Production of polyurethane foam

Abstract

The invention relates to a composition for producing polyurethane, preferably PU foam, particularly preferably rigid PU foam, comprising a polyisocyanate component, a polyol component, optionally a blowing agent, at least one solid filler, and optionally at least one catalyst that catalyzes the formation of a urethane or isocyanurate bond, the composition containing at least one surfactant based on a quarternary ammonium compound.

Description

[0001] Production of polyurethane foam

[0002] The present invention is in the field of polyurethanes, in particular polyurethane foams. In particular, it relates to the production of polyurethane foams using solid fillers and surfactants based on quaternary ammonium compounds, such as esterquats and / or alkylquats, compositions for producing such foams, and furthermore, the use of these foams.

[0003] Polyurethane (PU) in the context of the present invention is understood to mean, in particular, a product obtainable by reacting polyisocyanates and polyols or compounds with isocyanate-reactive groups. In addition to the polyurethane, other functional groups can also be formed, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and / or uretimines. Therefore, PU in the context of the present invention is understood to mean both polyurethane and polyisocyanurate, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretimine groups. Polyurethane foam (PU foam) in the context of the present invention is understood to mean foam that is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups. In addition to the eponymous polyurethane, other functional groups can also be formed, such asAllophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates, or uretimines. The terms "foam" and "foam" are used synonymously for the purposes of this invention.

[0004] When it comes to producing PU, preferably PU foams, especially rigid PU foams, it is particularly important to produce them cost-effectively. Another concern is to produce them sustainably, for example, through the use of bio-based and / or recycled materials. For this reason, various solids can also be used in the production of PU. The known prior art describes corresponding solids suitable for use in PU.

[0005] However, the use of solids typically entails significant problems with dispersion in the liquid starting materials and with processing. These include sedimentation, difficult redispersion after sedimentation, inhomogeneous distribution in the PU, and, above all, a resulting inhomogeneous property profile of the polyurethanes produced in this way. While there have been efforts to use dispersing additives to overcome these problems, so far there have been no truly convincing results. Among other things, the use of dispersing additives has always been accompanied by a significant increase in the viscosity of the components, which makes processing significantly more difficult or even impossible.

[0006] Against this background, the specific object of the present invention was to enable the provision of PU which contains solid fillers, but to overcome the above-mentioned problems of sedimentation, difficult redispersion after sedimentation, inhomogeneous distribution in the material, in particular while avoiding an excessive increase in the viscosity of the components.

[0007] In this context, it was surprisingly discovered within the scope of the present invention that the use of surfactants based on quaternary ammonium compounds, such as esterquats and / or alkylquats, enables the desired significant improvement in redispersion, sedimentation stability, and a more homogeneous property profile of the material. The viscosity of the components is affected to a much lesser extent.

[0008] The above-mentioned object is achieved by the subject matter of the invention. The subject matter of the invention is a composition for producing PU, preferably PU foam, in particular PU rigid foam, comprising a polyisocyanate component, a polyol component, optionally a blowing agent, at least one solid filler, and optionally at least one catalyst that catalyzes the formation of a urethane or isocyanurate bond. The composition contains at least one surfactant based on quaternary ammonium compounds, preferably based on a silicon-free quaternary ammonium compound, such as, for example, preferably esterquat, alkylquat, amidoamine quat, and / or imidazolinium quat.

[0009] For the purposes of this invention, “solid” filler means that the filler in question is in the solid state under normal ambient conditions, in particular at a temperature of 20°C and at a pressure of 1.01325 bar.

[0010] The subject matter according to the invention is accompanied by numerous advantages. For example, it enables the provision of PU, preferably PU foams, in particular rigid PU foams with high solids contents. This is advantageously possible without impairing the other properties of the material, in particular its mechanical properties. With regard to the provision of rigid PU foams, particularly fine-cell, uniform, and low-defect foam structures are also made possible. This makes it possible to provide corresponding polyurethanes with particularly good performance properties and a homogeneous property profile. The invention enables a particularly homogeneous distribution of solid fillers in the polyurethane. Overall, the invention enables simple processing of the solid fillers during production. The solid fillers can betogether with the at least one surfactant based on quaternary ammonium compounds, such as preferably esterquats and / or alkylquats, for example via one of the two reaction components (polyol component or polyisocyanate component). Introduction via the polyol component is preferred. Sedimentation problems during storage of the dispersion of reaction component and solid can be significantly reduced or even avoided entirely by the present invention. The invention also enables very good redispersibility of the solid in the event of sedimentation after very long storage, so that, for example, constant stirring or mixing during storage is no longer necessary. The invention also enables a more homogeneous distribution of the solid in the polyurethane, which leads to a more uniform property profile.

[0011] Surfactants based on quaternary ammonium compounds, such as esterquats, amidoaminequats, imidazoliniumquats, cetylpyridinium chloride, and / or alkylquats, are known to those skilled in the art. Esterquats and alkylquats, for example, are surfactants based on quaternary ammonium compounds with at least one long hydrocarbon residue. While alkylquats are generally tetraalkylammonium salts, esterquats are generally based on quaternary triethanolmethylammonium or quaternary diethanoldimethylammonium compounds that have been esterified with at least one fatty acid.

