Manufacture of polyurethane foam

Abstract

(a) A composition suitable for the production of polyurethane foam, the composition comprising at least one polyisocyanate component, a polyol component, optionally a catalyst that catalyzes the formation of urethane or isocyanurate bonds, and optionally a blowing agent, the composition further comprising a hydrocarbon HC, a Si-free surfactant, and an optional polyalkylsiloxane, (b) A method for producing a polyurethane foam under the use of a hydrocarbon HC, a Si-free surfactant, and an optional polyalkylsiloxane, (c) A polyurethane foam that can be obtained in such a manner, and (d) Its use is described.

Description

Technical Field

[0001] The present invention relates to the field of polyurethane foams. In particular, the present invention relates to the production of polyurethane foams using specific hydrocarbons and Si-free surfactants, and further to the use of the foams produced thereby.

[0002] Polyurethane (PU) is understood, within the scope of the present invention, to be a product that can be obtained by the reaction of a polyisocyanate with a polyol or a compound having an isocyanate-reactive group. Here, in addition to polyurethane, further functional groups such as, for example, uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea and / or uretoimine can also occur. Thus, in addition to polyurethane, polyisocyanurate, polyurea, and polyisocyanate reaction products containing uretdione groups, carbodiimide groups, allophanate groups, biuret groups and uretonimine groups are also understood to be PU in the sense of the present invention. Polyurethane foam (PU foam) is understood, within the scope of the present invention, to be a foam obtained as a reaction product based on a polyisocyanate and a polyol or a compound having an isocyanate-reactive group. Here, in addition to what is referred to as polyurethane, further functional groups such as, for example, allophanate, biuret, urea, carbodiimide, uretdione, isocyanurate or uretoimine can also occur.

[0003] Polyurethane foam is usually also referred to as polyurethane foam. Thus, the terms "foam" and "foam body" are used synonymously in the present invention.

[0004] When producing polyurethane foams and polyisocyanurate foams, cell stabilizing additives are usually used. These cell stabilizing additives provide a foam structure with a fine cell structure that is uniform and has few defects, and thus significantly positively affect the use properties of the foam, particularly its heat insulation ability. Usually, in this case, polyether siloxane foam stabilizers (PES) are used, especially for use in rigid foam applications. This Si-containing surfactant is considered a preferred option here. Therefore, Si-containing surfactants are usually a preferred type of foam stabilizer. However, the use of Si-free surfactants is also described in a number of documents.

[0005] EP 2511328 describes the use of carbamates as surfactants for foam stabilization.

[0006] DE 1020011007479 describes a mixture of acid amides and PES for use as a foam stabilizer in PU rigid foams.

[0007] EP 1985642 uses amidoamines and imidazoles based on carboxylic acids and polyethylene or polypropylene amines, such as diethylenetriamine, triethylenetetramine or tetraethylenepentamine, as additives for the production of PU foams.

[0008] US 3746663 describes the use of N-vinylpyrrolidone-based constructs as surfactants in the production of PU foams.

[0009] DE 3724716 describes the use of novolak-based ethoxylates as stabilizers in the production of PU foams.

[0010] EP 0734404 describes the production of PU foams using polyalkylene oxides, and polyalkylene oxides are synthesized using 10 - 90% butylene oxide.

[0011] EP 1985642 describes a composition for producing a PU foam using a C1-C36 carboxylic acid-based amide amine and / or imidazole.

[0012] US 5236961 describes the production of a polyurethane foam using an alkylphenol ethoxylate as a foam stabilizer. DE 2244350 A1 describes the use of a copolymer produced from N-vinylpyrrolidone and a maleic acid ester in the production of a polyurethane foam.

[0013] Therefore, the use of Si-free surfactants in PU foams is well known.

[0014] However, hitherto, those skilled in the art have considered that Si-free surfactants lead to a deterioration in foaming quality compared to Si-containing surfactants, especially polyether-modified siloxanes (PES). In particular, when a PU foam is intended to achieve good heat insulation performance, i.e., a low lambda value, Si-containing surfactants, especially polyether-modified siloxanes (PES), are often advantageous compared to Si-free surfactants.

[0015] However, there may be disadvantages in the use of Si-containing surfactants, especially polyether-modified siloxanes (PES). For example, this may impair the solubility of the blowing agent (e.g., pentane) in the polyol. This is particularly pronounced when the siloxane ratio of PES is high and thus the hydrophobicity is high. Furthermore, Si-containing surfactants are not based on renewable raw materials and are thus disadvantageous from the perspective of sustainability.

[0016] Therefore, it has been desired to provide a PU foam having high foaming quality and excellent heat insulation performance without the need to use Si-containing surfactants.

[0017] In addition to the use of silicon-free surfactants in PU foams, the use of hydrocarbons in PU foams is also well known. For example, hydrocarbons are frequently used in PU foams as blowing agents. In this case, compounds having a maximum of 7 carbon atoms, particularly those having 3 to 7 carbon atoms, are preferably used because these compounds evaporate during the foaming process due to having boiling points within an appropriate temperature range, and thus contribute to volume increase, i.e., foaming. Thereafter, in the completed foam, these blowing agents are still contained within the foam as cell gas. The use of these hydrocarbons is described in a number of documents.

[0018] U.S. Patent No. 20110218259 describes the use of cyclopentane in a PU rigid foam system with improved fluidity as required, for example, during the manufacture of cooling units and panels.

[0019] European Patent No. 421269 describes the use of cyclopentane, and mixtures of cyclopentane and cyclohexane, and various hydrocarbons having a maximum of 4 carbon atoms, as well as ethers and fluoroalkanes having a boiling point of less than 35°C. Therefore, here, hydrocarbons that evaporate completely during PU foaming and thus function as blowing agents are used.

[0020] International Publication No. 2016 / 202912 describes various hydrocarbons, as well as ethers, ketones, esters, acetals, and fluoroalkanes as blowing agents. Advantageously, the boiling point is less than 50°C.

[0021] Chinese Patent No. 101880452 describes the use of alkanes having 14 to 21 carbon atoms as phase change materials used as fillers in an amount of 10 to 30 parts per 100 parts of polyol. Here, the effect on the quality of the thermal conductivity of the PU foam produced using this is not described.

[0022] Japanese Patent Application Laid-Open No. 09-165427 describes the use of alkanes having 9 to 12 carbon atoms, which play a role in improving the storage stability of polyol mixtures, especially when pentane is used as a blowing agent. 1 to 10 parts of alkanes are used per 100 parts of polyol. Here, the effect on the quality of the thermal conductivity of the PU foam produced using this is not described.

[0023] U.S. Patent No. 20070066697 describes a PU flexible foam with improved compression hardness by using hydrocarbons having 10 to 70 carbon atoms. The supply amount is 0.01 to 100 pphp, 1 to 25 pphp, 2 to 8 pphp (pphp = parts per 100 parts of polyol).

[0024] Japanese Patent Application Laid-Open No. 04-018431 describes the use of non-reactive components such as paraffin and other hydrocarbons added in an amount of 0.1 to 10 pphp in PU rigid foams, and it is said that this improves the aging of the foam with respect to the lambda value. Here, it is shown that adding paraffin deteriorates the initial lambda value.

[0025] European Patent No. 3677610 describes the use of a combination of a polyether-modified siloxane and a specific hydrocarbon as a surfactant for obtaining a PU rigid foam with improved properties. This combination is disclosed as essential. The possibility of achieving an improvement in the properties of the PU rigid foam without the polyether-modified siloxane is not described.

[0026] None of the aforementioned documents disclose the combined use of a specific hydrocarbon (HC) having a boiling point exceeding 100 °C at standard pressure and a Si-free surfactant (SifS).

[0027] The object of the present invention was to overcome at least one drawback of the prior art. In particular, there was a problem of providing a polyurethane foam or a polyisocyanurate foam having particularly advantageous properties such as a particularly low thermal conductivity (good heat insulation performance) and / or a high foaming quality, particularly a good surface quality, without the need to use an Si-containing surfactant.

[0028] Surprisingly, it has been found that when combined with a specific hydrocarbon HC having a boiling point above 100 °C at standard pressure, the use of a Si-free surfactant does not reduce the foaming quality. In particular, by using a specific hydrocarbon HC, it is possible to produce a PU foam with improved lambda value without the need to use an Si-containing surfactant such as a polyether-modified siloxane.

[0029] Therefore, this problem is solved by the combined use of a specific hydrocarbon HC having a boiling point above 100 °C at standard pressure and a Si-free surfactant (SifS).

[0030] By combining a specific hydrocarbon HC having a boiling point above 100 °C at standard pressure with a Si-free surfactant, it is possible to produce a PU foam with improved service properties (such as particularly the lambda value). In particular, a low thermal conductivity and / or a good surface quality become possible. Furthermore, a good fine cell structure is achieved. Defects in the foam can be reduced.

[0031] Thus, according to the present invention, it becomes possible to manufacture products based on PU foams, such as insulation panels and cooling units, with higher quality or to make the manufacturing method more efficient. Even by adding a very small amount of the hydrocarbon HC according to the present invention, a similar improvement is possible due to the interaction with the Si-free surfactant (SifS).

