Stabilizer for polyurethane foam materials containing solids

Abstract

The present invention provides a composition for producing a polyurethane foam material, comprising: (A) a polyol component; (B) a polyisocyanate component; (C) at least one catalyst for catalyzing an isocyanate-polyol, isocyanate-water reaction and / or an isocyanate trimerization reaction; (D) at least one foam stabilizer; (E) at least one chemical and / or physical blowing agent; and (F) at least one solid material, wherein the at least one foam stabilizer is a polyol represented by Formula 1:M a M b 1 D c D d 1 The present invention relates to a composition in which the polyether siloxane is selected from the group of polyether siloxanes having a general average composition according to the following:

Description

[Technical Field]

[0001] The present invention relates to the field of polyurethanes, preferably polyurethane foams. In particular, the present invention relates to a composition for producing polyurethane foams, preferably rigid polyurethane foams, comprising, inter alia, a solid material and a specific polyethersiloxane, and a method for producing polyurethane foams, preferably rigid polyurethane foams, using, in particular, a solid material such as powdered waste plastic and a specific polyethersiloxane. Furthermore, the present invention relates to the resulting PU foams and their uses.

[0002] The terms polyurethane and polyurethane foam are established technical terms and have long been known to those skilled in the art. Within the scope of the present invention, polyurethane (PU) is understood to mean, in particular, a product obtained by the reaction of a polyisocyanate component with a polyol component. Here, not only polyurethane but also additional functional groups, such as uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea, and / or uretonimine, may be formed. Therefore, within the meaning of the present invention, polyurethane (PU) is understood to mean both polyurethanes and polyisocyanurates, polyureas, and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret, and / or uretonimine groups. Therefore, within the scope of the present invention, polyurethane foam (PU foam) is understood to mean a foam obtained as a reaction product of a polyisocyanate component with a polyol component. Here, not only the polyurethanes from which the name is derived but also further functional groups such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates and / or uretonimines may be formed.

[0003] Foams and PU foams are known per se. Polyurethane rigid foams (PU rigid foams) are established technical terms. The known fundamental difference between flexible and rigid foams is that flexible foams exhibit elastic behavior and therefore deformation is reversible. In contrast, rigid foams are permanently deformed. More information about polyurethane rigid foams can also be found in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3. Auflage 1993, Kapitel 6. Within the context of the present invention, the terms "foam" and "foam" are treated synonymously. Correspondingly, this also applies to terms based on these terms, such as rigid foam or rigid foam or PU foam or PU foam.

[0004] In relation to the provision of PU foams, especially PU rigid foams, it is of particular interest to produce them cost-effectively and improve their properties. However, in this respect, the liquid components typically used in the production of polyurethane foams often reach their limits. Therefore, solids can be used to further improve, for example, fire resistance or thermal insulation properties. A further interest is to produce PU foams, especially PU rigid foams, in a particularly sustainable manner, for example by using bio-based and / or recycled solids. German Patent Application Publication No. 19633891, German Patent Application Publication No. 4416749, Chinese Patent Application Publication No. 107722601, International Publication No. 2021116511, Spanish Patent Application Publication No. 2526724, Japanese Patent Application Publication No. 2020070410, European Patent Application Publication No. 0665251, Zhang, B., Feng, Z., Han, X. et al., J. Polym. Res. 28, 407 (2021) or Yang, Chunzhuang & Shao, Shuiyu, Frontiers in Materials 8, 712809m (2021) or Zhu H, Xu S., ACS Omega, Apr 22;5 (17) 9658-9667 (2020) or Heng Zhu and Shiai Xu ACS Known prior art, such as Lu, W., Zeng, Z., He, Z., Liang, Y., Sun, Y., Song, S., Wang, L., Liu, R., J. Appl. Polym. Sci. 2022, e53546, describes corresponding solids suitable for use in PU, preferably PU foam materials. For example, PU foams can be produced more sustainably using crushed solids from used mattresses, PU-based insulation boards, refrigerator PU insulation, other plastic-based waste streams, or bio-based materials such as lignin. Meanwhile, solid flame retardants, such as ammonium polyphosphate, red phosphorus, or melamine, can be used to improve fire resistance.