[0012] Alkyl quats and ester quats have long been used in cosmetics and detergents, such as fabric softeners, and their production has long been known to those skilled in the art. Alkyl quats can be produced, for example, by reacting the corresponding amine with methylating agents such as chloromethane or dimethyl sulfate. Ester quats can be produced, for example, by esterifying methyldiethanolamine or triethanolamine with fatty acids and subsequent quaternization with, for example, dimethyl sulfate or chloromethane.

[0013] US 20160264711 A1 describes the use of quaternary ammonium compounds in flexible polyurethane foams to improve the compatibility of polyether polycarbonate polyols without the use of a solid filler. US 5420186 A describes the use of quaternary ammonium compounds as an internal release agent in polyurethane elastomers without the use of a solid filler. The composition according to the invention necessarily contains at least one solid filler, preferably selected from the group consisting of calcium carbonate, lignin, lignocellulose, and plastic particles. The at least one solid filler is preferably in powder form. Mixtures of such solid fillers can also be used.

[0014] It corresponds to a particularly preferred embodiment of the invention if the plastic particle or particles are formed from at least one plastic, preferably selected from the group consisting of polyethylene, polypropylene, polyamide (in particular PA6, PA6.6, PA10, PA11 and / or PA12), polyester (in particular polyethylene terephthalate, polybutylene terephthalate and / or poly- e -caprolactone), polystyrene, polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymers, polyethers, polylactic acid, polyurethane, polysulfones, polyethersulfone, polyetherimide and polyimide, in particular polyurethane.

[0015] According to a particularly preferred embodiment of the invention, the plastic particle(s) may be formed entirely or partially from recycled plastics, preferably recycled polyurethanes.

[0016] According to a particularly preferred embodiment of the invention, the at least one solid filler preferably has a weight-average diameter of the primary particles, determined by means of dynamic light scattering, of > 50 nm, preferably greater than 100 nm, particularly preferably greater than 200 nm. The determination of the particle diameter by means of dynamic light scattering is known to the person skilled in the art and is preferably carried out in water.

[0017] Preferably, according to a particularly preferred embodiment of the present invention, the composition according to the invention does not contain any particles of metal oxide, in particular it does not contain any particles consisting of a material selected from the group consisting of SiO2, ZnO2, Al2O3, ZrO2 and TiO2.

[0018] According to a particularly preferred embodiment of the invention, the surfactant(s) based on quaternary ammonium compounds used are preferably at least one ester quat of the formula (1) or (2), an alkyl quat of the formula (3), an imidazolinium quat of the formula (4), an amidoamine quat of the formula (5) and / or cetylpyridinium chloride, where with R 1 an acyl radical of a saturated or mono- or polyunsaturated, linear or branched fatty acid with a chain length of 8 to 22 carbon atoms or the acyl radical of ricinoleic acid, or hydrogen, where a compound of formula (1) or (2) has different radicals R 1 and with the proviso that at least one radical R 1 must be one of the acyl residues mentioned, with

[0019] R 2 an alkyl radical having 1 to 6 carbon atoms or hydrogen, preferably hydrogen, methyl, ethyl, propyl or isopropyl, particularly preferably hydrogen or methyl, with

[0020] R 3 an alkyl radical having 1 to 6 carbon atoms, or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably methyl or hydrogen, with

[0021] R 4 an alkyl radical having 1 to 6 carbon atoms or a hydroxyethyl radical or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, where a compound of formula (1) or (2) has different radicals R 4 and wherein n = 0 to 20, preferably 0 to 10, particularly preferably 0, wherein a = 1 to 3 and b = 1 to 3, with the proviso that a + b = 4, and / or wherein Formula (3) with

[0022] R 5 a saturated or mono- or polyunsaturated, linear or branched alkyl radical having a chain length of 8 to 24 carbon atoms, where a compound of formula (3) has different radicals R 5 may contain, with

[0023] R 6 an alkyl radical having 1 to 6 carbon atoms or a hydroxyethyl radical or a benzyl radical or hydrogen, preferably methyl, ethyl, propyl, isopropyl or benzyl, particularly preferably ethyl or methyl, very particularly preferably methyl, where a compound of the formula (3) has different radicals R 6 and where c = 1 to 3 and d = 1 to 3, with the proviso that c + d = 4, and / or where Formula (4) with

[0024] R 7 an alkyl radical having 1 to 6 carbon atoms or a hydroxyethyl radical or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, most preferably methyl, with

[0025] R 8 a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 8 to 22 carbon atoms or a radical O(CO)R 10 , with R 10an aliphatic, saturated or mono- or polyunsaturated, linear or branched alkyl radical having 7 to 21 carbon atoms, with R 9 an aliphatic saturated or mono- or polyunsaturated, linear or branched alkyl radical having 7 to 21 carbon atoms, with

[0026] Z is an NH group or oxygen, where e can take on integer values ​​between 1 and 4, and / or where, with

[0027] R 11 a saturated or mono- or polyunsaturated, linear or branched alkyl radical with a chain length of 7 to 21 carbon atoms, with

[0028] R 12 an alkyl radical having 1 to 6 carbon atoms or a hydroxyethyl radical or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, where a compound of the formula (5) has different radicals R 12and where f can take on integer values ​​between 0 and 5, where h = 1 or 2 and g = 2 or 3, with the proviso that h + g = 4, where a compound of formula (5) for h = 2 can take on different values ​​for f and different radicals R 11 may contain, provided R 4 , R 6 , R 7 or R 12 comprises a hydroxyethyl radical, this may also be alkoxylated and this optionally alkoxylated hydroxyethyl radical may contain repeat units based on ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide and comprise 1-15 repeat units, preferably 1-10 repeat units.

