Bismuth-containing catalysts comprising dicarboxylate ligands

Abstract

The present invention relates to such a bismuth-containing catalyst, which is defined by the general formula (I) as specified below. The bismuth-containing catalyst comprises a divalent anion (R1) 2-as a dicarboxylate ligand according to the general formula (II), wherein the divalent anion (R1) 2-comprises groups R3, R4, R5 and R6 in the alpha-position. The invention also relates to a method for producing a bismuth-containing catalyst of this type, and to the use of such a bismuth-containing catalyst as esterification and transesterification catalysts and as catalysts for the ring-opening polymerization of lactones and epoxides in reactions for producing compounds containing urethane groups.

Description

[0001] describe

[0002] The present invention relates to such a bismuth-containing catalyst, which is defined by the general formula (I) described in detail below. The bismuth-containing catalyst comprises a divalent anion (R) according to the general formula (II) 1 ) 2- As a dicarboxylate ligand, wherein the divalent anion (R 1 ) 2 - contains a group R in the α-position 3 , R 4 , R 5 and R 6 The invention also relates to a process for preparing a bismuth-containing catalyst of this type and to the use of such a bismuth-containing catalyst as an esterification and transesterification catalyst in reactions for preparing compounds containing urethane groups and as a catalyst for the ring-opening polymerization of lactones and epoxides.

[0003] WO 2018 / 069018 relates to a coating composition system comprising components (A) to (C) and optional additional components. Component (A) is at least one compound containing a polyhydroxy group, and component (B) is at least one compound containing a polyisocyanate. In contrast, component (C) is a catalyst comprising at least two salts of aliphatic monocarboxylic acids having at least 4 carbon atoms. In this case, the metal component of the first salt is bismuth (Bi), and the second salt comprises magnesium (Mg), sodium (Na), potassium (K) or calcium (Ca) as a metal component. The coating composition system according to WO 2018 / 069018 can be configured according to a first option so that all components exist separately from each other, that is, the components are not mixed with each other, and according to the second option of the corresponding coating composition system, the corresponding components can also be completely or at least partially mixed with each other.

[0004] US-A 4,895,827 discloses a catalyst in the form of a metal salt, wherein the catalyst is a component of a thermosensitive color-forming composition, which, in addition to the catalyst, also includes a color-developing material, which includes an acidic developer and a suitable binder. The metal salt can include different metals as central metal atoms / metal ions, including, for example, zinc, tin, aluminum or nickel. The corresponding metal salt includes an organic compound as a ligand, which, in addition to a carboxyl group, also includes an aromatic fragment and a vinyl group. However, bismuth-containing catalysts are not disclosed in US-A 4,895,827.

[0005] JP-A 58 87 087 discloses the use of polyvalent metal salts of diphenylacetic acid, in particular zinc diphenylacetate, as colorants, wherein water-resistant color images can be produced. However, JP-A 58 87 087 does not disclose bismuth-containing metal salts or the use of these metal salts for the preparation of compounds containing urethane bonds.

[0006] WO 2020 / 160939 relates to a method comprising at least one group R 1 The bismuth-containing catalyst, the group R 1 The invention relates to a method for preparing a bismuth-containing catalyst and the use of a bismuth-containing catalyst for preparing a compound containing a carbamate group.

[0007] The preparation of compounds containing carbamate groups (carbamate bonds) is also well known. If a compound containing an isocyanate group is reacted with a compound containing a hydroxyl group, a compound with a carbamate group is usually obtained. The reaction is usually carried out in the presence of a catalyst. Although tin-containing catalysts show very high activity in such reactions, the use of such tin-containing catalysts, particularly alkyl-tin compounds, should be avoided due to their (very high) toxicity.

[0008] It was therefore an object of the present invention to provide novel catalysts which can be used for the preparation of compounds comprising urethane groups.

[0009] This object is achieved by a bismuth-containing catalyst of the general formula (I):

[0010] (R 1 ) 2- (R 2 ) - (Bi) 3+ (I)

[0011] The variables are defined as follows:

[0012] (R 1 ) 2- are independently divalent anions of the general formula (II)

[0013]

[0014] Where R 3 , R 4 , R 5 and R 6 are independently unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C14 -Aryl or C7-C 30 -aralkyl,

[0015] Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C 30 -alkyl and C6-C 14 -aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2, -SH or C1-C6-alkoxy,

[0016] and wherein A is unsubstituted or at least monosubstituted C1-C 30 -alkylene, wherein A can contain O, S, PR 12 and NR 12 The heteroatoms

[0017] Where R 12 is unsubstituted or at least monosubstituted C1-C 30 -alkyl or H, where R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 For unsubstituted C1-C 30 -alkyl or H,

[0018] (R 2 ) - are independently hydroxide anions, alkoxide anions, halide anions, bicarbonate anions, thiolate anions, R 7 , anion of general formula (III)

[0019]

[0020] or an anion of formula (IV)

[0021]

[0022] Where R 7 is unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl,

[0023] Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C 30 -alkyl and C6-C 14-aryl, and the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2, -SH or C1-C6-alkoxy,

[0024] And where R 8 and R 9 Each is phenyl and R 10 C1-C 12 -alkyl,

[0025] And where R 11 is unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl,

[0026] Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SR 14 , C1-C6-alkoxy, C1-C 30 -alkyl or C6-C 14 -aryl, wherein the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2 or C1-C6-alkoxy, and R 14 is H, unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl.

[0027] The bismuth-containing catalyst according to the invention is characterized in that, in particular, the use of toxic tin-containing catalysts in the production of compounds containing carbamate groups can be avoided. The bismuth-containing catalyst according to the invention has a catalytic activity comparable to known representatives of effective tin-containing catalysts that are catalytically active on the one hand but toxic on the other hand.

