RS54603B1 - PROCEDURE FOR OBTAINING SOLID POLYURETHANE FOAMS AND SOLID POLYISOCYANURATE FOAMS - Google Patents

Abstract

A process for the production of solid polyurethane foams comprising the reaction A) at least one polyisocyanate, B) at least one polyether ester polyol that can be obtained by esterification with 1) 10 to 70 mol. % composition of dicarboxylic acids comprising 11) 50 to 100 mol. %, based on the composition of dicarboxylic acids, one or more aromatic dicarboxylic acids or their derivatives, b12) 0 to 50 mol. %, based on said composition of dicarboxylic acids b1), one or more aliphatic dicarboxylic acids or their derivatives, b2) 2 to 30 mol. % of one or more fatty acids and / or fatty acid derivatives, b3) 10 to 70 mol. % of one or more aliphatic or cycloaliphatic diols having 2 to 18 carbon atoms or their alkoxylates, b4) 2 to 50 mol. % polyether polyol having a functionality of not less than 2 and an OH number of 300-1250 mg KOH / g, obtained by alkoxylation of a polyol having a functionality greater than 2, based on the total amount of components b1) to b4), wherein components b1 ) to b4) add up to 100 mol%, C) optionally other polyester polyols, which differ from component B), D) at least one polyether polyol, and E) optionally a flame retardant, F) one or more foaming agents, G) catalyst, iH) optionally other auxiliary or other auxiliary agents. wherein the mass ratio of the sum of the components B) and optionally C) to the component D) is at least 7. The application contains 13 more claims.

Description

Description of the invention

[0001] The present invention relates to a process for obtaining solid polyurethane foams or solid polyisocyanurate foams from certain polyetherester polyols based on aromatic dicarboxylic acids. The subject invention also relates to solid foams that can be obtained in this way, as well as to their application for obtaining sandwich elements that have solid or flexible outer layers. The subject invention further relates to basic polyol components.

Obtaining solid polyurethane foams by reaction of organic or modified organic di- or polyisocyanates with high molecular weight compounds having two or more reactive hydrogen atoms, and in particular with polyether polyols from the polymerization of alkylene oxides or with polyether polyols from the polycondensation of alcohols with dicarboxylic acids in the presence of polyurethane catalysts, chain-extending agents and/or cross-linking agents, agents for creating foams and other auxiliary or additional agents are known and described in many patents and published literature references.

[0003] In the context of the subject description of the invention, the terms "polyester polyol", "polyesterol", "polyester alcohol" and the abbreviation "PESOL" are used with the same meaning.

[0004] Common polyester polyols are polycondensates of aromatic and/or aliphatic dicarboxylic acids and alkanediols and/or triols, or other diols. However, it is also possible to process polyester waste, especially waste polyethylene terephthalate (PET) and/or polybutylene terephthalate (PBT). A whole series of procedures with this purpose is known and described. Some processes are based on the conversion of polyester into diester of terephthalic acid, for example, dimethyl terephthalate. DE-A 100 37 14 and US-A 5,051,528 describe such transesterifications using methanol and a transesterification catalyst.

[0005] Terephthalic acid-based esters are also known to be superior to phthalic acid-based esters in terms of combustion behavior, as described, for example, in WO 2010/043624.

[0006] When polyester polyols based on aromatic carboxylic acids or their derivatives (such as terephthalic acid or phthalic anhydride) are used to obtain solid polyurethane (PU) foams, then the high viscosity of polyester polyols often has a noticeable opposite effect, since it increases the viscosity of mixtures with polyesters. Which makes mixing with isocyanate noticeably more difficult. |0007] EP-A 1 058 701 describes low viscosity aromatic polyester polyols obtained by transesterification of a mixture of phthalic acid derivatives, diols, polyols and hydrophobic fat-based materials.

[0008] Additionally, certain systems for obtaining solid PU foams, such as, for example, those using glycerol as a high-functionality component of alcohol polyesters, can cause problems due to insufficient dimensional stability due to which the foam product is significantly deformed after removal from the mold or after the pressing section when processed by the double belt process.

[0009] Likewise, the problem with the behavior of solid PU foams in the event of fire has not been satisfactorily solved so far with all systems. For example, in case of fire, a toxic compound can be formed if trimethylolpropane (TMP) is used as a high-functionality component of alcohol polyesters.

[0010] A general problem in the production of solid foams is the formation of surface defects, especially on the boundary surface with metal outer layers. These defects on the surface of the foam lead to the formation of uneven metal surfaces in the sandwich elements and thus often lead to a visually unacceptable appearance of the product. Improving the surface of the foam reduces the frequency of such surface defects and leads to an improvement in the visual appearance of the surface of the sandwich elements.

[0011] Rigid polyurethane foams often exhibit high brittleness when cutting with pronounced occurrence of dust and high sensitivity of the foam, and also during sawing, where especially sawing of composite elements with metal outer layers and a core of polyisocyanurate foam can cause cracks in the foam.

[0012] Furthermore, it is generally desirable to realize a system that has a high intrinsic reactivity in order to be able to minimize the use of catalysts.

|0013]The aim of the invention is to realize a polyester polyol based on aromatic dicarboxylic acids for obtaining solid PU foams with low brittleness. A further aim of the invention is to realize a polyol component which contains a polyester polyol and has a high intrinsic reactivity.

[0014] In addition, other objectives are to improve, or at least not worsen, the dimensional tolerance of the final PU product, and also to reduce, or at least not worsen, the formation of toxic compounds in case of fire. In addition, it is necessary to improve the production characteristics regarding the occurrence of surface defects.

[0015] Furthermore, polyester polyols should have a low viscosity, to enable them to be easily metered and mixed during the production of solid PU foams. Solubility of foaming agents such as, for example. pentane, in the polyol component should also be extremely good.

[0016] This goal was achieved by the process of obtaining solid polyurethane foams or solid polyisocyanurate foams, which includes the reaction

A) at least one polyisocyanate,

B) at least one polyetherester polyol that can be obtained by esterification bi),

10 to 70 mol. % of the composition of dicarboxylic acids which includes

bll) 50 to 100 mol. %, based on the composition of dicarboxylic acids, one or more aromatic dicarboxylic acids or their derivatives,

bi2) 0 to 50 mol. %, based on the mentioned composition of dicarboxylic acids bi), one or more aliphatic dicarboxylic acids or their derivatives,

b2) 2 to 30 mol. % of one or more fatty acids and/or fatty acid derivatives,

b3) 10 to 70 mol. % of one or more aliphatic or cycloaliphatic diols having 2 to 18 carbon atoms or their alkoxylates,

b4) 2 to 50 mol. % polyether polyol that has a functionality of no less than 2 and an OH number of 300-1250 mg KOH/g, and was obtained by alkylation of a polyol that has a functionality of more than 2,

based on the total amount of components bi) to b4), whereby components bi) to b4) are added up to 100 mol %,

C) optionally other polyester polyols, which differ from component B),

D) at least one polyether polyol, i

E) optional flame retardant,

F) one or more foaming agents,

G) catalyst, and

H) optionally other auxiliary or other additional agents, whereby the mass ratio of the sum of components B) and optionally C) to component D) is at least 7.

