Catalyst comprising a bivalent metal and a dicarboxylate ligand Description
The present invention relates to a catalyst comprising a bivalent metal such as Sn, to processes for the preparation of the catalyst comprising a bivalent 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 bivalent 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 bivalent 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 catalyst
comprising at least two salts of an aliphatic monocarboxylic acid having at least 4 carbon atoms. 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 separately
from 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 radical R
1, 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 for
preparing 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 compound
comprising a hydroxyl group. The reaction generally takes place in the presence of a catalyst. On the one hand, tin-containing catalysts exhibit very high activity in such reactions. On the other hand, it is often tried to avoid the use of such tin-containing EB23-1631PC December 9, 2024
catalysts, especially alkyl-tin compounds, owing to their (often high) toxicity. Irrespective of that, is there is still a demand for new tin-containing catalysts due to their advantages in respect of the high activity.
The water stability of compounds such as Sn(II) carboxylates is an important consideration when using these compounds as catalysts or additives in various applications. Sn(II) carboxylates, such as dibutyltin diacetate or dibutyltin dilaurate, are commonly
used as catalysts in polymer synthesis, particularly in the production of polyurethanes. These carboxylates are generally stable in water and can tolerate limited exposure to moisture. However, prolonged or excessive contact with water can lead to hydrolysis of the Sn(II) carboxylate, resulting in reduced catalytic activity or potential decomposition of the compound. Nevertheless, it is important to note that the water stability of these compounds can vary depending 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 Sn(II)
carboxylates 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) ((R
1a)
2-)
x((R
1b)-)
y(R
2)-)
z(M
1)
2+ (I) in which the variables are defined as follows: (R
1a)
2- is a residue of a dianion of a general formula (IIa)
(IIa), w
herein R3, R4, R5 and R6 are mutually independently unsubstituted or at least monosubstituted C
1-C
30-alkyl, C
6-C
14-aryl or C
7-C
30-aralkyl, EB23-1631PC
wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF
3, -NH
2, -SH, C
1-C
6-alkoxy, C
1-C
30-alkyl and C
6-C
14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, -NH
2, -SH, o
r C1-C6-alkoxy, and wherein A is unsubstituted or at least monosubstituted linear C
3-30-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM
2, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14- aryl, -NH-C
7-30-aralkyl, -N(C
1-30-alkyl)
2, -N(C
6-14-aryl)
2, -N(C
7-30- aralkyl)
2, -SH, -S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1- 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, -CF
3, NH
2, -NH-C
1- 6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6-alkyl or -O-phenyl, wherein M
2 is H or an alkali m
etal, and wherein optionally at least one CH
2-group of linear C
3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C
1-30-alkyl, N-C
6-14-aryl a
nd N-C7-30-aralkyl, and wherein alkyl and aryl fragments of N-C1- 30-alkyl, N-C
6-14-aryl, N-C
7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S- phenyl, -O-C
1-6-alkyl or -O-phenyl, and in case two or more CH
2-groups of linear C
3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH
2-group of linear C
3-C
30-alkylene. x
is 0 or 1, (R
1b)- is mutually independently a residue of a general formula (IIb) EB23-1631PC
wherein R
3, R
4, R
5 and R
6 are mutually independently unsubstituted or at least monosubstituted C
1-C
30-alkyl, C
6-C
14-aryl or C
7-C
30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF
3, -NH
2, -SH, C
1-C
6-alkoxy, C
1-C
30-alkyl and C
6-C
14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, -NH
2, -SH,
or C1-C6-alkoxy, A is unsubstituted or at least monosubstituted linear C
3-30-alkylene, wherein the substituents are selected from the group consisting of - OH, halogen, -C(=O)-OM
2, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14- a
ryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)
2, -SH, -S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1-30- alkyl, -O-C
6-14-aryl, -O-C
7-30-aralkyl, C
1-30-alkyl and C
6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH- p
henyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, - O-C
1-6-alkyl or -O-phenyl, wherein M
2 is H or an alkali metal, and wherein optionally at least one CH
2-group of linear C
3-30-alkylene is replaced by at least one heteroatom independently selected from t
he group consisting of O, S, NH, N-C1-30-alkyl, N-C6-14-aryl and N- C
7-30-aralkyl, and wherein alkyl and aryl fragments of N-C
1-30-alkyl, N-C
6-14-aryl, N-C
7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6- a
lkyl or -O-phenyl, and in case two or more CH
2-groups of linear C
3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH
2-group of linear C
3-C30-alkylene, M
3 is H or an alkali metal, EB23-1631PC
y is 0, 1 or 2 (R
2)- is an anion selected from the group of HO-, R
8-O-, a halide anion, HO- C
(=O)-O-, R9-S- or an anion of a general formula (III) O || R
7 ^ C ^ O – (III) wherein R
7, R8 and R9 are mutually independently an organic residue, z is 0 or 1, wherein the sum of 2x y and z equals 2, (M
1)
2+ is a bivalent metal. The advantages of the catalysts according to the invention can be found in their ability
to enhance both the water stability and reactivity of other metal catalysts, including those based on tin(II), 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 metal
catalysts 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 C
3-30-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 higher temperatures (compared to room temperature). 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 EB23-1631PC
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 and there are no issues how the corresponding acid as a low molecular species behaves in the respective formulation and later in the polymeric material. Advantageous properties are then already obtained in the catalysts according to the invention if the dianion (R
1a)
2- according to the general formula (IIa), which is used as substituent/ligand of the bivalent central atom, comprises the radicals R
3, R
4, R
5 and R
6 in α-position and the diradical A. It is preferred that at least one of the radicals R
3, R
4, R
5 or R6 is 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 general formula (IIb) are used as (R
1b)- 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 chemical nomenclature are α-amino acids, where the α-C atom is the carbon atom to which the amino 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 carboxyl group is sometimes also referred to as position 2 in chemical nomenclature. In the context of the present invention, the dianion (R
1a)
2- according to the general formula (IIa) has two α-carbons. The said carboxyl groups of this substituent are located (spatially speaking) in proximity to the central bivalent metal atom M
1 of the catalyst. The catalysts according to the invention are represented as salts, wherein the central bivalent metal of the catalyst according to the invention is represented as a (double 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/radicals R
1a, R
1b and R
2 in the general formula (I) detailed above, form the corresponding anion components of the catalyst in this salt representation. The substituent/ligand R
1a is double negatively charged and the substituent/ligand R
1b and R
2 are both singly
negatively charged. As detailed below, the substituent R1a mandatorily comprises two carboxyl groups both being negatively charged (dianion), whereas the substituent R
2 may comprise one carboxyl group, for example, in case it is an anion of a general formula (III). The substituent R
1b also comprises two carboxyl groups, but only one of them is negatively charged (“monoanion”), whereas the second carboxyl group of the substituent
R1b is neutralized by either a proton or an alkali metal. In general, the negative charge in the 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 bivalent metal atom. EB23-1631PC
From a scientific standpoint however, it is also tenable, in place of the salt notation used in 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 bivalent
metal atoms and the ligands R1a, R1b and R2 according to general formula (I) is completely or at least partially formed in each case. Expressed in other words, this means that the central bivalent metal atom is not present as a positively charged cation and the corresponding 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 bivalent metal atom on the other hand. In the context of the present invention, the catalysts comprising a central bivalent metal atom disclosed according to the invention, therefore, also describe such a definition that is not based on a salt.
