MXPA98007790A - Stable emulsions during storage for the production of rigid foams of fine cells based on isocian - Google Patents

Abstract

Emulsions containing blowing agents comprise: a) compounds containing hydrogen atoms that react with isocyanates, b) expansion agents c) catalysts, auxiliaries and / or additives common in polyurethane chemistry, where the blowing agents b) are found present in the form of an emulsion in components a) and c), and polyester alcohols of the following structure are used as emulsification aids: where m = 0 - 15 n = 0 - 1 or = 0 - 15 p = 0 - 1 q = 0 - 15 r = 0 - 1 s = 0 - 15 t = 0 - 1 u = 0 - 10 v = 0 - 15 x = 1 - 5 y = 1 - 4 or mixtures of 1-3 where r - n / 0 z = 0 - 3 z1 = 0.1 - 3 R1 is an aliphatic structure without OH groups, based on the structure of polyhydric alcohols, preferably ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol and dipropylene glycol, 1,4- butanediol, 1,6-hexanediol, neopentyl glycol, 1,3-butanediol, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, where these substances can also be used The form of any mixture between them in the esterification and R1 can therefore also be a mixture of the corresponding structures, R2 is the radical of an adipic acid, terephthalic acid, o-phthalic acid, R3 is an alcohol radical,

Description

STABLE EMULSIONS DURING STORAGE FOR THE PRODUCTION OF FIBER CELL RIGID FOAMS BASED ON ISOCIANATE The present invention relates to storage stable emulsions free of CFC, for the production of rigid open cell and closed cell foams, based on isocyanate. The invention also relates to compositions of active hydrogen with emulsification aids for preparing these emulsions in order to produce rigid open cell and closed cell foams, based on isocyanate. The production of rigid foams based on isacyanate as thermal insulation material has been known for a long time. The most important initial chemical materials are functional isocyanates. As chemical structures formed from these polyisocyanates, it is possible that polyurethane, polyureas, pal isoacids and also additional isocyanate adducts with, for example, allophananes, biurets, carbodiimides and their isocyanate adducts, or: < azal idanas, polyimides, polyamides, etc. are present. The type of these structures is controlled by the reaction partners of the isocyanates, the catalysis and the reaction conditions. These isocyanate adducts are generally summarized under the term paliurethanes, since polyurethanes are the most important and widest group of materials among the polyisocyanate adducts. Rigid foams based on isacianata ss also call, therefore, rigid paliurethane foams (PUR). In the case of a proportion meaning iva of isocyanurate structures, these foams are known as rigid foams of palure urethane / polyisocyanate, rigid foams of PUR / PSR or simply rigid foams of PIR for short. The production of such rigid foams is described, for example, ep Kunststoffhandbuch, Volume VII, Polyurethane (Polyurethane), edited by S. Oertel, Cari-Hanser-Verlag, Munich, Visna, 1993. Most of these foams have been The date largely closed cell foams. These rigid foams are also being used, recently, as cores for vacuum insulation units and for this application they must be made up of completely open or completely open cells »EP 351 614 describes the preparation of stable emulsions in storage comprising perfluorinated, liquid, insoluble or slightly soluble compounds in the polyurethane forming components as blowing agents and open cell foams made therefrom. DE 4,143 148 discloses the production of rigid foams based on isocyanate by the use of a mixture of blowing agents comprising isoalkanes having 6 or more carbon atoms and fluorinated or perfluorinated organic ds with low boiling point present. together in the form of an emulsion. DE 42 00 558 describes the combination of fluorine compounds with C4-C8 hydrocarbons including cyclopentane. DE 41 21 161 also describes emulsions containing blowing agents comprising fl aminated compounds. These foams, also known as "emulsion foams", have very small cells that lead to low thermal conductivity. An important requirement for the production of these emulsions is the use of at least one highly fluorinated to perfluorinated organic compound, preferably together with other blowing agents, for example, hydrocarbons consisting of only hydrogen and carbon, as a mixture of blowing agents. Thus, according to DE 42 OO 558, a mixture of blowing agents can be used which consists of from 5 to 40 * / 'by weight of highly flavorylated and / or perfluorinated organic compounds, particularly hydrocarbons, from 30 to 95% by weight of cyclopeptane and from 0 to 457% by weight of aliphatic and / or cycloaliphatic hydrocarbons for the production of rigid closed cell paliurethane foam with a water content of 0.5 to 3% by weight. This provides a foam with very thin cells that has a thermal conductivity ba a. further, the use of highly fluorinated or perfluorinated organic compounds for the production of open cell emulsion foams for vacuum technology is described in EP 405 439, WO 96/25455, US 534 6 928 or EP 662 494 or in WO 95/15355 as well as in WO 95/15356 in combination with carbon black. JP 081 7 551 recommends the use of a very small amount of these highly fluorinated or perfluorinated organic compounds in closed cell foams. JP 08 104 771 describes the use of fluorine-containing surfactants, for example, fluarinated alkyl esters. W 0 95/02620 also describes the production of thin cell and open cell emulsion foams for vacuum technology which are produced with the aid of an insoluble, inert organic liquid which is present as a dispersed phase in a microemulsion. In the examples, this liquid comprises another see highly fluorinated or perfluorinated compounds. In EP 599 496, more soluble fluorinated compounds are also added as a tuent >; ie an emulsion. EP 543 536 also recommends the formation of an emulsion by the use of organic liquid which is insoluble in the reaction mixture, In the examples, this liquid is again represented by partially fluorinated or perfluorinated compounds. 