[0029] Corresponding compositions containing corresponding quaternary ammonium compounds show particularly advantageous results with regard to the advantages of the invention described above.

[0030] It corresponds to a further particularly preferred embodiment of the invention if in formula (1) and / or formula (2) R 1 is selected from the acyl residues of the acids from the group comprising oleic acid, isostearic acid, lauric acid, palmitic acid, elaidic acid, vaccenic acid, gadoleic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, alpha-linolenic acid, gamma-linolenic acid, calendulic acid, punicic acid, alpha-elaeostearic acid, beta-elaeostearic acid, arachidonic acid, timnodonic acid, clupanodonic acid and / or cervonic acid.

[0031] Furthermore, it is preferred if in formula (1) a = b = 2 and / or in formula (5) h = 1 and g = 3. This also corresponds to another particularly preferred embodiment of the invention.

[0032] A composition according to the invention containing at least one counter anion to the compound(s) of general formula (1), (2), (3), (4) and / or (5), selected from the group comprising chloride, bromide, iodide, alkyl sulfate, e.g. m ethyl sulfate, ethyl sulfate, alkylsulfonate, e.g. methylsulfonate, triflate, tosylate, phosphate, sulfate, hydrogen sulfate, lactate, glycolate, acetate and / or citrate, corresponds to a further particularly preferred embodiment of the invention.

[0033] If the at least one surfactant based on a quaternary ammonium compound is present in the composition according to the invention in a total amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.1 to 4 parts by weight, based on 100 parts by weight of polyols, then a further particularly preferred embodiment of the invention is present.

[0034] According to a further preferred embodiment of the invention, the at least one solid filler is contained in the composition according to the invention in a total amount of 1 to 80 parts by weight, preferably 5 to 60 parts by weight, particularly preferably 8 to 40 parts by weight, based on 100 parts by weight of polyols.

[0035] According to a further particularly preferred embodiment of the invention, the at least one solid filler is preferably present in the composition according to the invention in a total amount which leads to the production of PU, preferably PU foam, which contains > 2 wt.%, preferably > 5 wt.%, more preferably > 8 wt.%, even more preferably > 10 wt.% of the at least one solid filler, wt.% based on the resulting PU, preferably PU foam. A possible upper limit can preferably be < 30 wt.%, e.g., 15 wt.% or, for example, 20 wt.%.

[0036] Furthermore, it is particularly preferred if the composition according to the invention additionally contains at least one foam stabilizer, preferably based on a polyethersiloxane, preferably in amounts of 0.5 to 4 parts by weight, based on 100 parts by weight of polyols. This corresponds to a particularly preferred embodiment of the invention. Foam stabilizers, preferably based on a polyethersiloxane, are known per se. Suitable foam stabilizers are described further below.

[0037] The invention further relates to a process for producing PU, preferably PU foam, in particular PU rigid foam, based on reaction mixtures containing a polyisocyanate component, a polyol component, optionally blowing agent, at least one solid filler, optionally at least one catalyst and optionally further additives, wherein at least one surfactant based on quaternary ammonium compounds, preferably as described above, is used, preferably using a composition according to the invention as described above, in particular as described in more detail above in the preferred or particularly preferred embodiments.

[0038] In particular, it is preferred if the at least one surfactant based on a quaternary ammonium compound is used in a total amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.1 to 4 parts by weight, based on 100 parts by weight of polyols. This corresponds to a particularly preferred embodiment of the invention.

[0039] In particular, it is preferred if the at least one solid filler is used in a total amount of 1 to 80 parts by weight, preferably 5 to 60 parts by weight, particularly preferably 8 to 40 parts by weight, based on 100 parts by weight of polyols. This corresponds to a particularly preferred embodiment of the invention.

[0040] In particular, it is further preferred if at least one foam stabilizer, in particular based on a polyether siloxane, is additionally present in amounts of 0.5 to 4 parts by weight, based on 100 parts by weight of polyols. This corresponds to a particularly preferred embodiment of the invention.

[0041] Furthermore, it corresponds to a particularly preferred embodiment of the invention if the process according to the invention for producing PU, preferably PU foam, in particular PU rigid foam, is characterized in that the resulting PU, preferably PU foam, in particular PU rigid foam, contains the at least one solid filler in a total amount of > 2 wt. %, preferably > 5 wt. %, more preferably > 8 wt. %, even more preferably > 10 wt. %, wt. % based on the resulting PU, preferably PU foam, in particular PU rigid foam. A possible upper limit can preferably be < 30 wt. %, e.g. 15 wt. % or e.g. 20 wt. %.

[0042] Preferably, in the process according to the invention according to a particularly preferred embodiment of the present invention, no particles of metal oxide are used, in particular no particles consisting of a material selected from the group consisting of SiO2, ZnO2, Al2O3, ZrO2 and TiO2.

