CATALYST COMPOSITION FOR CYCLIC CARBONATE PRODUCTION FROM CO2 AND EPOXIDES

Abstract

The present invention relates to catalyst composition for cyclic carbonate production from CO.sub.2 and epoxides under mild conditions, which can effectively catalyze the cyclic carbonate synthesis and provides good selectivity to cyclic carbonate, wherein said catalyst composition comprising: a) the metal complex as shown in structure (I):

##STR00001## wherein, M represents transition metal atom; R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, amine group, phenyl group, benzyl group, cyclic hydrocarbon group comprising hetero atom, perfluoroalkyl group, or nitro group; R.sub.4 represents group selected from alkylene group, cycloalkylene group, or phenylene group; X represents group selected from hydrogen atom, acetate group, or triflate group; and b) the organic compound as the co-catalyst selected from compound containing nitrogen, compound of quaternary ammonium salts, or compound of iminium salts.

Claims

1. A catalyst composition for cyclic carbonate production from CO.sub.2 and epoxides, wherein said catalyst composition comprises: a) the metal complex as shown in structure (I): ##STR00016## wherein, M represents transition metal atom; R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, amine group, phenyl group, benzyl group, cyclic hydrocarbon group comprising hetero atom, perfluoroalkyl group, or nitro group; R.sub.4 represents group selected from alkylene group, cycloalkylene group, or phenylene group; X represents group selected from halogen atom, acetate group, or triflate group; and b) the organic compound as the co-catalyst selected from compound containing nitrogen, compound of quaternary ammonium salts, or compound of iminium salts.

2. The catalyst composition according to claim 1, wherein in the metal complex in a), M represents transition metal atom selected from chromium, cobalt, or iron.

3. The catalyst composition according to claim 2, wherein in the metal complex in a), M is chromium metal atom.

4. The catalyst composition according to claim 1, wherein in the metal complex in a), R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkenyl group having 1 to 4 carbon atoms, alkynyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, amine group, phenyl group, benzyl group, cyclic hydrocarbon group comprising hetero atom, perfluoroalkyl group, or nitro group.

5. The catalyst composition according to claim 1 or 4, wherein in the metal complex in a), R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, chlorine atom, methyl group, ethyl group, iso-propyl group, n-butyl group, tert-butyl group, methoxy group, ethoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, phenyl group, benzyl group, trifluoromethyl group, or nitro group.

6. The catalyst composition according to claim 5, wherein in the metal complex in a), R.sub.1 and R.sub.3 are tert-butyl group and R.sub.2 is hydrogen atom.

7. The catalyst composition according to claim 1, wherein in the metal complex in a), R.sub.4 represents group selected from alkylene group having 2 to 3 carbon atoms, cycloalkylene group having 6 carbon atoms, or phenylene group.

8. The catalyst composition according to claim 1 or 7, wherein in the metal complex in a), R.sub.4 represents group selected from ethylene group, 1,3-propylene group, 1,2-cyclohexylene group, or 1,2-phenylene group.

9. The catalyst composition according to claim 8, wherein in the metal complex in a), R.sub.4 is ethylene group.

10. The catalyst composition according to claim 1, wherein in the metal complex in a), X represents group selected from chlorine atom, bromine atom, iodine atom, acetate group, or triflate group.

11. The catalyst composition according to claim 1, wherein the metal complex in a) is selected from N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, or N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride.

12. The catalyst composition according to claim 1, wherein the organic compound as the co-catalyst in b) is selected from 4-dimethylaminopyridine (DMAP), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), tetrabutylammonium iodide (TBAI), imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine) iminium bromide, bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iminium iodide, or mixture thereof.

13. A process for cyclic carbonate production from CO.sub.2 and epoxides, comprising the contact of CO.sub.2 and epoxides to the catalyst composition at the temperature in the range of 50 to 180° C., wherein said catalyst composition comprises: a) the metal complex as shown in structure (I): ##STR00017## wherein, M represents transition metal atom; R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, amine group, phenyl group, benzyl group, cyclic hydrocarbon group comprising hetero atom, perfluoroalkyl group, or nitro group; R.sub.4 represents group selected from alkylene group, cycloalkylene group, or phenylene group; X represents group selected from halogen atom, acetate group, or triflate group; and b) the organic compound as the co-catalyst selected from compound containing nitrogen, compound of quaternary ammonium salts, or compound of iminium salts.

14. The process for cyclic carbonate production according to claim 13, wherein in the metal complex in a), M represents transition metal atom selected from chromium, cobalt, or iron.

