Manganese- and iron-containing catalysts with imine ligands for the synthesis of polyurethanes - Patent Application 20070122997

Abstract

The present invention relates to a process for producing polyurethanes, comprising the application of a manganese-containing catalyst and an iron-containing catalyst, the catalyst comprising at least an imine ligand and defined by general formula (I). The catalyst comprises a salicylic aldehyde-based imine according to general formula (II) as the imine ligand. The present invention further relates to a polyol component comprising the catalyst according to the present invention, and to polyurethanes produced according to such a process.

Description

[Technical Field]

[0001] The present invention relates to a process for producing polyurethanes, comprising the application of a manganese-containing catalyst and an iron-containing catalyst, the catalyst comprising at least one imine ligand and defined by general formula (I). The catalyst comprises a salicylic aldehyde-based imine according to general formula (II) as the imine ligand. The present invention further relates to a polyol component comprising the catalyst according to the present invention, and to polyurethanes produced according to such a process.

[0002] Polyurethanes are important technical polymers used in applications such as foams, elastomers, lenses, packaging, insulation, footwear, textiles, synthetic leather, coatings, paints, and sealants. Polyurethanes are essentially produced by the polyaddition reaction of polyols with polyisocyanates. This reaction is generally carried out in the presence of a catalyst. For the general composition of polyurethanes and the catalysts used, see Ullmann's Encyclopedia of Industrial Chemistry, Polyurethanes, 2012, DOI:10.1002 / 14356007.a21_665.pub2. Today, tin-based catalysts are still frequently used and have demonstrated very good performance in the formation of polyurethanes, such as polyurethane foams. However, the use of such tin-containing catalysts, especially alkyl-tin compounds, should be avoided due to their toxicity. Therefore, alternative tin-free catalysts that exhibit similar performance are highly desirable.

[0003] Polymer Journal, 2002, 23, 298-301, describes the use of Mn- and Fe-acetylacetonate catalysts as catalysts for the synthesis of polyurethanes. With additional ligands, the Mn- and Fe-acetylacetonate catalysts perform substantially worse than the benchmark tin catalyst dibutyltin dilaurate (DBTDL). Although the addition of the amine ligand triethylenediamine yields Mn- and Fe-acetylacetonate catalysts with higher activity, the activity is still significantly lower than that of the benchmark tin catalyst DBTDL. It is also unclear whether the Fe- and Mn-catalysts produced in this way are hydrolytically stable. Hydrolytic stability is an important property for polyurethane catalysts, as they are often exposed to water in the polyol component, for example, for the synthesis of water-blown polyurethane foams.

[0004] U.S. Patent Application Publication No. 2007 / 0010644 discloses the use of Fe-acetylacetonate in combination with an amine cocatalyst, such as dimethylaminopropylurea, for the synthesis of polyurethanes. The catalyst system has catalytic activity comparable to that of common tin catalysts. However, a drawback of this system is that it does not catalyze the foaming reaction in the presence of water, which is crucial for the synthesis of water-blown polyurethane foams. The extent to which this catalyst system is hydrolytically stable when stored in a water-containing polyol component is not disclosed.

[0005] U.S. Patent No. 5,733,945 discloses the use of Fe(III) acetylacetonate and additional acetylacetone, but does not disclose other ligands as catalysts. U.S. Patent No. 5,733,945 discloses that the less additional acetylacetone present, the faster the catalyst acts and the higher the temperature must be to remove excess acetylacetone. The hydrolytic stability of this catalyst system when stored in a water-containing polyol component is not disclosed.

[0006] WO 2018054725 discloses the use of [Mn(salen)](OAc) as a catalyst for the production of coatings. According to WO 2018054725, OAc is used as a counterion, not as a ligand. Furthermore, no method for producing polyurethane foams is disclosed. Compared to the production of solid coatings, the foaming reaction between isocyanate and water as a blowing agent and the gelling reaction between isocyanate and polyol must be controlled in the production of foams, otherwise the foam will collapse.

[0007] U.S. Patent Application Publication No. 2020 / 0332052 discloses organometallic compounds as hydrolysis and condensation catalysts for use in synthesizing polyurethane polymers containing at least one alkoxysilyl-polyurethane unit and at least one mercapto-containing compound. The catalysts include, inter alia, titanium, aluminum, tin, zirconium, iron, cobalt, manganese, nickel, bismuth, and zinc, particularly tin-based catalysts with organic ligands. These catalysts can be obtained from various metals, such as Ti, Al, Sn, Zr, Fe, Co, Mn, Ni, Bi, and Zn, along with acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetonimine, bisacetylaceton-alkylenedimine, salicylaldehyde imine, and the like. It is not disclosed whether such catalyst systems are suitable for synthesizing general polyurethanes, particularly polyurethane foams, that do not contain mercapto compounds. Moreover, suitable combinations of salicylaldehyde imines with dedicated metals and other ligands on the metals are not further specified or disclosed therein.

[0008] Toshio Nakamura, Etsuko Kuranuki, Kenshin Niwa, Manabu Fujiwara, and Takayuki Matsushita, "Preparation, Structures and Properties of Novel Mono- and Trinuclear Iron(III) Complexes with Mixed Ligands," Chemistry Letters 29(2), pp. 248-249, discloses the preparation of mono- and trinuclear iron(III) complexes.

[0009] German Patent No. 102009047038 discloses complexes of iron, molybdenum, manganese and / or tungsten with imine diols and their use as bleach catalysts in detergent solutions.

[0010] It was therefore an object of the present invention to provide a process for the preparation of polyurethanes using catalysts that are not characterized by the drawbacks of currently known systems and that exhibit in particular high efficiency, low toxicity and high stability in the presence of water.

[0011] This object is achieved by a method for producing polyurethanes, which comprises mixing (a) a polyisocyanate, (b) a polymeric compound having groups reactive towards isocyanates, (c) a catalyst, a manganese or iron-containing catalyst (c1), and optionally (d) a blowing agent, (e) a chain extender and / or crosslinker, and (f) an auxiliary to obtain a reaction mixture, and reacting the reaction mixture to obtain polyurethanes, wherein the manganese or iron-containing catalyst (c1) is a compound according to the general formula (I): [ka] Here, the variables are defined as follows: M is selected from manganese(II), manganese(III), iron(II) or iron(III); m is an integer from 0 to 2, n is an integer from 0 to 2, o is 0 or 1, p is 0 or 1, if o or p is 0, then both o and p are 0; q is 0 or 1, R 1 and R 2 are independently selected from the group consisting of F, Cl, Br, OH, CN, NH, NO, and hydrocarbon-containing residues; R 1 and R 2 may be joined to form a ring as a cycloaliphatic or aromatic ring; R 3 is selected from H and hydrocarbon-containing residues; R 4 and R 7 are independently selected from the group consisting of H, F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon-containing residues. R 4 and R 7 may be joined to form a ring as a cycloaliphatic or aromatic ring; R 5 and R 6 are independently selected from the group consisting of H, F, Cl, Br, OH, CN, NH, NO, and hydrocarbon-containing residues; If o is 0, R 6 and R 7 can both be O, X is O, S, or NR 8 , PR 8 is selected from R 8 is selected from H and hydrocarbon-containing residues; p is 0 and X is NR 8 If NR 8 The group is an R 7 may be double bonded to L is selected from the anionic organic ligands of the acetylacetonate or carboxylate class; Solv is a neutral ligand, Hydrocarbon-containing residues include C1-C 10 -alkyl, C3-C10 -cycloalkyl, C3-C containing at least one heteroatom selected from N, O and S 10 -heterocyclyl, C5-C 14 -aryl, C5-C containing at least one heteroatom selected from N, O and S 10 -heteroaryl, wherein the C1-C 10 -Alkyl C3-C 10 -Cycloalkyl, C3-C 10 -heterocyclyl, C5-C 14 -aryl, C5-C 10 -heteroaryl is optionally selected from F, Cl, Br, OH, CN, NH and C-C 10 -alkyl.