[0005] The use of solids entails significant problems regarding dispersion in the liquid starting material and during processing, including, inter alia, sedimentation, difficult redispersion after sedimentation, the resulting non-uniform distribution of the solids in the PU foam, and, in particular, also the resulting non-uniform property profile of the polyurethane foams thus produced.

[0006] In the production of polyurethane foams, especially corresponding rigid polyurethane foams, cell-stabilizing or foam-stabilizing additives (so-called foam stabilizers) are typically used, which are desirable for ensuring a finely cellular, uniform, and defect-free foam structure and thus significantly favorably influence the use properties, such as the thermal insulation capacity of the rigid foam. Polyether-modified siloxane-based surfactants are particularly effective here, and therefore represent a preferred class of foam stabilizers. These so-called polyether siloxane foam stabilizers (PES) are well known from the prior art and are described in detail, for example, in CN 103665385, CN 103657518, CN 103055759, CN 103044687, US 2008 / 0125503, US 2015 / 0057384, EP 1520870, EP 1211279, EP 0867464, EP 0867465 and EP 0275563.

[0007] Against this background, a specific object of the present invention was to provide a polyurethane foam material, in particular a rigid polyurethane foam material, containing solids, while overcoming the above-mentioned problems of settling, difficult redispersion after settling, and inhomogeneous distribution in the material.

[0008] This problem is solved by the subject matter of the present invention, which is a composition for producing polyurethane foam materials, preferably rigid polyurethane foam materials, comprising: (A) a polyol component; (B) a polyisocyanate component; (C) at least one catalyst that catalyzes the isocyanate-polyol and / or isocyanate-water reaction and / or the isocyanate trimerization reaction; (D) at least one foam stabilizer; (E) at least one chemical and / or physical blowing agent; (F) At least one solid material Including, At least one foam stabilizer is selected from the group consisting of a compound of Formula 1: M a M b 1 D c D d 1 (Formula 1) [In the formula, [ka] a=0 to 2, particularly preferably 1.5 to 2; b=0 to 2, particularly preferably 0 to 0.5; c=8 to 150, preferably 18 to 100, particularly preferably 18 to 70; d=0 to 20, preferably 1 to 16, particularly preferably 1 to 13; a+b=2, and when b=0, d>1, and when d=0, b=1.5~2, R=each independently the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, H, or -OR 2 , preferably methyl, ethyl, phenyl or H, particularly preferably methyl, R 2 = each independently of the other, the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, or H, R 1 = each independently of the other, the same or different polyether residues, preferably of formula 2: [ka] are the same or different polyether residues having a general average composition according to R 3 = each independently of one another, the same or different divalent alkyl residues having 2 to 15 carbon atoms, preferably the same or different divalent alkyl residues having 3 to 6 carbon atoms, particularly preferably -(CH2)3-, R 4 = each independently of the other, the same or different alkyl residues having 1 to 18 carbon atoms, optionally having an ether function, or the same or different aryl residues having 6 to 18 carbon atoms, optionally having an ether function, or H, preferably H, ethyl or benzyl, R 5 = R, each independently of the other 2 and C(O)R 2 are the same or different residues selected from the group consisting of: e=0 to 100, preferably 0 to 80, particularly preferably 0 to 50; f=0 to 100, preferably 0 to 80, particularly preferably 0 to 50; g=0 to 100, preferably 0 to 80, particularly preferably 0 to 50; h=0 to 100, preferably 0 to 40, particularly preferably 0; at least one of repeat units e, f, g, or h is greater than 0; Polyether residue R 1 It is very particularly preferred if at least one of the following categories 1 or 2 corresponds to at least one of the following categories: (Category 1 for Equation 2) e=8~16, f=g=h=0, or e+f+g=15~34, (f+g) / (e+f+g)>0 to 0.25, particularly preferably 0.1 to 0.2; h=0, (Category 2 for Equation 2) e+f+g=7~15, (f+g) / (e+f+g)≧0.15~0.8, h=0, or e+f+g=13~32, (f+g) / (e+f+g)≧0.25 to 0.8, particularly preferably 0.3 to 0.4; h=0] is selected from the group of polyether siloxanes having a general average composition according to The polyethersiloxanes according to formula 1 are used in a total amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total polyol component. It is a composition.

