Stabilizer for polyurethane foam materials containing recycled polyols

Abstract

The present invention provides a composition for producing a polyurethane foam material, comprising: (A) a polyol component comprising at least one recycled polyol; (B) a polyisocyanate component; (C) at least one catalyst for catalyzing an isocyanate-polyol and / or isocyanate-water reaction and / or an isocyanate trimerization reaction; (D) at least one foam stabilizer; and (E) at least one chemical and / or physical blowing agent, 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 composition is selected from the group of polyether siloxanes of general average composition according to formula (1):

Description

[Technical Field]

[0001] The present invention relates to the field of polyurethanes. In particular, the present invention relates to a method for producing polyurethane foam materials, preferably rigid polyurethane foam materials, using recycled polyols. Furthermore, the present invention relates to the use of suitable additives and uses of the polyurethane foams.

[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. PU rigid foams are an established technical term. The fundamental known difference between flexible and rigid foams is that flexible foams exhibit elastic behavior and are therefore reversible in deformation. 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, in particular PU rigid foams, it is of particular interest to produce them from particularly sustainable materials and contribute to the functioning of a circular economy in the area of ​​polyurethane foams. This can be achieved, for example, by using recycled polyols obtained by chemical regeneration, i.e., depolymerization of polyurethanes, in particular polyurethane foams, particularly preferably polyurethane rigid foams. The possibility of producing such recycled polyols is known and is described, in particular, in WO 2018 / 091575, CN 114106281, U.S. Pat. No. 3,441,616, EP 0105167, GDR 226575, U.S. Pat. No. 5,274,004, DE 4217024, DE 4234335, DE 4442379, EP This is described in detail in patent application publication no. 718349, DE patent application publication no. 19510638, DE patent application publication no. 19622761, US patent no. 5763692, WO 2022063764, WO 2015027319, CN patent application publication no. 105399985, WO 2020080619, WO 2019219814, WO 2021023889 and WO 2022135987. Here, methods such as glycolysis, alcoholysis, acidolysis, aminolysis, hydrolysis or solvolysis can be applied in particular.

[0005] Recycled polyols can preferably be produced from production waste obtained during polyurethane foam production, such as offcuts, sawdust, or material that does not pass quality control, but also from polyurethane foam waste that has reached the end of its useful life, so-called waste foam, such as, for example, foam from used refrigeration equipment, used insulation or insulation boards, used sealing foam, used mattresses, used furniture, used sound-absorbing materials, used packaging foam, or used vehicles.

[0006] However, to date, the use of high proportions of such recycled polyols has often resulted in reduced foam quality, and therefore, in general, the amount of recycled polyol in polyurethane foam materials has been significantly limited.

[0007] In the production of polyurethane foams, especially corresponding rigid 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.

[0008] Against this background, the object of the present invention was to make it possible to provide polyurethane foam materials which contain recycled polyols and which have particularly advantageous use properties, such as low thermal conductivity and / or good surface quality.

[0009] Surprisingly, it has been found within the scope of the present invention that this is possible through the inventive use of specific polyether siloxane foam stabilizers as claimed in claim 1.

[0010] 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 comprising at least one recycled polyol; (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 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 0 to 0.5; b=0 to 2, particularly preferably 1.5 to 2; 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, in particular 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 0 to 50; f=0 to 100, preferably 0 to 80, particularly 0 to 50; g=0 to 100, preferably 0 to 80, particularly 0 to 50; h=0 to 100, preferably 0 to 40, particularly preferably 0; e+f+g+h>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.

[0011] 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.

[0012] The subject matter of the present invention has various advantages. It thus makes it possible to provide PU foams that meet known requirements while offering significant advantages in terms of sustainability. The PU foams are advantageously dimensionally stable, hydrolytically stable, have very good insulating properties, and have a high surface quality. This is advantageously possible without compromising other material properties. Furthermore, with a view to providing PU rigid foams, a particularly fine-celled, uniform, and defect-free foam structure is possible.

[0013] The composition according to the present invention contains at least one polyethersiloxane of formula (1), and this polyethersiloxane contains polyether R 1 is characterized in that at least one of the above satisfies the above-mentioned category 1, where e=8 to 16 and f=g=h=0, which corresponds to a particularly preferred variant of category 1, and corresponds to a particularly preferred embodiment of the present invention.

[0014] A further particularly preferred embodiment of the present invention is when the composition according to the invention contains 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 the above-mentioned category 1 and at least one of which must satisfy the above-mentioned 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.

[0015] A further particularly preferred embodiment of the present invention is characterized in that 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 the above-mentioned category 1, and at least one of which contains at least one polyether of general formula (2) satisfying the above-mentioned 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.

[0016] A further particularly preferred embodiment of the present invention is characterized in that the composition according to the invention is characterized in that at least one recycled polyol is used in a total amount of at least 30 parts by weight, preferably more than 50 parts by weight, particularly preferably more than 70 parts by weight, based on 100 parts by weight of the total polyol component.