93/07201, emulsion formation is also carried out with the use, for example, of perfluorapentane The series of documents describing the use of fluorine compounds in emulsions for the production of rigid foams based on isocyanate indicates, however, the importance of the emulsions and the corresponding fluorine compounds for the production of thin cell foams »Even though the ozone destruction potential (ODP) of these metals is now zero in comparison with the chloraroquarcarbons (CFCs) used in the past However, fluorine compounds continue to contribute substantially to global warming potential (SWP). onformity with M.C »BOSDA et al. "Proceedings of Palyurethanes EPO '96" SPI, Las Vegas, Nevada, page 394-403, fluorine compounds decompose once they reach the atmosphere to form acidic and environmentally damaging decomposition products, especially hydrogen fluoride. " Similar considerations are also applied to blowing agents containing other halogens that will not be present in the future if the rigid foams are based on isocyanates. A halogen-free closed-cell emulsion foam is described in EP 394 769. It employs paliestepal, a commercial emulsifier and finely divided nitrogen as an emulsification aid. Obviously, such a halogen-free emulsion foam still contains very small amounts of chlorine compounds that are formed in the synthesis of the isocyanate but can not reach the atmosphere. However, a foam containing these chlorine bleach footprints will then be considered as halogen-free. "An emulsion foam is halogen, for example, described in JP 08 193 115. An essential aspect of this presentation is the simultaneous use of polyester alcohol and a prepsl polymer derived from isocyanate and pallather alcohol. DE 432 83 83 discloses a partially dissolved only blowing agent, composed of hydrocarbon which lacks only hydrogen and carbon or mixtures of these hydrocarbons having from 3 to 7 carbon atoms as an emulsion in the component ds pal iol »In In this presentation, polyethers containing oleic groups together with pali ethers and oxistyl groups are an essential aspect. However, it is known that < _? The use of axi-ethyl groups in rigid foamed formulations increases the intrinsic reactivity of the formulation, so that a smaller amount of catalyst can be used to obtain a desired fiber formation time. in the imparting disadvantage that the reaction ss performs more slowly after reaching the fiber time and the foam ss significantly less well. This is observed, for example, in the undesirably high times of mold removal when the foam formation ss It carries out in molds or ep the need for working speeds in the process of double conveyor belt. The solution described can only be used, if it can be used, to a very limited extent and subject to this disadvantage. DE 41 9 076 presents a duriferous poly / isocyanurate foam (PUR / PIR) expanded with peptana and isopentane having an isacyanate index above 200, where a resistance to the class-free halogen-free fires is achieved. B2 in accordance with DIN 4102, as a novelty. A benzyl n-butylphthalate or bisn is used as an emulsifying monafunctional polyether containing OH. Documents US 548 8 071, US 548 4 817 and US 546 4 562 propose monofunctional polymers of monofunctional polyols initiated by using fatty alcohols having 8 to 24 carbon atoms as emulsifiers and polyesters in the polyol mixture. DE 441 8 993 proposes the use of compounds based on castor oil as a polyal component in rigid paliuretans foams. A) Yes, the castor oil reacts with polyfunctional alkanols or amines and these reaction products serve as a unique palol component. Thus, for example, the product of castor oil esterification and glycerol has a hydroxyl number of 433 mg KOH / g is described and is used as a single polyol in clear, transparent, non-emulsified A components. for rigid foams ds paliu ethane. The use as an emulsification aid and of rigid isocyanate-based foams (ie, PUR foams as well as PUR / PIR foams) produced in this way are not described in DE 441 8 993. All the emulsions proposed up to and including the date have a number of disadvantages! * When fluorine compounds are used as expansion agents, the expansion action is insufficient to apply open cell foams that have a good fluid behavior for vacuum ds technology. The simple filling of the hollow spaces that are simply evacuated is not possible like this. * Foam 5 ds open cells, sxcsntas of halogens, which have cells small enough for vacuum technology have not been produced to date. * Rigid open cell foams expanded only by msdio of C02 formed by the reaction of water and isocyanate can not occur as a result. These foams are required as, for example, to fill hollow spaces of refrigerators or other isolation units subsequently evacuated. For example, if the evacuation is carried out only in the house, expansion gases can be used only completely to environmentally friendly, that is, even cyclopentane or other hydrocarbons are unsuitable for this purpose. * Previously known exogenous halogen emulsions for thin cell and similarly closed cell foams have an unsatisfactory shelf life. Only after a few hours or at most after one or two days, a demulsifi- cation is observed. The nature of fine cells of the foams which is essential for the use of the foams is therefore a function of the storage time within technically necessary storage times of less than 12 hours. This greatly limits the industrial handling of previously known halogen-free emulsions for the production of emulsion foams. Furthermore, the use of monofunctional agents that has been previously proposed for this purpose greatly reduces the total functionality of the mixture of palioles and results in reduced cross-linking with all its associated disadvantages, such as a limited curing of the mixture. reaction or a limited thermal stability of the liquid foam produced from there. In the case of the emulsifiers, the adhesion of the polyurethane to cover layers and the thermal stability, for example, are not significantly improved, as in the case of sjempla n-butylf alato of bspcilo. In rigid foams of closed cells based on isocyanate and deri In addition to halogen emulsions, the thermal conductivity is significantly higher than in the case of emulsions comprising halogen compounds, specifically fluorine. * When the combined use of halogenated and halogen-containing expansion agents is carried out, it is not possible to produce stable foams at very high temperatures, even when PUP / PIR structures are present. It is an object of the present invention to prepare emulsions You exceed CFCs for the production of rigid foams of abyssary cells and closed cells in bass to isocyanate that do not have all these disadvantages listed. We have found that this object is achieved by emulsions comprising the following constituents. a) compounds containing reactive hydrogen atoms, b) expansion agents and c) auxiliaries and additives, where the expansion agent is emulsified in the component and polyester alcohols having the following structure are used as emulsification aids: where: Rl is an aliphatic structure without hydroxy io groups based on the structure of palihydric alcohols: = O - 15 n = O - 1 or = 0 - 15 p = 0 - 1 q = 0 - 15 r = O - 1 s = O - 15 t = 0 - 1 u = 0 - 10 v = 0 - 15 x = 1 - 5 y = 1 - 4 or mixtures of 1 - 3 where r + n is different from O zl = 0 - 3 z2 = O - 3 zl + z2 = 1 - 3. The palstastales of the formula I used according to the present invention as emulsification