[0032] Accordingly, a first subject of the present invention is a composition for producing a polyurethane foam, the composition comprising at least one polyisocyanate component, a polyol component, optionally a catalyst for catalyzing the formation of urethane bonds or isocyanurate bonds, and optionally a blowing agent, the composition further comprising a hydrocarbon HC having a boiling point above 100 °C, preferably above 150 °C, at standard pressure (1.01325 bar), and a Si-free surfactant.

[0033] A further subject of the present invention is a method for producing a polyurethane foam by reacting one or more polyol components with one or more polyisocyanate components, characterized in that the reaction is carried out in the presence of a hydrocarbon HC, a Si-free surfactant, and optionally a polyalkylsiloxane, in particular under the use of the composition according to the present invention.

[0034] Yet a further subject of the present invention is the use of a combination of a hydrocarbon HC, a Si-free surfactant, and optionally a polyalkylsiloxane for the production of a polyurethane foam, preferably as a foam stabilizer, and particularly for improving the thermal insulation properties of the polyurethane foam, in particular under the use of the composition according to the present invention.

[0035] Yet a further subject of the present invention is a polyurethane foam obtainable by the method according to the present invention.

[0036] According to a preferred embodiment, the polyurethane foam obtainable by the present invention has a lambda value (unit: mW / m·K) of less than 24, preferably less than 23, and particularly less than 22.

[0037] The thermal conductivity, i.e., the lambda value (λ value, unit: mW / m·K), can advantageously be determined in the scope of the present invention in accordance with the provisions of standard EN 12667:2001-05, as shown in particular in the experimental part.

[0038] A still further subject of the present invention is the use of the polyurethane foam according to the invention, advantageously as a heat-insulating board and / or heat-insulating material for a cooling device.

[0039] Advantageous configurations of the subject matter of the present invention can be obtained from the claims, the examples and the detailed description of the invention. Furthermore, it is expressly pointed out that the disclosure regarding the subject matter of the present invention encompasses all combinations of the individual features of the detailed description of the invention and the claims here and hereinafter. In particular, an embodiment of a subject matter of the present invention is also applicable mutatis mutandis to an embodiment of another subject matter of the present invention.

[0040] The hydrocarbon HC according to the present invention has a boiling point exceeding 100 °C, preferably exceeding 150 °C, at standard pressure (1.01325 bar). Here, it is preferable that the boiling point at standard pressure is less than 400 °C, advantageously less than 350 °C. Thus, the hydrocarbon HC advantageously has a boiling point exceeding 100 °C and less than 400 °C, particularly exceeding 100 °C and less than 350 °C, at standard pressure. The hydrocarbon HC consists of carbon atoms, hydrogen atoms, and optionally up to three heteroatoms selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms. Advantageously, when the hydrocarbon HC contains heteroatoms, the hydrocarbon HC has only oxygen atoms as heteroatoms. It is preferable that the hydrocarbon HC has one heteroatom or no heteroatoms, and in that case, when the hydrocarbon HC has one heteroatom, the heteroatom is an oxygen atom. However, even more preferably, the hydrocarbon HC has no heteroatoms. Thus, it is particularly preferable that the hydrocarbon HC consists of only carbon atoms and hydrogen atoms. Both saturated hydrocarbon HC and unsaturated hydrocarbon HC can be used. Either aliphatic hydrocarbon HC or aromatic hydrocarbon HC can be used. The hydrocarbon HC may be branched or unbranched. This may be a cyclic hydrocarbon HC or an acyclic hydrocarbon HC.

[0041] Preferred hydrocarbon HC, according to a preferred embodiment of the present invention, is an olefin, paraffin, isoparaffin or alkylbenzene. Such materials are available, for example, from Sasol under the trade names HF-1000, LINPAR, SASOLAB, PARAFOL.

[0042] The hydrocarbon HC according to the present invention is preferably a hydrocarbon having 10 to 24 carbon atoms (branched or unbranched, saturated or unsaturated, cyclic or acyclic, aliphatic or aromatic). These can be produced, for example, by oligomerization of olefins as described in US Patent No. 4,647,707, German Patent Application Publication No. 10 2008 007 081, and German Patent Application Publication No. 10 2013 212 481.

[0043] It is also possible to use the corresponding material streams that occur during the production of oxo alcohols as described in US Patent No. 4,647,707, European Patent No. 1 515 934 and European Patent Application Publication No. 2 947 064. Here, intermediates or by-products called oxo oils are produced. Here, paraffin- and olefin-containing distillation fractions such as so-called light oxo fractions as described in US Patent No. 4,647,707 are preferred.

[0044] Very particularly preferably, the hydrocarbon HC according to the present invention is selected from the group consisting of decene, dodecene, dodecane, isododecane, tetradecane, tributene, tributane, tetrabutene, tetrabutane, alkylbenzenes having at least 10 carbon atoms and oxo oil.

[0045] Similarly, it is also possible to use hydrocarbons produced from renewable raw materials such as isododecane manufactured by Global Bioenergies by the method described in, for example, International Publication No. 2021 / 228824.

[0046] Particularly suitable hydrocarbons HC are described in particular in paragraph

[0112] of European Patent No. 3677610.

[0047] According to the invention, the hydrocarbon is used in combination with a silicon-free surfactant (SifS). The name "silicon-free" here means that the surfactant does not contain silicon atoms. Advantageously, the silicon-free surfactant is a compound consisting of carbon atoms, hydrogen atoms, and heteroatoms selected from oxygen atoms and nitrogen atoms. Surfactants are also called surface active substances or surfactants. The term "surfactant" is understood in the context of the present invention to be a substance that reduces the surface tension of water upon addition. Here, the silicon-free surfactant reduces the static surface tension of the mixture of the surfactant and water to less than 70 mN / m, preferably less than 60 mN / m, even more preferably less than 60 mN / m, even more preferably less than 50 mN / m, particularly preferably less than 40 mN / m at a concentration of 0.5% by weight in water (i.e., 0.5 parts by weight of the silicon-free surfactant per 99.5 parts by weight of water) at a temperature of 20 °C, preferably at standard pressure (1.01325 bar). Thus, a mixture of 5 parts of the silicon-free surfactant per 995 parts of water preferably has a static surface tension of less than 70 mN / m, preferably less than 60 mN / m, even more preferably less than 60 mN / m, even more preferably less than 50 mN / m, particularly preferably less than 40 mN / m at a temperature of 20 °C, preferably at standard pressure (1.01325 bar).

[0048] Here, the static surface tension is preferably determined in accordance with DIN EN 14370:2004-11 (Surface Active Substances - Determination of Surface Tension, German version EN 14370:2004).

[0049] Advantageously, the determination in accordance with DIN EN 14370:2004-11 is carried out as follows in this case: The surfactant is measured in double-distilled water. The mixture of the surfactant and water is calculated to 100 ml in this case and weighed out with an analytical balance. If foam occurs in the sample, it is removed by suction with a pipette. For the measurement, a Kruess K100MK2 tensiometer is used. For the plate method, a Kruess standard plate (Pt, 19.900×0.200×10.000 mm) is used, or for the ring method, a Kruess standard ring (Du Noüy) (Pt, r = 9.545 mm, thickness 0.370 mm) is used, and the ring method is preferred. For calibration, type I double-distilled water of Millipore Simplicity UV from Millipore (resistivity value 18.2 MΩcm, TOC content < 5 ppb, TOC = total organic carbon) and 1-octanol ≥ 99% from Sigma-Aldrich are used.

[0050] The Si-free surfactant can be selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants (zwitterionic surfactants).

[0051] Generally, all Si-free surfactants can be used. Advantageously, Si-free surfactants known to be suitable for use in the production of PU foams, especially rigid PU foams, are used.

[0052] Here, it may also be advantageous to use substances based on renewable raw materials. For example, European Patent Application Publication No. 2295485 describes the use of lecithin as a surfactant for the production of rigid PU foams, which can also be used here as a Si-free surfactant (SifS).

[0053] Advantageously, the Si-free surfactant is selected from the group of nonionic surfactants. For example, the following nonionic surfactants can be used.

[0054] A preferred class of Si-free surfactants is based on carboxylic acids that constitute the hydrophobic part of the surfactant. In this case, the Si-free surfactant is a carboxylic acid derivative. In this case, the carboxylic acid may be derivatized in various ways, such as esters, amides, imides, imidazolines, oxazolines, etc., depending on the species used to react the carboxylic acid or carboxylic acid derivative to produce the Si-free surfactant, i.e., they may be chemically bonded.

[0055] Therefore, it is preferred that the Si-free surfactant is a carboxylic acid derivative selected from the group consisting of esters, amides, imides, imidazolines and oxazolines.

[0056] As the carboxylic acid, for example, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids or their derivatives based on aliphatic or aromatic hydrocarbons can be used.

[0057] In this case, it is preferred that the carboxylic acid has 6 to 40 carbon atoms, particularly 8 to 22 carbon atoms.

[0058] The carboxylic acid may be, for example, saturated or unsaturated, cyclic or acyclic, linear or branched, aromatic or aliphatic. The carboxylic acid may have, for example, one or more double bonds and / or OH functional groups.

