CATALYST COMPOSITION FOR CYCLIC CARBONATE PRODUCTION FROM CO2 AND OLEFINS

Abstract

The present invention relates to catalyst composition for cyclic carbonate production from CO.sub.2 and olefins using halohydrin agent as the co-reactant 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 halogen atom, acetate group, or triflate group; b) the halohydrin agent in at least one solvent; and c) at least one base.

Claims

1. A catalyst composition for cyclic carbonate production from CO.sub.2 and olefins, wherein said catalyst composition comprises: a) the metal complex as shown in structure (I): ##STR00008## 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; b) the halohydrin agent in at least one solvent; and c) at least one base.

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, R.sub.2, and R.sub.3 are 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 1,2-phenylene 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 halohydrin agent in b) is the halogen compound.

13. The catalyst composition according to claim 12, wherein the halogen compound is selected from sodium iodide (NaI), sodium bromide (NaBr), sodium chloride (NaCl), potassium iodide (KI), potassium bromide (KBr), tetrabutylammonium iodide (TBAI), N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), iodine (I.sub.2), bromine (Br.sub.2), or mixture thereof.

14. The catalyst composition according to claim 12 or 13, wherein the halogen compound is N-bromosuccinimide.

15. The catalyst composition according to claim 1 or 12, wherein the halohydrin agent in b) further comprises the oxidant selected from potassium persulfate (K.sub.2S.sub.2O.sub.8), hydrogen peroxide (H.sub.2O.sub.2), tert-butyl hydroperoxide, calcium hypochlorite (Ca(OCl).sub.2), benzoyl peroxide, potassium nitrate (KNO.sub.3), or mixture thereof.

16. The catalyst composition according to claim 1, wherein at least one solvent is selected from water, acetone, dichloromethane, hexane, benzene, toluene, dimethylformamide, acetronitrile, or mixture thereof.

17. The catalyst composition according to claim 16, wherein the solvent is the mixture of water and acetone.

18. The catalyst composition according to claim 1, wherein at least one base is selected from potassium carbonate (K.sub.2CO.sub.3), sodium carbonate (Na.sub.2CO.sub.3), sodium bicarbonate (NaHCO.sub.3), cesium carbonate (Ce.sub.2CO.sub.3), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or mixture thereof.

19. A process for cyclic carbonate production from CO.sub.2 and olefins comprises the contact of the catalyst composition according to any one of the preceding claims to the mixture of CO.sub.2 and olefins.

20. The process for cyclic carbonate production from CO.sub.2 and olefins, comprising the following steps: i) the contact of olefins to the halohydrin agent in at least one solvent; and ii) the contact of the mixture obtained from step i), CO.sub.2 and at least one base to the metal complex catalyst as shown in structure (I): ##STR00009## 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; and X represents group selected from halogen atom, acetate group, or triflate group.

21. The process for cyclic carbonate production according to claim 20, wherein in the metal complex catalyst, M represents transition metal atom selected from chromium, cobalt, or iron.

22. The process for cyclic carbonate production according to claim 21, wherein in the metal complex catalyst, M is chromium metal atom.

23. The process for cyclic carbonate production according to claim 20, wherein in the metal complex catalyst, 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.

24. The process for cyclic carbonate production according to claim 20 or 23, wherein in the metal complex catalyst, 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.

25. The process for cyclic carbonate production according to claim 24, wherein in the metal complex catalyst, R.sub.1, R.sub.2, and R.sub.3 are hydrogen atom.

26. The process for cyclic carbonate production according to claim 20, wherein in the metal complex catalyst, R.sub.4 represents group selected from alkylene group having 2 to 3 carbon atoms, cycloalkylene group having 6 carbon atoms, or phenylene group.

27. The process for cyclic carbonate production according to claim 20 or 26, wherein in the metal complex catalyst, R.sub.4 represents group selected from ethylene group, 1,3-propylene group, 1,2-cyclohexylene group, or 1,2-phenylene group.

28. The process for cyclic carbonate production according to claim 27, wherein in the metal complex catalyst, R.sub.4 is 1,2-phenylene group.

29. The process for cyclic carbonate production according to claim 20, wherein in the metal complex catalyst, X represents group selected from chlorine atom, bromine atom, iodine atom, acetate group, or triflate group.

30. The process for cyclic carbonate production according to claim 20, wherein the metal complex catalyst 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.