auxiliaries are preferably sterolification products containing hydroxyl ds fatty acids and polyfunctional alkalols. Here it is possible to use saturated acids as insurances, referring to the use of unsaturated compounds. Due to the good compatibility with the other constituents of paliurethane, preference is given to the use of reaction products of ricinoleic acid and to castor oil and / or to fatty acid of wood pulp oil with functional and functional alcohols. The alkalies used are those used, in particular, alcohols having 2 to 6 carbon atoms, preferably 3 to 6 carbon atoms and particularly 3 to 5 carbon atoms. Examples are: e isngl icol, propi lepgl icol, die ilsngl icol, dipropilsngl icol, glycolrol, butanediol. The hydroxyl number of the compounds of the formula I containing active hydrogen is preferably greater than 160 mg KOH / g. The polyesterols used in accordance with the present invention are used, particularly in an amount of 1 to 5 * / step, preferably from 5 to 25 * / step, based on the tatal amount of components a) to c) . The preparation of such compounds is described, for example, in DE-A-44 18 993. The emulsions of the present invention are stable during storage for several weeks. To produce rigid polyurethane foams of thin cells, the emulsions containing the blowing agent of the present invention are reacted with pal isocyanate. The isocyanates used are the aliphatic and particularly aromatic customary isacyanates, such as, for example, ethylene hexane diisocyanate, isophorone diisocyanates, toluene diisocyanate (TDD), diisocyanate diisocyanate (MDS), for the production of rigid foam. of polyurethane, preference is given to the use of mixtures of di-phenemethane di-methane diisocyanate and polyisocyanates of polyisocyanate imatiene, also known as crude MDI.The polyisocyanates can also be modified, for example, by allophanata, biuret, isocyanurate or oxazole-idine groups. The polyurethanes are usually produced by mixing the emulsions of the present invention with the polyisocyanates, preferably in mixing heads, and curing the reaction mixture in open molds for cements. The rigid polyurethane foams produced in this way have very fine cells generally open. n for these products »Its use as a core material for vacuum insulation elements is especially advantageous» The following details can be provided regarding the components of the emulsions of the present invention: a) As excipients that have at least two atoms of Hydrogen that reacts with isocyanate and can be used together with the adjuvants of the emulsification of the formula S employed according to the present invention, it is possible to employ in the molecule the compounds having two or more reactive groups selected from OH groups, SH, NH groups, NH2 groups and CH acid groups, by sjempla. beta-diquets groups. It is advantageous to make use of those having a functionality of 2 to 8, of prsfsrsncia of 2 to 6, and a molecular weight of 300 to 8000, preferably of 400 to 4000. Useful compounds are, by sjampla, poliatarpal sheets and / or of selected polyols within the rump consisting of paliolas ds polietsr, palisades of paliéstsr, pslialss of pali ioéter, polstsramidas, polyacetals containing hidroi ilo and pal ica rbons to the iéticos hidraxilo containing or mixtures ds at least das ds pololss mentioned. Preference is given to the use of polysaccharides and polyether polyols. The hydroxyl number of these polyhydroxyl compounds is generally between 100 and 850 and between 200 and 600. Ss can prepare suitable palioster pallets, for example, from organic dicarboxylic acids having from 2 to 12 atoms. of earbsna, preferably aliphatic dicarboxylic acids having from 4 to 6 carbon atoms, and polyhydric alcohols, of praragence diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms. Examples of suitable dicarboxylic acids are: Swedish acid, glutaric acid, adipic acid, suberic acid, azelaic acid, ssbcic acid, decandicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. These acids dicarbo? í 1 icos can be used either individually or in mixture with each other. In place of the free dicarboxylic acids, it is also possible to use the corresponding derivatives of acid dicarbaxyl 1 as for these dicarboxylic esters having alcohols having 4 carbon atoms or 1-dicarbaxy anhydrides. Examples of dihydric and polyhydric alcohols, particularly diols, are; etandiol, die ileglycol, 1,2- or i, 3-propanediol, dipro i Isngl ical, 1, -butandial, 1,5-pentandial, 1,6-hexandial, 1, 10-decandial, glyceral and trimeti lolpropane »In order to prepare the psylester polyesters, organic acids, for example aromatic and aliphatic and / or branched acids, and palihydric alcohols can be polycondensed in the absence of catalysts, preferably in the presence of catalyst catalysts, with advantage in an atmosphere of inert gas as a pair of nitrogenous axis, carbon monoxide, hslia, argon, etc., ep the fusion at a temperature of 150 to 250 ° C, preferably 180 to 220 ° C, under atmospheric pressure at under reduced pressure to the acidity indices dsseated which is less preferred than IO, preferably less than 2. To prepare the polyester polyoids, the organic polycarboxylic acids and / or derivatives and pallyhydric alcohols are preferably concentrated in a molar proportion. Lar ds 1: 1-1.8, ds preference 1: 1.05-1.2 »Ablate polyester palols preferably have a functionality of 2 to 4, particularly 2 to 3, and a molecular weight of 300 to 3000, preferably 350 d. to 2000, and particularly from 400 to 600. However, the polyals employed are preferably polyether polyols prepared by known methods, for example, from one or more alkylene oxides which have from 2 to 4 carbon atoms per se. alkyl radical by anionic polymerization using alkali metal hydroxides such as for example sodium hydroxide or biep potassium hydroxide, or alkali metal alkoxides with, for example, sodium methoxide, sodium or potassium ethoxide, or potassium isopropoxide as catalysts with addition of at least one initiator molecule having from 2 to 8, preferably from 2 to 6 reactive hydrogen atoms in linked form, or by means of cationic polymerization using Lewis acids, for example, antimony pentachloride, bora fluoride arate, etc., or bleached earths as catalysts. Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-praylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and pre-oxide oxide etheylene oxide and 1,2-dioxide. -propi Isno »The oxides of alkyls can not be used individually, alternatively in succession or as mixtures. Examples of suitable initiator molecules are: water, organic acids or organic acids with, for example, succípica acid, adipic acid, phthalic acid and terphthalic acid, aliphatic and aromatic diamines, non-alkylated, -aminoacylated, N, N- and N.N'-dialkylated having 1 to 4 carbon atoms in the alkyl radical, for example, ethylenediamine, d ist i lsn riamine, tris i lentstramina, 1, 3- ropilend i ina, 1,3- or 1, 4-bu.ti land iami. Na, 1,2-, 1,3-, 1,4-, 1,5- and 1 * -hexa and the non-alkylated lendiamine, mono- and tetra-substituted diary »Additional suitable starter molecules are: alkanolamines as exemplary stanol ina, N-methystanolamine and N-st i letanolamine, dialkanolamipads with, for example, distanalamine, N-mstildietanolamipa and N-sti Idietanalamine, and trialkanola inas co for tr platanolamine, and ammonia. Preference is given to using polyhydric alcohols, in particular dihydric, trihydric and / or higher bed hydrics for example standiol, 1,2- and 1,3-propanediol, disti lengl icol, diprop and isngl icol, 1, 4-bu.tandiol, 1, 6-hsxandial, glycerol, tr i ilolpropana, pentaeri ri tol and sucrose. The polyether palladiums, preferably palladium-polyaprylate and palladium-iprapium-polyoxyethylene pallets, have a functionality preferably of 2 to 6 and particularly 2 to 4 ds and molecular weights of 300 to 100%, preferably 400 to 1500 and par- ticularly 420 to 1100, and suitable ioxy etrameth and leglomerals have a molecular weight up to about 3500. Polyether modified polyols are also suitable as polyether polyols.Preferably, grafted polyether polyols, particularly those based on styrene and / or acrylonitrile, which are prepared by in situ polymerization. of acri lopi ti la, styrene or gives preference to mixtures of styrene and acri lani lo, for example, in a weight ratio of 90:10 to 10:90, of preference from 70:30 to 30:70, with profit in the The aforementioned polyether polyols mediate the use of methods similar to those provided in German Patents 11 11 394, 12 22 669 (North American documents 3 304 273, 3 383 351, 3 523 093), 11 52 536 (GB ÍO 40 452) and 11 52 537 (BB 987 618), and also dispersions of polyols ds polyether which has a dispersed phase, has a Try in an amount ds 1 to B0 *? Sn psso, ds prsfsrencia ds 2 to 2514 by weight, for example, polyureas, psl ihidrazidas, poliuretapos containing tertiary bound groups and / or melamine, and are described, for example, in documents EP-B-l 1 752 (US 4 304 708), US-A-4 374 209 and DE-A-32 31 497. Like the polyols of the polyester, the polyols of the pallate can be used indi-idually or in the form of szclas. They can also be mixed with polyester polymers or polyether polyols grafted to either polystyrene palisates, palicarbonate, polyacetals, and / or polyester amides containing hydroxyl. Polyacetals which contain hydroxyl and are suitable, for example, are compounds which can be prepared from glycols with, for example, dis i lengl icol, trie i lengl icol, 4, 4 '-d ih idrox ietoxidi feni Id ime i lmetana or hexandiol and formaldshida. Suitable polyacetals can also be prepared by polymerization of cyclic acetals. Suitable polycarbonates containing hydroxy are the dsi type known psr ss, which can be prepared, for example, by the reaction of dials such as 1,3-propandiol, 1,4-butandial and / or 1,6-hexaandial, diethylene glycol, triethylglycol or bisn tetrae i lengl icol with diaryl carbonates, for example diphenyl carbonate, or phosgene. Polyester amides include, for example, linear pradominantsmsnts obtained from polybasic, saturated and / or unsaturated carboxylic acids, or their anhydrides already inaalcahales, and the saturated and / or unsaturated or mixtures of polyhydric alcohols function. and aminoalcohols and / or pal sheets. Suitable polystyrene layers can be prepared from the aforementioned polyether polyols by known methods. Examples that may be mentioned are the cyanoalkylation of palladiums of poiiaxyalkylsne and the subsequent hydragenation of the formed nitrile (US Pat. No. 3 267 050) or the partial or complete amination of polyalss ds polyoxyalkylsne using amines or ammonia in the presence of hydrogen and catalysts (DE 12 15 373). Compounds containing at least two active hydrogen atoms (a) also include chain extenders and / or reliculators. The addition of chain extenders, crosslinkers or, if desired, mixtures thereof may be helpful in modifying the metallic properties of the resultant polystyrene, e.g., hardness. Chain extenders and / or reliculators employed are diols and / or triols having molecular weights less than 400, preferably from 60 to 300. Suitable cation / scale extenders are, for example, aliphatic, cycloaliphatic and / or araliphatic diols. they have from 2 to 14, preferably from 4 to 10 carbon atoms, for example, et i lepgl icol, 1,3-propandiol, 1, 10-decandiol, o-, m-, p-dihydraxiciclohaxana, diethylene glycol, diprs and preferably 1,4-butapdial, 1,6-hexanedial and bis (2-hydroxyethyl) hyd oquinone, triols or for example 1,2,4- or 1, 3,5-tr ihydroxycyclohexane, glycerol and trimethylolpropane and ds pal ialqui oxides containing hydroxylated ds under molecular psso based on ethyl esters oxide and / or ds 1,2-propylene oxide and the aforementioned diols and / or triols as initiator molecules. If ss employ chain sxtsndedorss, crosslinkers or mixtures thereof for the production of rigid foams based on isocyanate, if used prsfsrsncia sn with an amount of up to 20M in psso, prsfßrsncia of 2 to B% sn weight, sn bass to the weight of campasnts (a ). b) As an expanding agent, it prefers to use water that removes the carbon dioxide by reaction with the isocyanate group. The water content, in particular, gives 0 to 4% by weight, preferably from 0.3 to 3% by weight. psso, particularly 0.5 to 2 '/ by weight, based on the total mass of all active hydrogen compounds. An excessively high amount of water can cause greater fragility and higher thermal conductivity of the foams. In addition to water, you can also use expansion agents that act physically. Particularly, low boiling point hydrocarbons, monofunction alcohols, lower acids, actals or partially halogenated hydrocarbons, known as HCFCs, can be used. It is preferred to use saturated cyclic hydrocarbons and low-boiling saturated acyloids having up to 12 carbon atoms, which may be individually or in mixtures between silos, particularly pentanes, where mixtures of the pentane isomers or the pentane isomers may be used. pure isomers. The amount of hydrocarbons is from 1 to 30 parts by weight, preferably from 16 to 22 parts by weight, particularly from 6 to 12 parts by weight, based on the weight of all the active hydrogen compounds. In addition, the use of psrofluorinated compounds as coexpansion agents is advantageous for some applications. Particularly, perfluoroalkanes are used, preferably n-per-f luoropsnt rto, n-per f luorohep t ño, n-arf luarooc y. The perfluorinated compounds can be used individually or in the form of mixtures. They are used ds prefsrsncia sn a quantity ds 0.1 to 6 partss sn step, in base sn the sum of the camponentes b) to d).

