Production of polyurethane or polyisocyanurate foam

Abstract

To provide polyurethane or polyisocyanurate foams, preferably rigid polyurethane or polyisocyanurate foams, which have particularly advantageous use characteristics, such as especially good compressive strength and / or indentation hardness after only a short reaction time.SOLUTION: A composition comprising a polyisocyanate component, a polyol component, at least one tertiary amine of formula (X), and at least one zinc(II) carboxylate, with the proviso that the zinc(II) carboxylate contained is employed in stoichiometric form, i.e., with Zn(II) and carboxylate in a molar ratio of 1:2, wherein the composition additionally contains at least one nitrogen-containing compound V having at least two N atoms and being a modified phenol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention is in the field of polyurethane (PU) and polyisocyanurate (PIR), in particular PU or PIR foams. In particular, the present invention relates to a composition for producing polyurethane or polyisocyanurate foams, a zinc(II) carboxylate-containing preparation suitable for catalysis in the production of PU or PIR foams, a method for producing polyurethane or polyisocyanurate foams, and polyurethane or polyisocyanurate foams, as well as uses of the foams produced thereby.

[0002] In the context of the present invention, polyurethane (PU) is understood to mean, in particular, products obtained by reacting polyisocyanates with polyols or compounds having isocyanate-reactive groups. In this case, in addition to polyurethane, further functional groups can also be formed, such as uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea, and / or uretonimine. Therefore, PU in the sense of the present invention is understood to mean not only polyurethanes, but also polyisocyanurates, polyureas, and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret, and uretonimine groups. In the context of the present invention, polyurethane foam (PU foam) is understood to mean, in particular, foams obtained as reaction products based on polyisocyanates with polyols or compounds having isocyanate-reactive groups. In this case, besides the polyurethane from which the name is derived, further functional groups, such as, for example, allophanate, biuret, urea, carbodiimide, uretdione, isocyanurate or uretonimine, can also be formed. In the context of the present invention, polyisocyanurate foams (PIR foams) are understood to mean, in particular, foams obtained as reaction products based on polyisocyanates and polyols or compounds having isocyanate-reactive groups, the isocyanate index, i.e., the ratio between isocyanates and isocyanate-reactive groups, being preferably greater than 180. In this case, besides the polyisocyanurates from which the name is derived, in each case polyurethane groups and, if necessary, further functional groups, such as, for example, allophanate, biuret, urea, carbodiimide, uretdione or uretonimine, are also formed.

[0003] In the context of the present invention, the focus is advantageously on the formation of polyisocyanurates (PIR). This reaction is formally called trimerization, since three isocyanate groups react to form an isocyanurate ring. For example, the production of PIR rigid foams is described in the literature and is advantageously carried out by reacting polyisocyanates with compounds containing hydrogen atoms reactive with isocyanate groups, typically polyetherols, polyesterols, or both, with an isocyanate index of preferably 180 or greater. This allows the formation of isocyanurate structures or other structures formed by the reaction of isocyanate groups with other groups, such as polyurethane groups, by the reaction of isocyanate groups themselves, in addition to the urethane structures formed by the reaction of isocyanates with compounds containing reactive hydrogen atoms.

[0004] In the production of polyurethane or polyisocyanurate foams, preferably polyurethane or polyisocyanurate rigid foams, various catalysts can be used to positively influence the foaming reaction profile and the use properties of the foam. The formation of polyisocyanurates is advantageous because it leads to good mechanical properties (high compression hardness) and improved flame retardant properties.

[0005] Various publications are known relating to the use of catalysts to improve the compressive hardness by supporting the trimerization reaction in the production of PU or PIR rigid foams.

[0006] EP 1 878 493 A1 describes the use of carbocationic compounds as trimerization catalysts, the anions of which are based on dicarbonyl compounds, but does not describe the use of zinc carboxylates.

[0007] U.S. Patent No. 4,452,829 describes the production of spray foams using triols with molar masses greater than 1000 g / mol, where Zn salts are used in combination with K salts to accelerate creaming, i.e., the initiation of the PU reaction with water, or where a Zn-containing catalyst (zinc octoate) is added to the K-containing catalyst to shorten the creaming time, i.e., to accelerate the reaction.

[0008] U.S. Pat. No. 4,200,699 describes a gel catalyst composition for producing PU rigid foams containing Zn carboxylate, K carboxylate and Sn carboxylate, preferably with a further gel catalyst from the group of tertiary amines, inorganic tin compounds or organotin compounds.

[0009] EP 1 745 847 A1 describes a trimerization catalyst based on potassium octoate and a solvent inert to the reaction with isocyanates.

[0010] WO 2016 / 201675 describes a trimerization catalyst consisting of a composition based on a sterically hindered carboxylate salt and a tertiary amine bearing an isocyanate-reactive group.

[0011] WO 2010 / 054317 describes imidazolium or imdazolinium salts as trimerization catalysts.

[0012] WO 2013 / 074907 describes the use of tetraalkylguanidine salts of aromatic carboxylic acids as catalysts for polyurethane foams.

[0013] WO 2015 / 179041 describes the use of zinc-based catalysts for crosslinking silicone resins. Various ligands, including phenolic ligands, are used. However, the catalysis of polyurethane or isocyanate reactions is not described.

[0014] WO 2022 / 218657 describes the production of polyurethane or polyisocyanurate rigid foams using zinc salts and / or zinc-containing preparations.

[0015] US Patent Application Publication No. 2009 / 099274 discloses PU or PIR rigid foams made from compositions including an isocyanate component, a polyol component, a blowing agent, an amine-based catalyst, and a zinc catalyst.

[0016] WO 2019 / 122923 discloses PU or PIR rigid foams made from polyisocyanates, polyether carbonates and zinc-based catalysts.

[0017] EP 0 010 407 A1 discloses a process for producing PU foam in the presence of a gel catalyst containing a zinc carboxylate.

[0018] The object of the present invention is to create a further option for providing polyurethane or polyisocyanurate foams, preferably polyurethane or polyisocyanurate rigid foams, that have particularly advantageous application properties, such as particularly good compression hardness and / or indentation hardness, even after short reaction times, while preferably minimizing the effect on the rise profile.

[0019] The solution of this problem is made possible by the subject matter of the present invention.

[0020] The subject of the present invention is a composition for producing polyurethane or polyisocyanurate foams, advantageously polyurethane or polyisocyanurate rigid foams, comprising: a) a polyisocyanate component; and b) a polyol component; and c) at least one zinc(II) carboxylate, wherein the zinc(II) carboxylate is used in stoichiometric form, i.e., in a molar ratio of Zn(II) to carboxylate of 1:2; d) Formula (X) [ka] [In the formula, m, in each occurrence, independently, is 1 or 2; A is O, S or NR e and R a , R b , R c , R d and R e are, in each occurrence, independently of one another, the same or different, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. and at least one tertiary amine of e) optionally at least one foam stabilizer; f) optionally at least one blowing agent; Including, The composition is additionally g) at least one nitrogen-containing compound V having at least two N atoms and being a modified phenol The composition comprises:

[0021] It has been found that the use of the compositions according to the invention in the production of PU or PIR foams, preferably PU or PIR rigid foams, leads to corresponding foams, preferably rigid foams, with improved application properties, in particular improved trimerization, which results in foams that cure quickly, i.e., have high compression hardness and high indentation hardness at an early stage.

[0022] A particular advantage of the present invention is also that the use of the compositions according to the invention nevertheless makes it possible to minimize the influence on the build-up profile, which is highly advantageous, since otherwise problems with the flowability of the reaction mixture may arise, which would lead to significant processing problems.

[0023] The compositions according to the invention also allow for slower build-up profiles if desired, allowing a great variety of options for adjusting the reactivity of the foaming system.