[0012] For purposes of the present invention, polyurethanes include all known polyisocyanate polyaddition products. These include addition products made from isocyanates and alcohols, as well as modified polyurethanes that may contain isocyanurate structures, allophanate structures, urea structures, carbodiimide structures, uretonimine structures, biuret structures, and other isocyanate addition products. These polyurethanes of the present invention particularly include compact polyisocyanate polyaddition products, such as thermoset resins, and foams based on polyisocyanate polyaddition products, such as flexible foams, semi-rigid foams, rigid foams, and integral foams, as well as polyurethane coatings and binders. For purposes of the present invention, the term polyurethane also encompasses polymer blends containing polyurethane and other polymers, as well as foams made from these polymer blends. The polyurethanes of the present invention are preferably polyurethane foams or compact polyurethanes that contain no polymers other than the polyurethane components (a) to (g) described below.

[0013] For the purposes of the present invention, the expression polyurethane foam means a foam according to DIN 7726. The compressive stress or compressive strength at 10% compression of the flexible polyurethane foams of the present invention according to DIN 53 421 / DIN EN ISO 604, respectively, is here 15 kPa or less, preferably 1 to 14 kPa, in particular 4 to 14 kPa. The compressive stress at 10% compression of the semirigid polyurethane foams of the present invention according to DIN 53 421 / DIN EN ISO 604 is more than 15 kPa and less than 80 kPa. The open-cell content of the semirigid and flexible polyurethane foams of the present invention according to DIN ISO 4590 is preferably more than 85%, particularly preferably more than 90%. Further details regarding the flexible and semi-rigid polyurethane foams of the present invention can be found in "Polyurethane Handbook [Plastics handbook], volume 7, Polyurethane [polyurethanes]," Hanser / Gardener publications, 2nd edition 1993, chapter 5.

[0014] The rigid polyurethane foams of the present invention have a compressive stress at 10% compression of at least 80 kPa, preferably at least 120 kPa, particularly preferably at least 150 kPa. Furthermore, the rigid polyurethane foams have a closed cell content according to DIN ISO 4590 of more than 80%, preferably more than 90%. Further details regarding the rigid polyurethane foams of the present invention can be found in "Polyurethane Handbook [Plastics handbook], volume 7, Polyurethane [polyurethanes]", Hanser / Gardener publications, 2nd edition 1993, chapter 6.

[0015] For the purposes of the present invention, the expression elastomeric polyurethane foams means polyurethane foams according to DIN 7726, which exhibit a residual deformation of less than 2% of their original thickness after 10 minutes of a short deformation of their thickness of 50% in accordance with DIN 53 577. The materials here can be rigid, semi-rigid or flexible polyurethane foams.

[0016] Integral polyurethane foams are polyurethane foams according to DIN 7726 in which the density of the peripheral zone is higher than that of the core as a result of the molding process, where the overall envelope density averaged over the core and peripheral zone is preferably greater than 100 g / L. Again, integral polyurethane foams for the purposes of the present invention can be rigid, semi-rigid, or flexible polyurethane foams. Further details regarding the integral polyurethane foams of the present invention can be found in the "Polyurethane Handbook," Hanser / Gardener publications, 2nd Edition 1993, Chapter 7.

[0017] In one embodiment of the present invention, the polyurethane is a compact polyurethane having a density of preferably more than 850 g / L, preferably 900 to 1400 g / L, particularly preferably 1000 to 1300 g / L. Here, the compact polyurethane is obtained without the addition of a blowing agent. For the purposes of the present invention, a small amount of a blowing agent, such as water, contained in the polyol as a result of the production process is not considered to mean the addition of a blowing agent. The reaction mixture for producing the compact polyurethane preferably contains less than 0.2 wt. %, particularly preferably less than 0.1 wt. %, and in particular less than 0.05 wt. % water.

[0018] In a preferred embodiment, the polyurethane of the present invention is a polyurethane foam having an average density of 10 to 850 g / L, preferably a semi-rigid polyurethane foam, a flexible polyurethane foam, or a rigid polyurethane foam, and particularly preferably an elastomeric flexible polyurethane foam, a semi-rigid polyurethane foam, or an elastomeric integral polyurethane foam. The density of the elastomeric integral polyurethane foam averaged over the core and peripheral zone is preferably 150 to 500 g / L. The average density of the flexible polyurethane foam is preferably 10 to 100 g / L. The average density of the semi-rigid polyurethane foam is preferably 70 to 150 g / L.

[0019] The polyurethanes of the present invention are preferably used in transportation means, such as ships, airplanes, trucks, cars, and buses, particularly preferably cars and buses, and particularly preferably in automobile interiors. Flexible polyurethane foams can be used as seat cushions, semi-rigid polyurethane foams can be used as foam backings for door panels or instrument panels, integral polyurethane foams can be used as steering wheels, control knobs, or headrests, and compact polyurethanes can be used, for example, as cable sheaths. Furthermore, the polyurethanes of the present invention can be polyurethane shoe soles or polyurethanes in furniture or mattresses.

[0020] The polyisocyanate component (a) used in the preparation of the polyurethanes of the present invention may be any of the polyisocyanates known for the preparation of polyurethanes. These include aliphatic, cycloaliphatic, and aromatic di- or polyfunctional isocyanates known from the prior art, as well as any desired mixtures thereof. Examples include diphenylmethane 2,2'-, 2,4'-, and 4,4'-diisocyanate, mixtures of monomeric diphenylmethane diisocyanate with diphenylmethane diisocyanate homologs having a higher number of rings (polymeric MDI), isophorone diisocyanate (IPDI) and its oligomers, tolylene 2,4- and 2,6-diisocyanate (TDI) and their mixtures, tetramethylene diisocyanate and its oligomers, hexamethylene diisocyanate (HDI) and its oligomers, naphthylene diisocyanate (NDI), and their mixtures.