[0059] Therefore, it is preferred that the Si-free surfactant is a carboxylic acid derivative of a carboxylic acid having 6 to 40 carbon atoms, particularly 8 to 22 carbon atoms, wherein the carboxylic acid derivative is selected from the group consisting of esters, amides, imides, imidazolines and oxazolines. These carboxylic acid derivatives, in this case, contain, as a structural element, the carbon skeleton of the base carboxylic acid. Instead of the oxygen atom of the carboxyl group of the base carboxylic acid, a heteroatom selected from oxygen atoms and nitrogen atoms is present in the carboxylic acid derivative.

[0060] The carboxylic acid is preferably selected from the group consisting of caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetracosanoic acid), palmitoleic acid ((Z)-9-hexadecenoic acid), oleic acid ((Z)-9-octadecenoic acid), elaidic acid ((E)-9-octadecenoic acid), cis-vaccenic acid ((Z)-11-octadecenoic acid), linoleic acid ((9Z,12Z)-9,12-octadecadienoic acid), α-linolenic acid ((9Z,12Z,15Z)-9,12,15-octadecatrienoic acid), γ-linolenic acid ((6Z,9Z,12Z)-6,9,12-octadecatrienoic acid), dihomo-γ-linolenic acid ((8Z,11Z,14Z)-8,11,14-eicosatrienoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-5,8,11,14-eicosatetraenoic acid), erucic acid ((Z)-13-docosenoic acid), nervonic acid ((Z)-15-tetracosenoic acid), ricinoleic acid, hydroxystearic acid and undecylenic acid, and mixtures thereof, such as rapeseed oil fatty acid, soybean fatty acid, sunflower fatty acid, peanut fatty acid and tall oil fatty acid. Furthermore, it is also possible to use dimers and oligomeric fatty acids such as those generated during the oligomerization of unsaturated fatty acids.

[0061] Suitable sources of fatty acids or fatty acid esters, especially glycerides, can be vegetable or animal fats, oils or waxes. For example, lard, tallow, goose fat, duck fat, chicken fat, horse fat, whale oil, fish oil, palm oil, olive oil, avocado oil, seed kernel oil, coconut oil, palm kernel oil, cocoa butter, cottonseed oil, pumpkin seed oil, corn germ oil, sunflower oil, wheat germ oil, grape seed oil, sesame oil, linseed oil, soybean oil, peanut oil, lupinus oil, rapeseed oil, mustard oil, castor oil, jatropha oil, walnut oil, jojoba oil, for example soybean, rapeseed or sunflower-based lecithin, bone oil, neat's-foot oil, lanolin, emu oil, deer wax, marmot oil, mink oil, borage oil, safflower oil, linseed oil, pumpkin oil, evening primrose oil, tall oil, and carnauba wax, beeswax, candelilla wax, ouricury wax, sugarcane wax, retama wax, caranday wax, raffia wax, esparto wax, alfalfa wax, bamboo wax, hemp wax, douglas fir wax, cork wax, sisal wax, linen wax, cotton wax, dammar wax, tea wax, coffee wax, rice wax, Chinese wax, beeswax and / or wool wax can be used.

[0062] Preferred options for Si-free surfactants are based on the carboxylic acids described above, which are converted via various chemical reactions into esters, amides, imides, imidazolines, oxazolines, or other structures.

[0063] Preferred carboxylic acid-based Si-free surfactants are described below.

[0064] In a preferred embodiment, the Si-free surfactant is a carboxylic acid ester of polyether, which is preferably selected from the group consisting of coconut oil fatty acid PEG-400, monomethyl ether coconut oil fatty acid PEG-500, monomethyl ether lauric acid PEG-500, ricinoleic acid PEG-8, coconut oil fatty acid PEG-7 glyceryl, coconut oil fatty acid PEG-30 glyceryl, stearic acid PEG-30 glyceryl, coconut oil fatty acid PEG-80 glyceryl, dipropylene glycol dibenzoate, propylene glycol oleic acid PEG-55, oleic acid PEG-18 glyceryl, distearic acid PEG-150, glycol distearate, stearic acid PEG-40 and sucrose stearate.

[0065] In a further preferred embodiment, the Si-free surfactant is a carboxylic acid ester of glycerin or polyglycerin, which is preferably selected from the group consisting of glyceryl stearate, glyceryl oleate, polyglyceryl-4 diisostearate, polyglyceryl-4 isostearate, polyglyceryl-3 oleate, polyceryl oleate ester; polyceryl fatty acid partial ester, diisostearoyl polyglyceryl-3, dimer dilinoleic acid ester, polyglyceryl-4 laurate and polyglyceryl-3 caprylate.

[0066] In a further preferred embodiment, the Si-free surfactant is an alkoxylated or non-alkoxylated carboxylic acid ester of sorbitan, which is preferably selected from the group consisting of sorbitan laurate, polysorbate 20, polysorbate 80, sorbitan oleate, sorbitan stearate and sorbitan trioleate.

[0067] Sorbitan esters have long been known as emulsifiers. Sorbitol is the reduced polyol form of glucose and is also known by the names sorbit or glucitol. Sorbitol undergoes self-condensation with elimination of water, during which so-called sorbitan is formed. Sorbitan is generally understood to be a product mixture resulting from the self-condensation of sorbitol, which substantially have the characteristics of 5-membered and 6-membered, monocyclic and bicyclic hydroxy-functional ether polyols. Since sorbitan carboxylic acid esters are carboxylic acid esters of sorbitan, they are acylation products of the above-mentioned product mixture, and this product mixture is usually acylated with 1 to 3 moles of carboxylic acid per mole of product, but substoichiometric acylation of the product mixture with less than 1 mole of carboxylic acid is also conceivable.

[0068] In a further preferred embodiment, the Si-free surfactant is a carboxylic acid amide. Amides can be produced based on a very wide variety of amines and the above-mentioned carboxylic acids.

[0069] For example, amines having at least one primary or secondary amine functional group and optionally one or more hydroxyl groups are suitable for amidation. Thus, suitable amines are, for example, ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, hexapropyleneheptamine, and higher homologs based on ethylenediamine or propylenediamine, 1,2-propylenediamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4-methylenediphenylenediamine, isophoronediamine, trimethylhexamethylenediamine, neopentanediamine, octamethylenediamine, polyetheramines such as polyetheramine D 2000 (BASF), polyetheramine D 230 (BASF), polyetheramine T 403 (BASF), polyetheramine T 5000 (BASF) or even the corresponding Jeffamine types from Huntsman, piperazine, aminoethylpiperazine, bis(aminoethyl)piperazine, 1,3-diaminopropane, 3-(cyclohexylamino)propylamine, 3-(methylamino)propylamine, N,N-bis(3-aminopropyl)methylamine, (3-(2-aminoethylamino)propylamine), dipropylenetriamine, N,N'-bis(3-aminopropyl)ethylenediamine.

[0070] Suitable hydroxylamines having at least one OH functional group are, for example, ethanolamine, propanolamine, alkyl ethanolamine, aryl ethanolamine, alkyl propanolamine, such as diethanolamine, monoethanolamine, diisopropanolamine, isopropanolamine, methyl isopropanolamine, diglycolamine (2-(2-aminoethoxy)ethanol), dimethylethanolamine, N-(2-hydroxyethyl)aniline, 1-(2-hydroxyethyl)piperazine, 2-(2-aminoethoxy)ethanol, 3-amino-1-propanol, 5-amino-1-pentanol, butyl ethanolamine, ethyl ethanolamine, N-methyl ethanolamine, aminopropyl monomethyl ethanolamine, 2-amino-2-methylpropanol, tris hydroxymethyl aminomethane (THMAM or TRIS), N-(2-aminoethyl)ethanolamine (AEEA).

[0071] It is also possible to use the corresponding alkoxylates of the amines, in particular ethoxylates and / or propoxylates, such as alkylamines having hydroxyethyl or hydroxypropyl units, or, for example, N-hydroxyethylcyclohexyl diamine, N-hydroxyethylisophorone diamine, N-hydroxyethylpiperazine, bis(hydroxyethyl)toluene diamine.

[0072] Particularly preferred are amides as described in European Patent Application Publication No. 2511315 and European Patent Application Publication No. 1985642, based on monoethanolamine (MEA) or diethanolamine (DEA), which are, for example, cocamide DEA, cocamide MEA, cocamide MIPA, soybean oil fatty acid amide DEA, undecenyl amide DEA, oleamide DEA, oleamide MEA, lauramide DEA, lauramide MEA, PEG-5 cocamide, PEG-3 oleamide, PEG-6 lauramide, ethoxylated isopropanolamide, conversion products from tall oil fatty acid and diethylenetriamine (DETA) to amides or imidazoles.

[0073] In a further preferred embodiment, the Si-free surfactant is imidazole. These can be produced, for example, by reacting a carboxylic acid with (2-aminoethylamino)ethanol (AEEA). These are known as intermediates in the production of betaines or Quats. Suitable imidazoles are, for example, the following compounds: 1-hydroxyethyl-2-heptadecenylimidazoline, 1-hydroxyethyl-2-norcocoalkylimidazoline, 1-hydroxyethyl-2-norlaurylimidazoline, 1-hydroxyethyl-2-heptylimidazoline.

[0074] In a further preferred embodiment, the Si-free surfactant is oxazoline. These can be produced, for example, by reacting a carboxylic acid with an amino alcohol. Suitable oxazolines are, for example, the following compounds: 2-(heptadecenyl)-2-oxazoline-4,4-dimethanol or 4-ethyl-2-(8-heptadecenyl)-2-oxazoline-4-methanol.