[0009] The polyethersiloxanes usable according to the invention, particularly as characterized in one of the patent claims, can be obtained by conventional routes known to those skilled in the art, for example by the known reaction of allyl polyethers with SiH-functional siloxanes using Pt catalysts. In the experimental section, this is demonstrated by way of example with a number of examples.

[0010] The subject matter of the present invention offers various advantages. It thus makes it possible to produce PU foams, preferably rigid PU 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 rigid PU foams, a particularly fine-celled, uniform, and defect-free foam structure is possible. This achieves the provision of corresponding polyurethane foams with particularly good application properties and a homogeneous property profile. Overall, the present invention allows for easy handling of solids during production. The solids can be introduced into the reaction mixture, for example, via one of the two reaction components (the polyol component or the polyisocyanate component). Here, 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 solids in the polyurethane foam material, which results in a more uniform property profile.

[0011] In a particularly preferred embodiment of the present invention, the composition according to the present invention comprises at least one polyethersiloxane according to formula (1) which contains at least two polyethers of general formula (2), at least one of which must satisfy category 1 and at least one of which must satisfy category 2, and the preferred ratio of polyethers of category 1 to polyethers of category 2 in the polyethersiloxane corresponds to 10:90 to 90:10% by weight, particularly preferably 20:80 to 80:20% by weight, in particular 30:70 to 70:30% by weight.

[0012] In a further particularly preferred embodiment of the present invention, the composition according to the invention comprises at least two polyethersiloxanes according to formula (1), at least one of which contains at least one polyether of general formula (2) satisfying category 1, and at least one of which contains at least one polyether of general formula (2) satisfying category 2, the preferred ratio of polyethersiloxane of formula (1) containing at least one polyether of category 1 to polyethersiloxane of formula (1) containing at least one polyether of category 2 being 10:90 to 90:10% by weight, particularly preferably 20:80 to 80:20% by weight, in particular 30:70 to 70:30% by weight.

[0013] Within the scope of the present invention, solids are understood in particular to be substances that are in a solid aggregate state at 25° C. and 101.325 kPa.

[0014] In a further particularly preferred embodiment of the present invention, the composition according to the invention is characterized in that the at least one solid is used in a total amount of 5 to 100 parts by weight, preferably 5 to 80 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the total polyol component.

[0015] At least one solid material is (a) a solid flame retardant, preferably ammonium polyphosphate, melamine, melamine-coated ammonium polyphosphate, ammonium polyphosphate microencapsulated with melamine, ammonium polyphosphate microencapsulated with melamine-formaldehyde resin, melamine cyanurate, red phosphorus, zinc borate, melamine polyphosphate, expandable graphite, and / or antimony trioxide; (b) plastic powder; and (c) calcium carbonate, graphite, graphene, lignin, and / or lignocellulose In a further particularly preferred embodiment of the present invention, the composition according to the invention is characterized in that it is selected from the group consisting of:

[0016] The at least one solid is in particular in powder form. Preferred particle sizes are described further below.

[0017] A further particularly preferred embodiment of the present invention is one in which the plastic powder usable according to the invention consists of at least one plastic selected from the group consisting of 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, or mixtures thereof, and the plastic powder may particularly preferably also be formed from waste plastic.

[0018] Waste plastics, in particular, (i) Plastics derived from manufacturing waste obtained during the manufacture of plastics, such as offcuts, sawdust, or materials that do not pass quality control; and / or (ii) Plastics obtained from plastics that have reached the end of their useful life, such as, for example, PU foam-based plastics from used refrigeration equipment, used insulation or insulation boards, used sealing foam, used mattresses, used furniture, used sound-absorbing materials, used packaging foam, foam from used vehicles, used packaging, pipes or other used plastic parts and / or plastic semi-finished products. is.

[0019] In a further particularly preferred embodiment of the present invention, the composition according to the invention also contains one or more plastic powders as solids, preferably from waste plastics, preferably recycled polyurethanes, particularly preferably recycled polyurethane foam materials.