[0024] The solution according to the invention therefore allows for the production of products based on PU or PIR foam, preferably PU or PIR rigid foam, such as, for example, insulating panels or cooling cabinets, with particularly high quality, and makes the process for producing PU or PIR foam, preferably PU or PIR rigid foam, more efficient.

[0025] An additional advantage of the present invention is the good ecotoxicological classification of the chemicals that can be used, especially the zinc(II) carboxylates, since the prior art often uses metal compounds (e.g. Sn, Pb, etc.) with questionable toxicological properties.

[0026] The present invention has the further advantage that it can be used to produce PU or PIR foams, advantageously PU or PIR rigid foams, with fewer foaming defects.

[0027] The present invention has the further advantage that it can allow for a high active concentration of zinc salt in the reaction mixture, which can be better dissolved, thus even reducing the total amount of zinc-containing preparation that needs to be used, for example, added to the reaction mixture.

[0028] The composition according to the invention advantageously comprises at least one zinc(II) carboxylate selected from the group consisting of zinc(II) acetate, zinc(II) propionate, zinc(II) pivalate, zinc(II) 2-ethylhexanoate (zinc(II) octanoate), zinc(II) isononanoate (zinc(II) 3,5,5-trimethylhexanoate), zinc(II) neodecanoate, zinc(II) ricinoleate, zinc(II) palmitate, zinc(II) stearate, zinc(II) oleate, zinc(II) laurate, zinc(II) naphthenate, zinc(II) benzoate, zinc(II) lactate, zinc(II) glycinate, zinc(II) hippurate, zinc(II) citrate and zinc(II) soaps, with zinc(II) acetate and / or zinc(II) ricinoleate being highly preferred. Preferably, the zinc(II) soaps that can be used are zinc oleate, zinc palmitate and / or zinc stearate.

[0029] The zinc(II) carboxylate contained in the composition according to the present invention is used in stoichiometric form, i.e., in a molar ratio of Zn(II) to carboxylate of 1:2. This means that no excess (carboxylate or) carboxylic acid is used or is not present. In technical methods for producing zinc salts, the base acid may be used in excess, so that the final product in each case still contains an excess of acid. The corresponding excess of acid is not useful in the present invention.

[0030] The at least one zinc(II) carboxylate contained in the composition according to the invention can be introduced into the composition by any known method, but it is preferred to introduce the zinc(II) carboxylate in dissolved form, advantageously using at least one nitrogen-containing compound V and, optionally, at least one carrier medium (i.e., solvent). In principle, all substances suitable as solvents can optionally be used as carrier mediums. Preferably, for example, glycols, alkoxylates, and / or oils of synthetic and / or natural origin can optionally be used. Preferably, protic or aprotic solvents can optionally be used.

[0031] It is highly preferred if the at least one zinc(II) carboxylate contained in the composition according to the invention is introduced into the composition in the form of a zinc(II) carboxylate-containing preparation, which advantageously comprises at least one nitrogen-containing compound V according to the invention and optionally at least one carrier medium. Corresponding, particularly preferably usable, zinc(II) carboxylate-containing preparations are described in more detail below.

[0032] The composition according to the invention advantageously comprises [ka] [In the formula, R=in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic, and optionally containing heteroatoms such as O or N; R 1 = in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic] The composition contains at least one nitrogen-containing compound V selected from the group consisting of:

[0033] The corresponding nitrogen-containing compounds V are known per se and can be obtained, for example, by reacting an optionally modified phenol with an aldehyde and an amine.

[0034] Advantageously, the at least one nitrogen-containing compound V can be prepared by reacting a phenol with an aldehyde, advantageously an aldehyde having 1 to 20 carbon atoms, advantageously formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, cinnamaldehyde, trimethylhexanal, pelargonic aldehyde, acrolein and / or furfural and an amine in the sense of the Mannich reaction; advantageously, modified phenols having at least one substituent on the aromatic nucleus, such as cresols, xylenols, propylphenols, styrylphenols, alkylphenols and / or cardanols, can also be used as starting materials; likewise, resorcinol- and / or catechol-based structures can advantageously be used as modified phenols; Preferably, the at least one nitrogen-containing compound V is a phenol, formaldehyde and advantageously dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethanolamine, diethanolamine, trimethylethanediamine, isophoronediamine, dimethylpropylamine, diethylenetriamine, triethylenetetramine, methylhydroxyethylamine, dimethylaminopropylamine, pyrrolidine, pyrrole, morpholine, piperazine, N,N-dimethyl-2-(2-methylaminoethoxy)ethan-1-amine, N- and at least one primary or secondary amine selected from the group consisting of [2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, diisopropyldimethyldiethylenetriamine, bis(dimethylaminopropyl)amine, trimethylaminoethylethanolamine, N,N'-diisopropyl-N-methyl-bis(aminoethyl)ether, and N,N'-diisobutyl-N-methyl-bis(aminoethyl)ether, again using a modified phenol as the starting material.

[0035] Particularly preferred is when the at least one nitrogen-containing compound V is [ka] [ka] [In the formula, R=in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic, and optionally containing heteroatoms such as O or N; R 1 = in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic] and wherein the group consisting of [ka] [In the formula, R=in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic, and optionally containing heteroatoms such as O or N; R 1 = in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic] The use of is highly advantageous.

[0036] Most preferred is the use of 2,6-bis[(dimethylamino)methyl]-4-methyl-phenol, 2,4,6-tris[(dimethylamino)methyl]cardanol, 2,4,6-tris[(dimethylamino)methyl]phenol, 2,6-bis[(dimethylamino)methyl]-cardanol, 2,4,6-tris[(hydroxyethylamino)methyl]phenol, 2,4,6-tris[(hydroxypropylamino)methyl]phenol and / or 2,4,6-tris[(dimethylaminopropylamino)methyl]phenol.

[0037] Advantageously, the at least one nitrogen-containing compound V is contained in the composition according to the invention in a total amount of from 1 to 80% by weight, preferably from 2 to 60% by weight, in each case based on the composition according to the invention as a whole.

[0038] It is preferable that the zinc carboxylate (II) contained as a whole in the composition according to the present invention and the nitrogen-containing compound V contained as a whole are present in a ratio of 1:0.5 to 1:5 parts by weight.

[0039] In the sense of the present invention, it is highly preferred to introduce at least one zinc(II) carboxylate for use in the PU or PIR reaction mixture in dissolved form (or in liquid form at 25° C. and standard pressure) using at least one carrier medium.

[0040] Advantageously, the combination of at least one zinc(II) carboxylate and at least one nitrogen-containing compound V can also be selected to ensure its introduction in dissolved form, and this combination itself may advantageously already have a sufficiently low viscosity and may not exhibit any tendency to crystallize.

[0041] The use of a carrier medium is optional, however it is preferred to add the at least one zinc(II) carboxylate according to the invention to the reaction mixture in at least one carrier medium.

[0042] The use of a carrier medium is optional, but may be advantageous and preferred, for example, since it may contribute to the fact that a desired viscosity can be set and / or, for example, that the possible tendency to crystallization can be reduced.

[0043] Particular preference is further given to the compositions according to the invention containing carboxylic acids, advantageously selected from ammonium, potassium and / or other alkali or alkaline earth metal carboxylates, Preferably selected from potassium carboxylates and carboxylates of ammonium cations, very preferably potassium acetate, potassium formate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium 2-ethylhexanoate, potassium pivalate, potassium octanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium decanoate, potassium ricinoleate, potassium stearate, potassium neodecanoate, and also tetramethylammonium, tetraethylammonium, triethylmethylammonium, tetrapropylammonium, tetrabutylammonium, dimethyldiallylammonium, trimethyl-(2-hydroxypropyl)ammonium, triethyl-(2-hydroxypropyl)ammonium, tripeptanoate. and / or dimethylbenzyl-(2-hydroxypropyl)ammonium, tributyl-(2-hydroxypropyl)ammonium, trimethyl-(2-hydroxyethyl)ammonium, triethyl-(2-hydroxyethyl)ammonium, tripropyl-(2-hydroxyethyl)ammonium, tributyl-(2-hydroxyethyl)ammonium, dimethylbenzyl-(2-hydroxyethyl)ammonium and / or dimethylbenzyl-(2-hydroxypropyl)ammonium carboxylates, which carboxylates are advantageously acetates, propionates, butanoates, pentanoates, pivalates, octanoates, nonanoates, decanoates, neodecanoates, ricinoleates and / or stearates.