[0075] In a further preferred embodiment, the Si-free surfactant is amidoamine. These are classified as the above-mentioned amides in the spirit of the present invention. These can be produced, for example, by reacting a carboxylic acid with dimethylaminopropylamine (DMAPA) or 2-(2-aminoethylamino)ethanol (AEEA). DMAPA-based amidoamines are common intermediate compounds in the production of betaines or Quats (quaternary ammonium compounds), and these are suitable as Si-free surfactants. Suitable amidoamines are, for example, castor oil amidoamine, coconut fatty acid amidoamine, stearic acid amidoamine, behenic acid amidoamine, lauric acid amidoamine, especially amidoamines based on 3-dimethylaminopropylamine or 2-(2-aminoethylamino)ethanol.

[0076] In a further preferred embodiment, the Si-free surfactant is an alcohol alkoxylate. The method for producing an alcohol alkoxylate is known to those skilled in the art. Advantageously, the alcohol alkoxylate is obtained by reacting an alcohol with an alkylene oxide. Thus, preferably, the Si-free surfactant is an alcohol alkoxylate that can be produced by reacting an alcohol with an alkylene oxide. Here, the alkylene oxide adds to the alcohol under ring opening. The alcohol may be linear or branched, saturated or unsaturated, aliphatic or aromatic, cyclic or acyclic. The alcohol can further have one or more hydroxyl groups. On the other hand, the alkylene oxide is preferably selected from the group consisting of ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and styrene oxide (SO). The alkylene oxide can be selectively supplied alternately and continuously in any metering order in a pure form individually, or can be supplied simultaneously in a mixed state. Thereby, the sequence of the repeating units of the oxyalkylene units or alkyleneoxy units in the formed polyether chain is determined. By this method, a polyether chain can be constructed that is reproducibly manufacturable as desired with respect to structure and molar mass. The sequence of the repeating units can be varied widely depending on the order of addition of the alkylene oxide. Here, for the production of the alcohol alkoxylate, it is particularly preferred to react an alcohol having 4 to 36 carbon atoms with an alkylene oxide unit selected from the group consisting of ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and styrene oxide (SO), and in this case, an average of 3 to 150 alkylene oxide units per hydroxyl group of the alcohol are used.Suitable alkoxylates are, for example, PPG-14 butyl ether, PPG-3 myristyl ether, PPG-15 stearyl ether, PEG-40 hydrogenated castor oil, isocetes-20, laureth-4, steareth-2, PEG-6 caprylic / capric glyceride, C9-alcohol ethoxylate, lauryl alcohol alkoxylate, tridecyl alcohol ethoxylate having 6 to 36 EO, mono-, di-, tristyrylphenol ethoxylate, alkylphenol ethoxylate. Suitable alcohol alkoxylates are also known, for example, under the name Tomadol® (Evonik) or Nonidet® (Shell Chemical Co.). Suitable alcohol alkoxylates containing BO or SO are described, for example, in German Patent Application Publication No. 19940797. Suitable alcohol alkoxylates based on diols as starters are likewise known. Here, the diol can be used directly as a starter or can also arise indirectly from the reaction of water and alkylene oxide as a starter. These alcohol alkoxylates advantageously have a block-like arrangement of oxyalkylene units and are known, for example, under the name Pluronics® (BASF) or Vorasurf® (Dow Chemical Company). Pluronics® are, for example, (OH-terminated) block copolymers of EO and PO. These compounds are also called poloxamers and have a triblock structure (EO-PO-EO). Vorasurf® 504 is, for example, an (OH-terminated) block copolymer of EO and BO as described, for example, in European Patent Application Publication No. 0734404.

[0077] In a further preferred embodiment, the Si-free surfactant is an alkoxylated amine. The method for producing an alkoxylated amine is known to those skilled in the art. Advantageously, an alkoxylated amine is obtained by reacting an amine with an alkylene oxide. Here, the alkylene oxide adds to the amine under ring opening. The amine may be linear or branched, aliphatic or aromatic, cyclic or acyclic. The amine can further have one or more amino groups. Advantageously, the amino groups are primary and / or secondary amino groups. Advantageously, the amine has 4 to 36 carbon atoms. Particularly preferred are tallow amine and coco amine. On the other hand, the alkylene oxide is advantageously selected from the group consisting of ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) and styrene oxide (SO). The alkylene oxide can be selectively supplied alternately and continuously in any metering order in pure form individually, or can be supplied simultaneously in a mixed state. Thereby, the sequence of the repeating units of the oxyalkylene units or alkyleneoxy units in the formed polyether chain is determined. By this method, a polyether chain can be constructed which is characterized by being reproducibly manufacturable as desired with respect to structure and molar mass. The sequence of the repeating units can be varied widely depending on the order of addition of the alkylene oxide. Alkoxylated amines suitable as Si-free surfactants are, for example, ethoxylated tallow amine and ethoxylated coco amine, in particular compounds obtained by reacting 2 to 15 moles of ethylene oxide per mole of tallow amine or coco amine.

[0078] In a further preferred embodiment, the Si-free surfactant is a novolak-based surfactant, for example, described as foam stabilizer A in the examples in German Patent Invention No. 3724716.

[0079] In a further preferred embodiment, the Si-free surfactant is a compound based on a hydrogenated or partially hydrogenated optionally alkoxylated ketone-aldehyde resin as described in European Patent No. 3320012.

[0080] Similarly suitable as Si-free surfactants are polymers based on N-vinylpyrrolidone and dibutyl maleate as described in U.S. Patent No. 3746663.

[0081] Similarly suitable as Si-free surfactants are N-vinylpyrrolidone polymers as described in German Patent Application Publication No. 2244350.

[0082] Compounds based on polyamines or polyimines as described in, for example, European Patent Application Publication No. 3222650 can likewise be used as Si-free surfactants.

[0083] Other polymer structures suitable as Si-free surfactants are described in European Patent Application Publication No. 1790682 and German Patent Application Publication No. 102006042338.

[0084] European Patent Application Publication No. 1790682 describes the use of grafted polyether copolymers for the stabilization of polyurethane foams, which are suitable as Si-free surfactants.

[0085] German Patent Application Publication No. 102006042338 describes the use of urethane group- or urea group-containing polyethers for the stabilization of polyurethane foams, which are likewise suitable as Si-free surfactants.

[0086] European Patent Application Publication No. 1790682 and German Patent Application Publication No. 102006042338 further disclose another Si-free foam stabilizer, which can also be used as a Si-free surfactant for stabilizing PU foams.

[0087] Generally speaking, it can be stated that the Si-free surfactant is preferably a carboxylic acid derivative selected from the group consisting of esters, amides, imides, imidazolines and oxazolines and / or a polyether compound or contains this. The polyether compound has at least 2, preferably 2 to 100, particularly 3 to 50 ether groups. Even more preferably, the Si-free surfactant is a carboxylic acid derivative selected from the group consisting of esters, amides, imides, imidazolines and oxazolines, or an alcohol alkoxylate that can be produced by reacting an alcohol with an alkylene oxide, or contains this. Therefore, the carboxylic acid derivative is, for example, a carboxylic acid ester or a carboxylic acid amide. The alcohol alkoxylate is preferably based on a monoalcohol or a diol as described above.

[0088] The Si-free surfactant and the hydrocarbon HC can be used in a mixed form in any mass ratio. Therefore, there is no limitation regarding the mass ratio. However, it is preferable to use the hydrocarbon HC in combination with the Si-free surfactant in a mass ratio of 1:4 to 1:200 in the composition according to the present invention. Here, the mass ratio is the ratio of the total mass of all hydrocarbons HC in the composition according to the present invention to the total mass of all Si-free surfactants.

[0089] In addition to the Si-free surfactant, a Si-containing surfactant can also be used in principle. However, it is preferable not to use the Si-containing surfactant and that the composition according to the present invention does not contain a Si-containing surfactant.

[0090] In a particularly preferred embodiment of the present invention, polyalkylsiloxane (PAS) is still further used, and in that case, a mixture or combination of hydrocarbon (HC), polyalkylsiloxane (PAS), and Si-free surfactant (SifS) is used.

[0091] Therefore, it is preferred that the composition according to the present invention further contains polyalkylsiloxane (PAS).

[0092] In this case, it is preferred that the polyalkylsiloxane contains less than 20, still more preferably less than 15, and particularly preferably less than 11 Si atoms. Further, it is preferred that the polyalkylsiloxane has at least 2 Si atoms. Thus, it is preferred that the polyalkylsiloxane contains less than 20, still more preferably less than 15, and particularly preferably less than 11 Si atoms, and in this case, each has at least 2 Si atoms.

[0093] Furthermore, it is preferred that the polyalkylsiloxane is used in a mass ratio of preferably 1:5 to 1:200, advantageously, with respect to the Si-free surfactant. Here, the mass ratio is the ratio of the total mass of all polyalkylsiloxanes in the composition according to the present invention to the total mass of all Si-free surfactants.

[0094] Therefore, in a preferred embodiment, the composition according to the present invention further contains polyalkylsiloxane, wherein the polyalkylsiloxane preferably contains less than 20, still more preferably less than 15, and particularly preferably less than 11 Si atoms, and the polyalkylsiloxane is used in a mass ratio of preferably 1:5 to 1:200, advantageously, with respect to the Si-free surfactant.