[0028] However, the catalytic activity of the bismuth-containing catalysts according to the invention is superior to the corresponding catalytic activity of the known bismuth-containing or zinc-containing catalysts.

[0029] In addition, compared with known bismuth-containing catalysts, bismuth-containing catalysts according to the present invention show improved hydrolytic stability. For example, a small amount of water may be enough to significantly or completely eliminate the catalytic activity of bismuth-containing catalysts such as laurate-containing bismuth catalysts based on pure aliphatic monocarboxylate radical ligands. Such catalysts known from the prior art begin to precipitate when contacting with water, and bismuth-containing catalysts according to the present invention are more stable. Due to the increase in hydrolytic stability and therefore the increase in storage stability, bismuth-containing catalysts according to the present invention show improved catalytic properties in a longer period of time.

[0030] Furthermore, in the case of the bismuth-containing catalyst according to the invention, it is not required that the catalyst as a salt be used in the presence of a protonated ligand. Therefore, the bismuth-containing catalyst according to the invention can be used with high catalytic activity in the absence of the corresponding acid to form compounds having carbamate groups, and there is no question of how the corresponding acid, as a low-molecular substance, acts in the corresponding formulation and subsequently in the polymer material.

[0031] If a divalent anion (R 1 ) 2- Contains a diradical A and contains a group R in the α-position 3 , R 4 , R 5 and R 6 , then advantageous properties are already obtained in the catalyst according to the invention. It is preferred that the group R 3 , R 4 , R 5 or R 6 At least one of them is unsubstituted or at least monosubstituted C6-C 14 - Aryl, especially phenyl.

[0032] In the context of the present invention, the "α-position" describes the carbon atom adjacent to the carbonyl carbon atom of the carboxylic acid. According to the present invention, this carbon atom is referred to as the α-carbon. Examples known for this purpose according to chemical nomenclature are α-amino acids, in which the α-C atom is the carbon atom to which the amino group and the carboxyl group are attached. Specific examples of this numbering from the field of amino acids are β-alanine and γ-aminobutyric acid. In chemical nomenclature, the carbonyl carbon is sometimes also counted and referred to as position 1. Therefore, the first carbon atom that is 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 divalent anion (R) according to the general formula (II) 1 ) 2- Has two α-carbons.

[0033] The carboxyl group of the substituent is located (sterically) in the vicinity of the bismuth central atom of the bismuth-containing catalyst. The bismuth-containing catalyst according to the invention is represented as a salt, wherein the bismuth central atom of the bismuth-containing catalyst according to the invention is represented as a (triply positively charged) cation of the corresponding salt (see, for example, general formula (I)). The substituent / group R in the general formula (I) described in detail above 1 and R 2 The corresponding substituents / ligands of the bismuth-containing catalyst represented by form the corresponding anionic component of the bismuth-containing catalyst in the salt representation. 1 Double negative charge, substituent / ligand R 2 As described in detail below, the substituent R 1Contains two carboxyl groups and the substituent R 2 One carboxyl group may be included. Generally, the negative charge in the corresponding substituent / ligand of the carboxyl group is localized and / or the corresponding carboxyl group is spatially located near the (positively charged) bismuth central atom.

[0034] However, from a scientific point of view, it is also possible to select a bismuth central atom according to the general formula (I) and a ligand R 1 and R 2 In the context of the present application, the bismuth-containing catalysts are represented by the symbol / representation that the chemical bond between them is in each case completely or at least partially formed, instead of the salt symbol used in the context of the present application. In other words, this means that the bismuth central atom is not present as a positively charged cation and the corresponding ligand is not present as a negatively charged anion, but the corresponding charges form a chemical bond between the corresponding ligand on the one hand and the bismuth central atom on the other hand. In the context of the present invention, the bismuth-containing catalysts disclosed according to the present invention therefore also describe this definition that is not based on salts.

[0035] In the context of the present invention, for example, for the group R in the above formula (II) 3 To R 6 Defined, such as C1-C 30 -alkyl means that the substituent (group) is an alkyl group with 1 to 30 carbon atoms, wherein the number of carbon atoms does not take into account the substituents that are optionally present. The alkyl group can be straight-chain or branched and optionally cyclic. Alkyl groups with both cyclic and straight-chain components also fall within this definition. The same applies to other alkyl groups, such as C1-C6-alkyl groups or C1-C 12 - Alkyl groups. Examples of alkyl groups are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu / t-Bu), pentyl, hexyl, heptyl, cyclohexyl, octyl, nonyl or decyl.

[0036] In the context of the present invention, such as defined for the group A in formula (II) above, definitions such as C1-C 30 -Alkylene means that the diradical is an alkylene diradical having a number of carbon atoms of 1 to 30, where the number of carbon atoms does not take into account any substituents which may be present. The alkyl group may be straight-chain or branched.

[0037] In the context of the present invention, a heteroatom is an atom which is not a carbon or hydrogen atom and which has replaced a C1-C 30 - any atom of a carbon atom in an alkylene bridge. Examples of heteroatoms are O, S, P and N.

[0038] In the context of the present invention, for example for the group R in the above formula (II) 3 To R 6 As defined herein, the term "aryl" or the term "C6-C 14 "-aryl" means that the substituent (group) is an aromatic system. The corresponding aromatic system has a number of 6 to 14 carbon atoms, wherein optionally present substituents are not taken into account in the number of carbon atoms. The aromatic system can be a monocyclic, bicyclic or optionally polycyclic aromatic system. In the case of bicyclic or polycyclic aromatic systems, the individual rings can optionally be fully or partially saturated. Preferably, all rings of the corresponding aromatic system are completely unsaturated. Preferred examples of aryl are phenyl, naphthyl or anthracenyl, in particular phenyl.

