Production of polyurethane foams

Abstract

The invention relates to a composition for producing polyurethanes, preferably PU foams, in particular rigid PU foams, comprising a polyisocyanate component, a polyol component, optionally a blowing agent, at least one solid filler, optionally at least one catalyst that catalyzes the formation of urethane or isocyanurate bonds, wherein the composition comprises at least one surfactant based on quaternary ammonium compounds.

Description

[0001] The present invention relates to the field of polyurethanes, in particular to the field of polyurethane foams. In particular, it relates to the production of polyurethane foams using solid fillers and surfactants based on quaternary ammonium compounds such as ester quaternary ammonium compounds and / or alkyl quaternary ammonium compounds, to compositions for the production of such foams, and also to the use of said foams.

[0002] In the context of the present invention, polyurethane (PU) is understood to mean the product that can be obtained by the reaction of polyisocyanate and polyol or the compound with isocyanate reactive groups in particular.Except polyurethane, other functional groups can also be formed here, such as uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea and / or uretonimine.For purposes of the present invention, PU is therefore not only understood to mean polyurethane, but also means polyisocyanurate, polyurea and the polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretonimine groups.In the context of the present invention, polyurethane foam (PU foam) is understood to mean the foam obtained as the reaction product based on polyisocyanate and polyol or the compound with isocyanate reactive groups.Except polyurethane of the same name, other functional groups can also be formed here, such as allophanate, biuret, urea, carbodiimide, uretdione, isocyanurate or uretonimine. In the context of the present invention, the terms "foam" and "foam material" are used synonymously.

[0003] With regard to the provision of PU, preferably PU foams, in particular PU rigid foams, producing these in a particularly cost-effective manner is a particularly important consideration. Another consideration is to produce these in a particularly sustainable manner, for example by using bio-based materials and / or recycled materials. Also for this reason, when providing PU, different solids can also be used. Suitable solids for PU are described in the known prior art.

[0004] However, the use of solids usually leads to considerable problems with the dispersion and processing of liquid raw materials. These include, in particular, sedimentation, difficulty in redispersion after sedimentation, inhomogeneous distribution in the PU, and, in particular, inhomogeneous property distribution in the resulting polyurethane. Attempts have been made to overcome these problems using dispersing additives, but so far, no really convincing results have been achieved. One of the problems is that each use of dispersing additives is accompanied by a sharp increase in the viscosity of the components, making processing significantly more difficult or even impossible.

[0005] In this context, the specific problem addressed by the present invention is to be able to provide a PU comprising solid fillers, but overcoming the above-mentioned problems of sedimentation, difficulty in redispersion after sedimentation and inhomogeneous distribution in the material, in particular avoiding an excessive increase in the viscosity of the components.

[0006] In this regard, it was surprisingly found in the context of the present invention that the use of surfactants based on quaternary ammonium compounds, such as ester quaternary ammonium compounds and / or alkyl quaternary ammonium compounds, can significantly improve redispersion, sedimentation stability and more uniform properties of the material. The viscosity of the components is only affected to a significantly lesser extent.

[0007] The subject matter of the present invention solves the above-mentioned problems. The present invention provides a composition for producing PU, preferably PU foam, especially rigid PU foam, comprising a polyisocyanate component, a polyol component, an optional blowing agent, at least one solid filler, optionally at least one catalyst for catalyzing the formation of urethane or isocyanurate bonds, the composition comprising at least one surfactant based on a quaternary ammonium compound, preferably based on a silicon-free quaternary ammonium compound, such as preferably an ester quaternary ammonium compound, an alkyl quaternary ammonium compound, an amide amine quaternary ammonium compound and / or an imidazolinium quaternary ammonium compound.

[0008] For the purposes of the present invention, a "solid" filler is intended to mean that the filler in question exists as a solid substance under normal ambient conditions, in particular at a temperature of 20°C and a pressure of 1.01325 bar.

[0009] The subject of the present invention is associated with a variety of advantages. For example, it is possible to provide PU, preferably PU foam, especially hard PU foam with a high solid content. Advantageously, this can be achieved without adversely affecting other properties of the material, particularly its mechanical properties. With regard to the provision of hard PU foam, a particularly fine-pored, uniform and defect-free foam structure can also be achieved. Therefore, a corresponding polyurethane with particularly good performance and uniform performance characteristics can be provided. The present invention makes solid fillers particularly uniformly distributed in polyurethane. In general, the present invention makes solid fillers easy to process during production. Solid fillers can be introduced into the reaction mixture in a very simple manner, for example, together with at least one surfactant based on quaternary ammonium compounds (such as preferably ester quaternary ammonium compounds and / or alkyl quaternary ammonium compounds), into the reaction mixture, for example, via one of two reaction components (polyol component or polyisocyanate component). Preferably, it is introduced via a polyol component. The present invention can significantly reduce or even avoid sedimentation problems during storage of dispersions of reaction components and solids. The present invention also allows very good redispersibility of solids in the case of sedimentation after very long storage, which means that, for example, continuous stirring or mixing is no longer required during storage. The present invention also provides for a more uniform distribution of solids in the polyurethane, resulting in more uniform performance characteristics.

