Manganese-containing and iron-containing catalysts for polyurethane synthesis comprising imine ligands

Abstract

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

Description

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

[0002] Polyurethanes are important technical polymers, for example for applications such as foams, elastomers, lenses, packaging, insulation materials, footwear, textiles, synthetic leather, coatings, paints or seals. Polyurethanes are essentially prepared by the polyaddition reaction of polyols with polyisocyanates. This reaction usually takes place in the presence of a catalyst. For the common compositions of polyurethanes and catalysts used, see Ullmann's Encyclopedia of Industrial Chemistry, Polyurethanes, 2012, DOI: 10.1002 / 14356007.a21_665.pub2. Currently, tin-based catalysts are still often used and are showing very good performance in the formation of polyurethanes as polyurethane foams. However, due to their toxicity, the use of such tin-containing catalysts, especially alkyltin compounds, should be avoided. Thus, there is a great need for alternative tin-free catalysts showing similar performance.

[0003] In Polymer Journal, 2002, 23, 298 - 301, the use of manganese acetylacetonate and iron acetylacetonate catalysts as catalysts for polyurethane synthesis is described. With additional ligands, the performance of the manganese acetylacetonate and iron acetylacetonate catalysts is significantly inferior to that of the reference tin catalyst dibutyltin dilaurate (DBTDL). By adding the amine ligand triethylenediamine, a more active manganese acetylacetonate and iron acetylacetonate catalyst can be obtained, but the activity is still significantly lower than that of the reference tin catalyst DBTDL. It is also not clear whether the resulting Fe and Mn catalysts are stable to hydrolysis. Hydrolytic stability is an important property of polyurethane catalysts since they are exposed to water in the polyol component in many cases, for example in the synthesis of water-blown polyurethane foams.

[0004] US2007 / 0010644 A1 discloses the use of iron acetylacetonate in combination with an amine (such as dimethylaminopropylurea) as a cocatalyst for polyurethane synthesis. This catalyst system has a catalyst activity comparable to that of common tin catalysts. However, the disadvantage of this system is that it does not catalyze the foaming reaction for the synthesis of very important water-blown polyurethane foams in the presence of water. Nor is it disclosed how stable this catalyst system is to hydrolysis when stored in a water-containing polyol component.

[0005] US 5733945 discloses the use of iron(III) acetylacetonate and additional acetylacetone but no other ligands as catalysts. US 5733945 discloses that the less additional acetylacetone present, the faster the catalyst acts, and the excess acetylacetone must be removed at a higher temperature. The stability of this catalyst system against hydrolysis when stored in water containing a polyol component is not disclosed.

[0006] WO2018054725 discloses the application of [Mn(salen)](OAc) as a catalyst for the production of coatings. According to WO2018054725, OAc is used as a counterion and not as a ligand. Additionally, a method for producing polyurethane foam is not disclosed. Compared with the production of solid coatings, for the production of foam, the foaming reaction of isocyanate and water as a blowing agent and the gelling reaction of isocyanate and polyol must be adjusted, otherwise the foam will break.

[0007] US2020 / 0332052 A1 discloses organometallic compounds as hydrolysis and condensation catalysts for the synthesis of polyurethane polymers containing at least one alkoxysilyl-polyurethane unit and at least one thiol-containing compound. As catalysts, titanium, aluminum, tin, zirconium, iron, cobalt, manganese, nickel, bismuth, and zinc are particularly mentioned, and especially tin-based catalysts with organic ligands. These catalysts can be obtained from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetone imine, diacetylacetone-alkylenediimine, salicylaldehyde imine, etc. with various metals such as Ti, Al, Sn, Zr, Fe, Co, Mn, Ni, Bi, and Zn. Whether such a catalyst system is suitable for the synthesis of ordinary polyurethanes without thiol-containing compounds, especially polyurethane foam, is not disclosed. Additionally, no further description or disclosure of the suitable combination of salicylaldehyde imine with a specific metal and other ligands on this metal is provided herein.

[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), pages 248 - 249 disclose the preparation of mono- and trinuclear iron(III) complexes.

[0009] DE 102009047038 discloses complexes of iron, molybdenum, manganese and / or tungsten with iminodiols and their use as bleach catalysts in detergent solutions.

[0010] Accordingly, it is an object of the present invention to provide a process for producing polyurethanes, in which a catalyst is used which does not have the disadvantages of the currently known systems and which, in particular, exhibits high efficiency, low toxicity and high stability in the presence of water.

[0011] This object has been achieved by a process for producing polyurethanes, in which (a) a polyisocyanate, (b) a polymeric compound having groups reactive toward isocyanates, (c) a catalyst comprising a manganese- or iron-containing catalyst (c1) and optionally, (d) a blowing agent, (e) a chain extender and / or crosslinking agent and (f) auxiliaries are mixed to give a reaction mixture, and the reaction mixture is reacted to give a polyurethane, wherein the manganese- or iron-containing catalyst (c1) is a compound according to general formula (I)

[0012]

[0013] wherein the variables are defined as follows:

[0014] M is selected from manganese(II), manganese(III), iron(II) or iron(III),

[0015] m is an integer from 0 to 2,

[0016] n is an integer from 0 to 2,

[0017] o is 0 or 1,

[0018] p is 0 or 1,

[0019] and if o or p is 0, then both o and p are 0,

[0020] q is 0 or 1,

[0021] R 1 and R 2 are each independently selected from the group consisting of:

[0022] F, Cl, Br, OH, CN, NH2, NO2 and hydrocarbon residues

[0023] and 1 and R 2 can also be joined to form a ring which is a cyclic aliphatic or aromatic ring,

[0024] R 3 is selected from H and hydrocarbon residues

[0025] R 4 and R 7Each independently selected from the group consisting of: H, F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon residues

[0026] wherein R 4 and R 7 can also be connected to form a ring of an aliphatic or aromatic ring

[0027] R 5 and R 6 Each independently selected from the group consisting of: H, F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon residues

[0028] and, if o is 0, then R 6 and R 7 together can be O

[0029] X is selected from O, S, NR 8 , PR 8 , wherein

[0030] R 8 is selected from H and hydrocarbon residues

[0031] wherein if p is 0 and X is NR 8 , then the NR 8 group can be connected to the carbon bearing R 7 by a double bond

[0032] L is selected from anionic organic ligands of the class derived from acetylacetonate or carboxylate esters, and Solv is a neutral ligand

[0033] wherein the hydrocarbon residue is selected from the group consisting of

[0034] C1-C 10 -alkyl

[0035] C3-C 10 -cycloalkyl

[0036] C3-C containing at least one heteroatom selected from N, O, and S 10 -heterocyclic group, C5-C 14 -aryl

[0037] 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 -heterocyclic group, C5-C 14 -aryl or C5-C 10- The heteroaryl optionally has one or more additional substituents selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C 10 - alkyl.