[0020] In the context of the present invention, the terms "waste plastic" and "recycled plastic" are used synonymously. In the context of the present invention, the terms "recycled polyurethane" and "PU recycle" are used synonymously. Therefore, "recycled polyurethane" or "PU recycle" refers to a polyurethane, preferably in powder form, in particular (i) waste polyurethanes obtained from manufacturing waste obtained during PU production, such as offcuts, sawdust, or materials that do not pass quality control; and / or (ii) Waste polyurethanes obtained from polyurethanes that have reached the end of their useful life. is.

[0021] The recycled polyurethane foam material is therefore waste polyurethane foam material, preferably in powder form.

[0022] In a further particularly preferred embodiment of the present invention, the composition according to the invention is characterized in that the solid matter is a powder having an average diameter of less than 500 μm, preferably less than 200 μm, particularly preferably less than 80 μm, where the average particle diameter is determined by laser diffraction spectroscopy in accordance with ISO 13320:2020. The value for the average diameter corresponds to the volume-based median, i.e., represents the diameter of a volume-equivalent sphere, compared to which 50% of the particles are smaller and 50% of the particles are larger.

[0023] The composition according to the present invention comprises (i) hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane, and / or n-pentane; and / or (ii) hydrofluoroolefins and / or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E), and / or 1336mzz; and water, which is essential. as a blowing agent is a further preferred embodiment of the present invention.

[0024] Preferred PU foam formulations, in particular PU rigid foam formulations, within the meaning of the present invention have the compositions listed in Table 1.

[0025] [Table 1]

[0026] A further subject of the present invention is a process for producing PU foams, preferably polyurethane rigid foams, based on a reaction mixture containing a composition as described above, in particular as defined in any one of claims 1 to 9.

[0027] The process for producing PU foams, preferably rigid polyurethane foams, according to the present invention can be carried out by any known method, 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 present invention can be carried out batchwise or continuously, using, for example, 1K, 1.5K, or 2K systems, as described in EP-A-3717538, U.S. Pat. No. 7776934, EP-A-1400547, or EP-A-2780384.

[0028] 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.

[0029] Another further subject of the present invention is 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.

[0030] The PU foam material according to the present invention, in particular the PU rigid foam material, has a viscosity of 5 to 900 kg / m 3 , preferably 5 to 350 kg / m 3 , especially 8 to 200 kg / m 3 In a preferred embodiment of the invention, the volume weight of the container is 100g.

[0031] The invention further relates to the use of the PU foams according to the invention, in particular PU rigid foams, as heat insulating materials and / or building materials, in particular in construction applications, in particular in spray foams and / or 1-component and 1.5-component can foams or in the cooling area, as sound absorbers, as packaging foams, as wood imitations, as modelling foams, as roof liners for automobiles, as interior trim for automobiles, as sealing foams or as pipe coverings for pipes.

[0032] A preferred composition according to the present invention comprises the following components: A) Polyol component B) Polyisocyanate component C) Catalysts that catalyze the isocyanate-polyol and / or isocyanate-water reaction and / or the isocyanate trimerization reaction D) Foam stabilizers E) Blowing Agent F) Solids according to the invention G) Optionally further additives, such as liquid flame retardants Contains:

[0033] The polyol component (A) comprises 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 multiple hydroxyl groups (-OH).

[0034] 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 meaning of the present invention, i.e., if an organic compound of the polyol component is evaluated both as a polyol and as an organic compound containing at least two groups reactive with isocyanates selected from the group consisting of OH groups, NH groups, and NH groups, it is classified exclusively as a polyol within the meaning of the present invention.

[0035] 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.

[0036] 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).

[0037] Corresponding compounds that can generally be used for the production of PU foams 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. Generally, compounds having an OH number in the range of 10 to 1200 mg KOH / g are used.

[0038] Particularly preferred compounds are all polyether polyols and / or polyester polyols that can be commonly used for the production of polyurethane systems, especially polyurethane foam materials. Polyether polyols can be obtained, for example, by reacting polyhydric alcohols or amines with alkylene oxides. Preferably usable polyester polyols are usually based on esters of polycarboxylic acids (which can be aliphatic, such as adipic acid, or aromatic, such as phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols).