[0039] In the context of the present invention, for example for the group R in the above formula (II) 3 To R 6 Defined, define "C7-C 30- "Aralkyl" means a substituent (group) comprising an alkyl group (such as C1-C6-alkyl according to the above definition), wherein the alkyl group is in turn substituted by an aryl group (according to the above definition). The corresponding aralkyl substituent has a number of 7 to 30 carbon atoms, wherein optionally present substituents are not taken into account in the number of carbon atoms. The alkyl groups present may themselves be straight-chain or branched and optionally cyclic.

[0040] In the context of the present invention, the radical R in the above formula (II) is defined as 3 To R 6 The term "C1-C6-alkoxy" means that in this case it is a substituent (group) derived from an alcohol. The corresponding substituent thus contains an oxygen fragment (-O-) which in turn is attached to an alkyl group such as C1-C6-alkyl (according to the above definition). The alkyl group itself may be straight-chain or branched and optionally cyclic.

[0041] In the context of the present invention, the radical R in the above formula (II) is defined as 3 To R 3 The term "halogen" means that the substituent (group) is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine, particularly preferably chlorine.

[0042] In the context of the present invention, for example, for the group R in the above formula (II) 3 To R 6 As defined herein, the term "unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30"-aralkyl" means that each of the total of four substituents (radicals) specified above corresponding to the definitions already specified can be present 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), suitable substituents are selected independently of one another from the substituent groups specified in each case.

[0043] For example, in the case of disubstituted C6-C 14 In the case of -aryl, the corresponding aryl unit such as phenyl can be replaced by hydroxyl and C1-C 30 - alkyl substituents such as methyl or ethyl substitution. According to the definition, the alkyl or aryl fragments themselves may contain at least one further substituent. The substitution may be at any desired position of the corresponding fragment.

[0044] Unless otherwise indicated in the following description, the group R 1 To R 11 The corresponding definitions of are in each case preferred unsubstituted definitions.

[0045] The present invention is further described below.

[0046] The present invention first relates to a bismuth-containing catalyst of general formula (I)

[0047] (R 1 ) 2 -(R 2 )-(Bi) 3+ (I)

[0048] The variables are defined as follows:

[0049] (R 1 ) 2- are independently divalent anions of the general formula (II)

[0050]

[0051] Where R 3 , R 4 , R 5 and R 6 are independently unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl,

[0052] Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C 30 -alkyl and C6-C 14-aryl, and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2, -SH or C1-C6-alkoxy,

[0053] and wherein A is unsubstituted or at least monosubstituted C1-C 30- Alkylene, wherein A can contain O, S, PR 12 and NR 12 The heteroatoms

[0054] Where R 12 is unsubstituted or at least monosubstituted C1-C 30- Alkyl or H, where R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 For unsubstituted C1-C 30- Alkyl or H,

[0055] (R 2 ) - are independently hydroxide anions, alkoxide anions, halide anions, bicarbonate anions, thiolate anions, R 7 , anion of general formula (III)

[0056]

[0057] or an anion of formula (IV)

[0058]

[0059] Where R 7 is unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl,

[0060] Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C 30 -alkyl and C6-C 14 -aryl, and the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2, -SH or C1-C6-alkoxy,

[0061] And where R 8 and R 9 Each is phenyl and R 10 C1-C 12 -alkyl,

[0062] And where R 11 is unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl,

[0063] Wherein the substituent is selected from hydroxyl, halogen, carboxyl, CF3, -NH2, -SR 14 , C1-C6-alkoxy, C1-C 30 -alkyl or C6-C 14 -aryl, wherein the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2 or C1-C6-alkoxy, and R 14 is H, unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl.

[0064] With regard to the groups (substituents / ligands) present in the general formula (I), in particular the essential groups R 1 and R 2 It should be noted that these groups R 1 or R 2 A further / precise chemical definition is that the radical R 3 To R 6 , A, R 12 and R 13 Relative to group R 1 The result is the group R 7 and R 14 and a group R of formula (III) or (IV) 8 To R 11 Relative to group R 2 result.

[0065] R 1

[0066] According to the invention, the divalent anion of the general formula (II) is preferably defined such that the radical R 3 , R 4 , R 5 or R 6 At least one of them is unsubstituted or at least monosubstituted C6-C 14 - aryl, more preferably, the group R 3 , R 4 , R 5 or R 6 At least two, most preferably at least three, and particularly preferably each is unsubstituted or at least monosubstituted C6-C14 -Aryl.

[0067] Therefore, another object of the present invention is a bismuth-containing catalyst in which the radical R 3 , R 4 , R 5 or R 6 At least one of them is unsubstituted or at least monosubstituted C6-C 14 - aryl, preferably, the group R 3 , R 4 , R 5 or R 6 At least two, more preferably at least three, and most preferably each of them is unsubstituted or at least monosubstituted C6-C 14 -Aryl.

[0068] In a preferred embodiment, the group R 3 , R 4 , R 5 or R 6 At least one, preferably at least two, more preferably at least three, and most preferably each of is phenyl.

[0069] Therefore, another object of the present invention is a bismuth-containing catalyst in which the radical R 3 , R 4 , R 5 or R 6 At least one, preferably at least two, more preferably at least three, and most preferably each of is phenyl.

[0070] In a preferred embodiment, A is an unsubstituted C1-C 30 -alkylene, preferably unsubstituted C3-C 12 -alkylene.

