Method for producing metal compounds
View Patent ↗The invention relates to processes for preparing metal(IV) compounds which are suitable especially as catalysts for preparation of polyesters, polyurethanes and polysiloxanes, and to the use of the metal compounds for preparation of polyesters, polyurethanes or polysiloxanes.
1. A process for preparing metal compounds of the general formula (I), (II) or (III) with at least one ligand containing at least one nitrogen and bonded via at least one oxygen or sulfur atom
[(L 1 ) n1 (L 2 ) n2 (L 3 ) n3 (L 4 ) n4 (M)(IV)] (I)
[(L 1 ) n1 (L 2 ) n2 (L 3 ) n3 (M)(IV)] 2 O (II)
[(L 1 ) n1 (L 2 ) n2 (M)(IV)] n (III)
M is Sn, Ti, Zr or Hf,
n1, n2, n3, n4 are each 0 or 1 and n is greater than or equal to 2,
L 1 , L 2 , L 3 , L b 4 each mono-, di-, tri- or tetravalent ligands, where at least one ligand per M is defined as follows:
—X—Y
in which
X is O, S, OC(O), OC(S), O(O)S(O),
Y is —R 1 —N(R 2 )(R 3 )or —R 1 —C(R 4 )═NR 2 ,
in which R 1 , R 2 , R 3 and R 4 are each independently saturated or unsaturated, cyclic or acyclic, branched or unbranched, substituted or unsubstituted hydrocarbyl radicals optionally interrupted by heteroatoms, or R 2 , R 3 , R 4 are each independently hydrogen, R 1 —X, or R 3 or R 2 and R 1 or R 3 and R 1 or R 4 and R 1 or R 4 and R 2 form a ring, where the remaining ligands are each independently —X—Y as defined above or are defined as follows:
saturated or unsaturated, cyclic or acyclic, branched or unbranched, substituted or unsubstituted hydrocarbyl radicals optionally interrupted by heteroatoms, or halides, hydroxides, amide radicals, oxygen, sulfur, R 2 or XR 2 , comprising the steps of
(a) providing a compound of the formula ML 4 where L is independently R, OR or Hal, where: R=C 1 to C 8 -alkyl, Hal=Cl, Br or I and M=Sn, Ti, Zr or Hf, and
(b) reacting the compound provided in process step (a) with at least one compound of the formula H—X—Y and/or M 1 -X—Y,
where X and Y are each as defined above and, M 1 =Li, Na, K, Ca, Mg, or NH 4 +
characterized in that the reaction in process step (b) is performed in the presence of one or more compounds selected from NH 3 , primary, secondary and tertiary amines, M 2 OH and M 2 O—R 5 , where R 5 is a hydrocarbyl radical having 1 to 6 carbon atoms and M 2 is Li + , Na + , Ca 2+ or Mg 2+ .
2. The process as claimed in claim 1 , characterized in that the reaction in process step (b) is performed in a solvent selected from the group of polyethylene glycols, polypropylene glycols, glycerol, glyceryl carbonate, C 1 to C 5 -alcohols, 1,2-propanediol, 1,3-propanediol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4- butanediol, neopentyl glycol, dicthylene glycol monomethyl ether, solvents of the formula H—X—Y according to claim 1 , dipropylene glycol and a mixture of 2, 3, 4 or 5 of the aforementioned solvents.
3. The process as claimed in claim 1 , characterized in that the reaction in process step (b) is performed at a temperature in the range from 40° C. to 120° C. over a period of 0.5 hour to 3 hours.
4. The process as claimed in claim 1 , characterized in that the reaction in process step (b) is performed in the presence of one or more compounds selected from NH 3 , 1,4-diazabicyclo[2.2.2]octane-1,8-diazabicyclo[5.4.O]non-5-ene, triethylamine, triethyldiamine, N-methylimidazole, N,N-dimethylethanolamine, N-methylmorpholine, N-ethylmorpholine, 2,2-dimorpholinodiethyl ether, bis(2-dimethylaminoethyl) ether, N-benzyldimethylamine, N,N′-dimethylcyclohexyl-amine, M 2 OH and M 2 O—R5 where R 5 is a hydrocarbyl radical having 1 to 4 carbon atoms and M 2 is Li + , Na + , Ca 2+ , or Mg 2+ .
5. The process as claimed in claim 4 , characterized in that the reaction in process step (b) is performed in the presence of NH 3 , NaOCH 3 , NaOC 2 H 5 , KOCH 3 or KOC 2 H 5 .
6. The process as claimed in claim 5 , characterized in that the reaction in process step (b) is performed in the presence of NaOCH 3 or NH 3 .
7. The process as claimed in claim 1 , characterized in that the at least one compound of the formula H—X—Y is selected from the group consisting of N-methyl diethanolarnine, N-ethyldiethanolamine and triethanolamine.
8. The process as claimed in claim 1 , characterized in that the molar ratio of metal in the compound ML 4 in step (a) to the at least one compound from the group consisting of NH 3 , primary, secondary and tertiary amines, M 2 OH and M 2 OR is 1:0.7-1.3.
9. The process as claimed in claim 1 , characterized in that the stoichiometric ratio of metal (M) to ligand XY is 1:0.8-1.2.
10. The process as claimed in claim 1 , characterized in that M in the formulae (I)-(III) is Sn.
11. The process as claimed in claim 10 , characterized in that the compound M(Hal) 4 provided in process step (a) is Sn(Cl) 4 .
12. The process as claimed in claim 10 , characterized in that a metal compound of the general formula [(L 1 ) n1 (L 2 ) n2 (C1) 2 Sn)(IV)] is prepared.
13. A catalyst comprising the metal compounds prepared by the process according to claim 1 .
14. A process for the preparation of polyisocyanate polyaddition products comprising the step of adding the catalyst according to claim 13 .
15. A process for performance of esterifications and transesterifications comprising the step of adding the catalyst according to claim 13 .
16. A process which comprises mixing a silicon resin and the catalyst according to claim 13 .