MXPA98007791A - Rigid foams thermically stable based on isocyanate and low fragility low and low conductivity term - Google Patents

Abstract

Thermally stable rigid foams based on isocyanate can be produced by the reaction of: a) polyisocyanates with b) compounds containing at least two hydrogen atoms that can react with isocyanate groups, c) water, in the presence of d) physically active blowing agents , in the presence or absence of e) catalysts and auxiliaries and / or additives, wherein component b) comprises bi) at least one polyether alcohol having a functionality of at least 1.5 and a hydroxyl index of 10 to 100 mg KOH / g in an amount of 0.2 to 80% by mass, based on ab), and bii) at least one polyester alcohol in an amount of 5 to 90% by mass, based on ab), water c) is present in a amount of at least 2% by mass, based on the sum of components b) to e), and component d) employed hydrocarbons and / or hydrocarbons containing fluorine in an amount of 5 to 30% by mass, based on the sum of the components b) a

Description

THERMALLY STABLE, RIGID FOAMS BASED ON ISOCYANATE AND WITH LOW FRAGILITY AND LOW THERMAL CONDUCTIVITY The present invention refers to 3 thermally stable sheets based on low brittleness and thermal conductivity, said foams have been produced without the use of expansion agents that damage the ozone layer. The production of rigid foams based on isocyanate as thermal insulation material has been known for a long time. The most important chemical starting materials for such compounds are functional isacianates. Chemical structures formed from the pallets of the saccyanates can be polyurethanes, polyureas, polyisocyanates and additional isocyanate adducts, such as, for example, born, biurets, carbodiides and their adducts of isacianata, oxazole and dopamine, paliimides, pal iamidas, etc. The type of antler structures is controlled by the reaction partners of the isocyanates, the catalysis and the reaction conditions. These isocyanate adducts are often summarized under the term rigid polyurethane foams < PUR), since polyurethanes are the largest and most important group of materials among the palpation adducts. Foams having a nificative content of isocyanurate structures are frequently known as urethane-poly-isocyanurate-PU-PIP foam foams. The production of foams of this type is described, for example, in e \ unststof f-Handbuch, vol '-men VII "pol íurethane" .polluo), 3rs. edition, edited by Günter Oertel, Carl-Ra f.ser-see lag, Munich, Vie a, 1993. Recently, rigid foams have been requested which have a very high thermal stability for the thermal insulation of pipes that carry very hot media. They must withstand temperatures of 180 ° C for more than 10 years. This means uis-,. In a warm storage experiment, the foams should remain without detectable damage for four weeks at a temperature of 200 ° C or for two weeks at a temperature of 220 ° C. Such high performance materials are required only for the isolation of heating pipes but also, for example, for space flights. At the same time, the foams still have a very low thermal conductivity at these high temperatures. However, the thermal resistance of foams based on isocyanates is usually limited. For example, if predominantly urethane groups are present in the foam, a long-term thermal resistance can be achieved for more than 10 years at only 500 ° C, which, in a storage test, corresponds to four to six weeks at 1H0. ° C, afn when very strong crosslinking polyals are used. At a temperature of 200 or 220 ° C, the foam is destroyed after only a few hours in the test. BÍ JO a load (iie Siuci e 0. N / m ..? 2 during 24 harp-ñ, in accordance with DIN --- Bí ^ ^ 70 5-g m3, these foams are stable up to a maximum of 170 * C .

In the case of PUP-PIP foams, thermal stability can be improved by raising the polyacrynatane content, but the friability of the foams is greatly increased. After storage for several weeks at 200 ° C or at high temperatures, the foam is so fragile that it breaks into small parts even with small mechanical loads. An additional disadvantage of previously known isocyanate-based rigid foams is excessively high thermal conductivity at high temperatures. Low thermal conductivity values are achieved using chlorofluorocarbons (CFCsJ as expansion agents, however, even when these expansion agents are used, they are no longer allowed due to their potential ozone destruction potential. (GWP), the thermal conductivity of rigid foams, for example in accordance with that described in GB-A-2,041, 953, CH-A-527 855 or EP-A-24 524, is increased to an undesirable level at high temperatures.

