Production of polyurethane foams

Abstract

Production of polyurethane foams.SOLUTION: A composition for producing polyurethane foams comprising a polyisocyanate component and a polyol component, wherein the composition comprises at least one organic compound V having at least one group R A, in which group R A * represents the bond to the remainder of the organic compound V and R1, independently of one another, are the same or different and are H or a branched or linear alkyl group having from 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to the field of polyurethanes, in particular to the field of polyurethane foams. Preferably, the present invention relates to a composition for producing a polyurethane foam, a method for producing a polyurethane foam, and a polyurethane foam produced by said method and its use. [Background technology]

[0002] Within the scope of the present invention, polyurethane (PU) is understood to mean, in particular, a product obtainable by the reaction of a polyisocyanate with a polyol or a compound having isocyanate-reactive groups. In addition to the polyurethane, further functional groups, such as uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea, and / or uretonimine, may also be formed. Therefore, within the scope of the present invention, PU is understood to mean not only polyurethanes, but also polyisocyanurates, polyureas, and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret, and / or uretonimine groups. Within the scope of the present invention, polyurethane foam (PU foam) is understood to mean, in particular, a foam obtainable as a reaction product based on a polyisocyanate with a polyol or a compound having isocyanate-reactive groups. In addition to the polyurethane from which the name derives, further functional groups may also be formed here, such as allophanate, biuret, urea, carbodiimide, uretdione, isocyanurate and / or uretonimine, with isocyanurate being particularly preferred.

[0003] When producing polyurethane foam, can usually use cell stabilizing additives, which ensures fine-celled, uniform and less defective foam structure, and thus has a substantial beneficial effect on the performance properties of said foam, especially its thermal insulation ability.In this regard, the prior art usually describes polyether-modified siloxane (PES), especially for rigid foam applications.But the prior art also describes the use of silicon (Si)-free surfactants.

[0004] Si-free surfactants may sometimes result in reduced foam quality compared to Si-containing surfactants, especially compared to polyether-modified siloxanes (PES). In particular, when the PU foam is to achieve good insulation performance, i.e., a low lambda value, Si-containing surfactants, especially polyether-modified siloxanes (PES), are often more advantageous than Si-free surfactants.

[0005] However, the use of Si-containing surfactants, especially polyether-modified siloxanes (PES), can also have drawbacks.For example, they can sometimes impair the solubility of blowing agents (for example, pentanes) in the polyol.This can be particularly pronounced when the PES has a high siloxane content, and therefore is very hydrophobic.In addition, the Si-containing surfactants are usually not based on renewable raw materials, which is therefore disadvantageous for sustainability reasons.

[0006] EP 2511328 A2 describes the use of carbamates as surfactants for foam stabilization.

[0007] DE 102011007479 A1 describes mixtures of acid amides and PES for use as foam stabilizers in rigid PU foams.

[0008] In EP 1985642 A1, amidoamines and imidazoles based on carboxylic acids and polyethyleneamines or polypropyleneamines, such as diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used as additives for producing PU foams.

[0009] US Pat. No. 3,746,663 describes the use of N-vinylpyrrolidone-based structures for use as surfactants in the production of PU foams.

[0010] DE 3724716 C1 describes the use of novolac-based ethoxylates as stabilizers in the production of PU foams.

[0011] WO 95 / 16721 A1 describes the production of PU foams using polyalkylene oxides, where the polyalkylene oxides are preferably formed by using 10 to 90% butylene oxide.

[0012] EP 1985642 A1 describes a composition for producing PU foams using amidoamides and / or imidazoles based on C1 to C36 carboxylic acids.

[0013] US Pat. No. 5,236,961 describes the production of polyurethane foams using alkylphenol ethoxylates as foam stabilizers.

[0014] DE 2244350 A1 describes the use of copolymers, preferably prepared from N-vinylpyrrolidone and maleic esters, for the production of polyurethane foams.

[0015] The use of Si-free surfactants in PU foams is therefore known from the prior art.

[0016] However, there is also a demand for further Si-free surfactants, particularly for example Si-free surfactants based on renewable raw materials, where these raw materials also preferably do not have applications in the food sector, so that there is no competitive situation here.

[0017] A large proportion of these silicon-free surfactants are based on fatty acids of animal or vegetable origin, such as lard, beef tallow, goose fat, duck fat, chicken fat, horse fat, whale oil, fish oil, palm oil, olive oil, avocado oil, seed oil, coconut oil, palm kernel oil, cocoa butter, cottonseed oil, pumpkin seed oil, corn germ oil, sunflower oil, wheat germ oil, grape seed oil, sesame oil, linseed oil, soybean oil. Chemically, these are linear, partially unsaturated carboxylic acids of different chain lengths, which can be derivatized in a wide variety of ways.

[0018] In addition to the use of Si-free surfactants in PU foams, the use of hydrocarbons in PU foams is also well known. For example, hydrocarbons are often used as blowing agents in PU foams. In this case, compounds with up to 7 carbon atoms, especially 3-7, can be preferably used, because these compounds have boiling points within a suitable temperature range, so they evaporate during the foaming process and thus contribute to the volume increase, i.e., foam formation. In the finished foam, these blowing agents are still present as cell gases. The use of these hydrocarbons is described in many documents.

[0019] US 2011 / 0218259 A1 describes the use of cyclopentane in rigid PU foam systems with improved flow, such as those required in the production of refrigerated freezer cabinets or panels.

[0020] DE 3933335 A1 describes the use of cyclopentane and mixtures thereof with cyclohexane and various hydrocarbons having up to four carbon atoms, as well as ethers and fluoroalkanes with boiling points below 35° C. For this reason, DE 3933335 A1 uses hydrocarbons that evaporate completely during PU foaming and are therefore utilized as blowing agents.

[0021] WO 2016 / 202912 A1 describes various hydrocarbons as well as ethers, ketones, esters, acetals and fluoroalkanes as blowing agents, where the boiling point thereof is preferably below 50°C.

[0022] CN 101880452 A describes the use of alkanes having 14 to 21 carbon atoms as phase change materials, which are used as fillers in an amount of 10 to 30 parts per 100 parts of polyol, without mentioning the effect on the thermal conductivity quality of the resulting PU foam.

[0023] JP09165427A describes the use of alkanes having 9 to 12 carbon atoms, which are used to improve the storage stability of polyol mixtures, especially when pentane is used as a blowing agent. JP09165427A uses 1 to 10 parts of the alkane per 100 parts of polyol. However, the effect on the thermal conductivity quality of the resulting PU foam is not described.

[0024] US 20070066697 A1 describes flexible PU foams in which better indentation force deflection is obtained by using hydrocarbons having 10 to 70 carbon atoms, said hydrocarbons preferably being added in amounts of 0.01 to 100 pphp (pphp = parts per hundred parts of polyol).

[0025] JP 04-18431 A describes the use of non-reactive components, such as paraffins or other hydrocarbons, in amounts of 0.1 to 10 pphp in rigid PU foams, which is said to improve the aging of the foam in terms of lambda value. The examples in JP 04-18431 A show that the initial lambda value becomes worse when paraffins are added.

[0026] EP 3677610 A1 describes the use of specific hydrocarbons as surfactants in combination with polyether-modified siloxanes to obtain rigid PU foams with improved properties. This combination is disclosed as essential. EP 3677610 A1 does not describe the possibility of achieving improved properties of rigid PU foams using organic compounds V, as defined more precisely below.