[0044] As such, the additional trimerization catalyst does not itself contain zinc.

[0045] The addition of at least one additional trimerization catalyst allows the reaction rate to be adjusted to a desired level, if desired. The at least one additional trimerization catalyst may be a constituent of the zinc(II) carboxylate-containing preparation. However, it can also be added to the composition according to the invention separately, i.e., separately from the zinc(II) carboxylate.

[0046] Preferred compositions according to the invention comprise at least one additional trimerization catalyst in a total amount of 10 to 90% by weight, advantageously 20 to 80% by weight, based on the total amount of the composition according to the invention.

[0047] The optionally (but advantageously obligatory) contained additional trimerization catalyst is preferably introduced into the composition according to the invention separately from the at least one zinc(II) carboxylate.

[0048] Furthermore, it is preferred if the composition according to the invention does not contain any Sb and / or Sn carboxylates.

[0049] The composition according to the invention, as already mentioned above, comprises a compound of formula (X) [ka] [In the formula, m, in each occurrence, independently, is 1 or 2; A is O, S or NR e and R a , R b , R c , R d and R e are, in each occurrence, independently of one another, the same or different, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. and at least one tertiary amine of the formula:

[0050] Especially preferred is when the at least one tertiary amine of formula (X) is selected from the group consisting of pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl)ether, tris-(dimethylaminopropyl)amine, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, diisopropyltrimethyldiethylenetriamine, bis-(dimethylaminopropyl)methylamine, trimethylaminoethylethanolamine, bis-(2-isopropylmethylaminoethyl)ether, bis-(2-isobutylmethylaminoethyl)ether, N,N'-diisopropyl-N,N'-dimethyl-bis(aminoethyl)ether, N,N,N'-triisopropyl-N'-methyl-bis(aminoethyl)ether and N,N'-diisobutyl-N,N'-dimethyl-bis(aminoethyl)ether.

[0051] At least one tertiary amine of formula (X), advantageously pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl)ether, tris(dimethylaminopropyl)amine, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, 2-[[2-[2-(dimethylamino)ethoxy]ethyl]methylamino]ethanol, diisopropyltrimethyldiethylenetriamine, bis-(dimethylaminopropyl)methylamine and / or trimethylaminoethylethanolamine, in particular has the function of acting as a catalyst.

[0052] Preferred compositions according to the invention comprise at least one tertiary amine of formula (X), advantageously pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl)ether, tris(dimethylaminopropyl)amine, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, 2-[[2-[2-(dimethylamino)ethoxy]ethyl]methylamino]ethanol, diisopropyltrimethyldiethylenetriamine, bis-(dimethylaminopropyl)methylamine and / or trimethylaminoethylethanolamine in a total amount of >0 to 20% by weight, advantageously 1 to 15% by weight, based on the total composition according to the invention.

[0053] That is, particularly preferred compositions according to the present invention comprise a polyisocyanate component, a polyol component, at least one zinc(II) carboxylate, at least one tertiary amine of formula (X), at least one nitrogen-containing compound V, and at least one additional trimerization catalyst.

[0054] A preferred embodiment of the present invention corresponds to the total mass fraction of zinc(II) carboxylates used in the finished polyurethane or polyisocyanurate foam as a whole, advantageously between 0.01 and 10% by weight, preferably between 0.1 and 5% by weight.

[0055] It is preferred if the composition according to the invention comprises water and / or at least one blowing agent, optionally at least one flame retardant and / or further additives that can be advantageously used in the production of polyurethane or polyisocyanurate foams. In addition to the zinc(II) carboxylate, other catalysts may also be contained.

[0056] Particularly preferred compositions according to the present invention comprise the following components: a) a polyisocyanate component; and b) a polyol component; and c) at least one zinc(II) carboxylate, wherein the zinc(II) carboxylate is used in stoichiometric form, i.e., in a molar ratio of Zn(II) to carboxylate of 1:2; d) Formula (X) [ka] [In the formula, m, in each occurrence, independently, is 1 or 2; A is O, S or NR e and R a , R b , R c , R d and R e are, in each occurrence, independently of one another, the same or different, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. and at least one tertiary amine of e) at least one foam stabilizer; f) at least one blowing agent; g) at least one nitrogen-containing compound V; h) at least one additional trimerization catalyst; i) optionally further additives, advantageously fillers and / or flame retardants; Contains:

[0057] As has already become apparent, the at least one zinc(II) carboxylate can be introduced into the composition according to the invention in various ways, for example in pure form, dissolved form or mixed with other components.

[0058] It is particularly preferable to introduce the at least one zinc(II) carboxylate into the composition according to the invention not in pure form but in the form of a zinc(II) carboxylate-containing preparation, which advantageously additionally comprises at least one nitrogen-containing compound V and can optionally contain at least one carrier medium.

[0059] A further subject of the present invention is therefore a preparation containing zinc(II) carboxylates suitable for catalysis in the production of PU or PIR foams, which preparation comprises i) at least one zinc(II) carboxylate in a total amount of 2 to 50% by weight, advantageously 5 to 45% by weight, particularly preferably 10 to 40% by weight, wherein the zinc(II) carboxylate is used in stoichiometric form, i.e. in a molar ratio of Zn(II) to carboxylate of 1:2; ii) optionally at least one carrier medium in a total amount of 0 to 95% by weight, advantageously 10 to 90% by weight, particularly preferably 20 to 70% by weight, iii) at least one nitrogen-containing compound V which has at least two N atoms and is a modified phenol, in a total amount of in each case from 1 to 90% by weight, advantageously from 2 to 60% by weight, particularly preferably from 5 to 50% by weight, based on the entire preparation; components (i) to (iii) together must advantageously represent at least 51% by weight, preferably at least 70% by weight and particularly preferably at least 80% by weight of the total preparation, Preferably in addition, iv) at least one tertiary amine as defined in claim 1 or 7 in an amount of 1 to 30% by weight, advantageously 2 to 25% by weight, particularly preferably 5 to 20% by weight, based on the total preparation, and v) optionally at least one additional trimerization catalyst, advantageously as defined in claim 8, again in each case in an amount of 1 to 90% by weight, advantageously 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the entire preparation; Including, Components i) to v) together should advantageously represent at least 52% by weight of the total preparation.

[0060] The zinc-containing preparations according to the invention allow, based on the respective preparation, higher zinc concentrations and / or lower viscosities than are known from the prior art.

[0061] Preferably, the zinc(II) carboxylate-containing preparation does not comprise an additional trimerization catalyst. In an alternative embodiment, it may be preferred that the zinc(II) carboxylate-containing preparation comprises, as a further component v), at least one additional trimerization catalyst, advantageously as defined in claim 8, again in each case preferably in an amount of 1 to 90% by weight, more preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the entire preparation, Components i) to v) together should advantageously represent at least 52% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight of the total preparation.

[0062] In order to provide a particularly suitable zinc(II) carboxylate-containing preparation that can be used without any complexities, it is preferable to use at least one carrier medium, for example, a mixture or solution that has little or no turbidity, i.e., advantageously not an emulsion, suspension or dispersion that may cause problems such as phase separation or sedimentation.

[0063] It is also preferred that the viscosity is as low as possible, so that, for example, the formulation does not impose special demands on pumps or other technical equipment for processing. Preferred viscosities are less than 10 Pa·s, preferably less than 8 Pa·s, and particularly preferably less than 6 Pa·s, measured at 25°C with a Brookfield viscometer.