[0017] The subject invention also realized a polyol component containing the above-mentioned components B) to H), whereby the mass ratio of all components B) and optionally C) to component D) is at least 7.

[0018] The present invention also realizes solid polyurethane and solid polyisocyanurate foams that can be obtained by the process according to the present invention and their application for obtaining sandwich elements that have solid or flexible outer layers.

[0019] The invention will now be described in more detail below. Combinations of preferred embodiments are not outside the scope of protection according to the present invention. This particularly applies to those embodiments of the individual components A) to H) of the subject invention which are characterized as desirable. The exemplary embodiments mentioned here in the context of components B) to H) relate not only to the process according to the present invention and the solid foams that can be obtained in this way, but also to the polyol components according to the present invention.

Component B

[0020] In the context of the subject description of the invention, the terms "polyester polyol" and "polyesterol" are used with the same meaning as the terms "polyether polyol" and "polyetherol".

[0021] Component bi 1) primarily comprises at least one compound selected from the group consisting of the following: terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET), phthalic acid, phthalic anhydride (PSA) and isophthalic acid. It is particularly desirable that component bll) contains at least one compound from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET) and phthalic anhydride (PSA). It is highly desirable that component bll) includes phthalic anhydride, dimethyl terephthalate (DMT), terephthalic acid and their mixtures. It is even more preferable that the aromatic dicarboxylic acids or their derivatives of component bll) are chosen from the above-mentioned aromatic dicarboxylic acids and dicarboxylic acid derivatives, and especially from terephthalic acid and/or dimethyl terephthalate (DMT). Terephthalic acid and/or DMT in component bll) lead to polyether ester B) which has particularly good flame retardant properties. Terephthalic acid is particularly preferred since, unlike DMT, it allows the formation of undesirable decomposition products to be avoided.

[0022] Generally, aliphatic dicarboxylic acids or derivatives (component bi 2)) are contained in the composition bi ) dicarboxylic acid from 0 to 30 mol. %, and primarily from 0 to 10 mol. %. It is particularly desirable that the bi)dicarboxylic acid composition does not contain aliphatic dicarboxylic acids or their derivatives and that it consists of 100 mol. % of one or more aromatic dicarboxylic acids or their derivatives, the previously mentioned being more preferred.

[0023] It is preferable that component b2) is used in amounts of 3 to 20 mol. %, and preferably from 5 to 18 mol. %.

[0024] It is preferable that component b3) is used in amounts of 20 to 60 mol. %, and preferably in the range of 25 to 55 mol. %, even more preferably in the range of 30 to 45 mol. %.

[0025] It is preferable that component b4) is used in amounts of 2 to 40 mol. %, and preferably from 8 to 35 mol. %, more preferably 15 to 25 mol. %.

[0026] In one embodiment of the invention, the fatty acid or fatty acid derivative b2) consists of a fatty acid or a mixture of fatty acids, one or more glycerol esters of fatty acids or a mixture of fatty acids, and/or one or more monoesters of a fatty acid, for example, biodiesel or a methyl ester of fatty acids, and it is particularly desirable for component b2) to consist of a fatty acid or a mixture of fatty acids and/or one or more monoesters of a fatty acid; even more preferably, component b2) consists of a fatty acid or a mixture of fatty acids and/or biodiesel, and component b2) especially preferably consists of a fatty acid or a mixture of fatty acids.

[0027] In one preferred embodiment of the invention, the fatty acid or fatty acid derivative b2) is selected from the group consisting of the following: castor oil, polyhydroxy fatty acids, ricinoleic acid, stearic acid, hydroxyl-modified oils, grape seed oil, black cumin oil, pumpkin seed oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, sunflower seed oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia oil, avocado oil, evening primrose oil, sesame oil, hemp oil, hazelnut oil, primrose oil, rosehip oil, safflower oil, walnut oil, animal fat, for example, beef tallow, fatty acids, hydroxyl-modified fats acids, biodiesel, fatty methyl esters acids and fatty acid esters based on myria stoleic acid, palmitoleic acid, oleic acid, vaccinic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, a- and y-linolenic acid, stearidonic acid, arachidonic acid, thymnodonic acid, clupanodonic acid and cervonic acid, as well as mixtures of fatty acids.

[0028] In one preferred embodiment of the present invention, the fatty acid or fatty acid derivative b2) is oleic acid, biodiesel, soybean oil, rapeseed oil or tallow, and particularly preferred is oleic acid, biodiesel, soybean oil, rapeseed oil or beef tallow, more preferably oleic acid or biodiesel, and most preferably oleic acid. The fatty acid or fatty acid derivative improves, among other things, the solubility of the foaming agent during the production of a rigid polyurethane foam.

[0029] It is extremely preferable that component b2) does not contain any triglycerides, especially oil or fat. Glycerol that is released from triglycerides by esterification, or transesterification has a detrimental effect on the dimensional stability of Rigid Foam, as mentioned above. Preferred fatty acids and fatty acid derivatives in the context of component b2) are therefore fatty acids themselves, and also alkyl monoesters of fatty acids or alkyl monoesters of fatty acid mixtures, especially fatty acids themselves and/or biodiesel.

[0030] It is preferable that the aliphatic or cycloaliphatic diol b3) is selected from the group consisting of the following: ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol and their alkoxylates. It is particularly preferred that the aliphatic diol b3) be monoethylene glycol or diethylene glycol, and diethylene glycol is particularly preferred.

[0031] Component b4) can especially be obtained using potassium hydroxide or amine as a catalyst. However, the use of KOH requires an additional processing step. In one preferred embodiment of the present invention, the amine as a catalyst for obtaining component b4) is selected from the group consisting of dimethylethanolamine (DMEOA), imidazole and imidazole derivatives, and also their mixtures, and even more preferably imidazole.

[0032] It is preferable to use such a polyether polyol b4) that has the above functionality 2, and which is obtained by alkylation of a polyol that has a functionality that is greater than or equal to 3.

|0033]According to the present invention, the polyether polyol b4) has a functionality greater than 2. It primarily has a functionality greater than or equal to 2.7 and even more preferably greater than or equal to 9. In general, it has a functionality less than or equal to 6, more preferably less than or equal to 5 and most preferably less than or equal to 4.