[0043] The process according to the invention for producing PU, preferably PU foam, in particular rigid PU foam, can be carried out using known methods, e.g., by hand mixing or, preferably, using foaming machines. If the process is carried out using foaming machines, high-pressure or low-pressure machines can be used. The process according to the invention can be carried out both batchwise and continuously.

[0044] A particularly preferred PU formulation in the sense of this invention results in a density of 5 to 900 kg / m 3and has the composition shown in Table 1, which corresponds to a preferred embodiment of the invention:

[0045] Table 1 :

[0046] Composition of a preferred PU rigid foam formulation For further preferred embodiments and configurations of the process according to the invention, reference is also made to the statements already made in connection with the composition according to the invention.

[0047] Yet another subject of the present invention is a PU, preferably PU foam, in particular PU rigid foam, produced according to the above-mentioned process according to the invention, in particular using a composition according to the invention.

[0048] If the PU according to the invention is a PU foam, in particular a PU rigid foam and has a density of 5 to 900 kg / m 3 , preferably 5 to 350 kg / m 3, especially 10 to 200 kg / m 3 This is a preferred embodiment of the invention.

[0049] Preferably, the PU according to the invention, preferably PU foam, in particular PU rigid foam, produced according to the aforementioned process according to the invention, in a particularly preferred embodiment contains the at least one solid filler in a total amount of > 2 wt.%, preferably > 5 wt.%, more preferably > 8 wt.%, even more preferably > 10 wt.%, wt.% based on the entire polyurethane, preferably PU foam, in particular PU rigid foam.

[0050] Preferably, the PU according to the invention, preferably PU foam, in particular PU rigid foam, in a particularly preferred embodiment contains no particles of metal oxide, in particular no particles consisting of a material selected from the group consisting of SiO2, ZnO2, Al2O3, ZrO2 and TiO2.

[0051] A further subject matter of the present invention relates to the use of PU and / or PU foam according to the invention, as mentioned above, as refrigerator insulation, as construction material, preferably as insulation board, sandwich element, spray foam and / or 1- & 1.5-component canned foam, as pipe insulation, imitation wood, model foam, packaging foam, mattress, furniture upholstery, automotive seat upholstery, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorption material, steering wheel, shoe sole, carpet backing foam, filter foam, sealing foam, sealant, adhesive or coating or for the production of corresponding products.

[0052] A preferred composition according to the invention contains in particular the following components: a) surfactant(s) based on quaternary ammonium compounds, in particular as defined above with formula (1), (2), (3), (4) and / or (5) b) polyol component c) polyisocyanate component d) catalyst e) optionally foam stabilizer f) optionally one or more blowing agents g) solid filler(s) h) optionally further additives, flame retardants, etc.

[0053] The polyol component (b) consists of at least one polyol and optionally at least one organic compound containing at least two isocyanate-reactive groups, preferably selected from the group consisting of OH, NH, and NH2 groups. Polyols are organic compounds containing at least two hydroxyl groups (-OH).

[0054] If one of the aforementioned organic compounds of the polyol component contains at least two OH groups, then it is exclusively classified as a polyol for the purposes of the invention. This means that if an organic compound of the polyol component can be classified both as a polyol and as an organic compound containing at least two isocyanate-reactive groups, preferably selected from the group consisting of OH, NH, and NH2 groups, then it is exclusively classified as a polyol for the purposes of the invention.

[0055] Based on its total weight, the polyol component preferably contains at least 50 wt.% of polyols which contain only hydroxyl groups (-OH) as isocyanate-reactive groups.

[0056] Based on the total number of isocyanate-reactive groups in the polyol component, it is preferred that at least 50% of these are hydroxyl groups (-OH).

[0057] Corresponding compounds that can typically be used in the production of PU are known to the person skilled in the art and are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethane," Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Compounds with OH numbers in the range of 10 to 1200 mg KOH / g are typically used. Particularly preferred compounds are all polyether polyols and polyester polyols commonly used for the production of polyurethane systems, in particular polyurethane foams. Polyether polyols can preferably be obtained by reacting polyhydric alcohols or amines with alkylene oxides. Polyester polyols are preferably based on esters of polybasic carboxylic acids (which can be either aliphatic, for example, adipic acid, or aromatic, for example, phthalic acid or terephthalic acid) with polyhydric alcohols (preferably glycols).

[0058] In addition, polyether polycarbonate polyols, natural oil-based polyols (NOPs; described in WO 2005 / 033167, US 2006 / 0293400, WO 2006 / 094227, WO 2004 / 096882, US 2002 / 0103091, WO 2006 / 116456, EP 1678232), filler polyols, prepolymer-based polyols and / or recycling polyols can be used.

[0059] Recycling polyols are polyols obtained from the chemical recycling of polyurethanes, for example, by solvolysis, such as glycolysis, hydrolysis, acidolysis, or aminolysis. The use of recycling polyols represents a particularly preferred embodiment of the invention.

[0060] The polyisocyanate component (c) consists of at least one polyisocyanate having two or more isocyanate groups. Suitable polyisocyanates for the purposes of this invention are all organic isocyanates having two or more isocyanate groups, in particular the known aliphatic, cycloaliphatic, arylaliphatic, and preferably aromatic polyfunctional isocyanates.