[0027] Similarly, the use of polyalkylsiloxanes is known from the prior art, as described, for example, in WO 2020 / 144003 A1. [Prior art documents] [Patent documents]

[0028] [Patent Document 1] European Patent Application Publication No. 2511328 [Patent Document 2] German Patent Application Publication No. 102011007479 [Patent Document 3] European Patent Application Publication No. 1985642 [Patent Document 4] U.S. Patent No. 3,746,663 [Patent Document 5] West German Patent Invention No. 3724716 [Patent Document 6] International Publication No. 95 / 16721 [Patent Document 7] European Patent Application Publication No. 1985642 [Patent Document 8] U.S. Patent No. 5,236,961 [Patent Document 9] West German Patent Application Publication No. 2244350 [Patent Document 10] US Patent Application Publication No. 2011 / 0218259 [Patent Document 11] West German Patent Application Publication No. 3933335 [Patent Document 12] International Publication No. 2016 / 202912 [Patent Document 13] Chinese Patent Application Publication No. 101880452 [Patent Document 14] Japanese Patent Application Publication No. 09-165427 [Patent Document 15] US Patent Application Publication No. 2007 / 0066697 [Patent Document 16] Japanese Patent Application Publication No. 04-18431 [Patent Document 17] European Patent Application Publication No. 3677610 [Patent Document 18] International Publication No. 2020 / 144003 [Patent Document 19] U.S. Patent No. 4,758,379 [Patent Document 20] International Publication No. 2019 / 006431 [Patent Document 21] Chinese Patent Application Publication No. 110387027 [Patent Document 22] International Publication No. 2019 / 177903 [Patent Document 23] Chinese Patent Application Publication No. 103709357 [Patent Document 24] European Patent Application Publication No. 2677030 [Patent Document 25] Chinese Patent Application Publication No. 101045785 [Patent Document 26] Chinese Patent Application Publication No. 101029124 [Patent Document 27] U.S. Patent No. 4,647,707 [Patent Document 28] German Patent Application Publication No. 102008007081 [Patent Document 29] German Patent Application Publication No. 102013212481 [Patent Document 30] European Patent No. 1515934 [Patent Document 31] European Patent Application Publication No. 2947064 [Patent Document 32] International Publication No. 2021 / 228824 [Patent Document 33] International Publication No. 2005 / 033167 [Patent Document 34] US Patent Application Publication No. 2006 / 0293400 [Patent Document 35] International Publication No. 2006 / 094227 [Patent Document 36] International Publication No. 2004 / 096882 [Patent Document 37] US Patent Application Publication No. 2002 / 0103091 [Patent Document 38] International Publication No. 2006 / 116456 [Patent Document 39] European Patent Application Publication No. 1678232 [Patent Document 40] European Patent Application Publication No. 1712578 [Patent Document 41] European Patent Application Publication No. 1161474 [Patent Document 42] International Publication No. 00 / 58383 [Patent Document 43] US Patent Application Publication No. 2007 / 0072951 [Patent Document 44] International Publication No. 2005 / 085310 [Patent Document 45] Chinese Patent Application Publication No. 103665385 [Patent Document 46] Chinese Patent Application Publication No. 103657518 [Patent Document 47] Chinese Patent Application Publication No. 103055759 [Patent Document 48] Chinese Patent Application Publication No. 103044687 [Patent Document 49] US Patent Application Publication No. 2008 / 0125503 [Patent Document 50] US Patent Application Publication No. 2015 / 0057384 [Patent Document 51] European Patent Application Publication No. 1520870 [Patent Document 52] European Patent Application Publication No. 1211279 [Patent Document 53] European Patent Application Publication No. 0867464 [Patent Document 54] European Patent Application Publication No. 0867465 [Patent Document 55] European Patent Application Publication No. 0275563 [Patent Document 56] European Patent Application Publication No. 2295485 [Patent Document 57] European Patent Application Publication No. 0734404 [Patent Document 58] European Patent Application Publication No. 3717538 [Patent Document 59] U.S. Patent No. 7,776,934 [Patent Document 60] European Patent No. 1400547 [Patent Document 61] European Patent No. 2780384 [Patent Document 62] International Publication No. 2021 / 144033 [Non-patent literature]

[0029] [Non-Patent Document 1] "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993 Summary of the Invention [Problem to be solved by the invention]

[0030] A particular object of the present invention was to make it possible to provide PU foams with additional Si-free surfactants. [Means for solving the problem]

[0031] Within the scope of the present invention, it has surprisingly been found that the use of at least one organic compound V, as defined more precisely below, makes it possible to solve said problem.

[0032] For example, such organic compounds V, as more precisely defined below, may preferably comprise abietic acid and / or certain derivatives thereof.

[0033] Abietic acid is a resin acid. It can be obtained, for example, from tree resin. Abietic acid derivatives are known in the prior art. The use of abietic acid derivatives has been described in the prior art for the preparation of polyester polyols.

[0034] US Patent No. 4,758,379 (US 4,758,379) describes the preparation of abietic acid esters, preferably using DEG, TEG, EG, PG, or also using pentaerythritol, but does not describe the use of the resulting esters.

[0035] WO 2019 / 006431 A1 describes the production of resin acid esters with low color numbers and their use in road marking and adhesive compositions. In particular, WO 2019 / 006431 A1 describes a method for producing a light-colored rosin and a method for producing a light-colored rosin ester.

[0036] CN 110387027 A describes the production of spray foams based on renewable raw materials, in which inter alia abietic acid ester polyols are also used as polyol components.

[0037] In WO 2019 / 177903 A1, a tackifier is used but no physical blowing agent is used, thereby producing a flexible foam with a longer recovery time. The foam in WO 2019 / 177903 A1 is an open-cell flexible foam.

[0038] CN 103709357 A describes abietic acid polyols with an OH value of 400-460 mg KOH / g. These high OH values ​​are necessary for use as polyols. CN 103709357 A does not describe their use as surfactants.

[0039] Similarly, EP 2677030 A1 describes tall oil / abietic acid-based polyols prepared by amidation with DEA ​​or esterification with TEA, and EP 2677030 A1 also does not describe their use as surfactants.

[0040] CN 101045785 also describes abietic acid-based polyols with an OH value of 250-500 mg KOH / g. Their use as surfactants is not mentioned in CN 101045785.

[0041] CN 101029124 describes abietic acid-based polyols based on dimeric abietic acid or phenolic abietic acid. CN 101029124 does not describe their use as surfactants.

[0042] A specific problem of the present invention is solved by the subject matter of the present invention, which is a composition for producing polyurethane foams, comprising a polyisocyanate component, a polyol component, optionally at least one catalyst for catalyzing the formation of urethane or isocyanurate bonds, and optionally at least one blowing agent, wherein the composition further comprises: [ka] at least one group R selected from the group consisting of A and at least one organic compound V having the formula where * represents a bond to the remainder of the organic compound V; and R 1are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N.

[0043] The subject of the present invention is to provide PU foam, especially rigid PU foam.Surprisingly, it has been found that the range or variation of Si-free surfactants that can be used in the production of PU foam can be expanded again by using at least one organic compound V.Therefore, the present invention can advantageously contribute to the production of PU foam-based products, such as insulating panels or refrigerated / freezer cabinets.

[0044] A further advantage of the present invention is that, for example, the use of said at least one organic compound V is also possible, preferably in combination with other surfactants, such as polyether-modified siloxanes and / or other Si-free surfactants.

[0045] Advantageously, the present invention may make it possible to obtain PU foams having at least sufficient or advantageous qualities, for example in terms of pore structure and / or for example in terms of insulating performance.

[0046] said at least one organic compound V being [ka] is selected from the group consisting of In the above formula, n=1-5, l=1~5, p=1~5, R are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N, R A are independently the same or different, [ka] is selected from the group consisting of where * represents a bond to the remainder of the organic compound V; and R 1 are preferably, independently of one another, the same or different, and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as, preferably, O and / or N.

[0047] As a possible example for further explanation, diesters of monoethylene glycol are illustratively shown here as possible organic compounds V, [ka] In the above formula, R A is as defined above.

[0048] Among them, for example, [ka] In such an exemplary case, the complete structural formula is: [ka] is obtained.

[0049] From this, it can be seen how the structure R A is incorporated into said organic compound V.

[0050] said at least one organic compound V being [ka] It is particularly preferred if the group is selected from the group consisting of In the above formula, m=1~15, r=1~15, k=1~6, R A are independently the same or different, [ka] is selected from the group consisting of where * represents a bond to the remainder of the organic compound V; and R 1 are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N, Very particular preference is given here to the diethylene glycol esters, triethylene glycol esters, polyglycerol esters, abietol, hydrogenated abietol and / or partially hydrogenated abietol.

[0051] The structural formula of abietol is [ka] is.

[0052] The at least one organic compound V preferably has an OH number of less than 150 mg KOH / g, preferably less than 100 mg KOH / g, particularly preferably less than 50 mg KOH / g.

[0053] Therefore, it is preferable that secondary components with higher OH values, which may be generated during the preparation of the organic compound V, are present, if at all, preferably only in correspondingly small proportions. Particularly preferably, such secondary components are not present at all. For example, monoethylene glycol esters [ka] In the production of [ka] can be formed, the OH number of which is calculated according to the above formula to be 162 mg KOH / g. Therefore, in order to achieve the preferred OH number of less than 150 mg KOH / g, it is preferred if secondary components with corresponding OH functions, which may arise during the preparation of the organic compound V, are present in correspondingly small proportions, if at all. Preferably, secondary components of this type are not present at all. Particularly preferred organic compounds V can be prepared, for example, by esterification of glycols, glycerol, polyglycerols and / or pentaerythritol, of the general formula R A It can be based on the esterification of COH with a carboxylic acid, where it is noted that the reaction is preferably carried out in such a way that as few free OH groups as possible remain in the product, so that the product preferably has a correspondingly low OH number.

