Polyurethane foam manufacturing

Abstract

A composition for producing polyurethane, preferably PU foam, particularly 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 urethane bonds or isocyanurate bonds, wherein the composition contains at least one surfactant based on a quaternary ammonium compound.

Description

[Technical Field]

[0001] The present invention relates to the field of polyurethanes, particularly polyurethane foams. In particular, the present invention relates to the production of polyurethane foams using solid fillers and quaternary ammonium compound-based surfactants, such as ester quats and / or alkyl quats, compositions for producing such foams, and uses of these foams.

[0002] In the context of the present invention, polyurethane (PU) is understood to mean, in particular, a product obtained by the reaction of a polyisocyanate with a polyol or with a compound having isocyanate-reactive groups. Here, not only polyurethane but also further functional groups, such as uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea, and / or uretimine, may be formed. Therefore, in the context of the present invention, PU is understood to mean both polyurethane and polyisocyanurate, polyurea, and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret, and uretimine groups. In the context of the present invention, polyurethane foam (PU foam) is understood to mean a foam obtained as a reaction product based on a polyisocyanate with a polyol or a compound having isocyanate-reactive groups. Here, not only the polyurethanes from which the name is derived but also further functional groups, such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines, may be formed. Within the scope of the present invention, the terms "foam" and "foam material" are used synonymously.

[0003] In connection with the provision of PU, preferably PU foam, in particular PU rigid foam, it is of particular interest to produce them particularly inexpensively.A further interest is to produce them particularly sustainably, for example by using bio-based and / or recycled materials.For this reason, various solids can also be used when providing PU.Known prior art describes corresponding solids suitable for use in PU.

[0004] However, the use of solids usually entails significant problems with regard to dispersion and processing in liquid starting materials. This includes, among other things, sedimentation, difficult redispersion after sedimentation, non-uniform distribution in the PU, and the resulting non-uniform property profile, especially of the polyurethanes produced in this way. Attempts have been made to use dispersing additives to solve these problems, but so far have not produced truly convincing results. In particular, the use of dispersing additives is accompanied by a significant increase in the viscosity of the respective components, making processing significantly more difficult or even impossible.

[0005] Against this background, a particular object of the present invention was to make it possible to provide PUs containing solid fillers, while still eliminating the above-mentioned problems of settling, difficult redispersion after settling, non-homogeneous distribution in the material, etc., while avoiding, in particular, an excessively significant increase in the viscosity of the components.

[0006] In this context, it has surprisingly been found within the scope of the present invention that the use of surfactants based on quaternary ammonium compounds, such as ester quats and / or alkyl quats, allows the desired significant improvement in redispersion and sedimentation stability, and a more homogeneous property profile of the material, while the viscosity of the components is no longer significantly affected.

[0007] The above-mentioned problems are solved by the subject matter of the present invention, which 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 for catalyzing the formation of urethane or isocyanurate bonds, wherein the composition also contains at least one surfactant based on a quaternary ammonium compound, preferably based on a silicon-free quaternary ammonium compound, such as, for example, preferably an ester quat, alkyl quat, amidoamine quat, and / or imidazolinium quat.

[0008] Within the scope of the present invention, a "solid" filler is understood to mean that the filler is in a solid agglomerate state at prevailing ambient conditions, in particular at a temperature of 20° C. and a pressure of 1.01325 bar.

[0009] The subject matter of the present invention offers various advantages. It thus makes it possible to produce PUs, preferably PU foams, especially PU rigid foams with a high solids content. Advantageously, this is possible without impairing other properties of the material, particularly its mechanical properties. Furthermore, with a view to producing PU rigid foams, a particularly fine-celled, uniform, and defect-free foam structure is possible. This achieves the provision of corresponding polyurethanes with particularly good application properties and a homogeneous property profile. The present invention allows for particularly homogeneous distribution of solid fillers in the polyurethane. Overall, the present invention allows for easy handling of solid fillers during production. The solid filler, together with at least one surfactant based on a quaternary ammonium compound, preferably an ester quat and / or alkyl quat, can be introduced very easily into the reaction mixture, for example, via one of the two reaction components (the polyol component or the polyisocyanate component). In this case, introduction via the polyol component is preferred. The problem of settling of dispersions of reaction components and solids during storage can be significantly reduced or even avoided by the present invention. The present invention also allows for very good redispersibility of the solids when settling occurs after very long storage, so that, for example, constant stirring or mixing during storage is no longer necessary. The present invention also allows for a more homogeneous distribution of the solids in the polyurethane, which results in a more uniform property profile.