[0064] A further subject of the present invention is a process for producing polyurethane or polyisocyanurate foams by reacting a polyol component with a polyisocyanate component, the process being carried out using a composition according to the invention as described above, advantageously according to one of claims 1 to 10, or advantageously using a zinc(II) carboxylate-containing preparation according to the invention, advantageously according to claim 11, When zinc(II) carboxylate-containing preparations are used, the total mass fraction of the zinc(II) carboxylate-containing preparations in the finished polyurethane foam is preferably 0.05 to 10% by weight, more preferably 0.2 to 5% by weight. The method is characterized by:

[0065] In addition to the zinc(II) carboxylate-containing preparations according to the invention which can be preferably used, a further catalyst can also be used, very preferably at least one tertiary amine of formula (X) as described above. The additional use of at least one trimerization catalyst as described above is also preferred.

[0066] The zinc(II) carboxylate-containing preparation comprises at least one carrier medium, and particularly preferably the zinc(II) carboxylate-containing preparation is fed to the reaction mixture for producing polyurethane or polyisocyanurate foams, advantageously PU or PIR rigid foams, in a carrier medium, advantageously a carrier medium comprising glycols, alkoxylates and / or oils of synthetic and / or natural origin.

[0067] A further subject of the present invention is a polyurethane or polyisocyanurate foam, preferably a polyurethane or polyisocyanurate rigid foam, obtainable by the process according to the invention, as described above.

[0068] A further subject of the present invention is the use of a composition according to any one of claims 1 to 10 or a preparation according to claim 11 in the production of polyurethane or polyisocyanurate foams, advantageously polyurethane or polyisocyanurate rigid foams, preferably for improving the use properties of polyurethane or polyisocyanurate foams, advantageously polyurethane or polyisocyanurate rigid foams, in particular for increasing the compression hardness (compression hardness can be measured in accordance with DIN EN ISO 844:2014-11) of polyurethane or polyisocyanurate foams, advantageously polyurethane or polyisocyanurate rigid foams, early compared to polyurethane or polyisocyanurate foams, advantageously polyurethane or polyisocyanurate rigid foams produced without zinc(II) carboxylate, the term "early" being understood to mean advantageously a time in the range from 3 minutes to 10 minutes 30 seconds, preferably 8 minutes, after the start of polymerization, advantageously by adding the polyisocyanate component.

[0069] Furthermore, a further subject of the present invention is the use of the polyurethane or polyisocyanurate foams according to the invention, preferably polyurethane or polyisocyanurate rigid foams, for thermal insulation purposes, preferably as insulating panels and / or insulation means and for cooling devices which have the polyurethane or polyisocyanurate foams according to the invention, preferably polyurethane or polyisocyanurate rigid foams, as insulation.

[0070] The individual, preferably usable components are described in further detail below.

[0071] Polyols suitable as the polyol component in the sense of the present invention are all organic compounds and preparations thereof that have at least two groups reactive with isocyanates, preferably OH groups. In particular, the polyol component comprises at least one organic compound containing at least two hydroxyl groups (-OH). Advantageously, a mixture of at least two suitable polyols can be used.

[0072] Preferred polyols are all polyether polyols and / or polyester polyols and / or hydroxyl-group-containing aliphatic polycarbonates, especially polyether polycarbonate polyols, and / or polyols of natural origin, so-called "natural oil polyols" (NOPs), which are commonly used for the production of polyurethane systems, in particular polyurethane coatings, polyurethane elastomers or even foams. Advantageously, the polyols have a functionality of 1.8 to 8 and a number-average molecular weight advantageously ranging from 500 to 15,000. Advantageously, polyols having an OH number ranging from 10 to 1,200 mg KOH / g are used.

[0073] Advantageously, polyether polyols can be used. These can be prepared by known methods, for example, by anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides, alkali alcoholates, or amines as catalysts, preferably with the addition of at least one starter molecule containing two or three reactive hydrogen atoms in bonded form, or by cationic polymerization of alkylene oxides in the presence of Lewis acids such as antimony pentachloride or boron trifluoride etherate, or by double metal cyanide catalysis. Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene group. Examples include tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, with ethylene oxide and 1,2-propylene oxide being preferred. The alkylene oxides can be used individually, cumulatively, in blocks, alternating successively, or as mixtures. In particular, compounds having at least two, preferably 2 to 8, hydroxyl groups, or compounds having at least two primary amino groups in the molecule, are used as starter molecules. Examples of starter molecules that can be used include water, dihydric, trihydric, or tetrahydric alcohols, such as ethylene glycol, propanediol-1,2 and -1,3, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, and the like, higher polyfunctional polyols, especially sugar compounds, such as glucose, sorbitol, mannitol, and sucrose, polyhydric phenols, resols, such as oligomeric condensation products of phenol and formaldehyde, and Mannich condensation products of phenol, formaldehyde, and dialkanolamines, as well as melamine, or amines, such as aniline, EDA, TDA, MDA, and PMDA, with TDA and PMDA being particularly preferred. The selection of suitable starter molecules depends on the respective application area of the resulting polyether polyol in polyurethane production.

[0074] Advantageously, polyester polyols can be used. These are based on esters of polyhydric aliphatic or aromatic carboxylic acids, preferably having 2 to 12 carbon atoms. Examples of aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, and fumaric acid. Examples of aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, and the isomeric naphthalenedicarboxylic acids. Polyester polyols are obtained by condensation of these polyhydric carboxylic acids with polyhydric alcohols, preferably diols or triols having 2 to 12, particularly preferably 2 to 6, carbon atoms, preferably trimethylolpropane and glycerol.

[0075] Advantageously, polyether polycarbonate polyols can be used. These are polyols containing carbon dioxide in the form of a carbonate bond. The use of carbon dioxide as a comonomer in alkylene oxide polymerization is particularly interesting from a commercial point of view, since carbon dioxide is formed in large quantities as a by-product in many processes in the chemical industry. Replacing part of the alkylene oxide in a polyol with carbon dioxide could significantly reduce the cost of polyol production. Furthermore, the use of CO2 as a comonomer is highly advantageous from an ecological perspective, since this reaction converts greenhouse gases into polymers. The production of polyether polycarbonate polyols by catalytically adding alkylene oxides and carbon dioxide to H-functional starting materials has been known for some time. Various catalyst systems can be used in this case: the first generation involved heterogeneous zinc or aluminum salts, as described, for example, in U.S. Pat. No. 3,900,424 or U.S. Pat. No. 3,953,383. Furthermore, mononuclear and binuclear metal complexes have been used in the copolymerization of CO with alkylene oxides (see, for example, WO 2010 / 028362, WO 2009 / 130470, WO 2013 / 022932, or WO 2011 / 163133). The most important class of catalyst systems for the copolymerization of carbon dioxide with alkylene oxides are double metal cyanide catalysts, also known as DMC catalysts (see, for example, U.S. Pat. No. 4,500,704, WO 2008 / 058913). Suitable alkylene oxides and H-functional starting materials are those also used in the preparation of carboxylate-free polyether polyols, as described above.

[0076] Advantageously, "natural oil polyols" (NOPs), which are polyols based on renewable raw materials, can be used. NOPs for the production of polyurethane foams are of increasing interest due to the long-term limited availability of fossil resources, i.e., oil, coal and gas, and rising crude oil prices, and have already been described many times in such applications (see, for example, WO 2005 / 033167; U.S. Patent Application Publications Nos. 2006 / 0293400, 2006 / 094227, 2004 / 096882, U.S. Patent Application Publication Nos. 2002 / 0103091, 2006 / 116456 and EP 1678232). Many of these polyols are currently commercially available from various manufacturers (see, for example, WO 2004 / 020497, US 2006 / 0229375, WO 2009 / 058367). Depending on the base raw material (e.g., soybean oil, palm oil, or castor oil) and subsequent processing, polyols with different property profiles can be obtained. In this case, it is essentially impossible to distinguish between two groups: a) polyols based on renewable raw materials that have been modified to the extent that they can be used 100% in the production of polyurethanes (see, for example, WO 2004 / 020497, US 2006 / 0229375); b) polyols based on renewable raw materials that, due to their processing and properties, can only be used to a certain extent to replace petrochemical-based polyols (see, for example, WO 2009 / 058367).