[0054] Preferred organic compounds V are, for example, those of the general formula R A The following carboxylic acids according to CO2H: [ka] and preferably reaction products of these carboxylic acids, for example in the sense of esterification with glycols, glycerol, polyglycerols and / or pentaerythritol, or for example in the sense of amidation, particularly preferred are the reactions to give esters, amides, imides, imidazolines and / or oxazolines.

[0055] Preferred organic compounds V are, for example, the corresponding ethylene glycol-, diethylene glycol-, triethylene glycol-, glycerin-, pentaerythritol-, trimethylolethane-, trimethylolpropane-, sucrose-, sorbitan- and / or polyglycerin-carboxylic acid esters, where the carboxylic acid esters are of the general formula R A The corresponding esters of the carboxylic acids of CO2H are meant here.

[0056] Different alcohols can be used for the esterification, such as butyl glycol, ethyl glycol and / or other monools, as well as species with multiple OH functionalities, such as polyglycerol, sucrose, sorbitol, propylene glycol, dipropylene glycol and / or polyalkylene glycols.

[0057] Preferably, the at least one organic compound V can be, for example, an alcohol alkoxylate, preferably an abietol alkoxylate, which can be prepared, for example, by reacting an alkylene oxide with abietol. Preferred are the ethoxylates and / or propoxylates of abietol. Suitable alcohol alkoxylates are further described in more detail below.

[0058] Preferably, for example, carboxylic acid amides can also be used as the at least one organic compound V. Such amides can be, for example, amines and preferably compounds of the general formula R A It can be produced based on the above carboxylic acids of CO2H.

[0059] Suitable, for example, for amidation may be amines having at least one primary or secondary amine function, said amines optionally having one or more hydroxy groups. Suitable amines are therefore, for example: ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, hexapropyleneheptamine, as well as higher homologues based on ethylenediamine or propylenediamine, 1,2-propylenediamine, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4-methylenediphenylenediamine, isophoronediamine, trimethylhexylmethylenediamine, neopentanediamine, octamethylenediamine, polyetheramines such as, for example, Polyetheramine D 2000 (BASF), Polyetheramine D 230 (BASF), Polyetheramine T 403 (BASF), Polyetheramine T 5000 (BASF) or the corresponding Jeffamin type from Huntsman, piperazine, aminoethylpiperazine, bis(aminoethyl)piperazine, 1,3-diaminopropane, 3-(cyclohexylamino)propylamine, 3-(methylamino)propylamine, dimethylaminopropylamine (DMAPA), N,N-bis-(3-aminopropyl)methylamine, (3-(2-aminoethylamino)propylamine), dipropylenetriamine and / or (N,N′-bis-(3-aminopropyl)-ethylenediamine).

[0060] Suitable hydroxylamines having at least one OH functionality may be, for example: ethanolamine, propanolamine, alkylethanolamine, arylethanolamine, alkylpropanolamine, such as: diethanolamine, monoethanolamine, diisopropanolamine, isopropanolamine, methylisopropanolamine, diglycolamine (2-(2-aminoethoxy)ethanol), dimethylethanolamine, N-(2-hydroxyethyl)aniline, 1-(2-hydroxyethyl)piperazine, 2-(2-aminoethoxy)ethanol, 3-amino-1-propanol, 5-amino-1-pentanol, butylethanolamine, ethylethanolamine, N-methylethanolamine, aminopropylmonomethylethanolamine, 2-amino-2-methylpropanol, trishydroxymethylaminomethane (THMAM or TRIS), N-(2-aminoethyl)ethanolamine (AEEA). It is also possible to use the corresponding alkoxylates, in particular ethoxylates and / or propoxylates of amines, such as alkylamines containing hydroxyethyl or hydroxypropyl units or, for example, N-hydroxyethylcyclohexyldiamine, N-hydroxyethylisophoronediamine, N-hydroxyethylpiperazine and / or bis(hydroxyethyl)toluenediamine.

[0061] Preferably, for example, alcohol alkoxylates can also be used as the at least one organic compound V. Methods for producing alcohol alkoxylates are known to those skilled in the art. The alcohol alkoxylates can be preferably obtained by reacting abietol with alkylene oxides. For example, abietol alkoxylates can be preferably prepared by reacting abietol with alkylene oxides. The alkylene oxides can then be added to the alcohol with ring-opening. The alkylene oxides are preferably selected from the group consisting of ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and styrene oxide (SO). The alkylene oxides can be added individually in pure form, alternately with each other in any dosage order, or simultaneously mixed. This determines the sequence of oxyalkylene or alkyleneoxy units as repeating units in the resulting polyether chain. This method allows the formation of polyether chains, which are characterized by their tailorable and reproducible production in terms of structure and molar mass. The sequence of the repeating units can be varied within a wide range depending on the order of addition of the alkylene oxides. It is particularly preferred to react alkylene oxide units selected from the group consisting of ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) and styrene oxide (SO) to prepare the alcohol alkoxylates, with an average of preferably 3 to 150 alkylene oxide units per hydroxy group of the alcohol.

[0062] Preferably, the at least one organic compound V is selected from the group consisting of esters, amides, imides, imidazolines, oxazolines and polyether compounds. Preferred polyether compounds have at least 2, preferably 2 to 100, in particular 3 to 50, ether groups.

[0063] Preferably usable organic compounds V may be, for example, derivatives of abietic acid, For example, esters of abietic acid: [ka] For example, the amide of abietic acid: [ka] For example, Abietol: [ka] In the above formula, R are independently the same or different and are H or branched or linear alkyl groups having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N.

[0064] The composition according to the invention can preferably comprise further components, so that it is preferred that the composition according to the invention further comprises at least one hydrocarbon KWS (Kohlwasserstoff), preferably having 10 to 24 carbon atoms and having a boiling point at a pressure of 1.01325 bar (standard pressure) of above 100°C, preferably above 150°C, particularly preferably decene, decane, isodecene, undecene, undecane, isoundecane, isoundecene, dodecene, dodecane, isododecane, isododecene, tridecane, tridecene, isotridecane, isotridecene, tetradecane, tetradecene, isotetradecane, isotetradecene, pentadecane, pentadecene, isopentene, The hydrocarbons KWS contained in the total amount of the organic compounds V are preferably used in a weight ratio of 1:5 to 1:200.

[0065] It has been found that the additional use of at least one hydrocarbon KWS can lead to further improved properties of the PU foam in the sense of the present invention.

[0066] It is particularly preferred that the boiling point of the hydrocarbon KWS usable according to the invention is below 400°C, preferably below 350°C, at standard pressure (i.e., at a pressure of 1.01325 bar). Therefore, the hydrocarbon KWS that can be preferably used preferably have a boiling point above 100°C and below 400°C, in particular above 100°C and below 350°C, at standard pressure (1.01325 bar). The hydrocarbon KWS consists of carbon atoms, hydrogen atoms, and optionally up to three heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur atoms. Preferably, the hydrocarbon KWS, if they contain heteroatoms, only contain oxygen atoms as heteroatoms. It is preferred that the hydrocarbon KWS have one or no heteroatoms, which, if the hydrocarbon KWS has one, is an oxygen atom. However, it is even more preferred that the hydrocarbon KWS have no heteroatoms. Therefore, it is particularly preferred that the hydrocarbon KWS consist exclusively of carbon and hydrogen atoms. Preferably, saturated and unsaturated hydrocarbons KWS can be used. Preferably, aliphatic or aromatic hydrocarbons KWS can be used. The hydrocarbons KWS can be branched or unbranched. They can be cyclic or acyclic hydrocarbons KWS.

[0067] Particularly preferred hydrocarbons KWS are olefins, paraffins, isoparaffins and / or alkylbenzenes. Such materials are available, for example, from Sasol under the trade name HF (登録商標) 1000, LINPAR (登録商標) , SASOLAB (登録商標) , PARAFOL (登録商標) It is available at.

[0068] The hydrocarbons KWS which can be preferably used according to the invention are preferably hydrocarbons (branched or unbranched, saturated or unsaturated, cyclic or acyclic, aliphatic) having 10 to 24 carbon atoms, which can be prepared, for example, by oligomerization of olefins, as described, for example, in US Pat. No. 4,647,707, DE 10 2008 007 081 A1 or DE 10 2013 212 481 A1.

[0069] Similarly, the corresponding streams of material obtained during the production of oxo alcohols can also be used, as described, for example, in US Patent No. 4,647,707, EP 1,515,934 B1 or EP 2,947,064 A1. In this case, intermediate products or by-products are obtained, which are called oxo oils. Preference is given here to paraffin- and olefin-containing distillation fractions, such as the so-called light oxo fractions, as described, for example, in US Patent No. 4,647,707.