15. The process for cyclic carbonate production according to claim 14, wherein in the metal complex in a), M is chromium metal atom.

16. The process for cyclic carbonate production according to claim 13, wherein in the metal complex in a), R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkenyl group having 1 to 4 carbon atoms, alkynyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, amine group, phenyl group, benzyl group, cyclic hydrocarbon group comprising hetero atom, perfluoroalkyl group, or nitro group.

17. The process for cyclic carbonate production according to claim 13 or 16, wherein in the metal complex in a), R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, chlorine atom, methyl group, ethyl group, iso-propyl group, n-butyl group, tert-butyl group, methoxy group, ethoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, phenyl group, benzyl group, trifluoromethyl group, or nitro group.

18. The process for cyclic carbonate production according to claim 17, wherein in the metal complex in a), R.sub.1 and R.sub.3 are tert-butyl group and R.sub.2 is hydrogen atom.

19. The process for cyclic carbonate production according to claim 13, wherein in the metal complex in a), R.sub.4 represents group selected from alkylene group having 2 to 3 carbon atoms, cycloalkylene group having 6 carbon atoms, or phenylene group.

20. The process for cyclic carbonate production according to claim 13 or 19, wherein in the metal complex in a), R.sub.4 represents group selected from ethylene group, 1,3-propylene group, 1,2-cyclohexylene group, or 1,2-phenylene group.

21. The process for cyclic carbonate production according to claim 20, wherein in the metal complex in a), R.sub.4 is ethylene group.

22. The process for cyclic carbonate production according to claim 13, wherein in the metal complex in a), X represents group selected from chlorine atom, bromine atom, iodine atom, acetate group, or triflate group.

23. The process for cyclic carbonate production according to claim 13, wherein the metal complex in a) is selected from N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5- trifluoromethyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, or N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride.

24. The process for cyclic carbonate production according to claim 13, wherein the organic compound as the co-catalyst in b) is selected from 4-dimethylaminopyridine (DMAP), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), tetrabutylammonium iodide (TBAI), imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine) iminium bromide, bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iminium iodide, or mixture thereof.

25. The process for cyclic carbonate production according to claim 13, wherein the mole ratio of the metal complex in a) to the organic compound as the co-catalyst in b) is in the range of 1:0.5 to 1:300.

26. The process for cyclic carbonate production according to claim 25, wherein the mole ratio of the metal complex in a) to the organic compound as the co-catalyst in b) is in the range of 1:0.5 to 1:200.

27. The process for cyclic carbonate production according to claim 13, wherein the mole ratio of the metal complex in a) to epoxides is in the range of 1:100 to 1:20000.

28. The process for cyclic carbonate production according to claim 27, wherein the mole ratio of the metal complex in a) to epoxides is in the range of 1:1000 to 1:20000.

29. The process for cyclic carbonate production according to claim 13, wherein the CO.sub.2 pressure is in the range of 15 to 600 psi.

30. The process for cyclic carbonate production according to claim 29, wherein the CO.sub.2 pressure is in the range of 15 to 300 psi.

31. The process for cyclic carbonate production according to claim 13, wherein the contact of CO.sub.2 and epoxides to the catalyst composition is operated under organic solvent-free condition, wherein the organic compound as the co-catalyst in b) is selected from 4-dimethylaminopyridine, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine) iminium bromide, bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iminium iodide, or mixture thereof.

32. The process for cyclic carbonate production according to claim 31, wherein the contact of CO.sub.2 and epoxides to the catalyst composition is operated under organic solvent-free condition, wherein the organic compound as the co-catalyst in b) is selected from tetrabutylammonium bromide.

33. The process for cyclic carbonate production according to claim 13, wherein the contact of CO.sub.2 and epoxides to the catalyst composition is operated under the presence of organic solvent selected from dichloromethane, hexane, benzene, toluene, dimethylformamide, or mixture thereof.

34. The process for cyclic carbonate production according to claim 33, wherein the organic solvent is dichloromethane.

35. The process for cyclic carbonate production according to claim 33 or 34, wherein the contact of CO.sub.2 and epoxides to the catalyst composition is operated under the presence of organic solvent, wherein the organic compound as the co-catalyst in b) is selected from 4-dimethylaminopyridine, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine) iminium bromide, bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iminium iodide, or mixture thereof.