In the context of the present invention, definitions such as C1-C30-alkyl, such as defined, for example, for the radicals R
3 to R
6 in formula (IIa) above, signifies that this substituent (radical) is an alkyl radical having a carbon atom number of 1 to 30, wherein substituents optionally 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 C
1-C
6-alkyl radical or a C
1-C
12-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) “C
1-C
30-alkyl” may alternatively be described as “C
1-30-alkyl”, both terms C
1-C
30-alkyl on the hand and “C
1-
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 C
3-30-alkylene (or alternatively refered to as “C
3-C
30-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 consideration in the carbon atom number. The C
3-30-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 a
carbon or a hydrogen atom and that has replaced a carbon atom in the backbone of the molecular structure of a compound, especially in the C
3-C
30-alkylene bridge of formula (IIa). Examples of heteroatoms are O, S, P and N. EB23-1631PC
In the context of the present invention, at least one CH
2-group of linear C
3-30-alkylene radical may optionally be replaced by at least one heteroatom. In case two or more CH
2-groups of linear C
3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH
2-group of linear
C3-C30-alkylene. Examples of linear unsubstituted C3-30-alkylene, wherein at least two not adjacent CH
2 groups are replaced by O as heteroatom are
. In the context of the present invention, the term “aryl" or the term “C
6-C
14-aryl", as defined, for example, for the radicals R
3 to R
6 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 polycyclic aromatic 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 “C
7-C
30-aralkyl", as defined for example for the radicals R
3 to R
6 in formula (IIa) above, signifies that the substituent (radical) comprises an alkyl radical (such as C
1-C
6-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 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 example as (additional) substituent of the radicals R
3 to R
6 in formula (IIa) above, signifies that it is 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 EB23-1631PC
radical, such as C
1-C
6-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 R3 to R6 in 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 least monosubstituted C
1-C
30-alkyl, C
6-C
14-aryl or C
7-C
30-aralkyl", such as defined for example
for the radicals R3 to R6 in 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 C
6-C
14-aryl for example, the corresponding aryl unit, such as phenyl for example, may be substituted for example by a hydroxyl and a C
1-C
30-alkyl substituent, 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 the radicals R
1 to R
9 are 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)2+ (I) in which the variables are defined as follows: (R
1a)
2- is a residue of a dianion of a general formula (IIa) EB23-1631PC
(IIa), wherein R
3, R
4, R
5 and R
6 are mutually independently unsubstituted or at least monosubstituted C
1-C
30-alkyl, C
6-C
14-aryl or C
7-C
30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF
3, -NH
2, -SH, C
1-C
6-alkoxy, C
1-C
30-alkyl and C
6-C
14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, -NH
2, -SH,
or C1-C6-alkoxy, and wherein A is unsubstituted or at least monosubstituted linear C
3-30-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM
2, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14- aryl, -NH-C
7-30-aralkyl, -N(C
1-30-alkyl)
2, -N(C
6-14-aryl)
2, -N(C
7-30- aralkyl)
2, -SH, -S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1- 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, -CF
3, NH
2, -NH-C
1- 6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6-alkyl or -O-phenyl, wherein M
2 is H or an alkali m
etal, and wherein optionally at least one CH
2-group of linear C
3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C
1-30-alkyl, N-C
6-14-aryl a
nd N-C7-30-aralkyl, and wherein alkyl and aryl fragments of N-C1- 30-alkyl, N-C
6-14-aryl, N-C
7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S- phenyl, -O-C
1-6-alkyl or -O-phenyl, and in case two or more CH
2-groups of linear C
3-30-alkylene are replaced by two or more heteroatoms, the two or more EB23-1631PC
heteroatoms are separated from each other by at least on CH
2-group of linear C
3-C
30-alkylene. x
is 0 or 1, (R
1b)- is mutually independently a residue of a general formula (IIb)
wherein R
3, R
4, R
5 and R
6 are mutually independently unsubstituted or at least monosubstituted C
1-C
30-alkyl, C
6-C
14-aryl or C
7-C
30-aralkyl, wherein the substituents are selected from the group consisting of h
ydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C30-alkyl and C
6-C
14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, -NH
2, -SH, or C
1-C
6-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)-OM
2, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14- aryl, -NH-C
7-30-aralkyl, -N(C
1-30-alkyl)
2, -N(C
6-14-aryl)
2, -N(C
7-30- aralkyl)
2, -SH, -S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1-30- a
lkyl, -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, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH- phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, - O-C
1-6-alkyl or -O-phenyl, wherein M
2 is H or an alkali metal, and wherein optionally at least one CH
2-group of linear C
3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C
1-30-alkyl, N-C
6-14-aryl and N- C
7-30-aralkyl, and wherein alkyl and aryl fragments of N-C
1-30-alkyl, N
-C6-14-aryl, N-C7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, EB23-1631PC
-N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6- alkyl or -O-phenyl, and in case two or more CH
2-groups of linear C
3-30-alkylene are r
eplaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH
2-group of linear C
3-C
30-alkylene, M
3 is H or an alkali metal, y
is 0, 1 or 2 (R
2)- is an anion selected from the group of HO-, R
8-O-, a halide anion, HO- C(=O)-O-, R
9-S- or an anion of a general formula (III) O || R
7 ^ C ^ O – (III) wherein R
7, R
8 and R
9 are mutually independently an organic residue, z
is 0 or 1, wherein the sum of 2x y and z equals 2, and (M
1)
2+ is a bivalent metal. In connection with the radicals (substituents/ligands) present in the general formula (I), particularly the necessary radicals R
1a, R
1b and R
2, it should be noted that the
further/exact chemical definition of these radicals R1a, R1b and R2 is a result of the radicals R
3 to R
6 and A of the general formulas (IIa) or (IIb) with respect to the radical R
1 and is a result of the radicals R
7 of the general formula (III) with respect to the radical R
2. In the context of the present invention, the variables x, y and z of the corresponding
substituents/ligands R1a, R1b and R2 of the catalyst in the general formula (I) as shown above, may be freely chosen under the proviso that the sum of the variables 2x, y and z equals 2. EB23-1631PC
This is due to the fact that the overall charge of the catalyst of the general formula (I) is 0, since the catalyst comprises an anionic fragment (made up of the corresponding substituents/ligands R
1a, R
1b and/or R
2) having a total charge of -2 and a cationic
fragment (made up of the bivalent metal (M1)2+) having a total charge of +2. By consequence, the general formula (I) comprises catalysts wherein i
) x is 1, or ii) y is 2, or iii) y is 1 and z is 1, preferably x is 1.