[0070] Very particularly preferred hydrocarbons KWS which can be used according to the invention are decene, decane, isodecane, isodecene, undecene, undecane, isoundecane, isoundecene, dodecene, dodecane, isododecane, isododecene, tridecane, tridecene, isotridecane, isotridecene, tetradecane, tetradecene, isotetradecane, isotetradecene, pentadecane, pentadecene, isopentadecane, isopentadecene, hexadecane, hexadecane, iso isohexadecane, isohexadecene, heptadecane, heptadecene, isoheptadecane, isoheptadecene, octadecane, octadecene, isooctadecane, isooctadecene, nonadecane, nonadecene, isonadecane, isononadecene, eicosane, eicosane, isoeicosane, isoeicosene, tributene, tributane, tetrabutene, tetrabutane, alkylbenzenes having at least 10 carbon atoms, and oxo oils.

[0071] Preferably usable hydrocarbons KWS are, for example, available as C4 oligomers, such as tributenes, tetrabutanes and / or tetrabutenes. Preferably usable hydrocarbons KWS are, for example, commercially available products referred to as intermediates and by-products: Oxo Oil HS 9, Oxo Oil LS 9 and / or Oxo Oil LS 13 from Evonik Performance Intermediates.

[0072] Similarly, for example, hydrocarbons KWS produced from renewable raw materials can be used, such as isododecane from Global Bioenergies (Evry-Courcouronnes, France), which can be produced, for example, by the method described in WO 2021 / 228824.

[0073] Preferably, for example, hydrocarbons KWS having no aromatic units and consisting of 9 to 21 carbon atoms can be used.

[0074] The composition according to the present invention preferably further comprises at least one polyalkylsiloxane PAS that is not polyether-modified and preferably contains less than 20, more preferably less than 15, and particularly preferably less than 11 silicon atoms, preferably in a mass ratio of 1:4 to 1:200 based on the total amount of organic compound V. In this case, it is preferred that the at least one polyalkylsiloxane PAS has at least two silicon atoms.

[0075] Within the scope of the present invention, whenever reference is made to "polyalkylsiloxane PAS", it is meant to refer to such polyalkylsiloxanes or polyalkylsiloxane PAS which do not have polyether modification.

[0076] In this regard, it is preferred that at least one polyalkylsiloxane PAS conforms to formula 1: M a D b T c Q d (Formula 1) In the above formula, M=R 11 R 12 R 13 SiO 1 / 2 D=R 14 R 15 SiO 2 / 2 T=R 16 SiO 3 / 2 Q=SiO 4 / 2 where: R 11 , R 12 , R 13 , R 14 , R 15 , R 16are, independently of one another, the same or different and are hydrocarbon radicals having 1 to 12, preferably 1 to 8, carbon atoms, which may be substituted by heteroatoms or are otherwise H, in particular phenyl-, CH3-, CH3CH2-, CH2CH-ClCH2CH2CH2- or H-, and a=2~6 b=0~8 c=0~4 d=0~2 provided that a+b+c+d<20, preferably <15, particularly preferably <11; where: R 16 But R 11 , R 12 , R 13 , R 14 and R 15 Unlike, and / or R 11 , R 12 and R 13 is different This is particularly preferred.

[0077] Furthermore, the total amount of the organic compound V used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass, based on 100 parts by mass of the total polyol components.

[0078] Preferably, a mixture of at least one hydrocarbon KWS, at least one polyalkylsiloxane PAS and at least one organic compound V can be used, particularly preferably together with a dispersing medium. Suitable dispersing mediums include, for example, glycols, alkoxylates and / or oils of synthetic and / or natural origin.

[0079] It is preferred if the total mass proportion of organic compound V, optional hydrocarbon KWS and optional polyalkylsiloxane PAS in the finished polyurethane foam is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on the finished polyurethane foam.

[0080] It is preferred if the at least one organic compound V is used together with at least one polyalkylsiloxane PAS and / or at least one hydrocarbon KWS, in which case the hydrocarbon KWS and / or polyalkylsiloxane PAS is preferably used in the composition according to the invention in a weight ratio of 1:4 to 1:200 in combination with the organic compound V. This weight ratio is then the ratio of the total weight of all hydrocarbon KWS and / or polyalkylsiloxane PAS to the total weight of all organic compounds V in the composition according to the invention.

[0081] Preferred quantitative ratios, based solely on the ratio of organic compound V, optional hydrocarbon KWS and / or optional polyalkylsiloxane PAS to one another, may be, for example: Total organic compound V used: 80 to 99.5 parts by weight, Total hydrocarbons KWS optionally used: 0.5 to 20 parts by weight, Total polyalkylsiloxane PAS optionally used: 0.5 to 20 parts by weight, Here, for the purposes of this exemplary discussion, the parts by weight of the total organic compounds V used, the total hydrocarbons KWS used and the total polyalkylsiloxanes PAS used add up to 100 parts by weight.

[0082] As already mentioned, the composition according to the invention can contain at least one hydrocarbon KWS. If a hydrocarbon KWS is present, the total amount of the hydrocarbon KWS used, the organic compounds V used and the optional polyalkylsiloxane PAS used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, and particularly preferably 1 to 3 parts by weight, based on 100 parts by weight of the total polyol components.

[0083] The composition according to the present invention may further preferably contain at least one polyether-modified siloxane (PES). When the polyether-modified siloxane (PES) is contained, the at least one polyether-modified siloxane is preferably used in a total amount of 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, particularly preferably 1 to 3 parts by mass, based on 100 parts by mass of the total polyol components.

[0084] As already explained, the composition according to the invention for producing polyurethane foams comprises a polyisocyanate component, a polyol component, optionally at least one catalyst that catalyzes the formation of urethane or isocyanurate bonds, and optionally at least one blowing agent, wherein the composition further comprises at least one organic compound V as defined above.

[0085] It is preferred if the composition according to the invention is a composition for producing a rigid PU foam, preferably a closed-cell rigid PU foam.

[0086] The ratio of the total polyisocyanate components used to the total polyol components used, expressed as an index of the blending, i.e., the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups multiplied by 100, is preferably within the range of 150 to 550, particularly preferably 200 to 500.

[0087] The entire polyol component used contains at least one polyester polyol, and preferably the polyester polyol has a melting point of less than 30°C. The total amount of polyester polyol used is preferably 20 to 100 parts by mass, preferably 40 to 99 parts by mass, and particularly preferably 70 to 98 parts by mass, based on 100 parts by mass of the entire polyol component.

[0088] It is preferred if the composition according to the invention comprises at least one blowing agent, preferably at least one hydrocarbon having 4 or 5 carbon atoms, in particular 5 carbon atoms, as blowing agent, wherein the composition preferably does not comprise a halogenated blowing agent.

[0089] Particularly preferred compositions according to the invention comprise the following components: Polyol components, Polyisocyanate components, at least one organic compound V, optionally at least one catalyst, optionally at least one blowing agent, Optionally, further additives, preferably selected from the group consisting of fillers and flame retardants.

[0090] As already mentioned above, particularly preferred compositions according to the invention can preferably further comprise at least one hydrocarbon KWS, at least one polyalkylsiloxane PAS and / or at least one polyether-modified siloxane (PES).

[0091] The total amount of the at least one organic compound V, the at least one hydrocarbon KWS, optionally at least one polyalkylsiloxane PAS, and optionally at least one polyether-modified siloxane (PES) used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass, based on 100 parts by mass of the total polyol components.

[0092] The polyol component comprises at least one polyol and, optionally, at least one organic compound, the organic compound containing at least two isocyanate-reactive groups, preferably groups selected from the group consisting of OH, NH, and NH groups. A polyol is an organic compound containing at least two hydroxyl groups (—OH). When one of the organic compounds of the polyol component contains at least two OH groups, it is included exclusively in the polyol category within the meaning of the present invention. That is, when an organic compound of the polyol component can be considered both as a polyol and as an organic compound containing at least two isocyanate-reactive groups, preferably groups selected from the group consisting of OH, NH, and NH groups, it is included exclusively in the polyol category within the meaning of the present invention. Based on their total weight, the polyol component preferably contains at least 50% by weight of such polyols containing only hydroxyl groups (—OH) as isocyanate-reactive groups. It is preferred that at least 50% of the groups are hydroxyl groups (--OH), based on the total number of isocyanate-reactive groups on the polyol component.