[0061] Examples which can be mentioned here are alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyl-tetramethylene-1,4-diisocyanate, 2-methyl-pentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene diisocyanate (PDI) and preferably hexamethylene-1,6-diisocyanate (HMDI), cycloaliphatic diisocyanates such as cyclohexane-1,3- and -1,4-diisocyanate and the corresponding isomer mixtures, 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,4- and 2,6-methylcyclohexyl diisocyanate and the corresponding isomer mixtures and preferably aromatic di- and polyisocyanates such as 2,4- and 2,6-Toluene diisocyanate (TDI) and the corresponding isomer mixtures, naphthylene diisocyanate, diethyltoluene diisocyanate, 4,4'- or 2,2'- or 2,4'-diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanates (PMDI, “polymeric MDI”).The organic polyisocyanates can be used individually or as mixtures. Corresponding "oligomers" of diisocyanates can also be used, such as the IPDI trimer based on isocyanurate, biurets, or urethdiones. Furthermore, the use of prepolymers based on the above-mentioned isocyanates is possible.

[0062] Particularly suitable is the mixture of MDI and higher condensed analogues with an average functionality of 2 to 4, known as "polymeric MDI" (also called "crude MDI"), as well as the various isomers of TDI in pure form or as a mixture of isomers.

[0063] It is also possible to use isocyanates modified by the incorporation of urethane, uretdione, isocyanurate, allophanate, and other groups, so-called modified isocyanates. Examples of particularly suitable isocyanates are also listed, for example, in EP 1712578, EP 1161474, WO 00 / 58383, US 2007 / 0072951, EP 1678232, and WO 2005 / 085310, which are incorporated herein by reference.

[0064] A preferred ratio of polyisocyanate component and polyol component, expressed as an index of the formulation (isocyanate index), i.e. as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups) multiplied by 100, is in the range of 10 to 1000, preferably 40 to 400. An index of 100 represents a molar ratio of the reactive groups of 1 to 1.

[0065] Suitable catalysts (d) that can be used for the production of polyurethanes, especially PU foams, and in particular those capable of catalyzing the formation of a urethane or isocyanurate bond, are known to the person skilled in the art. For the purposes of the present invention, in particular, all compounds capable of catalyzing the reaction of isocyanate groups with OH, NH, or other isocyanate-reactive groups and / or the reaction of isocyanate groups with one another can be used.

[0066] The usual catalysts known from the prior art can be used here, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and / or metal salts, preferably those of tin, iron, bismuth, potassium and / or zinc. In particular, mixtures of several such compounds can be used as catalysts. Foam stabilizers and their use in the production of PU foams are known to those skilled in the art. The use of foam stabilizers is optional; preferably, one or more foam stabilizers are used. They can serve to optimize the desired cell structure and the foaming process.

[0067] Within the scope of this invention, Si-containing compounds that support foam production (stabilization, cell regulation, cell opening, etc.) can be used. These compounds are well known in the art. Particularly preferably, at least one foam stabilizer based on a polyether siloxane can be used.

[0068] Corresponding siloxane structures which can be used in the sense of this invention are described, for example, in the following patent specifications, although the use is only described there in classic PU foams, as molded foam, mattresses, insulation material, construction foam, etc.: CN 103665385, CN 103657518, CN 103055759, CN 103044687, US 2008 / 0125503, US 2015 / 0057384, EP 1520870 A1, EP 1211279, EP 0867464, EP 0867465, EP 0275563. In addition to surface-active Si-containing compounds, Si-free surfactants can also be used. For example, EP2295485 A1 describes the use of lecithin, and US Pat. No. 3,746,663 describes the use of vinylpyrrolidone-based structures as foam stabilizers for the production of rigid PU foam. Other Si-free foam stabilizers are described, for example, in EP 2511328 B1, DE 1020011007479 A1, DE 3724716 C1, EP 0734404, EP 1985642, DE 2244350, and US Pat. No. 5,236,961.

[0069] Blowing agents (f) and their use in the production of PU foams are known to those skilled in the art. The use of blowing agents is optional; blowing agents are preferred. The use of one or a combination of several blowing agents (f) depends fundamentally on the type of foaming process used, the type of system, and the application of the resulting PU foam.

[0070] Chemical and / or physical blowing agents, or a combination of both, can be used. Depending on the amount of blowing agent used, a foam with high or low density is produced. For example, foams with densities of 5 kg / m 3 up to 900 kg / m 3 , preferably 5 to 350, particularly preferably 8 to 200 kg / m 3 , especially 8 to 150 kg / m 3 be manufactured.

[0071] One or more of the corresponding compounds with suitable boiling points and mixtures thereof, such as hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso-, n-pentane, fluorocarbons (HFC), preferably HFC 245fa, HFC 134a or HFC 365mfc, chlorofluorocarbons (HCFC), preferably HCFC 141b, hydrofluoroolefins (HFO) 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 as physical blowing agents.

[0072] As chemical blowing agents, one or more compounds can be used which react with NCO groups to release gases, such as water or formic acid, or which release gases due to the temperature increase during the reaction, such as sodium bicarbonate.

[0073] It corresponds to a particularly preferred embodiment if the composition according to the invention contains water as a blowing agent in combination with hydrocarbons having 5 carbon atoms, HFO, hydrohaloolefins or HFC or mixtures thereof.