For example, within the above-mentioned option i), wherein x is 1, both y and z are 0 each, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 2. On the other hand, within the above-mentioned option ii), wherein y is 2, both x and z are 0 each, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 2. Furthermore, within the above-mentioned option iii), wherein y is 1 and z is 1,
x must be 0, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 2. A preferred embodiment of the present invention relates to a catalyst of a general formula (I) ((R
1a)
2-)
x((R
1b)-)
y(R
2)-)
z(M
1)
2+ (I) in which the variables are defined as follows: (
R1a)2- is a residue of a dianion of a general formula (IIa)
wherein R
3, R
4, R
5 and R
6 are mutually independently unsubstituted or at l
east monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, EB23-1631PC
wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF
3, -NH
2, -SH, C
1-C
6-alkoxy, C
1-C
30-alkyl and C
6-C
14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, -NH
2, -SH, o
r C1-C6-alkoxy, and wherein A is unsubstituted or at least monosubstituted linear C
3-30-alkylene, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM
2, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14- aryl, -NH-C
7-30-aralkyl, -N(C
1-30-alkyl)
2, -N(C
6-14-aryl)
2, -N(C
7-30- aralkyl)
2, -SH, -S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1- 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, -CF
3, NH
2, -NH-C
1- 6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6-alkyl or -O-phenyl, wherein M
2 is H or an alkali m
etal, and wherein at least one CH
2-group of linear C
3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C
1-30-alkyl, N-C
6-14-aryl and N-C
7-30- a
ralkyl, and wherein alkyl and aryl fragments of N-C1-30-alkyl, N- C
6-14-aryl, N-C
7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6- alkyl or -O-phenyl, and in case two or more CH
2-groups of linear C
3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH
2-group of linear C
3-C
30-alkylene. x
is 0 or 1, (R
1b)- is mutually independently a residue of a general formula (IIb) EB23-1631PC
wherein R
3, R
4, R
5 and R
6 are mutually independently unsubstituted or at least monosubstituted C
1-C
30-alkyl, C
6-C
14-aryl or C
7-C
30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF
3, -NH
2, -SH, C
1-C
6-alkoxy, C
1-C
30-alkyl and C
6-C
14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, -NH
2, -SH,
or C1-C6-alkoxy, A is unsubstituted or at least monosubstituted linear C
3-30-alkylene, wherein the substituents are selected from the group consisting of - OH, halogen, -C(=O)-OM
2, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14- a
ryl, -NH-C7-30-aralkyl, -N(C1-30-alkyl)2, -N(C6-14-aryl)2, -N(C7-30- aralkyl)
2, -SH, -S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1-30- alkyl, -O-C
6-14-aryl, -O-C
7-30-aralkyl, C
1-30-alkyl and C
6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH- p
henyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, - O-C
1-6-alkyl or -O-phenyl, wherein M
2 is H or an alkali metal, and wherein at least one CH
2-group of linear C
3-30-alkylene is replaced by at least one heteroatom independently selected from the group c
onsisting 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-C
1-30-alkyl, N-C
6- 1
4-aryl, N-C
7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6- alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6-alkyl or -
O-phenyl, and in case two or more CH
2-groups of linear C
3-30-alkylene are replaced by two or more heteroatoms, the two or more heteroatoms are separated from each other by at least on CH
2-group of linear C
3-C30-alkylene, M
3 is H or an alkali metal, EB23-1631PC
y is 0, 1 or 2 (R
2)- is an anion selected from the group of HO-, R
8-O-, a halide anion, HO- C
(=O)-O-, R9-S- or an anion of a general formula (III) O || R
7 ^ C ^ O – (III) wherein R
7, R8 and R9 are mutually independently an organic residue, z is 0 or 1, wherein the sum of 2x y and z equals 2, (M
1)
2+ is a bivalent metal. Preferably, at least one of the radicals R
3, R
4, R
5 or R
6 of the residues according to
general formulas (IIa) and/or (IIb) is , mutually independently unsubstituted or at least monosubstituted C
6-C
14-aryl, preferably at least two, more preferably at least three, and most preferably each of the radicals R
3, R
4, R
5 or R
6 are unsubstituted or at least monosubstituted C
6-C
14-aryl,
wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF
3, -NH
2, -SH, C
1-C
6-alkoxy and C
1-C
30-alkyl. More preferably, mutually independently at least one, preferably at least two, more preferably at least three, and most preferably each of the radicals R
3, R
4, R
5 or R
6 of 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 preferred that A is unsubstituted or at least monosubstituted linear C
5-20-alkylene,
wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)- OM
2, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14-aryl, -NH-C
7-30-aralkyl, -N(C
1-30-alkyl)
2, -N(C
6- 14-aryl)
2, -N(C
7-30-aralkyl)
2, -SH, -S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1-30-alkyl, EB23-1631PC
-O-C
6-14-aryl, -O-C
7-30-aralkyl, C
1-30-alkyl and C
6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S- phenyl, -O-C
1-6-alkyl or -O-phenyl, wherein M
2 is H or an alkali metal, and wherein at least one CH
2-group of linear C
5-20-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O and S, and in case two or more CH
2-groups of linear C
5-C
20-alkylene are replaced by two or
more heteroatoms, the two or more heteroatoms are separated from each other by at least one CH
2-group of linear C
5-C
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 more
preferred that A is unsubstituted linear C5-20-alkylene, wherein at least one CH
2-group of linear C
5-20-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 more heteroatoms, the two or more heteroatoms are separated from each other by at least one CH
2-group of linear C
5-20-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 C
5-12-alkylene, wherein one, two or three CH
2-groups of linear C
5-12-alkylene are replaced by O as heteroatom each and in case two or three CH
2-groups of linear C
5-12-alkylene are replaced by O as heteroatom, the
two or three heteroatoms are separated from each other by one or two, preferably by two, CH
2-groups of linear C
5-12-alkylene, preferably A is unsubstituted linear C
8-10-alkylene, wherein one or two groups of linear C
8-10-alkylene are replaced by O as heteroatom each and in case two CH
2-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, CH
2-groups of linear C
8-10- alkylene, most preferably A is unsubstituted linear C
8-10-alkylene, wherein one group of linear C
8- 10-alkylene is replaced by O as heteroatom. As described above, the residue (R
2)- is an anion such as HO-, R
8-O-, a halide anion, HO-C(=O)-O-, R
9-S- or an anion of a general formula (III) and the residues R
7, R
8 and R
9 EB23-1631PC
are mutually independently an organic residue. Such residues (R
2)- are known to the skilled person. Any residues (R
2)- can be employed within the catalysts according to the present invention. The same holds true in respect of any suitable organic residues to be employed in connection with R
7, R
8 and R
9. In respect of the residue (R
2)- according to general formula (I), it is preferred that (R
2)- is an anion selected from the group of HO-, R
8-O-, Cl-, HO-C(=O)-O-, R
9-S- or an anion of a general formula (III) O || R
7 ^ C ^ O – (
III) wherein R
7, R
8 and R
9 are mutually independently unsubstituted or at least monosubstituted C
3- 30-alkyl, C6-14-aryl or C7-30-aralkyl, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM
2, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14-aryl, - NH-C
7-30-aralkyl, -N(C
1-30-alkyl)
2, -N(C
6-14-aryl)
2, -N(C
7-30-aralkyl)
2, -SH, -S-C
1-30-alkyl, -S- C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1-30-alkyl, -O-C
6-14-aryl, -O-C
7-30-aralkyl, C
1-30-alkyl and C
6- 14-aryl, and the alkyl and aryl fragments 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(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6-alkyl, O-phenyl or C
1-6- alkyl, wherein M
2 is H or alkali metal, and wherein one CH
2 group or at least two not adjacent CH
2 groups of C
3-30-alkyl can be
replaced by a heteroatom independently selected from the group consisting of O, S, NH, N-C
1-30-alkyl, N-C
6-14-aryl and N-C
7-30-aralkyl, wherein the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O- C
1-6-alkyl or -O-phenyl, preferably R
7, R
8 and R
9 are mutually independently unsubstituted or at least monosubstituted C
1-C
12-alkyl or C
6-C
14-aryl, wherein the substituents are selected from the group consisting of hydroxyl, chlorine, -CF
3 and C
1-C
6-alkyl.