[0093] Corresponding compounds that can typically be used in the production of PU are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.1. Generally, compounds having an OH value in the range of 10 to 1200 mg KOH / g are preferably used. Particularly preferred compounds are all polyether polyols and polyester polyols commonly used in the production of polyurethane systems, especially polyurethane foams. Polyether polyols are preferably obtainable by reacting polyhydric alcohols or amines with alkylene oxides. Polyester polyols are preferably based on esters of polycarboxylic acids (which may be either aliphatic, such as adipic acid, or aromatic, such as phthalic acid or terephthalic acid) with polyhydric alcohols (preferably glycols).

[0094] Furthermore, for example, polyether polycarbonate polyols, natural oil based polyols (NOPs), such as those described in WO 2005 / 033167, US 2006 / 0293400, WO 2006 / 094227, WO 2004 / 096882, US 2002 / 0103091, WO 2006 / 116456, 2006 / 116456), as described in EP 1678232), filled polyols, prepolymer-based polyols and / or recycled polyols can be used.

[0095] Recycled polyols are polyols obtained from the chemical recycling of polyurethanes, for example by solvolysis, such as glycolysis, hydrolysis, acidolysis or aminolysis.

[0096] As polyols, compounds can usually be used which preferably have an OH number in the range of 10 to 1200 mg KOH / g, the OH number being preferably determined in accordance with standard DIN EN ISO 4629-1:2016-12 (without catalyst) or standard DIN EN ISO 4629-2:2016-12 (with catalyst).

[0097] The polyol or the polyol component preferably has a number average molecular weight of 500 to 15,000 g / mol. The number average molecular weight can be determined, for example, by gel permeation chromatography (GPC), preferably according to standard DIN EN ISO 13885-1:2021-11 (THF as eluent), standard DIN EN ISO 13885-2:2021-11 (acrylamide as eluent) or standard ISO 13885-3:2020-07 (water as eluent), particularly preferably according to standard DIN EN ISO 13885-1:2021-11 (THF as eluent).

[0098] The polyisocyanate component comprises at least one polyisocyanate having two or more isocyanate groups. Suitable polyisocyanates in the sense 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. Examples that may be mentioned here include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, such as dodecane-1,12-diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methyl-pentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene diisocyanate (PDI) and preferably hexamethylene-1,6-diisocyanate (HMDI), cycloaliphatic diisocyanates, such as cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate and the corresponding isomer mixtures, 4,4′-methylenedicyclohexyl diisocyanate (HMDI), isocyanates such as cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate, and the corresponding isomer mixtures. Sophorone diisocyanate (IPDI), 2,4-methylcyclohexyl diisocyanate and 2,6-methylcyclohexyl diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates and polyisocyanates, such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI) and the corresponding isomer mixtures, naphthylene diisocyanate, diethyltoluene diisocyanate, 4,4'-diphenylmethane diisocyanate or 2,2'-diphenylmethane diisocyanate 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 thereof. Likewise, the corresponding "oligomers" of the diisocyanates can be used, such as IPDI trimers based on isocyanurates, biurets or uretdiones. In addition, prepolymers based on the above isocyanates can be used.Particularly suitable are mixtures of MDI with more highly condensed analogues having an average functionality of 2 to 4, known as "polymeric MDI" (also called "crude MDI" or "raw MDI"), as well as 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 described, for example, in European Patent Applications 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.

[0099] The preferred ratio of polyisocyanate component to polyol component, expressed as an index of the blending (isocyanate index), i.e., the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups), multiplied by 100, is in the range of 10 to 1000, preferably 40 to 400. An index of 100 represents a 1:1 molar ratio of reactive groups.

[0100] In a particularly preferred embodiment of the present invention, the index of the formulation is preferably in the range of 150 to 550, particularly preferably 200 to 500. That is, in a particularly preferred embodiment, there is preferably a clear excess of isocyanate groups relative to isocyanate-reactive groups, which leads to a trimerization reaction of the isocyanates, thus forming isocyanurates. These foam types are sometimes called polyisocyanurate (PIR) foams and are characterized by improved combustion behavior, i.e., poorer combustion. PIR foams are included in the broader category of PU foams within the meaning of the present invention and are particularly preferred. Particularly preferably, the polyol component comprises one or more polyester polyols.

[0101] The composition according to the invention can optionally contain at least one catalyst that catalyzes the formation of urethane or isocyanurate bonds. Suitable catalysts that can be used in the production of polyurethanes, especially PU foams, are known to those skilled in the art. These catalysts can catalyze the formation of urethane or isocyanurate bonds, or can catalyze the reaction of isocyanate-polyol and / or isocyanate-water and / or isocyanate trimerization. In the sense of the present invention, any compound capable of catalyzing the reaction of isocyanate groups with OH, NH, or other isocyanate-reactive groups and / or with each other can be used. In this case, catalysts known from the conventional prior art, such as amines (cyclic, acyclic; monoamines, diamines, oligomers containing one or more amino groups), ammonium compounds, organic metal compounds and / or metal salts, preferably those of iron, bismuth, potassium, and / or zinc, can be used. In particular, mixtures of several such compounds can be used as catalysts. The suitable amount used depends on the type of catalyst and can be, for example, in the range of 0.05 to 5 pphp (= parts by weight based on 100 parts by weight of polyol) in the case of amine catalysts or, for example, in the range of 0.1 to 10 pphp in the case of potassium salts.

[0102] Foam stabilizers and their use in the production of PU foams are known to those skilled in the art, as described above.The compositions according to the invention contain at least one organic compound V as foam stabilizer.

[0103] In addition to the at least one organic compound V, preferably one or more further foam stabilizers are used, for example polyether siloxane foam stabilizers, such as those described in Chinese Patent Application Publication No. 103665385 (CN 103665385), Chinese Patent Application Publication No. 103657518 (CN 103657518), Chinese Patent Application Publication No. 103055759 (CN 103055759), Chinese Patent Application Publication No. 103044687 (CN 103044687), US Patent Application Publication No. 2008 / 0125503 (US 2008 / 0125503), US Patent Application Publication No. 2015 / 0057384 (US 2015 / 0057384), European Patent Application Publication No. 1520870 (EP 1520870 A1), EP 1211279, EP 0867464, EP 0867465 or EP 0275563, and / or other Si-free surfactants, for example, can also be used.The use of lecithin is described, for example, in EP 2295485 A1, and vinylpyrrolidone-based structures are described, for example, in US Pat. No. 3,746,663. Further Si-free form stabilizers are described, for example, in EP 2511328, DE 102011007479, DE 3724716, EP 0734404, EP 1985642, DE 2244350 and U.S. Pat. No. 5,236,961.

[0104] Preferably, hydrocarbons KWS, polyalkylsiloxanes PAS, Si-free surfactants and / or optionally polyether-modified siloxanes (PES) can also be used.

[0105] Blowing agents and their use in the production of PU foams are known to those skilled in the art, where their use is optional within the meaning of the present invention, preferably at least one blowing agent can be used. The preferred use of one blowing agent or a combination of blowing agents preferably depends on the type of foaming method, the type of system, and the intended use of the resulting PU foam. Chemical blowing agents and / or physical blowing agents, as well as combinations of both, can be used. Depending on the amount of blowing agent used, foams with high or low density can be produced, for example. Thus, for example, 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 is possible to produce foams having densities of

[0106] As physical blowing agents, optionally, for example, one or more corresponding compounds having a suitable boiling point can be used, such as hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane or n-pentane, hydrofluorocarbons (HFCs), such as HFC 245fa, HFC 134a or HFC 365mfc, hydrochlorofluorocarbons (HCFCs), such as 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 hydrochlorocarbons, such as dichloromethane or 1,2-dichloroethane, as well as mixtures thereof.

[0107] As chemical blowing agents, it is possible to use, for example, one or more compounds which react with NCO groups to release a gas, such as water or formic acid, or which release a gas upon increasing the temperature during the reaction, such as sodium bicarbonate.

[0108] It is particularly preferred if the composition according to the invention contains, as blowing agent, water in combination with a hydrocarbon having 5 carbon atoms, an HFO, a hydrohaloolefin or an HFC or a mixture thereof.

[0109] Preference is given to using hydrocarbons with 4 or 5 carbon atoms.

[0110] The water content suitable in the sense of the present invention preferably depends on whether or not one or more blowing agents are used in addition to water. For foams blown purely with water, the preferred value is, for example, 1 to 20 parts by weight of water per 100 parts by weight of polyol. If further blowing agents are used, the preferred amount is preferably reduced to, for example, 0.1 to 5 parts by weight of water per 100 parts by weight of polyol.

[0111] As optional additives, for example, one or more substances known from the prior art and 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, dyes, pigments, color pastes, fragrances and / or emulsifiers, etc. may be used.