[0010] Quaternary ammonium compound-based surfactants, such as ester quats, amidoamine quats, imidazolinium quats, cetylpyridinium chloride and / or alkyl quats, are known to those skilled in the art.For example, ester quats and alkyl quats are quaternary ammonium compound-based surfactants that have at least one long hydrocarbon group.Alkyl quats are generally tetraalkylammonium salts, while ester quats are generally based on quaternary triethanol-methyl-ammonium or quaternary diethanol-dimethyl-ammonium compounds that are esterified with at least one fatty acid.

[0011] Alkyl quats and ester quats have long been used in cosmetics or detergents and cleaning agents, such as fabric softeners, and their preparation has long been known to those skilled in the art.Alkyl quats can be prepared, for example, by reacting the corresponding amine with a methylating agent, such as chloromethane or dimethyl sulfate.Ester quats can be prepared, for example, by esterifying methyldiethanolamine or triethanolamine with fatty acid, followed by quaternization with dimethyl sulfate or chloromethane.

[0012] US Patent Application Publication No. 20160264711 describes the use of quaternary ammonium compounds in polyurethane flexible foams to improve the compatibility of polyether polycarbonate polyols without the use of solid fillers. US Patent No. 5,420,186 describes the use of quaternary ammonium compounds as internal mold release agents in polyurethane elastomers without the use of solid fillers.

[0013] The composition according to the present invention must contain 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] This corresponds to a particularly preferred embodiment of the present invention when the plastic particles are made from at least one plastic, in particular polyurethane, 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-ε-caprolactone), polystyrene, polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymer, polyether, polylactic acid, polyurethane, polysulfone, polyethersulfone, polyetherimide and polyimide.

[0015] According to a particularly preferred embodiment of the present invention, the plastic particles may be formed wholly or partly from recycled plastic, preferably recycled polyurethane.

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

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

[0018] According to a particularly preferred embodiment of the present invention, as quaternary ammonium compound-based surfactants, preferably 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: [ka] [R 1 is an acyl group of a saturated or monounsaturated or polyunsaturated, straight-chain or branched fatty acid having a chain length of 8 to 22 carbon atoms, or an acyl group of ricinoleic acid, or hydrogen; The compounds of formula (1) or (2) may contain different groups R 1 provided that at least one group R 1 must be one of the acyl groups listed above, R 2 is an alkyl group having 1 to 6 carbon atoms or hydrogen, preferably hydrogen, methyl, ethyl, propyl or isopropyl, particularly preferably hydrogen or methyl, R 3 is an alkyl group having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably methyl or hydrogen, R 4 is an alkyl group having 1 to 6 carbon atoms or a hydroxyethyl group or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, The compounds of formula (1) or (2) may contain different groups R 4 may include n=0 to 20, preferably 0 to 10, particularly preferably 0; a=1 to 3, and b=1 to 3, However, a+b=4. and / or [ka] [R 5 is a saturated or mono- or polyunsaturated, linear or branched alkyl group having a chain length of 8 to 24 carbon atoms, The compound of formula (3) may be a compound having different groups R 5 may include R 6 is an alkyl group having 1 to 6 carbon atoms, or a hydroxyethyl group, or a benzyl group, or hydrogen, preferably methyl, ethyl, propyl, isopropyl or benzyl, particularly preferably ethyl or methyl, very particularly preferably methyl, The compound of formula (3) may be a compound having different groups R 6 may include c=1 to 3 and d=1 to 3, However, c+d=4. and / or [ka] [R 7 is an alkyl group having 1 to 6 carbon atoms or a hydroxyethyl group or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, R 8 is a saturated or mono- or polyunsaturated, straight-chain or branched alkyl group having 8 to 22 carbon atoms, or a group O(CO)R 10 and R 10 is an aliphatic saturated or mono- or polyunsaturated, linear or branched alkyl group having 7 to 21 carbon atoms, R 9 is an aliphatic saturated or mono- or polyunsaturated, linear or branched alkyl group having 7 to 21 carbon atoms, Z is an NH group or oxygen, e can take integer values ​​from 1 to 4. and / or [ka] [R 11is a saturated or mono- or polyunsaturated, linear or branched alkyl group having a chain length of 7 to 21 carbon atoms, R 12 is an alkyl group having 1 to 6 carbon atoms or a hydroxyethyl group or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, The compound of formula (5) may be a compound having different groups R 12 and f can take an integer value from 0 to 5; h=1 or 2 and g=2 or 3; However, h+g=4, Compounds of formula (5) can have different values ​​for f when h=2, and different groups R 11 may contain R 4 , R 6 , R 7 or R 12 contains a hydroxyethyl group, which may be alkoxylated, and this optionally alkoxylated hydroxyethyl group may contain ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide based repeat units and may contain 1 to 15 repeat units, preferably 1 to 10 repeat units. is used.