[0071] Therefore, another object of the present invention is a bismuth-containing catalyst, wherein A is an unsubstituted C1-C 30 -alkylene, preferably unsubstituted C3-C 12 -alkylene.

[0072] In another preferred embodiment, A is unsubstituted C1-C 30 -alkylene and contains a compound selected from O, S, PR 12 and NR 12 , preferably selected from O, S and NR 12 , more preferably a heteroatom selected from O and S,

[0073] Where R 12 is unsubstituted or at least monosubstituted C1-C 30 -alkyl or H, where R12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 For unsubstituted C1-C 30 -alkyl or H.

[0074] Therefore, another object of the present invention is a bismuth-containing catalyst, wherein A is an unsubstituted C1-C 30 -alkylene and contains a compound selected from O, S, PR 12 and NR 12 , preferably selected from O, S and NR 12 , more preferably a heteroatom selected from O and S,

[0075] Where R 12 is unsubstituted or at least monosubstituted C1-C 30 -alkyl or H, where R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 For unsubstituted C1-C 30 -alkyl or H.

[0076] In this case, it is further preferred that A is an unsubstituted C3-C 12 -alkylene and contains a compound selected from O, S, PR 12 and NR 12 , preferably selected from O, S and NR 12 , more preferably a heteroatom selected from O and S,

[0077] Where R 12 is unsubstituted C3-C5-alkyl or H, wherein R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 It is methyl.

[0078] Therefore, another object of the present invention is a bismuth-containing catalyst, wherein A is an unsubstituted C3-C 12 -alkylene and contains a compound selected from O, S, PR 12 and NR 12 , preferably selected from O, S and NR 12 , more preferably a heteroatom selected from O and S,

[0079] Where R 12 is unsubstituted C3-C5-alkyl or H, wherein R 12 Can contain selected from O, S, PR 13and NR 13 The heteroatom R 13 It is methyl.

[0080] The divalent anion (R 1 ) 2- The corresponding dicarboxylic acid

[0081]

[0082] Preferably, it has a negative ΔG value when it is exchanged for two monocarboxylate ligands (eg pivalate), as determined, for example, by ab initio or semi-empirical calculations at the DFT (density functional theory) level of theory.

[0083] Therefore, another object of the present invention is a bismuth-containing catalyst, in which the divalent anion (R 1 ) 2- The corresponding dicarboxylic acid

[0084]

[0085] It has a negative ΔG value when it is exchanged for two monocarboxylate ligands, as determined by ab initio or semiempirical calculations.

[0086] The divalent anion (R 1 ) 2- Examples of suitable corresponding dicarboxylic acids are shown in Table 1. The ΔG values ​​when exchanged for two monocarboxylate ligands (pivalate; see the reaction equation in the first row of Table 1) were determined by DFT (density functional theory) calculations. The program package TURBOMOLE (version 7.5.2) was used at the M06-2X / def2-TZVPD / / BP86 / def-TZVP / COSMO (ε=∞) theoretical level, using COSMO-RS solvation (BP_TZVPD_FINE_C30_1801.ctd parameterization, ethylhexyl-OC(=O)-NH-C6H 12 DFT calculations were performed on the following ligand exchange reactions (a 1:1 mixture of -NCO and EtOH at 25°C). Negative values ​​of ΔG for the following ligand exchange reactions indicate that the chelate is favored. Therefore, for dicarboxylic acids, the more negative these values ​​are, the more stable the chelate is expected to be, from which it can be inferred that the (hydrolytic) stability is higher. Based on these data, conclusions can be drawn about the optimal linker size and additional coordinating atoms.

[0087] Table 1

[0088]

[0089]

[0090] 2 The value of the most stable conformer of sulfide S coordinated with Bi is

[0091] R 2

[0092] Preferably, (R 2 )-are independently hydroxide anions, alkoxide anions, thiolate anions, chloride anions, R 7 , a group of the general formula (III) or a group of the general formula (IV),

[0093] Where R 7 is unsubstituted or at least monosubstituted C1-C 12 -alkyl or C6-C 14 -aryl, wherein the substituents are selected from hydroxy, chlorine, -CF3 and C1-C6-alkyl.

[0094] Therefore, another object of the present invention is a bismuth-containing catalyst, wherein (R 2 ) - are independently hydroxide anions, alkoxide anions, thiolate anions, chloride anions, R 7 , a group of the general formula (III) or a group of the general formula (IV),

[0095] Where R 7 is unsubstituted or at least monosubstituted C1-C 12 -alkyl or C6-C 14 -aryl, wherein the substituents are selected from hydroxy, chlorine, -CF3 and C1-C6-alkyl.

[0096] If (R 2 )- is an anion of the general formula (III), then R 8 and R 9 Preferably each is phenyl and R 10 C6-C 10 -alkyl, especially C8-alkyl.