[0038] For the purposes of the present invention, polyurethanes include all known polyisocyanate addition products. These include addition products prepared from isocyanates and alcohols, and modified polyurethanes which may contain isocyanurate structures, urethane structures, urea structures, carbodiimide structures, uretonimine structures, biuret structures, and other isocyanate addition products. These polyurethanes of the present invention particularly include dense polyisocyanate addition products, such as thermosetting plastics, and foams based on polyisocyanate addition products, such as flexible foams, semi-rigid foams, rigid foams, and integral skin foams, as well as polyurethane coatings and adhesives. For the purposes of the present invention, the term polyurethane also encompasses polymer blends comprising polyurethanes and other polymers, and foams made from these polymer blends. The polyurethanes of the present invention are preferably polyurethane foams or dense polyurethanes that do not contain polymers other than those in polyurethane components (a) to (g) explained below.

[0039] For the purposes of the present invention, the expression polyurethane foam means a foam according to DIN 7726. According to DIN 53 421 / DIN EN ISO 604, the compression stress or compression strength of the flexible polyurethane foam of the present invention under 10% compression is respectively 15 kPa or less, preferably 1 kPa to 14 kPa, and particularly 4 kPa to 14 kPa. According to DIN 53 421 / DIN EN ISO 604, the compression stress of the semi-rigid polyurethane foam of the present invention under 10% compression is greater than 15 kPa to less than 80 kPa. According to DIN ISO 4590, the open cell factor of the semi-rigid polyurethane foam and the flexible polyurethane foam of the present invention is preferably greater than 85%, particularly preferably greater than 90%. Further details regarding the flexible polyurethane foam and semi-rigid polyurethane foam of the present invention can be found in "Polyurethane Handbook [Plastics handbook], Volume 7, Polyurethane [polyurethanes]", Hanser / Gardener publications, 2nd edition 1993, Chapter 5.

[0040] The rigid polyurethane foam of the present invention has a compression stress under 10% compression greater than or equal to 80 kPa, preferably greater than or equal to 120 kPa, and particularly preferably greater than or equal to 150 kPa. In addition, the closed-cell factor of the rigid polyurethane foam according to DIN ISO 4590 is greater than 80%, preferably greater than 90%. Further details regarding the rigid polyurethane foam of the present invention can be found in "Polyurethane Handbook [Plastics handbook], Volume 7, Polyurethane [polyurethanes]", Hanser / Gardener publications, 2nd edition 1993, Chapter 6.

[0041] For the purposes of the present invention, the expression elastic polyurethane foam means a polyurethane foam according to DIN 7726 which, 10 minutes after a transient deformation of 50% of its thickness in accordance with DIN 53 577, does not exhibit a residual deformation of more than 2% of its initial thickness. Here the material can be a rigid polyurethane foam, a semi-rigid polyurethane foam or a flexible polyurethane foam.

[0042] Integral skin polyurethane foam is a polyurethane foam according to DIN 7726 which has a peripheral region which, due to the shaping process, has a higher density than the core. Here the total encapsulation density averaged across the core and the peripheral region is preferably higher than 100 g / L. In addition, the integral skin polyurethane foam for the purposes of the present invention can be a rigid polyurethane foam, a semi-rigid polyurethane foam or a flexible polyurethane foam. Further details regarding the integral skin polyurethane foam of the present invention can be found in "Polyurethane Handbook", Hanser / Gardener publications, 2nd edition 1993, Chapter 7.

[0043] In one embodiment of the present invention, the polyurethane is a dense polyurethane having a density preferably greater than 850 g / L, preferably from 900 g / L to 1400 g / L, and particularly preferably from 1000 g / L to 1300 g / L. Here the dense polyurethane is obtained without the addition of a blowing agent. For the purposes of the present invention, small amounts of blowing agent (such as water) contained in the polyol due to the production process are not construed as meaning the addition of a blowing agent. The reaction mixture for producing the dense polyurethane preferably contains less than 0.2% by weight, particularly preferably less than 0.1% by weight and especially less than 0.05% by weight of water.

[0044] In a preferred embodiment, the polyurethane of the present invention is a polyurethane foam having an average density of from 10 g / L to 850 g / L, preferably a semi-rigid polyurethane foam or a flexible polyurethane foam or a rigid polyurethane foam, particularly preferably a flexible elastic polyurethane foam, a semi-rigid polyurethane foam or an integral skin elastic polyurethane foam. The density of the integral skin elastic polyurethane foam averaged across the core and the outer peripheral region is preferably from 150 g / L to 500 g / L. The average density of the flexible polyurethane foam is preferably from 10 g / L to 100 g / L. The average density of the semi-rigid polyurethane foam is preferably from 70 g / L to 150 g / L.

[0045] The polyurethane of the present invention is preferably used in means of transportation, such as ships, airplanes, trucks, cars and buses, particularly preferably cars and buses, and especially cars, and is particularly preferably used for automotive interiors. The flexible polyurethane foam can be used as a seat cushion herein; the semi-rigid polyurethane foam can be used as a foam backing for door side elements or instrument panels herein; the integral skin polyurethane foam can be used as a steering wheel, a control knob or a headrest herein, and the dense polyurethane can be used as a cable sheath by way of example herein. In addition, the polyurethane according to the present invention can be a polyurethane sole or a polyurethane in furniture or mattresses.