[0019] Corresponding compositions containing corresponding quaternary ammonium compounds show particularly advantageous results with regard to the advantages according to the invention mentioned above.

[0020] This is because in formula (1) and / or formula (2), R 1corresponds to a further particularly preferred embodiment of the present invention, when is selected from the acyl radical of an acid 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-eleostearic acid, beta-eleostearic acid, arachidonic acid, timnodonic acid, clupanodonic acid and / or cervonic acid.

[0021] Furthermore, it is preferred if in formula (1) a=b=2 and / or in formula (5) h=1 and g=3, which likewise corresponds to further particularly preferred embodiments of the present invention.

[0022] Compositions according to the invention which contain at least one counteranion to the compounds of general formulae (1), (2), (3), (4) and / or (5) selected from the group comprising chloride, bromide, iodide, alkyl sulfate, e.g., methyl sulfate, ethyl sulfate, alkyl sulfonate, e.g., methyl sulfonate, triflate, tosylate, phosphate, sulfate, hydrogen sulfate, lactate, glycolate, acetate and / or citrate correspond to a further particularly preferred embodiment of the present invention.

[0023] It is a further particularly preferred embodiment of the present invention if the at least one surfactant based on a quaternary ammonium compound is contained 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 polyol.

[0024] According to a further preferred embodiment of the present 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 polyol.

[0025] Preferably, the at least one solid filler according to a further particularly preferred embodiment of the present invention is contained in the composition according to the invention in a total amount that results in the production of a PU, preferably a PU foam, which composition contains more than 2% by weight, preferably more than 5% by weight, more preferably more than 8% by weight, even more preferably more than 10% by weight of at least one solid filler, based on the resulting PU, preferably PU foam. A possible upper limit may preferably be 30% by weight or less, such as 15% by weight or such as 20% by weight.

[0026] Furthermore, it is particularly preferred if the composition according to the present invention further contains at least one foam stabilizer, preferably at least one foam stabilizer based on polyethersiloxane, preferably in an amount of 0.5 to 4 parts by weight based on 100 parts by weight of polyol. This corresponds to a particularly preferred embodiment of the present invention. Foam stabilizers, preferably polyethersiloxane-based foam stabilizers, are known per se. Suitable foam stabilizers are further described below.

[0027] A further subject of the present invention is a process for producing PUs, preferably PU foams, in particular PU rigid foams, based on a reaction mixture containing a polyisocyanate component, a polyol component, optionally a blowing agent, at least one solid filler, optionally at least one catalyst and optionally further additives, wherein at least one surfactant based on a quaternary ammonium compound is used, preferably at least one surfactant based on a quaternary ammonium compound as described above, preferably using a composition as described above, particularly preferred or as described in detail above in a particularly preferred embodiment.

[0028] In particular, it is preferred if 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 polyol, which corresponds to a particularly preferred embodiment of the present invention.

[0029] In particular, it is preferred if 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 polyol, which corresponds to a particularly preferred embodiment of the present invention.

[0030] It is particularly preferred if at least one foam stabilizer, in particular at least one foam stabilizer based on polyether siloxane, is further contained in an amount of 0.5 to 4 parts by weight based on 100 parts by weight of polyol, which corresponds to a particularly preferred embodiment of the present invention.

[0031] Furthermore, this corresponds to a particularly preferred embodiment of the present invention when the process according to the invention for producing a PU, preferably a PU foam, in particular a PU rigid foam, is characterized in that the resulting PU, preferably a PU foam, in particular a PU rigid foam, contains a total amount of at least one solid filler of more than 2% by weight, preferably more than 5% by weight, more preferably more than 8% by weight, even more preferably more than 10% by weight, based on the resulting PU, preferably PU foam, in particular a PU rigid foam. A possible upper limit may preferably be 30% by weight or less, for example 15% by weight or for example 20% by weight.

[0032] Preferably, in the method according to the invention according to a particularly preferred embodiment of the invention, no particles from metal oxides are used, in particular particles made of a material selected from the group consisting of SiO2, ZnO2, Al2O3, ZrO2 and TiO2.

[0033] The process according to the invention for producing PU, preferably PU foam, in particular PU rigid foam, can be carried out by known methods, for example by hand mixing or preferably by using a foaming machine. When the process is carried out by a foaming machine, high-pressure or low-pressure machines can be used. The process according to the invention can be carried out either batchwise or continuously.