[0010] Surfactants based on quaternary ammonium compounds such as ester quaternary ammonium compounds, amidoamine quaternary ammonium compounds, imidazolinium quaternary ammonium compounds, cetylpyridinium chloride and / or alkyl quaternary ammonium compounds are known per se to the person skilled in the art. For example, ester quaternary ammonium compounds and alkyl quaternary ammonium compounds are surfactants based on quaternary ammonium compounds having at least one long hydrocarbon group. Alkyl quaternary ammonium compounds are usually tetraalkylammonium salts, while ester quaternary ammonium compounds are usually based on triethanolmethyl quaternary ammonium compounds or diethanoldimethyl quaternary ammonium compounds esterified with at least one fatty acid.

[0011] Alkyl quaternary ammonium compounds and ester quaternary ammonium compounds have long been used in cosmetics or detergents and cleaning agents, such as fabric softeners, and their production has long been known to the person skilled in the art. Alkyl quaternary ammonium compounds can be produced, for example, by reaction of the corresponding amines with methylating agents such as methyl chloride or dimethyl sulfate. Ester quaternary ammonium compounds can be produced, for example, by esterification of methyldiethanolamine or triethanolamine with fatty acids, followed by quaternization with, for example, dimethyl sulfate or methyl chloride.

[0012] US20160264711 A1 describes the use of quaternary ammonium compounds in flexible polyurethane foams to improve the compatibility of polyether polycarbonate polyols without using solid fillers. US 5420186 A describes the use of quaternary ammonium compounds as internal mold release agents in polyurethane elastomers without using solid fillers.

[0013] The composition according to the invention must contain at least one solid filler, which is preferably selected from calcium carbonate, lignin, lignocellulose and plastic particles. At least one solid filler is preferably in powder form. Mixtures of such solid fillers can also be used.

[0014] If the plastic particles are formed from at least one plastic, which is preferably selected from polyethylene, polypropylene, polyamide (especially PA6, PA6.6, PA10, PA11 and / or PA12), polyester (especially 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, especially polyurethane, then it corresponds to a particularly preferred embodiment of the present invention.

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

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

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

[0018] In a particularly preferred embodiment of the present invention, the surfactant based on quaternary ammonium compounds preferably used is at least one ester quaternary ammonium compound of formula (1) or (2), an alkyl quaternary ammonium compound of formula (3), an imidazolinium quaternary ammonium compound of formula (4), an amide amine quaternary ammonium compound of formula (5) and / or cetylpyridinium chloride, wherein

[0019]

[0020] Where R 1 is an acyl radical of a saturated, monounsaturated or polyunsaturated, straight-chain or branched fatty acid having a chain length of 8 to 22 carbon atoms, or an acyl radical of ricinoleic acid, or hydrogen,

[0021] The compounds of formula (1) or (2) may contain different R 1 groups, provided that at least one group R 1 must be one of the acyl groups,

[0022] 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, wherein

[0023] 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, wherein

[0024] R 4 is an alkyl group or a hydroxyethyl group having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, especially preferably methyl,

[0025] The compounds of formula (1) or (2) may contain different groups R 4 , and among them

[0026] n=0 to 20, preferably 0 to 10, particularly preferably 0,

[0027] in

[0028] a=1 to 3, and

[0029] b = 1 to 3,

[0030] The condition is a+b=4,

[0031] and / or where

[0032]

[0033] in

[0034] R 5 is a saturated, monounsaturated or polyunsaturated, straight or branched chain alkyl group having a chain length of 8 to 24 carbon atoms,

[0035] The compounds of formula (3) may contain different groups R 5 ,in

[0036] R 6 is an alkyl group having 1 to 6 carbon atoms or a hydroxyethyl group or a benzyl group or hydrogen, preferably a methyl, ethyl, propyl, isopropyl or benzyl group, particularly preferably an ethyl or methyl group, especially preferably a methyl group,

[0037] The compounds of formula (3) may contain different groups R 6 ,and

[0038] in

[0039] c=1 to 3 and d=1 to 3,

[0040] The condition is c+d=4;

[0041] and / or where

[0042]

[0043] in

[0044] R 7 is an alkyl group or a hydroxyethyl group having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, especially preferably methyl, wherein

[0045] R 8 is a saturated or monounsaturated or polyunsaturated, straight-chain or branched alkyl radical having 8 to 22 carbon atoms or a radical O(CO)R 10 , where R 10 is an aliphatic, saturated or monounsaturated or polyunsaturated, straight or branched chain alkyl radical having 7 to 21 carbon atoms, wherein

[0046] R 9is an aliphatic, saturated or monounsaturated or polyunsaturated, straight-chain or branched alkyl group having 7 to 21 carbon atoms,

[0047] in

[0048] Z is an NH group or oxygen,

[0049] where e can be an integer between 1 and 4,

[0050] and / or where

[0051]