(R2)- is more preferably an anion of general formula (III), EB23-1631PC
wherein R
7 is unsubstituted or at least monosubstituted C
3-30-alkyl, wherein the substituents are selected from the group consisting of -OH, halogen, -C(=O)-OM
3, -CF
3, -NH
2, -NH-C
1-30-alkyl, -NH-C
6-14-aryl, -NH-C
7-30-aralkyl, -N(C
1-30-alkyl)
2, -N(C
6-14-aryl)
2, - N(C
7-30-aralkyl)
2, -SH, -S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1-30-alkyl, -O-C
6- 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, -C(=O)- OM
1, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1-6- alkyl, -S-phenyl, -O-C
1-6-alkyl, O-phenyl or C-
1-6-alkyl, wherein M
3 is H or alkali metal, and wherein one CH
2 group or at least two not adjacent CH
2 groups of C
3-30-alkyl can be replaced by a heteroatom independently selected from the group consisting of O, S, NH, N-C
1-30-alkyl, N-C
6-14-aryl and N-C
7-30-aralkyl, wherein alkyl and aryl fragments of N-C
1- 30-alkyl, N-C
6-14-aryl, N-C
7-30-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-C
1-6-alkyl or -O-phenyl. (R
2)- is even more preferably an anion of general formula (III), wherein R
7 is unsubstituted or at least monosubstituted C
3-30-alkyl, wherein the
substituents are selected from the group consisting -C(=O)-OM3 and C6-14-aryl, and the aryl fragments of these substituents may in turn be at least monosubstituted by -OH, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, -N(phenyl)
2, -SH, -S-C
1- 6-alkyl, -S-phenyl, -O-C
1-6-alkyl or -O-phenyl and C
1-6-alkyl, wherein M
3 is H or metal, and
wherein one CH2 group or at least two not adjacent CH2 groups of C3-30-alkyl can be replaced by a heteroatom independently selected from the group consisting of O and S. (R
2)- is even more preferably an anion of general formula (III),
wherein R7 is unsubstituted or at least monosubstituted C3-30-alkyl, wherein the substituents are selected from the group consisting -C(=O)-OM
3and phenyl, and wherein one CH
2 group or at least two not adjacent CH
2 groups of C
3-30-alkyl can be replaced by a O.
(R2)- is most preferably an anion of general formula (III), wherein R
7 is unsubstituted C
3-20-alkyl. (R
2)- 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. EB23-1631PC
As described above, the central metal (M
1)
2+according to formula (I) is a bivalent metal. Bivalent metals as such are known to the skilled person. Any bivalent metal can be employed within the catalysts according to the present invention.
Preferably, (M1)2+ is a bivalent metal selected from Sn2+, Zn2+, Ca2+, Mn2+, Co2+ and Mg2+, preferably selected from Sn
2+ Zn
2+, Ca
2+, and Mg
2+ , more preferably selected from Sn
2+ and Zn
2+ , most preferably Sn
2+. 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 R
3, R
4, R
5 und R
6 are mutually independently unsubstituted or at l
east monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from the group consisting of hydroxyl, halogen, carboxyl, -CF
3, -NH
2, -SH, C
1-C
6-alkoxy, C
1-C
30-alkyl and C
6-C
14-aryl and the alkyl and aryl fragments of these substituents may i
n turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2, -SH, or C
1-C
6-alkoxy, and wherein A is unsubstituted or at least monosubstituted linear C
3-30- alkylene, wherein the substituents are selected from the group consisting o
f -OH, halogen, -C(=O)-OM2, -CF3, -NH2, -NH-C1-30-alkyl, -NH-C6-14-aryl, -NH-C
7-30-aralkyl, -N(C
1-30-alkyl)
2, -N(C
6-14-aryl)
2, -N(C
7-30-aralkyl)
2, -SH, - S-C
1-30-alkyl, -S-C
6-14-aryl, -S-C
7-30-aralkyl, -O-C
1-30-alkyl, -O-C
6-14-aryl, -O- C
7-30-aralkyl, C
1-30-alkyl and C
6-14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by -OH, h
alogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, -N(C1-6-alkyl)2, - N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6-alkyl or -O-phenyl, wherein M
2 is H or an alkali metal, and EB23-1631PC
wherein optionally at least one CH
2-group of linear C
3-30-alkylene is replaced by at least one heteroatom independently selected from the group consisting of O, S, NH, N-C
1-30-alkyl, N-C
6-14-aryl and N-C
7-30- a
ralkyl, and wherein alkyl and aryl fragments of N-C1-30-alkyl, N-C6-14-aryl, N-C
7-30-aralkyl may in turn be at least monosubstituted by hydroxyl, halogen, -CF
3, NH
2, -NH-C
1-6-alkyl, -NH-phenyl, -N(C
1-6-alkyl)
2, - N(phenyl)
2, -SH, -S-C
1-6-alkyl, -S-phenyl, -O-C
1-6-alkyl or -O-phenyl, a
nd 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 CH
2-group of linear C
3-C
30-alkylene, i
i) optionally H2O, R8-OH, hydrogen halide, a HO-C(=O)-OH, R9-SH and/or at least one compound of a general formula (IIIa) O || R
7 ^ C ^ OH (IIIa) o
r a corresponding salt thereof, wherein R
7, R
8 and R
9 are mutually independently an organic residue and i
ii) at least one the metal M1-containing compound selected from the group consisting of an oxide, a carbonate, a hydrogencarbonate, a halide, a carboxylate, an alkoxylate, a thiolate, a (C
6-C
14-aryl)-containing compound, a (C
1-C
12-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. 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 salt thereof with a suitable alcohol, for example methanol or ethanol, optionally in the presence of a catalyst. The appropriate preparation methods of such carboxylic esters are known to a person skilled in the art. EB23-1631PC
It has to be noted that the compounds of the general formula (IIc) are the basis for both residues (R
1a)
2- and (R
1b)- of the catalyst of the general formula (I). Depending on the molar ratio of the respective compounds of the general formula (IIc) versus the metal M
1- containing compound as employed during synthesis, the presence residues (R
1a)
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 with temporarily partially blocked carboxy groups. Beyond that the additional employment of compounds such as R
8-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 M
1-containing compound is in the range of 1.0 /1.0 to 2.0/1.0, the catalyst of the general formula (I) predominately contains residues (R
1a)
2- instead of residues (R
1b)-, 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 (R
1a)
2- are contained within the catalyst of the general formula (I). Any metal M
1-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, an alkoxylate or a thiolate besides the metal M
1. In principle, any metal M
1-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 the appropriate compounds according to the general formulae (IIc) or (IIIa). Preferably, the M
1-containing compound is selected from the group consisting of SnCl
2,
Sn(carboxylate)2, Sn(neodecanoate)2, Sn(ethylhexanoate)2, Sn-mercaptans, dibutyltin mercaptan (DBTMC), dioctyltin mercaptan (DOTMC) and Sn-alkoxides, preferably the M
1-containing compound is SnCl
2. 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 (IIc), optionally at least one compound such as R
8-OH or according to the general formula (IIIa), with at least one metal M
1-containing compound , wherein
i) the reaction is carried out under a protective atmosphere and/or in the presence of at least one solvent, preferably toluene or tetrahydrofuran, and/or ii) the reaction is conducted for at least 3 hours and/or at a temperature in the range of -75 to 160° C, and/or EB23-1631PC
iii) following the reaction, volatile constituents are removed, the catalyst is dried under reduced pressure and/or a recrystallization is carried out. As mentioned above, the compounds according to the general formulae (IIc), wherein