[0034] Particularly preferred PU formulations within the scope of the present invention have a viscosity of 5 to 900 kg / m 3 and has the composition listed in Table 1, which corresponds to a preferred embodiment of the present invention:

[0035] [Table 1]

[0036] Furthermore, for further preferred embodiments and configurations of the method according to the invention, reference is made to the statements already made above in connection with the composition according to the invention.

[0037] Another further subject of the present invention is a PU, preferably a PU foam, in particular a PU rigid foam, produced by the aforementioned process according to the invention, in particular using the composition according to the invention.

[0038] The PU according to the present invention is a PU foam material, in particular a PU rigid foam material, and has a compressibility 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 present invention.

[0039] Preferably, the PU according to the invention, preferably PU foam, in particular PU rigid foam, produced by the aforementioned method according to the invention, in the scope of particularly preferred embodiments, contains a total amount of more than 2 wt.-%, preferably more than 5 wt.-%, more preferably more than 8 wt.-%, even more preferably more than 10 wt.-%, based on the total polyurethane, preferably PU foam, in particular PU rigid foam, of at least one solid filler.

[0040] Preferably, the PU, preferably PU foam, in particular PU rigid foam according to the invention, in the context of a particularly preferred embodiment, does not contain particles from metal oxides, in particular particles made of materials selected from the group consisting of SiO, ZnO, AlO, ZrO and TiO.

[0041] A further subject of the present invention relates to the use of the PU and / or PU foam materials according to the invention, as mentioned above, as refrigerator insulation, as building material, preferably as insulating boards, sandwich elements, spray foams and / or 1&1.5-component can foams, pipe insulation, wood imitation, model foams, packaging foams, mattresses, furniture cushions, car seat cushions, headrests, dashboards, car interior linings, car headliners, sound absorbers, steering wheels, shoe soles, carpet backing foams, filter foams, sealing foams, sealants, adhesives or coatings, or for producing corresponding products.

[0042] Preferred compositions according to the invention comprise in particular the following components: a) surfactants based on quaternary ammonium compounds, in particular surfactants based on quaternary ammonium compounds as defined above by formula (1), (2), (3), (4) and / or (5); b) Polyol component c) Polyisocyanate component d) Catalyst e) Optionally, a foam stabilizer f) optionally one or more blowing agents g) solid fillers h) optionally further additives, flame retardants, etc. Contains:

[0043] The polyol component (b) consists of at least one polyol and, optionally, at least one organic compound containing at least two groups reactive with isocyanates, preferably selected from the group consisting of OH, NH, and NH groups. A polyol is an organic compound containing at least two hydroxyl groups (-OH).

[0044] If one of the aforementioned organic compounds of the polyol component contains at least two OH groups, it is classified exclusively as a polyol within the scope of the present invention, i.e., if an organic compound of the polyol component can be evaluated both as a polyol and as an organic compound containing at least two groups reactive with isocyanates, preferably selected from the group consisting of OH groups, NH groups and NH groups, it is classified exclusively as a polyol within the scope of the present invention.

[0045] Based on its total weight, the polyol component preferably contains at least 50% by weight of polyols containing only hydroxyl groups (-OH) as groups reactive with isocyanates.

[0046] Based on the total number of isocyanate-reactive groups of the polyol component, it is preferred that at least 50% of these groups are hydroxyl groups (--OH).

[0047] Corresponding compounds that can generally be used for the production of PU are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3. Auflage 1993, Kapitel 3.1. In general, compounds with an OH number in the range of 10 to 1200 mg KOH / g are used.

[0048] Particularly preferred compounds are all polyether polyols and polyester polyols commonly used in the production of polyurethane systems, especially polyurethane foam materials. Polyether polyols are preferably obtainable by reacting polyhydric alcohols or amines with alkylene oxides. Polyester polyols are preferably based on esters of polycarboxylic acids (which may be aliphatic, such as adipic acid, or aromatic, such as phthalic acid or terephthalic acid) with polyhydric alcohols (preferably glycols).

[0049] Additionally, polyether polycarbonate polyols, natural oil-based polyols (natural oil-based polyols NOP as described in WO 2005 / 033167, U.S. Patent Application Publication No. 2006 / 0293400, WO 2006 / 094227, WO 2004 / 096882, U.S. Patent Application Publication No. 2002 / 0103091, WO 2006 / 116456, EP 1 678 232), filler polyols, prepolymer-based polyols and / or recycled polyols can be used.