[0039] 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.

[0040] Recycled polyols are polyols obtained from the chemical regeneration of polyurethanes, for example by glycolysis, hydrolysis, solvolysis, such as acidolysis or aminolysis of polyurethanes. The use of recycled polyols represents a particularly preferred embodiment of the present invention.

[0041] The polyisocyanate component (B) comprises at least one polyisocyanate having two or more isocyanate groups. Suitable polyisocyanates within the meaning 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.

[0042] Examples of suitable diisocyanates include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene residue, 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. Examples of suitable isocyanates include 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"). The organic polyisocyanates can be used individually or in the form of mixtures. Similarly, the corresponding "oligomers" of diisocyanates can be used, such as isocyanurate-, biuret-, or uretdione-based IPDI trimers. Furthermore, the use of the aforementioned isocyanate-based prepolymers is also possible. Particularly suitable are mixtures of MDI and more highly condensed analogues known as "polymeric MDI" (also called "crude MDI"), with an average functionality of 2 to 4, and the various isomers of TDI in pure form or as isomer mixtures. It is also possible to use isocyanates modified by the incorporation of urethane, uretdione, isocyanurate, allophanate, and other groups, so-called modified isocyanates.Examples of particularly suitable isocyanates are 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 entireties.

[0043] The preferred ratio of isocyanate groups to isocyanate-reactive groups, expressed as a formulation index (isocyanate index), i.e., as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups), multiplied by 100, is in the range of 10 to 1000, preferably 40 to 400. An index of 100 represents a molar ratio of reactive groups of 1 to 1.

[0044] Suitable catalysts (C) that can be used for the production of polyurethanes, in particular PU foams, are known to those skilled in the art. In the context of the present invention, in particular, all compounds that can catalyze the reaction of isocyanate groups with OH groups, NH groups or other isocyanate-reactive groups and / or with each other are usable.

[0045] Here, the usual catalysts known from the prior art can be used, such as 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.

[0046] The appropriate amount used varies depending on the type of catalyst, and may be, for example, preferably in the range of 0.05 to 5 pphp (= parts by weight based on 100 parts by weight of the polyol component) in the case of an amine catalyst, or, for example, in the case of a potassium salt, preferably in the range of 0.1 to 10 pphp.

[0047] Foam stabilizer (D) and its use in the production of PU foams are known to those skilled in the art, as described above. According to the present invention, at least one of the polyethersiloxane foam stabilizers according to the present invention is used. In addition to the polyethersiloxane foam stabilizer according to the present invention, other polyethersiloxane foam stabilizers and Si-free surfactants can also be used. For example, EP 2295485 A1 describes the use of lecithin, and U.S. Pat. No. 3,746,663 describes the use of vinylpyrrolidone-based structures. Further Si-free foam stabilizers are described, for example, in EP 2511328, DE 1020011007479, DE 3724716, EP 0734404, EP 1985642, DE 2244350, and U.S. Pat. No. 5,236,961.

[0048] The blowing agent (E) and its use in the production of PU foams are known to those skilled in the art. The use of a blowing agent is optional, and preferably a blowing agent is used. The use of one or more combinations of blowing agents depends essentially on the type of foaming method used, the type of system, and the intended use of the resulting PU foam. Chemical and / or physical blowing agents, as well as a combination of both, can be used. Depending on the amount of blowing agent used, high or low density foams can be produced. The foams can be produced at a density of 5 kg / m 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

[0049] As optional physical blowing agents, one or more corresponding compounds having an appropriate boiling point can be used, such as hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane or 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 methylformiat; ketones, preferably acetone; ethers, preferably dimethoxymethane; or chlorohydrocarbons, preferably dichloromethane or 1,2-dichloroethane, and mixtures thereof.

[0050] Optional chemical blowing agents include one or more compounds that either react with NCO groups to release a gas such as water or formic acid, or that release a gas upon increasing temperature during the reaction, such as sodium bicarbonate.