36. The process for cyclic carbonate production according to claim 35, wherein the contact of CO.sub.2 and epoxides to the catalyst composition is operated under the presence of organic solvent, wherein the organic compound as the co-catalyst in b) is selected from 4-dimethylaminopyridine.

37. The process for cyclic carbonate production according to claim 13, wherein epoxide is selected from ethylene oxide, propylene oxide, styrene oxide, 1-butene oxide, 1-hexene oxide, cyclohexene oxide, cyclopentene oxide, epichlorohydrin, 3,4-epoxy-1-butene, or 1,2-epoxy-3-phenoxypropane.

38. The process for cyclic carbonate production according to claim 37, wherein epoxide is epichlorohydrin.

39. The process for cyclic carbonate production according to claim 13, wherein the reaction temperature is in the range of 65 to 150° C.

Description

DESCRIPTION OF THE INVENTION

[0027] The present invention relates to the catalyst composition for cyclic carbonate production from CO.sub.2 and epoxides under mild conditions, wherein the catalyst according to the invention can efficiently catalyze the synthesis of cyclic carbonate with good selectivity to cyclic carbonate, wherein the catalyst according to the invention can be described according to the following embodiments.

[0028] Any aspect being described herein also means to include the application to other aspects of this invention unless stated otherwise.

[0029] Technical terms or scientific terms used herein have definitions as understood by an ordinary person skilled in the art unless stated otherwise.

[0030] Any tools, equipment, methods, or chemicals named herein mean tools, equipment, methods, or chemicals being operated or used commonly by those person skilled in the art unless stated otherwise that they are tools, equipment, methods, or chemicals specific only in this invention.

[0031] Use of singular noun or singular pronoun with “comprising” in claims or specification means “one” and also including “one or more”, “at least one”, and “one or more than one”.

[0032] All compositions and/or methods disclosed and claims in this application are intended to cover embodiments from any operation, performance, modification, or adjustment any factors without any experiment that significantly different from this invention, and obtain with object with utility and resulted as same as the present embodiment according to person ordinary skilled in the art although without specifically stated in claims. Therefore, substitutable or similar object to the present embodiment, including any minor modification or adjustment that can be apparent to person skilled in the art should be construed as remains in spirit, scope, and concept of invention as appeared in appended claims.

[0033] Throughout this application, term “about” means any number that appeared or expressed herein that could be varied or deviated from any error of equipment, method, or personal using said equipment or method.

[0034] Hereafter, invention embodiments are shown without any purpose to limit any scope of the invention.

[0035] This invention relates to the catalyst composition for cyclic carbonate production from CO.sub.2 and epoxides, which can efficiently catalyze the cyclic carbonate synthesis with good selectivity to cyclic carbonate, wherein said catalyst composition comprising:

[0036] a) the metal complex as shown in structure (I):

##STR00003##

[0037] wherein,

[0038] M represents transition metal atom;

[0039] R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, amine group, phenyl group, benzyl group, cyclic hydrocarbon group comprising hetero atom, perfluoroalkyl group, or nitro group;

[0040] R.sub.4 represents group selected from alkylene group, cycloalkylene group, or phenylene group;

[0041] X represents group selected from halogen atom, acetate group, or triflate group; and

[0042] b) the organic compound as the co-catalyst selected from compound containing nitrogen, compound of quaternary ammonium salts, or compound of iminium salts.

[0043] Preferably, in the metal complex in a), M represents transition metal atom selected from chromium, cobalt, or iron. More preferably, M is chromium metal atom.

[0044] In one aspect of the invention, in the metal complex in a), R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkenyl group having 1 to 4 carbon atoms, alkynyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, amine group, phenyl group, benzyl group, cyclic hydrocarbon group comprising hetero atom, perfluoroalkyl group, or nitro group.

[0045] In one aspect of the invention, in the metal complex in a), R.sub.1, R.sub.2, and R.sub.3 represent independent group selected from, but not limited to hydrogen atom, chlorine atom, methyl group, ethyl group, iso-propyl group, n-butyl group, tert-butyl group, methoxy group, ethoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, phenyl group, benzyl group, trifluoromethyl group, or nitro group. Preferably, in the metal complex in a), R.sub.1 and R.sub.3 are tert-butyl group and R.sub.2 is hydrogen atom.

[0046] In one aspect of the invention, in the metal complex in a), R.sub.4 represents group selected from alkylene group having 2 to 3 carbon atoms, cycloalkylene group having 6 carbon atoms, or phenylene group.