[0074] Solid fillers g) have already been described above.

[0075] As optional additives (h), one or more of the substances known in the art which are used in the production of polyurethanes, in particular PU foams, such as crosslinkers, chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, biocides, cell-refining additives, nucleating agents, cell openers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances and / or emulsifiers, etc., can be used.

[0076] As an optional flame retardant, the composition according to the invention can contain one or more of the known flame retardants suitable for the production of PU foams, such as, for example, halogen-containing or halogen-free organic phosphorus-containing compounds, such as triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP), dimethyl methanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), ammonium polyphosphate or red phosphorus, nitrogen-containing compounds such as, for example, melamine, melamine cyanurate or melamine polyphosphate or halogenated compounds, such as, for example, chlorinated and / or brominated polyether and / or polyester polyols. Mixtures of different flame retardants can also be used.Unless otherwise apparent from this description, any preferred or particularly preferred embodiment of the invention may be combined with one or more of the other preferred or particularly preferred embodiments of the invention.

[0077] The subject matters according to the invention have been and will be described below by way of example, without the invention being restricted to these exemplary embodiments. Where ranges, general formulas or classes of compounds are specified, these are intended to include not only the corresponding ranges or groups of compounds that are explicitly mentioned, but also all sub-ranges and sub-groups of compounds that can be obtained by removing individual values ​​(ranges) or compounds. If documents are cited within the scope of the present description, their content, particularly with regard to the facts in connection with which the document was cited, is intended to be fully incorporated into the disclosure of the present invention. Percentages are, unless otherwise stated, percentages by weight. Mean values ​​are, unless otherwise stated, weight averages.If parameters are specified that were determined by measurement, the measurements were carried out at a temperature of 25 °C and a pressure of 101325 Pa (normal pressure), unless otherwise stated.

[0078] In the examples listed below, the present invention is described by way of example, without the invention, the scope of which emerges from the entire description and the claims, being intended to be limited to the embodiments mentioned in the examples.

[0079] Examples:

[0080] Example 1: PIR rigid foam (PIR = polyisocyanurate)

[0081] For the application-related comparison, the formulation shown in Table 2 was used, and the compounds listed in Table 3 were investigated. The comparative foamings were carried out using a hand-mixing method. Polyol, catalysts, water, foam stabilizer, dispersant (Table 3), solid filler, and blowing agent were weighed into a beaker and mixed with a 6-cm diameter plate stirrer for 30 seconds at 1000 rpm (batch size 500 g). The amount of blowing agent evaporated during the mixing process was determined by reweighing and then replenished. The MDI was then added, the reaction mixture was stirred with the described stirrer for 5 seconds at 3000 rpm, and immediately transferred to a 25 cm x 50 cm x 7 cm aluminum mold lined with polyethylene film and thermostatted to 60 °C.

[0082] After 10 minutes, the foams were demolded. One day after foaming, the foams were analyzed. Surface and internal defects were subjectively assessed on a scale of 1 to 10, with 10 representing an (idealized) undisturbed foam and 1 representing extremely severely disturbed foam. The thermal conductivity (A-value in mW / m K) was measured on 2.5 cm thick panes using a Hesto Lambda Control device, model HLC X206, at an average temperature of 10 °C in accordance with the specifications of EN 12667:2001.

[0083] Table 2: PIR rigid foam formulation

[0084] *Stepanpol® PS 3152 from Stepan, OH number 315 mg KOH / g **POLYCAT® 5 from Evonik Operations GmbH

[0085] ***DABCO® TMR 12 from Evonik Operations GmbH

[0086] ****TEGOSTAB® B 84504 from Evonik Operations GmbH

[0087] *****Lignin from hardwood, CaCO3, PIR powder or PUR powder ******Polymeric MDI, 200 mPa*s, 31.5% NCO, functionality 2.7.

[0088] Table 3: Compounds investigated

[0089] The compounds of the invention were compared with non-inventive, commercially available surfactants (TEGOPREN® 6921, TEGOTEX® 8080, TEGO® Dispers 652, Thixatrol® ST). The results are summarized in Tables 4 and 5:

[0090] Table 4: Foam properties of PIR rigid foam with lignin as filler

[0091] Table 5: Cell structure surface / internal defects for PIR rigid foam

[0092] The results show that the relevant foam properties are not, or only insignificantly, affected by the compounds of the invention. Furthermore, the use of the compounds of the invention allows for a more homogeneous distribution of the solid filler in the foam, which is reflected in a significant improvement in both the surface and the pore structure / internal defects. In contrast, the non-inventive compounds frequently lead to significant coarsening of the foam (TEGOPREN® 6921), collapse (TEGOTEX® 8080), or show no improvement in the foam structure (TEGO® Dispers 652, Thixatrol® ST). Example 2: Dispersibility

[0093] For the application-related comparison, the formulations presented in Tables 6, 8, 10, and 12 were used, and the compounds presented in Table 3 were investigated. For this purpose, polyol and water were weighed (batch size 100 g) and mixed using a plate stirrer (6 cm diameter) for 30 s at 1000 rpm. The compound according to the invention was then added and mixed using a plate stirrer (6 cm diameter) for 30 s at 2000 rpm. For the reference experiment, mixing was also carried out for a further 30 s at 2000 rpm, but without the addition of the compound according to the invention. The solid filler was then added, with the plate stirrer still running at 2000 rpm, and mixed for a further 45 s. The formulations were then filled into glass vessels, sealed, and the time until complete sedimentation was measured.