[0034] It is preferable that the polyether polyol b4) is selected from the group containing reaction products of sorbitol, polyglycerol, glycerol, trimethylolpropane (TMP), pentaerythritol or their mixtures with alkylene oxide. |0035]In one embodiment of the present invention, the polyether polyol b4) can be obtained by reacting a polyol having a functionality greater than 2 with ethylene oxide and/or propylene oxide, preferably with ethylene oxide. It is particularly desirable that the polyether polyol b4) can be obtained by alkylation with ethylene oxide, which results in a solid polyurethane foam having improved fire-retardant properties.

[0036] It is preferable that the polyether polyol b4) can be obtained by alkoxylation, primarily by ethoxylation of a polyol selected from the group consisting of sorbitol, pentaerythritol, trimethylolpropane, glycerol, polyglycerol and their mixtures, and it is even more preferable that the polyol is selected from the group consisting of trimethylolpropane and glycerol.

[0037] In a special embodiment of the present invention, the polyether polyol b4) consists of the product of the reaction of glycerol with ethylene oxide and/or propylene oxide, primarily with ethylene oxide. This results in particularly high storage stability of component B.

[0038] In the following particular example of the implementation of the present invention, the polyether polyol b4) consists of the product of the reaction of trimethylolpropane with ethylene oxide and/or propylene oxide, and primarily with ethylene oxide. This also results in a particularly high storage stability of component B).

[0039] It is preferable that the polyether polyol b4) has an OH number in the range from 300 to 1250 mg KOH/g, more preferably from 300 to 950 mg KOH/g, and especially preferably from 500 to 800 mg KOH/g. In this range, it is possible to achieve particularly desirable mechanical properties, as well as fire resistance properties.

[0040] It is preferable to use at least 200 mmol, more preferably at least 400 mmol, and even more preferably at least 600 mmol, and even more preferably at least 800 mmol and most preferably at least 1000 mmol of component b4) per kg of polyetherester polyol B). In a particularly preferred embodiment of the present invention, polyether polyol b4) consists of the product of the reaction of trimethylolpropane or glycerol, and primarily glycerol, with ethylene oxide, wherein the OH number of polyether polyol b4) is in the range of 500 to 800 mg KOH/g, preferably from 500 to 650 mg KOH/g.

[0042] In a special, even more preferred embodiment of the present invention, the polyether polyol b4) consists of the reaction product of trimethylolpropane or glycerol, primarily glycerol. with ethylene oxide, wherein the OH number of the polyether polyol b4) is in the range from 500 to 800 mg KOH/g and preferably from 500 to 650 mg KOH/g, the aliphatic or cycloaliphatic diol b3) is diethylene glycol, and the fatty acid or fatty acid derivative b2) is oleic acid.

[0043] It is desirable that the numerical average functionality of polyetherester polyol B) be greater than or equal to 2, and preferably greater than 2, even more preferably greater than 2.2, and especially greater than 2.3, which leads to greater cross-linking of the polyurethane produced with it, and thus to better mechanical properties of the polyurethane foam. (0044) In order to obtain polyetherester polyols, aliphatic and aromatic polycarboxylic acids and/or derivatives and polyhydric alcohols can be polycondensed in the absence of a catalyst or, primarily, in the presence of a catalyst for esterification, preferably in an atmosphere of inert gas, e.g. nitrogen, in the melt at temperatures from 150 to 280 °C, preferably from 180 to 260 °C, optionally under reduced pressure, until desired acid number which is preferably less than 10, and preferably less than 2. In a preferred embodiment, the esterification mixture is polycondensed at the above-mentioned temperatures in an acid with a number of from 80 to 20, and preferably from 40 to 20, under atmospheric pressure, and then under a pressure of less than 500 mbar, and preferably from 40 to 400 mbar. As catalysts for esterification, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin as catalysts, in the form of metals, metal oxides or metal salts. However, the polycondensation can also be carried out in the liquid phase in the presence of diluents and/or azeotroping agents such as, e.g. benzene, toluene, xylene or chlorobenzene, with the aim of distilling the condensed water as an azeotrope.

[0045] To obtain polyetherester polyols, it is suitable that organic polycarboxylic acids and/or derivatives and polyhydric alcohols are polycondensed in a molar ratio of 1:1-2.2, preferably 1:1.05-2.1, and especially preferably 1:1.1-2.0.

[0046] The obtained polyetherester polyols generally have an average molecular weight value in the range of 300 to 3000, preferably in the range of 400 to 1000, and especially in the range of 450 to 800.

[0047] The proportion of polyetherester polyol B) according to the present invention is generally at least 10 wt. %, and primarily at least 20 wt %, more preferably at least 40 wt % and most preferably at least 50 wt %, based on the sum of components from B) to H).

[0048] To obtain solid polyurethane foam by the method according to the invention, in addition to the specific polyester polyol described above (polyetherester polyol B), ingredients known as such are used, which will be described in more detail below.

Component A

[0049] By polyisocyanate within the scope of the present invention is meant an organic compound that contains two or more than two reactive isocyanate groups per molecule, i.e. whose functionality is at least 2. When polyisocyanates or a mixture of several polyisocyanates are used, then there is no unique functionality, but the numerical average functionality of the used component A) is at least 2. jOO50]In the case of polyisocyanates A), aliphatic, cycloaliphatic, araliphatic and especially aromatic polyfunctional isocyanates, which are known as such, come into consideration. Poly functional isocyanates of this type are known as such or are obtained by processes known as such. Polyfunctional isocyanates can even more preferably be used as mixtures, in which case component A) contains different polyfunctional isocyanates. The number of isocyanate groups per molecule in polyfunctional isocyanates used as polyisocyanates is two (polyfunctional isocyanates are referred to as diisocyanates below) or more.