R3, R4, R5 and R6 and 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 R
3, R
4, R
5 and R
6 are phenyl each, the respective compound can be prepared by reacting compound of formula (IV)
with a compound auf formula (V) Cl
A Cl wherein A is as defined above. Usually the compound of formula (IV), usually dissolved in an organic solvent such as tetrahydrofuran, 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 reaction mixture is usually allowed to warm to room temperature and stirred at room temperature for 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 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 EB23-1631PC
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 a polystyrene standard. The molecular weight of KOH is 56 g/mol. The hydroxyl number can 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(propylene glycol) and tri(propylene glycol). Further examples of monoalcohols (B1) are benzylalcohol 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. 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- EB23-1631PC
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 and sucrose, 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. Polyurethane
polyols are usually obtained by reaction of diols with diisocyanates. The diol can be a polyester 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 from polymerizable 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 other
polymerizable unsaturated monomers, by methods known in the art such as emulsion polymerization. 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.
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 may comprise further linking groups in the main chain in lower number than the number of ester 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 as butan-1,4-diol, pentane-1,5-diol and hexane-1,6-diol. Polycarbonate polyols may EB23-1631PC
comprise 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 are
usually 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 chain of 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) or polyisocyanates 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. The
following characteristics of polyisocyanates (A) apply to the polyisocyanates carrying free 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 using
gel permeation chromatography calibrated to a polystyrene standard. The NCO content of the polyisocyanate is weight NCO/weight polyisocyanate. The molecular weight of NCO is 42 g/mol. 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 room temperature for five minutes. Then, the resulting reaction mixture is subjected to back titration 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 is 1 g. EB23-1631PC
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, heptamethylene
1,7-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-phenylene diisocyanate,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. 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. EB23-1631PC
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 from renewable resources such as plants. Whether the components are derived from renewable 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 1.5/1 to 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, acids such 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 that the amount of bivalent metal M
1 in the catalyst is in the range of 1 to 1500 ppm based on the weight of all polyisocyanate (A) (weight M
1/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. 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 the blocked 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 a composition comprising as separate components (i) at least one monoalcohol (B1) or polyol (B2) as first component and (ii) at least one polyisocyanate (A) as second EB23-1631PC
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) at
least 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 coating composition comprising as separate components (i) at least one monoalcohol (B1) or
polyol (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 organic
solvents 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 comprises
5 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 70 weight%, of polyisocyanate (A) based on the weight of the composition, and
1 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 composition of the present invention on a on a substrate. The layer can be a coating or adhesive layer The 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, 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 wood substrates, 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, leather substrates, ceramic substrates, mineral building material substrates such as molded EB23-1631PC
cement 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 the
present 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 reactions
for preparing compounds comprising a urethane group, preferably 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 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 present
invention as a catalyst for ring-opening polymerizations of lactones and epoxides. The invention is illustrated hereinafter by examples.
Preparation of inventive and comparative catalysts
I) Preparation of precursors/ligands Compound 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 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 stirred for 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °C EB23-1631PC
and 1,2-Bis(2-chloroethoxy)ethane (18.40 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 Et
2O (3 x
50 mL). Afterwards, the collected organic phases were washed with water, dried over MgSO
4 and decanted. Crystallization at – 27 °C gives a white solid. Yield: 72% (45.70 g, 84.50 mmol).
1H-NMR (400.03 MHz, CDCl
3): δ = 7.30 (m, 8H, aryl-H), 7.22 (m, 12H, aryl-H), 3.50 (t, 4H, CH
2), 3.46 (t, 4H, CH
2), 2.61 (t, 4H, CH
2). 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 stirred for 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °C and 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 Et
2O (3 x 50 mL). Afterwards, the collected organic phases were washed with water, dried over MgSO
4 and decanted. Crystallization at – 27 °C gives a white solid. Yield: 89% (61.2 g, 105.00 mmol).
1H-NMR (400.03 MHz, CDCl3): δ = 7.37 (m, 8H, aryl-H), 7.25 (m, 12H, aryl-H), 3.75 (m, 4H, CH
2), 3.48 (m, 4H, CH
2), 3.23 (t, 4H, CH
2), 2.71 (t, 4H, CH
2).
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 stirred EB23-1631PC
for 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °C and 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 MgSO
4 and decanted. Crystallization at – 27 °C gives a white solid. Yield: 75% (48.16 g, 87.45 mmol).
1H-NMR (400.03 MHz, CDCl
3): δ = 7.20 (m, 20H, aryl-H), 3.23 (t, 4H, CH
2), 2.30 (m, 4H,
CH2), 1.44 (m, 4H, CH2), 1.15 (m, 4H, CH2). II) General procedure for the preparation of the inventive catalysts The metal carboxylates were prepared by adding (1.00 – 5.00 eq.) dicarboxylic acid to
commercially available metal carboxylates (1.00 eq.) (Sn(II)-2-ethylhexanoate, Sigma Aldrich; 2-EH is 2-Ethylhexanoate) in 2-ethylhexanol, in polyol or organic solvent and stirred for 1h at ambient temperature.