[0095] The mass ratio of the total amount of hydrocarbon HC, Si-free surfactant, and any polyalkylsiloxane to 100 parts by mass of the polyol component is preferably 0.1 to 10 pphp, more preferably 0.5 to 5 pphp, and particularly preferably 1 to 3 pphp.

[0096] According to a preferred embodiment of the present invention, the polyalkylsiloxane has the formula 1: M a D b T c Q d (Formula 1) [wherein, M = R 11 R 12 R 13 SiO 1 / 2 D = R 14 R 15 SiO 2 / 2 T = R 16 SiO 3 / 2 Q = SiO 4 / 2 and here, R 11 、R 12 、R 13 、R 14 、R 15 、R 16 are the same or different hydrocarbon groups or H having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, wherein the hydrocarbon group is optionally substituted with heteroatoms, Particularly preferably, phenyl group, CH 3 group, CH 3 CH 2 group, CH 2 CH group, ClCH 2 CH 2 CH 2 group and H group, a = 2 to 6 b = 0 to 8 c = 0 to 4 d = 0 to 2 but provided that a + b + c + d < 20, preferably < 15, particularly preferably < 11.

[0097] Preferably, c + d > 0.5. Particularly preferably, c + d ≧ 1. Preferably, d = 0 and c > 0.5. Particularly preferably, d = 0 and c is 1 or more.

[0098] Preferably, c + d < 0.5. Particularly preferably, c + d < 0.1.

[0099] In a further preferred embodiment, R 16 is different from R 11 , R 12 , R 13 , R 14 and R 15 .

[0100] In a further preferred embodiment, R 11 , R 12 , R 13 are different, so that the M units in the siloxane have two or three different groups.

[0101] Preferred polyalkylsiloxanes conform to Formula 2:

Chemical formula

[0102] Preferred polyalkylsiloxanes of Formula 2 conform to Formula 3 or 4:

Chemical formula

Chemical formula

[0103] Preferred polyalkylsiloxanes are as follows:

Chemical formula

Chemical formula

Chemical formula

[0104] The hydrocarbon HC, Si-free surfactant and any polyalkylsiloxane (PAS) that can be used according to the present invention can also be used as part of a composition containing different carrier media.

[0105] Examples of the carrier medium include synthetic and / or natural-derived glycols, alkoxylates or oils. When the total mass ratio of the hydrocarbon HC, Si-free surfactant (SifS) and any polyalkylsiloxane (PAS) in the finished polyurethane foam is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, this corresponds to a preferred embodiment of the present invention.

[0106] The combination according to the present invention of the hydrocarbon HC, the Si-free surfactant SifS and any polyalkylsiloxane (PAS) is hereinafter also referred to as a "mixture", regardless of whether each component is supplied separately or together to the reaction mixture for producing the PU foam.

[0107] As already explained, the composition for producing a polyurethane foam according to the present invention comprises at least one polyisocyanate component, a polyol component, optionally a catalyst for catalyzing the formation of urethane bonds or isocyanurate bonds, and optionally a blowing agent, and the composition further comprises a hydrocarbon HC having a boiling point exceeding 100 °C, preferably exceeding 150 °C, at standard pressure, and a Si-free surfactant.

[0108] Here, the composition can include one or more polyisocyanate components, one or more polyol components, optionally one or more catalysts that catalyze the formation of urethane bonds or isocyanurate bonds, and optionally one or more blowing agents. The composition further includes one or more hydrocarbons HC having a boiling point exceeding 100°C, preferably exceeding 150°C, at standard pressure, and one or more Si-free surfactants.

[0109] The mixture according to the invention of hydrocarbon HC, Si-free surfactant SifS, and optional polyalkylsiloxane has the advantage that it can produce polyurethane foams or polyisocyanurate foams, especially rigid foams, which are characterized by a good fine cell structure and good heat insulation properties and at the same time have few foam defects.

[0110] A preferred composition according to the invention suitable for the production of polyurethane foams or polyisocyanurate foams includes at least one polyisocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane catalyst and / or isocyanurate catalyst, a blowing agent, optionally at least one flame retardant and / or further additives, and is characterized by the inclusion of at least one mixture according to the invention of hydrocarbon HC, Si-free surfactant SifS, and optional polyalkylsiloxane.

[0111] Therefore, the preferred composition according to the invention includes the following components: (a) One or more polyol components (b) One or more polyisocyanate components (c) Optionally one or more catalysts (d) A mixture of one or more hydrocarbons HC, one or more Si-free surfactants SifS, and optionally one or more polyalkylsiloxanes PAS (e) Optionally one or more blowing agents (f) Optionally one or more additives, preferably selected from the group consisting of fillers and flame retardants.

[0112] Thus, preferred compositions according to the invention comprise the following: (a) one or more polyol components (b) one or more polyisocyanate components (c) optionally one or more catalysts (d1) one or more hydrocarbons HC (d2) one or more Si-free surfactants SifS (d3) optionally one or more polyalkylsiloxanes PAS (e) optionally one or more blowing agents (f) optionally one or more additives, preferably selected from the group consisting of fillers and flame retardants.

[0113] In the composition according to the invention, the mass ratio of the mixture according to the invention (i.e., hydrocarbon HC, Si-free surfactant and optional polyalkylsiloxane PAS) d) to 100 parts by mass of the polyol component a) is preferably 0.1 to 10 pphp, preferably 0.5 to 5 pphp, particularly preferably 1 to 3 pphp.

[0114] As the polyol component (a), one or more compounds having OH groups, SH groups, NH groups and / or NH 2 groups and having a functionality of 1.8 to 8 are used. Here, the polyol component contains at least one compound having at least two isocyanate-reactive groups selected from OH groups, SH groups, NH groups and / or NH 2 groups, particularly OH groups.

[0115] For example, a functionality of 1.8 can result from, for example, mixing at least one compound having a relatively high functionality of 2 or more with at least one compound having a functionality of, for example, 1. This can occur particularly when a polyisocyanate component (b) having a functionality exceeding 2 or an additional crosslinking agent as an optional additive (f) is used.

[0116] Suitable compounds in the context of the invention are those having a functionality of 1.8 to 8 and having OH groups, SH groups, NH groups and / or NH2 All organic substances having a base, especially an OH group, and mixtures thereof.

[0117] Suitable compounds commonly used in the production of polyurethane foams are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1.

[0118] Advantageously, compounds with an OH number in the range of 10 - 1200 mg KOH / g are used. Here, the OH number is advantageously determined in accordance with standard DIN EN ISO 4629-1:2016-12 (without catalyst) or in accordance with standard DIN EN ISO 4629-2:2016-12 (with catalyst).

[0119] The polyol or polyol component preferably has a number average molecular weight in the range of 500 - 15000 g / mol. Here, the number average molecular weight can be determined, for example, by gel permeation chromatography (GPC), preferably in accordance with standard DIN EN ISO 13885-1:2021-11 (using THF as the eluent), in accordance with standard DIN EN ISO 13885-2:2021-11 (using acrylamide as the eluent), or in accordance with standard ISO 13885-3:2020-07 (using water as the eluent), and particularly preferably in accordance with standard DIN EN ISO 13885-1:2021-11 (using THF as the eluent).

[0120] Therefore, advantageously, the polyol or polyol component has a functionality of 1.8 - 8 and a number average molecular weight in the range of 500 - 15000 g / mol. Advantageously, a polyol with an OH number in the range of 10 - 1200 mg KOH / g is used, more preferably in the range of 30 - 800, even more preferably in the range of 50 - 600, and particularly in the range of 80 - 500 mg KOH / g.

[0121] Particularly preferred compounds are all polyether polyols and polyester polyols commonly used in the production of polyurethane-based, particularly polyurethane foams.

[0122] Furthermore, polyether polycarbonate polyols, natural oil-based polyols (natural oil-based polyols, NOPs; for example, WO 2005 / 033167, US Patent Application Publication No. 2006 / 0293400, WO 2006 / 094227, WO 2004 / 096882, US Patent Application Publication No. 2002 / 0103091, WO 2006 / 116456, European Patent No. 1678232), filled polyols, prepolymer-based polyols and / or recycled polyols can be used.

[0123] Recycled polyols are polyols obtained from polyurethanes by chemical recycling methods such as solvolysis, such as glycolysis, hydrolysis, acidolysis or aminolysis. The use of recycled polyols is a particularly preferred embodiment of the present invention.

[0124] Polyether polyols can be produced by known methods, for example, by anionic polymerization of alkylene oxides in the presence of an alkali metal hydroxide, an alkali metal alkoxide or an amine as a catalyst, preferably with the addition of at least one starter molecule containing preferably 2 or 3 reactive hydrogen atoms in a bonded state, or by cationic polymerization of alkylene oxides in the presence of a Lewis acid, such as antimony pentachloride or boron trifluoride etherate, or by double metal cyanide catalysis. Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene group. Examples include tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, and preferably ethylene oxide and 1,2-propylene oxide are used. The alkylene oxides can be used alone, cumulatively, in block form, alternately continuously, or as a mixture. As the starter molecule, in particular, a compound having at least 2, preferably 2 to 8 hydroxyl groups, or a compound having at least 2 primary amino groups in the molecule is used. Examples of the starter molecule include water, dihydric, trihydric or tetrahydric alcohols such as ethylene glycol, propane diol-1,2 and -1,3, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, especially sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols, such as oligomeric condensation products of phenol and formaldehyde, Mannich condensates of phenol, formaldehyde and dialkanolamine, and melamine, or amines such as aniline, EDA, TDA, MOA and PMDA, and particularly preferably TDA and PMDA can be used. The selection of a suitable starter molecule depends on the respective application fields of the polyether polyols obtained during polyurethane production.