It points out that the perfluarinated campuses are ipsoluble in their polysial component, they are usually emulsified in this component. As sulsifiers, it is preferred to employ (mst) acrylates, particularly those having fluorine-containing side chains, for example, fluorocarbon esters. c) The emulsions of the present invention comprise adam components important for the production of rigid foams of polyurethane, for example, carriers, au.x i 1 iarss and ad i t i vos. The catalysts used are, in particular, compounds that strongly accelerate the reaction of compounds (a) containing hydrogen atoms reactive with polyisocyanates. Preferred are tertiary amines, tin and bismuth compounds, carboxylates of alkali metal and carboxylates. of alkaline earth metalates, quaternary ammonium rooms, s-hydraxi triazines and tris (dialkylaminemet i 1) -fepoies. Especially preferred are tertiary alcohols of formula 1a R 1 R 2 R 30 H, where R 1 and R 2 are aliphatic or cycloaliphatic groups q._ > e have from 1 to 15 carbon atoms or R1 and R2 together form a single cycloaliphatic ring having from 3 to 15 carbon atoms, and the nitrogen atom in the ring and R3 is an aliphatic chain having from 1 to 15 carbon atoms. The carbon chains or rings ds R 1, R 2 and R 3 can also contain heteroatoms with or without sulfur pair or particularly oxygen atoms in the chain. Preferably, R 1 and R 2 together with the nitrogen atom form a structure of piperidine, pyrrolidipate, imidazole or morpholine, an alkaloid of the pyrrole idine / piperidine type or a bicyclic compound, for example an azanorbornane. An example that pusds mention is the compound marketed by Air Products. To form isocyanurate structures in the foam, the usual catalysts for this purpose are used, for example, metal carbons, for example potassium acetate, and other substances as described, for example, in the Kunststaff-Hapdbueh , Volume VII, Polyurethane (Polyurethane), 3rd. Edition, 1993, on page 108. The tasters are preferably in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the a), b) and c). Auxiliaries and additional additives are, for example, surfactants, foam stabilizers, cell regulators, flame retardants, hydrolysis inhibitors and inhibitors. Additional roles regarding the aforementioned initia tial atsrials and other initial materials can be found in the speci fi c literature, for example, in the H.J. Saunders and K.C. Frisch, "High Polymers", Volume XVI, Poi u ethanes (Pol iurstanas) Partss 1 and 2,? Pterscisnce Publishers 1962 and 1964 or bian in the Kunststsffhandbuch, Volume VII, Polyurethane (Polyurethane), Carl Hanser Varlag, Munich, Vienna , anger., 2nd »and 3rd. 1966, 1983 and 1993 editions. For reasons of cost, perfused expansion agents are used only when they can be recovered in the production process. This is the case, for example, in the production of pansls in a vacuum. ss svacuada foam before soldering sp a gas-tight cover »If you use hydrocarbons alone with physical expansion agents, ss are dispersions paricularly sstablss when component a) includes alcohols palisers that have a greater function than 1.5, preferably ds 2 »5 to 3» 5, and a hydro ilo number of 10 to 10 Og / KOH / g, preferably 25 to 50 mg KOH / g »These polyether alcohols are used, in particular, an amount from 1 to 50% by weight.

If only water is used as an expanding agent, the emulsions are prepared by simply mixing the a) to c). Even though the emulsions have, as described above, a very long shelf life, it may be beneficial to generate it only just before the formation of foam., for example, in the mixing head of the foam forming machine. The emulsions of the present invention mainly have the appearance of milky, cloudy liquids, but they can also render a transparent appearance to the naked eye. The invention is illustrated by ds the following e em. Raw materials used: Polial 1 Polials: palisate alcohol prepared from 25.2 parts of sorbitol and 74.8 parts of pyrylene oxide using KOH as a catalyst and 0.5 parts of water or co-initiator. The hydroxyl number (OH number or OHN) is 495 mg KOH / g, the viscosity at 20 ° C is 17,900 mPas. Functionality: 5. Polyol 2: polyether alcohol prepared from sucrose / gi icerai / water and pyrylene oxide, hydroxyl number 490 mg KOH / g, viscosity at 20 ° C 8000 mPas, functionality: .3 Polial 3: polyether alcohol prepared from sucrose (1 part), pentaerythritol (1 part), diethylene glycol (2 parts), water as initiator and propi isine oxide using KOH co or hydroxyl index catalyst 400 g KOH / g, viscosity a .0 ° C, 220 <; Paliol 4: alcohol ds psiieter prepared from 28.0% ds a szcla of 2,3- and 3, 4-tol i lendiamin, 22.0K of ethylene oxide and 50% of the optic acid using KOH co or catalyst. The OHN is 395 mg KOH / g, the viscosity at 20 ° C is 8176 mPas »Polial 5: polyester alcohol prepared from dico acid / anhydride acid / oleic acid in a ratio of 1: 2: 1 and 1, 1, 1-tr imet i lalpropane to provide an average molar mass of 530 g / mol, a hydraxyl group of 385 mg KOH / g and a viscosity at 75 ° C ds 1370 mPas. Polyol 5a: ds polyester alcohol derivative ds glycosol and castor oil qus tisne a hydroxy ids ds 500 mg KOH / g. Palial 5b: polyester alcohol derived from manoet i lengl icol and fatty acid from aceits ds pulpa ds wood and having a hydroxyl number of 161 mg KOH / g. Polyol 5c: Pali ester alcohol derived from tri etiolpropane and fatty acid ds acsite ds pulpa ds wood and having an index ds h idraxi lo of 293 mg KOH / g. Paliol 5d: polyester alcohol derived from glycerol and fatty acid from wood pulp oil with a hydroxyl number of 310 mg KOH / g. Polyol 5e: polyester alcohol dsrivado ds glycerol and castor oil and tißns a hydroxyl ipdice of 357 g KOH / g. Polyol 6: prepared from gliceroi co or initiator using propylene oxide as block primer and ethylene oxide as the terminal block and w has a hydroxylam number of 35 mg KOH / g and a viscosity of 850 mPas at 20 ° C. The mass ratio of prapilene oxide is 6.4. Polyol 7: Polyether polyester having a hydroxyl number of 460 mg KOH / g, a molecular weight of 470 and a functionality of 3.9, prepared by the reaction of e-lendiamine with propylene oxide. Psl iol 8: Palial da paliétsr which has a hydroxy values of 490 mg KOH / g, a molecular weight of 490 and a functionality of 4.3, prepared by the reaction of a mixture of sucrose, glycerol and water with propylene oxide. Palial 9: Palolimeter Pal that has a hydraxyl index of 555 mg KOH / g, and a function of 3.0, prepared by the reaction of tr i and lolpropane with prapiene oxide. Palial 10: Polyether polyester qus has a hydroxyl number of 400 mg KOH / g, a molecular weight of 