[0051] 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.

[0052] The usable solids (F) have already been described further above, where the average particle diameter is determined by laser diffraction spectroscopy in accordance with ISO 13320:2020. The value for the average particle diameter corresponds to the volume-based median, i.e. represents the diameter of a volume-equivalent sphere, compared to which 50% of the particles are smaller and 50% of the particles are larger.

[0053] As optional further additives (G) 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, color pastes, fragrances and / or emulsifiers.

[0054] 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), dimethylmethanephosphonate (DMMP), or dimethylpropanephosphonate (DMPP), or halogenated compounds. Mixtures of different flame retardants may also be used.

[0055] Unless stated otherwise from this specification, any preferred or particularly preferred embodiment of the present invention can be combined with one or more of the remaining preferred or particularly preferred embodiments of the present invention.

[0056] The subject matter of the present invention is described below by way of example, but the present invention, the scope of which will become apparent from the entire specification and the claims, should not be limited to these exemplary embodiments. When ranges, general formulas, or compound classes are described, they 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, particularly the factual content in the context in which they are cited, are fully incorporated into the disclosure of the present invention. Unless otherwise specified, percentages are by weight. When average values ​​are described, they are number averages unless otherwise specified. When parameters determined by measurement are described, these measurements were performed at a temperature of 23°C and atmospheric pressure, unless otherwise specified. [Example]

[0057] Synthesis of polyether siloxane foam stabilizer (PES). The Pt catalyst used to produce the polyethersiloxane was a xylene solution of Karstedt catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (CAS 68478-92-2)). The Pt content of the solution was 2 wt. %. The catalyst was purchased from Merck and used without further processing.

[0058] To synthesize the polyethersiloxane, the allyl polyether and SiH-functional siloxane were pre-charged into a three-neck flask equipped with a KPG stirrer and reflux condenser according to the composition listed in Table 2. The ratio of allyl polyether to SiH-functional siloxane was selected so that 1.4 moles of double bonds from the allyl polyether were present per mole of SiH functional group. The apparatus was inerted with nitrogen, and the mixture was subsequently heated to 80°C. Then, 10 ppm of Pt, based on the total metered feed, was added in the form of the previously described Pt catalyst. An exothermic reaction began. The temperature was kept below 110°C by cooling. The reaction mixture was then stirred at 100°C for 3 hours. Clear to slightly cloudy products were consistently obtained.

[0059] PES14 and PES15 were prepared by mixing the respective foam stabilizers in a 1:1 weight ratio.

[0060] The polyether siloxanes shown in Table 2 according to Formula 1 and Formula 2 were prepared and investigated in terms of application technology. For PES1-15, R = methyl, R 3 = -(CH2)3-, and h = 0. PES1-3 are considered to be comparative examples not according to the present invention.

[0061] [Table 2]

[0062] Application example 1: Polyurethane rigid foam (PUR) For comparison in terms of application technology, the formulations shown in Table 3 were used. Comparative foaming runs were performed using the manual mixing method. To do this, polyol, catalyst, water, foam stabilizer, solids, and blowing agent were weighed into a beaker and mixed with a plate stirrer (Tellerruehrer) (6 cm diameter) at 1000 rpm for 30 seconds. The amount of blowing agent evaporated during the mixing process was determined by reweighing and then replenished. MDI was then added, and the reaction mixture was stirred with the stirrer described at 3000 rpm for 5 seconds. It was then immediately transferred to an aluminum mold measuring 145 cm × 14 cm × 3.5 cm, tilted at a 10° angle (along the 145 cm long side) and lined with polyethylene foil, thermostated at 45°C, and measuring 145 cm × 14 cm × 3.5 cm. Here, the foaming formulation was injected from the deeper side, so that the expanding foam filled the mold in the injection zone and rose toward the higher side. The amount of foam formulation used was calculated to be approximately 10% more than the amount required for minimum mold filling.

[0063] 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 / mK) 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.

[0064] [Table 3]

[0065] Application example 2: Polyisocyanurate rigid foam (PIR) For comparison of application technology, the formulations shown in Table 4 were used. Comparative foaming runs were performed using the manual mixing method. To do so, polyol, catalyst, water, foam stabilizer, solids, 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 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 and thermostated at 60 °C.