[0125] The polyester polyol is preferably based on esters of aliphatic or aromatic polycarboxylic acids having 2 to 12 carbon atoms. Examples of aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid and fumaric acid. Examples of aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and isomeric naphthalenedicarboxylic acids. The polyester polyol is obtained by condensation of these polycarboxylic acids with polyhydric alcohols, preferably diols or triols having 2 to 12 carbon atoms, particularly preferably 2 to 6 carbon atoms, preferably trimethylolpropane and glycerin.

[0126] In a particularly preferred embodiment, a polyester polyol based on an aromatic carboxylic acid in excess of 50 pphp, preferably in excess of 70 pphp, based on 100 parts by weight of the polyol component is used.

[0127] When a polyester polyol having a melting point of less than 30 °C is used, this corresponds to a particularly preferred embodiment of the present invention.

[0128] In a further very particularly preferred embodiment, polyols based on phenolic resins produced from novolac and alkylene oxides are not used, and polyols based on aromatic amine polyols produced by alkoxylation of aromatic amines are not used, i.e., in this preferred embodiment, polyols based on phenolic resins produced from novolac and alkylene oxides are used in less than 20 pphp, preferably less than 10 pphp, particularly less than 2 pphp, most preferably not at all, and polyols based on aromatic amine polyols produced by alkoxylation of aromatic amines are not used at all.

[0129] Polyether polycarbonate polyol is a polyol that contains carbon dioxide in a bonded state as a carbonate. Since carbon dioxide is produced in large quantities as a by-product in many processes in the chemical industry, the use of carbon dioxide as a comonomer in alkylene oxide polymerization is particularly important from a commercial perspective. By replacing a part of the alkylene oxide of the polyol with carbon dioxide, it may be possible to significantly reduce the production cost of the polyol. Furthermore, using CO 2 as a comonomer is very advantageous environmentally because this reaction converts greenhouse gas into a polymer. It has long been known to produce polyether polycarbonate polyol by adding alkylene oxide and carbon dioxide to an H-functional starter substance using a catalyst. Here, various catalyst systems can be used. The first generation was heterogeneous zinc salts or aluminum salts as described, for example, in U.S. Patent No. 3,900,424 or U.S. Patent No. 3,953,383. Furthermore, mononuclear and binuclear metal complexes have been successfully used in the copolymerization of CO 2 with alkylene oxide (International Publication No. 2010 / 028362, International Publication No. 2009 / 130470, International Publication No. 2013 / 022932 or International Publication No. 2011 / 163133). The most important catalyst system for the copolymerization of carbon dioxide and alkylene oxide is the double metal cyanide catalyst, also known as the DMC catalyst (U.S. Patent No. 4,500,704, International Publication No. 2008 / 058913). Suitable alkylene oxides and H-functional starter substances are those also used for the production of carbonate-free polyether polyols as described above.

[0130] Natural oil-based polyols (NOPs), which are polyols based on renewable raw materials for polyurethane production, have attracted increasing interest against the backdrop of soaring crude oil prices with regard to the long-term limits of the availability of fossil resources, particularly oil, coal, and gas, and have already been described many times for such applications (International Publication No. WO 2005 / 033167; U.S. Patent Application Publication No. 2006 / 0293400, International Publication No. WO 2006 / 094227, International Publication No. WO 2004 / 096882, U.S. Patent Application Publication No. 2002 / 0103091, International Publication No. WO 2006 / 116456, and European Patent No. 1678232). A series of these polyols are currently commercially available from various manufacturers (International Publication No. WO 2004 / 020497, U.S. Patent Application Publication No. 2006 / 0229375, International Publication No. WO 2009 / 058367). Different polyols with different properties can be obtained depending on the base raw materials (such as soybean oil, palm oil, or castor oil) and subsequent post-treatment. Here, they can be substantially distinguished into the following two groups: a) polyols based on renewable raw materials and processed to be 100% usable in the production of polyurethanes (International Publication No. WO 2004 / 020497, U.S. Patent Application Publication No. 2006 / 0229375); b) polyols based on renewable raw materials that, due to their subsequent treatment and properties, can only partly replace petrochemical polyols (International Publication No. WO 2009 / 058367).

[0131] Another class of usable polyols is the so-called filled polyols (polymer polyols). These are characterized by containing a solid organic filler with a solids content of 40% or more in a dispersed state. Those that can be used are, in particular, SAN polyols, PUD polyols, and PIPA polyols. SAN polyols are highly reactive polyols containing a copolymer based on styrene acrylonitrile (SAN) in a dispersed state. PUD polyols are highly reactive polyols containing polyurethane in a similar dispersed form. PIPA polyols are highly reactive polyols containing, for example, polyurethane formed by an in-situ reaction of isocyanate and alkanolamine in a conventional polyol in a dispersed form.

[0132] Another class of polyols that can be used are polyols obtained as prepolymers by reacting a polyol and an isocyanate, preferably in a molar ratio of from 100:1 to 5:1, more preferably from 50:1 to 10:1. Such prepolymers are preferably produced in a state dissolved in the polymer, and in that case the polyol preferably corresponds to the polyol used in producing the prepolymer.

[0133] As the polyisocyanate component (b), one or more polyisocyanates having in total two or more isocyanate groups are generally used. Polyisocyanates suitable in the context of the present invention are all organic isocyanates having two or more isocyanate groups, in particular aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyvalent isocyanates known per se.

[0134] Examples that can be cited here include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene diisocyanate (PDI) and preferably hexamethylene-1,6-diisocyanate (HMDI), alicyclic diisocyanates, such as cyclohexane 1,3- and 1,4-diisocyanate, and corresponding isomer mixtures, 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,4- and 2,6-methylcyclohexyl diisocyanate, and corresponding isomer mixtures, and preferably aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate (TDI), and corresponding isomer mixtures, naphthalene diisocyanate, diethyltoluene diisocyanate, 4,4'- or 2,2'- or 2,4'-diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PMDI, "polymeric MDI"). The organic polyisocyanates can be used alone or in the form of their mixtures. Similarly, it is also possible to use corresponding "oligomers" of diisocyanates, such as IPDI trimers based on isocyanurate, biuret or uretdione. Furthermore, it is also possible to use prepolymers based on the above-mentioned isocyanates. Particularly suitable are mixtures of MDI with higher condensation analogues having an average functionality of 2 to 4, known as "polymeric MDI" (also called "crude MDI" or "raw MDI"), and various isomers of TDI in pure form or as isomer mixtures. It is also possible to use so-called modified isocyanates, which are isocyanates modified by incorporating groups such as urethane, uretdione, isocyanurate, allophanate, etc.Examples of particularly suitable isocyanates are also described, for example, in European Patent No. 1712578, European Patent No. 1161474, International Publication No. 00 / 58383, US Patent Application Publication No. 2007 / 0072951, European Patent No. 1678232 and International Publication No. 2005 / 085310, and these documents are incorporated herein by reference in their entirety.

[0135] The preferred ratio of the polyisocyanate component (b) to the polyol component (a) is represented as an index of the formulation, that is, as a value obtained by multiplying the stoichiometric ratio of the isocyanate group to the isocyanate-reactive group (e.g., OH group, NH group) by 100, and this is in the range of 10 to 1000, preferably 40 to 700, still more preferably 150 to 550, and particularly preferably 200 to 500. The index 100 represents a molar ratio of reactive groups of 1:1.

[0136] In a preferred embodiment of the present invention, the index of the formulation is in the range of 150 to 550, particularly preferably 200 to 500. That is, in a preferred embodiment, the isocyanate groups are clearly present in excess relative to the isocyanate-reactive groups. Thereby, the trimerization reaction of the isocyanate occurs, and thereby isocyanurate is formed. This foam type is also called a polyisocyanurate (PIR) foam and is characterized by an improvement in combustion behavior, that is, flame retardancy. This foam type is a preferred subject of the present invention. Here, particularly preferably, one or more polyester polyols are included as the polyol component (a).

[0137] Suitable catalysts (c) that can be used for the production of polyurethanes, particularly PU foams, are known to those skilled in the art from the prior art. In the context of the present invention, all compounds that can catalyze the reaction of isocyanate groups with OH groups, NH groups or other isocyanate-reactive groups, and the reaction of isocyanate groups with each other can be used.

[0138] Here, for example, conventional catalysts known from the prior art can be used, including amines (cyclic or acyclic; monoamines, diamines, oligomers having one or more amino groups), ammonium compounds, organometallic compounds and / or metal salts, preferably compounds of tin, iron, bismuth, potassium and / or zinc. In particular, mixtures of such plural compounds can be used as the catalyst.

[0139] As component (d), the mixture according to the invention (i.e., hydrocarbon HC, Si-free surfactant SifS and optional polyalkylsiloxane PAS) is used.