31. The process for cyclic carbonate production according to any one of claim 20 to 30, wherein the metal complex catalyst further comprises the organic compound as the co-catalyst selected from compound containing nitrogen, compound of quaternary ammonium salts, or compound of iminium salts.

32. The process for cyclic carbonate production according to claim 31, wherein the organic compound as the co-catalyst 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.

33. The process for cyclic carbonate production according to claim 20, wherein olefin is selected from ethylene, propylene, butylene, 1,4-butadiene, styrene, 1-hexene, or 1-octene.

34. The process for cyclic carbonate production according to claim 33, wherein olefin is ethylene.

35. The process for cyclic carbonate production according to claim 20, wherein the halohydrin agent in step i) is the halogen compound.

36. The process for cyclic carbonate production according to claim 35, wherein the halogen compound is selected from sodium iodide (NaI), sodium bromide (NaBr), sodium chloride (NaCl), potassium iodide (KI), potassium bromide (KBr), tetrabutylammonium iodide (TBAI), N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), iodine (I.sub.2), bromine (Br.sub.2), or mixture thereof.

37. The process for cyclic carbonate production according to claim 35 or 36, wherein the halogen compound is N-bromosuccinimide.

38. The process for cyclic carbonate production according to claim 20 or 35, wherein the halohydrin agent in step i) further comprises the oxidant selected from potassium persulfate (K.sub.2S.sub.2O.sub.8), hydrogen peroxide (H.sub.2O.sub.2), tert-butyl hydroperoxide, calcium hypochlorite (Ca(OCl).sub.2), benzoyl peroxide, potassium nitrate (KNO.sub.3), or mixture thereof.

39. The process for cyclic carbonate production according to claim 20, wherein at least one solvent in step i) is selected from water, acetone, dichloromethane, hexane, benzene, toluene, dimethylformamide, acetronitrile, or mixture thereof.

40. The process for cyclic carbonate production according to claim 20 or 39, wherein the solvent in step i) is the mixture of water and acetone.

41. The process for cyclic carbonate production according to claim 20, wherein at least one base in step ii) is selected from potassium carbonate (K.sub.2CO.sub.3), sodium carbonate (Na.sub.2CO.sub.3), sodium bicarbonate (NaHCO.sub.3), cesium carbonate (Ce.sub.2CO.sub.3), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or mixture thereof.

42. The process for cyclic carbonate production according to claim 20, wherein step ii) is operated under the presence of organic solvent selected from dichloromethane, hexane, benzene, toluene, dimethylformamide, or mixture thereof.

43. The process for cyclic carbonate production according to claim 20, wherein the temperature in step i) is in the range of 30 to 80° C.

44. The process for cyclic carbonate production according to claim 20, wherein the temperature in step ii) is in the range of 50 to 120° C.

45. The process for cyclic carbonate production according to claim 20, wherein the mole ratio of the metal complex to olefins is in the range of 1:10 to 1:10000.

46. The process for cyclic carbonate production according to claim 20, wherein the CO.sub.2 pressure in step ii) is in the range of 15 to 600 psi.

Description

DESCRIPTION OF THE INVENTION

[0022] The present invention relates to the catalyst composition for cyclic carbonate production from CO.sub.2 and olefins 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.

[0023] Any aspect being described herein also means to include the application to other aspects of this invention unless stated otherwise.

[0024] Technical terms or scientific terms used herein have definitions as understood by an ordinary person skilled in the art unless stated otherwise.

[0025] 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.

[0026] 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”.

[0027] 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.

[0028] 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.

[0029] Hereafter, invention embodiments are shown without any purpose to limit any scope of the invention.

[0030] This invention relates to the catalyst composition for cyclic carbonate production from CO.sub.2 and olefins using halohydrin agent as the co-reactant under mild conditions, which can efficiently catalyze the cyclic carbonate synthesis with good selectivity to cyclic carbonate, wherein said catalyst composition comprising:

[0031] a) the metal complex as shown in structure (I):

##STR00003##

[0032] wherein,

[0033] M represents transition metal atom;

[0034] 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;

[0035] R.sub.4 represents group selected from alkylene group, cycloalkylene group, or phenylene group;

[0036] X represents group selected from halogen atom, acetate group, or triflate group;

[0037] b) the halohydrin agent in at least one solvent; and

[0038] c) at least one base.

[0039] 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.