[0047] In one aspect of the invention, in the metal complex in a), R.sub.4 represents group selected from, but not limited to ethylene group, 1,3-propylene group, 1,2-cyclohexylene group, or 1,2-phenylene group. Preferably, in the metal complex in a), R.sub.4 represents group selected from ethylene group.

[0048] In one aspect of the invention, in the metal complex in a), X represents group selected from, but not limited to chlorine atom, bromine atom, iodine atom, acetate group, or triflate group.

[0049] In one aspect of the invention, the metal complex in a) is selected from N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride,

[0050] N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3,5 -di-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-ethane-1,2-diamino metal (III) chloride,

[0051] N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-propane-1,3-diamino metal (III) chloride,

[0052] N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-benzene-1,2-diamino metal (III) chloride,

[0053] N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(5-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(5-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, or N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-cyclohexane-1,2-diamino metal (III) chloride.

[0054] In one aspect of the invention, the metal complex in a) can be synthesized from the reaction between metal salt precursor and N-N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives, wherein the mole ratio of the reaction between metal salt and said ligand is in the range of 1:1 to 1:2.

[0055] In one aspect of the invention, the chromium metal salt precursor for the invention of the metal complex in a) may be selected from, but not limited to chromium (III) chloride (CrCl.sub.3), chromium (III) chloride tetrahydrofuran (CrCl.sub.3(THF).sub.3), chromium (II) chloride (CrCl.sub.2), chromium (III) chloride hexahydrate (CrCl.sub.3 6H.sub.2O), chromium (III) bromide (CrBr.sub.3), chromium (III) iodide (CrI.sub.3), chromium (III) acetate (Cr(C.sub.2H.sub.3O.sub.2).sub.3 ), or chromium (III) triflate (Cr(CF.sub.3SO.sub.3).sub.3). Preferably, the chromium metal salt precursor for the invention of the metal complex in a) is selected from chromium (III) chloride tetrahydrofuran (CrCl.sub.3(THF).sub.3 ) or chromium (II) chloride (CrCl.sub.2).

[0056] In one aspect of the invention, the cobalt metal salt precursor for the invention of the metal complex in a) may be selected from, but not limited to cobalt (II) chloride (CoCl.sub.2), cobalt (II) chloride hexahydrate (CoCl.sub.2 6H.sub.2O), cobalt (II) bromide (CoBr.sub.2), cobalt (II) iodide (CoI.sub.2), cobalt (II) acetate (Co(CH.sub.3CO.sub.2).sub.2), or cobalt (II) triflate (Co(CF.sub.3SO.sub.3).sub.2). Preferably, the cobalt metal salt precursor for the invention of the metal complex in a) is selected from cobalt (II) chloride (CoCl.sub.2).

[0057] In one aspect of the invention, the iron metal salt precursor for the invention of the metal complex in a) may be selected from, but not limited to iron (III) chloride (FeCl.sub.3), iron (III) chloride hexahydrate (FeCl.sub.3 6H.sub.2O), iron (III) bromide (FeBr.sub.3), iron (III) iodide (FeI.sub.3), iron (III) acetate (Fe(C.sub.2H.sub.3O.sub.3).sub.3), or iron (III) triflate (Fe(CF.sub.3SO.sub.3).sub.3). Preferably, the iron metal salt precursor for the invention of the metal complex in a) is selected from iron (III) chloride (FeCl.sub.3).

[0058] In one aspect of the invention, the N-N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives is selected from, but not limited to N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(ethylenesalicylidene)-cyclohexane-1,2-diamine,

[0059] N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-methyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(5-methyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-tert-butyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(5-tert-butyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-ethane-1,2-diamine, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-ethane-1,2-diamine,

[0060] N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-methyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(5-methyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-tert-butyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(5-tert-butyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-propane-1,3-diamine, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-propane-1,3-diamine,

[0061] N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-methyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(5-methyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-tert-butyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(5-tert-butyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3 methyl, 5-methoxy ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-benzene-1,2-diamine, N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-benzene-1,2-diamine,

[0062] N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3,5-di-methyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-methyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(5-methyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(5-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-methyl, 5-tert-butyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-methyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-trifluoromethyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-methoxy ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-nitro ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-tert-butyl, 5-chloro ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-methyl, 5-trifluoromethyl ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-methyl, 5-methoxy ethylenesalicylidene)-cyclohexane-1,2-diamine, N-N′-bis(3-methyl, 5-nitro ethylenesalicylidene)-cyclohexane-1,2-diamine, or N-N′-bis(3-methyl, 5-chloro ethylenesalicylidene)-cyclohexane-1,2-diamine.