420 and a functionality of 3.0, prepared by the reaction of glycerol with prapylene oxide. Sacyanate 1: Pol isocyanate, Lupranat (mr) M 20 (BASF AS), a mixture of diisocyanate ds difsni Imetapa and polyisocyanates of psilone ifenilpal imethylene that have a content of NCO ds 31.7 * 4 and a viscosity d? 209 mPas at 25 ° C. Isocyanate 2: Pol isocyanate, Lupranat (mr) M 50 (BASF AS), a di-diisocyanate mixture of di-methane and poly-phenyl-isocyanate isocyanates having an NCO content of 31.5 * 4 and a viscosity ds 550 mPas at 25 ° C. Experimental procedure Evaluation of the stability of the emulsion: After emptying the emulsion for 160 ml in a test tube having a diameter of 3.0 c and a height of 20 cm, the test tube is closed with a stopper and left to stand at room temperature. It observes the formation of separate phases sn dsl time function »Production and testing ds ias rigid foams ds paiiurstana or polyurethane / poly isocyanurate. Training in a cup; Components A and B were controlled by thermostat at a temperature of 20 ° C • +/- 0 »5 K» 240 g of components A and B were mixed for 10 seconds at 1750 revolutions per minute in a cardboard cup having a capacity ds approx imadamßnte 660 ml em leando a lab agitator dß Vol Ir th, diameter 65 mm. The ratio between A and B corresponds to the respective formulation. The component A ss a prsmezcla ds the palióles employees, auxiliaries and if agent of expansion, whereas if component B consists of dsl pol i isacianata. Crsma formation time, elevation time, fiber formation time are measured in known manner in the foam elevation and foam density, also known as density in the boards, is measured in a manner known as cured foam. The figure of the cells was compared visually and was estimated as "fine cells" (FC) or "very fine cells" (VFC). A comparison with microscopic measurements shows that the diameter of the cells for "FC" is ds 300 um to 400 u and for "VFC" as less than 250 μm. Particularly, thin cell foams (PFCs) have a cell diameter less than 180 μm. Production and molded elements of rigid foam The mixing is carried out using a high pressure foam forming machine PUROMAT (mr) HD 30 in an ELASTOGRAN manner. Other machines are indicated separately. The mixing ratio is established according to the formulation. Foams of predominantly closed cells: Ss empty 576 g of the mixture of component A and isacianata ds leaving the mixing head in a mold that has the following dimensions: 300 mx 400 mm x 80 mm (mol ds 9.6 1) and ss heated to 45 ° C, and the mold ss subsequently closed hermetically. The foam is formed with a compaction ds l »í a 2.0» The global density of the cursed object is 60 +/- 1 kg / m3 »In other variants, a global density ds 70 +/- 1 kg / m3 is established or bisn 80 +/- 1 k / m3 by adding 672 g or 768 g ds the mixture of foam formation sn itself mold, with a compaction of 1 »5 to 2» The index of NCO, vi z »the proportion mole of the NCO and the active hydrogen groups and the fiber formation time were kept constant for the comparators and for the sjem according to the present invention. After a mold removal time of 30 minutes, test samples were cut from the inner part of the foam block after 24 hours in order to measure the thermal conductivity and resistance to thermal distortion. The thermal conductivity at room temperature was measured using an ANACQN Model 88 instrument from Anacon, St. Peters Rsad, Maidsnhead, Berkshirs, England, at an average temperature of 23.9 ° C (gradients: 37.7 ° C / 10 ° C) and the thermal conductivity at temperature elsvada was measured using a Rapid-k VT 400 ds Halametrix instrument Inc., Boston, United States of America. In this measurement, the temperature gradient was varied within wide limits and this is also indicated in the tables. The thermal conductivity was measured 24 hours after the formation of foam (storage at room temperature) and also after open storage for 80 ° C diffusion for 120 hours. The resistance to thermal distortion was measured as a percentage of deformity in some samples according to DIN 18164 »of 50 mm x 50 x 50 mm after loading at 0.04 N / mm2 for 24 hours. The test temperatures are indicated in the tables. For some PUR / PIR formulations, 2.5 liter aluminum pressure flasks were charged with 250 g of the foaming mixture (corresponding to an overall density of 100 kg / m3), the bottles were closed tightly and the stored at 200 ° C for 4 weeks, in some cases at 220 ° C for 2 weeks (vial test). The foam was then evaluated visually. In manual tests of formation of foams similar to the formation in a cup, aluminum bottles correspondingly smaller were used sn as to sizes with a volume of 0.5 1 with 50 g ds mixture. Foams of mainly open cells. Formation of foam in a cup: The palladium component A and the component B of isacyanate were controlled in a thermostat at a temperature of 20 ° C +/- 0.5 K. SO g of the components A and B ss mixed for 10 seconds to 1750 revolutions per minute sn a cup qus tiane a capacity ds ÍIOO my using a laboratory agitator of Vollrath, diametre 65 m. The formation phase of the cream, the time of elsvaci? P, and the time of formation of fibers in the foam at elevation are determined and, after the layer is measured, the foam density formed is determined. 1 ibrsmsnts »Foam formation in machine: The polyalsic acid components in the mixing chamber of a high pressure foam forming machine PURONAT (mr) SV 20 of ELASTOGRAN were mixed and the mixture was introduced into an abyss mold with the following dimensions: 700 mm x 400 mm? 90 mm. After removing the olde, the mixtures were allowed to form foams. Samples can be produced dus prusba without compaction and with compaction, for example 1.1 or bis 1.2. To determine the content of abyssary cells, cell fineness, rssistapeia to compression, modulus E, density of foams and dimensional stability, ss can form samples from the foam blocks. In addition, test samples were cut ds the following dimensions: 190 mx 190 mm x 20 mm from the foam blocks, pretreated for two hours at 110 ° C and under atmospheric pressure or moss-raised bisn and subsequently packed in a bag of gas tight film and evacuated to final pressures ds 0.05 mbar and welded in closed condition. The thermal conductivity was then determined in accordance with DIN 52616 in a Hest Lambda Control A-50 instrument. The content of open cells was determined in accordance with AST MD 28 56-87, method B, in an Accup and c 1330. In the following tables the results of the foam formation tests according to the present invention are compared with examples that they are not in accordance with the present invention.