[0046] The polyisocyanate component (a) for producing the polyurethane of the present invention comprises any polyisocyanate known for producing polyurethanes. These polyisocyanates include aliphatic, cycloaliphatic and aromatic bifunctional or polyfunctional isocyanates known from the prior art, and also any desired mixtures thereof. Examples are diphenylmethane 2,2'-diisocyanate, 2,4'-diisocyanate and 4,4'-diisocyanate, a mixture of monomeric diphenylmethane diisocyanate and diphenylmethane diisocyanate homologues having a larger number of rings (polymeric MDI), isophorone diisocyanate (IPDI) and its oligomers, toluene 2,4- and 2,6-diisocyanate (TDI) and mixtures thereof, tetramethylene diisocyanate and its oligomers, hexamethylene diisocyanate (HDI) and its oligomers, naphthylene diisocyanate (NDI) and mixtures thereof.

[0047] Preferably, toluene 2,4-diisocyanate and / or 2,6-diisocyanate (TDI) or mixtures thereof, monomeric diphenylmethane diisocyanate and / or diphenylmethane diisocyanate homologues having a larger number of rings (polymeric MDI) and mixtures thereof are used. Other possible isocyanates are described by way of example in “Polyurethane Handbook”, Hanser / Gardener publications, 2nd edition 1993, Chapters 3.2 and 3.3.2.

[0048] 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 polyisocyanates (constituent (a-1)), for example, at a temperature of 30 °C to 100 °C, preferably about 80 °C, with a polymeric compound (b) (constituent (a-2)) having groups reactive to isocyanate and / or with a chain extender (c) (constituent (a-3)) to obtain an isocyanate prepolymer.

[0049] The polymeric compound (a-2) having groups reactive to isocyanate and the chain extender (a-3) are known to those skilled in the art and are described by way of example in "Polyurethane Handbook", Hanser / Gardener publications, 2nd edition 1993, chapter 3.1: By way of example, as the polymeric compound (a-2) having groups reactive to isocyanate, the polymeric compounds having groups reactive to isocyanate described under (b) can also be used.

[0050] As the polymeric compound (b) having groups reactive to isocyanate, any known compound having at least two hydrogen atoms reactive to isocyanate can be used, for example, those having a functionality of 2 to 8 and a number-average molar mass of 400 g / mol to 15,000 g / mol: By way of example, compounds selected from the group consisting of polyether polyols, polyester polyols, and mixtures thereof can be used.

[0051] Polyether alcohols are produced, by way of example, from epoxides (such as propylene oxide and / or ethylene oxide), or from tetrahydrofuran and a hydrogen-active starting compound (such as an aliphatic alcohol, phenol, amine, carboxylic acid, water, or a compound based on natural substances, such as sucrose, sorbitol, or mannitol), using a catalyst. Basic catalysts and double metal cyanide catalysts can be mentioned here, as described by way of example in PCT / EP2005 / 010124, EP 90444, or WO 05 / 090440.

[0052] Polyester alcohols are produced, by way of example, from aliphatic or aromatic dicarboxylic acids and polyols, polythioether polyols, polyester amides, hydroxylated polyacetals, and / or hydroxylated aliphatic polycarbonates, preferably in the presence of an esterification catalyst. Other possible polyols are mentioned by way of example in "Polyurethane Handbook", Hanser / Gardener publications, 2nd edition 1993, chapter 3.1.

[0053] In addition to the polyether alcohols and polyester alcohols described, other materials that can be used are polyether alcohols or polyester alcohols, which are also referred to as polymeric polyether alcohols or polymeric polyester alcohols and contain fillers. These compounds preferably contain dispersed particles made of a thermoplastic, such as dispersed particles composed of olefinic monomers such as acrylonitrile, styrene, (meth)acrylate, (meth)acrylic acid, and / or acrylamide. These polyols containing fillers are known and commercially available. The production processes for these are described by way of example in DE 111 394, US 3 304 273, US 3 383 351, US 3 523 093, DE 1152 536, DE 1 152 537, WO 2008 / 055952, and WO 2009 / 128279.

[0054] In a particularly preferred embodiment of the invention, component (b) comprises a polyether alcohol and more preferably does not comprise a polyester alcohol.

[0055] The catalyst (c) greatly accelerates the reaction of the polyol (b) and optionally the chain extender and crosslinker (f), as well as the chemical blowing agent (e) with the organic, optionally modified polyisocyanate (a). The catalyst (c) includes a manganese- or iron-containing catalyst (c1) and an amine catalyst (c2) that can optionally be incorporated in a preferred embodiment.

[0056] According to the invention, the manganese- or iron-containing catalyst (c1) is a compound according to general formula (I)

[0057]

[0058] wherein each variable is defined as follows:

[0059] M is selected from manganese (II), manganese (III), iron (II), or iron (III),

[0060] m is an integer from 0 to 2,

[0061] n is an integer from 0 to 2,

[0062] o is 0 or 1,

[0063] p is 0 or 1,

[0064] and if o or p is 0, then both o and p are 0,

[0065] q is 0 or 1,

[0066] R 1 and R 2 are each independently selected from the group consisting of:

[0067] F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon-containing residues

[0068] and R 1 and R 2 can also be linked to form a ring that is a cyclic aliphatic or aromatic ring,

[0069] R 3 is selected from H and hydrocarbon residues

[0070] R 4 and R 7 are each independently selected from the group consisting of: H, F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon residues

[0071] wherein R 4 and R 7 can also be linked to form a ring that is a cyclic aliphatic or aromatic ring,

[0072] R 5 and R 6 are each independently selected from the group consisting of: H, F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon residues,

[0073] and, if o is 0, then R 6 and R 7 together can be OX selected from O, S, NR 8 , PR 8 , preferably O, S, and NR 8 and particularly preferably X is O, wherein

[0074] R 8 is selected from H and hydrocarbon residues, preferably selected from H, CH3, and CH2-CH3,

[0075] wherein if p is 0 and X is NR 8 , then the NR 8 group can be linked via a double bond to the carbon bearing R 7 ,

[0076] L is selected from anionic organic ligands of the class from acetylacetonates or carboxylates, and Solv is a neutral ligand,

[0077] wherein the hydrocarbon residue is selected from the group consisting of:

[0078] C1-C 10 -alkyl,

[0079] C3-C 10 -cycloalkyl,

[0080] C3-C 10 -heterocyclic group containing at least one heteroatom selected from N, O, and S, C5-C 14 -aryl,

[0081] 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 -heterocyclic group, C5-C 14 -aryl or C5-C 10 -heteroaryl optionally has one or more additional substituents selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C 10 -alkyl.