[0050] Recycled polyols are polyols obtained from chemical regeneration, for example by glycolysis, hydrolysis, solvolysis, such as acidolysis or aminolysis, of polyurethanes. The use of recycled polyols is a particularly preferred embodiment of the present invention.

[0051] The polyisocyanate component (c) consists of at least one polyisocyanate having two or more isocyanate groups. Suitable polyisocyanates within the scope of the present invention are all organic isocyanates having two or more isocyanate groups, in particular the aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyisocyanates known per se.

[0052] Examples of suitable diisocyanates 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), cycloaliphatic diisocyanates, such as cyclohexane-1,3- and -1,4-diisocyanate, and the corresponding isomer mixtures, such as 4,4'-methylenedicyclohexyldiisocyanate. Mention may be made of 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 polyisocyanate (PMDI, "polymeric MDI").

[0053] The organic polyisocyanates can be used individually or in the form of their mixtures. Corresponding "oligomers" of diisocyanates can also be used, such as isocyanurate-, biuret- or uretdione-based IPDI trimers. In addition, the above-mentioned isocyanate-based prepolymers can also be used.

[0054] Particularly suitable are mixtures of MDI and more highly condensed analogues having an average functionality of 2 to 4 known as "polymeric MDI" (also called "crude MDI"), and the various isomers of TDI in pure form or as isomeric mixtures.

[0055] It is also possible to use isocyanates modified by the incorporation of urethane groups, uretdione groups, isocyanurate groups, allophanate groups and other groups, so-called modified isocyanates. Examples of particularly suitable isocyanates are listed, for example, in EP 1712578, EP 1161474, WO 00 / 58383, U.S. Patent Application Publication No. 2007 / 0072951, EP 1678232 and WO 2005 / 085310, which are hereby incorporated by reference in their entirety.

[0056] The preferred ratio of polyisocyanate component to polyol component, expressed as a formulation index (isocyanate index), i.e., 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 1 to 1 molar ratio of reactive groups.

[0057] Suitable catalysts (d) which can be used for the production of polyurethanes, in particular PU foams, and which are capable of catalyzing in particular the formation of urethane or isocyanurate bonds, are known to those skilled in the art. In the context of the present invention, in particular, all compounds which are capable of catalyzing the reaction of isocyanate groups with OH groups, NH groups or other isocyanate-reactive groups and / or with each other are usable.

[0058] Here, the usual catalysts known from the prior art can be used, including, for example, amines (cyclic, acyclic, monoamines, diamines, oligomers containing 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.

[0059] Foam stabilizers (e) and their use in the production of PU foams are known to those skilled in the art. The use of foam stabilizers is optional, and preferably, one or more foam stabilizers are used. These can serve to optimize the desired cell structure and the foaming process.

[0060] In the scope of the present invention, in particular, Si-containing compounds that assist foam production (stabilization, cell control, cell opening, etc.) can be used. These compounds are well known in the prior art. Particularly preferably, at least one foam stabilizer based on polyether siloxane can be used.

[0061] Corresponding siloxane structures that can be used within the scope of the present invention are described, for example, in the following patent documents, although their use is described only for classic PU foams as molded foams, mattresses, insulation materials, building foams, etc.: CN 103665385, CN 103657518, CN 103055759, CN 103044687, US 2008 / 0125503, US 2015 / 0057384, EP 1520870, EP 1211279, EP 0867464, EP 0867465, EP 0275563. Not only surface-active Si-containing compounds but also Si-free surfactants can be used. For example, EP 2295485 describes the use of lecithin, and US Patent No. 3746663 describes the use of vinylpyrrolidone-based structures as foam stabilizers for producing PU rigid foams. Further Si-free foam stabilizers are described, for example, in EP 2511328, DE 1020011007479, DE 3724716, EP 0734404, EP 1985642, DE 2244350 and US Patent No. 5236961.

[0062] Blowing agents (f) and their use in the production of PU foams are known to those skilled in the art. The use of a blowing agent is optional, and a blowing agent is preferably used. The use of one or more combinations of blowing agents (f) essentially depends on the type of foaming method used, the type of system, and the intended use of the resulting PU foam.

