Catalyst comprising a tetravalent metal and a dicarboxylate ligand

Abstract

The present invention relates to a catalyst comprising a tetravalent metal such as Zr, to processes for the preparation of the catalyst comprising a tetravalent metal, to a process for the preparation of a compound, oligomer or polymer comprising at least one urethane group using the catalyst comprising a bivalent metal, to a composition comprising (i) at least one monoalcohol (B1) or polyol (B2), (ii) at least one polyisocyanate (A) and (iii) at least one catalyst comprising a tetravalent metal, to a layer on a substrate formed from the composition, to a foam formed from the composition and to the use of the catalyst comprising a tetravalent metal for preparing compounds, oligomers or polymers comprising a urethane group, as esterification and transesterification catalyst and as catalyst for ring-opening polymerizations of lactones and epoxides.

Description

[0001]Catalyst comprising a tetravalent metal and a dicarboxylate ligand DescriptionThe present invention relates to a catalyst comprising a tetravalent metal such as Zr, toprocesses for the preparation of the catalyst comprising a tetravalent metal, to a process for the preparation of a compound, oligomer or polymer comprising at least one urethane group using the catalyst comprising a bivalent metal, to a composition comprising (i) at least one monoalcohol (B1) or polyol (B2), (ii) at least one polyisocyanate (A) and (iii) atleast one catalyst comprising a tetravalent metal, to a layer on a substrate formed fromthe composition, to a foam formed from the composition and to the use of the catalyst comprising a tetravalent metal for preparing compounds, oligomers or polymers comprising a urethane group, as esterification and transesterification catalyst and as catalyst for ring-opening polymerizations of lactones and epoxides. WO 2018 / 069018 relates to a coating composition system comprising the components (A) to (C) and optionally further components. The component (A) is at least one polyhydroxyl group-containing compound and the component (B) is at least one polyisocyanate-containing compound. In contrast, the component (C) is a catalystcomprising at least two salts of an aliphatic monocarboxylic acid having at least 4 carbonatoms. In this case, the metal component of the first salt is bismuth (Bi), while the second salt comprises magnesium (Mg), sodium (Na), potassium (K) or calcium (Ca) as metal component. The coating composition system according to WO 2018 / 069018 may be configured according to a first option such that all components are present separatelyfrom one another, i.e. the individual components are not mixed with one another,whereas according to a second option of the corresponding coating composition system, the respective components can also be present completely or at least partially mixed with one another.WO 2020 / 160939 relates to a bismuth-containing catalyst comprising at least one radicalR1, which comprises a carboxyl fragment, wherein a first carbon atom (α-carbon) is bonded to the carbon atom of the carboxyl group, which in turn is directly substituted with at least one aromatic system. WO 2020 / 160939 further relates to a method for preparing the bismuth-containing catalyst and to the use of the bismuth-containing catalyst forpreparing compounds comprising a urethane group.The preparation of compounds comprising a urethane group (urethane bond) has likewise been known for a long time. A compound having a urethane group is generally obtained if a compound comprising an isocyanate group is reacted with a compoundcomprising a hydroxyl group. The reaction generally takes place in the presence of acatalyst. Although tin-containing catalysts exhibit very high activity in such reactions, the EB23-1526PC December 9, 2024 use of such tin-containing catalysts, especially alkyl-tin compounds, should be avoided owing to their (very high) toxicity. The water stability of compounds such as zirconium acetylacetonate (acac) is animportant consideration when using these compounds as catalysts or additives in variousapplications. Zirconium acetylacetonate (acac) is a widely used zirconium-based catalyst in various organic transformations, including polymerization reactions. It exhibits good waterstability and can withstand exposure to water without significant degradation. Thisproperty makes zirconium acac a suitable choice for applications where water is present as a reaction medium or as a component of the reaction mixture. But with higher amount of water zr acac decomposes and the reactivity decreases.Nevertheless, it is important to note that the water stability of these compounds can varydepending on factors such as concentration, pH, temperature, and the presence of other reactive species. Therefore, it is essential to consider the specific reaction conditions and carefully evaluate the water stability of tin-containing catalysts such zirconium acetylacetonate (acac) before their use in a particular application. The object of the present invention, therefore, was to provide a novel catalyst, which can be used for preparing compounds comprising a urethane group. This object is achieved by a catalyst of a general formula (I) ((R1a)2-)x((R1b)-)y(R2)-)z(M1)4+(I) in which the variables are defined as follows: (R1a)2- is mutually independently a residue of a dianion of a general formula (IIa) (IIa), wherein R3, R4, R5and R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl,EB23-1526PC wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyl and C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C1-C6-alkoxy,and wherein A is unsubstituted or at least monosubstituted linear C3-30-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14- aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl,and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, andwherein optionally at least one CH2-group of linear C3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, and wherein alkyl and aryl fragments of N-C1-30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S- phenyl, -O-C1-6-alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene. xis 0, 1 or 2,(R1b)- is mutually independently a residue of a general formula (IIb) EB23-1526PC wherein R3, R4, R5and R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyl and C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH,or C1-C6-alkoxy,A is unsubstituted or at least monosubstituted linear C3-30-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14- aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30-aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30- alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6- alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, and wherein optionally at least one CH2-group of linear C3-30-alkylene is replaced by at least one heteroatom independently selectedfrom the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, and wherein alkyl and aryl fragments of N-C1- 30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least onCH2-group of linear C3-C30-alkylene, EB23-1526PC M3is H or an alkali metal, yis 0, 1, 2, 3 or 4,(R2)- is mutually independently an anion selected from the group of HO-, R8-O-, a halide anion, HO-C(=O)-O-, R9-S- or an anion of a general formula (III) O || R7^ C ^ O – (III) whereinR7, R8and R9are mutually independently an organic residue, zis 0, 1, 2 or 3,wherein the sum of 2x, y and z equals 4, and(M1)4+is a tetravalent metal.The advantages of the catalysts according to the invention can be found in their abilityto enhance both the water stability and reactivity of other metal catalysts, including those based on Zr(IV), due to the presence of a residue of a dianion of a general formula (IIa) or, alternatively, due to the presence of at least one residue of a general formula (IIb).This exciting finding opens up possibilities for improving the performance of these metalcatalysts in various chemical reactions. By incorporating these residues of a dianion of a general formula (IIa) or, alternatively, of a residue of a general formula (IIb) as additives or ligands, the stability, selectivity, and activity of the metal catalyst systems can be significantly enhanced, leading to more efficient and effective chemical processes. Additionally, it has been found that addition of some of the dicarboxylic acids, in particular those having at least 2 heteroatoms within the residue A (linear C3-30-alkylene residue) show a latency behavior (the inventive catalysts are thermolatent). Thermolatent means that the catalytic activity of the respective catalyst is significantly increased at highertemperatures (compared to room temperature).EB23-1526PC Furthermore, in the case of the catalysts according to the invention, it is also not required that the catalyst as a salt is employed in the presence of protonated ligand. The catalysts according to the invention can thus be used without the presence of the corresponding acid at high catalytic activity in order to form compounds having urethane groups andthere are no issues how the corresponding acid as a low molecular species behaves inthe respective formulation and later in the polymeric material. Last but not least, the tetravalent catalysts according to the invention are characterized in that, inter alia, the use of toxic tin-containing catalysts in the production of compoundscomprising a urethane group can be avoided. The tetravalent catalysts according to theinvention have a comparable catalytic activity as known representatives of the effective, on the one hand catalytically active, but on the other hand toxic, tin-containing catalysts. Advantageous properties are then already obtained in the catalysts according to theinvention if the dianion (R1a)2- according to the general formula (IIa), which is used assubstituent / ligand of the tetravalent central atom, comprises the radicals R3, R4, R5and R6in α-position and the diradical A. It is preferred that at least one of the radicals R3, R4, R5or R6is unsubstituted or at least monosubstituted C6-C14-aryl, especially phenyl. The same holds true in case, alternatively, at least one, preferably two residues, of a generalformula (IIb) are used as (R1b)- instead.