[0052] in

[0053] R 11 is a saturated or monounsaturated or polyunsaturated, straight or branched chain alkyl group having a chain length of 7 to 21 carbon atoms, wherein

[0054] R 12 is an alkyl group or a hydroxyethyl group having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, especially preferably methyl,

[0055] The compounds of formula (5) may contain different groups R 12 , and among them

[0056] f can be an integer between 0 and 5,

[0057] in

[0058] h = 1 or 2 and g = 2 or 3,

[0059] The condition is h+g=4,

[0060] The compounds of formula (5) may have different values ​​of f for h=2 and may contain different groups R 11 , if R 4 , R 6 , R 7 or R 12 If a hydroxyethyl group is included, the hydroxyethyl group may also be alkoxylated, and the optionally alkoxylated hydroxyethyl group may include repeating units based on ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide, and include 1 to 15 repeating units, preferably 1 to 10 repeating units.

[0061] With regard to the above-mentioned advantages of the present invention, corresponding compositions comprising corresponding quaternary ammonium compounds show particularly advantageous results.

[0062] When in formula (1) and / or formula (2), R 1When the acyl group is selected from the group consisting of oleic acid, isostearic acid, lauric acid, palmitic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, calendic acid, punicic acid, α-eleostearic acid, β-eleostearic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and / or cervonic acid, it corresponds to another particularly preferred embodiment of the present invention.

[0063] It is further preferred that in formula (1), a=b=2 and / or in formula (5), h=1 and g=3. This likewise corresponds to another particularly preferred embodiment of the present invention.

[0064] A composition according to the invention comprising at least one counteranion of a compound of the general formula (1), (2), (3), (4) and / or (5) selected from the group consisting of: chloride; bromide; iodide; alkyl sulfate, for example methyl sulfate, ethyl sulfate; alkyl sulfonate, for example methyl sulfonate; trifluoromethanesulfonate; toluenesulfonate; phosphate; sulfate; hydrogensulfate; lactate; glycolate; acetate and / or citrate corresponds to a further particularly preferred embodiment of the invention.

[0065] Another particularly preferred embodiment of the present invention is that 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 polyol.

[0066] In another particularly preferred embodiment of the invention, at least one solid filler is present 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.

[0067] According to another particularly preferred embodiment of the present invention, the at least one solid filler is preferably present in the composition according to the invention in a total amount resulting in a PU, preferably a PU foam, comprising > 2 wt.-%, preferably > 5 wt.-%, more preferably > 8 wt.-%, even more preferably > 10 wt.-%, based on the weight of the resulting PU, preferably PU foam. A possible upper limit may preferably be ≤ 30 wt.-%, for example 15 wt.-% or for example 20 wt.-%.

[0068] It is also particularly preferred that the composition according to the invention further comprises at least one foam stabilizer, preferably a foam stabilizer based on polyether siloxanes, in an amount 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 foam stabilizers based on polyether siloxanes, are known per se. Suitable foam stabilizers are described below.

[0069] The present invention further relates to a process for producing PU, preferably PU foam, in particular rigid PU foam, based on a reaction mixture comprising 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 as described above, preferably using a composition according to the invention as described above, in particular as described in more detail in preferred and / or particularly preferred embodiments.

[0070] In particular, it is preferred that 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. This corresponds to a particularly preferred embodiment of the present invention.

[0071] In particular, it is preferred that 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. This corresponds to a particularly preferred embodiment of the present invention.

[0072] In particular, it is further preferred that at least one foam stabilizer, in particular a foam stabilizer based on polyether siloxane, is additionally present 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 invention.

[0073] Furthermore, it corresponds to a particularly preferred embodiment of the present invention when the process according to the invention for producing PU, preferably PU foam, in particular rigid PU foam, is characterized in that the resulting PU, preferably PU foam, in particular rigid PU foam, comprises a total amount of >2 wt.-%, preferably >5 wt.-%, more preferably >8 wt.-%, even more preferably >10 wt.-%, based on the wt.-% of the resulting PU, preferably PU foam, in particular rigid PU foam, of at least one solid filler. A possible upper limit may preferably be ≤30 wt.-%, for example 15 wt.-% or for example 20 wt.-%.

[0074] According to a particularly preferred embodiment of the invention, preferably no particles of metal oxides are used in the method according to the invention, in particular no particles consisting of a material selected from the group consisting of SiO 2 , ZnO 2 , Al 2 O 3 , ZrO 2 and TiO 2 .

[0075] The process according to the invention for producing PU, preferably PU foam, in particular rigid PU foam, can be carried out by known methods, for example by manual mixing or preferably with the aid of a foaming machine. If the process is carried out using a foaming machine, high-pressure or low-pressure machines can be used. The process according to the invention can be carried out batchwise or continuously.