[0082] Preferably, L is acetylacetonate or a carboxylate ester, such as acetate or its higher analogues such as propionate, butyrate, cyclohexylbutyrate, or laurate. In a preferred embodiment, L is selected from L1 to L4:

[0083]

[0084] And particularly preferred L is acetylacetone.

[0085] In a preferred embodiment of the present invention, M is selected from Mn(III) and Fe(III).

[0086] In a preferred embodiment, Solv (if present) is selected from the group consisting of water, alcohol, ether, amine, amide, nitrile, ester, ketone, or phosphine, polyisocyanate (a), or polyol (b).

[0087] In a preferred embodiment of the present invention, the manganese- or iron-containing catalyst can be obtained by contacting an imine ligand (IL) with a manganese(II), manganese(III), iron(II), or iron(III) complex of the general formula ML w Solv q wherein M, L, Solv, and q are as defined above and w is 2 or 3, wherein the imine ligand (IL) is defined by formula (II)

[0088]

[0089] wherein m, n, o, p, X, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 and R 7 are as defined above.

[0090] The imine ligand (IL) is preferably selected from compounds according to formulas A to L:

[0091]

[0092] In a preferred embodiment, the catalyst according to formula (I) is prepared by reacting the corresponding iron and manganese acetylacetonates [M(AcAc)3] with a ligand according to formula II. In this case, two acetylacetonate ligands are replaced by 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 additionally coordinate with 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 a polyol from the reaction mixture.

[0093] In a preferred embodiment of the present invention, based on the total weight of the polyisocyanate (a), the manganese- or iron-containing catalyst (c1) is used in an amount of 0.001% by weight to 10% by weight, preferably 0.01% by weight to 5% by weight and particularly preferably 0.05% by weight to 3% by weight.

[0094] The incorporable amine catalyst (c2) has at least one, preferably 1 to 8 and particularly preferably 1 to 2 groups reactive to isocyanate, exemplified by primary amine group, secondary amine group, hydroxyl group, amide group or urea group, preferably primary amine group, secondary amine group, hydroxyl group. The incorporable amine catalyst (c2) is mainly used for producing low-emission polyurethanes especially for automotive interior parts. These catalysts are known and described by way of example in EP1888664. These include compounds which preferably contain one or more tertiary amino groups in addition to the groups reactive to isocyanate. Preferably, at least one of the tertiary amino groups of the incorporable catalyst bears at least two aliphatic hydrocarbon moieties, preferably each moiety having 1 to 10 carbon atoms, particularly preferably each moiety having 1 to 6 carbon atoms. Particularly preferably, the tertiary amino group bears two moieties independently selected from methyl and ethyl moieties and also bears another organic moiety. Examples of the incorporable catalyst (c2) that can be used are bis(dimethylaminopropyl)urea, bis(N,N-dimethylaminoethoxyethyl)carbamate, dimethylaminopropylurea, N,N,N-trimethyl-N-hydroxyethylbis(aminopropyl ether), N,N,N-trimethyl-N-hydroxyethylbis(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-N-(3-aminopropyl)bis(aminoethyl ether), 1,4-diazabicyclo[2.2.2]octane-2-methanol and 3-dimethylaminoisopropyldiisopropanolamine, and mixtures thereof.

[0095] In addition to the manganese- or iron-containing catalyst (c1) and optionally incorporable amine catalyst (c2), the catalyst according to the invention may include conventional catalysts used as amine-based or metal-based catalysts in the production of polyurethanes. The following may be used as conventional catalysts for the production of polyurethanes by way of example: 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 and preferably 1,4-diazabicyclo[2.2.2]octane, and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine and dimethylethanolamine.

[0096] Organometallic compounds may also be used, preferably tin-free compounds, such as bismuth carboxylates, such as bismuth(III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate, or mixtures thereof.

[0097] In a preferred embodiment of the invention, in addition to the manganese-based or iron-based catalyst (c1), the catalyst (c) does not include a tin-based catalyst and more preferably does not include a metal catalyst. Furthermore, in a particularly preferred embodiment of the invention, the catalyst (c) consists of a manganese-based or iron-based catalyst (c1) and optionally incorporable catalyst (c2).

[0098] If the intention is for the polyurethanes of the present invention to take the form of polyurethane foams, the reaction mixture of the present invention further comprises a blowing agent (d). Any blowing agent known for the production of polyurethanes can be used herein. These can include chemical and / or physical blowing agents. These blowing agents are described by way of example in "Polyurethane Handbook", Hanser / Gardener publications, 2nd edition 1993, chapter 3.4.5. The term chemical blowing agent herein means a compound that forms a gaseous product by reacting with the isocyanate. Examples of these blowing agents are water and carboxylic acids. The term physical blowing agent means a compound that is dissolved or emulsified in the starting materials used in the reaction for polyurethane production and evaporates under the conditions of polyurethane formation. These are by way of example hydrocarbons, halogenated hydrocarbons and other compounds, examples being perfluorinated alkanes such as perfluorohexane, chlorofluorocarbons and ethers, esters, ketones, acetals and / or liquid carbon dioxide. Any desired amount of blowing agent can be used here. The amount of blowing agent used is preferably such that the density of the resulting polyurethane foam is from 10 g / L to 850 g / L, in particular from 20 g / L to 500 g / L, and in particular from 25 g / L to 300 g / L. It is particularly preferred to use a water-containing blowing agent and particularly preferably a blowing agent consisting of water.

[0099] The chain extenders and crosslinking agents (e) used herein can be compounds having at least two groups reactive towards isocyanate with a molar mass of less than 400 g / mol. The term chain extender used herein refers to a molecule having two hydrogen atoms reactive towards isocyanate, and the term crosslinking agent used herein refers to a molecule having more than two hydrogen atoms reactive towards isocyanate. However, the chain extender or crosslinking agent can also be omitted herein. However, the addition of a chain extender, crosslinking agent or optionally a mixture thereof can prove advantageous for altering mechanical properties such as hardness.