As an alternative to CFCs that damage the environment, it has been proposed, for example, the use of expansion agents that have only carbon, hydrogen and fluorine in the molecule. An additional alternative e.-pansion agent is water. However, even these foams described, for example, in US-A-5, 38, 768 are stable for only 10 years at a temperature of about 140 ° C at the usual densities within a range of 60 to 80! < g / m3. Hydrocarbons, for example, pentanes, are also suitable as alternative expansion agents that act physically, but also cause the formation of rigid foams that have increased thermal conductivities. In addition, the flow capacity of these foams, as described, for example, in DE-A-42 22 519, is very limited. All previous foam formulations meet the requirements of high thermal resistance combined with very low brittleness and thermal conductivity even at elevated temperatures. It is an object of the present invention to provide rigid foams based on isocyanate which have a high thermal stability and a thermal conductivity and unsupervised. low fragility at high temperature, and that can be produced using expansion agents that do not harm the environment and that can be produced using conventional technology for the production of such rigid foams. We have found that this object is achieved through the use of sa) polyester alcohols -which have a functionality of at least 1.5, preferably 2.5 to 3.5, and a hydroxyl index of 10 to 100. mg! < OH / g, preferably 25 a. 50 mg KOH / g, in an amount of 0.2 to BOY. in bulk, preferably from 1 to -60% by mass, and particularly from 20 to SOY. in mass, in each case based on the palióles, b > alcohols ds polyester in an amount of 5% by mass to 90 *; in mass, gives preference of 20! mass by mass%, based on paliols, c > water in an amount of a maximum of 2 * 5 in m, preferably from 0. to t.6% by mass and particularly from 0.3 to IV * in mass based on the polio component, and d) expansion agents that they typically act as compounds of the carbon and hydrogen elements and / or of the carbon, hydrogen and fluorine elements in an amount of 5 to 30% by mass, preferably 10 to 25 * 4 by mass, based on the polyol component . The present invention therefore provides rigid foams based on isocyanate and having high thermal stability and low thermal conductivity and low brittleness at high temperatures, which can be produced by the reaction of: a) polyisocyanate with b) compounds containing 3.1 minus two hydrogen atoms that can react with groups i i i, c) agu. sn p e ti i-i d) expansion agents that act physically, in the presence or absence of e) catalysts and auxiliaries and / or additives, where the component b > comprises bi) at least one polyether alcohol having a functionality of at least 1.5, preferably 2.5 to 3.5, and a hydroxyl number of 10 to 100 g KOH / g, preferably 25 to 50 mg KOH / g , in an amount of 0.2 to 80% by mass, preferably from 1 to 70% by mass, and particularly preferred from 20 to 60% by mass, in bsse to component b), and bii) at least one alcohol of ps lstar in an amount of 5 to 90% by mass, of reference of 20 to 60% by mass, in each case in base ab), component c) is used in one. amount of at most 2% by mass, preferably from 0.2 to 1.6% by mass and particularly from 0.2 to% by mass, based on the sum of the components b > ae) and the comparator d) employed comprises hydrocarbons and / or hydrocarbons containing fluorine in an amount of 5 to 30% by mass, preferably 10 to 25% by mass, based on the sum of the components b) aa) .

As pallet ether alcohols bi), preference is given to the use of pallet alcohols which can be prepared according to methods known per se by the addition of propylene oxide and / or. ethylene oxide in initiator molecules with function 2 or polyfunction l.es, co or is described, for example, in Kunststoffhandbuch, loe, cit.,. pages 57 to 67. Suitable initiator molecules are, apart from water, all organic molecules containing active hydrogen atoms for Zera-ni tinoff. Examples that may be mentioned are ethylene glycol, dietary and lingual, propylene glycol, diphtheria glycol, glycerol, trimethylol lolprapane (TMP), et i lendiamine, tolylenediamine (TDA), triethanolane, peptaer iti tol, sarbitol, mannitol or good sucrose Paliols with function 2 to 3 are preferably used. It is also possible to use a mixture of polyols as component bi). These are obtained, for example, by the use of mixtures of initiators, for example, the addition of small amounts of water to the organic initiator molecules. The mixture of palióles is also possible. Adducts of prispile oxide and ethylene oxide in glycerol. or TMP are preferably used as component b). The alkylene oxides may be randomly distributed in the chains or blocks may be present, preferably with terminal ethylene oxide block. The polyester alcohols used in accordance with the present invention preferably prepare the reaction of polyfunctional alcohols with organic aromatic acids, at least bi functional and / or at least bifunctional organic acids containing doubles. bonds and / or at least bifunctional aliphatic carboxylic acids. The hydroxyl number of the polyol alcohols is preferably greater than 150 mg f-OH / g, particularly in the range of 200 to 600 mg KOH / g. Examples of polyester alcohols according to the present invention are products of the reaction of phthalic acid and / or terephthalic acid and / or isophthalic acid and / or adipic acid and / or aleic acid and / or ricinaleic acid with glycerol / or trimethylolpropane and / or ethylene glycol and / or diethylene glycol and / or propylene glycol and / or diprsp i lengl icol and / or pentaeptritol. Polyester alcohols having fatty acid esters are preferred, particularly those having 1 or more double bonds in the molecule, with those having unsaturated fatty acids, aromatic dicarboxylic acids and dicyklic acids being particularly preferred. aliphatic icos in a molecule. Expansion agents that act physically employed are, as described above, hydrocarbons and fluorine hydrocarbons.