[0112] As optional flame retardants, the compositions according to the invention may contain, for example, one or more known flame retardants suitable for the production of PU foams, such as halogen-containing or halogen-free organic phosphorus-containing compounds, such as triethyl phosphate (TEP), tris(1-chloro-2-propyl)phosphate (TCPP), tris(2-chloroethyl)phosphate (TCEP), dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), diethyl(hydroxymethyl)phosphonate, ammonium polyphosphate or red phosphorus, nitrogen-containing compounds, such as melamine, melamine cyanurate or melamine polyphosphate, or halogenated compounds, such as chlorinated and / or brominated polyether polyols and / or polyester polyols. Mixtures of different flame retardants may also be used.

[0113] Unless otherwise apparent from this specification, any preferred or particularly preferred embodiment of the present invention may be combined with one or more of the other preferred or particularly preferred embodiments of the present invention.

[0114] A further subject of the present invention is a process for producing polyurethane foams by reacting a polyol component with a polyisocyanate component, wherein the reaction is carried out in the presence of at least one organic compound V as defined above, preferably as defined in any one of claims 1 to 4, preferably using a composition as defined above, particularly preferably using a composition as defined in any one of claims 1 to 12.

[0115] The process for producing PU foam according to the present invention can be carried out by any known method, for example, by hand mixing or preferably using a foaming machine. When the process is carried out using a foaming machine, high-pressure or low-pressure machines can be used. The process according to the present invention can be carried out discontinuously as well as continuously, and for example, 1K, 1.5K, or 2K systems can be used, as described, for example, in EP 3717538 A1, U.S. Pat. No. 7776934 B2, EP 1400547 B1, or EP 2780384 B2.

[0116] In the sense of the present invention, preferred polyurethane foam formulations are those having a viscosity of 5 to 900 kg / m 3 and preferably has the composition set forth in Table 1.

[0117] Table 1: Composition of preferred polyurethane foam formulations: [Table 1]

[0118] For further preferred embodiments and configurations of the method according to the invention, reference is further made to the explanations already given above in connection with the composition according to the invention. These explanations preferably apply.

[0119] A further subject of the invention is a polyurethane foam obtainable by the process according to the invention.

[0120] The polyurethane foam has a viscosity of 5 to 900 kg / m 3 , more preferably 8 to 800 kg / m 3 , and more preferably 10 to 600 kg / m 3 , especially 30 to 150 kg / m 3 It is preferred that the foam density is

[0121] The polyurethane foam preferably has a lambda value of less than 25 mW / m K, more preferably less than 24 mW / m K, even more preferably less than 23 mW / m K, and especially less than 22 mW / m K. The lambda value is measured 24 hours after foaming on test specimens having dimensions of 20 x 20 x 2.5 cm. In accordance with DIN EN 12667:2001-05, the lambda values ​​were determined at an average temperature of 10°C.

[0122] Preferably, the polyurethane foam (PU foam) according to the invention is a rigid polyurethane foam (rigid PU foam), particularly preferably a closed-cell rigid PU foam.

[0123] "Rigid polyurethane foam" or "rigid PU foam" is an established technical term. The known and fundamental difference between flexible and rigid foams is that flexible foams exhibit elastic behavior, and therefore deformation is reversible, whereas rigid foams are permanently deformed. Within the scope of the present invention, rigid polyurethane foams are understood to be foams preferably according to DIN 7726:1982-05, which preferably have a compressive strength according to DIN 53421:1984-06 / DIN EN ISO 844:2014-11 of 20 kPa or more, preferably 80 kPa or more, more preferably 100 kPa or more, even more preferably 150 kPa or more, and particularly preferably 180 kPa or more. Furthermore, the rigid polyurethane foams preferably have a closed cell content of more than 50%, preferably more than 80% and particularly preferably more than 90%, where the closed cell content can preferably be determined in accordance with DIN EN ISO 4590:2016-12. Further details about rigid polyurethane foams can also be found in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 6.

[0124] Preferably, the PU foams according to the invention, in particular the rigid PU foams, can be used, for example, as or for the production of insulating materials, preferably insulation boards, refrigerators, insulating foams, headliners, packaging foams or spray foams.

[0125] A further object of the present invention is therefore the use of the polyurethane foam according to the invention as a heat insulating board and / or insulation, preferably for cooling devices, which in this case preferably have the polyurethane foam according to the invention as insulating material.

[0126] The PU foams according to the invention can be used advantageously in particular in the cold storage, refrigeration and household appliance industry, for example for the production of insulating boards for roofs and walls, as insulating material in containers and warehouses for frozen goods and for refrigeration and freezing equipment.

[0127] Further preferred areas of use are in vehicle construction, in particular for producing vehicle headliners, body parts, interior trim, refrigerated vehicles, large containers, transport pallets, packaging laminates, in the furniture industry, e.g. for furniture parts, doors, cladding, and in electronics applications.

[0128] Preferably, the PU foam according to the present invention can be used as an insulating material for cooling devices.

[0129] A further subject of the invention is the use of said PU foams as insulating material, as heat insulating boards, as spray foam, as one-component foam in refrigeration technology, in refrigerated freezer cabinets, in the construction, automotive, shipbuilding and / or electronics sectors.

[0130] A further subject of the present invention is the use of at least one organic compound V as defined above, preferably as defined in any one of claims 1 to 4, preferably in combination with at least one hydrocarbon KWS as defined above, preferably as defined in claim 5, and optionally with at least one polyalkylsiloxane PAS as defined above, preferably as defined in claim 6 or 7, in the production of polyurethane foams, preferably as foam stabilizers, preferably for improving the insulating properties of said polyurethane foams, particularly preferably using a composition according to the invention as defined above, preferably a composition according to the invention as claimed in any one of claims 1 to 12, in particular to provide polyurethane foams having a lambda value of less than 25, 24 or 23 mW / mK.

[0131] When ranges, general formulae or compound classes are given, these include not only the corresponding ranges or compound groups explicitly mentioned, but also all subranges and compound subgroups that can be obtained by extracting the individual values ​​(ranges) or compounds. When documents are cited within the scope of this specification, their content is fully incorporated into the disclosure content of the present invention, especially in relation to the context in which they are cited. Percentages are given in weight percent unless otherwise stated. When average values ​​are given, they are weight averages unless otherwise stated. When parameters determined by measurement are given, the measurements were carried out at a temperature of 25°C and preferably at a pressure of 1.01325 bar (standard pressure) unless otherwise stated.

[0132] The following examples are used to further illustrate the present invention, but the present invention is not limited to the following examples. [Example]

[0133] The following organic compounds V were used: V1: Staybelite TMEster 3-E: Eastman Chemical Company's triethylene glycol ester of abietic acid V2:Abitol TM E: Hydrogenated abietol from Eastman Chemical Company V3: Hydrogen (登録商標) Abietic acid - light hydrogenation from DRT (Les Derives resiniques et Terpeniques, 30 Rue Gambetta, 40100 Dax, France) V4:Hercolyn (登録商標) D: DRT hydrogenated abietic acid methyl ester V5: Staybelite TM Ester 10-E: Eastman Chemical Company's glycerol ester of abietic acid V6:Dertoline (登録商標) DEG:DRT diethylene glycol ester of abietic acid V7: Granolite (登録商標) TEG: Triethylene glycol ester of abietic acid, DRT.

[0134] The following materials were used as hydrocarbons KWS: KWS-A: Oxo Oil LS 13 from Evonik Operations GmbH. Oxo Oil LS 13 is a C12-rich hydrocarbon mixture with a high olefin content, which is obtained as a low boiler fraction in the production of isotridecanol by the oxoalcohol process.

[0135] The following materials were used as polyalkylsiloxane PAS: PAS-A: M corresponding to Formula 1 from International Publication No. WO2021 / 144033 (WO2021 / 144003 A1) a D b T c Q d where a=2; b=1; c=0; d=0; R 11 = methyl; R 12= methyl; R 13 = methyl; R 14 = octyl, R 15 = methyl; described, for example, in WO 2020 / 144003 as PAS No. 5.

[0136] Polyether-modified siloxane (PES) from Evonik Operations GmbH, TEGOSTAB (登録商標) B 84507 is used, which will be abbreviated as B 84507 hereinafter.

[0137] The following substances were used as comparison substances: Oleo No. 1: Diethanolamide based on soybean oil and diethanolamine, prepared as described in DE 10 2011 007 479 A1 in example 1b as amide 2.

[0138] Oleo No. 2: Sorbitan Monolaurate, TEGO from Evonik Operations GmbH (登録商標) Commercially available as SML.