[0063] Chemical and / or physical blowing agents, or a combination of both, can be used. Depending on the amount of blowing agent used, high or low density foams can be produced. Foams can be produced up to 5 kg / m². 3 ~900kg / m 3, preferably 5 to 350 kg / m 3 , particularly preferably 8 to 200 kg / m 3 , especially 8 to 150 kg / m 3 It can be manufactured at a density of

[0064] As physical blowing agents, one or more corresponding compounds and mixtures thereof having an appropriate boiling point can be used, for example, hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane, n-pentane, fluorohydrocarbons (HFCs), preferably HFC245fa, HFC134a or HFC365mfc, fluorochlorohydrocarbons (HCFCs), preferably HCFC141b, hydrofluoroolefins (HFOs) or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz, esters, preferably methyl formate, ketones, preferably acetone, ethers, preferably dimethoxymethane, or chlorohydrocarbons, preferably dichloromethane or 1,2-dichloroethane.

[0065] The chemical blowing agent may be one or more compounds that react with NCO groups to release a gas such as water or formic acid, or one or more compounds that release a gas upon increasing temperature during the reaction, such as sodium bicarbonate.

[0066] This corresponds to a particularly preferred embodiment when the composition according to the invention contains water in combination with a hydrocarbon having 5 carbon atoms, an HFO, a hydrohaloolefin or an HFC or a mixture thereof as blowing agent.

[0067] The solid fillers g) have already been mentioned above.

[0068] As optional additives (h) it is possible to use one or more substances known from the prior 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, colorants, pigments, color pastes, fragrances and / or emulsifiers.

[0069] As an optional flame retardant, the composition according to the invention may contain one or more known flame retardants suitable for the production of PU foams, such as halogen-containing or halogen-free organophosphorus-containing compounds, such as triethyl phosphate (TEP), tris(1-chloro-2-propyl)phosphate (TCPP), 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. Mixtures of different flame retardants may also be used.

[0070] Unless stated otherwise in this specification, any preferred or particularly preferred embodiment of the present invention may be combined with one or more of the remaining preferred or particularly preferred embodiments of the present invention.

[0071] Although the subject matter according to the present invention has been described and will be exemplified below, the present invention should not be limited to these exemplary embodiments. When ranges, general formulas, or compound classes are described, these include not only the corresponding ranges or compound groups explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by extracting the individual values ​​(ranges) or compounds. When documents are cited within this specification, their contents, especially the factual contents in the context in which this document is cited, are fully incorporated into the disclosure of the present invention. Unless otherwise specified, percentages are expressed in weight percent. When average values ​​are stated, they are weight averages unless otherwise specified. When parameters determined by measurement are stated, these measurements are carried out at a temperature of 25°C and a pressure of 101325 Pa (normal pressure) unless otherwise specified.

[0072] The present invention will be described illustratively in the examples listed below, but the scope of the present invention, the scope of which will become apparent from the entire specification and claims, should not be limited to the embodiments set forth in the examples.

[0073] Working Example: Example 1: PIR rigid foam (PIR = polyisocyanurate) For application technical comparisons, the formulations shown in Table 2 were used, and the compounds shown in Table 3 were investigated. Comparative foaming runs were performed using the manual mixing method. For this purpose, polyol, catalyst, water, foam stabilizer, dispersant (Table 3), solid filler, and blowing agent were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) at 1000 rpm for 30 seconds (batch size 500 g). The amount of blowing agent evaporated during the mixing process was determined by reweighing and replenished. MDI was then added, and the reaction mixture was stirred with the stirrer as described at 3000 rpm for 5 seconds and immediately transferred to a polyethylene foil-lined aluminum mold measuring 25 cm x 50 cm x 7 cm, thermostated at 60 °C.

[0074] After 10 minutes, the foams were demolded. One day after foaming, the foams were analyzed. Surface and internal defects were subjectively rated on a scale of 1 to 10, with 10 representing an (ideal) defect-free foam and 1 representing a foam with very severe defects. Thermal conductivity (λ value in mW / m·K) was measured on a 2.5 cm thick disc with a Hesto Lambda Control type device, model HLC X206, at an average temperature of 10 °C, corresponding to the requirements of standard EN 12667:2001.

[0075] [Table 2]

[0076] [Table 3]

[0077] The compounds according to the invention were compared with commercially available surfactants not according to the invention (TEGOPREN® 6921, TEGOTEX® 8080, TEGO® Dispers 652, Thixatrol® ST).

[0078] These results are summarized in Tables 4 and 5:

[0079] [Table 4]

[0080] [Table 5]

[0081] These results show that the compounds according to the present invention have no or only a small effect on the relevant foam properties.In addition, the use of the compounds according to the present invention can achieve a more homogeneous distribution of solid fillers in the foam, which is reflected in a significant improvement in both surface and pore structure / internal defects.On the other hand, compounds other than those according to the present invention often cause severe foam coarsening (TEGOPREN® 6921), collapse (TEGOTEX® 8080), or do not show any improvement in foam structure (TEGO® Dispers 652, Thixatrol® ST).