[0021] It is preferred to use tolylene 2,4- and / or 2,6-diisocyanate (TDI) or mixtures thereof, monomeric diphenylmethane diisocyanate and / or higher ring diphenylmethane diisocyanate homologues (polymeric MDI), and mixtures thereof. Other possible isocyanates are listed, by way of example, in the "Polyurethane Handbook", Hanser / Gardener publications, 2nd edition 1993, chapters 3.2 and 3.3.2.

[0022] The polyisocyanate component (a) used can be in the form of a polyisocyanate prepolymer. These polyisocyanate prepolymers can be obtained by reacting an excess of the above-mentioned polyisocyanate (component (a-1)) with a polymer compound (b) (component (a-2)) having an isocyanate-reactive group and / or a chain extender (c) (component (a-3)) at a temperature of, for example, 30 to 100°C, preferably about 80°C, to obtain an isocyanate prepolymer.

[0023] The polymeric compounds (a-2) having groups reactive with isocyanates and the chain extenders (a-3) are known to those skilled in the art and are described, for example, in Chapter 3.1 of the "Polyurethane Handbook," Hanser / Gardener publications, 2nd edition 1993. For example, the polymeric compounds having groups reactive with isocyanates described under (b) can also be used as the polymeric compounds (a-2) having groups reactive with isocyanates.

[0024] As the polymer compound (b) having groups reactive with isocyanates, any known compound having at least two hydrogen atoms reactive with isocyanates can be used, for example, a compound having a functionality of 2 to 8 and a number-average molar mass of 400 to 15,000 g / mol. For example, a compound selected from the group consisting of polyether polyols, polyester polyols, and mixtures thereof can be used.

[0025] Polyetherols are prepared, for example, from epoxides such as propylene oxide and / or ethylene oxide, or from hydrogen-active starting compounds such as aliphatic alcohols, phenols, amines, carboxylic acids, tetrahydrofuran together with water, or from compounds based on natural substances such as sucrose, sorbitol, or mannitol using catalysts. Here, basic catalysts and double metal cyanide catalysts can be mentioned, for example, as described in PCT / EP2005 / 010124, EP 90444, or WO 05 / 090440.

[0026] Polyesterols are prepared, for example, from aliphatic or aromatic dicarboxylic acids and polyhydric alcohols, polythioether polyols, polyesteramides, hydroxylated polyacetals, and / or hydroxylated aliphatic polycarbonates, preferably in the presence of an esterification catalyst. Other possible polyols are described, for example, in the "Polyurethane Handbook," Hanser / Gardener publications, 2nd edition 1993, chapter 3.1.

[0027] Other materials that can be used together with the described polyetherols and polyesterols are filled polyetherols or polyesterols, also called polymeric polyetherols or polymeric polyesterols. These compounds preferably contain dispersed particles made of thermoplastic resins composed of olefin monomers, such as acrylonitrile, styrene, (meth)acrylates, (meth)acrylic acid, and / or acrylamide. These filled polyols are known and commercially available. Their manufacturing processes are described, for example, in German Patent No. 111394, U.S. Patent No. 3,304,273, U.S. Patent No. 3,383,351, U.S. Patent No. 3,523,093, German Patent No. 1,152,536, German Patent No. 1,152,537, WO 2008 / 055952, and WO 2009 / 128279.

[0028] In a particularly preferred embodiment of the present invention, component (b) comprises a polyetherol, more preferably does not comprise a polyesterol.

[0029] The catalyst (c) significantly accelerates the reaction of the polyol (b) and optional chain extenders and crosslinkers (f), and chemical blowing agent (e) with the organic, optionally modified polyisocyanate (a). The catalyst (c) comprises a manganese or iron-containing catalyst (c1), and, in a preferred embodiment, an optional incorporateable amine catalyst (c2).

[0030] According to the present invention, the manganese or iron-containing catalyst (c1) is a compound according to the general formula (I): [ka] where the variables are defined as follows: M is selected from manganese(II), manganese(III), iron(II) or iron(III); m is an integer from 0 to 2, n is an integer from 0 to 2, o is 0 or 1, p is 0 or 1, if o or p is 0, then both o and p are 0; q is 0 or 1, R 1 and R 2 are independently selected from the group consisting of F, Cl, Br, OH, CN, NH, NO, and hydrocarbon-containing residues; R 1 and R 2 may also be joined to form a ring, either as a cycloaliphatic or aromatic ring; R 3 is selected from H and hydrocarbon-containing residues; R 4 and R 7 are independently selected from the group consisting of H, F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon-containing residues. R 4 and R 7 may be joined to form a ring as a cycloaliphatic or aromatic ring; R 5 and R 6are independently selected from the group consisting of H, F, Cl, Br, OH, CN, NH, NO, and hydrocarbon-containing residues; If o is 0, R 6 and R 7 can both be O, X is O, S, or NR 8 , PR 8 , preferably O, S and NR 8 Particularly preferably, X is O; R 8 is selected from H and hydrocarbon-containing residues, preferably H, CH3 and CH2-CH3; p is 0 and X is NR 8 If NR 8 The group is an R 7 may be double bonded to L is selected from the anionic organic ligands of the acetylacetonate or carboxylate class; Solv is a neutral ligand, Hydrocarbon-containing residues include C1-C 10 - alkyl, C3-C 10 -cycloalkyl, C3-C containing at least one heteroatom selected from N, O and S 10 -heterocyclyl, C5-C 14 -aryl, C5-C containing at least one heteroatom selected from N, O and S 10 -heteroaryl, wherein the C1-C 10 -Alkyl C3-C 10 -Cycloalkyl, C3-C 10 -heterocyclyl, C5-C 14 -aryl, C5-C 10 -heteroaryl is optionally selected from F, Cl, Br, OH, CN, NH and C-C 10 -alkyl.

[0031] Preferably, L is an acetylacetonate or a carboxylate, such as acetate or a higher analogue thereof, such as propionate, butyrate, cyclohexylbutyrate or dodecanate. In a preferred embodiment, L is selected from L1 to L4, [ka] A particularly preferred L is acetoacetone.

[0032] In a preferred embodiment of the present invention, M is selected from Mn(III) and Fe(III).

[0033] In a preferred embodiment, Solv, when present, is selected from the group consisting of water, alcohols, ethers, amines, amides, nitriles, esters, ketones or phosphines, polyisocyanates (a) or polyols (b).

[0034] In a preferred embodiment of the present invention, the manganese or iron containing catalyst comprises an imine ligand (IL) of the general formula ML w Solv q wherein M, L, Solv and q are defined as above, w is 2 or 3, and the imine ligand (IL) is defined by formula (II): [ka] In the formula, m, n, o, p, X, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is defined as above.