[0094] After upright storage for 14 days at room temperature, all samples were redispersed and their redispersibility was assessed on a scale of 1 to 3. A grade of 1 indicates that the sample could be redispersed by manually shaking the glass container for 30 seconds. A grade of 2 indicates that the sample could not be redispersed by manually shaking the glass container, but could be redispersed by using an electric laboratory stirrer (500 rpm for 60 seconds). A grade of 3 was awarded to samples in which a very solid, compact sediment formed that could not be redispersed by the two methods mentioned above.

[0095] Viscosity was determined using two measurement methods. Viscosities were measured using an Anton Paar MCR 302 rheometer (50 mm plate-to-plate, 0.5 mm gap) at 25 °C at various shear rates on freshly prepared formulations (Table 5), or using a DV2 T rheometer with LV04 (64) spindles at 21 °C and various shear rates on freshly prepared formulations.

[0096] The results for the dispersion behavior are shown in Tables 7, 9, 11, and 13. Table 6: Formulation for testing the dispersion behavior

[0097] *Stepanpol® PS 3152 from Stepan, OH number 315 mg KOH / g **Lignin from hardwood.

[0098] Table 7: Dispersibility - Lignin from hardwood

[0099] *Cone-Plate Rheometer Table 8: Formulation for testing the dispersion behavior

[0100] *Stepanpol® PS 3152 from Stepan, OH number 315 mg KOH / g **CaCO3.

[0101] Table 9: Dispersing behavior - CaCCh Table 10: Formulation for testing the dispersing behavior

[0102] *Stepanpol® PS 3152 from Stepan, OH number 315 mg KOH / g ** Pin mill ground PIR foam insulation board (cryogenic grinding with liquid

[0103] Nitrogen, peripheral speed 120 m / s).

[0104] Table 11: Dispersing behavior - PIR powder Viscosities measured with spindle type LV04 (64) Table 12: Formulation for testing the dispersion behavior

[0105] *Stepanpol® PS 3152 from Stepan, OH number 315 mg KOH / g ** PUR foam insulation board ground using a pin mill (cryogenic grinding with liquid

[0106] Nitrogen, peripheral speed 120 m / s).

[0107] Table 13: Dispersing behavior - PUR powder Viscosities measured with a spindle of type LV04 (64). In all cases investigated, an improvement in sedimentation stability and / or redispersibility was achieved compared to formulations without compounds according to the invention. In particular, the formation of a solid, compact sediment was avoided. The invention therefore enables very good redispersibility of the solid in the event of sedimentation after very long storage, so that, for example, constant stirring or mixing during storage is no longer necessary.

Claims

Patent claims:

1. Composition for producing PU, preferably PU foam, in particular PU rigid foam, comprising a polyisocyanate component, a polyol component, optionally blowing agent, at least one solid filler, optionally at least one catalyst which catalyzes the formation of a urethane or isocyanurate bond, characterized in that the composition contains at least one surfactant based on a quaternary ammonium compound, preferably based on a silicon-free quaternary ammonium compound.

2. Composition according to claim 1, characterized in that the at least one solid filler is selected from the group consisting of calcium carbonate, lignin, lignocellulose and plastic particles.

3. Composition according to claim 2, characterized in that the plastic particle or particles are formed from at least one plastic, preferably selected from the group consisting of polyethylene, polypropylene, polyamide (in particular PA6, PA6.6, PA10, PA11 and / or PA12), polyester (in particular polyethylene terephthalate, polybutylene terephthalate and / or poly- e -caprolactone), polystyrene, polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymers, polyethers, polylactic acid, polyurethane, polysulfones, polyethersulfone, polyetherimide and polyimide, in particular polyurethane.

4. Composition according to one of claims 2 or 3, characterized in that the plastic particle(s) are formed wholly or partly from recycled plastics.

5. Composition according to one of claims 1 to 4, characterized in that the composition contains lignin and / or plastic particles made of preferably recycled plastics, preferably recycled polyurethanes, as solid filler.