“α-position” in the context of the present invention describes the carbon atom next to the carbonyl carbon atom of the carboxylic acid. In accordance with the invention, this carbon atom is referred to as the α-carbon. Known examples for this purpose from chemicalnomenclature are α-amino acids, where the α-C atom is the carbon atom to which theamino group and the carboxyl group are attached. Specific examples for this numbering from the field of amino acids are β-alanine and gamma-aminobutyric acid. In chemical nomenclature, the carbonyl carbon is sometimes also counted and referred to as position 1. Accordingly, said first carbon atom directly adjacent to the carbon atom of the carboxylgroup is sometimes also referred to as position 2 in chemical nomenclature. In thecontext of the present invention, the dianion (R1a)2-according to the general formula (IIa) has two α-carbons. The said carboxyl groups of this substituent are located (spatially speaking) in proximityto the central tetravalent metal atom M1 of the catalyst. The catalysts according to theinvention are represented as salts, wherein the central tetravalent metal of the catalyst according to the invention is represented as a (fourtimes positively charged) cation of the corresponding salt (see for example the general formula (I)). The corresponding substituents / ligands of the catalyst, which are represented by the substituents / radicalsR1a, R1b and R2 in the general formula (I) detailed above, form the corresponding anioncomponents of the catalyst in this salt representation. The substituent / ligand R1ais double negatively charged and the substituent / ligand R1band R2are both singly negatively charged. As detailed below, the substituent R1amandatorily comprises two EB23-1526PC carboxyl groups both being negatively charged (dianion), whereas the substituent R2may comprise one carboxyl group, for example, in case it is an anion of a general formula (III). The substituent R1balso comprises two carboxyl groups, but only one of them is negatively charged (“monoanion”), whereas the second carboxyl group of the substituentR1b is neutralized by either a proton or an alkali metal. In general, the negative charge inthe corresponding substituents / ligands of said carboxyl groups is localized and / or the corresponding carboxyl groups are located in spatial proximity to the (positively charged) central tetravalent metal atom.From a scientific standpoint however, it is also tenable, in place of the salt notation usedin the context of the present application for the catalysts according to the invention, to select a notation / representation in which chemical bonds between the central tetravalent metal atoms and the ligands R1a, R1band R2according to general formula (I) is completely or at least partially formed in each case. Expressed in other words, this means that thecentral tetravalent metal atom is not present as a positively charged cation and thecorresponding ligands are also not present as negatively charged anions, but rather the corresponding charge form a chemical bond between the corresponding ligands on the one hand and the central tetravalent metal atom on the other hand. In the context of the present invention, the catalysts comprising a central tetravalent metal atom disclosedaccording to the invention, therefore, also describe such a definition that is not based ona salt. In the context of the present invention, definitions such as C1-C30-alkyl, such as defined, for example, for the radicals R3to R6in formula (IIa) above, signifies that this substituent(radical) is an alkyl radical having a carbon atom number of 1 to 30, wherein substituentsoptionally present are not taken into consideration in the carbon atom number. The alkyl radical may be either linear or branched as well as optionally cyclic. Alkyl radicals having both a cyclic and a linear component also fall under this definition. The same applies to other alkyl radicals such as a C1-C6-alkyl radical or a C1-C12-alkyl radical for example.Examples of alkyl radicals are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl,isobutyl, 2-ethylhexyl, tertiary-butyl (tert-Bu / t-Bu), pentyl, hexyl, heptyl, cyclohexyl, octyl, nonyl or decyl. Within the context of the present invention, the substituent (radical) “C1-C30-alkyl” mayalternatively be described as “C1-30-alkyl”, both terms C1-C30-alkyl on the hand and “C1-30-alkyl” on the other hand have exactly the same meaning. The same holds true in connection with any of the below mentioned definitions of further substituents / radicals as well.In the context of the present invention, definitions such as C3-30-alkylene (or alternativelyrefered to as “C3-C30-alkylene”), such as defined, for example, for the diradical A in formula (IIa) above, signifies that this diradical is an alkylene diradical having a carbon atom number of 3 to 30, wherein substituents optionally present are not taken into EB23-1526PC consideration in the carbon atom number. The C3-30-alkylene radical is linear in respect of the carbon atoms forming this radical, but without consideration of any substituents. In the context of the present invention, a heteroatom signifies any atom that is not acarbon or a hydrogen atom and that has replaced a carbon atom in the backbone of themolecular structure of a compound, especially in the C3-C30-alkylene bridge of formula (IIa). Examples of heteroatoms are O, S and N. In the context of the present invention, at least one CH2-group of linear C3-30-alkyleneradical may optionally be replaced by at least one heteroatom. In case two or moreCH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene. Examples of linear unsubstituted C3-30-alkylene, wherein at least two not adjacent CH2groups are replaced by O as heteroatom are . In the context of the present invention, the term “aryl" or the term “C6-C14-aryl", as defined,for example, for the radicals R3 to R6 in formula (IIa) above, signifies that the substituent(radical) is an aromatic system. The corresponding aromatic system has a carbon atom number of 6 to 14, wherein substituents optionally present are not taken into consideration in the carbon atom number. The aromatic system may be a monocyclic, bicyclic or optionally polycyclic aromatic system. In the case of bicyclic or polycyclicaromatic systems, individual rings may optionally be fully or partially saturated.Preferably, all rings of the corresponding aromatic systems are fully unsaturated. Preferred examples of aryl are phenyl, naphthyl or anthracyl, especially phenyl. In the context of the present invention, the definition “C7-C30-aralkyl", as defined forexample for the radicals R3 to R6 in formula (IIa) above, signifies that the substituent(radical) comprises an alkyl radical (such as C1-C6-alkyl according to the definitions above), wherein this alkyl radical is in turn substituted by an aryl radical (according to the definitions above). The corresponding aralkyl substituent has a carbon atom number of 7 to 30, wherein substituents optionally present are not taken into consideration in the EB23-1526PC carbon atom number. The alkyl radical itself present therein may be either linear or branched as well as optionally cyclic. In the context of the present invention, the term “C1-C6-alkoxy", as defined for exampleas (additional) substituent of the radicals R3 to R6 in formula (IIa) above, signifies that itis a substituent (radical) in this case which is derived from an alcohol. The corresponding substituent thus comprises an oxygen fragment (-O-), which is in turn linked to an alkyl radical, such as C1-C6-alkyl (according to the definitions above). The alkyl radical itself may be either linear or branched as well as optionally cyclic. In the context of the present invention, the term “halogen", as defined for example as (additional) substituent of the radicals R3to R6in formula (II) above, signifies that the substituent (radical) is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine, particularly preferably chlorine. Examples of halide anions are fluoride, chloride, bromide and iodide. Examples of alkali metals are lithium, sodium and potassium.In the context of the present invention, the term “unsubstituted or at leastmonosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl", such as defined for example for the radicals R3to R6in formula (IIa) above, signifies that each of the in total four substituents (radicals) detailed corresponding to their definitions already specified above may be present either in unsubstituted form or have at least one further substituent(monosubstituted). If one or more substituents are present (for example disubstituted,trisubstituted or even higher substituted), the appropriate substituents are selected independently of one another from the substituent groups specified in each case. In the case of a disubstituted C6-C14-aryl for example, the corresponding aryl unit, suchas phenyl for example, may be substituted for example by a hydroxyl and a C1-C30-alkylsubstituent, such as methyl or ethyl. Alkyl or aryl fragments may themselves in turn comprise at least one additional substituent according to the definitions stated. The substitution may be at any desired position of the corresponding fragment.Unless otherwise specified in the following description, the respective definitions of theradicals R1to R9are in each case the preferred unsubstituted definitions. The present invention is further specified herein below.The present invention firstly relates to a catalyst of a general formula (I)((R1a)2-)x((R1b)-)y(R2)-)z(M1)4+(I) EB23-1526PC in which the variables are defined as follows: (R1a)2-is mutually independently a residue of a dianion of a general formula (IIa) (IIa),wherein R3, R4, R5and R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting ofhydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyl and C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C1-C6-alkoxy, and wherein A is unsubstituted or at least monosubstituted linear C3-30-alkylene, wherein the substituents are selected from the group consisting of-OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14- aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and aryl fragments of these substituents may in turnbe at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, and wherein optionally at least one CH2-group of linear C3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, and wherein alkyl and aryl fragments of N-C1- 30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at leastmonosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, EB23-1526PC -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S- phenyl, -O-C1-6-alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or moreheteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene. xis 0, 1 or 2,(R1b)- is mutually independently a residue of a general formula (IIb) wherein R3, R4, R5and R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyland C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C1-C6-alkoxy, Ais unsubstituted or at least monosubstituted linear C3-30-alkylene,wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14- aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30- alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, andthe alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6- alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, - S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, andEB23-1526PC wherein optionally at least one CH2-group of linear C3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, and wherein alkyl and aryl fragments of N-C1- 30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at leastmonosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S- phenyl, -O-C1-6-alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene arereplaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene, M3 