[0097] The present invention also relates to a method for preparing a bismuth-containing catalyst according to the general formula (I) defined above. The method for preparing such a bismuth-containing catalyst according to the present invention may comprise, for example, reacting the following substances:

[0098] i) at least one compound of the general formula (IIa)

[0099]

[0100] or its corresponding salt,

[0101] Where R 3, R 4 , R 5 and R 6 are independently unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl,

[0102] Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C 30 -alkyl and C6-C 14 -aryl, and the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2, -SH or C1-C6-alkoxy,

[0103] and wherein A is unsubstituted or at least monosubstituted C1-C 30 -alkylene, wherein A can contain O, S, PR 12 and NR 12 The heteroatoms

[0104] Where R 12 is unsubstituted or at least monosubstituted C1-C 30 -alkyl or H, where R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 For unsubstituted C1-C 30 -alkyl or H,

[0105] ii) optionally at least one compound of the general formula (IIIa)

[0106]

[0107] or its corresponding salt,

[0108] Where R 8 and R 9 Each is phenyl and R 10 C1-C 12 -alkyl, or

[0109] At least one compound of the general formula (IVa)

[0110]

[0111] or its corresponding salt,

[0112] Where R 11 is unsubstituted or at least monosubstituted C1-C 30-alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl, wherein the substituent is selected from hydroxy, halogen, carboxyl, -CF3, -NH2, -SR 14 , C1-C6-alkoxy, C1-C 30 -alkyl or C6-C 14 -aryl, wherein the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2 or C1-C6-alkoxy, and R 14 is H, unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl, and

[0113] iii) at least one bismuth-containing compound selected from the group consisting of Bi2O3, bismuth carbonate, bismuth bicarbonate, bismuth halide, bismuth carboxylate, bismuth alkoxide, Bi(C6-C 14 -aryl)3, Bi(C1-C 12 -alkyl)3 and metallic bismuth.

[0114] The reactants listed above, i.e., the acids according to the general formula (IIa) to (IVa) or such appropriate corresponding salts are known to those skilled in the art. The corresponding salt used may be, for example, a sodium salt, a potassium salt or a calcium salt. Optionally, in addition to the above-mentioned acids according to the general formula (IIa) to (IVa) or their corresponding salts, corresponding carboxylates (e.g., methyl esters or ethyl esters) may also be used as reactants. Such carboxylates may be prepared by reacting the above-mentioned acids or their corresponding salts with suitable alcohols (e.g., methanol or ethanol) optionally in the presence of a catalyst. Suitable methods for the preparation of such carboxylates are known to those skilled in the art.

[0115] In principle, any bismuth-containing compound can be used in the process according to the invention, which is suitable for the purpose of forming a bismuth central atom in a bismuth-containing catalyst of the general formula (I) according to the invention by reacting with a suitable compound according to the general formula (IIa) to (IVa). Such bismuth-containing compounds are known to the person skilled in the art. According to the invention, if a bismuth halide is used as the bismuth-containing compound, a chlorine-containing compound is preferably used, in particular BiCl3. Any particular substituent / substitution pattern such as the group R 8 To R 10 Such substituents / substitution patterns may already be present in the corresponding reactants. Optionally, such substituents / substitution patterns may also be attached or completed even after the preparation of the bismuth-containing catalysts according to the above-described general formula (I).

[0116] Preferably, the bismuth-containing compound is selected from Bi2O3, BiCl3, bismuth alkoxide, bismuth carboxylate, Bi(C6H5)3 and metallic bismuth.

[0117] In a preferred embodiment, the bismuth-containing catalyst according to the invention according to the general formula (I) is prepared by reacting at least one compound of the general formula (IIa) and at least one compound of the general formula (IIIa) or (IVa) with at least one bismuth-containing compound, wherein

[0118] 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

[0119] ii) the reaction is carried out for at least 3 hours and / or at a temperature in the range of -75°C to 160°C, and / or

[0120] iii) After the reaction, the volatile components are removed, the bismuth-containing catalyst is dried under reduced pressure and / or recrystallized.

[0121] Furthermore, as mentioned above, the at least one compound of the general formula (IIa) preferably has a negative ΔG value when it is exchanged for two monocarboxylate ligands, as determined by ab initio or semi-empirical calculations.

[0122] The at least one bismuth-containing catalyst according to the above definition can be used for Lewis acid-catalyzed reactions, such as esterification; transesterification; ring-opening polymerization of ethers, lactones, epoxides and amines; epoxidation; and for reactions for preparing compounds containing carbamate groups, preferably for reactions for preparing compounds containing carbamate groups.

[0123] The present invention therefore also relates to the use of at least one bismuth-containing catalyst according to the above definition in a reaction for preparing compounds comprising urethane groups.

[0124] The present invention therefore also relates to the use of at least one bismuth-containing catalyst according to the above definition as an esterification and transesterification catalyst.

[0125] The present invention therefore also relates to the use of at least one bismuth-containing catalyst according to the above definition as catalyst for the ring-opening polymerization of lactones and epoxides.

[0126] The present invention is illustrated hereinafter by means of examples. Example

[0127] Preparation of the catalyst of the present invention and the comparative catalyst

[0128] I) Preparation of Precursors

[0129] Ia) Precursor 1: 2,2,9,9-tetraphenyldecanedioic acid (compound of general formula (IIa); tpddH)

[0130] 2,2,9,9-Tetraphenylsebacic acid was prepared using a modified literature procedure (C. Destabel, JD Kilburn, J. Knight, Tetrahedron, 1994, Vol. 50, 11267).

[0131] In a Schlenk flask, 2,2-diphenylacetic acid (50.0 g, 235.57 mmol, 1.00 equivalent) was dissolved in 156 mL THF (tetrahydrofuran) and cooled to -15 ° C. Then, 2.5 M n-butyl lithium in n-hexane solution (210 mL, 525 mmol, 2.20 equivalent) was slowly added, and the resulting red solution was stirred at this temperature for 45 minutes. Subsequently, the reaction solution was cooled to -45 ° C and 1,6-dibromohexane (28.73 g, 117.79 mmol, 0.50 equivalent) was slowly added. The mixture was then stirred at room temperature overnight and terminated by adding a 1.0 M HCl aqueous solution. During the acidification process, a solid precipitate was obtained, which was then washed with water and dried overnight in vacuo at 80 ° C to obtain a dicarboxylic acid.