[0076] Particularly preferred PU formulations in the context of the present invention give 5 kg / m 3 Up to 900kg / m 3 The foam density is , and has the composition shown in Table 1, which corresponds to a preferred embodiment of the present invention:

[0077] Table 1:

[0078] Composition of preferred rigid PU foam formulations

[0079] Components Weight Polyols >0 to 99.9 Surfactants based on quaternary ammonium compounds, preferably according to formula (1), (2), (3), (4) and / or (5) 0.1 to 10 Solid filler 1 to 80 Amine Catalyst 0 to 5 Metal Catalysts 0 to 10 Foam stabilizer, preferably polyether siloxane 0 to 5 water 0 to 20 Foaming agent >0 to 40 Other additives 0 to 300 Isocyanate index: 10 to 1000

[0080] With regard to further preferred embodiments and configurations of the method according to the invention, reference is likewise made to the details already given above in connection with the composition according to the invention.

[0081] The present invention also provides PU, preferably PU foam, in particular rigid PU foam, which is produced according to the above-described process according to the invention, in particular using the composition according to the invention.

[0082] When the PU according to the present invention is a PU foam, especially a hard PU foam and has a mass of 5 to 900 kg / m 3 , preferably 5 to 350 kg / m 3 , especially 10 to 200 kg / m 3 When the foam density is 200 μm, it is a preferred embodiment of the present invention.

[0083] In the context of particularly preferred embodiments, the PU according to the invention, preferably a PU foam, in particular a rigid PU foam produced according to the above-described process of the invention, preferably comprises a total amount of >2 wt.-%, preferably >5 wt.-%, more preferably >8 wt.-%, even more preferably >10 wt.-%, based on the weight % of the total polyurethane, preferably PU foam, in particular a rigid PU foam, of at least one solid filler.

[0084] In the context of particularly preferred embodiments, the PU, preferably PU foam, especially rigid PU foam according to the invention preferably does not contain any metal oxide particles, in particular does not contain any particles consisting of a material selected from SiO2, ZnO2, Al2O3, ZrO2 and TiO2.

[0085] The present invention further relates to the use of the PU and / or PU foam according to the invention as mentioned above as refrigerator insulation, as building material, preferably as insulation board, sandwich element, spray foam and / or 1-component and 1.5-component canned foam, as pipe insulation, imitation wood, modeling foam, packaging foam, mattresses, furniture pads, car seat cushions, headrests, dashboards, car interiors, car roof linings, sound absorbers, steering wheels, shoe soles, carpet backing foams, filter foams, sealing foams, sealants, adhesives or coatings, or for the production of corresponding products.

[0086] Preferred compositions according to the invention comprise in particular the following ingredients:

[0087] a) Surfactants based on quaternary ammonium compounds, in particular quaternary ammonium compounds as defined above by formula (1), (2), (3), (4) and / or (5)

[0088] b) Polyol component

[0089] c) Polyisocyanate component

[0090] d) Catalyst

[0091] e) Optional foam stabilizer

[0092] f) optionally one or more blowing agents

[0093] g) Solid fillers

[0094] h) Optional other additives, flame retardants, etc.

[0095] The polyol component (b) is composed of at least one polyol and optionally at least one organic compound, the organic compound comprising at least two isocyanate reactive groups, the isocyanate reactive groups being preferably selected from OH, NH and NH2 groups. A polyol is an organic compound comprising at least two hydroxyl groups (-OH).

[0096] If one of the above-mentioned organic compounds of the polyol component contains at least two OH groups, then in the context of the present invention, this is only attributed to the polyol. This means that if the organic compound of the polyol component can be classified as a polyol and an organic compound containing at least two isocyanate-reactive groups, preferably selected from OH, NH and NH2 groups, then it is only attributed to the polyol in the context of the present invention.

[0097] The polyol component preferably comprises at least 50% by weight, based on its total weight, of such polyols which comprise exclusively hydroxyl groups (—OH) as isocyanate-reactive groups.

[0098] Based on the total number of isocyanate-reactive groups of the polyol component, it is preferred that at least 50% of these are hydroxyl groups (—OH).

[0099] Suitable compounds which can usually be used in the production of PU foams are known to the person skilled in the art and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane [Plastics Handbook, volume 7, Polyurethanes]", Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.1. Compounds having an OH number in the range of 10 to 1200 mg KOH / g are usually used.

[0100] Particularly preferred compounds are all polyether polyols and polyester polyols which are customarily used for producing polyurethane systems, especially polyurethane foams. Polyether polyols are preferably obtainable by reacting polyols 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 polyols (e.g. diols).

[0101] Furthermore, polyether polycarbonate polyols, natural oil-based 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), filled polyols, prepolymer-based polyols and / or recycled polyols may be used.

[0102] Recycled polyols are polyols obtained by chemical recovery of polyurethanes, for example by solvolysis, such as glycolysis, hydrolysis, acidolysis or aminolysis. The use of recycled polyols constitutes a particularly preferred embodiment of the present invention.

[0103] The polyisocyanate component (c) consists of at least one polyisocyanate having two or more isocyanate groups. Suitable polyisocyanates for the purposes of the present invention are all organic isocyanates having two or more isocyanate groups, in particular the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se.