is H or an alkali metal,y is 0, 1, 2, 3 or 4,(R2)- is mutually independently an anion selected from the group of HO-, R8-O- ,a halide anion, HO-C(=O)-O-, R9-S- or an anion of a general formula (III)O || R7^ C ^ O – (III) wherein R7, R8 and R9 are mutually independently an organic residue,z is 0, 1, 2 or 3,wherein the sum of 2x, y and z equals 4, and (M1)4+is a tetravalent metal. In connection with the radicals (substituents / ligands) present in the general formula (I),particularly the necessary radicals R1a, R1b and R2, it should be noted that thefurther / exact chemical definition of these radicals R1a, R1band R2is a result of the radicals EB23-1526PC R3to R6and A of the general formulas (IIa) or (IIb) with respect to the radical R1and is a result of the radicals R7of the general formula (III) with respect to the radical R2. In the context of the present invention, the variables x, y and z of the correspondingsubstituents / ligands R1a, R1b and R2 of the catalyst in the general formula (I) as shownabove, may be freely chosen under the proviso that the sum of the variables 2x, y and z equals 4. This is due to the fact that the overall charge of the catalyst of the general formula (I) is0, since the catalyst comprises an anionic fragment (made up of the correspondingsubstituents / ligands R1a, R1band / or R2) having a total charge of -4 and a cationic fragment (made up of the tetravalent metal (M1)2+) having a total charge of +4. By consequence, the general formula (I) comprises catalysts wherein i) x is 1 and z is 2, orii) y is 2 and z is 2, oriii) x is 1, y is 1 and z is 1, oriv) x is 2,preferably x is 1 and z is 2. For example, within the above-mentioned option i), wherein x is 1 and z is 2, y must be 0,, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 4.On the other hand, within the above-mentioned option ii), wherein y is 2 and z is 2,, xmust be 0, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 4. Furthermore, within the above-mentioned option iii), wherein x is 1, y is 1 and z is 1, the requirement that the sum of the variables 2x, y and z equals 4 is also fullfilled. Furthermore, within the above-mentioned option iv), wherein x is 2, both y and z are 0each, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 4.A preferred embodiment of the present invention relates to catalyst of a general formula (I) ((R1a)2-)x((R1b)-)y(R2)-)z(M1)4+ (I)in which the variables are defined as follows: (R1a)2-is mutually independently a residue of a dianion of a general formula (IIa) EB23-1526PC (IIa), wherein R3, R4, R5and R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyl and C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH,or C1-C6-alkoxy,and wherein A is unsubstituted or at least monosubstituted linear C3-30-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14- aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl,and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, andwherein at least one CH2-group of linear C3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30- aralkyl, and wherein alkyl and aryl fragments of N-C1-30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6- alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or more EB23-1526PC heteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene. xis 0, 1 or 2,(R1b)- is mutually independently a residue of a general formula (IIb) wherein R3, R4, R5and R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyland C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C1-C6-alkoxy, Ais unsubstituted or at least monosubstituted linear C3-30-alkylene,wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14- aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30- alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, andthe alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6- alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, - S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, andwherein at least one CH2-group of linear C3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30- aralkyl, and wherein alkyl and aryl fragments of N-C1-30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, EB23-1526PC -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6- alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or moreheteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene, M3is H or an alkali metal, yis 0, 1, 2, 3 or 4,(R2)- is mutually independently an anion selected from the group of HO-, R8-O- , a halide anion, HO-C(=O)-O-, R9-S- or an anion of a general formula (III) O || R7^ C ^ O – (III) wherein R7, R8and R9are mutually independently an organic residue, zis 0, 1, 2 or 3,wherein the sum of 2x, y and z equals 4, and (M1)4+ is a tetravalent metal.Preferably, at least one of the radicals R3, R4, R5or R6of the residues according togeneral formulas (IIa) and / or (IIb) is , mutually independently unsubstituted or at leastmonosubstituted C6-C14-aryl, preferably at least two, more preferably at least three, and most preferably each of the radicals R3, R4, R5or R6are unsubstituted or at least monosubstituted C6-C14-aryl,wherein the substituents are selected from the group consisting of hydroxyl, halogen,carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy and C1-C30-alkyl. EB23-1526PC More preferably, mutually independently at least one, preferably at least two, more preferably at least three, and most preferably each of the radicals R3, R4, R5or R6of the residues according to general formulas (IIa) and / or (IIb) is phenyl.In respect of the residue A according to general formulas (IIa) and / or (IIb, it is preferredthat A is unsubstituted or at least monosubstituted linear C5-20-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)- OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14-aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30-aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl,-O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S- phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, and wherein at least one CH2-group of linear C5-20-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O and S, and in case two or more CH2-groups of linear C5-C20-alkylene are replaced by two ormore heteroatoms, the two or more heteroatoms are separated from each other by atleast one CH2-group of linear C5-C20-alkylene, most preferably the at least one heteroatom is O. In respect of the residue A according to general formulas (IIa) and / or (IIb), it is morepreferred that A is unsubstituted linear C5-20-alkylene,wherein at least one CH2-group of linear C5-20-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O and S,and in case two or more CH2-groups of linear C5-20-alkylene are replaced by two or moreheteroatoms, the two or more heteroatoms are separated from each other by at least one CH2-group of linear C5-20-alkylene, most preferably the at least one heteroatom is O. In respect of the residue A according to general formulas (IIa) and / or (IIb), it is most preferred that A is unsubstituted linear C5-12-alkylene, wherein one, two or three CH2-groups of linear C5-12-alkylene are replaced by O as heteroatom each and in case two or three CH2-groups of linear C5-12-alkylene are replaced by O as heteroatom, thetwo or three heteroatoms are separated from each other by one or two, preferably bytwo, CH2-groups of linear C5-12-alkylene, EB23-1526PC preferably A is unsubstituted linear C8-10-alkylene, wherein one or two groups of linear C8-10-alkylene are replaced by O as heteroatom each and in case two CH2-groups of linear C8-10-alkylene are replaced by O as heteroatom, the two heteroatoms are separated from each other by one or two, preferably by two, CH2-groups of linear C8-10-alkylene,most preferably A is unsubstituted linear C8-10-alkylene, wherein one group of linear C8-10-alkylene is replaced by O as heteroatom.As described above, the residue (R2)- is an anion such as HO-, R8-O-, a halide anion,HO-C(=O)-O-, R9-S- or an anion of a general formula (III) and the residues R7, R8and R9are mutually independently an organic residue. Such residues (R2)- are known to the skilled person. Any residues (R2)- can be employed within the catalysts according to the present invention. The same holds true in respect of any suitable organic residues to beemployed in connection with R7, R8 and R9.In respect of the residue (R2)- according to general formula (I), it is preferred that (R2)- is an anion selected from the group of HO-, R8-O-, Cl-, HO-C(=O)-O-, R9-S- or an anion of a general formula (III) O || R7^ C ^ O – (III) whereinR7, R8 and R9 are mutually independently unsubstituted or at least monosubstituted C3-30-alkyl, C6-14-aryl or C7-30-aralkyl, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14-aryl, - NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30-aralkyl)2, -SH, -S-C1-30-alkyl, -S- C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at leastmonosubstituted by -OH, halogen, -C(=O)-OM2, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl, O-phenyl or C1-6- alkyl, wherein M2is H or alkali metal, andwherein one CH2 group or at least two not adjacent CH2 groups of C3-30-alkyl can bereplaced by a heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, wherein the alkyl and aryl fragments of EB23-1526PC these substituents may in turn be at least monosubstituted by -OH halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O- C1-6-alkyl or -O-phenyl,preferably R7, R8 and R9 are mutually independently unsubstituted or at leastmonosubstituted C1-C12-alkyl or C6-C14-aryl, wherein the substituents are selected from the group consisting of hydroxyl, chlorine, -CF3and C1-C6-alkyl. (R2)- is more preferably an anion of general formula (III),wherein R7 is unsubstituted or at least monosubstituted C3-30-alkyl, wherein thesubstituents are selected from the group consisting of -OH, halogen, -C(=O)-OM3, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14-aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, - N(C7-30-aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and aryl fragments ofthese substituents may in turn be at least monosubstituted by -OH, halogen, -C(=O)-OM1, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6- alkyl, -S-phenyl, -O-C1-6-alkyl, O-phenyl or C-1-6-alkyl, wherein M3is H or alkali metal, andwherein one CH2 group or at least two not adjacent CH2 groups of C3-30-alkyl can bereplaced by a heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, wherein alkyl and aryl fragments of N-C1-30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl can at least be monosubstituted by -OH halogen, - CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl.(R2)- is even more preferably an anion of general formula (III), wherein R7is unsubstituted or at least monosubstituted C3-30-alkyl, wherein the substituents are selected from the group consisting -C(=O)-OM3and C6-14-aryl, and thearyl fragments of these substituents may in turn be at least monosubstituted by -OH,halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl and C1-6-alkyl, wherein M3is H or metal, and wherein one CH2group or at least two not adjacent CH2groups of C3-30-alkyl can bereplaced by a heteroatom independently selected from the group consisting of O and S.