[0132] Yield: 98% (58.20 g, 115 mmol)

[0133] pass 1 H-NMR, 13 C-NMR, HRMS (high resolution mass spectrometry) and infrared spectroscopy characterization.

[0134] Ib) Precursor 2: 6,6′-oxybis(2,2-diphenylhexanoic acid (compound of general formula (IIa); O-bis(dph)H)

[0135] 6,6'-Oxybis(2,2-diphenylhexanoic acid) was prepared using a modified literature procedure.

[0136] In a Schlenk flask, 2,2-diphenylacetic acid (50.0 g, 235.57 mmol, 1.00 equivalent) was dissolved in 156 mL THF and cooled to -15 ° C. Then, 2.5 M n-butyl lithium in n-hexane solution (210 mL, 525 mmol, 2.20 equivalent) was slowly added, and the resulting red solution was stirred at this temperature for 45 minutes. Subsequently, the reaction solution was cooled to -45 ° C and bis (4-chlorobutyl) ether (21.70 mL, 117.79 mmol, 0.50 equivalent) was slowly added. The mixture was then stirred at room temperature overnight and terminated by adding 1.0 M HCl aqueous solution. Subsequently, the phases were separated in a separatory funnel, and the aqueous phase was extracted with Et2O (3 × 50 mL). Then, the collected organic phase was washed with water, dried over MgSO4 and decanted. Crystallization at -27 ° C gave a white solid.

[0137] Yield: 75% (48.16 g, 87.45 mmol)

[0138] The products were characterized by 1H-NMR, 13C-NMR, HRMS (high resolution mass spectrometry) and infrared spectroscopy.

[0139] Ic) Precursor 3: 2,2-diphenyldecanoic acid (compound of general formula (IIIa); dpdH)

[0140]

[0141] Under a protective gas atmosphere (argon or nitrogen), 2,2-diphenylacetic acid (10.6 g; 48 mmol) was dissolved in 75 mL of anhydrous tetrahydrofuran (THF) in a 200 mL Schlenk flask and cooled to -15°C. A 1.6 M solution of n-butyl lithium in hexane (60 mL; 96 mmol) was then added over a period of 30 minutes with stirring. The reaction solution was stirred at -15°C for one hour and cooled to -78°C to add 1-bromooctane (8.3 mL; 48 mmol). Subsequently, the reaction solution was slowly warmed to room temperature and stirred for another 24 hours.

[0142] For post-treatment and purification of 2,2-diphenyldecanoic acid, saturated ammonium chloride solution (60 mL) was added to the reaction solution and stirred for 30 minutes. The aqueous phase was separated using a separatory funnel and extracted with 3×25 mL of diethyl ether. The combined organic phases were dried over magnesium sulfate (MgSO4). Then, the mixture was decompressed (1·10 -3 mbar) to remove all volatile solvents, and the resulting solid was dried under reduced pressure at 140 °C (1·10 -3 mbar) for 24 hours.

[0143] pass 1 H-NMR, 13 C_NMR, HRMS (high resolution mass spectrometry) and infrared spectroscopy characterization.

[0144] II) General procedure for preparing the catalyst of the invention

[0145] The bismuth (III) carboxylate of the present invention according to the general formula (I) is prepared according to a modified synthesis procedure of Levent et al. (E. Levent, O. Sala, LFB Wilm, P. Loewe, F. Dielmann, Green Chem., 2021, Vol. 23: p. 2747).

[0146] As monocarboxylic acids, 2,2-diphenyldecanoic acid (dpdH; compound of the general formula (IIIa)), neodecanoic acid (ndaH; compound of the general formula (IVa)), 2,2-diphenylpropionic acid (dppH; commercially available from Sigma-Aldrich; compound of the general formula (IIIa)), lauric acid (lauH; compound of the general formula (IVa)) and 2-((phenylthio)methyl)benzoic acid (SPhbzaH; commercially available from Sigma-Aldrich; compound of the general formula (IVa)) were used.

[0147] A Schlenk flask was charged with BiPh3 (1.00 equiv), a dicarboxylic acid (1.00 equiv; a compound of formula (IIa)), and a monocarboxylic acid (1.00 equiv). Anhydrous toluene or tetrahydrofuran (3 mL / mmol BiPh3) was added and the reaction mixture was heated at 110°C for at least 16 hours. 1 The reaction mixture was monitored by H-NMR to confirm complete consumption of BiPh3. Subsequently, all volatiles were removed under reduced pressure and the residue was dried under vacuum at 80°C overnight to afford bismuth (III) carboxylate as an off-white solid.

[0148] pass 1 H-NMR, 13 C-NMR, HRMS (high resolution mass spectrometry) and infrared spectroscopy characterization.

[0149] The prepared catalysts of the present invention are shown in Table 2.

[0150] Table 2

[0151]

[0152] tpdd, dpd, etc. correspond to the corresponding anions of the (di)carboxylic acids tpddH, dpdH, etc.

[0153] III) Preparation of comparative catalysts

[0154] IIIa) Comparative Example C1: Bi(2,2-diphenyldecanoate)3 (Bi(dpd)3)

[0155] First, triphenylbismuth (1.1 g; 2.5 mmol) and 2,2-diphenyldecanoic acid (2.43 g; 7.5 mmol) were placed in a 25 mL three-necked flask equipped with a stirring bar, a reflux condenser, a thermometer, and an inlet for a protective gas atmosphere (argon or nitrogen) under a protective gas atmosphere. 12.5 mL of anhydrous tetrahydrofuran or anhydrous toluene (5 mL solvent / 1 mmol triphenylbismuth) was added to the reactants, and the mixture was heated at 110 ° C for at least 16 hours under a protective gas atmosphere. 1The progress of the reaction was monitored by H-NMR (nuclear magnetic resonance spectroscopy). After the triphenylbismuth was completely converted and benzene was formed, the reaction was terminated and cooled. The pressure was then reduced (1.10 -3 mbar) to remove all volatile solvents, and the resulting solid was dried under reduced pressure at 60 °C (1·10 -3 mbar) for 24 hours. The resulting compound was purified from toluene and hexane at -40°C or by recrystallization from hot toluene as required.