[0077] Another class of polyols that can be advantageously used are so-called filler polyols (polymer polyols). These are characterized by the presence of a solid organic filler, preferably with a solids content of 40% or more, dispersed in the polyol. Among these, SAN polyols, PHD polyols, and PIPA polyols can be used. SAN polyols are highly reactive polyols containing dispersed styrene / acrylonitrile (SAN)-based copolymers. PHD polyols are highly reactive polyols that also contain dispersed polyureas. PIPA polyols are highly reactive polyols that contain dispersed polyurethanes formed, for example, by the in situ reaction of isocyanates with alkanolamines in conventional polyols.

[0078] Preferably, polyols with a molar mass of less than 1000 g / mol can be used. Even more preferred are polyols with a functionality of less than 3. In particular, it is preferred not to use triols with a molar mass of more than 1000 g / mol. This corresponds in each case to a particularly preferred embodiment of the present invention.

[0079] Preferred ratios of isocyanate to polyol, expressed as a blend index, i.e., the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups), multiplied by 100, are in the range of 10 to 1000, preferably 40 to 700, more preferably 60 to 600, even more preferably 150 to 550, still more preferably 250 to 500, and very preferably 300 to 450. An index of 100 represents a 1:1 molar ratio of reactive groups.

[0080] Preferred are PIR formulations based on at least 70, 80 or 90% by weight polyester in the polyol component.

[0081] In a particularly preferred embodiment, the aromatic carboxylic acid-based polyester polyol is used in an amount of more than 50 parts by weight, preferably more than 70 parts by weight, based on 100 parts by weight of the total polyol component.

[0082] Preferred aromatic polyester polyols have an OH number in the range of 150 to 400 mg KOH / g, preferably 170 to 350, very preferably 180 to 300 mg KOH / g.

[0083] Advantageously, at least one organic polyisocyanate having at least two isocyanate functional groups is used as the polyisocyanate component.

[0084] Suitable polyisocyanates within the meaning of the present invention are all isocyanates containing at least two isocyanate groups. Advantageously, all known aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates can be used. Particularly preferably, isocyanates are used in an amount ranging from 60 to 200 mol %, based on the total of the isocyanate-consuming components.

[0085] Advantageously, a mixture of at least two suitable polyisocyanates can be used.

[0086] Illustratively, in this case, alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene diisocyanate-1,4, 2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate-1,4, and advantageously hexamethylene diisocyanate-1,6 (HMDI), cycloaliphatic diisocyanates, such as cyclohexane-1,3- and 1,4-diisocyanate, and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate), Examples of suitable diisocyanates include 2,4- and 2,6-hexahydrotoluylene diisocyanate (TDI) and mixtures of the corresponding isomers, and advantageously aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate (TDI) and mixtures of the corresponding isomers, naphthalene diisocyanate, diethyltoluene diisocyanate, mixtures of 2,4'- and 2,2'-diphenylmethane diisocyanate (MDI) with polyphenylpolymethylene polyisocyanate (crude MDI), and mixtures of crude MDI with toluene diisocyanate (TDI). The organic diisocyanates and polyisocyanates can be used alone or in the form of mixtures. Corresponding "oligomers" of diisocyanates can also be used (e.g., IPDI trimers based on isocyanurate, biuret, and / or uretdione formation). Furthermore, it is also possible to use prepolymers based on the isocyanates mentioned above.

[0087] It is also possible to use isocyanates which have been modified by the incorporation of urethane groups, uretdione groups, isocyanurate groups, allophanate groups and other groups, so-called modified isocyanates.

[0088] Particularly suitable and therefore particularly preferably applied organic polyisocyanates are the various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomer mixtures of different composition), 4,4'-diphenylmethane diisocyanate (MDI), so-called "crude MDI" or "polymeric MDI" (which contain, in addition to the 4,4'-isomer of MDI, the 2,4'- and 2,2'-isomers and higher cyclic products), and bicyclic products based on 2,4'- and 4,4'-isomer mixtures or prepolymers thereof, referred to as "pure MDI". Examples of particularly suitable isocyanates are described, for example, in EP 1712578, EP 1161474, WO 00 / 58383, U.S. Patent Application Publication No. 2007 / 0072951, EP 1678232 and WO 2005 / 085310, which are hereby incorporated by reference in their entirety.

[0089] In addition to the catalyst according to the invention, i.e., at least one zinc(II) carboxylate as described above, optional catalysts can be used: at least one tertiary amine of formula (X) and at least one additional trimerization catalyst, for example as described above, can also serve as possible catalysts.

[0090] Suitable, advantageously suitable additional optional catalysts within the meaning of the present invention are all compounds that can promote the reaction of isocyanates with OH, NH or other isocyanate-reactive groups, as well as with isocyanates themselves. In this case, conventional catalysts known from the prior art can be used, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and metal salts, preferably those of potassium, tin, iron and bismuth. In particular, mixtures of several components can be used as catalysts.

[0091] Substances known from the prior art, advantageously Si-free surfactants or even organomodified siloxanes, can be used as optional foam stabilizers.

[0092] The use of such substances in the production of PU or PIR foams is known. In this regard, in the context of the present invention, all compounds that assist foam production (stabilizing, cell regulating, cell opening, etc.) can optionally be used. These compounds are well known from the prior art.

[0093] Corresponding siloxanes that can be used in the context of the present invention are described, for example, in the following patent documents: CN 103665385, CN 103657518, CN 103055759, CN 103044687, US Patent Application Publication No. 2008 / 0125503, US Patent Application Publication No. 2015 / 0057384, EP 1520870, EP 1211279, EP 0867464, EP 0867465, EP 0275563. These aforementioned documents are incorporated herein by reference and are considered to form part of the disclosure of the present invention. The use of polyether-modified siloxanes is particularly preferred.

[0094] The use of blowing agents is optional, depending on the foaming process used. Chemical and physical blowing agents can be used. The choice of blowing agent here depends strongly on the nature of the system.

[0095] In a particularly preferred embodiment, no HFO is used as the blowing agent.

[0096] Depending on the amount of blowing agent used, high or low density foams can be produced, e.g., 5 kg / m 3 ~900kg / m 3 A foam having a density of 8 to 800 kg / m can be produced. 3, particularly preferably 10 to 600 kg / m 3 , especially 30 to 150 kg / m 3 is.

[0097] As a physical blowing agent, a corresponding compound with a suitable boiling point can be used.Chemical blowing agents that react with NCO groups and release gases such as water or formic acid can also be used.Examples of blowing agents include liquefied CO2, nitrogen, air, highly volatile liquids, such as hydrocarbons with 3, 4, or 5 carbon atoms, preferably cyclo-, iso-, and / or n-pentane, hydrofluorocarbons, preferably HFC245fa, HFC134a, and / or HFC365mfc, hydrochlorofluorocarbons, preferably HCFC141b, hydrofluoroolefins (HFOs) and / or hydrohaloolefins, such as 1234ze, 1234yf, 1233zd(E) or 1336mzz, oxygen-containing compounds, such as methyl formate, acetone, and / or dimethoxymethane, and / or hydrochlorocarbons, preferably dichloromethane and / or 1,2-dichloroethane.

[0098] The water content suitable within the meaning of the present invention depends on whether one or more blowing agents are used in addition to water. For purely water-blown foams, the value is preferably 1 to 20 pphp; if other blowing agents are also used, the amount used is preferably reduced to 0.1 to 5 pphp. The abbreviation pphp stands for parts per 100 parts of polyol, i.e., parts by weight per 100 parts by weight of polyol. This is a method commonly used in the industry to determine the amounts of components in foam formulations.