Ahem 1 and 2 Number 1 comp. the comp, 2 ds conformity with the present invention paliol 5 35.61 psliol 1 25.61 57 »22 palial 6 31.61 31.61 dipropilßngl icol 16.65 16» 65 16.65 stilenglical 2.72 mixture of sstabi- 2.56 2.56 2.56 2.56 water i zador 0.38 O.38 0.38 acstato ds potassium 2.41 2.41 2.41 tertiary amine 0.26 .26 0.26 cyclopentane 17.80 17.80 17.80 total IOO.OOOOOOOOOO 100.00 Omp number, 1st comp In accordance with the present invention isocyanate 1 300 300 300 ie a ds farm »18 18 18 ds c sma (s) tismpo ds form» 29 29 29 fibr (s) time 43-43 43 43% density (s) of 64.9 64.9 64.9 foam kg / m3 content da > 90 > 90 > 90 closed cells immediate emulsion stability EEE after 4 h EEE after ds 1 day PP PP E after ds 7 days PC PC E after 3 se- PC PC E manas after ds 2 months PC PC E structures of ss- FC FC PFC pu a E = emulsion without separation ds fasss, PP = separation ds f ses, parc l, PC = separation of f sss, complete, FC = fine cells, VFC = very fine cells ds conformity with visual imaging sst »Tis reaction in the I was recently and ulsified. Axis lss 3 to 6 Number: omp, 4 ds canf, 5 of canf. 6 ds conf. with the one with the prssssnts prsssnts presents ipvenci? n invention invention poiial 5 31.14 31.14 31.14 polioi 5a 31 »14 polial 6 38.47 38.47 38.47 38.47 38.47 dipropilsn- 20.25 20.25 20.25 20.25 glycol ethylene glycol 3.30 3.30 3.30 mixture of 3.12 3» 12 3.12 3.12 water stabilizer O.47 0.47 0.47 0.47 acetate 2.93 2.93 2.93 2.93 potassium amine tertiary- 0.32 0.32 0.32 0.32 ria to l 10 »OO 1 O, 0 1OO» 00 1 »oo Rll 56.3 isopentane 17.0 cyclopstane 17.0 17.0 isa ianato i 390 390 390 390 tismpo ds form. 17 13 18 ds crsma (s> time of fsrm »39 39 36 of fibr (s) density of 51 52 70 foam kg / m3 cantenido ds 90> 90> 90> 90 cells closed conductivity 18.4 19.9 19.9 20.0 thermal in mW / mK at 23 ° C, 7 days emulsion stability immediately EEEE after 4 h EEEE after 1 day PP EEE after 7 days PC EEE structure ds FC FC PFC PFC foam foam test foam foam black bottle light clear 2 weeks, destroyed firm, firm 200aC 1 crack E = emulsion without separation ds phases, PP = phase separation, partial, PC = phase separation, complete, FC = fine cells, VFC = very fine cells ds compliance with the estimation isu l Times of reaction sn if recently emulsified state »Examples 7 and 8 Number 7 in accordance with 8 in accordance with the present invention the present invention paliol 5 25.61 25.61 polyol 6 31.62 31.62 dipropylepgl icol 16.65 16.65 stilsnglycol 2.71 2.71 mixture of stabilizer 2.56 2.56 1 gua leader 0.38 0.38 potassium achate 2.41 2.41 tertiary amine 0.26 0.26 cyclopentane 17.80 17 »80 total 100.00 100.00 TEP 0 11.5 isaci n to 2 320 322 B 2 Test DIN 4102 > 19 cm / B3 12.5 cm / K content of cel- > 90 > 90 closed cells stability ds immediate emulsion E E dssfter ds 4 h E E after a day E E after 7 days E E E = Smulsion without separation of fasss TEP = tr ie i 1 phosphate Component Ex. 9 (C) Ex 10 (gives conf.Ex. 11 (ds conf, ds polyol with the present with the present invention) invention) Pa1 io1 7 20 20 20 Polisl 8 30 20 40 Polyol 9 50 50 30 P Poolliiooll 5 5aa i 10 B8 19 - .. "/ 3 3 B8863Z 1 1 1 FC 430 1 1 Dabco AN 20 5 5 5 Water 0.5 2.3 0.5 Cyclops 7 7 Perfluorohexane 4 4 isaciapata 1 144 145 147 density íg / i) 55.3 54.7 55.0 concentration of 83 lOO 100 open cells canducity 13 7.5 thermal 7.0 sn mW / mK at Ol mbar immediate emulsion stability E after 4 h EEE after 1 day PP EE after 7 days PC EE C = comparison example, E = emulsion without phase separation, PP = phase separation, partial, PC = phase separation, complete.

Component Ex. 12 (of Ex. 13 (ex. 34 (ex. Ex. 15 (of palial compliance conformance compliance conformance with that with the present tense present invention) invention) invention) invention) Pal iol 7 15 15 15 10 Polial 8 17.5 22.5 20 10 Polial 9 41 36 40 43 Polyol 5d 5 14 Paliol 5b 5 Polial 5c B8 19 3 3 3 4.5 E > OOQ? 1 1 l 1.4 FC 430 1 1 1 Dabco AN 20 5 5 5 2.8 Water »5 0.5 0.5 2.2 Ciclapentana 7 7 7 Perfluorahexapa 4 4 4 15 isacianata 1 117 116 149 ISO density (g / l) 55 52 53 55 content of 95 71 73 96 open cells conductivity 7.5 14 13 6.9 ? 0 thermal in mW / mH sta iity of the immediate e. S E E E E after 4 h E E e E ^ 5 after 1 day E E E E after 7 daysEC C = comparison example, E = emulsion without phase separation, pp = phase separation, partial, PC = separation of fasss, complete.