[0139] In foaming experiments to produce rigid PU foams, the organic compounds V, as well as, respectively, as can be seen from Table 4, were used, for example in mixtures with the hydrocarbons KWS-A or polyalkylsiloxanes PAS-A and / or with the polyether-modified siloxanes (PES).

[0140] In this case, the following mixtures were used, as summarized in Table 2:

[0141] Table 2: Description of organic compounds V / PAS and V / KWS mixtures [Table 2]

[0142] For the production of the foam, the following raw materials were used: Stepanpol (登録商標)PS 2412: Stepan polyester polyol TCPP: Tris(2-chloroisopropyl)phosphate (flame retardant) from Fyrol POLYCAT (登録商標) 5. Evonik Operations GmbH, Amine catalyst Kosmos (登録商標) 70 LO, Evonik Operations GmbH, catalyst based on potassium octoate MDI (44V20): Covestro's Desmodur (登録商標) 44V20L, diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues.

[0143] The foaming was carried out by hand mixing. To do this, all components according to Table 3, except for the polyisocyanate (MDI), were weighed into a beaker and mixed for 30 seconds at 1000 rpm using a disk stirrer (diameter 6 cm). The amount of blowing agent evaporated during the mixing process was determined by weighing again and replenished. Subsequently, the polyisocyanate (MDI) was added, and the reaction mixture was stirred for 5 seconds at 3000 rpm using the stirrer.

[0144] For the foam formulations used herein for panel applications, such as building insulation, the mixture was immediately introduced into an aluminum mould thermostatted at 65°C with dimensions 50cm x 25cm x 7cm.

[0145] The amount of foam formulation used was then measured out so that it was sufficient for the minimum filling of the mold. The foam was demolded after 10 minutes and subsequently stored at room temperature for 24 hours.

[0146] Based on a cross section through the foam, the degree of internal defects and pore structure are visually assessed on a scale of 1 to 10, where 10 represents a foam with no defects and 1 represents a foam with severe defects.

[0147] Its thermal conductivity (λ value in mW / m·K) was measured on a 2.5 cm thick disc using an apparatus of the type Hesto Lambda Control, model HLC X206, after 1 day (1d) and 7 days (7d) at an average temperature of 10 °C according to the provisions of standard EN 12667:2001-05.

[0148] Table 3 summarizes the foam formulations used in the examples.

[0149] Table 3 (parts by weight) [Table 3]

[0150] The results of the foaming experiments are summarized in Table 4. As above, panels were fabricated and the lambda value (mW / m·K) was measured after 1 day and 7 days, and the internal defects were rated on a scale of 1 to 10. The lower the lambda value, the better the insulating performance.

[0151] Table 4: Results of foaming experiments [Table 4-1] [Table 4-2]

[0152] From the above experiments it is clear that the organic compound V or mixtures containing V according to the invention can in part result in foam quality comparable to or even better than foams produced using oleosurfactants or polyether-modified siloxanes (PES).

[0153] For example, V2 (Experiment No. 5) achieved better results, i.e., lower lambda values, than the oleo candidates (Comparative Experiments 3 and 4). Other compounds V (Experiments 3, 7, and 9) without the addition of KWS or PAS gave higher lambda values ​​compared to Comparative Experiments 3 and 4. The mixtures of KWS or PAS and the compound V even showed in part particularly improved foam properties. This can be seen below: Examples 1 and 2 compared to Example 3 Example 6 compared to Example 7 Example 8 compared to Example 9.

[0154] In experiments in which Compound V with PES or V / KWS or V / PAS was combined with PES, it was found that in most cases the combination resulted in better lambda values ​​than PES alone. For example, in experiments 10, 11, 12, 14, 16, 18, 20, and 22, lower lambda values ​​were achieved after one day than in Comparative Example 1 or Comparative Example 2.

[0155] Preferred embodiments of the present invention are as follows: 1. A composition for producing polyurethane foam, comprising a polyisocyanate component, a polyol component, optionally at least one catalyst that catalyzes the formation of urethane or isocyanurate bonds, and optionally at least one blowing agent, The composition further comprises: [ka] at least one group R selected from the group consisting of A and at least one organic compound V having the formula where * represents a bond to the remainder of the organic compound V; and R 1 are independently the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N. The composition, characterized in that

[0156] 2. The at least one organic compound V is [ka] is selected from the group consisting of In the above formula, n=1-5, l=1~5, p=1~5, R are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N, R A = independently of each other, the same or different, [ka] is selected from the group consisting of where * represents a bond to the remainder of the organic compound V; and R 1 are independently the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N. The composition according to 1 above, characterized in that

[0157] 3. The at least one organic compound V is [ka] is selected from the group consisting of In the above formula, R A are independently the same or different, [ka] is selected from the group consisting of In the above formula, * represents a bond to the remainder of the organic compound V, and in the above formula: m=1~15, r=1~15 k=1~6, R 1are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N, Very particular preference is given here to diethylene glycol esters, triethylene glycol esters, polyglycerol esters, abietol, hydrogenated abietol and / or partially hydrogenated abietol. The composition according to 1. or 2. above,

[0158] 4. A composition according to any one of claims 1 to 3, characterized in that the at least one organic compound V has an OH number of less than 150 mg KOH / g, preferably less than 100 mg KOH / g, in particular less than 50 mg KOH / g.

[0159] 5. The composition further comprises at least one hydrocarbon KWS, the hydrocarbon KWS preferably having 10 to 24 carbon atoms and a boiling point above 100°C, preferably above 150°C at a pressure of 1.01325 bar, and is preferably decene, decane, isodecane, isodecene, undecene, undecane, isoundecane, isoundecene, dodecene, dodecane, isododecane, isododecene, tridecane, tridecene, isotridecane, isotridecene, tetradecane, tetradecene, isotetradecane, isotetradecene, pentadecane ... isopentadecane, isopentadecene, hexadecane, hexadecene, isohexadecane, isohexadecene, heptadecane, heptadecene, isoheptadecane, isoheptadecene, octadecane, octadecene, isooctadecane, isooctadecene, nonadecane, nonadecene, isonadecane, isononadecene, eicosane, eicosane, isoeicosane, isoeicosene, tributene, tributane, tetrabutene, tetrabutane, alkylbenzenes having at least 10 carbon atoms and oxo oils, The composition according to any one of 1. to 4. above, characterized in that the total amount of the hydrocarbons KWS contained is used in combination with the total amount of the organic compounds V contained, preferably in a mass ratio of 1:5 to 1:200.

[0160] 6. The composition further comprises at least one polyalkylsiloxane PAS that is free of polyether modification and preferably contains less than 20, more preferably less than 15, and particularly preferably less than 11 silicon atoms; The total amount of polyalkylsiloxane PAS used is preferably used in a mass ratio of 1:4 to 1:200 based on the total amount of organic compound V used, Preferably, the at least one polyalkylsiloxane PAS is represented by formula 1: M a D b T c Q d (Formula 1) In accordance with the above formula, M=R 11 R 12 R 13 SiO 1 / 2 D=R 14 R 15 SiO 2 / 2 T=R 16 SiO 3 / 2 Q=SiO 4 / 2 where: R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are, independently of one another, the same or different and are hydrocarbon radicals having 1 to 12, preferably 1 to 8, carbon atoms, which may be substituted with heteroatoms or are otherwise H, in particular phenyl-, CH3-, CH3CH2-, CH2CH-ClCH2CH2CH2- or H-, and a=2~6 b=0~8 c=0~4 d=0~2 provided that a+b+c+d<20, preferably <15, particularly preferably <11; where: R 16 is R 11 , R 12 , R 13 , R 14 and R 15 Unlike, and / or R 11 , R 12 and R 13 is different The composition according to any one of the above items 1 to 5, characterized in that the case is particularly preferred.

[0161] 7. The composition according to any one of 1. to 6. above, characterized in that the total amount of organic compound V used is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass, based on 100 parts by mass of all polyol components.

[0162] 8. The composition according to any one of items 5 to 7 above, characterized in that the total amount of the hydrocarbons KWS used, the total amount of the organic compounds V used, and the total amount of the polyalkylsiloxanes PAS used, based on 100 parts by mass of all polyol components, is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass.

[0163] 9. The composition according to any one of 1. to 8. above, characterized in that the composition further contains at least one polyether-modified siloxane in a total amount of preferably 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass, based on 100 parts by mass of all polyol components.

[0164] 10. A composition according to any one of 1. to 9. above, characterized in that the ratio of the total polyisocyanate components used to the total polyol components used, expressed as a blending index, i.e., the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups multiplied by 100, is in the range of 150 to 550, particularly preferably 200 to 500.