[0035] The imine ligand (IL) is preferably selected from compounds according to formulae AL. [ka]

[0036] In a preferred embodiment, the catalyst according to formula (I) is prepared by reacting the corresponding acetylacetonates of iron and manganese [M(AcAc)3] with a ligand according to formula II. In this case, two acetylacetonate ligands are replaced with one ligand according to formula II. If the reaction is carried out in a solvent, the solvent, such as water, alcohol, ether, amine, amide, nitrile, ester, or ketone, can further coordinate to the metal center in the catalyst according to formula I as an additional neutral ligand Solv. The neutral ligand Solv can also be a polyisocyanate or polyol from the reaction mixture.

[0037] In a preferred embodiment of the present invention, the manganese- or iron-containing catalyst (c1) is used in an amount of 0.001 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.05 to 3% by weight, based on the total weight of the polyisocyanate (a).

[0038] The incorporable amine catalyst (c2) has at least one, preferably 1 to 8, particularly preferably 1 to 2, isocyanate-reactive groups, such as primary amine, secondary amine, hydroxy, amide, or urea groups, preferably primary amine, secondary amine, or hydroxy groups. The incorporable amine catalyst (c2) is primarily used in the production of low-emission polyurethanes, particularly those used in the automotive interiors sector. These catalysts are known and are described, for example, in EP 1 888 664. They include compounds that preferably contain one or more tertiary amino groups in addition to the isocyanate-reactive groups. Preferably, at least one of the tertiary amino groups of the incorporable catalyst has at least two aliphatic hydrocarbon moieties, preferably having 1 to 10 carbon atoms per moiety, particularly preferably having 1 to 6 carbon atoms per moiety. The tertiary amino group has two moieties independently selected from methyl and ethyl moieties, and it is particularly preferred that it also has another organic moiety. Examples of incorporable catalysts (c2) that can be used are bis(dimethylaminopropyl)urea, bis(N,N-dimethylaminoethoxyethyl)carbamate, dimethylaminopropyl urea, N,N,N-trimethyl-N-hydroxyethyl bis(aminopropyl ether), N,N,N-trimethyl-N-hydroxyethyl bis(aminoethyl ether), diethylethanolamine, bis(N,N-dimethyl-3-aminopropyl)amine, dimethylaminopropylamine, 3-dimethylaminopropyl-N,N-dimethylpropane-1 ,3-diamine, dimethyl-2-(2-aminoethoxyethanol), (1,3-bis(dimethylamino)propan-2-ol), N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, bis(dimethylaminopropyl)-2-hydroxyethylamine, N,N,N-trimethyl-(3-aminopropyl)bis(aminoethyl ether), 1,4-diazabicyclo[2.2.2]octane-2-methanol and 3-dimethylaminoisopropyldiisopropylpropanolamine, and mixtures thereof.

[0039] In addition to the manganese or iron-containing catalyst (c1) and the optionally incorpo- rated amine catalyst (c2), the catalyst according to the invention may comprise conventional catalysts used in the production of polyurethanes as amine-based catalysts or metal-based catalysts. Examples of conventional catalysts that can be used for the production of polyurethanes include amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl, N-ethyl, and N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane, preferably 1,4-diazabicyclo[2.2.2]octane, and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine, and dimethylethanolamine.

[0040] It is also possible to use organometallic compounds, preferably tin-free compounds, as bismuth carboxylates, such as bismuth(III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octoate, or mixtures thereof.

[0041] In a preferred embodiment of the present invention, the catalyst (c) does not comprise a tin-based catalyst, more preferably does not comprise a metal catalyst other than the manganese- or iron-based catalyst (c1). Furthermore, in a particularly preferred embodiment of the present invention, the catalyst (c) consists of the manganese- or iron-based catalyst (c1) and the optionally incorporable catalyst (c2).

[0042] If the polyurethane of the present invention is intended to be in the form of a polyurethane foam, the reaction mixture of the present invention also contains a blowing agent (d). Any blowing agent known for use in the production of polyurethanes can be used. These can include chemical and / or physical blowing agents. Examples of these blowing agents are described, for example, in Chapter 3.4.5 of the "Polyurethane Handbook," Hanser / Gardener Publications, 2nd Edition, 1993. Chemical blowing agents refer to compounds that form gaseous products upon reaction with isocyanates. Examples of these blowing agents are water and carboxylic acids. The term physical blowing agents refers to compounds that are dissolved or emulsified in the starting materials for the polyurethane-forming reaction and vaporize under the conditions for polyurethane formation. These include, for example, hydrocarbons, halogenated hydrocarbons, and other compounds, such as perfluorinated alkanes (e.g., perfluorohexane, fluorochlorocarbons), as well as ethers, esters, ketones, acetals, and / or liquid carbon dioxide. Any desired amount of blowing agent can be used herein. The amount of blowing agent used is preferably such that the density of the resulting polyurethane foam is 10 to 850 g / L, particularly 20 to 500 g / L, and particularly 25 to 300 g / L. It is particularly preferred to use a blowing agent containing water, and it is particularly preferred to use a blowing agent consisting of water.

[0043] The chain extenders and crosslinkers (e) used herein may be compounds with a molar mass of less than 400 g / mol that have at least two isocyanate-reactive groups, where the term chain extender is used herein for molecules with two hydrogen atoms that are isocyanate-reactive, and the term crosslinker is used herein for molecules with three or more hydrogen atoms that are isocyanate-reactive. However, it is also possible to omit the terms chain extender or crosslinker here. However, the addition of a chain extender, crosslinker, or possibly a mixture thereof, can prove advantageous for modifying mechanical properties, such as hardness.

[0044] If chain extenders and / or crosslinkers are intended to be used, the amounts typically used are in each case from 0.5 to 60% by weight, preferably from 1 to 40% by weight, particularly preferably from 1.5 to 20% by weight, based on the total weight of components (b) to (e).

[0045] When using chain extenders and / or crosslinkers (e), known chain extenders and / or crosslinkers for polyurethane production can be used. These are preferably low molecular weight compounds with isocyanate-reactive functional groups, such as glycerol, trimethylolpropane, glycols, and diamines. Other possible low molecular weight chain extenders and / or crosslinkers are described, for example, in the "Polyurethane Handbook," Hanser / Gardener Publications, 2nd Edition 1993, Chapters 3.2 and 3.3.2.

[0046] Further, auxiliary substances and / or additives (f) can be used. Any auxiliary substances and additives known for the production of polyurethanes can be used. Examples include surface-active substances, foam stabilizers, cell regulators, mold release agents, fillers, dyes, pigments, flame retardants, hydrolysis stabilizers, antioxidants, aldehyde-scavenging compounds, fungistatic substances, and bacteriostatic substances. These substances are known and are described, for example, in the "Polyurethane Handbook," Hanser / Gardener publications, 2nd edition 1993, chapters 3.4.4 and 3.4.6 to 3.4.11.