For purposes of the present invention, hydrocarbons are the compounds that contain only the carbon and hydrogen elements - ^ p the molecule. P < < To the rigid foams of the present? Nver. > -? ón, is preferable to those who have from 3 to 10 carbon atoms in the molecule, particularly marshes, preferably cyclopentane, as fluorinated hydrocarbons, they prefer Specifically, those with 2 to 6 carbon atoms in the molecule, for example pentaf, luaropropane, pantafluarobutane and tetrafluoroethane- The physically acting expansion agents mentioned can be used either individually or as bed mixtures. Expansions that act physically, free of hl? gepa, additional, in mixtures with the hydrocarbons and hydrocarbon fluopnadss described.Examples are methyl, methyl, alcohols of ba or molecular weight, diethyl ether, acetone. components bx) and bii), additional compounds containing active hydrogen atoms may be present in compound b) in an amount of at least 50% by mass, based on the mass of campanent b). These can be, on the one hand, the known and customary palioles for the production of rigid foams, for example pallatheric alcohols which have a functionality of at least 3, preferably of at least 3.5, and a water index. The amount greater than 100 mg / OH, in particular greater than 300 mg KOH / g which can be prepared by the addition of ethylene oxide and / or partially, or propylene oxide in initiator substances with a functionality of at least 4. , for example, aromatic amines such as tolylene iamine or diphenylmethane, or compounds containing hydralapoly, such as, for example, sorbitol, sicrase, anitol, lignin, phenol condensates and idle farm. On the other hand, they can be strongly branched polyester alcohols, which preferably have functionalities of 4 lO and hydraxylates of 150 to 400 mg K.OH / g. Components b) also include chain extenders and / or reticlers. The chain extenders employed are bifunctional alcohols of b or molecular weight, particularly those having a molecular weight of up to 40O, for example, ethylene glycol. , propi lengl icol, butandial, hexandiol. The crosslinkers used are at least optional, low-molecular-weight alcohols, for example giicerol, trimetheolpropane, pentaer, tri-tol, sucrose or sorbital. The components bi) and bii) according to the present invention can be soluble or insoluble in the other components of component b). The e.p-msion agents that act f icamen d) can also be soluble or irtol? Bl s in the items b) to e) and their mixture. With the use of the usual and known aliphatic polyisocyanates and particularly suitable polyisocyanates, the di-methane di-methane di methane (DM1) mixture is preferred, and particularly mixtures of MD1 and isocyanate polysaccharides are preferred. pol ifeni Ipol imet i lena (raw MDI). The catalysts used are the known compounds which accelerate the reaction between isacyanate groups and hydroxyl groups, for example tertiary amine catalysts such as, for example, lamellar imidels, imidazoles, orphans or heavy metal compounds, for example organic compounds of tin. If isocyanurate groups are to be formed, additional catalysts are added which catalyze the isocyanurate formulation, for example potassium acetate. Examples of auxiliaries and / or additives are stabilizers, cell regulators, flame retardants or re-lumbering agents. Complete information on the individual form components can be found, for example, in Kunstoff-Handbuch, loe. cit.