[0099] As further optional additives, it is possible to use advantageously all substances known from the prior art which are used in the production of polyurethanes, in particular polyurethane foams or PIR foams, such as crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, cell refining additives, cell opening agents, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, etc.

[0100] The process according to the invention for producing PU or PIR foams, preferably PU or PIR rigid foams, can be carried out according to known methods, for example by hand mixing or, preferably, by using a foaming machine. When a foaming process is carried out, high-pressure or low-pressure machines can be used. The process according to the invention can be carried out either discontinuously or continuously.

[0101] Preferred polyurethane or polyisocyanurate foam formulations within the meaning of the present invention have a density of 5 to 900 kg / m 3 and advantageously have the compositions listed in Table 1.

[0102] [Table 1]

[0103] For further preferred embodiments and configurations of the method according to the invention, reference is also made to the explanations already given above in connection with the composition according to the invention.

[0104] As already mentioned, a further subject of the present invention is a PU or PIR foam, advantageously a PU or PIR rigid foam, obtainable by the process described above.

[0105] PU or PIR rigid foam is an established technical term. The fundamental difference between soft and rigid foams is that soft foams exhibit elastic behavior, and therefore deformation is reversible. In contrast, rigid foams are permanently deformed. In the context of the present invention, PU or PIR rigid foam is understood to mean, in particular, foams according to DIN 7726:1982-05, which have a compression hardness according to DIN 53 421 / DIN EN ISO 604:2003-12 of preferably ≥ 20 kPa, preferably ≥ 80 kPa, more preferably ≥ 100 kPa, even more preferably ≥ 150 kPa, and particularly preferably ≥ 180 kPa. Furthermore, PU or PIR rigid foams according to DIN EN ISO 4590:2016-12 advantageously have a closed cell content of more than 50%, preferably more than 80%, and particularly preferably more than 90%. PU or PIR rigid foams are especially preferred in the context of the present invention as a whole.

[0106] Advantageously, the polyurethane or PIR foam has a strength of preferably 5 to 900 kg / m 3 , more preferably 8 to 800, and particularly preferably 10 to 600 kg / m 3 , especially 30 to 150 kg / m 3 It has a density of

[0107] Advantageously, a predominantly closed-cell foam can be produced, advantageously with a closed-cell content of >80%, preferably >90%.

[0108] The PU or PIR foams according to the invention can preferably be used as or for the production of thermal insulation, advantageously as insulation panels, refrigerators, insulating foams, headliners, packaging foams or spray foams.

[0109] The PU or PIR foams according to the invention can be used advantageously, in particular as insulation in the cold storage, refrigeration equipment and household appliances industry, e.g. in the manufacture of insulating panels for roofs and walls, in containers and warehouses for frozen goods and for refrigeration and freezing equipment.

[0110] Further preferred fields of application are vehicle construction, in particular vehicle headliners, bodywork parts, interior trim, refrigerated vehicles, large containers, transport pallets, the manufacture of packaging laminates, the furniture industry, e.g. for furniture parts, doors, linings, electronics applications.

[0111] Advantageously, the PU or PIR foams (polyurethane or polyisocyanurate foams) according to the invention can be used as thermal insulation for cooling devices.

[0112] A further subject of the present invention is the use of PU or PIR foams as insulation, as insulation panels, as spray foams, as one-component foams in refrigeration technology, refrigeration cabinets, in the construction, automotive, shipbuilding and / or electronics sectors.

[0113] The present invention will be further illustrated by the following examples without limiting the present invention in any way. When a range, a general formula, or a class of compounds is indicated, it is intended to include not only the corresponding range or group of compounds explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by extracting the individual values (ranges) or compounds. When a document is cited in the context of this specification, its content is considered to be part of the disclosure of the present invention in its entirety, especially with regard to the issues in the context in which the document is cited. Unless otherwise specified, percentages are expressed in weight %. When average values are indicated, they are weight average values unless otherwise specified. When parameters determined by measurement are indicated, the measurements were carried out at a temperature of 25°C and at normal pressure (preferably 101325 Pa) unless otherwise specified.

[0114] Working Example: The following ingredients were used: Stepanpol® PS 2352: Polyester polyol from Stepan Daltolac® 471: Huntsman polyether polyol TCPP: Tris(2-chloroisopropyl) phosphate from ICL KOSMOS® 75 from Evonik Operations GmbH, a catalyst based on potassium octoate KOSMOS® 33 MEG from Evonik Operations GmbH, a potassium acetate-based catalyst POLYCAT® 5, an amine catalyst, from Evonik Operations GmbH POLYCAT® DP, an amine catalyst, from Evonik Operations GmbH POLYCAT® 9, an amine catalyst, from Evonik Operations GmbH POLYCAT® 206, an amine catalyst, from Evonik Operations GmbH POLYCAT® 77, an amine catalyst, from Evonik Operations GmbH TEGOAMIN® BDE, an amine catalyst, from Evonik Operations GmbH DABCO® T, an amine catalyst from Evonik Operations GmbH DABCO® NE 300, an amine catalyst, from Evonik Operations GmbH Amine No. 1: consists of N,N'-diisopropyl-N,N'-dimethyl-bis(aminoethyl) ether, N,N,N'-triisopropyl-N'-methyl-bis(aminoethyl) ether as described in Example 4 of WO 2023 / 043980 as structures V and VI. Amine No. 2: consists of N,N'-diisobutyl-N,N'-dimethyl-bis(aminoethyl) ether as described in Example 8 of WO 2023 / 043980 as structure XVII.

[0115] MDI (44V20): Covestro's Desmodur® 44V20L, diphenylmethane-4,4'-diisocyanate (MDI) and its isomers and higher functional homologs Tegostab® B 8460 from Evonik Operations GmbH, a foam stabilizing surfactant.

[0116] Preparation of zinc-containing preparations: Various preparations are produced which can then be combined by foaming to obtain a composition according to the invention (or not according to the invention).

[0117] The corresponding components can be preblended or added as individual components to the reaction mixture to be foamed.

[0118] The zinc-containing examples are examples according to the present invention.

[0119] Raw materials for the production of zinc-containing preparations: Zn-Ac: Zinc acetate dihydrate (available from Sigma-Aldrich) Zn-Riz: Zinc ricinoleate (available from Evonik as TEGODEO® PY 88 G) EDA-PO: N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (described in WO 2022 / 218657 and available from BASF) V1: 2,4,6-tris[(dimethylamino)methyl]phenol (available from Sigma-Aldrich) DEG: diethylene glycol.

[0120] Preparation of the formulation: Liquid components such as DEG, EDA-PO or V1 were charged first, followed by the addition of zinc salt Zn-Ac or Zn-Riz, and the mixture was stirred at about 50°C to obtain a clear mixture.

[0121] Table 1 summarizes the formulation compositions, showing the parts by weight of the individual components.

[0122] The viscosity was measured at room temperature of 23°C using a Brookfield viscometer.

[0123] [Table 2]

[0124] With V1 it was possible to produce mixtures with higher zinc content that were less viscous and less crystallized than with EDA-PO.

[0125] Thus, at 40% zinc acetate, the viscosity with EDA-PO was greater than 500 Pa·s (composition B) and with V1 was approximately 200 Pa·s (formulation A).

[0126] The same trend was observed when zinc ricinoleate was used at >200 Pa·s (composition D) and 60 Pa·s (preparation C).

[0127] Such high viscosities are practically impossible to process, but the advantage of V1, which contributes to low viscosity, is recognized.

[0128] For good flowability, a viscosity of less than 10,000 mPa·s, better still less than 3,000 mPa·s, is expedient.