[0017] In a further particularly preferred embodiment of the present invention, the composition according to the invention is characterized in that at least one recycled polyol used is obtained by depolymerization of polyurethane, preferably by hydrolysis, solvolysis, aminolysis, acidolysis, alcoholysis or glycolysis, preferably by depolymerization of polyurethane by glycolysis, hydrolysis or aminolysis, particularly preferably by glycolysis, and it is also possible to use different recycled polyols from different depolymerization methods.

[0018] A further particularly preferred embodiment of the present invention is likewise characterized in that the composition according to the invention is characterized in that the at least one recycled polyol used is obtainable by depolymerization of a polyurethane foam material, preferably a rigid polyurethane foam material, particularly preferably a rigid polyurethane foam material containing a polyether polyol and / or a polyester polyol, by the method recited in claim 6, particularly preferably by glycolysis.

[0019] The at least one recycled polyol is preferably selected from the group consisting of recycled polyether polyols and recycled polyester polyols. Polyether polyols and polyester polyols are well known to those skilled in the art, and their known reaction with polyisocyanates allows for the production of polyurethanes, which has proven to be very successful.

[0020] A further particularly preferred embodiment of the present invention is when the composition according to the invention is characterized in that the recycled polyol used is obtained from PU waste foam material.

[0021] PU waste foam material is especially (i) PU foam materials obtained from production waste materials obtained during polyurethane foam production, such as offcuts, sawdust or materials that do not pass quality control; and / or (ii) PU foams obtained from PU foams that have reached the end of their useful life, such as foams from used refrigeration equipment, used insulation or insulation boards, used sealing foams, used mattresses, used furniture, used sound-absorbing materials, used packaging foams, or foams from used vehicles. is.

[0022] (i) one or more hydrocarbons having 3, 4, or 5 carbon atoms, preferably cyclopentane, isopentane, and / or n-pentane; and / or (ii) one or more hydrofluoroolefins and / or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E), and / or 1336mzz; and water, which is essential. as blowing agent likewise corresponds to a further particularly preferred embodiment of the present invention.

[0023] Preferred PU foam formulations, in particular PU rigid foam formulations, within the meaning of the present invention have the compositions listed in Table 1.

[0024] [Table 1]

[0025] 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 according to the invention as described above, in particular as defined in any one of claims 1 to 9.

[0026] 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.

[0027] 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.

[0028] A 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.

[0029] 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.

[0030] 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.

[0031] A preferred composition according to the present invention comprises the following components: A) a polyol component containing at least one recycled polyol 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) Optionally further additives, preferably fillers, liquid flame retardants, etc. Contains:

[0032] 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).

[0033] 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 can be 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.

[0034] 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.

[0035] 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).

[0036] 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.

[0037] 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).

[0038] Additionally, polyether polycarbonate polyols, natural oil-based polyols (natural oil-based polyols NOP 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, and / or prepolymer-based polyols can be used.

[0039] According to the invention, recycled polyols as already described above are at least partly used, i.e. the polyol component comprises at least one recycled polyol.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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, 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

[0048] 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.

[0049] 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.

[0050] 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.

[0051] As optional further additives (F) 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, solid fillers, antistatic additives, thickeners, colorants, pigments, color pastes, fragrances and / or emulsifiers.

[0052] As an optional flame retardant, the composition according to the present invention may contain one or more known flame retardants suitable for the production of PU foams, such as halogen-containing or halogen-free organophosphorus-containing compounds, such as triethyl phosphate (TEP), tris(1-chloro-2-propyl)phosphate (TCPP), tris(2-chloroethyl)phosphate (TCEP), dimethylmethane phosphonate (DMMP), dimethylpropane phosphonate (DMPP), ammonium polyphosphate or red phosphorus, nitrogen-containing compounds, such as melamine, melamine cyanurate or melamine polyphosphate, or halogenated compounds. Mixtures of different flame retardants may also be used.

[0053] 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.

[0054] 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]

[0055] 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.

[0056] 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.

[0057] PES14 and PES15 were prepared by mixing the respective foam stabilizers in a 1:1 weight ratio.

[0058] 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.

[0059] [Table 2]

[0060] Recycled Polyol 1 was produced by glycolysis according to the 2012 H&S Anlagentechnik specifications: https: / / www.dbu.de / OPAC / ab / DBU-Abschlussbericht-AZ-29395.pdf. To this end, a Parr Instrumental Company reactor with a glass inner vessel and a mechanical stirrer was filled with 294.0 g of compressed PU foam pieces (approximately 1 cm x 1 cm). The polyurethane foam used for glycolysis was produced as follows according to formulation A in Table 3, using TEGOSTAB® B 8462 from Evonik Operations GmbH as the foam stabilizer. Then, 152.3 g of polyol Daltolac® R 471, 75.1 g of phthalic acid, and 11.6 g of aqueous hydrogen peroxide solution (30 wt. % in water) were added to the foam pieces. The reaction mixture was heated to 250°C and maintained within the temperature range of 237°C to 256°C for 5 hours. After the reaction time, the heat was turned off, and once a reaction temperature of 160°C was reached, a second portion of 144.6 g of Daltolac® 471 was added under nitrogen counterflow. The liquid reaction mixture was cooled to room temperature, decanted, and then used as Recycled Polyol 1. The recycle process was applied repeatedly to provide sufficient amounts of recycle polyol for foaming experiments.