The molar ratio between the NCO groups and the hydrogen atoms that can react with NCO groups, known as the índio-i, is QP 1.5 a, 1 preferably 2.8 to 4., in the case of highly rigid foams, and 1.5 to 2.8 in case of more flexible rigid foams. The rigid foams of the present invention have excellent thermal stability. Even at high temperatures, the thermal conductivity is low. Due to the good flowability, forms still compiled with the foam can be filled. The foams of the present invention are very suitable for the insulation of long-distance heating pipes or for sandwich elements carrying loads. The invention is illustrated by means of the examples. next. Raw materials used: Pallas Psl iol Pthalioster Alcohol prepared from adipic acid / anhydridic acid / oleic acid at a ratio of 1: 2 to 1, 1, 1-t imet i lalp opane and with a molar mass average of 530 g / mol, a hydraxyl index of 385 mg KOH / g and a viscosity at 75 ° C of 1370 mPas Poliol Ib Polyester alcohol prepared from castor oil and glycerol and having a hydro of 500 mg KOH / g Pal iol.es 2 Polyol 2a, prepared from glycerol as initiator and propylene oxide as first block and ethylene oxide camo terminal block and having a hydroxyl number of 35 mg K.OH / g and a viscosity of 850 mPas at 20 ° C. The mass ratio between propylene oxide and ethylene oxide is 6.4, Polyol 2b, prepared from trimethylolpropane primer and propylene oxide as the first block and oxide of ethylene co or terminal block and having a hydroxyl number of 26.5 mg K.OH / g and a viscosity of 1225 mPas at 20 C. The mass ratio between the pyrylene oxide and the oxide of et i 2c, prepared from glyceral as initiator and propylene oxide as the first block and ethylene oxide or terminal block and which has a hydroxyl number of 28 mg KOH / g and a viscosity of 1130 mPas at a temperature of 20 * C. The mass ratio between propylene oxide and ethylene oxide is 6.1. 2d, prepared from polypropylene or initiator and propylene oxide and having a hydroxyl number of 55 g K.OH / g and a viscosity of 325 Pas at 20"C. ready camo one. mixture of lignin and onoet i lengl. terminal block and having a hydroxyl number of 50 mg K.0H / g and a viscosity of 850 mPas at 20 ° C. 2f, prepared from propi lengl. icol as initiator and propylene oxide as the first block and ethylene oxide or terminal block and having a hydroxyl number of 29 mg KOH / g and a viscosity of 780 mPas at 20 ° C. The mass ratio between propylene oxide and ethylene oxide is 4.4. Palial 3, prepared from 25.2 parts of sarbitol and 74.8 parts of prapi lena oxide using potassium hydride, catalyst bed and 0.5 parts of water as co-initiator. The hydroxy ia value is 495 mg K.OH / g, the viscosity at 200C is 17,900 mPas and the functionality is 5. Ssoc iana.to 1 A mixture of diphenylmethane diisocyanate and polyisocyanates of pol if ni Ipol imeti They have an NCO content of 31.7% and a viscosity of 209 mPas at 25"C. Isocyana to 2 A mixture of diisocyanate and diphenyl ethane and polyisocyanates of polyphenol Ipol imet i leno having an NCQ content of 31.5% and a viscosity of 550 mPas at a temperature of 25 ° C. Isocyanate 3 A mixture of diphenylmethane diisocyanate and polyphenol polyisocyanates with an NCO content of 30.5% and a viscosity of 2200 mPas to Production and testing of rigid poly foams. iuretañopo1 i i oi nurato; Formation of foam in a cup: Components A and B were controlled by thermostat at 20 ° C +/- 0.5 K. 78 g of component A and component B were mixed for 10 seconds in a cardboard cup having a capacity of Approximately 660 ml using a laboratory stirrer (rotation speed of 1750 rpm) equipped with a Vol Ira th impeller (diameters 65 mm). The proportion between component A and component B corresponded to the proportion of the respective formulation. Component A was a premix of the polyals used, auxiliaries and the blowing agent while component B consisted of polyisocyanate. The time until reaching a creamy appearance, the time of expansion and the time to obtain