(R2)- is even more preferably an anion of general formula (III), wherein R7is unsubstituted or at least monosubstituted C3-30-alkyl, wherein thesubstituents are selected from the group consisting -C(=O)-OM3and phenyl, andwherein one CH2group or at least two not adjacent CH2groups of C3-30-alkyl can be replaced by a O. EB23-1526PC (R2)- is most preferably an anion of general formula (III), wherein R7is unsubstituted C3-20-alkyl.(R2)- is in particular neodecanoate.Examples of the alkali metals M2, and / or M3, as optionally contained within the substituents as described above, are lithium, sodium and potassium.As described above, the central metal (M1)4+ according to formula (I) is a tetravalent metal.Tetravalent metals as such are known to the skilled person. Any tetravalent metal can be employed within the catalysts according to the present invention. Preferably, (M1)4+is a tetravalent metal selected from Zr4+, Pb4+, Ti4+, Sn4+and Hf4+,preferably selected from Zr4+, Ti4+, Sn4+ and Hf4+, most preferably Zr4+.The present invention further relates also to a method for preparing a catalyst of the general formula (I) according to the definitions above. The method according to the invention for preparing such catalysts can comprise, for example, reacting i) at least one compound of a general formula (IIc) or a corresponding salt thereof,wherein R3, R4, R5und R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting ofhydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyl and C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C1-C6-alkoxy, and wherein A is unsubstituted or at least monosubstituted linear C3-30- alkylene, wherein the substituents are selected from the group consisting EB23-1526PC of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14-aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30-aralkyl)2, -SH, - S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O- C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH,halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, - N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, and wherein optionally at least one CH2-group of linear C3-30-alkylene isreplaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30- aralkyl, and wherein alkyl and aryl fragments of N-C1-30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene,ii) optionally H2O, R8-OH, hydrogen halide, a HO-C(=O)-OH, R9-SH and / orat least one compound of a general formula (IIIa) O || R7^ C ^ OH (IIIa)or a corresponding salt thereof, wherein R7, R8and R9are mutually independently an organic residue and iii) at least one the metal M1-containing compound selected from the groupconsisting of an oxide, a carbonate, a hydrogencarbonate, a halide, a carboxylate, an alkoxylate, a thiolate, a (C6-C14-aryl)-containing compound, a (C1-C12-alkyl)-containing compound and the metal as such.The reactants listed above, i.e. the acids according to the general formulae (IIc) or (IIIa) or the appropriate corresponding salts as such, are known to those skilled in the art. The corresponding salts used can be, for example, sodium, potassium or calcium salts. EB23-1526PC Optionally, instead of the aforementioned acids according to the general formulae (IIc) or (IIIa) or corresponding salts thereof as reactants, it is also possible to use corresponding carboxylic esters, for example a methyl or ethyl ester. Such carboxylic esters can be prepared by reacting the aforementioned acids or a corresponding saltthereof with a suitable alcohol, for example methanol or ethanol, optionally in thepresence of a catalyst. The appropriate preparation methods of such carboxylic esters are known to a person skilled in the art. It has to be noted that the compounds of the general formula (IIc) are the basis for bothresidues (R1a)2- and (R1b)- of the catalyst of the general formula (I). Depending on themolar ratio of the respective compounds of the general formula (IIc) versus the metal M1- containing compound as employed during synthesis, the presence residues (R1a)2-and (R1b)- within the catalyst of the general formula (I) can be governed. This can be also done by adjusting the pH-value during synthesis and / or by employing compounds withtemporarily partially blocked carboxy groups. Beyond that the additional employment ofcompounds such as R8-OH, hydrogen halide, or a compound of a general formula (IIIa) in an equimolar ratio to the compounds of the general formula (IIc) promotes the formation of catalyst of the general formula (I) containing more residues (R1b)- .If the molar ratio of compound of formula (IIc) / metal M1-containing compound is in therange of 1.0 / 1.0 to 2.0 / 1.0, the catalyst of the general formula (I) predominately contains residues (R1a)2-instead of residues (R1b)-, especially in case of an in situ reaction mode. The higher the molar ratio of compound of formula (IIc) versus that of the metal M1- containing compound is, the more residues (R1a)2-are contained within the catalyst ofthe general formula (I).Any metal M1-containing compound known to the skilled person may be employed. For the sake of completeness, it is indicated that said metal M1-containing compound additionally contains further functional groups such as a halide, a carboxylate, analkoxylate or a thiolate besides the metal M1.In principle, any metal M1-containing compound can be used in the method according to the invention, which is suitable for the purpose of forming the metal central atom in the catalyst of the general formula (I) according to the invention, by reaction with theappropriate compounds according to the general formulae (IIc) or (IIIa).Preferably, the M1-containing compound is selected from the group consisting of Zr(2-ethylhexanoate)4, Zr(isopropanoate)4, ZrCl4, Zr(acetylacetonate)4, Zr(n-butanolat)4, Zr(tert-butoxide)4, or Zr(neodecanoate)4, preferably selected from Zr(2-ethylhexanoate)4or Zr(isopropanoate)4.In one embodiment, the catalysts according to the general formula (I) according to the invention may be prepared by reacting at least one compound of the general formula EB23-1526PC (IIc), optionally at least one compound such as R8-OH or according to the general formula (IIIa), with at least one metal M1-containing compound , whereini) the reaction is carried out under a protective atmosphere and / or in the presenceof at least one solvent, preferably toluene or tetrahydrofuran, and / orii) the reaction is conducted for at least 6 hours and / or at a temperature in the rangeof -75 to 160° C, and / oriii) following the reaction, volatile constituents are removed, the catalyst is driedunder reduced pressure and / or a recrystallization is carried out. As mentioned above, the compounds according to the general formulae (IIc), wherein R3, R4, R5and R6and A are as defined above, can be prepared by methods known in the art. In the context of the present invention, it is preferred that within compounds according to the general formulae (IIc), wherein R3, R4, R5and R6are phenyl each, therespective compound can be prepared by reacting compound of formula (IV)(V) wherein A is as defined above.Usually the compound of formula (IV), usually dissolved in an organic solvent such astetrahydrofuran, is treated with a strong base such as n-butyl lithium at a temperature in the range of -80 to 0 °C, preferably in the range of -20 to -10 °C, followed by slow addition of the compound of formula (V) at temperature in the range of -80 to 0 °C, preferably in the range of -60 to -30 °C. After addition of the compound of formula (V) the reactionmixture is usually allowed to warm to room temperature and stirred at room temperaturefor about 6 to 24 hours. The reaction can be terminated by addition of an acid such as HCl. The molar ratio of n-butyl lithium to compound of formula (IV) is usually in the range of 1.8 / 1.0 to 2.6 / 1.0. The molar ratio of compound of formula (V) to compound of formula (IV) is usually in the range of 0.3 / 1 to 0.7 / 1.0, Another subject of the present invention is a process for the preparation of a compound, oligomer or polymer comprising at least one urethane group, which process comprises EB23-1526PC the step of reacting at least one monoalcohol (B1) or polyol (B2) with at least one polyisocyanate (A) in the presence of at least one catalyst of the present invention. Monoalcohols (B1) have an OH functionality of below 1.5.Polyols (B2) have an OH functionality of at least 1.5.The OH functionality is (hydroxyl number polyol or monoalcohol [g KOH / g] x molecular weight polyol or monoalcohol) / molecular weight KOH. If the polyol or monoalcohol is an oligomer or polymer, the number average molecular weight of the polyol or monoalcohol is used, which can be determined using gel permeation chromatography calibrated to apolystyrene standard. The molecular weight of KOH is 56 g / mol. The hydroxyl numbercan be determined according to DIN53240, 2016. Monoalcohols (B1) and polyols (B2), respectively, can be compounds, oligomers or polymers. Examples monoalcohols (B1) are ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, neopentanol, n-hexanol, n-heptanol, n-octanol, 2- ethyl-hexanol, n-decanol and neodecanol. Further examples of monoalcohols (B1) are the methyl and ethyl monoesters of (ethylene glycol), tri(ethylene glycol), di(propyleneglycol) and tri(propylene glycol). Further examples of monoalcohols (B1) arebenzylalcohol and cyclohexanol. Examples of polyols (B2) are diols such ethylene glycol, propane-1,2-diol, propane-1,3- diol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3-diol, pentane-1,2-diol,pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane-2,3-diol, pentane-2,4-diol,hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane-1,6-diol, hexane-2,5-diol, heptane-1,2-diol, heptane-1,7-diol, octane-1,8-diol, octane-1,2-diol, nonane-1,9-diol, decane-1,2-diol, decane-1,10-diol, dodecane-1,2-diol, dodecane-1,12- diol, hexa-1,5-diene-3,4-diol, neopentyl glycol, 2-methyl-pentane-2,4-diol, 2,4-dimethyl-pentane-2,4-diol, 2-ethyl-hexane-1,3-diol, 2,5-dimethyl-hexane-2,5-diol, 2,2,4-trimethyl-pentane-1,3-diol, pinacol and hydroxypivalinic acid neopentyl glycol ester. Further examples of polyols (B2) are diols such as are di(ethylene glycol), tri(ethylene glycol), di(propylene glycol) and tri(propylene glycol). Further examples polyols (B2) are triols such as glycerol, trimethylolmethane, 1,1,1- trimethylolethane, 1,1,1-trimethylolpropane, 1,2,4-butanetriol and 1,3,5-tris(2- hydroxyethyl) isocyanurate and condensates thereof with ethylene oxide, propylene oxide and / or butylene oxide. EB23-1526PC Further examples of polyols (B2) are pentaerythritol, diglycerol, triglycerole, condensates of at least four glycerols, di(trimethylolpropane), di(pentaerythritol), and condensates thereof with ethylene oxide, propylene oxide and / or butylene oxide.Examples of polyols (B2) are diols such as 