[0156] pass 1 H-NMR, 13 C-NMR, C / H / N elemental analysis, and infrared spectroscopy characterization.

[0157] IIIb) Comparative Example C2: Bi(nda)3

[0158] nda is neodecanoate (commercially available catalyst from Sigma Aldrich); metal content in neodecanoic acid is 21 wt%

[0159] IV) Determination of catalytic activity of catalyst

[0160] The corresponding catalytic activity of each of the inventive examples and comparative examples was tested by a reaction in which a compound containing a carbamate group was formed, wherein an IR spectrometer (FT-IR spectrometer 7000e, Agilent; measuring range 500 cm -1 Up to 4000cm -1 ) to measure the NCO conversion.

[0161] The catalytic crosslinking reaction between NCO groups (of the polyisocyanate) and OH groups (of the OH-functional polyacrylate) to form polyurethanes was investigated by heatable horizontal ATR-IR spectroscopy at 60°C. The measurement was carried out directly after the addition of the curing agent solution to the mixed varnish. The onset was measured at ambient temperature with a catalyst-free formulation. The reaction was subsequently monitored at 60°C over a period of 30 minutes with a step size of 3 minutes. The free isocyanate was detected at 2260 cm -1 The conversion was determined by the decrease in the intensity of the band at 1690 cm -1 The spectra were normalized to the isocyanurate band at .

[0162] A mixture of 95 parts of HMDI trimer (NCO content 23.5%±0.5%) and 5 parts of IPDI trimer (NCO content 11.9%±0.4%) diluted to 85% solids in a 1:1 mixture of butyl acetate and xylene was used as polyisocyanate (item 6; curing agent).

[0163] As OH-functional polyacrylates, polyacrylate polyols with an OH number of 150 mg KOH / g (based on solids content) and an acid number of 1 to 15 mg KOH / g (based on solids content) were used (item 1). The following monomers were used in the preparation of the polyacrylate polyols: methyl methacrylate, n-butyl acrylate, butyl methacrylate, hydroxypropyl methacrylate.

[0164] A 1:1 mixture of xylene / butyl acetate (solvent) was used as diluent (entry 7).

[0165] The composition of the mixed varnish is shown in Table 3. The concentration values ​​are absolute amounts (expressed in parts) based on the entire mixed varnish (excluding the catalyst).

[0166] Table 3

[0167]

[0168]

[0169] To prepare the mixed varnish, items 1 to 4 of Table 3 were combined under stirring. The corresponding amount of catalyst was added to the mixed varnish and mixed. The curing agent (item 6) and the diluent (item 7) were added just before the experimental determination of the paint-specific values ​​(IR measurement).

[0170] To test the water stability (in Table 4 and Table 5: Example + HO), items 1 to 4 of Table 3 were combined under stirring. The corresponding amount of catalyst was mixed with 1.0 wt. % (based on the total weight of the reactants) of water and diluent, and the mixture was allowed to stand for 10 minutes. The mixture was then added to the mixed varnish. The curing agent (item 6) was added just before the experimental determination of the paint-specific values ​​(IR measurement).

[0171] The results are shown in Table 4 (Examples of the present invention) and Table 5 (Comparative Examples).

[0172]

[0173] Table 5

[0174]

[0175] From Tables 4 and 5 it can be inferred that according to the inventive examples O1 to O6, the catalysts according to the invention show comparable or higher catalytic activity compared to the known catalysts according to the comparative examples C1 and C2, respectively. After the addition of water, according to the inventive examples I1 to I6, the catalysts according to the invention show significantly increased catalytic activity compared to the known catalysts according to the comparative examples C1 and C2, which indicates that their hydrolytic stability is significantly increased. It should be particularly emphasized here that the hydrolytic stability of the inventive examples I1 to I6 is increased compared to the comparative examples C1 and C2, as determined based on the percentage loss of reactivity due to the addition of water (comparative examples C1 and C2 show the greatest loss of reactivity due to the addition of water).

Claims

1. A bismuth-containing catalyst of general formula (I) (R 1 ) 2- (R 2 ) - (Would) 3+ (I) The variables are defined as follows: (R 1 ) 2- are independently divalent anions of the general formula (II) Where R 3 , R 4 , R 5 and R 6 are independently unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl, Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C 30 -alkyl and C6-C 14 -aryl, and the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2, -SH or C1-C6-alkoxy, and wherein A is unsubstituted or at least monosubstituted C1-C 30 -alkylene, wherein A can contain O, S, PR 12 and NR 12 The heteroatoms Where R 12 is unsubstituted or at least monosubstituted C1-C 30 -alkyl or H, where R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 For unsubstituted C1-C 30 -alkyl or H, (R 2 ) are independently hydroxide anions, alkoxide anions, halide anions, bicarbonate anions, thiolate anions, R 7 , anion of general formula (III) or an anion of formula (IV) Where R 7 is unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl, Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C 30 -alkyl and C6-C 14 -aryl, and the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2, -SH or C1-C6-alkoxy, And where R 8 and R 9 Each is phenyl and R 10 C1-C 12 -alkyl, And where R 11 is unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl, Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SR 14 , C1-C6-alkoxy, C1-C 30 -alkyl or C6-C 14 -aryl, wherein the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2 or C1-C6-alkoxy, and R 14 is H, unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl.