[0040] 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.

[0041] 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, R.sub.2, and R.sub.3 are hydrogen atom.

[0042] 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.

[0043] 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 1,2-phenylene group.

[0044] 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.

[0045] 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, 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.

[0046] 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.

[0047] 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 (Crl.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).

[0048] 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).

[0049] 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.2).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).

[0050] 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, 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, 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, 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, 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.

[0051] In one aspect of the invention, the halohydrin agent in b) is the halogen compound selected from sodium iodide (NaI), sodium bromide (NaBr), sodium chloride (NaCl), potassium iodide (KI), potassium bromide (KBr), tetrabutylammonium iodide (TBAI), N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), iodine (I.sub.2), bromine (Br.sub.2), or mixture thereof. Preferably, the halohydrin agent in b) is the halogen compound selected from N-bromosuccinimide.

[0052] In one aspect of the invention, the halohydrin agent in b) further comprises the oxidant selected from potassium persulfate (K.sub.2S.sub.2O.sub.8), hydrogen peroxide (H.sub.2O.sub.2), tert-butyl hydroperoxide, calcium hypochlorite (Ca(OCl).sub.2), benzoyl peroxide, potassium nitrate (KNO.sub.3), or mixture thereof.

[0053] In one aspect of the invention, at least one solvent is selected from, but not limited to water, acetone, dichloromethane, hexane, benzene, toluene, dimethylformamide, acetronitrile, or mixture thereof. Preferably, the solvent is the mixture of water and acetone.

[0054] In one aspect of the invention, at least one base is selected from potassium carbonate (K.sub.2CO.sub.3), sodium carbonate (Na.sub.2CO.sub.3), sodium bicarbonate (NaHCO.sub.3), cesium carbonate (Ce.sub.2CO.sub.3), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or mixture thereof.

[0055] In one aspect of the invention, this invention relates to the process for cyclic carbonate production from CO.sub.2 and olefins, comprising the contact of the catalyst composition as described above to the mixture of CO.sub.2 and olefins

[0056] In another aspect of the invention, this invention relates to the process for cyclic carbonate production from CO.sub.2 and olefins, comprising the following steps: [0057] i) the contact of olefins to the halohydrin agent in at least one solvent; and [0058] ii) the contact of mixture obtained from step i), CO.sub.2 and at least one base to the metal complex catalyst selected from the metal complex as described above.

[0059] In one aspect of the invention, the metal complex catalyst further comprises the organic compound as the co-catalyst selected from compound containing nitrogen, compound of quaternary ammonium salts, or compound of iminium salts.

[0060] In one aspect of the invention, the metal complex catalyst further comprises the organic compound as the co-catalyst selected from, but not limited to 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.

[0061] In one aspect of the invention, olefin is selected from ethylene, propylene, butylene, 1,4-butadiene, styrene, 1-hexene, or 1-octene. Preferably, olefin is ethylene.

[0062] In one aspect of the invention, the halohydrin agent in step i) is the halogen compound selected from sodium iodide (NaI), sodium bromide (NaBr), sodium chloride (NaCl), potassium iodide (KI), potassium bromide (KBr), tetrabutylammonium iodide (TBAI), N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), iodine (I.sub.2), bromine (Br.sub.2), or mixture thereof.

[0063] Preferably, the halohydrin agent in step i) is the halogen compound selected from N-bromosuccinimide.

[0064] In one aspect of the invention, the halohydrin agent in step i) further comprises the oxidant selected from potassium persulfate (K.sub.2S.sub.2O.sub.8), hydrogen peroxide (H.sub.2O.sub.2), tert-butyl hydroperoxide, calcium hypochlorite (Ca(OCl).sub.2), benzoyl peroxide, potassium nitrate (KNO.sub.3), or mixture thereof.

[0065] In one aspect of the invention, at least one solvent in step i) is selected from water, acetone, dichloromethane, hexane, benzene, toluene, dimethylformamide, acetronitrile, or mixture thereof. Preferably, the solvent in step i) is the mixture of water and acetone.

[0066] In one aspect of the invention, at least one base in step ii) is selected from potassium carbonate (K.sub.2CO.sub.3), sodium carbonate (Na.sub.2CO.sub.3), sodium bicarbonate (NaHCO.sub.3), cesium carbonate (Ce.sub.2CO.sub.3), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or mixture thereof.