1,1-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxymethyl)-cyclohexane, 1,3-bis(hydroxymethyl)-cyclohexane, 1,4- bis(hydroxymethyl)-cyclohexane, 1,1-bis(hydroxyethyl)-cyclohexane, 1,2- bis(hydroxyethyl)-cyclohexane, 1,3-bis(hydroxyethyl)-cyclohexan, 1,4- bis(hydroxyethyl)-cyclohexane, 2,2,4,4-tetramethyl-1,3-cyclobutandiol, cyclopentane-1,2-diol, cyclopentane-1,3-diol, 1,2-bis(hydroxymethyl) cyclopentane, 1,3-bis(hydroxymethyl) cyclopentane, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cycloheptane-1,3-diol and cycloheptane-1,4-diol and cycloheptane-1,2-diol.Further examples of polyols (B2) are inositol, sugars such as glucose, fructose andsucrose, sugar alcohols such as sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), malitol and isomalt, as well as tris(hydroxymethyl)amine, tris(hydroxyethyl)amine and tris(hydroxypropyl)amine.Further examples of polyols (B2) are also polyurethane polyols, acrylic polymeric polyols,hybrids of polyurethane polyol and acrylic polymeric polyol, polyester polyols, polycarbonate polyols, polyether polyols, polythioether polyols and polyacrylate polyols. Polyurethane polyols are polymeric polyols comprising urethane linkages. Polyurethanepolyols are usually obtained by reaction of diols with diisocyanates. The diol can be apolyester diol, acrylic polymer diol, polycarbonate diol or polyetherdiol. Polyurethane polyols may comprise further linking groups in the main chain in lower number than the number of urethane groups such as ester, ether, thioether or urethane linkages.Acrylic polymeric polyols are polymeric polyols obtainable by radical polymerization frompolymerizable unsaturated monomers carrying OH groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth) acrylate, 4- hydroxybutyl (meth)acrylate and (meth)allyl alcohol, and polymerizable unsaturated monomers comprising acrylic acid esters or methacrylic acid esters and optionally otherpolymerizable unsaturated monomers, by methods known in the art such as emulsionpolymerization. Examples of other polymerizable unsaturated monomers are polymerizable unsaturated monomers carrying acidic groups such as acrylic acid, methacrylic acid, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride and itaconic anhydride. Hybrids of polyurethane polyol and acrylic polymer polyol can be obtained, for example, by preparing the acrylic polymer polyol as described above, but in the presence of a polyurethane polyol. EB23-1526PC Polyester polyols are polymeric polyols comprising monomers linked via an ester linkage. Polyester polyols are usually obtained by an esterification reaction or transesterification reaction of a component carrying two acidic groups and a diol. Polyester polyols maycomprise further linking groups in the main chain in lower number than the number ofester groups such as amide, urea, carbonate, ether, thioether or urethane linking groups. Polycarbonate polyols are polymeric polyols comprising carbonate linkages. Polycarbonate polyols are usually obtained by reaction of carbonates with diols such asbutan-1,4-diol, pentane-1,5-diol and hexane-1,6-diol. Polycarbonate polyols maycomprise further linking groups in the main chain in lower number than the number of carbonate groups such as ester, amide, urea, ether, thioether or urethane linkages. Polyether polyols are polymeric polyols comprising ether linkages. Polyether polyols areusually prepared by acid catalyzed polymerization of ethers such as ethyleneoxide,propylene oxide, butylene oxide or tetrahydrofuran using an alcohol. Polyether poyols may comprise further linking groups in the main chain in lower number than the number of ether groups such as ester, amide, urea, carbonate, thioether or urethane linkages.Polythioether polyols are polymeric polyols comprising thioether groups in the main chainof the polymer. Polythioether polyols may comprise further linking groups in the main chain in lower number than the number of thio ether groups such as ester, carbonate, ether or urethane groups.Polyisocyanates (A) can be polyisocyanates carrying free NCO groups (A1) orpolyisocyanates carrying blocked NCO groups, so-called “blocked polyisocyanates” (A2). Polyisocyanates carrying blocked NCO groups (A2) can be de-blocked to yield the corresponding polyisocyanate carrying free NCO groups (A2*) under specific conditions, for example at elevated temperatures, such as at temperatures above 110°C. Thefollowing characteristics of polyisocyanates (A) apply to the polyisocyanates carryingfree NCO groups (A1) as well as to the polyisocyanates carrying free NCO groups (A2*) obtained by de-blocking the blocked polyisocyanates (A2). Polyisocyanates (A) have an NCO functionality of at least 1.5. The NCO functionality of a polyisocyanate is NCO content x (molecular weight polyisocyanate / molecular weight NCO). If the polyisocyanate is a polymeric polyisocyanate, the average weight molecular weight of the polyisocyanate is used. The average weight molecular weight of a polymeric polyisocyanate can be determined usinggel permeation chromatography calibrated to a polystyrene standard. The NCO contentof the polyisocyanate is weight NCO / weight polyisocyanate. The molecular weight of NCO is 42 g / mol. EB23-1526PC The NCO content of a polyisocyanate can be determined as follows: 10 mL of a 1 N solution of n-dibutyl amine in xylene is added to 1 g of a polisocyanate dissolved in 100 mL of N-methylpyrrolidone. The resulting mixture is stirred at roomtemperature for five minutes. Then, the resulting reaction mixture is subjected to backtitration using 1 N hydrochloric acid to measure the volume of the hydrochloric acid needed for neutralizing the unreacted n-dibutyl amine. This then reveals how much mol n-dibutyl amine reacted with NCO groups. The NCO content is (“mol reacted n-dibutyl amine” x molecular weight NCO) / weight polyisocyanate. The weight of polyisocyanate is1 g.Polyisocyanate (A) can be a monomeric or polymeric polyisocyanate. Examples of monomeric polyisocyanates (A) are tetramethylene 1,4-diisocyanate,pentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate, heptamethylene1,7-diisocyanate, octamethylene 1,8-diisocyanate, decamethylene 1,10-diisocyanate, dodecamethylene 1,12-diisocyanate, tetradecamethylene 1,14-diisocyanate, methyl 2,6- diisocyanatohexanoate, ethyl 2,6-diisocyanatohexanoate, 2,2,4-trimethylhexane 1,6-diisocyanate and 2,4,4-trimethylhexane 1,6-diisocyanate. Further examples of monomeric polyisocyanates are 1,4,8-triisocyanatononane and 2’-isocyanatoethyl 2,6-diisocyanatohexanoate. Examples of monomeric polyisocyanates are 1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,2-diisocyanatocyclohexane, 4,4’- di(isocyanatocyclohexyl)-methane, 2,4’-di(isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl)cyclohexane (isophorone diisocyanate), 1,3- bis(isocyanatomethyl)- cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 2,4- diisocyanato-1-methyl- cyclohexane, 2,6-diisocyanato-1-methylcyclohexane and 3(or 4),8(or 9)-bis(isocyanatomethyl)tricyclo[5.2.1.0(2,6)]decane.Examples of monomeric polyisocyanates are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 2,4’-diisocya- natodiphenylmethane, 4,4’-diisocyanatodiphenylmethane, 1,3-phenylenediisocyanate,1,4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylene 4,4’-diisocyanate, 4,4’-diisocyanato-3,3’- dimethylbiphenyl, 3-methyldiphenylmethane 4,4’-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene and diphenyl ether 4,4’-diisocyanate.Further examples of monomeric polyisocyanates are 2,4,6-triisocyanatotoluene,triphenylmethane triisocyanate and 2,4,4’-triisocyanatodiphenyl ether. EB23-1526PC Examples of polymeric polyisocyanate are polymers having an NCO functionality of at least 1.5 and comprising at least two units derived from monomeric polyisocyanates. Polymeric polyisocyanates can also comprise at least one structural unit selected from the group consisting of uretdione, isocyanurate, biuret, urea, carbodiimide, uretonimine,urethane, allophanate, oxadiazinetrione and iminooxadiazinedione.Another example of polymeric polyisocyanate is polymeric diphenyl methane diisocyanate.The NCO functionality of polyisocyanate (A) is usually in the range of from 1.6 to 10.0,preferably in the range of 1.6 to 8.0, more preferably in the range of 1.7 to 5.4, even more preferably in the range of 1.8 to 3.4, and most preferably in the range of 1.8 to 2.4. Polyisocyanate (A), monoalcohol (B1) and polyol (B2) can be derived from fossil or fromrenewable resources such as plants. Whether the components are derived fromrenewable resources or not can be determined by the C-14 / C-12 isotope ratio. The equivalent ratio of OH groups derived from monoalcohol (B1) and polyol (B2) to NCO groups derived from polyisocyanate (A) is preferably in the range of 5 / 1 to 1 / 5,more preferably in the range of 2.5 / 1 to 1 / 2.5, and most preferably in the range of 1.5 / 1to 1 / 1.5. The reaction can be conducted in the presence of at least one organic solvent.Examples of organic solvents are aliphatic ketones such as acetone, ethyl methylketone(2-butanone) and isobutyl methyl ketone, aliphatic amides such as N-methylpyrrolidone and N-ethylpyrrolidone, ethers such as tetrahydrofuran, dipropylene glycol dimethyl ether and dioxane, hydrocarbons such as n-heptane, cyclohexane, toluene, ortho-xylene, meta-xylene, para-xylene, and xylene isomer mixture, esters such as butyl acetate, acidssuch as acetic acid or neodecanoic acid, as well as nitriles such as acetonitrile.The reaction is usually conducted at a temperature in the range of 15 to 200 °C, preferably in the range of 20 to 80 °C.The at least one catalyst of the present invention is usually used in an amount, so thatthe amount of tetravalent metal M1in the catalyst is in the range of 1 to 1500 ppm based on the weight of all polyisocyanate (A) (weight M1 / weight all polyisocyanate), preferably in the range of 1 to 750 ppm, more preferably in the range of 1 to 500 ppm, and most preferably in the range of 1 to 100 ppm. EB23-1526PC The reaction can be performed, for example, by adding the catalyst of the present invention to the at least one monoalcohol (B1) or polyol (B2), which is optionally dissolved in at least one organic solvent or, if only blocked polyisocyanates (A2) are present, in water, and then adding the at least one polyisocyante (A) to start the reaction.If a blocked polyisocyanate (A2) is used, the reaction is started upon de-blocking of theblocked polyisocyanate (A2). The reaction mixture is then stirred at the desired temperature until the desired NCO value, which is usually below 1.5%, is reached. Another subject of the present invention is an at least two-component coating acomposition comprising as separate components (i) at least one monoalcohol (B1) orpolyol (B2) as first component and (ii) at least one polyisocyanate (A) as second component, and (iii) at least one catalyst of the present invention as third component or mixed with either the first or second component.In one embodiment the composition is a one-component composition