[0100] If a chain extender and / or crosslinking agent is intended to be used, the usual amount thereof in each case is from 0.5% by weight to 60% by weight, preferably from 1% by weight to 40% by weight and particularly preferably from 1.5% by weight to 20% by weight, based on the total weight of components (b) to (e).

[0101] If a chain extender and / or crosslinking agent (e) is used, chain extenders and / or crosslinking agents known in polyurethane production can be used. These are preferably low molecular weight compounds having functional groups reactive towards isocyanate, such as glycerol, trimethylolpropane, diols and diamines. Other possible low molecular weight chain extenders and / or crosslinking agents are mentioned by way of example in "Polyurethane Handbook", Hanser / Gardener publications, 2nd edition 1993, chapters 3.2 and 3.3.2.

[0102] In addition, auxiliaries and / or additives (f) can also be used. Any auxiliaries and additives known for the production of polyurethanes can be used here. Surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, flame retardants, hydrolysis stabilizers, antioxidants, aldehyde scavenging compounds, fungistatic substances and bacteriostatic substances can be mentioned by way of example. These substances are known and are described by way of example in "Polyurethane Handbook", Hanser / Gardener publications, 2nd edition 1993, chapters 3.4.4 and 3.4.6 to 3.4.11.

[0103] During the production of the polyurethanes of the present invention, the amounts of reaction of the polyisocyanate (a), polyol (b), blowing agent (c) and optionally, blowing agent (d), chain extender and / or crosslinker (e) are generally such that the equivalent ratio of the NCO groups of the polyisocyanate (a) to all the reactive hydrogen atoms of components (b), (c) and (if used) (d) and (e) is from 0.75 to 1.5:1, preferably from 0.80 to 1.25:1. If the cellular plastics contain at least some isocyanurate groups, the ratio of the NCO groups of the polyisocyanate (a) to all the reactive hydrogen atoms of components (b), (c) and (d) and (e) used is generally from 1.5 to 20:1, preferably from 1.5 to 8:1. A ratio of 1:1 corresponds here to an isocyanate index of 100.

[0104] When it is intended to produce a thermoplastic polyurethane, soft foam, semi-rigid foam, rigid foam or integral skin foam as the polyurethane of the present invention, the specific starting materials (a) to (f) for the production of the polyurethanes of the present invention differ only slightly, respectively, in quantity and quality. By way of example, no blowing agent is used for the production of dense polyurethanes, and thermoplastic polyurethanes mainly use strictly bifunctional starting materials. In addition, the elasticity and hardness of the polyurethanes of the present invention can be varied, by way of example, by the functionality and chain length of relatively high molecular weight compounds having at least two reactive hydrogen atoms. Such modifications are known to the person skilled in the art.

[0105] The starting materials for the production of dense polyurethanes are described by way of example in EP 0989146 or EP 1460094; the starting materials for the production of flexible foams are described by way of example in PCT / EP2005 / 010124 and EP 1529792; the starting materials for the production of semi-rigid foams are described by way of example in "Polyurethane Handbook", Hanser / Gardener publications, 2nd edition 1993, chapter 5.4; the starting materials for the production of rigid foams are described in PCT / EP2005 / 010955; and the starting materials for the production of integral skin foams are described in EP 364854, US5506275 or EP 897402. Then in each case the compound (d) is also added to the starting materials described in said documents.

[0106] In a preferred embodiment of the invention, the polyurethane is produced by a two-component process. In the two-component process, the isocyanate component comprises the isocyanate (a) and a polyol component which comprises (b) a polymeric compound having groups reactive towards isocyanates, (c) a catalyst which comprises the use of a manganese- or iron-containing catalyst (c1) and optionally (d) a blowing agent, (e) a chain extender and / or crosslinking agent, and (f) auxiliaries. In a preferred embodiment, the polyol component comprises the blowing agent (d) which comprises water.

[0107] The invention not only provides the process of the invention, but also polyurethanes obtainable by the process of the invention. The polyurethanes of the invention are preferably polyurethane foams in the form of flexible polyurethane foams, semi-rigid polyurethane foams or integral skin polyurethane foams. The polyurethanes according to the invention are preferably used in enclosed spaces, for example as thermal insulation materials in residential buildings, for example for the thermal insulation of pipes and refrigerators, in furniture construction, for example as decorative elements or as seat cushions, as mattresses, and in the interior of vehicles, for example for automotive interiors, for example as steering wheels, dashboards, door linings, carpet backing foams, sound-absorbing foams, for example roof linings, and headrests or control knobs. Another potential use of the polyurethanes according to the invention is soles of shoes. In addition to their low toxicity, their high efficiency and their good stability in the presence of water, the use of the catalysts of the invention also reduces the emission of volatile organic compounds from the polyurethanes according to the invention.

[0108] The present invention will be illustrated using examples. The room temperature in the examples is 20 °C. The gelation time of urethane synthesis was determined by mixing the reactants and the catalyst, and the mixture was vortexed for 10 seconds and allowed to react at room temperature. The formation of a viscous liquid in the reaction mixture was visually monitored, and the liquid subsequently solidified over time. A glass pipette was then used to probe the reaction mixture to ensure that the contents were completely solidified. The time from vortexing the reactants until the reaction mixture solidified was the gelation time.

[0109] General Synthesis of Salicylaldimine Ligands

[0110] 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 obtain the corresponding imine.

[0111] Synthesis of Salicylaldimine ONO Tridentate Manganese(III) Acetylacetonate Catalysts 1 to 3

[0112] 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. After that, the reaction mixture was cooled to room temperature, 5 ml of methanol was added and stirred. Then 2 g of Mn(acac)3 (5.67 mmol) was added to the mixture and another 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 dried in vacuo and the residue was washed with 3 × 10 ml of hexane. Then the product was dried in vacuo for 12 hours.