III) Determination of the catalytic activity of the catalysts in water containing system 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 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 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 2260 cm
-1 and 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 CH
2 groups (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 H
12MDI (Dicyclohexylmethane 4,4'-Diisocyanate), 34.55 mmol of EB23-1631PC
absolute 2-Ethylhexanol was added 200ppm catalyst at ambient temperature followed by 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 2260 cm
-1 and 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 CH
2 groups (3000 – 2870 cm
-1). EB23-1631PC
BASF SE 231631EP01 34 C
° 0 8 &
T R )I
I ( n i T
e 5 i b -
3 ) a 3 8 , 8 , 9 , 7 , 7 , 7 , 5 , 1 , 3, 9 7 8 G
b p 1 4
3 3 3 3 3 3 3 2 0 , 8 , 7 , 6 E 2 1 1 1 1 1 1 1 1 1 P
d 2 2 . ,
x 8 . , q2 E 6 e( 1 2s i b -
3 ) a 8 6 9 , 9 , 9 , 9 , 9 , 9 , 6 , 7 , 4 , 1, 8
, 9 8
, Gb p 6 3 1 3 1 3 1 3 1 3 1 3 1 3 2 1 0 7 E P
d 2 1 1 1 1 .
2 1 . q , 2 x E 8 , 6
e 1 ( s 1 i
b H
1 2 2 9, 4 8 9 8 9 8 6 2 6 3 9 3 1 , 3
, 3
, 3
, 3
, 3
, 3
, , , , E 9 - 1 1 1 1 3 2 2 1 2 ) . p 2 1 1 1 1 1 1 1 I
I( m
8 , n
o C 6 1 S 0 5 01 51 02 52 03 53 04 54 05 55 06 n
i m
/ t 32 32 32 32 32 32 32 08 08 08 08 08 08 C
° / T EB23-1631PC
As can be deduced from table 1 the catalysts according to the invention show, according to inventive examples Ex1 to Ex9, a higher catalytic activity compared to the known catalysts according to comparative example C1 or without using any catalyst according to comparative example C2. EB23-1631PC
(IIa), wherein R3, R4, R5 and R6 are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, EB23-1631PC
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 M2 is 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 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. x is 0 or 1, (R1b)- is mutually independently a residue of a general formula (IIb) EB23-1631PC
wherein R3, R4, R5 and R6 are 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 M2 is 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 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, M3 is H or an alkali metal, EB23-1631PC
y is 0, 1 or 2 (R2)- is 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 or 1, wherein the sum of 2x y and z equals 2, (M1)2+ is a bivalent metal. The advantages of the catalysts according to the invention can be found in their ability to enhance both the water stability and reactivity of other metal catalysts, including those based on tin(II), 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 metal catalysts 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 higher temperatures (compared to room temperature). 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 EB23-1631PC
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 and there are no issues how the corresponding acid as a low molecular species behaves in the respective formulation and later in the polymeric material. Advantageous properties are then already obtained in the catalysts according to the invention if the dianion (R1a)2- according to the general formula (IIa), which is used as substituent/ligand of the bivalent central atom, comprises the radicals R3, R4, R5 and R6 in α-position and the diradical A. It is preferred that at least one of the radicals R3, R4, R5 or R6 is 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 general formula (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 chemical nomenclature are α-amino acids, where the α-C atom is the carbon atom to which the amino 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 carboxyl group is sometimes also referred to as position 2 in chemical nomenclature. In the context 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 proximity to the central bivalent metal atom M1 of the catalyst. The catalysts according to the invention are represented as salts, wherein the central bivalent metal of the catalyst according to the invention is represented as a (double 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/radicals R1a, R1b and R2 in the general formula (I) detailed above, form the corresponding anion components of the catalyst in this salt representation. The substituent/ligand R1a is double negatively charged and the substituent/ligand R1b and R2 are both singly negatively charged. As detailed below, the substituent R1a mandatorily comprises two carboxyl groups both being negatively charged (dianion), whereas the substituent R2 may comprise one carboxyl group, for example, in case it is an anion of a general formula (III). The substituent R1b also comprises two carboxyl groups, but only one of them is negatively charged (“monoanion”), whereas the second carboxyl group of the substituent R1b is neutralized by either a proton or an alkali metal. In general, the negative charge in the 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 bivalent metal atom. EB23-1631PC
From a scientific standpoint however, it is also tenable, in place of the salt notation used in 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 bivalent metal atoms and the ligands R1a, R1b and R2 according to general formula (I) is completely or at least partially formed in each case. Expressed in other words, this means that the central bivalent metal atom is not present as a positively charged cation and the corresponding 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 bivalent metal atom on the other hand. In the context of the present invention, the catalysts comprising a central bivalent metal atom disclosed according to the invention, therefore, also describe such a definition that is not based on a salt. In the context of the present invention, definitions such as C1-C30-alkyl, such as defined, for example, for the radicals R3 to R6 in formula (IIa) above, signifies that this substituent (radical) is an alkyl radical having a carbon atom number of 1 to 30, wherein substituents optionally 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” may alternatively 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 alternatively refered 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 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 a carbon or a hydrogen atom and that has replaced a carbon atom in the backbone of the molecular structure of a compound, especially in the C3-C30-alkylene bridge of formula (IIa). Examples of heteroatoms are O, S, P and N. EB23-1631PC
In the context of the present invention, at least one CH2-group of linear C3-30-alkylene radical may optionally be replaced by at least one heteroatom. 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. Examples of linear unsubstituted C3-30-alkylene, wherein at least two not adjacent CH2 groups 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 polycyclic aromatic 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 for example 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 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 example as (additional) substituent of the radicals R3 to R6 in formula (IIa) above, signifies that it is 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 EB23-1631PC
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 R3 to R6 in 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 least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl", such as defined for example for the radicals R3 to R6 in 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, such as phenyl for example, may be substituted for example by a hydroxyl and a C1-C30-alkyl substituent, 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 the radicals R1 to R9 are 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)2+ (I) in which the variables are defined as follows: (R1a)2- is a residue of a dianion of a general formula (IIa) EB23-1631PC
(IIa), wherein R3, R4, R5 and R6 are 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 M2 is 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 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 EB23-1631PC
heteroatoms are separated from each other by at least on CH2-group of linear C3-C30-alkylene. x is 0 or 1, (R1b)- is mutually independently a residue of a general formula (IIb)
wherein R3, R4, R5 and R6 are 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 M2 is 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 least monosubstituted by hydroxyl, halogen, -CF3, NH2, -NH-C1-6-alkyl, -NH-phenyl, EB23-1631PC
-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, M3 is H or an alkali metal, y is 0, 1 or 2 (R2)- is 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 or 1, wherein the sum of 2x y and z equals 2, and (M1)2+ is a bivalent 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 the further/exact chemical definition of these radicals R1a, R1b and R2 is a result of the radicals R3 to R6 and A of the general formulas (IIa) or (IIb) with respect to the radical R1 and is a result of the radicals R7 of 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 corresponding substituents/ligands R1a, R1b and R2 of the catalyst in the general formula (I) as shown above, may be freely chosen under the proviso that the sum of the variables 2x, y and z equals 2. EB23-1631PC
This is due to the fact that the overall charge of the catalyst of the general formula (I) is 0, since the catalyst comprises an anionic fragment (made up of the corresponding substituents/ligands R1a, R1b and/or R2) having a total charge of -2 and a cationic fragment (made up of the bivalent metal (M1)2+) having a total charge of +2. By consequence, the general formula (I) comprises catalysts wherein i) x is 1, or ii) y is 2, or iii) y is 1 and z is 1, preferably x is 1. For example, within the above-mentioned option i), wherein x is 1, both y and z are 0 each, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 2. On the other hand, within the above-mentioned option ii), wherein y is 2, both x and z are 0 each, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 2. Furthermore, within the above-mentioned option iii), wherein y is 1 and z is 1, x must be 0, in order to fulfill the requirement that the sum of the variables 2x, y and z equals 2. A preferred embodiment of the present invention relates to a catalyst of a general formula (I) ((R1a)2-)x((R1b)-)y(R2)-)z(M1)2+ (I) in which the variables are defined as follows: (R1a)2- is a residue of a dianion of a general formula (IIa)
wherein R3, R4, R5 and R6 are mutually independently unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, EB23-1631PC
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 M2 is H or an alkali metal, and wherein 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. x is 0 or 1, (R1b)- is mutually independently a residue of a general formula (IIb) EB23-1631PC
wherein R3, R4, R5 and R6 are 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 M2 is H or an alkali metal, and wherein 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, M3 is H or an alkali metal, EB23-1631PC
