Transition metal-based heterogeneous carbonylation reaction catalyst and method for preparing lactone or succinic anhydride using catalyst
The present invention relates to a transition metal-based heterogeneous carbonylation reaction catalyst that has an excellent catalytic activity and selectivity in the carbonylation reaction and is easily separated from a product, by crosslinking polymerizing a transition metal-based homogeneous catalyst unit through a Friedel-Craft reaction; and a method for preparing lactone using the same. The transition metal-based heterogeneous carbonylation reaction catalyst allows to produce lactone or succinic anhydride with an epoxide compound while showing a high selectivity, and can be applied in industrial very usefully due to easy separation from the product and thus reusing thereof.
1. A transition metal-based heterogeneous carbonylation reaction catalyst, wherein a transition metal-based homogeneous catalyst unit represented by Chemical formula (1) below is bonded through a Friedel-Crafts reaction:
M(L-R n )X Chemical Formula (1)
in Chemical formula (1), M is a transition metal of Al, Ir, Pt, Pd, Ru, Rh, Ni, Fe, Cu, V, Co, Cr, Au, Re, W, Zr, Mo, Ti, Th or Si, L is a ligand having three or more metal coordination numbers, R is a phenyl ring capable of carrying out the Friedel-Crafts reaction, n is an integer of 2 or more, and X is a counter anion of [Co(CO) 4 ] − .
2. The transition metal-based heterogeneous carbonylation reaction catalyst according to claim 1 , wherein the L is phthalocyanine, porphyrin, salen, or salphen.
3. The transition metal-based heterogeneous carbonylation reaction catalyst according to claim 1 , wherein the R is represented by Chemical formula (2) below:
in Chemical formula (2), X 2 to X 6 are each independently selected from the group consisting of a hydrogen, C 1 to C 20 alkyl group, C 2 to C 20 alkenyl group, C 2 to C 20 alkynyl group, C 6 to C 40 aryl group, a phenoxy group, C 1 to C 20 alkoxy group, and a halogen group, provided that at least one of them should be a hydrogen.
4. The transition metal-based heterogeneous carbonylation reaction catalyst according to claim 1 , represented by Chemical formula (3) below:
in Chemical formula (3), M is a transition metal of Al, Ir, Pt, Pd, Ru, Rh, Ni, Fe, Cu, V, Co, Cr, Au, Re, W, Zr, Mo, Ti, Th or Si, X 1 to X 4 are each independently selected from the group consisting of a hydrogen, C 1 to C 20 alkyl group, C 2 to C 20 alkenyl group, C 2 to C 20 alkynyl group, C 6 to C 40 aryl group, a phenoxy group, C 1 to C 20 alkoxy group, and a halogen group, X is 0 or 1, provided that a sum thereof must be 2 or more, n is an integer from 4 to 100,000, and m is an integer from 20 to 500,000.
5. A method for preparing lactone, comprising carbonylating an epoxide and a carbon monoxide in a solvent in the presence of the catalyst of claim 1 .
6. The method for preparing the lactone according to claim 5 , wherein the epoxide is represented by Chemical formula (6) below:
in Chemical formula (6), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen, straight-chain or branched-chain alkyl, allyl, alkenyl, vinyl, aryl, alkylether, arylether, alkylester, arylester, cyclic ether, cyclic ester, thiol, silyl, amine, amide, nitro, cyano, thioether, thioalkyl, sulfonyl, a halogen or a hydroxy, wherein the alkyl has carbon atoms of 1 to 20, the allyl, the alkenyl and the vinyl have carbon atoms of 2 to 20, and the aryl has carbon atoms of 6 to 40.
7. The method for preparing the lactone according to claim 5 , wherein the epoxide is one or more selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, 1,2-epoxybutane, 2-vinyloxirane, cyclooctene oxide, 1,2-epoxy-1-carbonitrile, 1,2-epoxydodecane, n-butyl glycidylether, 2,3-epoxypropyl phenyl ether, and styrene oxide.
8. The method for preparing the lactone according to claim 5 , wherein the solvent is selected from the group consisting of dimethoxy ethane (DME), tetrahydrofuran, dioxane, diglyme, tetraethylene glycol dimethyl ether, diethylether, 2-(2-methoxyethoxy)ethanol, and anisole.
9. The method for preparing the lactone according to claim 5 , wherein the method is performed at a temperature of 20 to 120° C. and a CO pressure of 0.1 to 30 MPa.
10. A method for preparing succinic anhydride, comprising carbonylating a lactone and a carbon monoxide in a solvent in the presence of the catalyst of claim 1 .
11. The method for preparing the succinic anhydride according to claim 10 , wherein the lactone is represented by Chemical formula (7) below:
in Chemical formula (7), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen, straight-chain or branched-chain alkyl, allyl, alkenyl, vinyl, aryl, alkylether, arylether, alkylester, arylester, cyclic ether, cyclic ester, thiol, silyl, amine, amide, nitro, cyano, thioether, thioalkyl, sulfonyl, a halogen or a hydroxy, wherein the alkyl has carbon atoms of 1 to 20, the allyl, the alkenyl and the vinyl have carbon atoms of 2 to 20, and the aryl has carbon atoms of 6 to 40.
12. The method for preparing the succinic anhydride according to claim 10 , wherein the solvent is selected from the group consisting of dimethoxy ethane (DME), tetrahydrofuran, dioxane, diglyme, tetraethylene glycol dimethylether, diethylether, 2-(2-methoxyethoxy)ethanol, and anisole.
13. The method for preparing the succinic anhydride according to claim 10 , wherein the method is performed at a temperature of 20 to 120° C. and a CO pressure of 0.1 to 30 MPa.