[0082] Example 2: Dispersion Behavior For application technical comparison, the compounds shown in Table 3 were investigated using the formulations shown in Tables 6, 8, 10, and 12. For this purpose, polyol and water were weighed (batch size 100 g) and mixed with a plate stirrer (diameter 6 cm) at 1000 rpm for 30 seconds. Subsequently, the compound according to the invention was added and mixed with a plate stirrer (diameter 6 cm) at 2000 rpm for 30 seconds. For the reference test, mixing was also carried out at 2000 rpm for another 30 seconds, except that the compound according to the invention was not added. Subsequently, while the plate stirrer was still running at 2000 rpm, the solid filler was added and mixed for another 45 seconds. Subsequently, the formulation was filled into a glass container, sealed, and the time until complete settling was measured.

[0083] After 14 days of upright storage at room temperature, all samples were redispersed and redispersibility was rated on a scale of 1 to 3, where a rating of 1 means that the sample could be redispersed by manually shaking the glass container for 30 seconds. A rating of 2 means that the sample could be redispersed again with an electric laboratory stirrer (500 rpm, 60 seconds) rather than by manual shaking. A rating of 3 was assigned to samples that formed a very hard, dense sediment that could not be redispersed again by the two methods mentioned above.

[0084] The viscosity was determined by two measurement methods: either by an Anton Paar MCR 302 type rheometer (50 mm between plates, 0.5 mm spacing) at 25°C and various shear rates on freshly prepared formulations (Table 5), or by a DV2T type rheometer with an LV04(64) type spindle at 21°C and various shear rates on freshly prepared formulations.

[0085] The results of the dispersion behavior are shown in Tables 7, 9, 11 and 13.

[0086] [Table 6]

[0087] [Table 7]

[0088] [Table 8]

[0089] [Table 9]

[0090] [Table 10]

[0091] [Table 11]

[0092] [Table 12]

[0093] [Table 13]

[0094] In all cases investigated, it was possible to achieve an improvement in sedimentation stability and / or redispersibility compared to formulations without the compound according to the invention.

[0095] In particular, the formation of hard, dense sediments could be avoided. The invention therefore allows for very good redispersibility of the solids in the event of sedimentation after very long storage, so that, for example, constant stirring or mixing during storage is no longer necessary.

Claims

1. 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 urethane bonds or isocyanurate bonds, wherein the composition contains at least one surfactant based on a quaternary ammonium compound, preferably based on a silicon-free quaternary ammonium compound.

2. 2. The composition of claim 1, wherein the at least one solid filler is selected from the group consisting of calcium carbonate, lignin, lignocellulose, and plastic particles.

3. 3. The composition according to claim 2, characterized in that the plastic particles are made from at least one plastic, in particular polyurethane, 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-ε-caprolactone), polystyrene, polyacrylate, polymethyl methacrylate, polycarbonate, styrene-acrylonitrile copolymer, polyether, polylactic acid, polyurethane, polysulfone, polyethersulfone, polyetherimide and polyimide.

4. 4. The composition of claim 2 or 3, wherein the plastic particles are formed wholly or partly from recycled plastic.

5. 5. The composition according to claim 1, wherein the composition contains, as solid filler, lignin and / or plastic particles, preferably from recycled plastic, preferably recycled polyurethane.

6. 6. The composition according to claim 1, wherein the at least one solid filler has a weight-average diameter of the primary particles, determined by dynamic light scattering, of more than 50 nm, preferably more than 100 nm, particularly preferably more than 200 nm.