[0063] In one aspect of the invention, the organic compound as the co-catalyst in b) is selected from 4-dimethylaminopyridine (DMAP), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), tetrabutylammonium iodide (TBAI), imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine) iminium bromide, bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iminium iodide, or mixture thereof.

[0064] In another aspect of the invention, this invention relates to the process for cyclic carbonate production from CO.sub.2 and epoxides, comprising the contact of CO.sub.2 and epoxides to the catalyst composition at the temperature in the range of 50 to 180° C., wherein said catalyst composition is selected from the compositions described above.

[0065] In one aspect of the invention, the mole ratio of the metal complex in a) to the organic compound as the co-catalyst in b) is in the range of 1:0.5 to 1:300, the mole ratio of the metal complex in a) to epoxides is in the range of 1:100 to 1:20000 and the CO.sub.2 pressure is in the range of 15 to 600 psi.

[0066] Preferably, the process for cyclic carbonate production is operated at the temperature in the range of 65 to 150° C., wherein the mole ratio of the metal complex in a) to the organic compound as the co-catalyst in b) is in the range of 1:0.5 to 1:200, the mole ratio of the metal complex in a) to epoxides is in the range of 1:1000 to 1:20000 and the CO.sub.2 pressure is in the range of 15 to 300 psi.

[0067] In one aspect of the invention, the contact of CO.sub.2 and epoxides to the catalyst composition is operated under organic solvent-free condition, wherein the organic compound as the co-catalyst in b) is selected from 4-dimethylaminopyridine, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine) iminium bromide, bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iminium iodide, or mixture thereof. Preferably, the organic compound as the co-catalyst in b) is tetrabutylammonium bromide.

[0068] In one aspect of the invention, the contact of CO.sub.2 and epoxides to the catalyst composition is operated under the presence of organic solvent selected from dichloromethane, hexane, benzene, toluene, dimethylformamide, or mixture thereof. Preferably, the organic solvent is dichloromethane.

[0069] In one aspect of the invention, the contact of CO.sub.2 and epoxides to the catalyst composition is operated under the presence of organic solvent, wherein the organic compound as the co-catalyst in b) is selected from 4-dimethylaminopyridine, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine) iminium bromide, bis(triphenylphosphine) iminium chloride, bis(triphenylphosphine) iminium iodide, or mixture thereof. Preferably, the organic compound as the co-catalyst in b) is 4-dimethylaminopyridine.

[0070] In one aspect of the invention, epoxide is selected from ethylene oxide, propylene oxide, styrene oxide, 1-butene oxide, 1-hexene oxide, cyclohexene oxide, cyclopentene oxide, epichlorohydrin, 3,4-epoxy-1-butene, or 1,2-epoxy-3-phenoxypropane. Preferably, epoxide is epichlorohydrin.

[0071] The cyclic carbonate production from CO.sub.2 and epoxides according to this invention may further comprise the drying step if necessary, wherein said step may be selected from, but not limited to stir-drying or vacuum drying, etc.

[0072] In one aspect, the cyclic carbonate production from CO.sub.2 and epoxides according to this invention may be operated in the reactor, but not limited to fixed-bed reactor. The operation may be performed in batch or continuous manner.

[0073] The following examples are for demonstrating one aspect of the invention only and not intended to be limitation of the scope of this invention in any way.

EXAMPLE 1

Synthesis of N-N′-bis(ethylenesalicylidene)-diamine Ligand and its Derivatives to be Used in the Synthesis of Metal Complex Catalyst Containing said Ligand

[0074] Synthesis of Ligand to be Used in the Synthesis of Catalyst A

[0075] The solution of 7-hydroxy-1-indanone in ethanol at the concentration of 0.67 M was prepared by dissolving 0.30 g (2 mmol) of 7-hydroxy-1-indanone in 3 mL of ethanol. Then, the 1,2-ethylene diamine was added into said solution. The mole ratio of 7-hydroxy-1-indanone to 1,2-ethylene diamine was 2:1. After that, the acetic acid was added about 1-2 drops. The obtained mixture was stirred while heated until reflux for 48 hours. Then, the obtained mixture was filtered to separate the solid. The obtained solid was washed with 10 mL of diethyl ether for 3 times. The N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamine ligand was obtained as yellow solid.

[0076] Synthesis of Ligand to be Used in the Synthesis of Catalyst B

[0077] The synthesis of ligand to be used in the synthesis of catalyst B was prepared by the same method as the synthesis of ligand to be used in the synthesis of catalyst A.