[0140] According to a further preferred embodiment, the total amount of the mixture used (i.e., the whole of all hydrocarbons HC, Si-free surfactants and optional polyalkylsiloxanes) is such that the mass ratio to the finished polyurethane is 0.01 to 10% by weight, preferably 0.1 to 3% by weight.

[0141] The use of blowing agents and their use in the production of PU foams are known to those skilled in the art. The use of one blowing agent (e) or a combination of two or more blowing agents (e) depends in principle on the type of blowing method used, the type of system, and the use of the resulting PU foam. Chemical and / or physical blowing agents, as well as combinations of both, can be used. Depending on the amount of blowing agent used, high-density or low-density foams are produced. For example, foams with a density of 5 to 900 kg / m 3 , preferably 5 to 350 kg / m 3 , particularly preferably 8 to 200 kg / m 3 , in particular 8 to 150 kg / m 3 can be produced.

[0142] As the physical blowing agent, all suitable compounds having an appropriate boiling point and mixtures thereof can be used. For example, hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane, n-pentane, hydrofluorocarbons (HFCs), preferably HFC 245fa, HFC 134a or HFC 365mfc, hydrochlorofluorocarbons (HCFCs), preferably HCFC 141b, hydrofluoroolefins (HFOs) or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz, esters, preferably methyl formate, ketones, preferably acetone, ethers, preferably dimethoxymethane or chlorinated hydrocarbons, preferably dichloromethane or 1,2-dichloroethane can be used. When hydrocarbons having 3, 4 or 5 carbon atoms, preferably hydrocarbons having 4 or 5 carbon atoms, particularly hydrocarbons having 5 carbon atoms are used, this corresponds to a particularly preferred embodiment of the present invention, and in that case, preferably no halogenated blowing agent is used.

[0143] As the chemical blowing agent, for example, all compounds that react with NCO groups to release gas, such as water or formic acid, or all compounds that release gas during the reaction as a result of a temperature increase, such as sodium bicarbonate, can be used.

[0144] When the composition according to the present invention contains water in combination with a hydrocarbon having 5 carbon atoms, an HFO, a hydrohaloolefin or an HFC or a mixture thereof as the blowing agent, this corresponds to a particularly preferred embodiment of the present invention. When only a combination of water and a hydrocarbon having 5 carbon atoms is used as the blowing agent, this corresponds to a very particularly preferred embodiment of the present invention.

[0145] The water content suitable for the purpose of the present invention varies depending on whether one or more blowing agents are still used in addition to water. In the case of pure water-foamed foam, the preferred value is typically 1 to 20 pphp, and when other blowing agents are further used, the preferred amount used usually decreases to 0.1 to 5 pphp.

[0146] As additive f), all substances known in the prior art and used in the production of polyurethanes, especially polyurethane foams, can be used. For example, crosslinking agents and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, cell refinement additives, cell opening agents, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, etc. can be used.

[0147] As the flame retardant, the composition according to the present invention can contain all known flame retardants suitable for the production of PU foams, for example, halogen-containing or halogen-free organophosphorus compounds, such as triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP, also called tris(2-chloroisopropyl) phosphate), tris(2-chloroethyl) phosphate (TCEP), dimethylmethane phosphonate (DMMP), dimethylpropane phosphonate (DMPP), ammonium polyphosphate or red phosphorus, nitrogen-containing compounds, such as melamine, melamine cyanurate or melamine polyphosphate, or halogenated compounds, such as chlorinated and / or brominated polyether polyols and / or polyester polyols. The use of a mixture of various flame retardants is also possible. Advantageously, the flame retardant is a liquid flame retardant.

[0148] A further subject of the present invention is a method for producing a polyurethane foam by reacting one or more polyol components with one or more polyisocyanate components, characterized in that the reaction is carried out in the presence of a hydrocarbon HC, a Si-free surfactant, and optionally a polyalkylsiloxane, especially under the use of the composition according to the present invention.

[0149] Thus, a further subject of the present invention is a method for producing a polyurethane foam by reacting one or more polyol components with one or more polyisocyanate components, wherein the reaction is carried out in the presence of one or more hydrocarbons HC, one or more Si-free surfactants, and optionally one or more polyalkylsiloxanes, in particular under the use of the composition according to the present invention.

[0150] Here, it is preferable to supply each component of the hydrocarbon HC, the Si-free surfactant, and the optional polyalkylsiloxane separately or together to the reaction mixture for producing the polyurethane foam.

[0151] The method for producing a PU foam according to the present invention can be carried out by all known methods, for example, by a hand mixing method or preferably using a foaming machine. When carrying out the method using a foaming machine, high-pressure or low-pressure equipment can be used. The method according to the present invention can be carried out in a batch or continuous manner, and for example, a 1K system, a 1.5K system, or a 2K system as described in European Patent Application Publication No. 3717538, US Patent No. 7776934, European Patent No. 1400547, or European Patent No. 2780384 can be used.

[0152] Preferred polyurethane foam formulations or polyisocyanurate foam formulations in the spirit of the present invention result in a unit volume weight of 5 to 900 kg / m 3 and have the composition shown in Table 1.

[0153]

Table 1

[0154] For further preferred embodiments and configurations of the method according to the present invention, reference is further made to the detailed discussion already given above in connection with the composition according to the present invention. Advantageously, these detailed discussions are valid.

[0155] A further subject of the present invention is a polyurethane foam obtainable by the method described above.

[0156] According to a preferred embodiment of the present invention, the polyurethane foam has a unit volume weight of 5 to 900 kg / m 3 , preferably 8 to 800 kg / m 3 , still more preferably 10 to 600 kg / m 3 , particularly 30 to 150 kg / m 3 .

[0157] Advantageously, the polyurethane foam (PU foam) according to the present invention is a rigid polyurethane foam (PU rigid foam).

[0158] "Rigid polyurethane foam" or "PU rigid foam" is an established technical term. The known fundamental difference between a flexible foam and a rigid foam is that a flexible foam exhibits elastic behavior and thus the deformation is reversible. In contrast, a rigid foam is permanently deformed. In the context of the present invention, a rigid polyurethane foam is in particular understood to be a foam compliant with DIN 7726 and having a compressive strength compliant with DIN 53 421 / DIN EN ISO 604 of advantageously 20 kPa or more, advantageously 80 kPa or more, preferably 100 kPa or more, more preferably 150 kPa or more, particularly preferably 180 kPa or more. Preferably, a rigid polyurethane foam compliant with DIN ISO 4590 advantageously has a closed-cell ratio of more than 50%, advantageously more than 80%, particularly preferably more than 90%. Detailed information on rigid polyurethane foams is also described in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3. Auflage 1993, Kapitel 6.

[0159] PU foams, especially rigid PU foams, can be used as thermal insulation materials, preferably as thermal insulation boards, refrigerators, thermal insulation foams, roof liners, packaging foams or spray foams.

[0160] Accordingly, a further subject of the present invention is the use of the polyurethane foam or polyisocyanurate foam according to the invention, preferably as a thermal insulation board and / or thermal insulation material for a cooling device. Here, the cooling device preferably comprises the polyurethane foam or polyisocyanurate foam according to the invention as a thermal insulation material.

[0161] In particular, in the cooling warehouse industry, the cooling equipment industry and the household equipment industry, for example, in the manufacture of thermal insulation boards for roofs and walls, as a thermal insulation material for containers and warehouses for refrigerated goods, and in cooling equipment and refrigeration equipment, the PU foam according to the invention can be advantageously used.

[0162] Further preferred fields of use are vehicle manufacturing, especially for vehicle roof liners, body parts, interior trims, refrigerated vehicles, large containers, transport pallets, the manufacture of packaging laminates, the furniture industry, for example furniture parts, doors, linings, and electronic equipment applications.

[0163] The cooling device according to the invention comprises the PU foam (polyurethane foam or polyisocyanurate foam) according to the invention as a thermal insulation material.

[0164] A further subject of the present invention is the use of the PU foam as a thermal insulation material, as a thermal insulation board, as a spray foam, as a one-component foam, in cryogenic technology, cooling units, the construction field, the automotive field, the shipbuilding field and / or the electronics field.

[0165] The subject matter according to the present invention will be illustratively described below, but the present invention is not limited to these exemplary embodiments. When ranges, general formulas or compound classes are shown below, these include not only the corresponding ranges or compound groups explicitly mentioned, but also all partial ranges and subgroups of compounds that can be obtained by extracting individual values (ranges) or compounds. When a document is cited within the scope of this specification, its content, particularly the content regarding the situation in the context in which the document is cited, shall constitute an integral part of the entire disclosure of the present invention. Unless otherwise specified, percent data is data in weight percent units. When an average value is shown below, unless otherwise specified, this is a weight average. When parameters determined by measurement are shown below, unless otherwise specified, the measurement was performed at a temperature of 25°C and a pressure of 101,325 Pa.

[0166] The examples shown below illustratively explain the present invention. The scope of application of the present invention is clear from the entire specification and the scope of the claims, and the present invention is not limited to the embodiments listed in the examples.

Examples

[0167] The following materials were used as the silicon-free surfactant (SifS).