7. As quaternary ammonium compounds, 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: 【Chemical 1】 [R １ is the acyl radical of a saturated or mono- or polyunsaturated, straight-chain or branched fatty acid having a chain length of 8 to 22 carbon atoms, or the acyl radical of ricinoleic acid, or hydrogen; The compounds of formula (1) or (2) may be formed by adding different groups R １ provided that at least one group R １ must be one of the acyl groups listed above, R ２ is an alkyl group having 1 to 6 carbon atoms or hydrogen, preferably hydrogen, methyl, ethyl, propyl or isopropyl, particularly preferably hydrogen or methyl, R ３ is an alkyl group having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably methyl or hydrogen, R ４ is an alkyl group having 1 to 6 carbon atoms, or a hydroxyethyl group, or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, The compounds of formula (1) or (2) may be formed by adding different groups R ４ may include n=0 to 20, preferably 0 to 10, particularly preferably 0; a=1 to 3 and b=1 to 3; However, a+b=4. and 【Chemistry 2】 [R ５ is a saturated or mono- or polyunsaturated, straight-chain or branched alkyl group having a chain length of 8 to 24 carbon atoms, The compound of formula (3) may contain different groups R ５ may include R ６ is an alkyl group having 1 to 6 carbon atoms, or a hydroxyethyl group, or a benzyl group, or hydrogen, preferably methyl, ethyl, propyl, isopropyl or benzyl, particularly preferably ethyl or methyl, very particularly preferably methyl, The compound of formula (3) may contain different groups R ６ may include c=1 to 3 and d=1 to 3; However, c + d = 4. and 【Chemistry 3】 [R ７ is an alkyl group having 1 to 6 carbon atoms, or a hydroxyethyl group, or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, R ８ is a saturated or mono- or polyunsaturated, linear or branched alkyl group having 8 to 22 carbon atoms, or a group O(CO)R １０ and R １０ is an aliphatic saturated or mono- or polyunsaturated, straight-chain or branched alkyl group having 7 to 21 carbon atoms, R ９ is an aliphatic saturated or mono- or polyunsaturated, straight-chain or branched alkyl group having 7 to 21 carbon atoms, Z is an NH group or oxygen; e can take an integer value from 1 to 4. and 【Chemistry 4】 [R １１ is a saturated or mono- or polyunsaturated, straight-chain or branched alkyl group having a chain length of 7 to 21 carbon atoms, R １２ is an alkyl group having 1 to 6 carbon atoms, or a hydroxyethyl group, or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, very particularly preferably methyl, The compound of formula (5) may contain different groups R １２ where f can take an integer value from 0 to 5; h=1 or 2 and g=2 or 3; However, h+g=4, The compounds of formula (5) can have different values ​​for f when h=2 and different groups R １１ and R ４ , R ６ , R ７ or R １２ contains a hydroxyethyl group, which may be alkoxylated, and this optionally alkoxylated hydroxyethyl group may comprise ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide based repeat units and may comprise 1 to 15 repeat units, preferably 1 to 10 repeat units.

7. The composition according to claim 1, wherein:

8. In formula (1) and / or formula (2), R １ is selected from the acyl group of 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-eleostearic acid, beta-eleostearic acid, arachidonic acid, timnodonic acid, clupanodonic acid and / or cervonic acid.

9. 9. The 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.

10. 10. The composition according to any one of claims 7 to 9, characterized in that it further contains at least one counter anion to the compounds of general formula (1), (2), (3), (4) and / or (5) selected from the group comprising chloride, bromide, iodide, alkyl sulfate, e.g., methyl sulfate, ethyl sulfate, alkyl sulfonate, e.g., methyl sulfonate, triflate, tosylate, phosphate, sulfate, hydrogen sulfate, lactate, glycolate, acetate and / or citrate.

11. 11. The composition according to claim 1, wherein the at least one surfactant based on a quaternary ammonium compound is contained 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 polyol.

12. 12. The composition according to claim 1, wherein the at least one solid filler is contained 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 polyol.

13. 13. The composition according to claim 1, further comprising at least one foam stabilizer, in particular at least one foam stabilizer based on polyether siloxane, in an amount of 0.5 to 4 parts by weight, based on 100 parts by weight of polyol.

14. The composition does not contain particles from metal oxides, in particular SiO ２ , ZnO ２ , Al ２ O ３ , ZrO ２ and TiO ２ 14. The composition according to claim 1, wherein the composition does not contain particles made of a material selected from the group consisting of:

15. 13. A method for producing a PU, preferably a PU foam, in particular a PU rigid foam, based on a reaction mixture containing a polyisocyanate component, a polyol component, optionally a 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 at least one surfactant based on a quaternary ammonium compound as defined in any one of claims 7 to 10, is used, in particular using a composition as defined in any one of claims 1 to 14.

16. 16. A polyurethane, preferably a PU foam, in particular a PU rigid foam, produced by the method of claim 15.

17. 17. Use of the PU and / or PU foam material according to claim 16 as refrigerator insulation, as building material, preferably as insulating boards, sandwich elements, spray foams and / or 1&1.5-component can foams, pipe insulation, wood imitation, model foam, packaging foam, mattresses, furniture cushions, car seat cushions, headrests, dashboards, car interior linings, car headliners, sound absorbers, steering wheels, shoe soles, carpet backing foams, filter foams, sealing foams, sealants, adhesives or coatings, or for producing corresponding products.

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