[0165] 11. The composition according to any one of 1. to 10. above, wherein the entire polyol component used comprises at least one polyester polyol, preferably the polyester polyol has a melting point of less than 30°C, and wherein the amount of the entire polyester polyol used is preferably 20 to 100 parts by mass, preferably 40 to 99 parts by mass, and particularly preferably 70 to 98 parts by mass, based on 100 parts by mass of the entire polyol component.

[0166] 12. The composition according to any one of claims 1 to 11, characterized in that the composition contains at least one blowing agent, preferably at least one hydrocarbon having 4 or 5 carbon atoms, especially 5 carbon atoms, as the blowing agent, and the composition preferably does not contain any halogenated blowing agents.

[0167] 13. A method for producing polyurethane foam by reacting a polyol component with a polyisocyanate component, characterized in that the reaction is carried out in the presence of at least one organic compound V as defined in any of 1. to 4. above, in particular using a composition as defined in any of 1. to 12. above.

[0168] 14. A polyurethane foam obtainable by the method described in 13 above.

[0169] 15. Use of polyurethane foams as defined in paragraph 14 above for insulating purposes, preferably as heat insulating boards and / or insulation, in particular for cooling devices.

[0170] 16. Use of at least one organic compound V as defined in any of items 1 to 4 above, preferably in combination with at least one hydrocarbon KWS as defined in item 5 above and optionally at least one polyalkylsiloxane PAS as defined in item 6 or 7 above, in the production of polyurethane foams, preferably as a foam stabilizer, preferably for improving the insulating properties of said polyurethane foams, particularly preferably using a composition as defined in any of items 1 to 12 above, in particular to provide polyurethane foams having a lambda value of less than 25, 24 or 23 mW / m K.

Claims

1. A composition for producing polyurethane foam, comprising a polyisocyanate component, a polyol component, optionally at least one catalyst that catalyzes the formation of urethane or isocyanurate bonds, and optionally at least one blowing agent, The composition further comprises: 【Chemistry 1】 At least one group R selected from the group consisting of Ａ and at least one organic compound V having the formula: In the above formula, * represents a bond to the remainder of the organic compound V; and R １ are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N; The composition, characterized in that

2. said at least one organic compound V being 【Chemistry 2】 is selected from the group consisting of In the above formula, n=1 to 5, l = 1 to 5, p=1 to 5, R are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N, R Ａ are independently the same or different, 【Transformation 3】 is selected from the group consisting of In the above formula, * represents a bond to the remainder of the organic compound V; and R １ are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N; The composition according to claim 1 .

3. said at least one organic compound V being 【Chemistry 4】 is selected from the group consisting of In the above formula, R Ａ are independently the same or different, 【Transformation 5】 is selected from the group consisting of In the above formula, * represents a bond to the remainder of the organic compound V, and in the above formula: m=1 to 15, r = 1 to 15 k = 1 to 6, R １ are, independently of one another, the same or different and are H or a branched or linear alkyl group having 1 to 30 carbon atoms and optionally containing heteroatoms, such as preferably O and / or N, Very particular preference is given here to diethylene glycol esters, triethylene glycol esters, polyglycerol esters, abietol, hydrogenated abietol and / or partially hydrogenated abietol.

3. The composition according to claim 1 or 2, characterized in that

4. 4. The composition according to claim 1, wherein the at least one organic compound V has an OH number of less than 150 mg KOH / g, preferably less than 100 mg KOH / g, in particular less than 50 mg KOH / g.

5. The composition further comprises at least one hydrocarbon KWS, the hydrocarbon KWS preferably having 10 to 24 carbon atoms and a boiling point above 100°C, preferably above 150°C at a pressure of 1.01325 bar, and is preferably decene, decane, isodecane, isodecene, undecene, undecane, isoundecane, isoundecene, dodecene, dodecane, isododecane, isododecene, tridecane, tridecene, isotridecane, isotridecene, tetradecane, tetradecene, isotetradecane, isotetradecene, pentadecane, pentadecane, isopentadecene, isopentadecene, hexadecane, hexadecene, isohexadecane, isohexadecene, heptadecane, heptadecene, isoheptadecane, isoheptadecene, octadecane, octadecene, isooctadecane, isooctadecene, nonadecane, nonadecene, isonadecane, isononadecene, eicosane, eicosane, isoeicosane, isoeicosene, tributene, tributane, tetrabutene, tetrabutane, alkylbenzenes having at least 10 carbon atoms and oxo oils; 5. Compositions according to any one of claims 1 to 4, characterized in that the total amount of hydrocarbons KWS present is used in combination with the total amount of organic compounds V present, preferably in a weight ratio of 1:5 to 1:

200.

6. the composition further comprises at least one polyalkylsiloxane PAS which is free of polyether modification and which preferably contains less than 20, more preferably less than 15, particularly preferably less than 11 silicon atoms, The total amount of polyalkylsiloxanes PAS used is preferably used in a weight ratio of 1:4 to 1:200, based on the total amount of organic compounds V used, Preferably, said at least one polyalkylsiloxane PAS is of formula 1: M ａ D ｂ T ｃ Q ｄ (Equation 1) In accordance with the above formula, M=R １１ R １２ R １３ SiO １／２ D=R １４ R １５ SiO ２／２ T=R １６ SiO ３／２ Q=SiO ４／２ where: R １１ , R １２ , R １３ , R １４ , R １５ , R １６ are, independently of one another, the same or different and are hydrocarbon radicals having 1 to 12, preferably 1 to 8, carbon atoms, where the hydrocarbon radicals may be substituted with heteroatoms or are otherwise H, in particular phenyl-, CH ３ -, CH ３ CH ２ -, CH ２ CH-ClCH ２ CH ２ CH ２ - or H-, and a = 2 to 6 b = 0 to 8 c=0 to 4 d = 0 to 2 provided that a+b+c+d<20, preferably <15, particularly preferably <11; where: R １６ is R １１ , R １２ , R １３ , R １４ and R １５ Unlike, and / or R １１ , R １２ and R １３ is different 6. Composition according to any one of claims 1 to 5, characterized in that the case is particularly preferred.

7. The composition according to any one of claims 1 to 6, characterized in that the total amount of organic compound V used is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and particularly preferably 1 to 3 parts by weight, based on 100 parts by weight of the total polyol components.

8. The composition according to any one of claims 5 to 7, characterized in that the total amount of the hydrocarbons KWS used, the total amount of the organic compounds V used and the total amount of the polyalkylsiloxanes PAS used is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight and particularly preferably 1 to 3 parts by weight, based on 100 parts by weight of the total polyol components.

9. 9. The composition according to claim 1, further comprising at least one polyether-modified siloxane, preferably in a total amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, particularly preferably 1 to 3 parts by weight, based on 100 parts by weight of the total polyol component.

10. 10. The composition according to claim 1, wherein the ratio of the total polyisocyanate components used to the total polyol components used, expressed as a blending index, i.e. the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups multiplied by 100, is in the range from 150 to 550, particularly preferably from 200 to 500.

11. The composition according to any one of claims 1 to 10, characterized in that the total polyol component used comprises at least one polyester polyol, preferably the polyester polyol has a melting point of less than 30°C, and the total amount of polyester polyol used is preferably 20 to 100 parts by weight, preferably 40 to 99 parts by weight, and particularly preferably 70 to 98 parts by weight, based on 100 parts by weight of the total polyol component.

12. 12. The composition according to claim 1, wherein the composition comprises at least one blowing agent, preferably at least one hydrocarbon having 4 or 5 carbon atoms, in particular 5 carbon atoms, as the blowing agent, and wherein the composition preferably does not contain any halogenated blowing agents.

13. 13. A method for producing a polyurethane foam by reacting a polyol component with a polyisocyanate component, characterized in that the reaction is carried out in the presence of at least one organic compound V as defined in any one of claims 1 to 4, in particular using a composition as defined in any one of claims 1 to 12.

14. Polyurethane foam obtainable by the process according to claim 13.

15. 15. Use of polyurethane foams according to claim 14 for insulating purposes, preferably as heat insulating boards and / or insulation, in particular for cooling devices.

16. Use of at least one organic compound V as defined in any one of claims 1 to 4, preferably in combination with at least one hydrocarbon KWS as defined in claim 5 and optionally at least one polyalkylsiloxane PAS as defined in claim 6 or 7, in the production of polyurethane foams, preferably as a foam stabilizer, preferably for improving the insulating properties of said polyurethane foams, particularly preferably using a composition as defined in any one of claims 1 to 12, in particular to provide polyurethane foams having a lambda value of less than 25, 24 or 23 mW / m K.

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