[0078] Synthesis of Ligand to be Used in the Synthesis of Catalyst C

[0079] The solution of 4,6-di-tert-butyl-7-hydroxy-2,3-dihydro-1-indanone in ethanol at the concentration of 0.67 M was prepared by dissolving 0.52 g (2 mmol) of 4,6-di-tert-butyl-7-hydroxy-2,3-dihydro-1-indanone in 3 mL of ethanol. Then, the 1,2-ethylene diamine was added into said solution. The mole ratio of 4,6-di-tert-butyl-7-hydroxy-2,3-dihydro-1-indanone to 1,2-ethylene diamine was 2:1. After that, the acetic acid was added about 1-2 drops. The obtained mixture was stirred while heated until reflux for 48 hours. Then, the obtained mixture was filtered to separate the solid. The obtained solid was washed with 10 mL of diethyl ether for 3 times. The N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-ethane-1,2-diamine ligand was obtained as yellow solid.

EXAMPLE 2

Synthesis of Metal Complex Catalyst Containing N-N′-bis(ethylenesalicylidene)-diamine Ligand and its Derivatives

[0080] Synthesis of Catalyst A

[0081] The solution of N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamine ligand in toluene at the concentration of 0.062 M was prepared by dissolving 0.20 g (0.62 mmol) of N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamine ligand in 10 mL of toluene. Then, 0.10 g (0.62 mmol) of iron (III) chloride (FeCl.sub.3) and triethylamine were mixed, respectively. The mole ratio of N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamine ligand to iron (III) chloride to triethylamine was 1:1:2. After that, the obtained mixture was stirred and heated at the temperature of 100° C. until reflux under nitrogen atmosphere for 12 hours. The obtained mixture was filtered through celite. Then, the obtained solution was evaporated under vacuum condition. The catalyst A was obtained as red-brown solid.

[0082] Synthesis of Catalyst B

[0083] The solution of N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamine ligand in tetrahydrofuran at the concentration of 0.031 M was prepared by dissolving 0.10 g (0.31 mmol) of N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamine ligand in 10 mL of tetrahydrofuran. Then, 0.015 g (0.62 mmol) of sodium hydride was mixed into said solution and stirred at room temperature for 1 hour. Then, the obtained mixture was mixed with 0.12 g (0.31 mmol) of chromium (III) chloride tetrahydrofuran (CrCl.sub.3 (THF).sub.3). The mole ratio of N-N′-bis(ethylenesalicylidene)-ethane-1,2-diamine ligand to chromium (III) chloride tetrahydrofuran to sodium hydride was 1:1:2. After that, the obtained mixture was stirred at room temperature under nitrogen atmosphere for 12 hours. The obtained mixture was filtered. The obtained solid was washed with saturated sodium chloride solution and water, respectively. Then, the obtained solid was evaporated under vacuum condition. The catalyst B was obtained as light brown solid.

[0084] Synthesis of Catalyst C

[0085] The solution of N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-ethane-1,2-diamine ligand in tetrahydrofuran at the concentration of 0.018 M was prepared by dissolving 0.10 g (0.18 mmol) of N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-ethane-1,2-diamine ligand in 10 mL of tetrahydrofuran. Then, 0.0088 g (0.37 mmol) of sodium hydride was mixed into said solution and stirred at room temperature for 1 hour. Then, the obtained mixture was mixed with 0.068 g (0.18 mmol) of chromium (III) chloride tetrahydrofuran (CrCl.sub.3 (THF).sub.3). The mole ratio of N-N′-bis(3,5-di-tert-butyl ethylenesalicylidene)-ethane-1,2-diamine ligand to chromium (III) chloride tetrahydrofuran to sodium hydride was 1:1:2. After that, the obtained mixture was stirred at room temperature under nitrogen atmosphere for 12 hours. The obtained mixture was filtered. The obtained solid was washed with saturated sodium chloride solution and water, respectively. Then, the obtained solid was evaporated under vacuum condition. The catalyst C was obtained as light brown solid.

EXAMPLE 3

Preparation of Cyclic Carbonate from the Reaction between CO.SUB.2 .and Epoxides

[0086] The metal complex catalyst containing N-N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention which are catalyst A, B, and C will be tested for the ability in cyclic carbonate production from the reaction between CO.sub.2 and epoxides in order to compare with the comparative catalysts which are the metal complex REFCAT1, REFCAT2, and REFCAT3, which are N,N′-bis(salicylidene)ethylenediaminoiron (III) chloride, N,N′-bis(3,5-di-tert-butylsaliylidene)-1,2-diphenylethylenediaminochromium (III) chloride, and N,N′-bis(3,5-di-tert-butylsalicylidene)-pyrrolidine-diaminochromium (III) chloride, respectively.