[0066] 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 / mK) 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.

[0067] [Table 4]

[0068] These results are summarized in Tables 5 to 14. For formulations C to E and H to J, the foam stabilizers that showed the most promising results in formulations B and G were selected.

[0069] [Table 5]

[0070] [Table 6]

[0071] [Table 7]

[0072] [Table 8]

[0073] [Table 9]

[0074] [Table 10]

[0075] [Table 11]

[0076] [Table 12]

[0077] [Table 13]

[0078] [Table 14]

[0079] These results show that polyethersiloxanes not according to the invention result in a significantly worse property profile when used as a solid, in particular higher thermal conductivity and a worse surface, whereas polyethersiloxanes according to the invention can significantly improve the property profile compared to polyethersiloxanes not according to the invention.

[0080] Application example 3: Dispersion behavior For comparison in terms of application technology, the formulations shown in Table 15 were used. For this purpose, the polyol and polyether siloxane were weighed (batch size 250 g) and mixed for 30 seconds at 1000 rpm with a plate stirrer (diameter 6 cm). Subsequently, while the plate stirrer (2000 rpm) was still running, the solids were added and mixed for a further 45 seconds. Subsequently, the formulations were filled into glass containers, sealed, and the time until complete settling was measured.

[0081] 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 for 60 seconds) rather than by manual shaking. A rating of 3 was given to samples that formed a very hard, dense sediment that could not be redispersed by one of the two methods listed.

[0082] [Table 15]

[0083] These results are summarized in Tables 16 and 17: [Table 16]

[0084] [Table 17]

[0085] In the cases tested, improvements in sedimentation stability and redispersibility could be achieved compared to formulations without polyethersiloxane or compared to formulations without polyethersiloxane according to the invention.

[0086] 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 long storage is no longer necessary.

Claims

1. 1. A composition for producing a polyurethane foam material, preferably a polyurethane rigid foam material, comprising: (A) a polyol component, (B) a polyisocyanate component; (C) at least one catalyst that catalyzes the isocyanate-polyol and / or isocyanate-water reaction and / or the isocyanate trimerization reaction; (D) at least one foam stabilizer; (E) at least one chemical and / or physical blowing agent; (F) at least one solid material; In a composition comprising: The at least one foam stabilizer is represented by Formula 1: M ａ M ｂ １ D ｃ D ｄ １ (Equation 1) [In the formula, 【Chemistry 1】 a=0 to 2, particularly preferably 1.5 to 2; b=0 to 2, particularly preferably 0 to 0.5; c=8 to 150, preferably 18 to 100, particularly preferably 18 to 70; d=0 to 20, preferably 1 to 16, particularly preferably 1 to 13; a+b=2, and when b=0, d>1, and when d=0, b=1.5 to 2; R=each independently of the other, the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, H, or —O—R ２ , preferably methyl, ethyl, phenyl or H, particularly preferably methyl, R ２ = each independently of the other, the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, or H, R １ = each independently of the other, the same or different polyether residues, preferably of formula 2: 【Chemistry 2】 are the same or different polyether residues having a general average composition according to R ３ = each independently of the other, the same or different divalent alkyl residues having 2 to 15 carbon atoms, preferably the same or different divalent alkyl residues having 3 to 6 carbon atoms, particularly preferably -(CH ２ ) ３ - and R ４ = each independently of the other, the same or different alkyl residues having 1 to 18 carbon atoms, optionally having an ether function, or the same or different aryl residues having 6 to 18 carbon atoms, optionally having an ether function, or H, preferably H, ethyl or benzyl, R ５ = each independently of the other, R ２ and C(O)R ２ are the same or different residues selected from the group consisting of: e=0 to 100, preferably 0 to 80, particularly preferably 0 to 50; f=0 to 100, preferably 0 to 80, particularly preferably 0 to 50; g=0 to 100, preferably 0 to 80, particularly preferably 0 to 50; h=0 to 100, preferably 0 to 40, particularly preferably 0; at least one of repeat units e, f, g, or h is greater than 0; The polyether residue R １ It is very particularly preferred if at least one of the following categories 1 or 2 corresponds to at least one of the following categories: (Category 1 for Formula 2) e=8 to 16, f = g = h = 0, or e+f+g=15~34, (f+g) / (e+f+g)>0 to 0.25, particularly preferably 0.1 to 0.2; h=0, (Category 2 for Formula 2) e+f+g=7~15, (f+g) / (e+f+g)≧0.15-0.8, h=0, or e+f+g=13~32, (f+g) / (e+f+g)≧0.25 to 0.8, particularly preferably 0.3 to 0.4; h = 0] is selected from the group of polyether siloxanes having a general average composition according to The polyethersiloxanes according to formula 1 are used in a total amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polyol component as a whole. A composition characterized by:

2. 2. The composition according to claim 1, comprising at least one polyethersiloxane according to formula (1) which contains at least two polyethers of general formula (2), wherein at least one of the polyethers must satisfy category 1 and at least one of the polyethers must satisfy category 2, and wherein the preferred ratio of category 1 polyethers to category 2 polyethers in the polyethersiloxane corresponds to 10:90 to 90:10% by weight, particularly preferably 20:80 to 80:20% by weight, in particular 30:70 to 70:30% by weight.

3. 3. The composition according to claim 1, wherein at least two polyethersiloxanes according to formula (1) are contained, at least one of which contains at least one polyether of general formula (2) that satisfies category 1, and at least one of which contains at least one polyether of general formula (2) that satisfies category 2, wherein the preferred ratio of the polyethersiloxane of formula (1) containing at least one polyether of category 1 to the polyethersiloxane of formula (1) containing at least one polyether of category 2 is from 10:90 to 90:10% by weight, particularly preferably from 20:80 to 80:20% by weight, in particular from 30:70 to 70:30% by weight.

4. 4. The composition according to claim 1, wherein the at least one solid is used in a total amount of 5 to 100 parts by weight, preferably 5 to 80 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the polyol component as a whole.

5. The at least one solid material is (a) a solid flame retardant, preferably ammonium polyphosphate, melamine, melamine-coated ammonium polyphosphate, melamine-microencapsulated ammonium polyphosphate, melamine-formaldehyde resin-microencapsulated ammonium polyphosphate, melamine cyanurate, red phosphorus, zinc borate, melamine polyphosphate, expandable graphite, and / or antimony trioxide; (b) Plastic powders; and (c) calcium carbonate, graphite, graphene, lignin, and / or lignocellulose The composition of any one of claims 1 to 4, selected from the group consisting of:

6. 6. The composition according to claim 5, wherein the plastic powder is made of at least one plastic 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, or mixtures thereof; and the plastic powder is particularly preferably made from waste plastics, particularly preferably from PU waste plastics.

7. 7. The composition according to claim 1, wherein the solid material comprises one or more plastic powders from waste plastics, preferably recycled polyurethanes.

8. 8. The composition according to claim 1, wherein the solid is a powder having an average diameter of less than 500 μm, preferably less than 200 μm, particularly preferably less than 80 μm.

9. The composition comprises: (i) hydrocarbons having 3, 4, or 5 carbon atoms, preferably cyclopentane, isopentane, and / or n-pentane; and / or (ii) hydrofluoroolefins and / or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E), and / or 1336mzz; and water, which is essential.

9. The composition according to claim 1, wherein the composition comprises as a foaming agent:

10. 10. A method for producing a PU foam, preferably a polyurethane rigid foam, based on a reaction mixture containing a composition as defined in any one of claims 1 to 9.

11. 11. A PU foam, in particular a PU rigid foam, produced by the method according to claim 10.

12. 12. Use of the PU foam, in particular PU rigid foam, according to claim 11 as a heat insulating material and / or building material, in particular in construction applications, in particular in spray foams and / or 1-component and 1.5-component can foams, or in cooling areas, as sound absorbers, as packaging foams, as wood imitation foams, as modeling foams, as roof liners for automobiles, as interior trim for automobiles, as sealing foams or as pipe coverings for pipes.

Images