig ha en mycket storre skum.stabiliseran- de verkan under framstallningen av celluretanmaterial frail polyetrar i jamforelse med de vanliga metylpolysiloxanerna. Det enklaste sattet vid framstallningen av cellpolyuretanprodukter fran polyetrar och polyisocyanat i ett ettstegsforfarande innebar sarntidig reaktion av polyetern, polyisocyanatet och vatten; cla man fOrsoker detta fOrfarande med anvandning av de vardiga dimetylpolysiloxanerna blir emellertid skummet ofta sa instabilt, att dot tenderar att sjunka ihop, och framstallning i stor skala Or i sadana fall icke mOjlig. Om man i stallet anvander metylfenylpolysiloxaner vid detta ettstegsforfarande, stabiliseras emellertid skummet i overraskande h6g grad. Denna stabiliserande verkan till foljd av metyl-fenylpolysiloxanerna mojliggOr framstallning av cellmaterial frau polyetrar och polyisocyanat med mycket lagre densitet och med acceptabla belastningsuppbarande egenskaper, On vad som kan erhallas genom anvandning av vanliga metylpolysiloxaner. The hydroxyl group-containing polymer can e.g. be a polyester, polyesteramide or polyether. However, the set according to the invention is particularly suitable for the production of foam products from polyethers. The methylphenylpolysiloxanes have been found to have a much greater foaming stabilizing effect during the production of cell urethane material from polyethers compared to the usual methylpolysiloxanes. The simplest method of preparing cellular polyurethane products from polyethers and polyisocyanate in a one-step process involved the simultaneous reaction of the polyether, polyisocyanate and water; If one tries this process using the worthy dimethylpolysiloxanes, however, the foam often becomes so unstable that the dot tends to collapse, and large-scale production is in such cases not possible. However, if methylphenylpolysiloxanes are used in the stable in this one-step process, the foam stabilizes to a surprisingly high degree. This stabilizing effect due to the methylphenylpolysiloxanes makes it possible to prepare cellular materials from polyethers and polyisocyanates with very lower densities and with acceptable load-bearing properties, which can be obtained by using ordinary methylpolysiloxanes.

Polyestrarna eller polyesteramiderna kunna framstallas frail dikarbonsyror on glykoler och om ntidvandigt, diaminer eller aminoalkoholer. Lampliga dikarbonsyror omfattar barnstens-, glutamin-, adipin-, suberin-, azelain- och sebacinsyra och polymeriserade fettsyror, avensom aromatiska syror, sasom fisofial- cock tereftalsyra. Bland- ningar av syror kunna anvandas. Exempel pa glykoler Oro etylenglykol, 1,2-propylenglykol, 1,3- butylenglykol, dietylenglykol, trirnetylenglykol, tetrametylenglykol, pentametylenglykol, hexametylenglykol, dekametylenglykol och 2,2-dimetyltrimetylenglykol. Blandningar av glykoler kunna anvandas och flervarda alkoholer, sasom trimetylolpropan, pentaerytritol eller glycerin, kunna inblandas i olika mangder alit efter den styvhet man onskar hos de fardiga produkterna. Exempel pa diaminer och aminoalkoholer omfatta etylendiamin, hexametylendiamin, monoetanolamin, fenylendiaminer och bensidin. The polyesters or polyesteramides can be prepared from dicarboxylic acids on glycols and, if present, diamines or amino alcohols. Suitable dicarboxylic acids include succinic, glutamic, adipic, suberic, azelaic and sebacic acids and polymerized fatty acids, as well as aromatic acids, such as physophilic terephthalic acid. Mixtures of acids can be used. Examples of glycols Oro ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol and 2,2-dimethyltrimethylene glycol. Mixtures of glycols can be used and polyhydric alcohols, such as trimethylolpropane, pentaerythritol or glycerin, can be mixed in different amounts alit according to the desired stiffness of the finished products. Examples of diamines and amino alcohols include ethylenediamine, hexamethylenediamine, monoethanolamine, phenylenediamines and benzidine.