[0104] Examples which may be mentioned here are alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, for example dodecane-1,12-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, methylenedicyclohexyl 4,4'-diisocyanate. -diisocyanate (H12MDI), isophorone diisocyanate (IPDI), methylcyclohexyl 2,4- and 2,6-diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates and polyisocyanates such as toluene 2,4- and 2,6-diisocyanate (TDI) and the corresponding isomer mixtures, naphthalene diisocyanate, diethyltoluene diisocyanate, diphenylmethane 4,4'- or 2,2'- or 2,4'-diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PMDI, "polymeric MDI").

[0105] Organic polyisocyanates can be used alone or in the form of mixtures thereof. The corresponding "oligomers" of diisocyanates can also be used, such as IPDI trimers based on isocyanurates, biuret or uretdione. In addition, prepolymers based on the above-mentioned isocyanates can be used.

[0106] Mixtures of MDI and more highly condensed analogs having an average functionality of 2 to 4, known as polymeric MDI (also known as "crude MDI"), and the various isomers or isomer mixtures of TDI in pure form are particularly suitable.

[0107] Isocyanates modified by incorporation of carbamates, uretdione, isocyanurates, allophanates and other groups (referred to as modified isocyanates) can also be used. Examples of particularly suitable isocyanates are also described in detail in, for example, EP 1712578, EP 1161474, WO 00 / 58383, US 2007 / 0072951, EP 1678232 and WO 2005 / 085310, which are incorporated herein by reference in their entirety.

[0108] The preferred ratio of the polyisocyanate component and the polyol component, expressed as an index of the formulation (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 and preferably 40 to 400. An index of 100 represents a molar ratio of reactive groups of 1:1.

[0109] Suitable catalysts (d) which can be used for the production of polyurethanes, in particular PU foams, and which are in particular capable of catalyzing the formation of urethane or isocyanurate bonds are known to the person skilled in the art from the prior art. Compounds which can be used in the context of the present invention are 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 the reaction of isocyanate groups with one another.

[0110] Conventional 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, the catalyst used may be a mixture of two or more such compounds.

[0111] 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; preferably one or more foam stabilizers are used. They can be used to optimize the desired cell structure and foaming process.

[0112] In the context of the present invention, in particular Si-containing compounds which assist foam generation (stabilization, cell regulation, cell opening, etc.) can be used. These compounds are well known in the prior art. Particular preference is given to using at least one foam stabilizer based on polyether siloxanes.

[0113] Corresponding siloxane structures that can be used for the purposes of the present invention are described, for example, in the following patent documents, although these patent documents only describe the use in conventional PU foams, as molded foams, mattresses, insulation materials (insulation material), building foams, etc.: CN 103665385, CN 103657518, CN 103055759, CN 103044687, US2008 / 0125503, US 2015 / 0057384, EP 1520870 A1, EP 1211279, EP 0867464, EP0867465, EP 0275563. In addition to surface-active silicon-containing compounds, Si-free surfactants can also be used. For example, EP2295485 A1 describes the use of lecithin, and US 3746663 describes the use of structures based on vinylpyrrolidone as foam stabilizers for the production of rigid PU foams. Other Si-free foam stabilizers are described, for example, in EP 2 511 328 B1, DE 10 2001 1 007 479 A1, DE 3 7 24 716 C1, EP 0 734 404, EP 1 985 642, DE 2 244 350 and US Pat. No. 5,236,961.

[0114] 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; preferably, blowing agents are used. The use of a blowing agent (f) or a combination of two or more blowing agents (f) depends in principle on the properties of the foaming method used, the properties of the system and the use of the PU foam obtained.

[0115] Chemical and / or physical blowing agents can be used, as well as combinations of the two. Depending on the amount of blowing agent used, foams with high or low density are produced. For example, a foam with a density of 5 kg / m 3 Up to 900kg / m 3 , preferably 5kg / m 3 Up to 350kg / m 3 , particularly preferably 8kg / m 3 Up to 200kg / m 3 , especially 8kg / m 3 Up to 150kg / m 3 of bubbles.

[0116] Physical blowing agents that can be used are one or more suitable compounds with a suitable boiling point and mixtures thereof, for example hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane and n-pentane, hydrofluorocarbons (HFCs), preferably HFC 245fa, HFC 134a or HFC 365mfc, hydrochlorofluorocarbons (HCFCs), preferably HCFC 141b, hydrofluoroolefins (HFOs) or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz, esters, preferably methyl formate, ketones, preferably acetone, ethers, preferably dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane or 1,2-dichloroethane.

[0117] The chemical blowing agents used may be one or more compounds which react with NCO groups and release gas, such as water or formic acid, or compounds which release gas as a result of the increase in temperature during the reaction, such as sodium bicarbonate.

[0118] It is a particularly preferred embodiment when the composition according to the invention comprises as blowing agent a combination of water and a hydrocarbon having 5 carbon atoms, an HFO, a hydrohaloolefin or an HFC or a mixture thereof.