fibers, allowed for is.npfj > - > -no --- < The foam in the foam was rising and the foam density, also known as density in the boards, was measured in a known manner in the cured foam. Fragility was evaluated manually. The fineness of the cells was compared visually and was estimated as "fine cells" (FC) and "very fine cells" (VFC). A comparison with myreoscopic measurements shows that the diameter of the cells in the case of "FC" is 300 μm to 400 pro while each "VFC" is less than or equal to 250 μm. Production of molded objects of rigid foams and their verification The mixing was carried out, unless otherwise indicated, using a maximum deformation of high pressure foam PUROMAT R) HD 30 of Elastogran. The mixing ratio was established to correspond to the formulation. 576 g of the mixture of component A and isocyanate leaving the mixing head of an alde of 300 mm x 400 mx 80 mm (mold of 9.6 1) heated at a temperature of 4 ° C were drained, and the mold was Subsequently closed hermetically. The foam was formed with a csmpactation of 1.1 to 2.0. The overall density of the molded object was 70 +/- 1 kg / m3. In other variants, an overall density of 70 +/- 1 kg / m-3 or 80 +/- 1 g / -3 was attained by placing 672 g or 768 g of the mixture and the um ^ ^ n the same mold, with a range of 1.5 to 2. The NCO ín ie, viz. the molar ratio of NCO between the groups with active oxygen, the time for fiber formation were kept constant for the comparative examples and the examples according to the present invention. After a 30-minute demoulding time, ss cut test samples from the inner part of the foam block after 25 hours with the purpose of edging the thermal conductivity and thermal distortion resistance. In an additional variant, the foam that came out of the machine was either formed in foams freely in a cubic mold of 10.5 1 open at the top and which had an edge length of 21.9 cm or were placed small shot, one on top of the other, in layers with a thickness of approx. 2 cm. In the case of the formation of machine foams, very small cells smaller than 150 μm can be produced by using the formulations according to the present invention? the size of the cells was considered as "VFC" or described by the value determined directly by microscopy. The thermal conductivity at room temperature was measured using an Anacon model 88 instrument from Anacon, St. Peter Poad, Maidenhead, Berkshire, England, at an average temperature of 23. "C-gradient 37.7 C / 10 <; 1C) and thermal conductance 3 elevated temperature was measured using a Rapid-t VT 400 instrument from Hala etrix Inc., Boston, United States of America. In this measurement, the temperature gradient can vary within a wide range and is also indicated in the tables. The thermal conductivities were measured 24 hours after foam formation and also after > Open storage for diffusion for 120 hours at 80 ° C. The resistance to thermal distortion was measured as percentage deformation in accordance with DIN 18164 in samples having dimensions of 50 m x 50 mm x 50 mm after falling to 0.04 N / mm2 for 24 hours. The test temperatures are indicated in the tables. For some PUR-PIR formulations, aluminum pressure jars of 2.5 13 tros were loaded with 250 g of the mixture > The formation of foam (which depends on an overall density of 100 kg / m3), closes said bottles tightly and stored at 200 ° C for 4 weeks, sometimes at 220 ° C for 2 weeks ( flask test.) Subsequently, visual foam was evaluated.In manual experiments in the form of foam>, it was necessary to use vials correspondingly smaller than those with a volume of 0.5 1 with 50 μm. g of reaction mixture The following tables show the results of the foam formation tests according to the present invention compared to the non-canfarmide examples with the present invention: Examples 1 to 6 (foaming) It can be seen from the examples 1 to 6 that only the combination of polyols according to the present invention can be compared with the ductile, relatively non-fragile foams