Som exempel pa polyetrar, lampliga att anvanda vid sattet enligt uppfinningen, kunna namnas polymerer med hydroxylslutgrupper och sampolymerisat av cykliska etrar, isynnerhet av etylenoxid, epiklorhydrin, 1,2-propylenoxid, 1,2- butylenoxid eller andra alkylenoxider, oxacyklobutan och substituerade oxacyklobutaner och tetrahydrofuran. Sadana polyetrar kunna vara linjara polyetrar, som kunna framstallas t. ex. genom polymerisation av en alkylenoxid i narvaro av en initiator, sasom vatten och en katalysator sasom kaliumhydroxid. Alternativt kunna grenade polyetrar anvandas, framstallda t. ex. genom polymerisation av en alkylenoxid i narvaro av en for- 3 cuing, som innehaller flera an 2 aktiva vateatomer, t. ex. glycerin, pentaerytritol och etylendiamin. Blandningar av linjara och grenade polyetrar eller blandningar av polyestrar och polyetrar, kunna om sa onskas anvandas. Examples of polyethers suitable for use in the process according to the invention are polymers having hydroxyl end groups and copolymers of cyclic ethers, in particular ethylene oxide, epichlorohydrin, 1,2-propylene oxide, 1,2-butylene oxide or other alkylene oxides, oxacyclobutane and substituted oxacyclobutanes. tetrahydrofuran. Such polyethers can be linear polyethers, which can be produced e.g. by polymerizing an alkylene oxide in the presence of an initiator such as water and a catalyst such as potassium hydroxide. Alternatively, branched polyethers can be used, produced e.g. by polymerizing an alkylene oxide in the presence of a forcuing which contains several 2 active hydrogen atoms, e.g. glycerin, pentaerythritol and ethylenediamine. Mixtures of linear and branched polyethers or mixtures of polyesters and polyethers, may be used if desired.

Samverkan mellan polyisocyanat, hydroxylgrupphaltigt amne och eventuellt anvant vatten kan genomforas med anvandning av redan kanda forfaranden under anvandning av kontinuerligt eller diskontinuerligt blandningssatt. Reaktionen kan om sa onskas modifieras genom inblandning av andra komponenter och kanda hjalpmedel, inkluderande basiska katalysatorer, t. ex. tertiara aminer, organometallforeningar, sasom dibutyl-tenndilaurat, ytaktiva Lunen, t. ex. anj oniska och icke-j oniska ytaktiva amnen, skumstabili- satorer, sasom sampolymerisat av siloxaner och alkylenoxider, pigment, fargamnen, mjukningsmedel, sasom dioktylftalat och eldbestandighetsforlanande amnen, sasom trikloretylfosfat. The interaction between polyisocyanate, hydroxyl group-containing amine and any water used can be carried out using already known procedures using continuous or discontinuous mixing batch. The reaction may, if desired, be modified by admixture with other components and known adjuvants, including basic catalysts, e.g. tertiary amines, organometallic compounds, such as dibutyltin dilaurate, Lunen surfactants, e.g. anionic and non-ionic surfactants, foam stabilizers, such as copolymers of siloxanes and alkylene oxides, pigments, dyes, plasticizers, such as dioctyl phthalate and flame retardants, such as trichlorethyl phosphate.

Metyl-fenylpolysiloxanen kan inblandas genom upplosning i den hydroxylgrupper innehallande polymeren, det organiska polyisocyanatet eller i -en ftirpolymer-reaktionsprodukt av den hydroxyl-grupper innehallande polymeren och polyisocya- =natet, eliere kan inblandas vid blandningen av ,nagon annan komponent, sasom vatten, och katalysatorn, eller med mjukningsmedlet eller det eldbestandighetsforlanande amnet. Uppfinningen belyses med tillhj alp av, men -är inte begransad till foljande exempel, i vilka angivna delar och procentsalser aro utlryckta vikt. The methylphenylpolysiloxane can be mixed by dissolving in the hydroxyl group-containing polymer, the organic polyisocyanate or in a polymer reaction product of the hydroxyl group-containing polymer and the polyisocyanate, or it can be mixed in the mixture of any other component, such as water, and the catalyst, or with the plasticizer or fire retardant. The invention is illustrated with the aid of, but is not limited to, the following examples, in which the parts and percentages given are by weight.