[0119] The solid fillers g) have already been described above.

[0120] The optional additives (h) used may be one or more substances known from the prior art and used for the production of polyurethanes, especially PU foams, such as crosslinkers, chain extenders, stabilizers against oxidative degradation (called antioxidants), flame retardants, biocides, cell refining additives, nucleating agents, cell openers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances and / or emulsifiers, etc.

[0121] As optional flame retardants, the composition according to the invention may contain one or more known flame retardants suitable for the production of PU foams, for example halogen-containing or halogen-free organic phosphorus-containing compounds, for example triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP), dimethyl methylphosphonate (DMMP), dimethyl propylphosphonate (DMPP), ammonium polyphosphate or red phosphorus, nitrogen-containing compounds, for example melamine, melamine cyanurate or melamine polyphosphate, or halogenated compounds, for example chlorinated and / or brominated polyether polyols and / or polyester polyols. Mixtures of different flame retardants can also be used.

[0122] Unless something to the contrary is apparent from the present description, any preferred or particularly preferred embodiment of the present invention may be combined with one or more other preferred or particularly preferred embodiments of the present invention.

[0123] The subject matter of the present invention is described by way of the following examples, but it is not intended that the present invention be limited to these exemplary embodiments. In the case of a specified range, a general formula of a compound or a class, these are intended not only to include the corresponding range or group of compounds explicitly mentioned, but also to include all sub-ranges and sub-groups of compounds that can be obtained by removing a single value (range) or a compound. In the case of citing a document in the context of this specification, its entirety, particularly with respect to the subject matter of the context in which the document is cited, is intended to form a part of the disclosure of the present invention. Unless otherwise stated, percentages are by weight percentage. Unless otherwise stated, in the case of stating an average value, these values ​​are weight averages. Unless otherwise stated, when reporting parameters determined by measurement, the measurement is carried out at a temperature of 25° C. and a pressure (standard pressure) of 101325Pa.

[0124] The following examples describe the invention by way of illustration without intending to limit the invention to the embodiments specified in the examples, the scope of application of the invention being clear from the entire description and claims. Example:

[0125] Example 1: PIR rigid foam (PIR = polyisocyanurate)

[0126] For comparison of specific applications, the formulations shown in Table 2 were used and the compounds shown in Table 3 were investigated. Comparative foaming operations were performed by manual mixing. For this purpose, polyols, catalysts, water, foam stabilizers, dispersants (Table 3), solid fillers and blowing agents were weighed into a beaker and mixed for 30 seconds (batch size 500 g) at 1000 rpm with a disk stirrer (6 cm in diameter). The beaker was reweighed to determine the amount of blowing agent evaporated during the mixing operation and to replenish it. MDI was then added and the reaction mixture was stirred for 5 seconds at 3000 rpm with the stirrer and immediately transferred to a 25 cm × 50 cm × 7 cm aluminum mold lined with a polyethylene sheet and thermostated to 60 ° C.

[0127] After 10 minutes, the foam was demoulded. After one day of foaming, the foam was analyzed. Surface and internal defects were subjectively evaluated on a scale of 1 to 10, where 10 represents an (ideal) defect-free foam and 1 represents a very obviously defective foam. The thermal conductivity (λ value in mW / m·K) was measured on a 2.5 cm thick disk at an average temperature of 10° C., according to the specifications of standard EN12667:2001, using an instrument of the Hesto Lambda Control type (model HLC X206).

[0128] Table 2: Rigid PIR foam formulations

[0129] Components Weight Polyester polyols* 100 Amine Catalyst** 0.6 Potassium trimerization catalyst*** 4 Foam Stabilizer**** 2 water 0.8 Compounds of the present invention 0 / 0.5 Solid filler***** 10 Cyclopentane / isopentane 70:30 18 MDI****** 286

[0130] *From Stepan PS 3152, OH value 315mg KOH / g

[0131] **From Evonik Operations GmbH 5

[0132] ***From Evonik Operations GmbH TMR 12

[0133] ****From Evonik Operations GmbH B 84504

[0134] *****Lignin from hardwood, CaCO3, PIR powder or PUR powder

[0135] ******Polymeric MDI, 200mPa*s, 31.5% NCO, functionality 2.7.

[0136] Table 3: Compounds studied

[0137]

[0138]

[0139] Compounds according to the invention were mixed with commercial surfactants not according to the invention ( 6921, 8080, Dispers 652, ST) for comparison.

[0140] The results are summarized in Tables 4 and 5:

[0141] Table 4: Foam properties of rigid PIR foams with lignin as filler

[0142]

[0143]

[0144] Table 5: Cell structure surface / internal defects of rigid PIR foam

[0145]

[0146] The results show that the compounds according to the invention only influence the relevant foam properties negligibly or not at all. Furthermore, by using the compounds according to the invention, a more uniform distribution of the solid filler in the foam can be achieved, which is manifested in a significant improvement in the surface and pore structure / internal defects. In contrast, compounds not according to the invention often lead to a high degree of coarsening of the foam ( 6921), collapse( 8080), or showed no improvement in foam structure ( Dispers 652, ST).