that it has. very thin cells as pr e-requi it for low thermal conductivity. Formulations of rigid foams > PUR-PSR. The parts are provided in bulk, the stabilizers are from B > oldsch idt FC = thin cells, VFC = very thin cells, B = fragile, VEP = very easily sprayable, that is, extraordinarily fragile, T = robust, that is, it can deform without destruction, C = comparative example. Example KC) 2 (C) 3 4 5 6 Pol iol la 57.22 25 .61 25.61 25.61 25 .61 25 .61 Pol iol 3 31 .61 Po ial 2 a 31.61 Polisl 2b 31.61 Polyol 2c 31.61 Polyol 2d 31.61 Dipropi len- 16 .65 16 .65 16 .65 16.65 16 .65 16.65 gl icol Efe ilen- 2-.72 • ^ .72 2, .72 2, ~ 7- ~? l Mixing of * "? .56 .56 2, .56 - £, xJC, 2, .56 2.56 Stabilizers Water O, L OOO O, i Of O, i / 0 kx 38, .38 .38 Acetate of *? .41 2, .41 .41 2.41, 41 -4 »i potassium Amina 0. .26 O, 26 0. .26 0.26 0. -26 0.26 ter» ?: iaria Cyclopentane 17, -SO 17. SO 17. 80 17.80 17.eo 17.80 Total 100., 00 100. -00 100. .00 100.00 100., 00 100.00 Isoci nats 1 300 300 300 300 300 300 Time of 17 15 8 19 17 18 cream formation in s Time of 26 25 29 29 29 28 fiber formation in s Time of 40 39 43 44 43 42 elevation in S Density of 70 66 65 63 68 66 foam in kg / m2 Frility VEP VEP TTTT Structure FC FC VFC VFC VFC VFC foam Example »-3S 7 to 10 Training > of foam in a cup / mixed manual for bottle test Formulations of foams ri »3i > d s PUR-PIR, the parts are provided en masse, the installers are > ~ te Goldschmidt, FC = fine cells, VFC = very thin cells, T = robust, that is, it can deform without destruction, C = comparison example Example 7 (O 8 Polisl la 31.14 31.14 Paliol ib Pal iol 2a 38.47 38.47 Dipropi lenglical 20.25 20.25 Etilen licol 3.30 3.30 Stabilized mixture 3.12 3.12 Water 0.47 .47 Potassium acetate 2.93 2.93 Tertiary amine 0.32 0.32 Tot l 100 100 R 11 56.3 Isopentane 17.0 Cyclopentane Isocyanate 1 390 390 Time of cream formation at s Time > Fiber formation in s Time »Rie elevation 39 in s Foam density 51 in kg / m3 Fragi 1 idad TT FC FC foam structure Full bottle formation training - 2 weeks, 200ßC foam black, destroyed clear, firm, a gieta E j e p 1 or 9 10 Poli >; .l the 31.14 Polyol Ib 31.14 Polyol 2a 38.47 38.47 Dipropi lei lolol 20.25 *? ^ 5 E i lengl icol 3.30 3.30 Mixture of is tab i Left 3.12 3.12 Water 0.47 0.47 Potassium acetate 2.93 ¿- * Of A. na te i i .32 0.32 Total 100 100 R 11 Isopentane Cyclopentane 17.0 17.0 Isocyanate 1 590 90 Time > - formation 18 of cream in s Training time 40 fiber in s Lifting time 36 in s Foam density 70 76 in kg / m3 Fragility TT Foam structure VFC VFC Test ds bottle foam color foam color 2 weeks, 200 * 0 cl ra, of course, firm fi Examples 11 to 14 Foam forming in the machine Formulations of rigid foams PUR-PIR, the parts are provided in bulk, the foundations are »------» -----) es de ßoldsch idt , PUPOMAT (R) SV 20/2, foam-free formation in cube of 10.5 1 and formation in mold foam TC = thermal conductivity in mW / mK. , HDR = resistance to thermal distortion in accordance with DIN 18164? Load 0.04 N / mm2, 24 h. "free" = free-foam formation, temperature gradients in TC measurements: TC 23 * C? 10 ° C / 36 ° C, TC 95 ° C (the sample was heated to 800 ° C for 120 hours while it was open for "diffusion =" heated "); 140 * C / 50 ° C, C = comparison example Example 11 (O 12 Polyol 25.61 25.61 Polyol 2a 31.62 31.62 Dipr> api iengl icol 16.65 16.65 Ethylene glycol 2.71 2.71 Mixture of 2.56 2.56 stabilizer Water 0.38 .38 Acetate 2.41 2.41 pota io Tertiary amine 0.26 0.26 R 11 34.8 Cyclopentane 17.8 HFC 245 fa Total 117.00 100.00 Isocyanate 1 O00 500 Isocyanate 2 I acia ao 3 Cream formation time in s Formation time 11 fiber in s Lifting time 50 18 in s "Free" density 54.9 in kg / m-3 Properties for molds of 9.6 1 Density, kg / m3 70 70 TC 23 ° C, 7 days 18.4 19.9 TC 23 ° C, heated 25.6 24.4 TC 95ßC, heated 37.3 35. -3 Cell diameter 230 133 μm HDR, ¡.00 * C, 9.3 8.2 Black foam bottle test, clear foam 4 weeks, destroyed 200"C tot coffee, firm, 220 ° C destroyed cracks Example 