[0129] The advantage of V1 over EDA-PO is similarly evident in formulations such as F and G. A liquid product with a viscosity of 2100 mPa·s is much easier to process than a material with a viscosity of 8800 mPa·s.

[0130] By using V1 as a blend component, it was possible to achieve a viscosity of 7000 mPa·s, as can be seen from composition J, where zinc acetate dihydrate accounts for 45% of the blend, i.e., a lower viscosity than blends such as G, which used 30% zinc acetate dihydrate.

[0131] Furthermore, formulation L also showed precipitation after a few days, despite a very low viscosity of less than 1000 mPa·s. In contrast, formulation K, which contained V1 instead of EPA-PO, remained stable and clearly soluble for several weeks.

[0132] This clearly demonstrates the superiority of the preparation according to the invention over previously known compositions.

[0133] Additional trimerization catalysts that may be part of the composition: Component M: Potassium acetate based trimerization catalyst: Kosmos® 33 MEG from Evonik Operations GmbH. Component N: Potassium octoate based trimerization catalyst: Kosmos® 75 from Evonik Operations GmbH. Component O: Potassium neodecanoate based trimerization catalyst: Kosmos® K 65 LO from Evonik Operations GmbH. Component P: Potassium propionate-based trimerization catalyst: KPROP 14 from Schill & Seilacher

[0134] PU and PIR foam manufacturing: Foaming was carried out by manual mixing. For this purpose, the compound according to the present invention, polyol, flame retardant, catalyst according to the present invention or a catalyst not according to the present invention, water, siloxane surfactant, and blowing agent 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 reweighed and replenished. Subsequently, isocyanate (MDI) was added, and the reaction mixture was stirred for 5 seconds at 3000 rpm using the described stirrer.

[0135] The reaction mixture was placed in a suitable beaker with a diameter of 20 cm at the top to obtain a free-rising foam. The volume of the reaction mixture was selected so that the tip of the foam dome was 10-15 cm above the top of the beaker.

[0136] During foaming, the gel time was measured to evaluate the effect of the catalyst on the foaming rate.

[0137] After 2 minutes, the foam dome was cut off at the top of the beaker, leaving a round foam surface on which the foam indentation hardness was measured.

[0138] Indentation hardness measurement method: For this purpose, the force required to press a 4 cm diameter die into the foam was measured. The pressing force was measured at a pressing depth of 5 mm. Measurements were taken at 90 second intervals, i.e., after 3 minutes, 5.5 minutes, 8 minutes, and 10.5 minutes, with the die being pressed into the cut surface in a circular configuration at four different points.

[0139] Compression hardness measurement method The compression hardness of the foam is measured according to DIN EN ISO 844:2014-11 using cube-shaped test specimens with a side length of 5 cm up to a compression of 10% (the maximum compressive stress occurring in this measuring range is indicated).

[0140] Table 2 summarizes the foam formulations used (Formulation 1 to Formulation 9), with the parts by weight of each of the components shown.

[0141] These formulations were then further mixed with additional catalysts corresponding to compositions according to the invention or not according to the invention, and the results are summarized in Table 3.

[0142] [Table 3-1] [Table 3-2]

[0143] Foaming results Table 3: Summary of foam testing using various catalysts and foam formulations The components used (components A to P according to the composition according to the invention and the composition not according to the invention), their amounts (parts by weight) (called Dos.) and the formulation used from Table 2 are given, as well as the gel time (GZ) (in seconds) and the indentation hardness (in Newtons) after the specified time (in minutes) (after mixing with MDI).

[0144] A catalyst composition ZZ which does not contain V1 or which does not contain zinc is not according to the invention.

[0145] The trimerization catalyst, amine, and ZZ components can also be premixed. For clarity, in the examples herein, the components such as the tertiary amine, zinc salt, nitrogen-containing compound V1), and trimerization catalyst are shown separately via the formulation in Table 2 and the additional components in Table 3.

[0146] [Table 4-1] [Table 4-2]

[0147] Example 1 achieved a significantly higher indentation hardness than Comparative Example 1, which did not use a zinc-containing composition according to the present invention.

[0148] The advantages of the composition according to the invention are also evident in Comparative Example 2. In combination with L (not according to the invention), 2 parts of M must be used to achieve the same gel time and full cure compared to Example 1. Here, 1.4 parts of M are sufficient to achieve a gel time of 60 seconds and the same full cure / indentation force.

[0149] Therefore, K is more efficient as a catalyst than L.

[0150] In Example 7, a gel time of 60 seconds and improved indentation hardness was achieved using only 0.3 parts J and 1.2 parts Kosmos 33.

[0151] This demonstrates the advantage of the zinc-phenol combination in that it provides a more efficient catalyst for full cure.

[0152] The desired effect on foam hardness was also achieved with P and O at low dosages of J, as can be seen from Examples 8 and 9.

[0153] Further testing with different formulations shows the same effect.

[0154] This demonstrates that the present invention can improve foam cure in a wide variety of formulations, in some cases even extending gel time or even maintaining a constant gel time to further improve the positive effect on full cure.

[0155] This is a great advantage since a small effect on gel time means that the processability of the reaction mixture is maintained, e.g., with regard to the flowability of the foaming mixture, while at the same time the hardening of the foam is accelerated.

[0156] As can be clearly seen from the tests, the zinc-containing preparations according to the invention or the compositions according to the invention lead to an improved hardening of the foam. The very good results described above for the indentation hardness of the foams according to the invention are in agreement with the results for the compression hardness.

Claims

1. 1. A composition for producing a polyurethane or polyisocyanurate foam, comprising: a) a polyisocyanate component; b) a polyol component; and c) at least one zinc(II) carboxylate, wherein the zinc(II) carboxylate is used in stoichiometric form, i.e., in a molar ratio of Zn(II) to carboxylate of 1:2; d) Formula (X) 【Chemical 1】 [In the formula, m is, in each occurrence, independently 1 or 2; A is O, S or N-R ｅ and R ａ , R ｂ , R ｃ , R ｄ and R ｅ are, in each occurrence, independently of one another, the same or different, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. and at least one tertiary amine of e) optionally at least one foam stabilizer; f) optionally at least one blowing agent; In a composition comprising: The composition additionally comprises: g) at least one nitrogen-containing compound V having at least two N atoms and being a modified phenol A composition comprising:

2. 2. The composition according to claim 1, wherein the at least one zinc(II) carboxylate is selected from the group consisting of zinc(II) acetate, zinc(II) propionate, zinc(II) pivalate, zinc(II) 2-ethylhexanoate (zinc(II) octanoate), zinc(II) isononanoate (zinc(II) 3,5,5-trimethylhexanoate), zinc(II) neodecanoate, zinc(II) ricinoleate, zinc(II) palmitate, zinc(II) stearate, zinc(II) oleate, zinc(II) laurate, zinc(II) naphthenate, zinc(II) benzoate, zinc(II) lactate, zinc(II) glycinate, zinc(II) hippurate, zinc(II) citrate, and zinc(II) soap, the use of zinc(II) acetate and / or zinc(II) ricinoleate being highly preferred.

3. said at least one nitrogen-containing compound V being 【Chemistry 2】 [In the formula, R = in each occurrence, independently of one another, H or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic and optionally containing heteroatoms such as O or N; R １ = in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic.