[0067] In one aspect of the invention, step ii) is operated under the presence of organic solvent selected from dichloromethane, hexane, benzene, toluene, dimethylformamide, or mixture thereof.

[0068] In one aspect of the invention, the temperature in step i) is in the range of 30 to 80° C. and the temperature in step ii) is in the range of 50 to 120° C.

[0069] In one aspect of the invention, the mole ratio of the metal complex to olefins is in the range of 1:10 to 1:10000 and the CO.sub.2 pressure in step ii) is in the range of 15 to 600 psi.

[0070] The cyclic carbonate production from CO.sub.2 and olefins according to this invention may further comprises the drying step if necessary, wherein said step may be selected from, but not limited to stir-drying or vacuum drying, etc.

[0071] In one aspect, the cyclic carbonate production from CO.sub.2 and olefins 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.

[0072] 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

[0073] Synthesis of ligand to be used in the synthesis of catalyst A 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-ehtylene diamine was added into said solution. The mole ratio of 7-hydroxy-1-indanone to 1,2-ehtylene 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.

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

[0075] 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.

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

[0077] 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-ehtylene 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-ehtylene 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.

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

[0079] 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-phenylene diamine was added into said solution. The mole ratio of 7-hydroxy-1-indanone to 1,2-phenylene 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)-benzene-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.

[0086] Synthesis of Catalyst D

[0087] The solution of N—N′-bis(ethylenesalicylidene)-benzene-1,2-diamine ligand in tetrahydrofuran at the concentration of 0.027 M was prepared by dissolving 0.10 g (0.27 mmol) of N—N′-bis(ethylenesalicylidene)-benzene-1,2-diamine ligand in 10 mL of tetrahydrofuran. Then, 0.013 g (0.54 mmol) of sodium hydride was mixed into said solution and stirred at room temperature for 1 hour. Then, the obtained mixture was mixed with 0.10 g (0.27 mmol) of chromium (III) chloride tetrahydrofuran (CrCl.sub.3 (TIF).sub.3). The mole ratio of N—N′-bis(ethylenesalicylidene)-benzene-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 D was obtained as light brown solid.

Example 3: Preparation of Cyclic Carbonate from the Reaction Between CO.SUB.2 .and Olefins

[0088] The metal complex catalyst containing N—N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention which are catalyst A, B, C, and D will be tested for the ability in cyclic carbonate production from the reaction between CO.sub.2 and olefins as follows:

[0089] Testing for the Ability in Cyclic Carbonate Production of the Catalyst According to the Invention

[0090] Under the Condition of Halogen Compound as Halohydrin Agent and Further Comprising Oxidant Testing for the ability in cyclic carbonate production of the metal complex catalyst containing N—N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention under the condition of halogen compound as halohydrin agent and further comprising oxidant can be performed according to the following steps.

[0091] Step i):

[0092] 1 mmol of olefins, 1 mmol of halogen compound which was sodium iodide or sodium bromide, 1 mmol of oxidant which was potassium persulfate, and 2 mL of water solvent were added into the reactor. The reactor was heated at the temperature of 60° C. for 2 to 5 hours; and

[0093] Step ii):

[0094] About 4.06-7.30 mg of metal complex catalyst, 1.30 mg of organic compound as the co-catalyst which was 4-dimethylaminopyridine, 1 mmol of base which was potassium carbonate, and 2 mL of organic solvent which was dimethylformamide were added into the reactor containing the mixture from step i). Then, carbon dioxide gas was added into the reactor at the pressure of 300 psi. The reactor was heated at the temperature of 60° C. for 1 to 5 hours. After the reaction time was reached, the temperature of the reactor was reduced to the room temperature. The obtained product was cyclic carbonate which would be identified by NMR spectrometry technique.

[0095] Testing for the Ability in Cyclic Carbonate Production of the Catalyst According to the Invention Under the Condition of Halogen Compound as Halohydrin Agent

[0096] Testing for the ability in cyclic carbonate production of the metal complex catalyst containing N—N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention under the condition of halogen compound as halohydrin agent can be performed according to the following steps.