1o 1 Polio !, the .61 25.61 Polyol 2a 31 .62 31.62 Dipropi lengl icol 16 .65 16.65 Et ilengl icol 2, .71 2.71 Mixture of «56 2.56 stable A Agguuaa 0 0 ,, .3388 0.38 Acetate 2, .41 2.41 potassium Tertiary amine 0,, 26 0, R 11 C Ciiccllooppeennttaannoa 17., .88 HFC 245 fa Total lOO. 00 100. OO Isocyanate 1 Isocyanate 2 300 I Issaacciiaannaattaa 33 500 Training time 5 8 of cream in s Training time 9 12 of fiber in s Eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee 1188 20 * 7" in s Density "free" 38, in kg / m3 Properties for molds of 9.6 1 Density, kg / m3 70 100 TC 23 * C, 7 days 19.9 TC 2-: heated 24.9 28.4 TC 95 ° C, heated 34.7 Diameter of cell 125 130 μm HDR, 200'C, and < Firm foam jar test, firm foam, 4 weeks, cracks not destroyed 200 ° C 2 weeks, coffee, fi re, 2200C cracks, Example 14a Psl iol la 25.61 Polial 2a 31.62 Dipropylene glycol 16.65 Eti lengl icol 2.71 Mixture of 2.56 stabili zad-ar Water 0.38 Acetate of 2.41 pota io Amina tecia ia 0.26 R 11 Ciclspentane HFC 245 fa 34.8 Total 117.00 Isocyanate 1 300 Isocyanate 2 Isaci n or 3 Tiemp »---} of formation 7 of cream in s Training time 12 of fiber in s Lifting time 19 in s Density "free" 38 in kg / m3 Pr »Dimensions for molds of 9.6 1 Den i» id, kg / m3 70 TC 23 ° C, 7 days 19.0 TC 23 ° C, heated 24.0 TC 95 * C, heated 35.

Cell diameter 135 μm HDR, 20 'C,% 4. 8 Foam bottle test f i me, 4 weeks, I did not destroy > ~ At 200 ° C 2 weeks, 220 ° C Examples 15 to 18 Formation of foam in a cup Manual mixing to test the flask, mixtures of blowing agents in mass parts, C = comparative example Example 15 (O 16 Palial ib 31.14 31.14 Polial 2a 38.47 38.47 Dipropylene glycol 0.25 20.25 Eti lengl icol 3.30 Mix3 of 3.12 3.12 stabilizer Water 0.47 0.47 Potassium acetate 2.93 Termination amine 0.32 .32 Total 100.00 100. OO R. 11 56 50 Isopen ana / acetone 17.5 1: 1 Isopentane / form of met i la 1: 1 Isocyanate 1 390 390 Formation time 17 17 of cream in s Time of form »ri n 28 24 of fiber in s Time of 39 34 elevation in s Densida-d > of 51 62 foam in kg / m-3 Flask test Black foam, Yellow foam and 11a, weeks, 200 * C completely firm, 1 crack destroyed Example 17 18 Polio! Ib 31.14 31.14 Polial 2a 38.47 38.47 Diprapi lenol ic 20.25 20.25 Et ilepgl icol 3.30 Ui - - ti Mixture of T 1 * "* stabilizer A-ua O.47 .47 Potassium acetate 2.93 2.93 Tertiary amine 0.32 0.32 Total 100 OO 100.00 R 11 Isopentane / acetone 1: 1 Isapentan.D / f-arm to 17.5 21.1 methyl 1: 1 Isoci no 1 390 390 Time> D of formation 14 15 of cream in s Time of formation 21 21 of fiber in s Time of 30 32 elevation in s Density of 66 57 foam in kg / m3 Bottle test Yellow foam Yellow foam 2 weeks, 200aC pale pale Examples 19 to 21 Formation of foam in a cup Rigid PUR-P IR formulations, flexible variant, parts by mass, stabilizers cie 8adschmi > dt FC = fine cells, VFC = very fine cells > in accordance with visual estimation. With a higher water content, the HDR. at 200 ° C it remains below a deformation of the i despite a lower density. Flux test: 100 g of foam mixture in a tube that has a diameter of 46 mm. Reported as length of flow in cm. C = example of comparison Example 19 (O 20 21 (C) Polyol 1 25.61 25.61 25.71 Polyol 2a 31.62 31.62 31.77 D Diipprrooppyilleennggll iiccooll 1 166..6655 1 166..6655 16.72 Eti lengl icol 2.71 2.71 2.73 Mixture of 2.56 2.56 2.58 Mixture of water 0.38 1.6 0.0 Potassium acetate 2.41 2.41 2.43 Tertiary amine 0.26 0.26 0.26 Cit lspentana 17.8 16.58 17.8 Total 100.00 100.00 100.00 Density in kg / cm3 62 39 85 Isocyanate 2 320 7? HDR, 200 * C, in «6.8 9.2 Roughness a little more r? fle ible Behavior of - 96 120 41 flu.ia when foam is formed in cm

Claims (15)