Exempel 1. 0,5 delar av en metyl-fenylpolysiloxan, i vilken fOrhallandet mellan antalet metyl- grupper och fenylgrupper utgor c:a. 3:1, loses i 100 viktdelar av en fOrpolymer med en isocyanathalt av 9,9 %, erhallen genom reaktion mellan a ena sidan 90 delar polypropylenglykol med ett hydroxyltal av 56 mg KOH per gram och 10 delar av en oxipropylerad glycerin med ett hydroxyltal av 56 mg KOH per gram, och a andra sidan delar av en 75:25 blandning av 2,4- och 2,6- isomererna av tolylendiisocyanat. Den erhallna blandningen blandas kontinuerligt med 4,5 delar av en blandning bestaende av 2 delar vatten, 1 del N,N-dimetylcyklohexylamin och 1,5 delar av en oktylfenyl/etylenoxid-reaktionsprodukt. Example 1. 0.5 parts of a methyl-phenylpolysiloxane, in which the ratio between the number of methyl groups and phenyl groups is approx. 3: 1, dissolved in 100 parts by weight of a polymer having an isocyanate content of 9.9%, obtained by reaction between on the one hand 90 parts of polypropylene glycol having a hydroxyl number of 56 mg KOH per gram and 10 parts of an oxypropylated glycerin having a hydroxyl number of 56 mg KOH per gram, and on the other hand parts of a 75:25 mixture of the 2,4- and 2,6-isomers of tolylene diisocyanate. The resulting mixture is continuously mixed with 4.5 parts of a mixture consisting of 2 parts of water, 1 part of N, N-dimethylcyclohexylamine and 1.5 parts of an octylphenyl / ethylene oxide reaction product.

Den sa erhallna blandningen tommes i formar och mom loppet av 30 minuter erhffiles en elastisk cellprodukt, som har en specifik vikt av 0,035. The resulting mixture is emptied into molds and in the course of 30 minutes an elastic cell product is obtained which has a specific gravity of 0.035.

Exempel 2. 1 del av en metylfenylpolysiloxan, i vilken forhallandet mellan antalet metylgrupper och fenylgrupper utgor c:a 2:1 och som har en viskositet av 500 cS vid 25° C och 0,25 delar dimetylbensylamin losas i 100 delar polypropylen- glykol med en molekylvikt av 2025. 38 delar av en 80:20 blandning av toluen-2,4- och 2,6-diisocyanat tillsattes darefter blandningen. Example 2. 1 part of a methylphenylpolysiloxane, in which the ratio between the number of methyl groups and phenyl groups is about 2: 1 and which has a viscosity of 500 cS at 25 ° C and 0.25 parts of dimethylbenzylamine is dissolved in 100 parts of polypropylene glycol with a molecular weight of 2025. 38 parts of an 80:20 mixture of toluene-2,4- and 2,6-diisocyanate were then added to the mixture.

Efter 24 timmar forsattes den erhallna blandningen med en lOsning av 1,0 delar N-metyl- pyrrolidin, 0,5 delar av en oktylfenolietylenoxidreaktionsprodukt och 2,15 delar vatten. Hela blandningen Mlles i en form. Efter 30 minuter erhalles en elastisk cellprodukt, som liar en specifik vikt av 0,032. After 24 hours, the resulting mixture was continued with a solution of 1.0 part of N-methylpyrrolidine, 0.5 parts of an octylphenolethylene oxide reaction product and 2.15 parts of water. The whole mixture is mixed in a mold. After 30 minutes, an elastic cell product is obtained which has a specific gravity of 0.032.

Exempel 3. 0,17 delar av en fenyl-metylpolysiloxan, med c:a 3 metylgrupper per fenylgrupp och med en viskositet av 120 cS vid 25° G delar dimetylbensylamin blandas med 100 delar polypropylenglykol med en molekylvikt av 2025, innehallande 0,14 delar vatten. 38 delar av en 80:20 blandning av 2,4- ocb. 2,6-isomererna av tolylen-diisocyanat tillsattas losningen. Example 3. 0.17 parts of a phenylmethylpolysiloxane, having about 3 methyl groups per phenyl group and having a viscosity of 120 cS at 25 ° G parts of dimethylbenzylamine are mixed with 100 parts of polypropylene glycol having a molecular weight of 2025, containing 0.14 parts water. 38 parts of an 80:20 mixture of 2,4- ocb. The 2,6-isomers of tolylene diisocyanate are added to the solution.