y is 0, 1 or 2 (R2)- is 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 or 1, wherein the sum of 2x y and z equals 2, (M1)2+ is a bivalent metal. Preferably, at least one of the radicals R3, R4, R5 or R6 of the residues according to general formulas (IIa) and/or (IIb) is , mutually independently unsubstituted or at least monosubstituted C6-C14-aryl, preferably at least two, more preferably at least three, and most preferably each of the radicals R3, R4, R5 or R6 are 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. 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, R5 or R6 of 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 preferred that 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, EB23-1631PC
-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 M2 is 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 or more heteroatoms, the two or more heteroatoms are separated from each other by at least 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 more preferred 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 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. 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, 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 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, R8 and R9 EB23-1631PC
are 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 be employed 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) wherein R7, 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 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 M2 is H or alkali metal, and wherein one CH2 group or at least two not adjacent CH2 groups 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, R8 and R9 are 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. (R2)- is more preferably an anion of general formula (III), EB23-1631PC
wherein R7 is unsubstituted or at least monosubstituted C3-30-alkyl, wherein the substituents 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 of these 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 M3 is H or alkali metal, and wherein one CH2 group or at least two not adjacent CH2 groups 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 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 R7 is unsubstituted or at least monosubstituted C3-30-alkyl, wherein the substituents are selected from the group consisting -C(=O)-OM3 and C6-14-aryl, and the 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 and C1-6-alkyl, wherein M3 is H or metal, and wherein one CH2 group or at least two not adjacent CH2 groups of C3-30-alkyl can be replaced 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 R7 is unsubstituted or at least monosubstituted C3-30-alkyl, wherein the substituents are selected from the group consisting -C(=O)-OM3and phenyl, and wherein one CH2 group or at least two not adjacent CH2 groups of C3-30-alkyl can be replaced by a O. (R2)- is most preferably an anion of general formula (III), wherein R7 is 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. EB23-1631PC
As described above, the central metal (M1)2+according to formula (I) is a bivalent metal. Bivalent metals as such are known to the skilled person. Any bivalent metal can be employed within the catalysts according to the present invention. Preferably, (M1)2+ is a bivalent metal selected from Sn2+, Zn2+, Ca2+, Mn2+, Co2+ and Mg2+, preferably selected from Sn2+ Zn2+, Ca2+, and Mg2+ , more preferably selected from Sn2+ and Zn2+ , most preferably Sn2+. 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, R5 und R6 are 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 M2 is H or an alkali metal, and EB23-1631PC
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 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/or at least one compound of a general formula (IIIa) O || R7 ^ C ^ OH (IIIa) or a corresponding salt thereof, wherein R7, R8 and R9 are mutually independently an organic residue and iii) at least one the metal M1-containing compound selected from the group consisting 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. 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 salt thereof with a suitable alcohol, for example methanol or ethanol, optionally in the presence of a catalyst. The appropriate preparation methods of such carboxylic esters are known to a person skilled in the art. EB23-1631PC
It has to be noted that the compounds of the general formula (IIc) are the basis for both residues (R1a)2- and (R1b)- of the catalyst of the general formula (I). Depending on the molar 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 with temporarily partially blocked carboxy groups. Beyond that the additional employment of compounds 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 the range 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 of the 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, an alkoxylate 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 the appropriate compounds according to the general formulae (IIc) or (IIIa). Preferably, the M1-containing compound is selected from the group consisting of SnCl2, Sn(carboxylate)2, Sn(neodecanoate)2, Sn(ethylhexanoate)2, Sn-mercaptans, dibutyltin mercaptan (DBTMC), dioctyltin mercaptan (DOTMC) and Sn-alkoxides, preferably the M1-containing compound is SnCl2. 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 (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 , wherein i) the reaction is carried out under a protective atmosphere and/or in the presence of at least one solvent, preferably toluene or tetrahydrofuran, and/or ii) the reaction is conducted for at least 3 hours and/or at a temperature in the range of -75 to 160° C, and/or EB23-1631PC
iii) following the reaction, volatile constituents are removed, the catalyst is dried under reduced pressure and/or a recrystallization is carried out. As mentioned above, the compounds according to the general formulae (IIc), wherein R3, R4, R5 and R6 and 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, R5 and R6 are phenyl each, the respective compound can be prepared by reacting compound of formula (IV)
with a compound auf formula (V) ClA Cl wherein A is as defined above. Usually the compound of formula (IV), usually dissolved in an organic solvent such as tetrahydrofuran, 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 reaction mixture is usually allowed to warm to room temperature and stirred at room temperature for 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 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 EB23-1631PC
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 a polystyrene standard. The molecular weight of KOH is 56 g/mol. The hydroxyl number can 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(propylene glycol) and tri(propylene glycol). Further examples of monoalcohols (B1) are benzylalcohol 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. 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- EB23-1631PC
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 and sucrose, 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. Polyurethane polyols are usually obtained by reaction of diols with diisocyanates. The diol can be a polyester 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 from polymerizable 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 other polymerizable unsaturated monomers, by methods known in the art such as emulsion polymerization. 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. 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 may comprise further linking groups in the main chain in lower number than the number of ester 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 as butan-1,4-diol, pentane-1,5-diol and hexane-1,6-diol. Polycarbonate polyols may EB23-1631PC
comprise 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 are usually 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 chain of 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) or polyisocyanates 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. The following characteristics of polyisocyanates (A) apply to the polyisocyanates carrying free 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 using gel permeation chromatography calibrated to a polystyrene standard. The NCO content of the polyisocyanate is weight NCO/weight polyisocyanate. The molecular weight of NCO is 42 g/mol. 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 room temperature for five minutes. Then, the resulting reaction mixture is subjected to back titration 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 is 1 g. EB23-1631PC
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, heptamethylene 1,7-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-phenylene diisocyanate,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. 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. EB23-1631PC
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 from renewable resources such as plants. Whether the components are derived from renewable 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 1.5/1 to 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, acids such 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 that the amount of bivalent metal M1 in 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. 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 the blocked 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 a composition comprising as separate components (i) at least one monoalcohol (B1) or polyol (B2) as first component and (ii) at least one polyisocyanate (A) as second EB23-1631PC
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) at least 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 coating composition comprising as separate components (i) at least one monoalcohol (B1) or polyol (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 organic solvents 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 comprises 5 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 70 weight%, of polyisocyanate (A) based on the weight of the composition, and 1 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 composition of the present invention on a on a substrate. The layer can be a coating or adhesive layer The 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, 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 wood substrates, 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, leather substrates, ceramic substrates, mineral building material substrates such as molded EB23-1631PC
cement 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 the present 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 reactions for preparing compounds comprising a urethane group, preferably 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 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 present invention as a catalyst for ring-opening polymerizations of lactones and epoxides. The invention is illustrated hereinafter by examples.