[0047] The amounts of polyisocyanate (a), polyol (b), blowing agent (c), and optional blowing agent (d), chain extender, and / or crosslinker (e) reacted during the preparation of the polyurethanes of the present invention are generally such that the equivalent ratio of NCO groups of polyisocyanate (a) to the total reactive hydrogen atoms of components (b), (c), and, if used, (d) and (e) is 0.75 to 1.5:1, preferably 0.80 to 1.25:1. When the cellular plastic contains at least some isocyanurate groups, the ratio of NCO groups of polyisocyanate (a) to the total reactive hydrogen atoms of components (b), (c), and, if used, (d) and (e) is usually 1.5 to 20:1, preferably 1.5 to 8:1. A ratio of 1:1 corresponds to an isocyanate index of 100.

[0048] The specific starting materials (a)-(f) for producing the polyurethanes of the present invention vary only slightly quantitatively and qualitatively, depending on whether the present invention is intended to produce thermoplastic polyurethanes, flexible foams, semi-rigid foams, rigid foams, or integral foams. For example, compact polyurethanes are produced without blowing agents, while thermoplastic polyurethanes are produced using mostly strictly difunctional starting materials. The elasticity and hardness of the polyurethanes of the present invention can further be varied, for example, by the functionality and chain length of the relatively high molecular weight compounds having at least two reactive hydrogen atoms. Such modifications are known to those skilled in the art.

[0049] Starting materials for producing compact polyurethanes are described, for example, in EP 0989146 or EP 1460094, starting materials for producing flexible foams are described, for example, in PCT / EP2005 / 010124 and EP 1529792, starting materials for producing semi-rigid foams are described, for example, in the "Polyurethane Handbook," Hanser / Gardener publications, 2nd edition 1993, chapter 5.4, starting materials for producing rigid foams are described, for example, in PCT / EP2005 / 010955, and starting materials for producing integral foams are described in EP 364854, U.S. Pat. No. 5506275 or EP 897402. Compound (d) is then also added in each case to the starting materials described in the above documents.

[0050] In a preferred embodiment of the present invention, the polyurethane is produced by a two-component process. The two-component process includes an isocyanate component (a) containing an isocyanate, a polyol component (b) containing a polymeric compound having an isocyanate-reactive group, (c) a catalyst, such as a manganese- or iron-containing catalyst (c1), and optionally (d) a blowing agent, (e) a chain extender and / or crosslinker, and (f) a coagent. In a preferred embodiment, the polyol component includes a blowing agent (d) containing water.

[0051] The present invention provides not only the process of the present invention, but also polyurethanes obtainable by the process of the present invention. The polyurethanes of the present invention are preferably polyurethane foams, such as flexible polyurethane foams, semi-rigid polyurethane foams, or integral polyurethane foams. The polyurethanes of the present invention are preferably used in enclosed spaces, for example, as insulation materials in residential buildings, for example, pipe and refrigerator insulation, in furniture construction, for example, as decorative elements, seat cushions, mattresses, and in vehicle interiors, for example, in automobile interiors, for example, as steering wheels, dashboards, door cladding, carpet backing foam, sound-absorbing foam, for example, roof lining, and even headrests or control knobs. Another potential use of the polyurethanes of the present invention is shoe soles. In addition to their low toxicity, high efficiency, and excellent stability in the presence of water, the application of the present catalyst also reduces the emission of volatile organic compounds from the polyurethanes of the present invention.

[0052] The present invention is illustrated by the following examples. The room temperature in the examples is 20°C. The gel time for urethane synthesis was determined after mixing the reactants and catalyst, vortexing the mixture for 10 seconds, and allowing it to react at room temperature. The reaction mixture was then visually monitored for the formation of a viscous liquid that solidified over time. A glass pipette was then used to probe the reaction mixture to ensure the contents had completely solidified. The gel time was the time it took for the reaction mixture to solidify after vortexing the reactants.

[0053] A general synthesis of salicylaldimine ligands Salicylaldehyde (0.063 ml, 0.567 mmol) was added to the appropriate amino alcohol (0.567 mmol) and the mixture was heated directly at 80° C. for 3 hours to give the corresponding imine.

[0054] Synthesis of salicylaldimine ONO tridentate Mn acetylacetonate catalysts 1-3 Salicylaldehyde (0.63 ml, 5.67 mmol) was added to the appropriate amino alcohol (5.67 mmol), and the mixture was heated directly at 80°C for 3 hours. Following this, the reaction mixture was cooled to room temperature, and 5 ml of methanol was added and stirred. 2 g of Mn(acac)3 (5.67 mmol) was then added to the mixture, and an additional 5 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 10 ml of hexane. The product was then dried under vacuum for 12 hours.

[0055] Catalyst 1:ESI-ESI-MS:m / z:388.04[M+Na] + (1.4%), IR Spectroscopy v / cm -1 :1595(m)1536(m)1513(m)1480(s)1461(s)1435(s)1374(m)1305(m)1257(m)1224(s)11 71(m)1145(m)1127(m)1022(m)960(m)924(m)860(m)838(m)789(s)735(s)673(s)635(s)

[0056] Catalyst 2:ESI-MS:m / z:635.098[M] + (18.1%), m / z: 535.048 [M-acac] + (3.1%), IR Spectroscopy v / cm -1 :1631(m)1595(m)1511(m)1448(m)1385(m)1300(m)1257(m)1214(m)1153(s)1130(s)1033(s)923(s)898(s)796(s)754(s)671(s)625(s)

[0057] Catalyst 3:ESI-MS:m / z:690.1558[M] + (12.2%), m / z:591.1105[M-acac] + (26.8%), IR Spectrsocopy v / cm -1:1666(m)1600(m)1541(m)1514(m)1446(m)1388(m)1310(m)1259(s)121 4(s)1150(s)1115(s)1021(s)930(s)893(s)864(s)759(m)640(s)607(s)