2. The bismuth-containing catalyst according to claim 1, wherein the divalent anion (R 1 ) 2- The corresponding dicarboxylic acid It has a negative ΔG value when it is exchanged for two monocarboxylate ligands, as determined by ab initio or semiempirical calculations.

3. The bismuth-containing catalyst according to claim 1 or 2, wherein the group R 3 , R 4 , R 5 or R 6 At least one of them is unsubstituted or at least monosubstituted C6-C 14 - aryl, preferably, the group R 3 , R 4 , R 5 or R 6 At least two, more preferably at least three, and most preferably each of them is unsubstituted or at least monosubstituted C6-C 14 -Aryl.

4. The bismuth-containing catalyst according to any one of claims 1 to 3, wherein the group R 3 , R 4 , R 5 or R 6 At least one, preferably at least two, more preferably at least three, and most preferably each of is phenyl.

5. The bismuth-containing catalyst according to any one of claims 1 to 4, wherein A is an unsubstituted C1-C 30 -alkylene, preferably unsubstituted C3-C 12 -alkylene.

6. The bismuth-containing catalyst according to any one of claims 1 to 4, wherein A is an unsubstituted C1-C 30 -alkylene and contains a compound selected from O, S, PR 12 and NR 12 , preferably selected from O, S and NR 12 , more preferably a heteroatom selected from O and S, Where R 12 is unsubstituted or at least monosubstituted C1-C 30 -alkyl or H, where R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 For unsubstituted C1-C 30 -alkyl or H.

7. The bismuth-containing catalyst according to claim 6, wherein A is an unsubstituted C3-C 12 -alkylene and contains a compound selected from O, S, PR 12 and NR 12 , preferably selected from O, S and NR 12 , more preferably a heteroatom selected from O and S, Where R 12 is unsubstituted C3-C5-alkyl or H, wherein R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 It is methyl.

8. The bismuth-containing catalyst according to any one of claims 1 to 7, wherein (R 2 ) - are independently hydroxide anions, alkoxide anions, thiolate anions, chloride anions, R 7 , a group of the general formula (III) or a group of the general formula (IV), Where R 7 is unsubstituted or at least monosubstituted C1-C 12 -alkyl or C6-C 14 -aryl, wherein the substituents are selected from hydroxy, chlorine, -CF3 and C1-C6-alkyl.

9. A method for preparing a bismuth-containing catalyst of general formula (I) according to any one of claims 1 to 8, the method comprising reacting the following substances: i) at least one compound of the general formula (IIa) or its corresponding salt, Where R 3 , R 4 , R 5 and R 6 are independently unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl, Wherein the substituent is selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, -SH, C1-C6-alkoxy, C1-C 30 -alkyl and C6-C 14 -aryl, and the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2, -SH or C1-C6-alkoxy, and wherein A is unsubstituted or at least monosubstituted C1-C 30 -alkylene, wherein A can contain O, S, PR 12 and NR 12 The heteroatoms Where R 12 is unsubstituted or at least monosubstituted C1-C 30 -alkyl or H, where R 12 Can contain selected from O, S, PR 13 and NR 13 The heteroatom R 13 For unsubstituted C1-C 30- Alkyl or H, ii) optionally at least one compound of the general formula (IIIa) or its corresponding salt, Where R 8 and R 9 Each is phenyl and R 10 C1-C 12 -alkyl, or At least one compound of the general formula (IVa) or its corresponding salt, Where R 11 is unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl, wherein the substituent is selected from hydroxy, halogen, carboxyl, -CF3, -NH2, -SR 14 , C1-C6-alkoxy, C1-C 30 -alkyl or C6-C 14 -aryl, wherein the alkyl and aryl fragments of these substituents can in turn be at least monosubstituted by hydroxy, halogen, -CF3, -NH2 or C1-C6-alkoxy, and R 14 is H, unsubstituted or at least monosubstituted C1-C 30 -alkyl, C6-C 14 -Aryl or C7-C 30 -aralkyl, and iii) at least one bismuth-containing compound selected from the group consisting of Bi2O3, bismuth carbonate, bismuth bicarbonate, bismuth halide, bismuth carboxylate, bismuth alkoxide, Bi(C6-C 14 -aryl)3, Bi(C1-C 12 -alkyl)3 and metallic bismuth.

10. The method according to claim 9, wherein the bismuth-containing compound is selected from Bi2O3, BiCl3, bismuth alkoxide, bismuth carboxylate, Bi(C6H5)3 and metallic bismuth.

11. The method according to claim 9 or 10, 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 carried out for at least 3 hours and / or at a temperature in the range of -75°C to 160°C, and / or iii) After the reaction, the volatile components are removed, the bismuth-containing catalyst is dried under reduced pressure and / or recrystallized.

12. The method according to any one of claims 9 to 11, wherein the at least one compound of formula (IIa) has a negative ΔG value when it is exchanged for two monocarboxylate ligands, as determined by ab initio or semi-empirical calculations.

13. Use of at least one bismuth-containing catalyst according to any one of claims 1 to 8 in a reaction for preparing compounds comprising urethane groups.

14. Use of at least one bismuth-containing catalyst according to any one of claims 1 to 8 as an esterification and transesterification catalyst.

15. Use of at least one bismuth-containing catalyst according to any one of claims 1 to 8 as catalyst for the ring-opening polymerization of lactones and epoxides.

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