[0113] Catalyst 1: ESI-ESI-MS: m / z: 388.04 [M+Na] + (1.4%), IR spectrum v / cm -1 : 1595(m) 1536(m) 1513(m) 1480(s) 1461(s) 1435(s) 1374(m) 1305(m) 1257(m) 1224(s) 1171(m) 1145(m) 1127(m) 1022(m) 960(m) 924(m) 860(m) 838(m) 789(s) 735(s) 673(s) 635(s)

[0114] Catalyst 2: ESI-MS: m / z: 635.098 [M] + (18.1%), m / z: 535.048 [M-acac] + (3.1%), IR spectrum 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)

[0115] Catalyst 3: ESI-MS: m / z: 690.1558 [M] + (12.2%), m / z: 591.1105 [M - acac] + (26.8%), IR spectrum v / cm -1 : 1666(m) 1600(m) 1541(m) 1514(m) 1446(m) 1388(m) 1310(m) 1259(s) 1214(s) 1150(s) 1115(s) 1021(s) 930(s) 893(s) 864(s) 759(m) 640(s) 607(s)

[0116] Synthesis of Amino-Substituted Salicylaldimine ONO Tridentate Manganese(III) 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 h. After that, the reaction mixture was cooled to room temperature, and the solution was filtered using a PTFE filter with a pore size of 0.20 μm. Then the filtrate was dried to obtain the crude ligand. Then 0.050 g (0.28 mmol) of the ligand prepared above was added to 0.098 g (0.28 mmol) of Mn(acac)3 and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h.

[0117] Synthesis of Amino-Substituted Salicylaldimine ONO Tridentate Manganese(III) 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 h. After that, the reaction mixture was cooled to room temperature, and the solution was filtered using a PTFE filter with a pore size of 0.20 μm. Then the filtrate was dried to obtain the crude ligand. Then 0.12 g (0.45 mmol) of the ligand prepared above was added to 0.16 g (0.45 mmol) of Mn(dpvm)3 (tris(2,2,6,6 - tetramethyl - 3,5 - heptanedionato)manganese(III)) and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h.

[0118] Synthesis of Diol ONO Tridentate Manganese(III) Acetylacetonate Catalyst 6

[0119] 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. The product was then dried in vacuo for 12 hours.

[0120] Synthesis of Diol ONO Tridentate Manganese(III) Acetylacetonate Catalyst 7

[0121] 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. The product was then dried in vacuo for 12 hours.

[0122] Synthesis of Diacid ONO Tridentate Manganese(III) Acetylacetonate Catalyst 8

[0123] 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. The product was then dried in vacuo for 12 hours.

[0124] Synthesis of Salicylaldimine ONNO Tetradentate Manganese(III) Acetylacetonate Catalysts 9 to 11

[0125] 1.74 ml of salicylaldehyde (16.32 mmol) was added to the appropriate diamine (8.16 mmol), and the mixture was heated directly at 80 °C for 3 hours. After that, the reaction mixture was cooled to room temperature, 10 ml of ethanol was added and stirred. Then 2.87 g of Mn(acac)3 (8.16 mmol) was added to the mixture and another 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 dried in vacuo and the residue was washed with 3 × 10 ml of hexane. The product was then dried in vacuo for 12 hours.

[0126] General Catalytic Activity in Model Urethane Reactions

[0127] 0.23 ml of 1-butanol (2.5 mmol) was added to 5 mg of the catalytic material prepared as above (2.5 wt% based on the alcohol ROH used), and the mixture was vortexed for 10 seconds. After that, 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 reacted at room temperature. The time from vortexing the reactants until the reaction mixture solidified was the gel time. The solubility of the catalyst in the alcohol-isocyanate mixture was also recorded. At a 1 wt% ROH catalyst loading, 5 mg of the catalytic 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 the catalytic 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 the catalytic 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).

[0128]

[0129]

[0130]

[0131] Examples 6, 7, 8, 12, and 13 are comparative examples that demonstrate the benefits of the catalyst according to the present invention, particularly the influence of the ligand according to the present invention.

[0132] Catalyst Loading from 1 wt% ROH to 0.25 wt% ROH Using Mn acac Salicylaldimine Catalysts

[0133]

[0134]

[0135] Examples 21, 22, 26, and 27 are comparative examples that demonstrate the benefits of the catalyst according to the present invention and can match the activity of the prior art DBTL tin catalyst.

[0136] Solubility and Water Stability Tests of Catalysts in Polyols

[0137] 25 mg of the 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 value of 35 mg KOH / g and a functionality of 2.7).

[0138] Then, 0.125 g of water was added to the mixture and stirred. Then, the acetone was dried in vacuo to produce a yellowish-black viscous solution containing water. Then, the solution was allowed to stand at room temperature or at 60 °C for an extended period of time. Changes in the physical appearance and precipitation of the material were noted.

[0139] Solubility and Water Stability Tests of Catalysts in Acetone

[0140] 5 mg of catalyst 1 to 2 was dissolved in 0.1 ml of acetone, then 5 μl of water was added, and the mixture was allowed to stand at room temperature for 18 days. Then, the acetone was dried in vacuo to give a yellowish-black residue, to which 0.23 ml of 1-butanol (2.5 mmol) was added and vortexed. Then, 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) (h-MDI) was added, and the mixture was vortexed for 10 s and reacted at room temperature to obtain a polyurethane foam. The time after vortexing the reactants and when the reaction mixture solidifies is the gel time.

[0141]

[0142] Example 30 of the present invention demonstrates the beneficial effect of the salicyl ligand on the water stability of the Mn catalyst.

[0143] Synthesis of Hydroxy-Substituted Salicylaldimine ONO Tetradentate Manganese(III) Acetylacetonate Catalysts 12 to 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 h. After this, the reaction mixture was cooled to room temperature, 2 ml of methanol was added and stirred. Then, 0.25 g (0.7 mmol) of Mn(acac)3 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then, the product was dried in vacuo for 12 h.

[0144] Evaluation of Catalytic Activity According to the Reported Procedure at a Catalyst Loading of 2.5 wt.% ROH

[0145]

[0146] Synthesis of Bromo-Substituted Salicylaldimine ONO Tetradentate Manganese(III) Acetylacetonate Catalysts 18 to 20

[0147] 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 h. After that, the reaction mixture was cooled to room temperature, 2 ml of methanol was added and stirred. Then 0.085 g (0.24 mmol) of Mn(acac)3 was added to the mixture, and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h.

[0148] Synthesis of Bromo-Substituted Salicylaldimine ONNO Tetradentate Manganese(III) Acetylacetonate Catalysts 21 to 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 h. After that, the reaction mixture was cooled to room temperature, 2 ml of methanol was added and stirred. Then 0.085 g (0.24 mmol) of Mn(acac)3 was added to the mixture, and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h.