[0058] Synthesis of amino acid-based salicylaldimine ONO tridentate Mn acetylacetonate catalyst 4 1.18 ml of salicylaldehyde (11.3 mmol) was added to 0.85 g of glycine (11.3 mmol) in 15 ml of methanol, and the mixture was heated at 80 °C for 24 hours. After this, the reaction mixture was cooled to room temperature, and the solution was filtered using a PTFE filter with a 0.20 μm pore size. The filtrate was then dried to obtain the crude ligand. 0.050 g (0.28 mmol) of the ligand prepared above was then added to 0.098 g (0.28 mmol) of Mn(acac)3, and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 × 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0059] Synthesis of amino acid-based salicardimine ONO tridentate Mn acetylacetonate catalyst 5 1.18 ml of salicylaldehyde (11.3 mmol) was added to 1.88 g of phenylalanine (11.3 mmol) in 15 ml of methanol, and the mixture was heated at 80 °C for 24 hours. After this time, the reaction mixture was cooled to room temperature, and the solution was filtered using a PTFE 0.20 μm pore size filter. The filtrate was then dried to obtain the crude ligand. Next, 0.12 g (0.45 mmol) of the ligand prepared above was added to 0.16 g (0.45 mmol) of Mn(dpvm) (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III)), and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo, and the residue was washed with 3 × 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0060] Synthesis of diol ONO tridentate Mn acetylacetonate catalyst 6 0.1 g of diethanolamine (0.95 mmol) was added to 0.335 g of Mn(acac)3 (0.95 mmol) and 5 ml of methanol was added as a solvent. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0061] Synthesis of diol ONO tridentate Mn acetylacetonate catalyst 7 0.1 g of pyridine-2,6-diyldimethanol (0.72 mmol) was added to 0.253 g of Mn(acac)3 (0.72 mmol) and 5 ml of methanol was added as a solvent. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0062] Synthesis of diacid ONO tridentate Mn acetylacetonate catalyst 8 0.050 g of 2,2'-(methylazanediyl)diacetic acid (0.34 mmol) was added to 0.119 g of Mn(acac)3 (0.34 mmol) and 5 mL of methanol was added as a solvent. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 mL of hexane. The product was then dried under vacuum for 12 hours.

[0063] Synthesis of salicylaldimine ONNO tetradentate Mn acetylacetonate catalysts 9-11 1.74 ml (16.32 mmol) of salicylaldehyde was added to the appropriate diamine (8.16 mmol), and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature, and 10 ml of ethanol was added and stirred. 2.87 g of Mn(acac) (8.16 mmol) was then added to the mixture, and an additional 10 ml of ethanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 10 ml of hexane. The product was then dried under vacuum for 12 hours.

[0064] General catalytic activity in model urethane reactions 0.23 ml of 1-butanol (2.5 mmol) was added to 5 mg of the catalyst material prepared above (2.5 wt % relative to the alcohol ROH used), and the mixture was vortexed for 10 seconds. Then, 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) (h-MDI) was added, and the mixture was vortexed for 10 seconds and allowed to react at room temperature. The gel time was measured as the time it took for the reaction mixture to solidify after vortexing the reaction mixture. The solubility of the catalyst in the alcohol-isocyanate mixture was also recorded. At a 1 wt % ROH catalyst loading, 5 mg of catalyst material catalyzed the reaction between 0.57 ml of 1-butanol (6.25 mmol) and 0.77 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (3.12 mmol). At a 0.5 wt% ROH loading, 5 mg of catalyst material catalyzed the reaction between 1.15 ml of 1-butanol (12.5 mmol) and 1.55 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (6.25 mmol). At a 0.25 wt% ROH loading, 5 mg of catalyst material catalyzed the reaction between 2.3 ml of 1-butanol (25 mmol) and 3.1 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (12.5 mmol). [ka]

[0065] [Table 1]

[0066] Examples 6, 7, 8, 12 and 13 are comparative examples which demonstrate the advantages of the catalysts according to the invention, and in particular the influence of the ligands according to the invention.

[0067] Catalyst loadings from 1 wt% ROH to 0.25 wt% ROH using Mn acac salicylaldimine catalyst [Table 2]

[0068] Examples 21, 22, 26 and 27 are comparative examples that demonstrate the advantages of the catalysts according to the invention and their ability to match the activity of state-of-the-art DBTL tin catalysts.

[0069] Testing the solubility and water stability of catalysts in polyols 25 mg of catalyst was dissolved in 1 ml of acetone and added to 2.5 g of Polyol 1 (Polyol 1 is a glycerol-initiated polyether polyol based on ethylene oxide and propylene oxide, characterized by a hydroxyl number of 35 mg KOH / g and a functionality of 2.7).

[0070] 0.125 g of water was then added to the mixture and stirred. The acetone was then dried in a vacuum to give a yellowish-black viscous water-containing solution. The solution was then left at room temperature or 60°C for an extended period of time. A change in the physical appearance of the material as well as precipitation were observed.

[0071] Testing the solubility and water stability of the catalyst in acetone 5 mg of catalysts 1-2 were dissolved in 0.1 ml of acetone, followed by the addition of 5 μl of water, and the mixture was left at room temperature for 18 days. The acetone was then dried under vacuum to give a yellowish-black residue, to which 0.23 ml of 1-butanol (2.5 mmol) was added and vortexed. 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) (h-MDI) was then added, and the mixture was vortexed for 10 seconds and allowed to react at room temperature to yield a polyurethane foam. The time it took for the reaction mixture to solidify after vortexing was the gelation time. [Table 3]

[0072] Non-inventive Example 30 demonstrates the beneficial role of the salicylic ligand on the water stability of the Mn catalyst.

[0073] Synthesis of hydroxy-substituted salicylaldimine ONO tetradentate Mn acetylacetonate catalysts 12-14 0.1 g of 2,5-dihydroxybenzaldehyde (0.72 mmol) was added to the appropriate amino alcohol (0.72 mmol), and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature, and 2 ml of methanol was added and stirred. 0.25 g (0.7 mmol) of Mn(acac)3 was then added to the mixture, and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0074] The evaluation of catalytic activity follows the reported procedure with a catalyst loading of 2.5 wt% ROH. [Table 4]

[0075] Synthesis of Bromo-Substituted Salicylaldimine ONO Tetradentate Mn Acetylacetonate Catalysts 18-20 0.049 g of 5-bromo-2-hydroxybenzaldehyde (0.24 mmol) was added to the appropriate amino alcohol (0.24 mmol) in 1 ml of methanol, and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature, and 2 ml of methanol was added and stirred. 0.085 g (0.24 mmol) of Mn(acac) was then added to the mixture, and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0076] Synthesis of bromo-substituted salicylaldimine ONNO tetradentate Mn acetylacetonate catalysts 21-23 0.097 g of 5-bromo-2-hydroxybenzaldehyde (0.48 mmol) was added to the appropriate diamine (0.24 mmol), and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature, and 2 ml of methanol was added and stirred. 0.085 g (0.24 mmol) of Mn(acac)3 was then added to the mixture, and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0077] The evaluation of catalytic activity follows the reported procedure with a catalyst loading of 2.5 wt% ROH. [Table 5]

[0078] Synthesis of naphthaldimine ONO tetradentate Mn acetylacetonate catalysts 24-26 0.042 g of 3-hydroxy-2-naphthaldehyde (0.24 mmol) was added to the appropriate amino alcohol (0.24 mmol) in 1 ml of methanol, and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature, and 2 ml of methanol was added and stirred. 0.085 g (0.24 mmol) of Mn(acac) was then added to the mixture, and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0079] Synthesis of naphthaldimine ONNO tetradentate Mn acetylacetonate catalysts 27-29 0.042 g of 3-hydroxy-2-naphthaldehyde (0.24 mmol) was added to the appropriate diamine (0.12 mmol) in 1 ml of methanol, and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature, and 2 ml of methanol was added and stirred. 0.043 g (0.12 mmol) of Mn(acac) was then added to the mixture, and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0080] The evaluation of catalytic activity follows the reported procedure with a catalyst loading of 2.5 wt% ROH. [Table 6]

[0081] Synthesis of Mn(dpvm)3 (tris(2,2,6,6-tetramethyl-3,5-heptanedionate)manganese(III)) 0.116 g (0.58 mmol) of MnCl₂·4H₂O dissolved in 1 mL of methanol was added dropwise to 0.244 mL (1.17 mmol) of 2,2,6,6-tetramethylheptane-3,5-dione in 1 mL of methanol. The mixture was stirred at room temperature for 3 hours, after which 0.027 g (0.67 mmol) of NaOH was added. The solution was then allowed to stand for 16 hours. The solvent was then evaporated at room temperature and atmospheric pressure to give the title compound.