In particular, the following can be mentioned: alkylene diisocyanates having from 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylenediisocyanate-1,4,2-methylpentamethylenediisocyanate-1,5, tetramethylenediisocyanate-1,4, and especially hexamethylenediisocyanate-1,6; cycloaliphatic diisocyanates such as cyclohexane 1,3- and 1,4-diisocyanate, and also any desired mixture of these isomers, 1-isocyanato-3, 3,5-trimethyl-5-isocyanatomethylcyclohexane (1PD1), 2,4- and 2,6-hexahydrotolylene diisocyanate, and also the corresponding isomeric mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and also corresponding isomeric mixtures, and preferred aromatic polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate and corresponding isomeric mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and corresponding isomeric mixtures, mixtures of 4,4'- and 2,2'-diphenylmethane diisocyanate, polyphenylpolymethylene polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates (crude MDI) and mixtures of crude MD1 and tolylene diisocyanates. (0052) Particularly suitable are 2,2'-, 2,4'- and/or 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (ND1), 2,4- and/or 2,6-tolylene diisocyanate (TD1), 3,3'-dimethyl-biphenyl diisocyanate, 1,2-diphenylethane diisocyanate and/or p-phenylene diisocyanate (PPDI), tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2- methylpentamethylene 1,5- diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5- diisocyanate, butylene 1,4- diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPD1), 1,4- and/or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and/or -2,6-cyclohexane diisocyanate and 4,4'-, 2,4'- and/or 2,2'- dicyclohexylmethane diisocyanate. |0053]Rnomodified polyisocyanates are also often used, i.e. products obtained by chemical conversion of organic polyisocyanates and which have two or more reactive isocyanate groups per molecule. In particular, polyisocyanates containing ester, urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione, carbamate and/or urethane groups can be mentioned.

[0054] In the following embodiments as polyisocyanates of component A) are particularly preferred: i) polyfunctional isocyanates based on tolylene diisocyanate (TDI), especially 2,4-TDI or 2,6-TDI or mixtures of 2,4- and 2,6-TDI; ii) polyfunctional isocyanates based on diphenylmethane diisocyanate (MDI), and in particular 2,2'-MDI or 2,4-MDI or 4,4-MDI or oligomeric MDI, which is also known as polyphenylpolymethylene isocyanate, or mixtures of two or three of the aforementioned diphenylmethane diisocyanates, or crude MDI, which is obtained in the production of MDI, or mixtures of at least one oligomer of MDI and at least one of the aforementioned derivatives low molecular weight MDI; iii) mixtures of at least one aromatic isocyanate according to embodiment i) and at least one aromatic isocyanate according to embodiment ii).

[0055] Polymeric diphenylmethane diisocyanate is particularly preferred as the poly isocyanate. Polymeric diphenylmethane diisocyanate (hereinafter referred to as polymeric MDI) is a mixture of binuclear MDI and oligomeric condensation products and such derivatives of diphenylmethane diisocyanate (MDI). Polyisocyanates may also preferably be formed from a mixture of monomeric aromatic diisocyanates and polymeric MDI.

[0056] Polymeric MDI, in addition to binuclear MDI, contains one or more polynuclear condensation products of MDI with a functionality greater than 2, and especially 3 or 4 or 5. Polymeric MDI is known and often called polyphenylpolymethylene isocyanate or, otherwise, oligomeric MDI. Polymeric MDI is usually formed from mixtures of MDI-based isocyanates with different functionalities. Polymeric MDI is usually used as a supplement to monomeric MDI.

[0057] The functionality (average) of the polyisocyanate containing polymeric MDI can vary in the range from about 2.2 to about 5, especially from 2.3 to 4, and especially from 2.4 to 3.5. Crude MDI, obtained as an intermediate in the production of MDI, is particularly one such mixture of MDI-based polyfunctional isocyanates having different functionalities.

[0058] Polyfunctional isocyanates or mixtures of two or more polyfunctional isocyanates based on MDI are known and can be obtained, for example, from BASF Polvurethanes GmbH under the name Lupranate. [0059] It is desirable that the functionality of component A) be at least two, more preferably at least 2.2, and most preferably at least 2.4. It is preferable that the functionality of component A) is from 2.2 to 4, and even more preferably from 2.4 to 3. |0060] It is preferable that the content of the isocyanate group of component A) be from 5 to 10 mmol/g, especially from 6 to 9 mmol/g and even more preferably from 7 to 8.5 mmol/g. A person skilled in the relevant field is aware of the reciprocal relationship between the isocyanate group content in mmol/g and the so-called equivalent weight in g/equivalents. The content of the isocyanate group in mmol/g is obtained from the content by weight. % according to ASTM D-5155-96 A.

In a particularly preferred embodiment, component A) consists of at least one polyfunctional isocyanate selected from diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate and oligomeric diphenylmethane diisocyanate. In a preferred embodiment, component (al) even more preferably contains oligomeric diphenylmethane diisocyanate and has a functionality of at least 2.4.

[0062] The viscosity of the component A) used can vary within wide limits. The viscosity of component A) is preferably in the range of 100 to 3000 mPa<*>s, and even more preferably in the range of 200 to 2500 mPa<*>s.

Component C

[0063] Suitable polyester polyols C) differ from polyetherester polyols B) and can be obtained, for example, from organic dicarboxylic acids that have from 2 to 12 carbon atoms, primarily aromatic ones, or a mixture of aromatic and aliphatic dicarboxylic acids, and polyhydroxyl alcohols, and primarily diols, that have from 2 to 12 carbon atoms, and preferably from 2 to 6 carbon atoms.

[0064] Possible dicarboxylic acids are in particular the following: succinic acid, glutamic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decandicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. It is also possible to use derivatives of these dicarboxylic acids, such as dimethyl terephthalate, for example. Dicarboxylic acids can be used either individually or in addition to another. Instead of free dicarboxylic acids, it is also possible to use suitable derivatives of dicarboxylic acids, e.g. dicarboxylic esters of alcohol having from 1 to 4 carbon atoms or dicarboxylic anhydrides. With aromatic dicarboxylic acids, it is convenient to use phthalic acid, phthalic anhydride, terephthalic acid and/or isophthalic acid as a mixture or separately. With aliphatic dicarboxylic acids, it is convenient to use mixtures of dicarboxylic acids succinic, glutaric and adipic acid with weight ratios, for example, 20-35: 35-50: 20-32 parts by weight, especially adipic acid. Examples of dibasic and polyhydroxyl alcohols, especially diols. are: ethanediol, diethylene glycol, 1,2 or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerol, trimethylolpropane and pentaerythritol. The following are primarily used: ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures of at least two mentioned diols, and especially mixtures of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. It is also possible to use polyester polyols derived from lactones, e.g. c-caprolactone, or hydroxycarboxylic acid, e.g. co-hydroxycaproic acid.