[0168] SifS No.1: Diethanolamide based on soybean oil and diethanolamine, produced as described as Amide 2 in Example 1b of German Patent Application Publication No. 102011007479. SifS No.2: Imidazole based on N-(2-aminoethyl)ethanolamine and coconut fatty acid, described in Example 3 of US Patent No. 2267965. SifS No.3: Sorbitan monolaurate commercially available from Evonik as TEGO SML. SifS No.4: Novolak-based surfactant described as Foam Stabilizer A in German Patent Invention No. 3724716. SifS No.5: Ethoxylate of hydrogenated ketoaldehyde resin described as OHV-3 in European Patent No. 3320012.

[0169] The following materials were used as hydrocarbons (HC).

[0170] HC-A: Iso-C 13 An oxo oil based on the hydroformylation product of dodecene, which is a by-product during the production of alcohol and occurs as a low-boiling fraction, so-called light oxo fraction, and is commercially available from Evonik as Oxooel LS 13.

[0171] HC-B: Tetrabutene produced as an oligomer based on butene as described in German Patent Application Publication No. 102008007081 and commercially available from Evonik as tetrabutene.

[0172] The following materials were used as polyalkylsiloxane (PAS): PAS-A: M as defined by Formula 1 above a D b T c Q d [wherein, a = 2; b = 1; c = 0; d = 0; R 11 = methyl; R 12 = methyl; R 13 = methyl; R 14 = octyl, R 15 = methyl], a tricosiloxane having an octyl side chain, as described as PAS No. 5 in International Publication No. 2020 / 144003.

[0173] In the production of the rigid PU foam according to the present invention, a Si-free surfactant was used by mixing or combining with various hydrocarbons and polyalkylsiloxanes.

[0174] Here, the following mixtures summarized in Table 2 were used.

[0175]

Table 2

[0176] In the foaming test, a foam containing one of the aforementioned mixtures of Si-free surfactant, hydrocarbon HC, and optionally polyalkylsiloxane PAS was compared with a composition containing only the corresponding Si-free surfactant instead of the aforementioned mixture in terms of its properties: Compare SifS No.1 with mixtures 1, 6, and 9. Compare SifS No.2 with mixtures 2, 7, and 10. Compare SifS No.3 with mixtures 3, 8, and 11. Compare SifS No.4 with mixture 4. Compare SifS No.5 with mixtures 5 and 12.

[0177] The following raw materials were used for the production of the foam: Stepanpol PS 2412: Polyester polyol manufactured by Stepan TCPP: Tris(2-chloroisopropyl) phosphate (flame retardant) manufactured by Fyrol POLYCAT 5 manufactured by Evonik Operations GmbH, an amine-based catalyst Kosmos 75 manufactured by Evonik Operations GmbH, a potassium octoate-based catalyst Polycat 5 manufactured by Evonik Operations GmbH, an amine catalyst MDI (44V20): Desmodur 44V20L manufactured by Covestro, which is diphenylmethane-4,4'-diisocyanate (MDI) containing isomers and higher-functional homologues

[0178] Production of PU foam: Foaming was carried out by the hand mixing method. For this purpose, all the components listed in Table 3 except for the polyisocyanate (MDI) were weighed into a beaker and mixed with a disk-type stirrer (6 cm in diameter) at 1000 rpm for 30 seconds. By weighing again, the amount of the blowing agent evaporated during the mixing process was determined and replenished to restore it to the original amount. Then, the polyisocyanate (MDI) was added and the reaction mixture was stirred with the above stirrer at 3000 rpm for 5 seconds.

[0179] In the case of the PIR formulation (polyisocyanurate formulation) for panel applications such as building insulation used here, the mixture was immediately poured into an aluminum mold with dimensions of 50 cm × 25 cm × 7 cm whose temperature was controlled by a thermostat at 65°C. Here, the amount of the foam formulation used was determined to be sufficient for the minimum filling amount of the mold. The foam was demolded after 10 minutes and then stored at room temperature for 24 hours.

[0180] Based on the cut surface of the foam, the degree of internal defects and the pore structure were visually evaluated on a scale of 1 to 10, where 10 represents a foam without defects and 1 represents a foam with a very large number of defects.

[0181] The thermal conductivity (lambda value, unit: mW / m·K) of a disk-shaped object with a thickness of 2.5 cm was measured after 1 day (1d) and 7 days (7d) at an average temperature of 10°C in accordance with the provisions of Standard EN 12667:2001-05 using a Hesto Lambda Control HLC X206 type device.

[0182] Table 3 summarizes the foam formulations used.

[0183]

Table 3

[0184] The results of the foaming test of the mixture of SifS, HC, and optionally PAS are summarized in Table 4 and compared with the case of SifS alone. The panels were manufactured as described above, and the lambda values (unit: mW / m·K) were measured after 1 day and 7 days, and the internal defects were evaluated on a scale of 1 to 10.

[0185]

Table 4

[0186] From these tests, it is clear that the mixture according to the present invention, which consists of hydrocarbon HC, Si-free surfactant SifS, and optionally polyalkylsiloxane PAS, improves the heat insulation properties compared to the case of SifS alone.

[0187] It should be particularly emphasized here that adding a very small amount of HC and optionally adding PAS alone also leads to a measurable improvement.

Claims

1. A composition for producing a polyurethane foam, said composition comprising at least one polyisocyanate component, a polyol component, optionally a catalyst for catalyzing the formation of urethane bonds or isocyanurate bonds, and optionally a blowing agent, said composition further comprising a hydrocarbon HC having a boiling point exceeding 100° C., preferably exceeding 150° C., at standard pressure, and a Si-free surfactant.

2. The composition according to claim 1, wherein the hydrocarbon HC has 10 to 24 carbon atoms and is preferably selected from the group consisting of decene, dodecene, dodecane, isododecane, tetradecane, tributene, tributane, tetrabutene, tetrabutane, alkylbenzene having at least 10 carbon atoms, and oxo oil.

3. The composition according to claim 1 or 2, wherein the Si-free surfactant reduces the static surface tension of the mixture of the surfactant and water to less than 70 mN / m, preferably less than 60 mN / m, more preferably still less than 60 mN / m, more preferably still less than 50 mN / m, and particularly preferably less than 40 mN / m at a concentration of 0.5% by weight in water and a temperature of 20° C.

4. The composition according to any one of claims 1 to 3, wherein the Si-free surfactant is a nonionic surfactant or contains the same.

5. The composition according to any one of claims 1 to 4, wherein the Si-free surfactant is a carboxylic acid derivative selected from the group consisting of esters, amides, imides, imidazolines, and oxazolines and / or a polyether compound or contains the same.

6. The composition according to any one of claims 1 to 5, wherein the hydrocarbon HC is used in combination with the Si-free surfactant at a mass ratio of 1:5 to 1:

200.

7. The composition according to any one of claims 1 to 6, wherein the composition further comprises a polyalkylsiloxane, the polyalkylsiloxane preferably contains less than 20 Si atoms, more preferably still less than 15 Si atoms, and particularly preferably less than 11 Si atoms, and the polyalkylsiloxane is used at a mass ratio of preferably 1:4 to 1:200 with respect to the Si-free surfactant.

8. The composition according to any one of claims 1 to 7, characterized in that the total mass ratio of the hydrocarbon HC, the Si-free surfactant, and the optional polyalkylsiloxane to 100 parts by mass of the polyol component is 0.1 to 10 pp hp, preferably 0.5 to 5 pp hp, particularly preferably 1 to 3 pp hp.

9. The polyalkylsiloxane is represented by Formula 1: M ａ D ｂ T ｃ Q ｄ (Formula 1) [In the formula, M = R １１ R １２ R １３ SiO １／２ D = R １４ R １５ SiO ２／２ T = R １６ SiO ３／２ Q = SiO ４／２ where R １１ 、 R １２ 、 R １３ 、 R １４ 、 R １５ 、 R １６ are the same or different hydrocarbon groups or H having 1 to 12, preferably 1 to 8 carbon atoms, where the hydrocarbon groups may be substituted with heteroatoms, Particularly preferably, a phenyl group, CH ３ group, CH ３ CH ２ group, CH ２ CH group, ClCH ２ CH ２ CH ２ group and H group, and a = 2 to 6 b = 0 to 8 c = 0 to 4 d = 0 to 2 However, a + b + c + d < 20, preferably < 15, particularly preferably < 11], and the composition according to claim 7 or 8, characterized in that it conforms to this.

10. R １６ where R １１ , R １２ , R １３ , R １４ and R １５ is different from, and / or R １１ , R １２ and R １３ are different, the composition according to claim 9.

11. A method for producing a polyurethane foam by reacting one or more polyol components with one or more polyisocyanate components, characterized in that the reaction is carried out in the presence of a hydrocarbon HC, a Si-free surfactant, and optionally a polyalkylsiloxane, particularly under the use of the composition according to any one of claims 1 to 10.

12. The method according to claim 11, characterized in that each component of the hydrocarbon HC, the Si-free surfactant, and the optional polyalkylsiloxane is supplied to the reaction mixture for producing the polyurethane foam separately or together.

13. Use of a combination of a hydrocarbon HC, a Si-free surfactant, and optionally a polyalkylsiloxane, preferably as a foam stabilizer, particularly for improving the heat insulation properties of the polyurethane foam, under the use of the composition according to any one of claims 1 to 10, in the production of a polyurethane foam.

14. A polyurethane foam obtainable by the method according to claim 11 or 12.

15. Use of the polyurethane foam according to claim 14, preferably as a heat insulation board and / or heat insulation material for a cooling device.

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