[0147] Example 2: Dispersive Behavior

[0148] In order to compare specific applications, the formulations shown in Tables 6, 8, 10 and 12 were used, and the compounds shown in Table 3 were studied. For this purpose, polyol and water (batch size 100 g) were weighed and mixed for 30 seconds at 1000 rpm with a disc agitator (6 cm in diameter). The compound according to the present invention was then added, and mixed for 30 seconds at 2000 rpm with a disc agitator (6 cm in diameter). For reference experiments, the same mixture without adding the compound according to the present invention was also mixed for 30 seconds at 2000 rpm. Solid fillers were then added while the disc agitator was still running at 2000 rpm, and mixed for 45 seconds. The formulation was then transferred to a glass container, sealed and measured until the time of complete sedimentation.

[0149] After 14 days of upright storage at room temperature, all samples were redispersed and the redispersibility was assessed using a scale of 1 to 3. In this scale, a score of 1 means that the sample could be redispersed by manually shaking the glass container for 30 seconds. A score of 2 means that, although this could not be achieved by manual shaking, the sample could be redispersed using an electric laboratory stirrer (500 rpm, 60 seconds). For samples in which very fine, dense sediments were formed that could not be redispersed by the above two methods, a score of 3 was given.

[0150] The viscosity was determined using two measurement methods. The viscosity was measured at 25° C. on freshly prepared formulations at different shear rates with the aid of an Anton Paar MCR 302 rheometer (50 mm plate-plate, 0.5 mm gap) (Table 5) or at 21° C. on freshly prepared formulations at different shear rates with the aid of a DV2 T rheometer using a spindle type LV04 (64).

[0151] The results of the dispersion behavior are shown in Tables 7, 9, 11 and 13.

[0152] Table 6: Formulations used to test dispersion behavior

[0153] Components Weight Polyester polyols* 100 water 0.8 Compounds of the present invention 0.5 Solid fillers** 10

[0154] *From Stepan PS 3152, OH value 315mg KOH / g

[0155] **Lignin from hardwood

[0156] Table 7: Dispersion behavior - lignin from hardwood

[0157]

[0158]

[0159] *Cone / Plate Rheometer

[0160] Table 8: Formulations used to test dispersion behavior

[0161] Components Weight Polyester polyols* 100 water 0.8 Compounds of the present invention 5 Solid fillers** 8

[0162] *From Stepan PS 3152, OH value 315mg KOH / g**CaCO3.

[0163] Table 9: Dispersion behavior – CaCO3

[0164]

[0165]

[0166] Table 10: Formulations used to test dispersion behavior

[0167] Components Weight Polyester polyols* 100 water 0.8 Compounds of the present invention 0.5 Solid fillers** 10

[0168] *From Stepan PS 3152, OH value 315mg KOH / g

[0169] **PIR foam insulation board ground using a pin-on-disk mill (cryogrinding with liquid nitrogen, peripheral speed 120 m / s).

[0170] Table 11: Dispersion behavior – PIR powders

[0171]

[0172] Viscosity measured with LV04(64) spindle

[0173] Table 12: Formulations used to test dispersion behavior

[0174]

[0175]

[0176] *From Stepan PS 3152, OH value 315mg KOH / g

[0177] **PUR foam insulation board ground using a pin-on-disk mill (cryogenic grinding with liquid nitrogen, peripheral speed 120 m / s).

[0178] Table 13: Dispersion behavior – PUR powder

[0179]

[0180] Viscosity measured with LV04(64) spindle

[0181] In all cases investigated, an improvement in the sedimentation stability and / or redispersibility was achieved compared to formulations which did not contain the compound according to the invention.

[0182] In particular, the formation of solid, dense sediments can be avoided. The invention thus allows very good redispersibility in the event of sedimentation of solids after prolonged storage, so that, for example, continuous stirring or mixing during storage is no longer necessary.

Claims

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

2. The 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. The composition according to claim 2, characterized in that The plastic particles are formed from at least one plastic, which is preferably selected from polyethylene, polypropylene, polyamide (especially PA6, PA6.6, PA10, PA11 and / or PA12), polyester (especially 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, especially polyurethane.

4. The composition according to any one of claims 2 or 3, characterized in that The plastic particles are formed entirely or partly from recycled plastic.

5. The composition according to any one of claims 1 to 4, characterized in that The composition comprises lignin and / or plastic particles as solid filler, the plastic particles preferably consisting of recycled plastic, preferably recycled polyurethane.

6. The composition according to any one of claims 1 to 5, characterized in that The weight-average diameter of the primary particles of the at least one solid filler, determined by dynamic light scattering, is >50 nm, preferably greater than 100 nm, particularly preferably greater than 200 nm.