[0065] For obtaining other polyester polyols C), bio-based starting materials and/or their derivatives are also suitable, for example, the following: castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grape seed oil, cumin oil, pumpkin seed oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, seed oil sunflower oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia oil, avocado oil, sea buckthorn oil, sesame oil, hemp oil, hazelnut oil, primrose oil, rosehip oil, safflower oil, walnut oil, fatty acids, hydroxyl-modified fatty acids and fatty acid esters based on myristolein acids, palmitoleic acid, oleic acid, vaccinic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α- and y-linoleic acid, stearidonic acid, arachidonic acid, thymnodonic acid, clupanodonic acid and cervonic acid. The mass ratio of polyetherester polyol B) to polyester polyol C) is generally at least 0.1, preferably at least 0.25, even more preferably at least 0.5 and especially at least 0.8.

[0066] In a particularly preferred embodiment, no other polyester polyols are used

C).

Component D

J0067]According to the present invention, at least one polyether polyol D) is used as component D). Polyetherols D) can be obtained by known methods, for example, by anionic polymerization of one or more alkylene oxides having from 2 to 4 carbon atoms with hydroxides of alkali metals, such as e.g. sodium or potassium hydroxide, or alkali metal alkoxides, such as e.g. sodium methoxide, sodium or potassium ethoxide or potassium isopropoxide, or catalysts for amine alkylation, such as dimethylethanolamine (DMEOA), imidazole and/or imidazole derivatives, using at least one starting molecule containing from 2 to 8, and preferably from 2 to 6, reactive hydrogen atoms in bound form, or by cationic polymerization using Lewis acids, e.g. antimony pentachloride, boron fluoride etharate, or bleaching clay.

[0068] Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide, and primarily ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternatively successively or as mixtures. Preferred alkylene oxides are propylene oxide and ethylene oxide, with ethylene oxide being particularly preferred. [0069] As starting molecules come into consideration, for example: water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-monoalkyl-, N,N-dialkyl- and N,N'-dialkyl-substituted diamines having from 1 to 4 carbon atoms in the alkyl radical, such as e.g. optionally monoalkyl- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6- hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-tolylenediamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane. Particularly preferred are the mentioned diprimary amines, for example, ethylenediamine.

[0070] Further possible starting molecules are: alkanolamines such as ethanolamine, N-methylethanolamine and N-ethylethanolamine, dialkanolamines such as diethanolamine, N-methyldiethanolamine and N-ethyldiethanolamine and trialkanolamines, e.g. triethanolamine, and ammonia.

[0071] It is preferable to use dibasic or polyhydroxyl alcohols, e.g. ethanediol, 1,2- and 1,3-propanediol, diethylene glycol (DEG), dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose.

[0072] Polyether polyols D), preferably polyoxypropylene polyols and polyoxyethylene polyols, even more preferably polyoxyethylene polyols, have a functionality preferably from 2 to 6, even more preferably from 2 to 4, and especially from 2 to 3 and specifically 2 and an average molecular weight value from 150 to 3000 g/mol, preferably from 200 to 2000 g/mol, and especially from 250 to 1000 g/mol. [0073] In one preferred embodiment of the invention, an alkoxylate diol is used, preferably an ethoxylate diol, for example, ethoxylate ethylene glycol, as polyether polyol D), wherein polyethylene glycol is preferred.

[0074] In a special embodiment of the invention, polyetherol component D) consists exclusively of polyethylene glycol, primarily with an average molecular weight value of 250 to 1000 g/mol.

[0075] Udco polyether polyol D) is generally in the range of 0 to 11 wt %, preferably in the range of 2 to 9 wt %. % and even more preferably in the range of 4 to 8 wt. %, based on the sum of components from B) to H). [0076|The mass ratio of the sum of components B) and C) to component D) in accordance with the present invention is greater than 7, preferably greater than 7.5, even more preferably greater than 8, even more preferably greater than 10 and most preferably greater than 12. {0077] The mass ratio of the sum of components B) and C) to component D) according to the present invention is less than 80, and preferably less than 40, more preferably less than 30, even more preferably less than 20, even more preferably less than 16, and most preferably less than 14.

Component E

[0078] As flame retardants E), it is generally possible to use flame retardants which are known from the state of the art. Suitable flame retardants are, for example, brominated esters, brominated ethers (Ixol) or brominated alcohols, such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol, and also chlorinated phosphates, such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate (TCPP), tris(1,3-dichloropropyl) phosphate, tricresyl phosphate, tris(2,3-dibromopropyl) phosphate, tetrakis(2-chloroethyl) ethylenediphosphate, dimethyl methanephosphonate, diethanolaminomethylphosphonic acid diethyl ester, and also commercially available halogen-containing flame retardant polyols. As other phosphates or phosphonates, it is possible to use diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propylphosphonate (DMPP) or diphenyl cresyl phosphate (DPK) as liquid flame retardants.

[0079] In addition to the above-mentioned flame retardants, it is also possible to use inorganic or organic flame retardants such as red phosphorus, preparations containing red phosphorus, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expanding graphite or derivatives of cyanomauric acid, such as melamine, or mixtures of at least two flame retardants, e.g. ammonium polyphosphate and melamine, and optionally corn starch or ammonium polyphosphate, melamine, expanding graphite, and optionally aromatic polyester in order to achieve fire resistance of solid polyurethane foam.

[0080] Preferred flame retardants do not have isocyanate reactive groups. Flame retardants are preferably liquid at room temperature. Especially preferred are TCPP, DEEP, TEP,

DMPP and DPK.

[0081] The proportion of flame retardant E) is generally in the range of 2 to 50 wt. %, preferably in the range of 5 to 30 wt. % and more preferably in the range of 8 to 25 wt.%, based on components B) to H).

Component F

[0082] The foaming agents F) used to obtain solid polyurethane foam include primarily water, formic acid and their mixtures. They react with isocyanate groups to form carbon dioxide, and in the case of formic acid, carbon dioxide and carbon monoxide. Because these foaming agents release gas through a chemical reaction with isocyanate groups, they are called chemical foaming agents. In addition, physical foaming agents such as low-boiling hydrocarbons may be used. Particularly suitable are liquids which are inert to polyisocyanates A) and have a boiling point below 100 °C, preferably below 50 °C, at atmospheric pressure, so that they evaporate under the conditions of an exothermic polyaddition reaction. Examples of such liquids that can primarily be used are alkanes, such as heptane, hexane, n-pentane and isopentane, and preferably industrial mixtures of n-pentane and isopentane, n-butane and isobutane and propane, cycloalkanes, such as cyclopentane and/or cyclohexane, ethers, such as furan, dimethyl ether and diethyl ether, ketones, such as acetone and methyl ethyl ketone, alkyl esters of carboxylic acids, such as methyl formate, dimethyl oxalate and ethyl acetate and halogenated hydrocarbons, such as methylene chloride, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethanes, 1,1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane and heptafluoropropane. Mixtures of these low-boiling liquids with each other and/or with other substituted or unsubstituted hydrocarbons may also be used. Also suitable are organic carboxylic acids such as formic acid, acetic acid, oxalic acid, ricinoleic acid and compounds containing carboxylic groups.