[0082] Synthesis of salicylaldimine ONO tridentate Mn dpvm catalysts 30-33 Catalyst 30-31: 0.3 μl of salicylaldehyde (0.567 mmol) was added to the appropriate amino alcohol (0.567 mmol) in 1 ml of methanol, and the mixture was heated directly at 80 °C for 3 h. Following this, the reaction mixture was cooled to room temperature, and 2 ml of methanol was added and stirred. Then, 0.342 g of Mn(dpvm) (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III)) prepared above was added to the mixture, and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 h, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 h.

[0083] Catalyst 32: 1.18 ml of salicylaldehyde (11.3 mmol) was added to 0.85 g of glycine (11.3 mmol) in 10 ml of methanol, and the mixture was heated at 80 °C for 24 hours. After this time, the reaction mixture was cooled to room temperature, and the solution was filtered using a PTFE 0.20 μm pore size filter. The filtrate was then dried to obtain the crude ligand. Next, 0.021 g (0.12 mmol) of the ligand prepared above was added to 0.073 g of Mn(dpvm) (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III)), and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo, and the residue was washed with 3 × 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0084] Catalyst 33: 1.18 ml of salicylaldehyde (11.3 mmol) was added to 1.88 g of phenylalanine (11.3 mmol) in 10 ml of methanol, and the mixture was heated at 80 °C for 24 hours. After this time, the reaction mixture was cooled to room temperature, and the solution was filtered using a PTFE 0.20 μm pore size filter. The filtrate was then dried to obtain the crude ligand. Next, 0.036 g (0.13 mmol) of the ligand prepared above was added to 0.081 g of Mn(dpvm) (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III)), and an additional 2 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo, and the residue was washed with 3 × 5 ml of hexane. The product was then dried under vacuum for 12 hours.

[0085] The evaluation of catalytic activity follows the reported procedure with a catalyst loading of 2.5 wt% ROH. [Table 7]

[0086] Comparative experiment not according to the present invention: Examination of the solubility and water stability of Mn(dpvm)3 in acetone 5 mg of Mn(dpvm)3 was dissolved in 0.1 ml of acetone, followed by the addition of 5 μl of water, and the mixture was left at room temperature for 18 days. The acetone was then dried in vacuo to give a yellowish-black residue, to which 0.23 ml of 1-butanol (2.5 mmol) was added and vortexed. 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) (h-MDI) was added, and the mixture was vortexed for 10 seconds and allowed to react at room temperature. The time it took for the reaction mixture to solidify after vortexing the reaction was the gelation time. [Table 8]

[0087] Synthesis of salicylaldimine ONO tridentate Mn acetate catalysts 34-35 0.63 ml (5.67 mmol) of salicylaldehyde was added to the appropriate amino alcohol (5.67 mmol), and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature, and 5 ml of methanol was added and stirred. 1.5 g (5.67 mmol) of Mn(acetate)3 was then added to the mixture, and an additional 5 ml of methanol was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 10 ml of hexane. The product was then dried under vacuum for 12 hours.

[0088] Catalyst 35: ESI-MS: m / z: 591.0161 [M-acetate] + (26.8%), IR Spectrsocopy v / cm -1 :1705(m)1631(m)1555(m)1414(m)1304(s)1275(s)1224(s)1203(s)1172(s)1145(s)1026(s)901(s)839(s)758(s)659(m)615(m)

[0089] The evaluation of catalytic activity follows the general procedure reported above. [Table 9]

[0090] Examination of the solubility and water stability of Mn(acetate)3 salicylaldimine catalyst in acetone. 5 mg of catalyst 35 was dissolved in 0.1 ml of acetone, followed by the addition of 5 μl of water, and the mixture was left at room temperature for 11 days. The acetone was then dried in vacuo to give a yellowish-black residue, to which 0.23 ml of 1-butanol (2.5 mmol) was added and vortexed. 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) (h-MDI) was added, and the mixture was vortexed for 10 seconds and allowed to react at room temperature. The time it took for the reaction mixture to solidify after vortexing the reaction was the gelation time. [Table 10]

[0091] Comparative Example 55, not of the present invention, shows the beneficial effect of a salicylic ligand in combination with Mn acetate.

[0092] Synthesis of salicylaldimine ONO tridentate Fe acetylacetonate catalysts 36-41 30 μl (0.28 mmol) of salicylaldehyde was added to the appropriate amino alcohol (0.28 mmol) in 1 ml of solvent (methanol / DCM), and the mixture was heated directly at 80° C. for 3 hours. Following this, the reaction mixture was cooled to room temperature. 0.1 g of Fe(acac)3 (0.28 mmol) was then added to the mixture, and an additional 2 ml of solvent (methanol / DCM) was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3×5 ml of hexane. The product was then dried under vacuum for 12 hours. [Table 11]

[0093] Examination of the solubility and water stability of salicylaldimine Fe(acac)3 catalyst in acetone 5 mg of catalysts 38-41 were dissolved in 0.1 ml of acetone, followed by the addition of 5 μl of water, and the mixture was left at room temperature for 30 days. The acetone was then evaporated in vacuo to give a crude residue, to which 0.23 ml of 1-butanol (2.5 mmol) was added and vortexed. 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) (h-MDI) was added, and the mixture was vortexed for 10 seconds and allowed to react at room temperature. The gelation time was the time it took for the reaction mixture to solidify after vortexing. [Table 12]

[0094] Examination of the solubility and water stability of salicylaldimine Fe(acac)3 catalyst in 1-butanol 5 mg of catalysts 36-40 were dissolved in 0.23 ml of 1-butanol (2.5 mmol) at room temperature. 10 mg of water was then added, and the mixture was heated at 60 °C for 48 h. 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) was then added, and the mixture was vortexed for 10 seconds. The reaction was then monitored at room temperature to determine the gelation time. [Table 13]

[0095] The catalyst is partially soluble in Polyol 1. Mixing the catalyst with methanol followed by mixing with Polyol 1 results in complete solubilization.

