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WO2025131841A1 - Catalyseur comprenant un métal bivalent et un ligand dicarboxylate - Google Patents

Catalyseur comprenant un métal bivalent et un ligand dicarboxylate Download PDF

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Publication number
WO2025131841A1
WO2025131841A1 PCT/EP2024/085359 EP2024085359W WO2025131841A1 WO 2025131841 A1 WO2025131841 A1 WO 2025131841A1 EP 2024085359 W EP2024085359 W EP 2024085359W WO 2025131841 A1 WO2025131841 A1 WO 2025131841A1
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Prior art keywords
alkyl
aryl
phenyl
group
aralkyl
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Emre LEVENT
Peter Deglmann
Simon SPATZ
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/42—Tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

Definitions

  • 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.
  • the component (C) is a catalyst comprising at least two salts of an aliphatic monocarboxylic acid having at least 4 carbon atoms.
  • the metal component of the first salt is bismuth (Bi)
  • 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 ( ⁇ -carbon) is bonded to the carbon atom of the carboxyl group, which in turn is directly substituted with at least one aromatic system.
  • 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
  • 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).
  • 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 ⁇ -position and the diradical A.
  • 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.
  • at least one, preferably two residues, of a general formula (IIb) are used as (R 1b )- instead.
  • “ ⁇ -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 ⁇ -carbon.
  • ⁇ -amino acids where the ⁇ -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 ⁇ -alanine and gamma-aminobutyric acid.
  • 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.
  • the dianion (R 1a ) 2- according to the general formula (IIa) has two ⁇ -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.
  • 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.
  • 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.
  • alkyl radicals such as a C 1 -C 6 -alkyl radical or a C 1 -C 12 -alkyl radical for example.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • substituent anions are fluoride, chloride, bromide and iodide.
  • alkali metals are lithium, sodium and potassium.
  • 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.
  • 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.
  • 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 ,
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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,
  • 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 .
  • 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
  • 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.
  • the alkali metals M2, and/or M3 ,as optionally contained within the substituents as described above, are lithium, sodium and potassium.
  • 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.
  • (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
  • 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.
  • corresponding carboxylic esters 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.
  • any metal M 1 -containing compound known to the skilled person may be employed.
  • 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 .
  • 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).
  • 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 .
  • 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.
  • 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
  • at least one metal M 1 -containing compound wherein i) the reaction is carried out under
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • monoalcohols (B1) are benzylalcohol and cyclohexanol.
  • 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-
  • polyols (B2) are diols such as are di(ethylene glycol), tri(ethylene glycol), di(propylene glycol) and tri(propylene glycol).
  • 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.
  • 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.
  • 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, cyclo
  • 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.
  • 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
  • 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.
  • polymerizable unsaturated monomers examples include 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.
  • 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.
  • 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.
  • monomeric polyisocyanates are 1,4,8-triisocyanatononane and 2’-isocyanatoethyl 2,6-diisocyanatohexanoate.
  • 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- cyclohe
  • 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’
  • monomeric polyisocyanates are 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate and 2,4,4’-triisocyanatodiphenyl ether.
  • 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.
  • 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.
  • organic solvents examples include 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.
  • aliphatic ketones such as acetone, ethyl methylketone (2-butanone) and isobutyl methyl ketone
  • 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.
  • A weight M 1 /weight all polyisocyanate
  • 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.
  • compositions 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.

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Abstract

La présente invention se rapporte à un catalyseur comprenant un métal bivalent, tel que le Sn, à des procédés de préparation du catalyseur comprenant un métal bivalent, à un procédé de préparation d'un composé, oligomère ou polymère comprenant au moins un groupe uréthane utilisant le catalyseur comprenant un métal bivalent, à une composition comprenant (i) au moins un monoalcool (B1) ou polyol (B2), (ii) au moins un polyisocyanate (A) et (iii) au moins un catalyseur comprenant un métal bivalent, à une couche sur un substrat formée à partir de la composition, à une mousse formée à partir de la composition et à l'utilisation du catalyseur comprenant un métal bivalent pour la préparation de composés, d'oligomères ou de polymères comprenant un groupe uréthane, comme catalyseur d'estérification et de transestérification et comme catalyseur pour les polymérisations par ouverture de cycle de lactones et d'époxydes.
PCT/EP2024/085359 2023-12-20 2024-12-09 Catalyseur comprenant un métal bivalent et un ligand dicarboxylate Pending WO2025131841A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0100129A1 (fr) * 1982-07-29 1984-02-08 Dsm Resins B.V. Procédé de préparation d'un oligomère d'un diisocyanate
US5462906A (en) * 1993-12-27 1995-10-31 Jakubowycz; Stan Esterification catalyst for the production of high boiling esters and process of making the high boiling esters
US9062155B2 (en) * 2008-12-19 2015-06-23 University Of Sydney Organometallic catalyst and preparation thereof
US20160002437A1 (en) * 2013-03-25 2016-01-07 Nof Corporation Urethane curable composition
WO2018069018A1 (fr) 2016-10-13 2018-04-19 Basf Coatings Gmbh Système d'agent de revêtement à base de sels d'un acide monocarboxylique aliphatique
US20200087438A1 (en) * 2017-06-01 2020-03-19 Covestro Deutschland Ag Polyurethane foams based on polyethercarbonate polyols
WO2020160939A1 (fr) 2019-02-07 2020-08-13 Basf Se Catalyseur contenant du bismuth comprenant au moins un substituant aromatique

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0100129A1 (fr) * 1982-07-29 1984-02-08 Dsm Resins B.V. Procédé de préparation d'un oligomère d'un diisocyanate
US5462906A (en) * 1993-12-27 1995-10-31 Jakubowycz; Stan Esterification catalyst for the production of high boiling esters and process of making the high boiling esters
US9062155B2 (en) * 2008-12-19 2015-06-23 University Of Sydney Organometallic catalyst and preparation thereof
US20160002437A1 (en) * 2013-03-25 2016-01-07 Nof Corporation Urethane curable composition
WO2018069018A1 (fr) 2016-10-13 2018-04-19 Basf Coatings Gmbh Système d'agent de revêtement à base de sels d'un acide monocarboxylique aliphatique
US20200087438A1 (en) * 2017-06-01 2020-03-19 Covestro Deutschland Ag Polyurethane foams based on polyethercarbonate polyols
WO2020160939A1 (fr) 2019-02-07 2020-08-13 Basf Se Catalyseur contenant du bismuth comprenant au moins un substituant aromatique

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