[0083] It is preferred not to use any halogenated hydrocarbons as foaming agents. It is preferable to use water, formic acid-water mixture or formic acid as chemical foaming agents, and formic acid-water mixture or formic acid are particularly preferred chemical foaming agents. Pentane isomers or mixtures of pentane isomers are primarily used as physical foaming agents.

[0084] Chemical foaming agents can be used alone, ie, without the addition of physical foaming agents, or together with physical foaming agents. Chemical foaming agents are preferably used together with physical foaming agents, in which case it is preferred to use formic acid-water mixtures or pure formic acid together with pentane isomers or mixtures of pentane isomers.

[0085] The foaming agents are either completely or partially dissolved in the polyol component (ie B+C+D+E+F+G+H) or are introduced via a stationary mixer just prior to foaming the polyol component. It is common for water, formic acid-water mixture, or formic acid to be fully or partially dissolved in the polyol component, and the physical foaming agents (for example, pentane) and any remaining chemical foaming agent to be added "on-line". |0086]The polyol component is added with pentane in situ, possibly with some of the chemical foaming agents, and also with all or some of the catalysts. Auxiliary and additional agents as well as flame retardants are already included in the polyol mixture. [0087] The amount of foaming agent or foaming agent mixture used is in the range of 1 to 45 wt. %, preferably in the range of 1 to 30 wt. % and even more preferably in the range of 1.5 to 20 wt. %, all based on the sum of components B) to H).

[0088] When water, formic acid or a formic acid-water mixture is used as a foaming agent, it is preferable to add it to the polyol component (B+C+D+E+F+G+H) in an amount of 0.2 to 10 wt. %, based on component B). The addition of water, formic acid or a formic acid-water mixture can be done in combination with the use of other described foaming agents. It is preferred to use formic acid or a formic acid-water mixture in combination with pentane.

Component G

[0089] Special compounds containing reactive hydrogen atoms, especially hydroxyl groups, which substantially accelerate the reaction of components B) to H) with polyisocyanates A) are used as catalysts G) used to obtain solid polyurethane foam.

[0090] It is preferred to use basic polyurethane catalysts, for example, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N,N,N',N'-tetramethyldiaminodiethyl ether, bis(dimethylaminopropyl)urea, N-methylmorpholine or N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N',N<r->tetra-methylethylenediamine, N,N,N,N-tetramethylbutanediamine, N,N,N,N- tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1- azabicyclo(2,2,0)octane, 1,4-diaza-bicyclo(2,2,2)octane (Dabco) and alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol, N,N',N"- tris(dialkylaminoalkyl)hexahydrotriazines, eg N,N',N"-tris(dimethylaminopropyl)-s-hexahydrotriazine, and triethylenediamine. However, metal salts such as ferric chloride, zinc chloride, lead octoate, and especially tin salts such as stannous dioctoate, stannous diethylhexoate and dibutyltin dilaurate, and also especially mixtures of tertiary amines and organotin salts are also suitable.

As catalysts further come into consideration: amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, alkali metal hydroxides such as sodium hydroxide and alkali metal alcoholates such as sodium methylate and potassium isopropylate, alkali metal carboxylates and also alkali metal salts with long chain fatty acids having from 10 up to 20 carbon atoms and an optional side OH group. Primarily, 0.001 to 10 parts by weight of catalyst or combination of catalysts, based (ie calculated) on 100 parts by weight of component B) is used. It is also possible to allow the reaction to proceed without a catalyst. In this case, the catalytic activity of the amine-initiated polyol is used.

[0092] When, during foam formation, a relatively large excess of polyisocyanates is used, other suitable catalysts for the trimerization reaction of excess NCO groups with each other are the following: catalysts that form isocyanurate groups, for example, ammonium ion salts or alkali metal salts, and especially ammonium or alkali metal carboxylates, either alone or in combination with tertiary amines. The formation of isocyanurates leads to fire-resistant PIR foams that are primarily used in industrial Rigid foam, for example, in construction as insulating panels or sandwich elements.

[0093] Further information regarding the above-mentioned and other starting materials can be found in the technical literature, for example, Kunststoffhandbuch, Volume VII, Polvurethane, Carl Hanser Verlag Munich, Vienna, 1st, 2nd and 3rd editions, 1966, 1983 and 1993.

Component H

[0094] Other auxiliary and/or additional agents H) can optionally be added to the reaction mixture to obtain a solid polyurethane foam. For example, surfactants, foam stabilizers, cell structure regulators, fillers, dyes, pigments, hydrolysis inhibitors, fungistatic and bacteriostatic substances can be mentioned.

[0095] As surface-active substances come into consideration, for example, compounds that serve to stimulate the homogenization of starting materials, and can also be suitable for regulating the cellular structure of polymers. Mention may be made, for example, of emulsifiers such as sodium salts of sulfates of castor oil or fatty acids, and also salts of fatty acids with amines, e.g. diethylamine of oleic acid, diethanolamine of stearic acid, diethanolamine of ricinoleic acid, salts of sulfonic acids, e.g. with alkali metals or ammonium salts of dodecylbenzenedisulfonic or dinaphthylmethanedisulfonic acid and ricinoleic acid; foam stabilizers such as siloxanexalkylene mixed polymer and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffinic oils, castor oil esters or ricinoleic acid esters, sulfonated castor oil and peanut oil, and cell structure regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes. Oligomeric acrylates having polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving emulsification, cell structure and/or for foam stabilization. Surfactants are typically applied in amounts of 0.01 to 10 parts by weight, based (ie, calculated) on 100 parts by weight of component B).

[0096] Common organic and inorganic fillers, reinforcing materials, weight-increasing agents, agents for improving abrasive behavior in paints, coating compositions, etc. are used as fillers according to the present invention, and in particular reinforcing fillers. which are known per se. Specific examples are: inorganic fillers such as minerals containing silicon, for example, micas, such as antigorite, serpentine, hornblende, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts, such as chalk, barite and inorganic pigments such as cadmium sulphide and zinc sulphide, and also glass, etc. The advantage is the use of kaolin (China clay), aluminum silicate and co-precipitate of barium sulfate and aluminum silicate, as well as natural and synthetic fibrous minerals, such as wollastonite, metal fibers and especially glass fibers of different lengths, which can be coated. Possible organic fillers are, for example: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers, and also cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and/or aliphatic dicarboxylic esters, and especially carbon fibers.