comprising (i) atleast one monoalcohol (B1) or polyol (B2), (ii) at least one blocked polyisocyanate (A2) and (iii) at least one catalyst of the present invention. In another embodiment the composition is an at least two-component coatingcomposition comprising as separate components (i) at least one monoalcohol (B1) orpolyol (B2) as first component and (ii) at least one polyisocyanate (A) as second component, and (iii) at least one catalyst of the present invention as third component or mixed with either the first or second component.The composition can also comprise at least one organic solvent. Examples of organicsolvents are listed above. If only blocked polyisocyanates (A2) are present and no polyisocyanates carrying free NCO groups (A1) the composition can also comprise water as solvent.The composition usually comprises5 to 85 weight%, preferably from 10 to 70 weight%, more preferably from 20 to 70 weight%, of the sum of monoalcohol (B1) and polyol (B2) based on the weight of the composition, 5 to 85 weight%, preferably from 10 to 70 weight%, more preferably from 20 to 70weight%, of polyisocyanate (A) based on the weight of the composition, and1 to 1000 ppm, preferably 1 to 500 ppm, more preferably 1 to 100 ppm of at least one catalyst of the present invention based on the weight of polyisocyanate (A). Another subject of the present invention is a coating layer formed from the compositionof the present invention on a on a substrate. The layer can be a coating or adhesive layerThe coating or compositions of the present invention can be applied to the substrate by any method known in the art such as by draw down bar, spraying, troweling, knifecoating, EB23-1526PC brushing, rolling, rollercoating, flowcoating and laminating, doctor blades, various printing processes such as gravure, transfer, lithographica and ink jet printing and by using a bar.The substrate can be any suitable substrate. Examples of substrates are woodsubstrates, wood-based substrates, plastic substrates such as melamine formaldehyde substrate, paper substrates, recycled paper substrates, paperboard (also called cardboard) substrate, recycled paperboard (also called recycled cardboard) substrates, metal substrates, stone substrate, glass substrates, textiles substrates, leathersubstrates, ceramic substrates, mineral building material substrates such as moldedcement blocks and fiber-cement slabs, and composite substrates formed from a combination of the substates mentioned before in this paragraph. Another subject of the present invention is foam formed from the composition of thepresent invention. The foam can be a rigid or flexible foam.The at least one catalyst according to the definitions above can be used in Lewis-acid catalysed reactions, for example, in esterifications, transesterifications, ring-opening polymerizations of ethers, lactones, epoxides and amines, epoxidations and in reactionsfor preparing compounds comprising a urethane group, preferably in reactions forpreparing compounds comprising a urethane group. Another subject of the present invention is the use of at least one catalyst of the present invention in reactions for preparing compounds comprising a urethane group. Another subject of the present invention is the use of at least one catalyst of the present invention as an esterification and transesterification catalyst. Another subject of the present invention is the use of at least one catalyst of the presentinvention as a catalyst for ring-opening polymerizations of lactones and epoxides.The invention is illustrated hereinafter by examples. Examples Preparation of inventive and comparative catalystsI) Preparation of precursors / ligandsEB23-1526PC 31 1: 4,4'-(ethane-1,2-diylbis(oxy))bis(2,2-diphenylbutanoic acid) equates to PEG2- bis(2,2dpba) was prepared using the procedure as follows.In a Schlenk flask, 2,2-diphenylacetic acid (50.0 g, 235.57 mmol, 1.00 eq.) was dissolvedin 156 mL THF and cooled to -15 °C. Then, a 2.5 M solution of n-butyllithium in n-hexane (210 mL, 525 mmol, 2.20 eq.) was slowly added and the resulting red solution was stirred for 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °C and 1,2-Bis(2-chloroethoxy)ethane (18.40 mL, 117.79 mmol, 0.50 eq.) was slowlyadded. The mixture was then stirred overnight at room temperature and terminated bythe addition of a 1.0 M aqueous solution of HCl. Subsequently, the phases were separated in a separatory funnel and the aqueous phase was extracted with Et2O (3 x 50 mL). Afterwards, the collected organic phases were washed with water, dried over MgSO4and decanted. Crystallization at – 27 °C gives a white solid. Yield: 72% (45.70g, 84.50 mmol).1H-NMR (400.03 MHz, CDCl3): δ = 7.30 (m, 8H, aryl-H), 7.22 (m, 12H, aryl-H), 3.50 (t, 4H, CH2), 3.46 (t, 4H, CH2), 2.61 (t, 4H, CH2). Compound 2: 4,4'-((oxybis(ethane-2,1-diyl))bis(oxy))bis(2,2-diphenylbutanoic acid) equates to PEG3-bis(2,2dpba) was prepared using the procedure as follows.In a Schlenk flask, 2,2-diphenylacetic acid (50.0 g, 235.57 mmol, 1.00 eq.) was dissolved in 156 mL THF and cooled to -15 °C. Then, a 2.5 M solution of n-butyllithium in n-hexane (210 mL, 525 mmol, 2.20 eq.) was slowly added and the resulting red solution was stirredfor 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °Cand bis-[2-(2-chlorethoxy)-ethyl]-ether (23.10 mL, 117.79 mmol, 0.50 eq.) was slowly added. The mixture was then stirred overnight at room temperature and terminated by the addition of a 1.0 M aqueous solution of HCl. Subsequently, the phases were separated in a separatory funnel and the aqueous phase was extracted with Et2O (3 x50 mL). Afterwards, the collected organic phases were washed with water, dried overMgSO4and decanted. Crystallization at – 27 °C gives a white solid. Yield: 89% (61.2 g, 105.00 mmol). EB23-1526PC1H-NMR (400.03 MHz, CDCl3): δ = 7.37 (m, 8H, aryl-H), 7.25 (m, 12H, aryl-H), 3.75 (m, 4H, CH2), 3.48 (m, 4H, CH2), 3.23 (t, 4H, CH2), 2.71 (t, 4H, CH2). 6,6´-o-bis ) prepared using the procedure as follows.In a Schlenk flask, 2,2-diphenylacetic acid (50.0 g, 235.57 mmol, 1.00 eq.) was dissolved in 156 mL THF and cooled to -15 °C. Then, a 2.5 M solution of n-butyllithium in n-hexane (210 mL, 525 mmol, 2.20 eq.) was slowly added and the resulting red solution was stirredfor 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °Cand bis(4-chlorobutyl)ether (21.70 mL, 117.79 mmol, 0.50 eq.) was slowly added. The mixture was then stirred overnight at room temperature and terminated by the addition of a 1.0 M aqueous solution of HCl. Subsequently, the phases were separated in a separatory funnel and the aqueous phase was extracted with Et2O (3 x 50 mL).Afterwards, the collected organic phases were washed with water, dried over MgSO4and decanted. Crystallization at – 27 °C gives a white solid. Yield: 75% (48.16 g, 87.45 mmol).1H-NMR (400.03 MHz, CDCl3): δ = 7.20 (m, 20H, aryl-H), 3.23 (t, 4H, CH2), 2.30 (m, 4H, CH2), 1.44 (m, 4H, CH2), 1.15 (m, 4H, CH2).II) General procedure for the preparation of the inventive catalystsInventive examples Ex1 - Ex3: Zirconium alkoxide carboxylates were prepared following a modified synthetic procedure of Ashutosh Pandey et.al, Inorganica ChimicaActa, 2006, 359, 4511–4518. A Schlenk flask was charged with Zr(OiPr)4(HOiPr)(1.00 eq.) and the respective dicarboxylic acid (1.00 eq.). Anhydrous toluene or tetrahydrofuran (6 mL per mmol of Zr(OiPr)4(HOiPr)) was added slovely at room temperature and the reaction mixture was stirred for 6 hour. Subsequently, all volatiles where removed under reduced pressure and the residue was dried in vacuo at 80 °Covernight to afford the Zr(IV) carboxylates as an off-white solid.Characterization by1H-NMR, Elemental analysis Comparative examples Comp1-3: Zr(acac)4, Zr(2-EH)4, Zr(OiPr)4(HOiPr) were purchased from Sigma Aldrich 2-EH is 2-Ethylhexanoate, OiPr is isopropanoate, acac is acetylacetonateEB23-1526PCIII) Determination of the catalytic activity of the catalysts in water containingsystem The catalyst activity of the individual inventive and comparative examples was tested ina water containing system using the following urethane-forming model reaction: To asolution of 19 mmol of H12MDI (Dicyclohexylmethane 4,4'-Diisocyanate), 34.55 mmol of absolute 2-Ethylhexanol was added 200ppm catalyst and 1wt% water at 60°C (ratio of NCO to OH is 1.05 to 1.00).The isocyanate conversion and thus the formation of a urethane group are investigatedby horizontal ATR-IR spectroscopy. For this purpose, an aliquot of 0.05 mL is taken from the reaction mixture at defined time intervals and analyzed directly by IR spectroscopy. The relative intensity decrease of the asymmetric isocyanate stretching band at 2260 cm-1and the was used to determine the conversion. The initial free isocyanate contentof the reaction mixture was determined at room temperature in the absence of a catalyst.All IR spectra were normalized to the bands of the symmetrical and asymmetrical stretching vibrations of the CH2groups (3000 – 2870 cm-1).IV) Determination of the catalytic activity of the catalysts (latency)The catalyst activity of the individual inventive and comparative examples was tested in a water containing system using the following urethane-forming model reaction: To a solution of 19 mmol of H12MDI (Dicyclohexylmethane 4,4'-Diisocyanate), 34.55 mmol of absolute 2-Ethylhexanol was added 200ppm catalyst at ambient temperature followedby heating to 80°C after 30 minutes (ratio of NCO to OH is 1.05 to 1.00).The isocyanate conversion and thus the formation of a urethane group are investigated by horizontal ATR-IR spectroscopy. For this purpose, an aliquot of 0.05 mL is taken from the reaction mixture at defined time intervals and analyzed directly by IR spectroscopy.The relative intensity decrease of the asymmetric isocyanate stretching band at 2260cm-1and the was used to determine the conversion. The initial free isocyanate content of the reaction mixture was determined at room temperature in the absence of a catalyst. All IR spectra were normalized to the bands of the symmetrical and asymmetrical stretching vibrations of the CH2groups (3000 – 2870 cm-1). EB23-1526PCBASF SE 231526EP0134 Table 1 taxE rbpO613131 101, ,5iPd2WO2H C(r,Z2(+°0 s6ibm uinnio 0 00 0 cm0 3 5 3 6 8r / 6t1 3iZ+)r2PiC.pO°0 3 mH( 68,6,4,7, 29,9 o,)r4 / O261313121 1 9 7CiP O H (rZnim 0 0 / 0 3 5 03 06 86t1 3 / O21. Hp+C38,2,4,9mo)4 °c0 8, 461 33 2,0 4,7a6 1 1 1 1 1Cca(rZni 00 0 m0 3 5 / 3 06 2t 163EB23-1526PC Ta Pi2 O .2p H(9m4724,3,1,1, 49,4,8 or8 ,3,4,8,5 )4 4 4 41 329 8 7 6,6P,61 1 1 1 1 1CiO1(rZ3H.E2p22-922,1,9,9, 48,3,9,1,6,3,9 m)oVI(8,461413131 1 313111110101,9CrZ 1nim0 5 01 5 0 5 0 5 0 5 0 5 0 / 1 2 2 3 3 4 4 5 5 6tC° / 3 3 3 3 3 3 3 0 0 0 0 0 0T 2 2 2 2 2 2 2 8 8 8 8 8 8EB23-1526PC As can be deduced from tables 1 and 2 the catalysts according to the invention show, according to inventive examples Ex1 to Ex3, a higher catalytic activity compared to the known catalysts according to comparative example Comp 1 to Comp 3 or without using any catalyst according to comparative example C4. EB23-1526PC