Preparation of inventive and comparative catalysts I) Preparation of precursors/ligands Compound 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 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 stirred for 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °C EB23-1631PC
and 1,2-Bis(2-chloroethoxy)ethane (18.40 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 MgSO4 and decanted. Crystallization at – 27 °C gives a white solid. Yield: 72% (45.70 g, 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 stirred for 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °C and 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 x 50 mL). Afterwards, the collected organic phases were washed with water, dried over MgSO4 and decanted. Crystallization at – 27 °C gives a white solid. Yield: 89% (61.2 g, 105.00 mmol). 1H-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 stirred EB23-1631PC
for 45 min at this temperature. Subsequently, the reaction solution was cooled to -45 °C and 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 MgSO4 and 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 catalysts The metal carboxylates were prepared by adding (1.00 – 5.00 eq.) dicarboxylic acid to commercially available metal carboxylates (1.00 eq.) (Sn(II)-2-ethylhexanoate, Sigma Aldrich; 2-EH is 2-Ethylhexanoate) in 2-ethylhexanol, in polyol or organic solvent and stirred for 1h at ambient temperature. III) Determination of the catalytic activity of the catalysts in water containing system 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 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 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 2260 cm-1 and 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 CH2 groups (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 EB23-1631PC
absolute 2-Ethylhexanol was added 200ppm catalyst at ambient temperature followed by 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 2260 cm-1 and 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 CH2 groups (3000 – 2870 cm-1). EB23-1631PC
BASF SE 231631EP01 34 C° 0 8 & T R )II ( n i T
e 5 i b -3 ) a 3 8 , 8 , 9 , 7 , 7 , 7 , 5 , 1 , 3, 9 7 8 Gb p 1 4 3 3 3 3 3 3 3 2 0 , 8 , 7 , 6 E 2 1 1 1 1 1 1 1 1 1 Pd 2 2 . , x 8 . , q2 E 6 e( 1 2s i b -3 ) a 8 6 9 , 9 , 9 , 9 , 9 , 9 , 6 , 7 , 4 , 1, 8, 9 8 , Gb p 6 3 1 3 1 3 1 3 1 3 1 3 1 3 2 1 0 7 E Pd 2 1 1 1 1 . 2 1 . q , 2 x E 8 , 6 e 1 ( s 1 i b H 1 2 2 9, 4 8 9 8 9 8 6 2 6 3 9 3 1 , 3 , 3 , 3 , 3 , 3 , 3 , , , , E 9 - 1 1 1 1 3 2 2 1 2 ) . p 2 1 1 1 1 1 1 1 II( m 8 , no C 6 1 S 0 5 01 51 02 52 03 53 04 54 05 55 06 n i m / t 32 32 32 32 32 32 32 08 08 08 08 08 08 C ° / T EB23-1631PC
As can be deduced from table 1 the catalysts according to the invention show, according to inventive examples Ex1 to Ex9, a higher catalytic activity compared to the known catalysts according to comparative example C1 or without using any catalyst according to comparative example C2. EB23-1631PC
(IIa), wherein R3, R4, R5 and R6 are 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 M2 is H or an alkali metal, and EB23-1631PC
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 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. x is 0 or 1, (R1b)- is mutually independently a residue of a general formula (IIb)
wherein R3, R4, R5 and R6 are 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- EB23-1631PC
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 M2 is 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 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, M3 is H or an alkali metal, y is 0, 1 or 2 (R2)- is 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 or 1, EB23-1631PC
wherein the sum of 2x y and z equals 2, and (M1)2+ is a bivalent metal. 2. The catalyst according to claim 1, wherein i) x is 1, or ii) y is 2, or iii) y is 1 and z is 1, preferably x is 1. 3. The catalyst as claimed in claim 1 or 2, wherein mutually independently at least one of the radicals R3, R4, R5 or R6 of 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 each of the radicals R3, R4, R5 or R6 are 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 independently at least one, preferably at least two, more preferably at least three, and most preferably each of the radicals R3, R4, R5 or R6 of 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)2+ is a bivalent metal selected from Sn2+, Zn2+, Ca2+, Mn2+, Co2+ and Mg2+ , preferably selected from Sn2+ Zn2+, Ca2+, and Mg2+ , more preferably selected from Sn2+ and Zn2+ , most preferably Sn2+. 6. The catalyst as claimed in any of claims 1 to 5, wherein 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- EB23-1631PC
phenyl, -N(C1-6-alkyl)2, -N(phenyl)2, -SH, -S-C1-6-alkyl, -S-phenyl, -O-C1-6-alkyl or -O-phenyl, wherein M2 is 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 or more heteroatoms, the two or more heteroatoms are separated from each other 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 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 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, wherein 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, 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 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. EB23-1631PC
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 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 of claims 1 to 9, comprising reacting i) at least one compound of a general formula (IIc) EB23-1631PC
or a corresponding salt thereof, wherein R3, R4, R5 und R6 are 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 M2 is 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 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, EB23-1631PC
ii) optionally H2O, R8-OH, hydrogen halide, a HO-C(=O)-OH, R9-SH and/or at least one compound of a general formula (IIIa) O || R7 ^ C ^ OH (IIIa) or a corresponding salt thereof, wherein R7, R8 and R9 are mutually independently an organic residue and iii) at least one the metal M1-containing compound selected from the group consisting 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 is selected from the group consisting of SnCl2, Sn(carboxylate)2, Sn(neodecanoate)2, Sn(ethylhexanoate)2, Sn-mercaptans, dibutyltin mercaptan (DBTMC), dioctyltin mercaptan (DOTMC) and Sn-alkoxides, preferably the M1-containing compound is SnCl2. 12. A process for the preparation of a compound, oligomer or polymer comprising at least 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 at least one catalyst as claimed in any of claims 1 to 9. 13. A composition comprising (i) at least one monoalcohol (B1) or polyol (B2), (ii) at least one polyisocyanate (A) and (iii) at least one catalyst of any of claims 1 to 9. 14. A layer formed from the composition of claim 13 on a substrate. 15. A foam formed from the composition of claim 13 on a substrate. 16. The use of at least one catalyst as claimed in any of claims 1 to 9 in reactions for preparing compounds comprising a urethane group, as an esterification and EB23-1631PC
transesterification catalyst or as a catalyst for ring-opening polymerizations of lactones and epoxides. EB23-1631PC