Efter 24 timmar forsattes blandningen med en blandning av 2 delar N-metylmorfolin, 1 del N,Ndimetylcyklohexylamin, 0,25 delar av en oktylfenolletylenoxid-reaktionsprodukt och 2,15 delar vatten. Hela blandningen halles i en form. Efter 30 minuter erhalles en elastisk cellprodukt, som har en specifik vikt av 0,031. After 24 hours, the mixture was continued with a mixture of 2 parts of N-methylmorpholine, 1 part of N, N-dimethylcyclohexylamine, 0.25 parts of an octylphenol ethylene oxide reaction product and 2.15 parts of water. The whole mixture is poured into a mold. After 30 minutes, an elastic cell product is obtained, which has a specific gravity of 0.031.

Exempel 4. 0,04 delar av en metyl-fenylpolysiloxan med 3 metylgrupper per fenylgrupp och .med en viskositet av 120 cS vid 25° C, 0,25 delar dimetylbensylamin och 100 delar polypropylenglykol med en molekylvikt av 2025 blandas med 38 delar av en 80:20 blandning av tolylen-2,4- och '-2,6-diiso cyanat. Example 4. 0.04 parts of a methyl-phenylpolysiloxane having 3 methyl groups per phenyl group and having a viscosity of 120 cS at 25 ° C, 0.25 parts of dimethylbenzylamine and 100 parts of polypropylene glycol having a molecular weight of 2025 are mixed with 38 parts of a 80:20 mixture of tolylene-2,4- and '-2,6-diisocyanate.

Efter 24 timmar forsattes blandningen med en ,blandning av 1,5 delar N,N-dimetylcyklohexyl.amin, 0,25 delar av en oktylfenyl/etylenoxidreaktionsprodukt och 2,15 delar vatten. Hela blandningen Mlles i en form och efter 30 minuter erMlles en elastisk cellprodukt, som har en specifik vikt av 0,030. After 24 hours, the mixture was continued with a mixture of 1.5 parts of N, N-dimethylcyclohexylamine, 0.25 parts of an octylphenyl / ethylene oxide reaction product and 2.15 parts of water. The whole mixture is formed into a mold and after 30 minutes an elastic cell product is formed which has a specific gravity of 0.030.

Exempel 5. 0,2 delar av en fenyl-metylpolysiloxan med 3 metylgrupper per fenylgrupp och med en viskositet av 120 cS vid 25° C, 0,25 delar dimetylbensylamin, 100 delar polypropylenglykol med en molekylvikt av 2025 och 57 delar av en 80:20 blandning av tolylen-2,4- och -2,6-diisocyanat blandas tffisammans. Example 5. 0.2 parts of a phenylmethylpolysiloxane having 3 methyl groups per phenyl group and having a viscosity of 120 cS at 25 ° C, 0.25 parts of dimethylbenzylamine, 100 parts of polypropylene glycol having a molecular weight of 2025 and 57 parts of an 80: A mixture of tolylene-2,4- and -2,6-diisocyanate is mixed together.

Efter 24 timmar forsattes denna blandning med en blandning innehallande 0,75 delar N,N-dimetylcyklohexylamin, 0,5 delar av en oktylfenol/etylenoxidreaktionsprodukt och 3,1 delar vatten. Hela blandningen Mlles i en form. Efter 10 minuter erhalles en elastisk cellprodukt, som har en specifik vikt av 0,019. After 24 hours, this mixture was continued with a mixture containing 0.75 parts of N, N-dimethylcyclohexylamine, 0.5 parts of an octylphenol / ethylene oxide reaction product and 3.1 parts of water. The whole mixture is mixed in a mold. After 10 minutes, an elastic cell product is obtained, which has a specific gravity of 0.019.