3. The composition according to claim 1 or 2, characterized in that it is selected from the group consisting of:

4. the at least one nitrogen-containing compound V is prepared by reacting a phenol with an aldehyde, preferably an aldehyde having 1 to 20 carbon atoms, preferably formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, cinnamaldehyde, trimethylhexanal, pelargonaldehyde, acrolein and / or furfural, and an amine in the sense of the Mannich reaction, As starting materials, advantageously modified phenols having at least one substituent on the aromatic nucleus, such as cresols, xylenols, propylphenols, styrylphenols, alkylphenols and / or cardanols, can also be used, as well as resorcinol- and / or catechol-based structures, which can advantageously be used as modified phenols; Preferably, the at least one nitrogen-containing compound V is a compound selected from the group consisting of phenol, formaldehyde and advantageously dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethanolamine, diethanolamine, trimethylethanediamine, isophoronediamine, dimethylpropylamine, diethylenetriamine, triethylenetetramine, methylhydroxyethylamine, dimethylaminopropylamine, pyrrolidine, pyrrole, morpholine and / or piperazine, N,N-dimethyl-2-(2-methylaminoethoxy)ethane-1 N,N'-diisopropyl-N-methyl-bis(aminoethyl)ether and N,N'-diisobutyl-N-methyl-bis(aminoethyl)ether, and at least one primary or secondary amine selected from the group consisting of N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, diisopropyldimethyldiethylenetriamine, bis(dimethylaminopropyl)amine, trimethylaminoethylethanolamine, N,N'-diisopropyl-N-methyl-bis(aminoethyl)ether, and again, modified phenols can be used as starting materials.

4. The composition according to claim 1, wherein the composition is a hydroxybenzoate.

5. said at least one nitrogen-containing compound V being 【Chemistry 3-1】 【Chemistry 3-2】 [In the formula, R = in each occurrence, independently of one another, H or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic and optionally containing heteroatoms such as O or N; R １ = in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic. is selected from the group consisting of Particularly preferred are: 【Chemistry 4】 [In the formula, R = in each occurrence, independently of one another, H or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic and optionally containing heteroatoms such as O or N; R １ = in each case, independently of one another, H or a linear, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which may be saturated, unsaturated or aromatic. The use of Highly preferred is Use of 2,6-bis[(dimethylamino)methyl]-4-methyl-phenol, 2,4,6-tris[(dimethylamino)methyl]cardanol, 2,4,6-tris[(dimethylamino)methyl]phenol, 2,6-bis[(dimethylamino)methyl]cardanol, 2,4,6-tris-[(hydroxyethylamino)methyl]phenol, 2,4,6-tris[(hydroxypropylamino)methyl]phenol and / or 2,4,6-tris[(dimethylaminopropylamino)methyl]phenol.

5. The composition according to claim 1, wherein the composition is a hydroxybenzoate.

6. 6. The composition according to claim 1, wherein the total amount of zinc(II) carboxylate and the total amount of nitrogen-containing compound V are present in a ratio of 1:0.5 to 1:5 parts by weight.

7. 7. The composition of claim 1, wherein the at least one tertiary amine of formula (X) is selected from the group consisting of pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl)ether, tris-(dimethylaminopropyl)amine, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, diisopropyltrimethyldiethylenetriamine, bis-(dimethylaminopropyl)methylamine, trimethylaminoethylethanolamine, bis-(2-isopropylmethylaminoethyl)ether, bis-(2-isobutylmethylaminoethyl)ether, N,N'-diisopropyl-N,N'-dimethyl-bis(aminoethyl)ether, N,N,N'-triisopropyl-N'-methyl-bis(aminoethyl)ether and N,N'-diisobutyl-N,N'-dimethyl-bis(aminoethyl)ether.

8. Furthermore, they are advantageously selected from ammonium, potassium and / or other alkali or alkaline earth metal carboxylates, Preferably selected from potassium carboxylates and carboxylates of ammonium cations, very preferably potassium acetate, potassium formate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium 2-ethylhexanoate, potassium pivalate, potassium octanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium decanoate, potassium ricinoleate, potassium stearate, potassium neodecanoate, and also tetramethylammonium, tetraethylammonium, triethylmethylammonium, tetrapropylammonium, tetrabutylammonium, dimethyldiallylammonium, trimethyl-(2-hydroxypropyl)ammonium, triethyl-(2-hydroxypropyl)ammonium, trimethyl ...ethyl-(2-hydroxypropyl)ammonium, triethyl-(2-hydroxypropyl)ammonium, triethyl-(2-hydroxypropyl)ammonium, triethyl and at least one additional trimerization catalyst selected from the group consisting of carboxylates of tripropyl-(2-hydroxypropyl)ammonium, tributyl-(2-hydroxypropyl)ammonium, trimethyl-(2-hydroxyethyl)ammonium, triethyl-(2-hydroxyethyl)ammonium, tripropyl-(2-hydroxyethyl)ammonium, tributyl-(2-hydroxyethyl)ammonium, dimethylbenzyl-(2-hydroxyethyl)ammonium and / or dimethylbenzyl-(2-hydroxypropyl)ammonium, wherein the carboxylate is advantageously acetate, propionate, butanoate, pentanoate, pivalate, octanoate, nonanoate, decanoate, neodecanoate, ricinoleate and / or stearate.

8. The composition according to claim 1, wherein the composition is a hydroxybenzoate.

9. 9. The composition according to claim 1, wherein 70 to 100% by weight of the total polyol component is composed of an aromatic polyester polyol having an OH number of 150 to 400 mg KOH / g, preferably 170 to 350 mg KOH / g, and very preferably 180 to 300 mg KOH / g.

10. 10. The composition according to any one of claims 1 to 9, characterized in that it comprises at least one physical blowing agent advantageously selected from the group consisting of hydrocarbons having 3, 4 and / or 5 carbon atoms, preferably selected from the group consisting of n-butane, cyclo-, iso- and n-pentane.

11. A zinc(II) carboxylate-containing preparation suitable for catalysis in the production of PU or PIR foams, i) at least one zinc(II) carboxylate, preferably as defined in claim 1 or 2, in a total amount of 2 to 50% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight, with the proviso that the zinc(II) carboxylate contained is used in stoichiometric form, i.e. in a molar ratio of Zn(II) to carboxylate of 1:2, ii) optionally at least one carrier medium in a total amount of 0 to 95% by weight, advantageously 10 to 90% by weight, particularly preferably 20 to 70% by weight, iii) at least one nitrogen-containing compound V, which has at least two N atoms and is a modified phenol, preferably as defined in claims 3 to 5, in a total amount of in each case from 1 to 90% by weight, preferably from 2 to 60% by weight, particularly preferably from 5 to 50% by weight, based on the entire preparation; wherein the components (i) to (iii) together advantageously must represent at least 51% by weight of the total formulation, Advantageously, additionally, iv) at least one tertiary amine as defined in claim 1 or 7 in an amount of 1 to 30% by weight, advantageously 2 to 25% by weight, particularly preferably 5 to 20% by weight, v) optionally at least one additional trimerization catalyst, preferably as defined in claim 8, again in each case in an amount of 1 to 90% by weight, preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the preparation as a whole; Including, The components i) to v) together should preferably represent at least 52% by weight of the total formulation. A preparation characterized in that

12. 1. A process for producing a polyurethane or polyisocyanurate foam by reacting a polyol component with a polyisocyanate component, comprising: The method is carried out using a composition according to any one of claims 1 to 10 or using a zinc(II) carboxylate-containing preparation according to claim 11, When using a zinc(II) carboxylate-containing preparation according to claim 11, it is preferred that the total mass fraction of the zinc(II) carboxylate-containing preparation in the finished polyurethane foam is 0.05 to 10% by weight, preferably 0.2 to 5% by weight. A method characterized by:

13. Use of a composition according to any one of claims 1 to 10 or a preparation according to claim 11 in the production of polyurethane or polyisocyanurate foams, advantageously polyurethane or polyisocyanurate rigid foams, preferably for improving the use properties of polyurethane or polyisocyanurate foams, in particular for an earlier increase in the compression hardness of polyurethane or polyisocyanurate foams (compression hardness can be determined in accordance with DIN EN ISO 844:2014-11) compared to polyurethane or polyisocyanurate foams produced without zinc(II) carboxylate.

14. A polyurethane or polyisocyanurate foam obtainable by the process of claim 13.

15. 15. Use of the polyurethane or polyisocyanurate foams according to claim 14 for thermal insulation purposes, preferably as insulating panels and means and for cooling devices.

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