[0087] Testing for the Ability in Cyclic Carbonate Production of the Catalyst according to the Invention under the Presence of Organic Solvent

[0088] Testing for the ability in cyclic carbonate production under the presence of organic solvent of the metal complex catalyst containing N-N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention can be performed according to the following process.

[0089] The 0.02 mmol of metal complex catalyst, 0.02 mmol of organic compound as the co-catalyst, 26.66 mmol of epoxides, and 0.25 to 1 mL of organic solvent were added into the reactor. Then, CO.sub.2 was added into the reactor at the pressure of 100 psi. The reactor was heated at the temperature of 65 to 110° C. for 1 to 24 hours. After the set time had been reached, the temperature of the reactor was reduced to room temperature. The obtained product was cyclic carbonate which would be identified by NMR spectrometry technique.

[0090] Testing for the Ability in Cyclic Carbonate Production of the Catalyst according to the Invention under Organic Solvent-Free Condition

[0091] Testing for the ability in cyclic carbonate production under organic solvent-free condition of the metal complex catalyst containing N-N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention can be performed according to the following process.

[0092] The 0.02 mmol of metal complex catalyst, 0.06 to 4 mmol of organic compound as the co-catalyst, and 100 to 400 mmol of epoxides were added into the reactor. Then, CO.sub.2 was added into the reactor at the pressure of 300 psi. The reactor was heated at the temperature of 80 to 120° C. for 0.25 to 6 hours. After the set time had been reached, the temperature of the reactor was reduced to room temperature. The obtained product was cyclic carbonate which would be identified by NMR spectrometry technique.

[0093] Testing for the Ability in Cyclic Carbonate Production under Metal Complex Catalyst-Free and Organic Solvent-Free Condition

[0094] Testing for the ability in cyclic carbonate production under metal complex catalyst-free and organic solvent-free condition can be performed according to the same process as the testing for the ability in cyclic carbonate production under organic solvent-free condition, except the addition of metal complex catalyst.

[0095] Structure of the Catalyst according to the Invention

[0096] The structure of the synthesized metal complex catalyst containing N-N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives is shown in table 1.

TABLE-US-00001 TABLE 1 Structure of the metal complex catalyst containing N-N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention Sample Name Structure Catalyst A N-N′- bis(ethylenesalicylidene)- ethane-1,2-diaminoiron (III) chloride [00004] Catalyst B N-N′- bis(ethylenesalicylidene)- ethane-1,2- diaminochromium (III) chloride [00005] Catalyst C N-N′-bis(3,5-di-tert- butyl ethylenesalicylidene)- ethane-1,2- diaminochromuin (III) chloride [00006]

[0097] Structure of the Comparative Catalyst

[0098] The comparative catalyst REFCAT1, REFCAT2, and REFCAT3 were N,N′-bis(salicylidene)ethylenediaminoiron (III) chloride, N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-diphenylethylenediaminochromium (III) chloride, and N,N′-bis(3,5-di-tert-butylsalicylidene)-pyrrolidine-diaminochromium (III) chloride, respectively. The comparative catalyst REFCAT1 was synthesized according to the steps disclosed in Dalton Transactions, 2018, 47, 13229-13238, except the use of toluene instead of methanol in the synthesis. This synthesized catalyst REFCAT1 was tested for the ability in cyclic carbonate production by the same process as the catalyst according to the invention. While the comparative catalyst REFCAT2 and REFCAT3 were the catalysts disclosed before in Journal of the American Chemical Society, 2001, 123, 11498-11499 and Tetrahedron Letters, 2008, 49, 6589-6592, respectively. The structure of three comparative catalysts is shown in table 2.