6. Composition according to one of claims 1 to 5, characterized in that the at least one solid filler has a weight-average diameter of the primary particles, determined by means of dynamic light scattering, of > 50 nm, preferably greater than 100 nm, particularly preferably greater than 200 nm. Composition according to one of claims 1 to 6, characterized in that at least one ester quat of formula (1) or (2), an alkyl quat of formula (3), an imidazolinium quat of formula (4), an amidoamine quat of formula (5) and / or cetylpyridinium chloride is used as quaternary ammonium compound, where with R 1an acyl radical of a saturated or mono- or polyunsaturated, linear or branched fatty acid with a chain length of 8 to 22 carbon atoms or the acyl radical of ricinoleic acid, or hydrogen, where a compound of formula (1) or (2) has different radicals R 1 and with the proviso that at least one radical R 1 must be one of the acyl residues mentioned, with R 2 an alkyl radical having 1 to 6 carbon atoms or hydrogen, preferably hydrogen, methyl, ethyl, propyl or isopropyl, particularly preferably hydrogen or methyl, with R 3 an alkyl radical having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably methyl or hydrogen, with R 4an alkyl radical having 1 to 6 carbon atoms or a hydroxyethyl radical or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, where a compound of formula (1) or (2) has different radicals R 4 may contain and where n = 0 to 20, preferably 0 to 10, particularly preferably 0, where a = 1 to 3 and b = 1 to 3, with the proviso that a + b = 4, and where Formula (3) with R 5 a saturated or mono- or polyunsaturated, linear or branched alkyl radical having a chain length of 8 to 24 carbon atoms, where a compound of formula (3) has different radicals R 5 may contain, with R 6an alkyl radical having 1 to 6 carbon atoms or a hydroxyethyl radical or a benzyl radical or hydrogen, preferably methyl, ethyl, propyl, isopropyl or benzyl, particularly preferably ethyl or methyl, very particularly preferably methyl, where a compound of the formula (3) has different radicals R 6 and where c = 1 to 3 and d = 1 to 3, with the proviso that c + d = 4, and where Formula (4) with R 7 an alkyl radical having 1 to 6 carbon atoms or a hydroxyethyl radical or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, most preferably methyl, with R 8 a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 8 to 22 carbon atoms or a radical O(CO)R 10 , with R 10an aliphatic, saturated or mono- or polyunsaturated, linear or branched alkyl radical having 7 to 21 carbon atoms, with R 9 an aliphatic saturated or mono- or polyunsaturated, linear or branched alkyl radical having 7 to 21 carbon atoms, with Z is an NH group or oxygen, where e can take integer values ​​between 1 and 4, with R 11 a saturated or mono- or polyunsaturated, linear or branched alkyl radical with a chain length of 7 to 21 carbon atoms, with R 12 an alkyl radical having 1 to 6 carbon atoms or a hydroxyethyl radical or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, where a compound of the formula (5) has different radicals R 12and where f can take on integer values ​​between 0 and 5, where h = 1 or 2 and g = 2 or 3, with the proviso that h + g = 4, where a compound of formula (5) for h = 2 can take on different values ​​for f and different radicals R 11 may contain, provided R 4 , R 6 , R 7 or R 12 comprises a hydroxyethyl radical, this may also be alkoxylated and this optionally alkoxylated hydroxyethyl radical may contain repeat units based on ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide and comprise 1-15 repeat units, preferably 1-10 repeat units. Composition according to claim 7, characterized in that in formula (1) and / or formula (2) R 1is selected from the acyl residues of the acids from the group comprising oleic acid, isostearic acid, lauric acid, palmitic acid, elaidic acid, vaccenic acid, gadoleic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, alpha-linolenic acid, gamma-linolenic acid, calendulic acid, punicic acid, alpha-elaeostearic acid, beta-elaeostearic acid, arachidonic acid, timnodonic acid, clupanodonic acid, and / or cervonic acid. Composition according to claim 7 or 8, characterized in that in formula (1) a = b = 2 and / or in formula (5) h = 1 and g = 3. Composition according to one of claims 7 to 9, characterized in that it additionally contains at least one counter anion to the compound(s) of the general formulas (1), (2), (3), (4) and / or (5), selected from the group comprising chloride, bromide, iodide, alkyl sulfate, e.g. methyl sulfate, ethyl sulfate, alkylsulfonate, e.g.Methylsulfonate, triflate, tosylate, phosphate, sulfate, hydrogensulfate, lactate, glycolate, acetate, and / or citrate. Composition according to one of claims 1 to 10, characterized in that the at least one surfactant based on a quaternary ammonium compound is present in a total amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.1 to 4 parts by weight, based on 100 parts by weight of polyols. Composition according to one of claims 1 to 11, characterized in that the at least one solid filler is present in a total amount of 1 to 80 parts by weight, preferably 5 to 60 parts by weight, particularly preferably 8 to 40 parts by weight, based on 100 parts by weight of polyols.Composition according to one of claims 1 to 12, characterized in that it additionally contains at least one foam stabilizer, in particular based on a polyether siloxane, in amounts of 0.5 to 4 parts by weight, based on 100 parts by weight of polyols. Composition according to one of claims 1 to 13, characterized in that it contains no metal oxide particles, in particular no particles consisting of a material selected from the group consisting of SiO2, ZnO2, Al2O3, ZrO2, and TiO2.

15. A process for producing PU, preferably PU foam, in particular PU rigid foam based on reaction mixtures containing a polyisocyanate component, a polyol component, optionally blowing agent, at least one solid filler, optionally at least one catalyst and optionally further additives, characterized in that at least one surfactant based on a quaternary ammonium compound, preferably as defined in one of claims 7 to 10, is used, in particular using a composition as defined in one of claims 1 to 14.

16. Polyurethane, preferably PU foam, in particular PU rigid foam produced according to the process of claim 15.

17. Use of PU and / or PU foam according to claim 16 as refrigerator insulation, as construction material, preferably as insulation board, sandwich element, spray foam and / or 1- & 1.5-component canned foam, as pipe insulation, imitation wood, model foam, packaging foam, mattress, furniture upholstery, automotive seat upholstery, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorption material, steering wheel, shoe sole, carpet backing foam, filter foam, sealing foam, sealant, adhesive or coating or for the production of corresponding products.

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