[0061] Recycled Polyol 2 was prepared in the same way as Recycled Polyol 1. Instead of freshly prepared foam, foam pieces of post-consumer PU insulation board based on polyether polyol were used.

[0062] 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, blowing agent, and optional additional additives were weighed into a beaker and mixed for 30 seconds at 1000 rpm using a plate stirrer (Tellerruehrer) (diameter 6 cm). The amount of blowing agent evaporated during the mixing process was determined by weighing again and replenished. MDI was then added, and the reaction mixture was stirred for 5 seconds at 3000 rpm using the stirrer described above. It was then immediately transferred to an aluminum mold measuring 145 cm x 14 cm x 3.5 cm, inclined at a 10° angle (along the 145 cm long side) and lined with polyethylene foil, thermostated at 45°C, and measuring 145 cm x 14 cm x 3.5 cm. Here, the foaming formulation was injected from the deeper side, so that the expanding foam filled the mold in the injection area and rose toward the higher side.

[0063] To determine the flow behavior, the amount of foam formulation used was calculated to be approximately 10% less than the amount required for minimum mold filling (approximately 260 g). After 10 minutes, the foam was demolded and the average length of the sample pieces was determined. The shortened length was then determined as the quotient of the product of the average length of the sample pieces, the measured air pressure, and the average weight of all examined sample pieces, and the product of the standard air pressure (1013.25 hPa) and the weight of the sample pieces. The flow differences reported in Tables 4-8 are reported as the percentage difference in shortened length of the sample pieces compared to reference sample pieces produced with PES1 as the foam stabilizer and the respective formulation.

[0064] To determine all further properties, for the second sample piece, the amount of foam formulation used was calculated so that it was approximately 10% more than the amount required for minimum mold filling. After 10 minutes, the foam was demolded. One day after foaming, the foam's properties were analyzed. Surface quality 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 disk at an average temperature of 10 °C with a Hesto Lambda Control type device, model HLC X206, in accordance with the requirements of standard EN 12667:2001.

[0065] These results are summarized in Tables 4-8.

[0066] [Table 3]

[0067] [Table 4]

[0068] [Table 5]

[0069] [Table 6]

[0070] [Table 7]

[0071] [Table 8]

[0072] For formulations C and E, which have a higher recycled polyol content, the foam stabilizer that showed the most promising results in formulations B and D was selected.

[0073] These results show that foam stabilizers other than those according to the present invention result in significantly poorer property profiles, characterized in particular by higher thermal conductivity, poorer flow, and poorer surface, when recycled polyol is used in formulations B through E. In contrast, foam stabilizers according to the present invention significantly improve the property profile, achieving performance comparable to formulations without recycled polyol.

Claims

1. 1. A composition for producing a polyurethane foam material, preferably a polyurethane rigid foam material, comprising: (A) a polyol component comprising at least one recycled polyol; (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; 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 0 to 0.5; b=0 to 2, particularly preferably 1.5 to 2; 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, in particular 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, in particular 0 to 50; f=0 to 100, preferably 0 to 80, in particular 0 to 50; g=0 to 100, preferably 0 to 80, in particular 0 to 50; h=0 to 100, preferably 0 to 40, particularly preferably 0; e+f+g+h>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. At least one polyether siloxane of the formula (1) is contained, and the polyether siloxane is １ The composition according to claim 1, characterized in that at least one of the following satisfies category 1, and corresponds to a particularly preferred variant of category 1 when e = 8 to 16 and f = g = h = 0.

3. 3. The composition according to claim 1, wherein the composition contains 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 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.

4. 4. 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, and 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.

5. 5. The composition according to claim 1, wherein the at least one recycled polyol is used in a total amount of at least 30 parts by weight, preferably more than 50 parts by weight, particularly preferably more than 70 parts by weight, based on 100 parts by weight of the total polyol component.

6. 6. The composition according to claim 1, wherein the recycled polyol used is obtained by depolymerization of polyurethane, preferably by hydrolysis, solvolysis, aminolysis, acidolysis, alcoholysis or glycolysis, preferably by depolymerization of polyurethane by glycolysis, hydrolysis or aminolysis, particularly preferably by glycolysis, and it is also possible to use different recycled polyols from different depolymerization methods.

7. 7. The composition according to claim 1, wherein the recycled polyol used is obtained by depolymerization of a polyurethane foam material, preferably a rigid polyurethane foam material, particularly preferably a rigid polyurethane foam material containing a polyether polyol and / or a polyester polyol, by a method as recited in claim 6, particularly preferably by glycolysis.

8. 8. The composition according to claim 1, wherein the recycled polyol used is obtained from PU waste foam material.

9. The composition comprises: (i) one or more hydrocarbons having 3, 4, or 5 carbon atoms, preferably cyclopentane, isopentane, and / or n-pentane and / or (ii) one or more 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, preferably 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.

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