[0096] Examples 66, 67 and 68, which are not of the present invention, demonstrate the advantages of the present invention.

[0097] Synthesis of hydroxyl-substituted salicylaldimine ONO tridentate Fe acetylacetonate catalysts 42-47 0.1 g of 2,5-dihydroxybenzaldehyde (0.72 mmol) was added to the appropriate amino alcohol (0.72 mmol) in 1 ml of solvent (methanol / DCM), and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature. 0.25 g of Fe(acac) (0.72 mmol) was then added to the mixture, and an additional 2 ml of solvent (methanol / DCM) was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours and tested as disclosed above. [Table 14]

[0098] Synthesis of Bromo-Substituted Salicylaldimine ONO Tridentate Fe Acetylacetonate Catalysts 48-53 0.048 g of 2,5-dihydroxybenzaldehyde (0.24 mmol) was added to the appropriate amino alcohol (0.24 mmol) in 1 ml of solvent (methanol / DCM), and the mixture was heated directly at 80 °C for 3 hours. Following this, the reaction mixture was cooled to room temperature. 0.085 g of Fe(acac) (0.24 mmol) was then added to the mixture, and an additional 2 ml of solvent (methanol / DCM) was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3 x 5 ml of hexane. The product was then dried under vacuum for 12 hours and tested as disclosed above. [Table 15]

[0099] Synthesis of salicylaldimine ONO tridentate Fe acetylacetonate catalysts 54-59 0.042 g of 3-hydroxy-2-naphthaldehyde (0.24 mmol) was added to the appropriate amino alcohol (0.24 mmol) in 1 ml of solvent (methanol / DCM), and the mixture was heated directly at 80° C. for 3 hours. Following this, the reaction mixture was cooled to room temperature. 0.085 g of Fe(acac) (0.24 mmol) was then added to the mixture, and an additional 2 ml of solvent (methanol / DCM) was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 hours, after which the solvent was evaporated in vacuo and the residue was washed with 3×5 ml of hexane. The product was then dried under vacuum for 12 hours and tested as disclosed above. [Table 16]

Claims

1. A method for producing polyurethane, comprising the steps of: a) polyisocyanates, b) a polymeric compound having groups reactive with isocyanates; c) a catalyst, a manganese or iron-containing catalyst (c1), and optionally d) a blowing agent; e) chain extenders and / or crosslinkers, and / or f) auxiliaries, to obtain a reaction mixture, and reacting the reaction mixture to obtain the polyurethane; The manganese or iron-containing catalyst (c1) is represented by the general formula (I): 【Chemistry 1】 is a compound according to where the variables are: M is selected from manganese(II), manganese(III), iron(II) or iron(III); m is an integer from 0 to 2; n is an integer from 0 to 2, o is 0 or 1; p is 0 or 1; when o or p is 0, then both o and p are 0; q is 0 or 1; R １ and R ２ are independently F, Cl, Br, OH, CN, NH ２ , NO ２ and hydrocarbon-containing residues, R １ and R ２ may be joined to form a ring as a cycloaliphatic or aromatic ring; R ３ is selected from H and hydrocarbon-containing residues; R ４ and R ７ are independently H, F, Cl, Br, OH, CN, NH ２ , NO ２ and hydrocarbon-containing residues, R ４ and R ７ may be joined to form a ring as a cycloaliphatic or aromatic ring; R ５ and R ６ are independently H, F, Cl, Br, OH, CN, NH ２ , NO ２ and hydrocarbon-containing residues, When o is 0, R ６ and R ７ can both be O, X is O, S, NR ８ , P.R. ８ is selected from R ８ is selected from H and hydrocarbon-containing residues; p is 0 and X is NR ８ If NR ８ The group is an R ７ may be double bonded to L is selected from anionic organic ligands from the class of acetate or its higher analogues acetylacetonate or carboxylate; Solv is a neutral ligand; The hydrocarbon-containing residue is C １ -C １０ - alkyl, C ３ -C １０ -cycloalkyl, C containing at least one heteroatom selected from N, O and S ３ -C １０ -heterocyclyl, C ５ -C １４ -aryl, C containing at least one heteroatom selected from N, O and S ５ -C １０ -heteroaryl, wherein said C １ -C １０ -Alkyl C ３ -C １０ -cycloalkyl, C ３ -C １０ -heterocyclyl, C ５ -C １４ -aryl or C ５ -C １０ Heteroaryl is optionally F, Cl, Br, OH, CN, NH ２ and C １ -C １０ -having one or more further substituents selected from the group consisting of alkyl.

2. L is L1 to L4; 【Chemistry 2】 The method of claim 1 , wherein the compound is selected from the group consisting of:

3. 3. The method of claim 1, wherein M is selected from Mn(III) and Fe(III).

4. The manganese or iron-containing catalyst (c1) comprises an imine ligand (IL) represented by the general formula ML ｗ Solv ｑ wherein M, L, Solv and q are defined in claim 1, w is 2 or 3, and the imine ligand (IL) is of formula (II); 【Transformation 3】 Defined by m, n, o, p, X, R １ , R ２ , R ３ , R ４ , R ５ , R ６ and R ７ 4. The method according to any one of claims 1 to 3, wherein:

5. The imine ligand (IL) is represented by formula A to L; 【Chemistry 4】 5. The method of claim 4, wherein the compound is selected from the group consisting of:

6. 6. The method of claim 4 or 5, wherein w is 3, q ​​is 0, and L is acetylacetone (L1).

7. 7. The method of claim 1, wherein X is O.

8. 8. The method according to any one of claims 1 to 7, wherein the amount of the manganese or iron-containing catalyst (c1), based on the total weight of the polyisocyanate (a), is 0.001 to 10 wt.%.

9. 9. The method of any one of claims 1 to 8, wherein the polyurethane is a polyurethane foam and the applied blowing agent (d) comprises water.

10. 10. The method of any one of claims 1 to 9, wherein the catalyst (c) comprises an incorporable amine catalyst (c2).

11. 11. The method of claim 10, wherein the incorporable catalyst (c2) comprises a compound having one or more tertiary aliphatic amino groups along with groups reactive toward isocyanates.

12. 12. The method of any one of claims 1 to 11, wherein the polyurethane is part of a mattress or an item of furniture.

13. 12. The method of any one of claims 1 to 11, wherein the polyurethane is an automotive interior part.

14. (b) a polymeric compound having a group reactive with an isocyanate; (c) a catalyst, including the use of a manganese or iron-containing catalyst (c1) as defined in claim 1, and optionally (d) a blowing agent, which comprises water; (e) a chain extender and / or crosslinker, and (f) containing an auxiliary agent; Polyol component for producing polyurethanes.

15. A polyurethane obtainable by the method according to any one of claims 1 to 13.

16. 16. The polyurethane of claim 15, wherein the polyurethane is a flexible foam, a semi-rigid foam, or an integral foam.

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