[0097] Inorganic and organic fillers can be used individually or as mixtures, and preferably added to the reaction mixture in amounts of 0.5 to 50 wt. %, primarily from 1 to 40 wt. %, based on the weight of components A) to H), although the content of lint, non-woven fabrics and fabrics from natural and synthetic fibers can reach a value of up to 80 wt. %, based on the weight of components A) to H).

[0098] Further information related to the aforementioned common auxiliary and additional agents can be found in the technical literature, for example, in the monograph of J.H. Saunders and K.C. Frisch "High Polvmers", Volume XVI, Polvurethanes, Parts 1 and 2, Interscience Publishers 1962 and 1964, or Kunststoff-Handbuch, Polvurethanes, Volume VII, Hanser-Verlag, Munich, Vienna, 1st and 2nd editions, 1966 and 1983.

[0099] The subject invention further describes a polyol component comprising:

10 to 90 wt. % polyetherester polyol B),

0 to 60 wt. % of other polyester polyols C),

0.1 to 11 wt. % polyether polyol D),

2 to 50 wt. % flame retardant E),

1 to 45 wt. % foaming agent F),

0.5 to 10 wt. % of catalyst G), i

0.5 to 20 wt. % of other auxiliary and additional agents H),

as defined above and based on the total weight of components B) to H), whereby the weight % add up to 100 wt. %, and the mass ratio of the sum of components B) and C) to component D) is at least 7.

[0100] It is particularly desirable that the polyol component contains

50 to 90 wt. % polyetherester polyol B),

0 to 20 wt. % of other polyester polyols C),

2 to 9 wt. % polyether polyol D),

5 to 30 wt. % flame retardant E),

1 to 30 wt. % foaming agent F),

0.5 to 10 wt. % of catalyst G), i

0.5 to 20 wt. % of other auxiliary and additional agents H),

as defined above and based on the total weight of components B) to H), whereby the weight % add up to 100 wt. %, and the mass ratio of the sum of components B) and C) to component D) is at least 7.5.

[0101] According to the present invention, it is preferable that the mass ratio of the sum of components B) and optionally C) to component D) in the polyol components according to the present invention is less than 80, preferably less than 40, even more preferably less than 30, even more preferably less than 20, even more preferably less than 16, and most preferably less than 14.

[0102] To obtain solid polyurethane foams according to the invention, optionally modified organic polyisocyanates A), specific polyetherester polyols B) according to the invention, optionally other polyester polyols C), polyetherols D) and other components E) to H) are mixed in such quantities that the equivalent ratio of NCO groups of polyisocyanates A) to the sum of reactive hydrogen atoms of components B) and optionally C) and D) to H) is 1-6:1, and primarily 1.6-5:1 and especially 2.5-3.5:1.

[0103] The following examples illustrate the invention.

Examples

The following specific polyester polyols (polyesterols 1 and 3) and polyetherester polyols (polyesterol 2 and polyesterol 4) were used.

[0105] Polyesterol 1 (example for comparison): esterification product 34 mol. % terephthalic acid, 9 mol. % oleic acid, 40 mol. % diethylene glycol and 17 mol. % glycerol with hydroxyl functionality of 2.33, hydroxyl number of 244 mg KOH/g and oleic acid content in polyesterol of 20.3 wt. %.

[0106] Polyester 2 (according to the invention): esterification product 31 mol. % terephthalic acid, 8 mol. % oleic acid, 43 mol. % diethylene glycol and 18 mol. % polyether based on glycerol and ethylene oxide with an OH functionality of 3 and a hydroxyl number of 535 mg KOH/g. The polyester has a hydroxyl functionality of 2.31, and a hydroxyl number of 238 mg KOH/g and an oleic acid content of the polyesterol of 14.7 wt. %.

[0107] Polyesterol 3 (example for comparison): esterification product 30.5 mol. % phthalic anhydride, 12 mol. % oleic acid, 39.5 mol. % diethylene glycol and 18 mol. % of trimethylolpropane with a hydroxyl functionality of 2.22, a hydroxyl number of 247 mg KOH/g and an oleic acid content in polyesterol of 24.9 wt. %.

[0108] Polyester 4 (according to the invention): esterification product 25 mol. % phthalic anhydride, 15 mol. % oleic acid, 37 mol. % diethylene glycol and 23 mol. % polyether based on trimethylolpropane and ethylene oxide with an OH functionality of 3 and a hydroxyl number of 610 mg KOH/g. The polyester has a hydroxyl functionality of 2.22, and a hydroxyl number of 244 mg KOH/g and an oleic acid content of the polyesterol of 24.5 wt. %.

Determination of hardness and brittleness of solid polyurethane foam

[0109] Hardness was determined by the indenter test. To this end, 2.5, 3, 4, 5, 6 and 7 minutes after mixing the polyurethane foam components in a polystyrene cup, a steel indenter with a spherical head of 10 mm diameter was pressed by a tensile/compression testing machine 10 mm deep into the foam forming a mushroom shape. The maximum force required for this in N was a measure of the hardness of the foam.

[0110] The brittleness of the solid polyisocyanurate foam was determined based on the time after which visible zones with indenter test cracks would appear on the surface of the solid foam (indenter test fracture). Brittleness was further determined subjectively (subjective brittleness) immediately after making the foam by compacting it, and it was graded on a scale from 1 to 6, where 1 indicates a weakly brittle foam, while 6 indicates a highly brittle foam.

Determination of intrinsic reactivity of polyurethane systems

[0111] The curing time of the polyurethane systems described here was adjusted by varying the concentration of the polyurethane catalyst. When the system required a lower catalyst concentration, it meant that the system had a higher intrinsic reactivity.

Examples 1 and 2 and Comparative Examples 1 and 2

Obtaining solid polyurethane foam (version 1)

[0112] From isocyanates and also isocyanate-reactive components foam was made together with foaming agents, catalysts and all other additional agents with a constant ratio of polyols and isocyanates in the mixture of 100:190.

Polyol component:

[0113]

79 parts by weight of polyesterol according to the examples, or examples for comparison,

6 parts by weight of polyetherol from ethoxylated ethylene glycol having a hydroxyl functionality of 2 and a hydroxyl number of 190 mg KOH/g,

13 parts by weight of trichloroisopropyl phosphate (TCPP) as a flame retardant,

2.0 parts by weight Tegostab B8443 stabilizer (silicone-containing stabilizer).