Camponente Ex. 16 (of Ex. 17 (ex. Ex. 18 (ex. 19 of polyol conformity conformance conformance conformance with the one with the present present invention present) i nvenc in) i nvenc i on ) invention) Polial 7 10 10 10 10 Polyol 8 1 1 10 10 Polyol 9 43 43 43 43 Polial 5β 12 12 12 12 Polyol 10 20 20 20 20 Ortsgol 501 3.6 3.6 B 8919; »6 3.6 B 8870 0.8 1.4 Dabca AN 20 Water *? 5 2.3 isocyanate 1 190 1 0 190 190 density (g / 1) 59 58 59 60 content ds 96 96 95 96 cells abyss conductivity 7.8 7.5 thermal 8.1 in mW / mK emulsion stability in ediata EEEE after 4 h EEEE after ds 1 day EEEE after dß 7 daysE EEE C = comparative comparison, E = emulsion without phase separation, PP = phase separation, partial, PC = complete separation of fasss.

Components Ex. 20 (ex. 21 (ex. 22 (polyol d.sub.conformity compliance conformance with that with the present invention). Invention) invention) Polial 5 26 26. Polyol 6 32 ipropylene- 17 gl icol B 8461 1.3 1.3 1.3 B 8409 1.3 1.3 1.3 B 8919 2 UAX 6164 2 Water 0.4 0. 0.4 Lupragen VP 9104 5.1 5.1 5.1 L? Pragsn N 301 0.3 0.3 0.3 Cyclopsinane 18 18 18 isocyanate 2 320 320 320 density (g / l) 65 64 61 content of 3.2 95.6 92.4 open cells conductivity 31 6.9 8.1 thermal sn mW / mK to Ol mbar instant emulsion stability EEE after 4 h EEE after ds 1 day EEE after 7 days EEE C = comparison example, E = emulsion without phase separation, PP = separation of phases, partial, PC = separation of phases, complete,

Claims (9)

1. CLAIMS 1. An emulsion containing an expanding agent, comprising; a) compounds containing hydrophobic atoms that interact with isoeionates, b) agsntss of expansion, c) catalysts, auxiliaries and / or additives common in polyurethane chemistry, where the blowing agents are present in the form of an emulsion in components a) and c), and palyther alcohols of the following structure are used as co-emulsification aids: where = O - 15 n = 0 - 1 a = 0 - 15 P = 0 - 1 q = 0 - 15 r - 0 - 1 s = O - 15 t = O - 1 u. = O - 10 v = O - 15 x = 1 - 5 y = i - a well mixtures of 1-3 dande r + p ss different from O z = O - 3 zi = Ol - 3 Rl is an aliphatic structure without rumps GH, based on the structure of the palihydric alcohols, preferably ethylene glycol, die i lengl icol, tr iet ilengl icol, 1.2-prapi lengl icol and dipropi lengl icol, 1,4-butanediol, 6-hexanediol, neapentilgl icol, 1, 3-butanediol, tri-ethylolpropane, trimethylolethane, glycerol, pentaerythritol, these substances can also be used in any mixture between them in the esterification and Rl puads therefore also be a mixture of the corresponding structures, R2 is the radical of a polycarboxylic acid without COOH groups, for example, adipic acid, tersphthalic acid, orthalic acid, R3 is an alcohol radical as RI.
2. 2. An emulsion containing an expansion agent according to claim 1, wherein the extrusion aids which form the structure I are products of the esterification of naturally occurring substances and alcohols.
3. The emulsion containing emulsification agents containing ds expansion according to the embodiment 1, donds the emulsification aids that have structure I form from .1 to B sn weight of the total a) compounds that can react with isocyanate.
4. 4. An emulsion containing expansion agents according to claim 1, wherein the emulsification aids having the structure I form 5 to 50 * 4 by weight of the total compounds a) which can be reacted with isocyanate.
5. 5. An emulsion containing expansion agents in accordance with the rei indication 1, dande the sraulsif icacióp aids that have the structure I make up from 10 to 20% sn of the total compounds a) qus can react with isocyanate.
6. 6. An emulsion containing blowing agents according to claim 1, wherein compounds a) containing hydrogen atoms that react with isocose are mixtures of compounds of structure I with polials having a functionality greater than 1.5 and a hydroxyl number of 10 mg KOH / g to 600 mg K0H / g «
7. 7. An emulsion containing blowing agents according to claim 1, where the compounds containing hydrogen atoms that react with isocyanate are mixtures of compounds which they have the structure I and products of the reaction of trimeti lalprapana and alkylene oxides.
8. 8. A process for the production of rigid polyurethane foams of closed cells and open cells by the reaction of emulsions containing expansion agents according to that claimed in rei-indication 1 with polyisocyanate.
9. 9. The use of alcohols of palésésr ds formula S bed emulsifiers for stable emulsions, which cantisnsn agents ds expansion, for the production of rigid foams based on isocyanate. SUMMARY OF THE INVENTION Emulsions containing expansion agents comprise: a > campuses that are hydrogen atoms that react with isacyanates, b > d) expansion agents, c) catalysts, auxiliaries and / or additives common in the chemistry of paliurethane, where the expansion agents b) are present in the form of an emulsion in the components a > and e), and polystyrene alcohols of the following structure are employed with emulsification engines: where m = O - 15 n = 0 - lo = O - 15 p = 0 - 1 q = O - 15 r = O - 1 s = O - 15 t = O - 1 u = O - 10 v = 0 - 15 x = 1 - 5 y = l - 4 or mixtures of 1-3 where r + n ft 2 = 0 - 3 zi = 0.1 - 3 Ri is an aliphatic structure without OH groups, based on the structure of polyhydric alcohols, preferably ethylanglion, diisocyanol, triethylglycol, 1 * 2-propylene glycol and dipropylene glycol, 1, 4-bu.tapdiol, 1,6-hexandial, neopentyl glycol, 1,3-butanediol, tri-ethylolppars, trimethylolethane, glycerol, pentaerythritol, where these substances can also be used in any mixture of these, in the asrification, and Ri can therefore also be a mixture of the corresponding structures, R2 is the radical of a polycarboxylic acid without COOH groups, by ejsmpls, adipic acid, tsrsphthalic acid, oidophthalic acid, P.3 as an alcohol radical as Rl.