1. CLAIMS 1. A thermally stable rigid foam based on isocisfiate and which can be produced by a) polyacrylate with b) compounds containing at least two hydrogen atoms that can react with satiety groups, c) water, in the presence of d) physically acting expansion agents, presence in the absence of e) catalysts and additives / additives, »dap of component b) comprises bi) at least one alcohol > of polyether "having a functionality of at least 1.5, and an indure of hydroxyls of 10 to 100 > 3 KOH / g, in an amount of 0.2 to SO? in bulk, based on component b), and bu) at least one polyester alcohol in an amount of 5 to 90 by mass, based on b), water c) is present in a > rant? > a maximum of 2 * 4 by mass, based on 13. sum of components b) to e) and component d) used «comprises hydrocarbons and / or hydrocarbons containing fluorine in an amount of 5 to 30 * 4 by mass , based on the sum of the c-amponents b) ae), 2. A thermally stable foam based on isocyanate of > ampsr i »da» d with claim 1, wherein the psi ether alcohol bi) has a functionality of 2.5 to 3. A rigid thermally stable isocyanate-based foam according to claim 1, wherein the polyether alcohol bi) has an index > of hydroxyl of 25 to 50 mg KOH / g. 4. A rigid thermally stable foam based on isocyanate according to claim 1, wherein the polyether alcohol is used in an amount of 1 to 70 * 4 by mass, based on component b). 5. A rigid thermally stable foam based on isocyanate »according to claim 1, give alcohol > Rie polyether bi) is used in an amount of 20 to E Y * ep mass, based on component b). 6. A rigid thermally stable isacyanate-based foam according to claim 1, wherein the polyether alcohol b) can be separated by the addition of ethylene oxide and / or prapilene oxide to initiating substances with H functionality. thermally stable isocyanate-based according to the rei indication 1, wherein the p-aliéter bi-alcohol can be prepared by the addition of ethylene oxide and pyridine oxide in glycerol and / or trimethyolprapane. 8. A thermally stable rigidified foam based on isozianata according to claim 1, wherein the polyether poly (bi-zoles) can be prepared by the reaction of fatty acids with palfined alcohols. 9. A thermally stable rigid foam b ^ sa »in caiifo isocyanate pa id > . in claim 3, wherein the polyether moles (bute) can be prepared by the reaction of unsaturated fatty acids with functional polyhydric alcohols. 10. A rigid thermally stable foam based on isocyanate in accordance with the rei indication. , where alcohols > of p »r.l ester b) to preheat unsaturated fatty acids, aromatic acidic acids and dicarboxylic acid aliphatic acids. in a molecule, 11. A thermally stable rigid isocyanate-based foam according to claim 1, wherein water c) is used in an amount of 0.1 to 2% by mass, based on the sum of b) ae). 12. A stable thermally stable foam based on isocyanate according to claim 1, wherein the water is used in an amount of 0.2 to 1.6 * 4 by mass, based on the sum of b) to e). 13. A rigid thermally stable foam based on isocyanate according to claim 1, > where the expanding agents d) that act physically employed are hydrocarbons and / or fluorinated hydrocarbons. 14. A rigid, thermally stable foam based on isocyanate in accordance with reagent 1, where the physically acting expansion agents d) are used in u-j amount »of 5 to 30 * 4 by mass, based on the sum > -ie b? a) 15. A process for the preparation of thermally stable rigid foams based on isacyanate by the reaction of; a) pal isocyanate with b) compounds containing at least hydrogen bonds that can react with isocyanate groups, c) water, in the presence of d) physically acting expansion agents, in the presence or absence of e) catalysts and auxiliaries and / or additives, wherein the candidate b) comprises bi) at least one palyther alcohol hg a functionality of at least 1.5, and a hydroxyl index of IO at 100 mg KOH / g, in an amount of 0.2 to 80 * 4 in mass, based on component b), and bii) at least one polyester alcohol in an amount of 5 to 90 * 4 by mass, based on ab), water c) is present in an amount of as a maximum 2M in mass, based on the sum of the components b) to e) and the candidate d) used: -} it comprises hydrocarbons and / or hydrocarbons containing fluorine in an amount of 5 to 58 * /. mass, based on the sum of the components fa) to e).