Exempel 6. 4,7 delar av en laming, framstalld av 50 delar av en oktylfenol/etylenoxid-reaktionsprodukt, 34 delar av natriumsaltet av sulfonerat metyloleat och 151 delar vatten, blandas med 0,3 delar natriumhydroxid, och den pa sa satt erhallna emulsionen tillsattes 100 delar polypropylenglykol med en molekylvikt av 2000. Blandningen omrores kraftigt under 4 minuter och far darefter sta 2 minuter. Example 6. 4.7 parts of a paralysis, prepared from 50 parts of an octylphenol / ethylene oxide reaction product, 34 parts of the sodium salt of sulfonated methyl oleate and 151 parts of water, mixed with 0.3 parts of sodium hydroxide, and the emulsion thus obtained 100 parts of polypropylene glycol having a molecular weight of 2000 were added. The mixture was stirred vigorously for 4 minutes and then allowed to stand for 2 minutes.

Darefter tillsattas 40 delar av en 80:blandning av 2,4- och 2,6-tolylendiisocyanat, innehallande 0,7 delar metylfenylpolysiloxan, med 3 metylgrupper per fenylgrupp och med en viskositet av 120 cS vid 25° C och blandningen omrOres hastigt samt Mlles i en form. Efter 5 minuter erhalles en elastisk cellprodukt med lag densitet, och klibbfri yta, som har en specifik vikt av 0,033. Then 40 parts of an 80: mixture of 2,4- and 2,6-tolylene diisocyanate, containing 0.7 parts of methylphenylpolysiloxane, with 3 methyl groups per phenyl group and having a viscosity of 120 cS at 25 ° C are added and the mixture is stirred rapidly and in a form. After 5 minutes, an elastic cell product with low density and tack-free surface is obtained, which has a specific gravity of 0.033.

Exempel 7. 4,7 delar av en losning, beredd acr 4— = delar av en oktylfen.olfetylencodd-reaktionsprodukt, 34 delar av natriumsaltet av sulfonerat metyloleat och 151 delar vatten, blandas med 0,3 delar 4-dimetylaminopyridin, 0,2 delar Nmetylpyrrolidin och 0,2 delar dimetylbensylamin. Den pa sá satt erhallna losningen tillsattes 100 delar polypropylenglykol med en molekylvikt ay 2000. Blandningen omrOres under 2 minuter och far darefter sta under 2 minuter. Example 7. 4.7 parts of a solution, prepared acr 4 = parts of an octylphene.olphethylene codd reaction product, 34 parts of the sodium salt of sulfonated methyl oleate and 151 parts of water, mixed with 0.3 parts of 4-dimethylaminopyridine, 0.2 parts parts Nmethylpyrrolidine and 0.2 parts dimethylbenzylamine. To the solution thus obtained was added 100 parts of polypropylene glycol having a molecular weight of 2000. The mixture was stirred for 2 minutes and then allowed to stand for 2 minutes.

Darefter tillsattas 42,5 delar av en 80:20 blandning av 2,4- och. 2,6-tolylendiisocyanat, innehallande 0,2 delar ay en metyl-fenylpolysiloxan med 3 metylgrupper per fenylgrupp och med en viskositet av 120 cS vid °C, och blandningen omrores hastigt samt Mlles i en form. Efter 15 minuter erhalles en elastisk, klibbfri cellprodukt, som liar en specifik vikt ay 0,030 och som uppvisar goda belastningsuppbarande egenskaper. Then 42.5 parts of an 80:20 mixture of 2,4- and. 2,6-tolylene diisocyanate, containing 0.2 parts of a methyl-phenylpolysiloxane having 3 methyl groups per phenyl group and having a viscosity of 120 cS at ° C, and the mixture is stirred rapidly and Mlles in a mold. After 15 minutes, an elastic, tack-free cell product is obtained, which has a specific weight of 0.030 and which exhibits good load-bearing properties.