Claims

Claims1. A catalyst of a general formula (I)((R1a)2-)x((R1b)-)y(R2)-)z(M1)4+ (I)in which the variables are defined as follows: (R1a)2-is mutually independently a residue of a dianion of a general formula (IIa)(IIa), wherein R3, R4, R5and R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyl and C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C1-C6-alkoxy,and wherein A is unsubstituted or at least monosubstituted linear C3-30-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14- aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl,and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, andEB23-1526PCwherein optionally at least one CH2-group of linear C3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, and wherein alkyl and aryl fragments of N-C1- 30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at leastmonosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S- phenyl, -O-C1-6-alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene arereplaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene. xis 0, 1 or 2,(R1b)- is mutually independently a residue of a general formula (IIb)wherein R3, R4, R5and R6are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting ofhydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyl and C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C1-C6-alkoxy, A is unsubstituted or at least monosubstituted linear C3-30-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14- aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and EB23-1526PCthe alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6- alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, - S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, andwherein optionally at least one CH2-group of linear C3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, and wherein alkyl and aryl fragments of N-C1-30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S- phenyl, -O-C1-6-alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene, M3is H or an alkali metal, yis 0, 1, 2, 3 or 4,(R2)- is mutually independently an anion selected from the group of HO-, R8-O-, a halide anion, HO-C(=O)-O-, R9-S- or an anion of a general formula (III) O || R7^ C ^ O – (III) whereinR7, R8and R9are mutually independently an organic residue, zis 0, 1, 2 or 3,wherein the sum of 2x, y and z equals 4, andEB23-1526PC(M1)4+is a tetravalent metal.