7. The composition according to any one of claims 1 to 6, characterized in that The quaternary ammonium compound used is at least one ester quaternary ammonium compound of formula (1) or (2), an alkyl quaternary ammonium compound of formula (3), an imidazolinium quaternary ammonium compound of formula (4), an amidoamine quaternary ammonium compound of formula (5) and / or cetylpyridinium chloride, in in R 1 is an acyl radical of a saturated, monounsaturated or polyunsaturated, straight-chain or branched fatty acid having a chain length of 8 to 22 carbon atoms, or an acyl radical 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, where 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, wherein 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, wherein R 4 is an alkyl group or a hydroxyethyl group having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, especially preferably methyl, The compounds of formula (1) or (2) may contain different groups R 4 , and among them n=0 to 20, preferably 0 to 10, particularly preferably 0, wherein a=1 to 3, and b=1 to 3, The condition is a+b=4, And among them in R 5 is a saturated, monounsaturated or polyunsaturated, straight or branched chain alkyl group having a chain length of 8 to 24 carbon atoms, The compounds of formula (3) may contain different groups R 5 ,in R 6 is an alkyl group having 1 to 6 carbon atoms or a hydroxyethyl group or a benzyl group or hydrogen, preferably a methyl, ethyl, propyl, isopropyl or benzyl group, particularly preferably an ethyl or methyl group, especially preferably a methyl group, The compounds of formula (3) may contain different groups R 6 , and among them c=1 to 3 and d=1 to 3, The condition is c+d=4; And among them in R 7 is an alkyl group or a hydroxyethyl group having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, especially preferably methyl, wherein R 8 is a saturated or monounsaturated or polyunsaturated, straight-chain or branched alkyl radical having 8 to 22 carbon atoms or a radical O(CO)R 10 , where R 10 is an aliphatic, saturated or monounsaturated or polyunsaturated, straight or branched chain alkyl radical having 7 to 21 carbon atoms, wherein R 9 is an aliphatic, saturated or monounsaturated or polyunsaturated, straight or branched chain alkyl radical having 7 to 21 carbon atoms, wherein Z is an NH group or oxygen, where e can be an integer between 1 and 4, And among them in R 11 is a saturated or monounsaturated or polyunsaturated, straight or branched chain alkyl group having a chain length of 7 to 21 carbon atoms, wherein R 12 is an alkyl group or a hydroxyethyl group having 1 to 6 carbon atoms or hydrogen, preferably methyl, ethyl, propyl or isopropyl, particularly preferably ethyl or methyl, especially preferably methyl, The compounds of formula (5) may contain different groups R 12 ,and where f can be an integer between 0 and 5, h = 1 or 2 and g = 2 or 3, The condition is h+g=4, The compounds of formula (5) may have different values ​​of f for h=2 and may contain different groups R 11 , if R 4 , R 6 , R 7 or R 12 If a hydroxyethyl group is included, the hydroxyethyl group may also be alkoxylated, and the optionally alkoxylated hydroxyethyl group may include repeating units based on ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide, and include 1 to 15 repeating units, preferably 1 to 10 repeating units.

8. The composition according to claim 7, characterized in that In formula (1) and / or formula (2), R 1 An acyl group selected from the group consisting of oleic acid, isostearic acid, lauric acid, palmitic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, eleostearic acid, punicic acid, α-eleostearic acid, β-eleostearic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and / or docosahexaenoic acid.

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. The composition according to any one of claims 7 to 9, characterized in that The composition further comprises at least one counteranion of a compound of formula (1), (2), (3), (4) and / or (5), the counteranion being selected from: chloride; bromide; iodide; alkyl sulfate, e.g. methyl sulfate, ethyl sulfate; alkyl sulfonate, e.g. methyl sulfonate; trifluoromethanesulfonate; toluenesulfonate; phosphate; sulfate; hydrogen sulfate; lactate; glycolate; acetate and / or citrate.

11. The composition according to any 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 the polyol.

12. The composition according to any 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 polyol.

13. The composition according to any one of claims 1 to 12, characterized in that At least one foam stabilizer, in particular one based on polyether siloxanes, is additionally present in an amount of 0.5 to 4 parts by weight, based on 100 parts by weight of polyol.

14. The composition according to any one of claims 1 to 13, characterized in that It does not contain any metal oxide particles, in particular does not contain any particles consisting of a material selected from SiO2, ZnO2, Al2O3, ZrO2 and TiO2.

15. A process for producing PU, preferably PU foam, in particular rigid PU foam, based on a reaction mixture comprising 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 Use of at least one surfactant based on a quaternary ammonium compound, preferably as defined in any one of claims 7 to 10, in particular use of a composition as defined in any one of claims 1 to 14.

16. Polyurethane, preferably PU foam, especially rigid PU 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 building material, preferably as insulation board, sandwich element, spray foam and / or 1-component and 1.5-component canned foam, as pipe insulation, imitation wood, modeling foam, packaging foam, mattresses, furniture pads, car seat cushions, headrests, dashboards, car interiors, car roof linings, sound absorbers, steering wheels, shoe soles, carpet backing foams, filter foams, sealing foams, sealants, adhesives or coatings, or for the production of corresponding products.

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