[0149] Evaluation of Catalytic Activity According to the Reported Procedure at a Catalyst Loading of 2.5 Wt% ROH

[0150]

[0151] Synthesis of Naphthalimide ONO Tetradentate Manganese(III) Acetylacetonate Catalysts 24 to 26

[0152] 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 h. After that, the reaction mixture was cooled to room temperature, 2 ml of methanol was added and stirred. Then 0.085 g (0.24 mmol) of Mn(acac)3 was added to the mixture, and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h.

[0153] Synthesis of Naphthalimide ONNO Tetradentate Manganese(III) Acetylacetonate Catalysts 27 to 29

[0154] 0.042 g of 3-hydroxy-2-naphthaldehyde (0.24 mmol) was added to an appropriate diamine (0.12 mmol) in 1 ml of methanol, and the mixture was heated directly at 80 °C for 3 h. After that, the reaction mixture was cooled to room temperature, 2 ml of methanol was added and stirred. Then 0.043 g (0.12 mmol) of Mn(acac)3 was added to the mixture, and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h.

[0155] Evaluation of Catalytic Activity According to the Reported Procedure at a Catalyst Loading of 2.5 Wt% ROH

[0156]

[0157] Synthesis of Mn(dpvm)3 (Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III))

[0158] 0.116 g (0.58 mmol) of MnCl2·4H2O dissolved in 1 ml of methanol was added dropwise to a solution of 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 h, then 0.027 g (0.67 mmol) of NaOH was added. Then the solution was left standing for 16 h. Then the solvent was evaporated off at room temperature and atmospheric pressure to give the title compound.

[0159] Synthesis of Salicylaldimine ONO Tridentate Mndpvm Catalysts 30 to 33

[0160] Catalysts 30 to 31: 60.3 μl of salicylaldehyde (0.567 mmol) was added to an appropriate amino alcohol (0.567 mmol) in 1 ml of methanol, and the mixture was heated directly at 80 °C for 3 h. After that, the reaction mixture was cooled to room temperature, 2 ml of methanol was added and stirred. Then 0.342 g of Mn(dpvm)3 (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III)) prepared as above was added to the mixture, and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h.

[0161] 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 that, the reaction mixture was cooled to room temperature, and the solution was filtered using a PTFE filter with a pore size of 0.20 μm. Then the filtrate was dried to obtain the crude ligand. Then 0.021 g (0.12 mmol) of the ligand prepared above was added to 0.073 g of Mn(dpvm)3 (manganese(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionato)) prepared as above, and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 hours.

[0162] 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 that, the reaction mixture was cooled to room temperature, and the solution was filtered using a PTFE filter with a pore size of 0.20 μm. Then the filtrate was dried to obtain the crude ligand. Then 0.036 g (0.13 mmol) of the ligand prepared above was added to 0.081 g of Mn(dpvm)3 (manganese(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionato)) prepared as above, and another 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 dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 hours.

[0163] Evaluation of Catalytic Activity According to the Reported Procedure at a Catalyst Loading of 2.5 Wt% ROH

[0164]

[0165] Comparative Experiment Not of This Invention: Solubility and Water Stability Tests of Mn(dpvm)3 in Acetone

[0166] 5 mg of Mn(dpvm)3 was dissolved in 0.1 ml of acetone, then 5 μl of water was added and the mixture was allowed to stand at room temperature for 18 days. Then the acetone was dried in vacuo to obtain a yellowish-black residue, to which 0.23 ml of 1-butanol (2.5 mmol) was added and vortexed. 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 reacted at room temperature. The time after vortexing the reactants and when the reaction mixture solidifies is the gelation time.

[0167]

[0168] Synthesis of Salicylaldimine ONO Tridentate Manganese(III) Acetate Catalysts 34 to 35

[0169] 0.63 ml of salicylaldehyde (5.67 mmol) was added to the appropriate amino alcohol (5.67 mmol), and the mixture was heated directly at 80 °C for 3 h. After that, the reaction mixture was cooled to room temperature, 5 ml of methanol was added and stirred. Then 1.5 g (5.67 mmol) of Mn(acetate)3 was added to the mixture, and another 5 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 dried in vacuo and the residue was washed with 3 × 10 ml of hexane. Then the product was dried in vacuo for 12 h.

[0170] Catalyst 35: ESI-MS: m / z: 591.0161 [M - acetate] + (26.8%), IR spectrum 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)

[0171] The evaluation of the catalytic activity was carried out according to the procedure generally reported above.

[0172]

[0173]

[0174] Solubility and Water Stability Tests of Mn(Acetato)3 Salicylaldimine Catalysts in Acetone

[0175] 5 mg of catalyst 35 was dissolved in 0.1 ml of acetone, then 5 μl of water was added and the mixture was allowed to stand at room temperature for 11 days. Then the acetone was dried in vacuo to give a yellowish-black residue, to which 0.23 ml of 1-butanol (2.5 mmol) was added and vortexed. Then 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) (h-MDI) was added, and the mixture was vortexed for 10 s and reacted at room temperature. The time after vortexing the reactants and when the reaction mixture solidified was the gelation time.

[0176]

[0177] Comparative Example 55 of the present invention shows the beneficial effects of the combination of the salicyl ligand and manganese acetate.

[0178] Synthesis of Salicylaldimine ONO Tridentate Iron(III) Acetylacetonate Catalysts 36 to 41

[0179] 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 h. After that, the reaction mixture was cooled to room temperature. Then 0.1 g of Fe(acac)3 (0.28 mmol) was added to the mixture and another 2 ml of solvent (methanol / DCM) was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 h, after which the solvent was dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h.

[0180]

[0181] Solubility and Water Stability Tests of Salicylaldimine Fe(acac)3 Catalysts in Acetone

[0182] 5 mg of catalyst 38 to 41 was dissolved in 0.1 ml of acetone, then 5 μl of water was added, and the mixture was allowed to stand at room temperature for 30 days. Then the acetone was dried in vacuo to give a crude residue, to which 0.23 ml of 1-butanol (2.5 mmol) was added and vortexed. Then 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) (h-MDI) was added, and the mixture was vortexed for 10 s and reacted at room temperature. The time after vortexing the reactants and when the reaction mixture solidifies is the gelation time.