2. The catalyst according to claim 1, whereini) x is 1 and z is 2, orii) y is 2 and z is 2, oriii) x is 1, y is 1 and z is 1, oriv) x is 2,preferably x is 1 and z is 2.

3. The catalyst as claimed in claim 1 or 2, wherein mutually independently at leastone of the radicals R3, R4, R5or R6of the residues according to general formulas (IIa) and / or (IIb) is unsubstituted or at least monosubstituted C6-C14-aryl, preferably at least two, more preferably at least three, and most preferably eachof the radicals R3, R4, R5or R6are unsubstituted or at least monosubstituted C6- C14-aryl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy and C1-C30-alkyl.

4. The catalyst as claimed in any of claims 1 to 3, wherein mutually independentlyat least one, preferably at least two, more preferably at least three, and most preferably each of the radicals R3, R4, R5or R6of the residues according to general formulas (IIa) and / or (IIb) is phenyl.

5. The catalyst as claimed in any of claims 1 to 4, wherein (M1)4+ is a tetravalentmetal selected from Zr4+, Pb4+, Ti4+, Sn4+and Hf4+, preferably selected from Zr4+, Ti4+, Sn4+and Hf4+, most preferably Zr4+.

6. The catalyst as claimed in any of claims 1 to 5, wherein A is unsubstituted or atleast monosubstituted linear C5-20-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14-aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30-aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl,wherein M2is H or an alkali metal, and EB23-1526PCwherein at least one CH2-group of linear C5-20-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O and S, and in case two or more CH2-groups of linear C5-C20-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from eachother by at least one CH2-group of linear C5-C20-alkylene, most preferably the at least one heteroatom is O.

7. The catalyst according to any of claims 1 to 6, wherein A is unsubstituted linearC5-20-alkylene,wherein at least one CH2-group of linear C5-20-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O and S, and in case two or more CH2-groups of linear C5-20-alkylene are replaced by twoor more heteroatoms, the two or more heteroatoms are separated from each other by at least one CH2-group of linear C5-20-alkylene, most preferably the at least one heteroatom is O.

8. The catalyst as claimed in any of claims 1 to 7, whereinA is unsubstituted linear C5-12-alkylene, wherein one, two or threeCH2-groups of linear C5-12-alkylene are replaced by O as heteroatom each and in case two or three CH2-groups of linear C5-12-alkylene are replacedby O as heteroatom, the two or three heteroatoms are separated from each other by one or two, preferably by two, CH2-groups of linear C5-12-alkylene, preferably A is unsubstituted linear C8-10-alkylene, wherein one or twogroups of linear C8-10-alkylene are replaced by O as heteroatom each and in case two CH2-groups of linear C8-10-alkylene are replaced by O as heteroatom, the two heteroatoms are separated from each other by one or two, preferably by two, CH2-groups of linear C8-10- alkylene, most preferably A is unsubstituted linear C8-10-alkylene, wherein one group of linear C8-10-alkylene is replaced by O as heteroatom.

9. The catalyst as claimed in any of claims 1 to 8, wherein (R2)- is mutuallyindependently an anion selected from the group of HO-, R8-O-, Cl-, HO-C(=O)-O-, R9-S- or an anion of a general formula (III) EB23-1526PCO || R7^ C ^ O – (III) wherein R7, R8 and R9 are mutually independently unsubstituted or at leastmonosubstituted C3-30-alkyl, C6-14-aryl or C7-30-aralkyl, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14-aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, - N(C7-30-aralkyl)2, -SH, -S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, - O-C6-14-aryl, -O-C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and arylfragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -C(=O)-OM2, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, - N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl, O-phenyl or C1-6-alkyl, wherein M2is H or alkali metal, and wherein one CH2group or at least two not adjacent CH2groups of C3-30-alkyl can be replaced by a heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30-aralkyl, wherein the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by - OH halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, preferably R7, R8and R9are mutually independently unsubstituted or at least monosubstituted C1-C12-alkyl or C6-C14-aryl, wherein the substituents are selected from the group consisting of hydroxyl, chlorine, -CF3 and C1-C6-alkyl.

10. A method for preparing a catalyst of the general formula (I) as claimed in any ofclaims 1 to 9, comprising reacting i) at least one compound of a general formula (IIc)EB23-1526PCor a corresponding salt thereof,wherein R3, R4, R5 und R6 are mutually independently unsubstituted or atleast monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyland C6-C14-aryl and the alkyl and aryl fragments of these substituents mayin turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C1-C6-alkoxy, and wherein A is unsubstituted or at least monosubstituted linear C3-30-alkylene, wherein the substituents are selected from the group consistingof -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14-aryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30-aralkyl)2, -SH, - S-C1-30-alkyl, -S-C6-14-aryl, -S-C7-30-aralkyl, -O-C1-30-alkyl, -O-C6-14-aryl, -O- C7-30-aralkyl, C1-30-alkyl and C6-14-aryl, and the alkyl and aryl fragments ofthese substituents may in turn be at least monosubstituted by -OH,halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2is H or an alkali metal, andwherein optionally at least one CH2-group of linear C3-30-alkylene isreplaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N-C7-30- aralkyl, and wherein alkyl and aryl fragments of N-C1-30-alkyl, N-C6-14-aryl, N-C7-30-aralkyl may in turn be at least monosubstituted by hydroxyl,halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2,-N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, and in case two or more CH2-groups of linear C3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separatedfrom each other by at least on CH2-group of linear C3-C30-alkylene,EB23-1526PCii) optionally H2O, R8-OH, hydrogen halide, a HO-C(=O)-OH, R9-SH and / orat least one compound of a general formula (IIIa) O || R7^ C ^ OH (IIIa) or a corresponding salt thereof, wherein R7, R8and R9are mutually independently an organic residue andiii) at least one the metal M1-containing compound selected from the groupconsisting of an oxide, a carbonate, a hydrogencarbonate, a halide, a carboxylate, an alkoxylate, a thiolate, a (C6-C14-aryl)-containing compound, a (C1-C12-alkyl)-containing compound and the metal as such.

11. The method as claimed in claim 10, wherein the M1-containing compound isselected from the group consisting of Zr(2-ethylhexanoate)4, Zr(isopropanoate)4, ZrCl4, Zr(acetylacetonate)4, Zr(n-butanolat)4, Zr(tert-butoxide)4, or Zr(neodecanoate)4, preferably selected from Zr(2-ethylhexanoate)4 orZr(isopropanoate)4.

12. The method as claimed in claim 10 or 11, whereini) the reaction is carried out under a protective atmosphere and / or in thepresence of at least one solvent, preferably toluene or tetrahydrofuran, and / or ii) the reaction is conducted for at least 6 hours and / or at a temperature inthe range of -75 to 160° C, and / oriii) following the reaction, volatile constituents are removed, the catalyst isdried under reduced pressure and / or a recrystallization is carried out.

13. A process for the preparation of a compound, oligomer or polymer comprising atleast one urethane group, which process comprises the step of reacting at least one monoalcohol (B1) or polyol (B2) with at least one polyisocyanate (A) in the presence of the catalyst as claimed in any of claims 1 to 9. EB23-1526PC14. A composition comprising (i) at least one monoalcohol (B1) or polyol (B2), (ii) atleast one polyisocyanate (A) and (iii) at least one catalyst of any of claims 1 to 9.

15. A layer formed from the composition of claim 14 on a substrate.

16. A foam formed from the composition of claim 14 on a substrate.

17. The use of at least one catalyst as claimed in any of claims 1 to 9 in reactions forpreparing compounds comprising a urethane group, as an esterification andtransesterification catalyst or as a catalyst for ring-opening polymerizations of lactones and epoxides. EB23-1526PC

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