TABLE-US-00002 TABLE 2 Structure of the comparative catalysts Sample Name Structure Catalyst REFCAT1 N-N′- bis(salicylidene)ethylenediaminoiron (III) chloride [00007] Catalyst REFCAT2 N-N′-bis(3,5-di-tert- butylsalicylidene)-1,2- diphenylethylenediaminochromium (III) chloride [00008] Catalyst REFCAT3 N-N′-bis(3,5-di-tert- butylsalicylidene)-pyrrolidine- diaminochromium (III) chloride [00009]

[0099] Cyclic Carbonate Formation

[0100] The catalytic ability for the cyclic carbonate formation from the reaction between CO.sub.2 and epoxides of the metal complex catalyst containing N-N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention which are catalyst A, B, and C comparing to the catalytic ability for the cyclic carbonate formation of the comparative catalyst REFCAT1, REFCAT2, and REFCAT3 is shown in table 3. It was found that the catalyst according to the invention had better catalytic ability for the cyclic carbonate formation than the comparative catalyst REFCAT1, REFCAT2, and REFCAT3, wherein the yield percentage of cyclic carbonate is higher with shorter time. This shows that the catalyst according to the invention had better catalytic ability for the cyclic carbonate formation than those three comparative catalysts. Moreover, the synthesis process of the catalyst according to this invention is easier and cheaper comparing to the comparative catalyst REFCAT3.

TABLE-US-00003 TABLE 3 Catalytic ability for the cyclic carbonate formation of the metal complex catalyst containing N-N’-bis(ethylenesalicylidene)- diamine ligand and its derivatives according to the invention comparing to the comparative catalyst Cyclic Catalyst system Temper- CO.sub.2 Mole ratio of percentage Co- Time ature pressure catalyst:co- carbonate yield TOF.sup.a Catalyst catalyst Epoxides Solvent (hr) (° C.) (psi) catalyst:epoxides (% Yield) (h.sup.−1) REFCAT1 DMAP propylene DCM 24 65 100 1:1:1333 42 23 oxide A DMAP propylene DCM 24 65 100 1:1:1333 88 49 oxide A TBAB propylene DCM 24 65 100 1:1:1333 54 30 oxide B DMAP propylene DCM 6 65 100 1:1:1333 93 207 oxide B TBAB propylene DCM 6 65 100 1:1:1333 69 153 oxide REFCAT2.sup.b DMAP propylene DCM 1 100 100 1:1:1333 69 916 oxide B DMAP propylene DCM 1 110 100 1:1:1333 92 1222 oxide C DMAP propylene DCM 1 110 100 1:1:1333 88 1180 oxide REFCAT3.sup.c — propylene neat 1 80 300 1:0:5000 39 1936 oxide C TBAB propylene neat 1 80 300 1:3:5000 66 3300 oxide C TBAB propylene neat 1 80 300 1:5:5000 76 3800 oxide C TBAB propylene neat 1 80 300 1:10:5000 86 4300 oxide — TBAB propylene neat 1 80 300 0:5:5000 1 65 oxide C TBAB propylene neat 1 80 300 1:50:10000 81 8100 oxide C TBAB propylene neat 1 80 300 1:100:20000 46 9200 oxide C TBAB propylene neat 1 80 300 1:200:20000 58 11600 oxide C TBAB propylene neat 1 100 300 1:200:20000 78 15600 oxide C TBAB propylene neat 1 120 300 1:200:20000 83 16600 oxide neat is solvent-free, DCM is dichloromethane .sup.aamount of product formed per catalyst per time .sup.boperating condition: 0.042 mmol of catalyst, 0.042 mmol of co-catalyst, 57.2 mmol of epoxides, 0.5 mL of solvent .sup.c operating condition: 0.04 mmol of catalyst, 200 mmol of epoxides

TABLE-US-00004 TABLE 4 Catalytic ability for the cyclic carbonate formation from different epoxides using catalyst C under solvent-free condition, mole ratio of catalyst:co-catalyst(TBAB):epoxides at 1:50:5000, CO.sub.2 pressure of 300 psi, temperature of 80° C. Conversion Time percentage.sup.a Epoxides (hr) (% conversion) TOF.sup.b(h.sup.−1) % selectivity to carbonate.sup.c % selectivity to polycarbonate.sup.c [00010] 0.25 83 16600 100 0 [00011] 1 78 3900 100 0 [00012] 1 65 3250 100 0 [00013] 1 55 2750 100 0 [00014] 0.25 50 10000 100 0 [00015] 6 50 417 100 0 .sup.acalculated from epoxides in the mixture at before and after reaction using .sup.1H NMR spectroscopy .sup.bamount of product formed per catalyst per time .sup.ccalculated from product formed using .sup.1H NMR spectroscopy

BEST MODE OR PREFERRED EMBODIMENT OF THE INVENTION

[0101] Best mode or preferred embodiment of the invention is as provided in the description of the invention.