[0183]

[0184] Solubility and Water Stability Tests of Salicylaldimine Fe(acac)3 Catalysts in 1-Butanol

[0185] 5 mg of catalyst 36 to 40 was dissolved in 0.23 ml of 1-butanol (2.5 mmol) at room temperature. After that, 10 mg of water was added and the mixture was heated at 60 °C for 48 h. After that, 0.31 ml of 4,4'-methylenebis(cyclohexyl isocyanate) (1.25 mmol) was added and the mixture was vortexed for 10 s. Then the reaction was monitored at room temperature to determine the gelation time.

[0186]

[0187] The above catalyst is partially soluble in polyol 1. Mixing the catalyst with methanol and then with polyol 1 results in complete dissolution.

[0188] Examples 66, 67, and 68 of the non-invention demonstrate the benefits of the present invention.

[0189] Synthesis of Hydroxy-Substituted Salicylaldimine ONO Tridentate Iron(III) Acetylacetonate Catalysts 42 to 47

[0190] 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 h. After that, the reaction mixture was cooled to room temperature. Then 0.25 g of Fe(acac)3 (0.72 mmol) was added to the mixture and another 2 ml of solvent (methanol / DCM) was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 h, after which the solvent was dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h and tested as disclosed above.

[0191]

[0192]

[0193] Synthesis of Bromo-Substituted Salicylaldimine ONO Tridentate Iron(III) Acetylacetonate Catalysts 48 to 53

[0194] 0.048 g of 5-bromo-2-hydroxybenzaldehyde (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 h. After that, the reaction mixture was cooled to room temperature. Then 0.085 g of Fe(acac)3 (0.24 mmol) was added to the mixture and another 2 ml of solvent (methanol / DCM) was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 h, after which the solvent was dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h and tested as disclosed above.

[0195]

[0196] Synthesis of Salicylaldimine ONO Tridentate Iron(III) Acetylacetonate Catalysts 54 to 59

[0197] 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 h. After that, the reaction mixture was cooled to room temperature. Then 0.085 g of Fe(acac)3 (0.24 mmol) was added to the mixture and another 2 ml of solvent (methanol / DCM) was added to the reaction mixture. The resulting mixture was stirred at room temperature for 24 h, after which the solvent was dried in vacuo and the residue was washed with 3 × 5 ml of hexane. Then the product was dried in vacuo for 12 h and tested as disclosed above.

[0198]

Claims

1. A method for producing polyurethane, wherein a) a polyisocyanate, b) a polymeric compound having groups reactive to isocyanate, c) a catalyst, said catalyst comprising a manganese- or iron-containing catalyst (c1), and optionally d) a blowing agent, e) a chain extender and / or crosslinking agent, and / or f) an auxiliary agent, are mixed to obtain a reaction mixture, and the reaction mixture is reacted to obtain the polyurethane, wherein the manganese- or iron-containing catalyst (c1) is a compound according to general formula (I) wherein 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, and if o or p is 0, then both o and p are 0, q is 0 or 1, R 1 and R 2 are each independently selected from the group consisting of: F, Cl, Br, OH, CN, NH2, NO2 and hydrocarbon residues and R 1 and R 2 can also be connected to form a ring that is an aliphatic or aromatic ring in a cyclic form, R 3 selected from H and hydrocarbon residues R 4 and R 7 are each independently selected from the group consisting of: H, F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon residues wherein R 4 and R 7 can also be linked to form a ring that is an aliphatic or aromatic ring in a ring shape, R 5 and R 6 are each independently selected from the group consisting of: H, F, Cl, Br, OH, CN, NH2, NO2, and hydrocarbon residues, And, if o is 0, then R 6 and R 7 together can be O X is selected from O, S, NR 8 , PR 8 , wherein R 8 selected from H and hydrocarbon-containing residues wherein if p is 0 and X is NR 8 , then the NR 8 group can be linked via a double bond to the carbon bearing R 7 . L is selected from anionic organic ligands from the following categories: acetylacetonate or carboxylate esters such as acetate or its higher analogues, and Solv is a neutral ligand wherein the hydrocarbon residues are selected from the group consisting of: C1-C 10 -alkyl, C3-C 10 -cycloalkyl, C3-C containing at least one heteroatom selected from N, O, and S 10 -heterocyclic group, C5-C 14 -aryl, C5-C containing at least one heteroatom selected from N, O, and S 10 -heteroaryl, wherein said C1-C 10 - alkyl, C3-C 10 - cycloalkyl, C3-C 10 - heterocyclic group, C5-C 14 - aryl or C5-C 10 - heteroaryl optionally has one or more additional substituents selected from the group consisting of: F, Cl, Br, OH, CN, NH2, and C1-C 10 - alkyl.

2. The method according to any one of claims 1, wherein L is selected from L1 to L4:

3. The method according to claim 1 or 2, wherein M is selected from Mn(III) and Fe(III).

4. The method according to any one of claims 1 to 3, wherein the manganese- or iron-containing catalyst (c1) is obtained by contacting an imine ligand (IL) with a manganese(II), manganese(III), iron(II) or iron(III) complex of the general formula ML w Solv q wherein M, L, Solv and q are as defined in claim 1 and w is 2 or 3, and wherein the imine ligand (IL) is defined by formula (II) wherein m, n, o, p, X, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in claim 1.

5. The method according to claim 4, wherein the imine ligand (IL) is selected from compounds according to formulas A to L:

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

7. The method according to any one of claims 1 to 6, wherein X is O.

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

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

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

11. The method according to claim 10, wherein the incorporable catalyst (c2) comprises a compound having one or more tertiary aliphatic amino groups in addition to the groups reactive to isocyanate.

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

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

14. A polyol component for producing polyurethane, the polyol component comprising (b) a polymeric compound having groups reactive to isocyanate, (c) a catalyst, said catalyst comprising a manganese- or iron-containing catalyst (c1) as defined in claim 1, and optionally (d) a blowing agent, said blowing agent comprising water (e) a chain extender and / or crosslinking agent, and (f) an auxiliary agent.

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

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

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