Exempel 8. 87 delar av en 65:35 blandning av tolylen-2,4- och -2,6-diisocyanat blandas med 130 delar ay ett propylenoxid/hexantriolkondensat med en molekylvikt ay 1500, 0,325 delar N-dimetylbensylamin och 0,015 delar av den i exempel 1 beskrivna silikonvatskan. Blandningen forvaras under 21 timmar, efter vilken tid den resulterande NCO-halten uppgar till 14,2 %. 100 delar blandas darefter med en blandning, innehallande 3,1 delar vatten, 0,35 delar N-dimetylcyklohexylamin och 1 del av ett alkylfenolietylenoxidkondensat. En elastisk cellprodukt erhalles, som liar en specifik vikt ay 0,024. Example 8. 87 parts of a 65:35 mixture of tolylene-2,4- and -2,6-diisocyanate are mixed with 130 parts of a propylene oxide / hexanetriol condensate having a molecular weight of 1500, 0.325 parts of N-dimethylbenzylamine and 0.015 parts of the the silicone liquid described in Example 1. The mixture is stored for 21 hours, after which time the resulting NCO content is 14.2%. 100 parts are then mixed with a mixture containing 3.1 parts of water, 0.35 parts of N-dimethylcyclohexylamine and 1 part of an alkylphenolethylene oxide condensate. An elastic cell product is obtained which has a specific gravity of 0.024.

Exempel 9. En blandning av 50 delar polypropylenoxid med en molekylvikt ay 2000, 50 delar ay ett propylenoxidiglycerinkondensat med en molekylvikt av 2000, 38 delar av en 80:20 blandning av tolylen-2,4- och -2,6-dlisocyanat och 0,25 delar N-dimetylbensylamin foryaras under 24 timmar. 88 delar ay blandningen blandas kontinuerligt med 12 delar tolylendiisocyanat, innehallande 0,3 delar av den i exempel 1 beskrivna silikonoljan och 4,45 delar ay den i exempel 8 beskrivna blandningen ay vatten, N-dimetylcyklohexylamin och alkylfenolietylenoxidkondensat. En elastisk cellprodukt erhalles, som bar en specifik vikt av 0,023. Example 9. A mixture of 50 parts of polypropylene oxide having a molecular weight ay of 2000, 50 parts of a propylene oxide glycerin condensate having a molecular weight of 2000, 38 parts of an 80:20 mixture of tolylene-2,4- and -2,6-dlisocyanate and 25 parts of N-dimethylbenzylamine are preheated for 24 hours. 88 parts of the mixture are continuously mixed with 12 parts of tolylene diisocyanate, containing 0.3 parts of the silicone oil described in Example 1 and 4.45 parts of the mixture of water, N-dimethylcyclohexylamine and alkylphenolethylene oxide condensate described in Example 8. An elastic cell product is obtained, which had a specific gravity of 0.023.

Claims

Patent claims:

A method of producing, by foaming, cellular polyurethane materials by the co-reaction between organic polyisocyanates and hydroxyl groups containing polymers, characterized in that the reaction is carried out in the presence of a methyl-phenylpolysiloxane.

2. A claim according to claim 1, characterized in that the ratio between the number of methyl groups and phenyl groups in the methyl-phenylpolysiloxane is 10: 1--1: 1.

3. A kit according to claim 1, characterized in that the ratio between the number of methyl groups and phenyl groups in the methyl-phenylpolysiloxane is 10: 1-2: 1.

4. According to any one of claims 1-3, it may be claimed that the methylphenylpolysiloxane jute contains isocyanate-reactive groups.

5. A set according to any one of claims 1-4, characterized in that the amount of methylphenylpolysiloxane amounts to 0.005-5%, calculated on the weight of the whole reaction mixture.

6. A set according to any one of claims 1-4, characterized in that the amount of methylphenylpolysiloxane upper to 0.02-1%, calculated on the weight of the whole reaction mixture.

7. A kit according to any one of claims 1-6, characterized in that the methyl-phenylpolysiloxane is mixed by mixing the hydroxyl group-containing polymer, or the reaction product thereof, with a molar excess of the polyisocyanate, in order to prepare a stock mixture, which is then mixed with more hydroxyl groups containing polymer, or a polyisocyanate reaction product thereof, and optionally other desired components in such amounts that the desired concentration of polysiloxane in the final mixture is obtained.

8. Set according to claim 7, characterized in that the stock mixture contains about 5-30% by weight of methylphenylpolysiloxane.

9. According to one of claims 1 to 8, it is claimed that the polymer containing hydroxyl groups is a polyether.

10. according to claim 9, characterized in that the cooperation is carried out in the form of a one-step process, involving the simultaneous reaction of polyether, polyisocyanate and. water.

11. Genor foaming obtained cellular polyurethane materials, prepared according to any one of claims 1-10. Request Publication No. Patents from France 1 224 15 2.