Additional agents:

[0114|15.0 parts by weight Pentane S 80:20 (contains 80 wt. % n-pentane and 20 wt. %

isopentane),

about 1.9 weight of water,

parts

1.6 parts by weight of potassium acetate solution (47% by weight in ethylene glycol),

plus a solution of bis(2-dimethylaminoethyl) ether (70 wt.% in dipropylene glycol) to adjust the curing time, hereinafter referred to as catalyst 1.

Isocyanate component:

[0115] 190 parts by weight of Luprunata® M50 (polymeric methylenediphenyl diisocyanate (PMDI),

which has a viscosity of about 500 mPa* s at 25 "C from BASF SE).

[0116] The components were mixed vigorously using a laboratory mixer. Foam density was adjusted to 32 +/- 1 g/L by varying the water content while maintaining a constant pentane amount of 15.0 parts. The foam curing time was further adjusted to 49 +/- 1 by varying the proportion of bis(2-dimethylaminoethyl) ether solution (70 wt.% in dipropylene glycol) (catalyst 1).

[0117] The results are summarized in Table 1.

Table 1:

Polyester 1 Polyester 2 Polyester 3 Polyester 4 hardness

2.5 min 36 "~39 "~32 35 3 min 47 47 39 42

4 min 66 63 57 56~ sum (2,5,3 and 4 min) 149 149 128 133

brittleness (subjective) 6 2.5 6 2

breakability in the test with 3 min without breaking 2.5 min without breaking with a presser

catalyst 1 1 04" <X9 0^6

[0118] Here it is evident that the polysler polyols 2 and 4 according to the invention reduce the brittleness of the insulating material and increase the system's own reactivity without negative effects on curing.

Examples 3 and 4 according to the invention, as well as comparative examples 3 and 4

Obtaining solid polyurethane foam (version 2)

[0119] Foaming was done analogously as in version 1, except that water as a chemical foaming agent used in version 1 was replaced in version 2 with a solution of formic acid (85% by weight in water) as a chemical foaming agent,

[0120] The components were mixed vigorously using a laboratory mixer. The density of the foam was adjusted to 32 +/- 1g/L by varying the amount of formic acid solution (85 wt.% in water) while maintaining a constant pentane content of 15.0 parts. The curing time was further adjusted to 51 +/- 1 by varying the ratio of bis(2-dimethylaminoethyl) ether solution (70 wt% in dipropylene glycol; (catalyst 1)).

[0121] The results are summarized in Table 2.

[0122] Here it is evident that polyesterols 2 and 4 reduce the brittleness of the insulating material according to the invention and that they increase the system's own reactivity without negative effects on curing.

Claims (14)

1. A process for obtaining solid polyurethane foams that includes the reaction of A) at least one polyisocyanate, B) at least one polyetherester polyol that can be obtained by esterification bi) 10 to 70 mol. % of the composition of dicarboxylic acids which includes bll) 50 to 100 mol. %, based on the composition of dicarboxylic acids, one or more aromatic dicarboxylic acids or their derivatives, bi2) 0 to 50 mol. %, based on the used composition of dicarboxylic acids bi), one or more aliphatic dicarboxylic acids or their derivatives, b2) 2 to 30 mol. % of one or more fatty acids and/or fatty acid derivatives, b3) 10 to 70 mol. % of one or more aliphatic or cycloaliphatic diols having 2 to 18 carbon atoms or their alkoxylates, b4) 2 to 50 mol. % polyether polyol that has a functionality of no less than 2 and an OH number of 300-1250 mg KOH/g, and was obtained by alkylation of a polyol that has a functionality of more than 2, based on the total amount of components bi) to b4), wherein components bi) to b4) are added up to 100 mol %, C) optionally other polyester polyols, which differ from component B), D) at least one polyether polyol, and E) optionally a flame retardant, F) one or more foaming agents. G) catalysts, and H) optionally other auxiliary or other additional agents. where the mass ratio of the sum of components B) and optionally C) to component D) is at least 7. 2. The method according to claim 1, characterized in that the mass ratio of polyetherester polyol B) to other polyester polyols C), which are different from component B), is at least 0.1. 3. Method according to claim 1 or 2, characterized in that no other polyester polyols C) are used. 4. The method according to one or more requirements I to 3, characterized in that the polyether alcohol b4) has a functionality > 2. 5. The method according to one or more claims 1 to 4, characterized in that the polyether alcohol b4) is obtained by alkylation of a polyol, which is selected from the group consisting of sorbitol, pentaerythritol, trimethylolpropane, glycerin, polyglycerin or their mixtures. 6. The method according to one or more claims 1 to 5, characterized in that the polyether alcohol b4) is obtained by alkylation with ethylene oxide. 7. The method according to one or more claims 1 to 6, characterized in that component bi 1) contains one or more compounds selected from the group consisting of terephthalic acid, dimethyl terephthalate, polyethylene terephthalate, phthalic acid, phthalic anhydride and isophthalic acid. 8. The method according to one or more claims 1 to 7, characterized in that the dicarboxylic acid composition bi) does not contain aliphatic dicarboxylic acids b 12). 9. The method according to one or more claims 1 to 8, characterized in that the fatty acid or fatty acid derivative b2) is selected from the group consisting of the following: castor oil, polyhydroxy fatty acids, castor oleic acid, hydroxyl-modified oils, grape seed oil, black cumin oil, pumpkin seed oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, sunflower seed oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia oil, avocado oil, sea buckthorn oil, sesame oil, hemp oil, hazelnut oil, primrose oil, rosehip oil, safflower oil, walnut oil, as well as fatty acids, hydroxyl-modified fatty acids, and fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, vaccinic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, a- and y-linolenic acid, stearidonic acid, arachidonic acid, thymnodonic acid, clupanodonic acid and cervonic acid. 10. The method according to claim 9, characterized in that the fatty acid or fatty acid derivative b2) is selected from the group consisting of oleic acid and oleic acid methyl ester. 11. The method according to one or more of claims 1 to 10, characterized in that the aliphatic or cycloaliphatic diols b3) are selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol and their alkoxylates. 12. Polyurethane rigid foam obtainable by the process according to one or more of claims 1 to 11. 13. Application of polyurethane rigid foam according to claim 12 for the production of sandwich elements with rigid or flexible outer layers. 14. Polyol components for obtaining solid polyurethane foams containing 10 to 90 wt. % polyetherester polyol B), 0 to 60 wt. % of other polyester polyols C), 0.1 to 11 wt. % polyether polyol D), 2 to 50 wt. % fire retardant E), 1 to 45 wt. % foaming agent F), 0.5 to 10 wt. % of catalyst G), 0.5 to 20 wt. % of other auxiliary and additional agents H), as defined in one or more claims 1 to 11, wherein the mass ratio of the sum of components B) and C) to component D) is at least 7.