[0097] Step i):

[0098] 1 mmol of olefins, 1 mmol of halogen compound which was N-Bromosuccinimide (NBS), 2 mL of acetone solvent, and 2 mL of water solvent were added into the reactor. The reactor was heated at the temperature of 40° C. for 2 hours; and

[0099] Step ii):

[0100] About 4.06-7.30 mg of metal complex catalyst, 1.30 mg of organic compound as the co-catalyst which was 4-dimethylaminopyridine, and 1 mmol of base which was potassium carbonate were added into the reactor containing the mixture from step i). Then, carbon dioxide gas was added into the reactor at the pressure of 300 psi. The reactor was heated at the temperature of 60° C. for 2 hours. After the reaction time was reached, the temperature of the reactor was reduced to the room temperature. The obtained product was cyclic carbonate which would be identified by NMR spectrometry technique.

[0101] Testing for the Ability in One Step Cyclic Carbonate Production of the Catalyst According to the Invention Under the Condition of Halogen Compound as Halohydrin Agent and Further Comprising Oxidant

[0102] Testing for the ability in one step cyclic carbonate production of the metal complex catalyst containing N—N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention under the condition of halogen compound as halohydrin agent and further comprising oxidant can be performed according to the following steps.

[0103] 1 mmol of olefins, 1 mmol of halogen compound which was sodium iodide, 1 mmol of oxidant which was potassium persulfate, 2 mL of water solvent, 1 mL of dimethylformamide solvent, 1 mmol of base which was potassium carbonate, and about 4.06-7.30 mg of metal complex catalyst including 1.30 mg of organic compound as the co-catalyst which was 4-dimethylaminopyridine were added into the reactor. Then, carbon dioxide gas was added into the reactor at the pressure of 300 psi. The reactor was heated at the temperature of 60° C. for 10 hours. After the reaction time was reached, the temperature of the reactor was reduced to the room temperature. The obtained product was cyclic carbonate which would be identified by NMR spectrometry technique.

[0104] Structure of the Catalyst According to the Invention

[0105] 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- diaminochromium (III) chloride [00006] Catalyst D N-N′-bis(ethylenesalicylidene)- benzene-1,2-diaminochromium (III) chloride [00007]

[0106] Cyclic Carbonate Formation

[0107] The catalytic ability for the cyclic carbonate formation from C %2 and olefins of the metal complex catalyst containing N—N′-bis(ethylenesalicylidene)-diamine ligand and its derivatives according to the invention which are catalyst A, B, C, and D comparing to the non-catalytic conditions is shown in table 2 and 3.

TABLE-US-00002 TABLE 2 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 Mole ratio Metal of catalyst: Time for Time for % % Yield of complex Halohydrin co-catalyst: step i) step ii) Conversion cyclic catalyst Olefins agent olefins (hr) (hr) of olefins carbonate None styrene NaI/K.sub.2S.sub.20.sub.8 0:1:100 2 4 96 39 A styrene NaI/K.sub.2S.sub.20.sub.8 1:1:100 2 4 91 58 B styrene NaI/K.sub.2S.sub.20.sub.8 1:1:100 2 4 89 65 B styrene NaI/K.sub.2S.sub.20.sub.8 1:1:100 2 1 82 66 B styrene NaI/K.sub.2S.sub.20.sub.8 1:1:100 2 2 86 77 C styrene NaI/K.sub.2S.sub.20.sub.8 1:1:100 2 2 86 59 D styrene NaI/K.sub.2S.sub.20.sub.8 1:1:100 2 2 95 87 D 1-hexene NaI/K.sub.2S.sub.20.sub.8 1:1:100 2 2 96 85 B styrene NaBr/K.sub.2S.sub.20.sub.8 1:1:100 5 5 87 77 B 1-hexene NaBr/K.sub.2S.sub.20.sub.8 1:1:100 5 5 100 94 D styrene NBS 1:1:100 2 2 100 96 D 1-hexene NBS 1:1:100 2 2 100 88 D styrene NBS 1:0:100 2 2 100 95 D.sup.a styrene NBS 1:0:200 2 2 100 87 D.sup.b styrene NBS  1:0:1000 2 2 100 83 D 1-hexene NBS 1:0:100 2 2 100 87 D 1-octene NBS 1:0:100 2 2 100 85 D 1,4-butadiene NBS 1:0:100 2 2 100 97 D ethylene NBS 1:0:100 2 2 100 100 .sup.aamount of metal complex catalyst 0.5% mole .sup.bamount of metal complex catalyst 0.1% mole

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 Metal Mole ratio complex Halo- of cata- % Conver- % Yield cata- hydrin lyst:co-cata- sion of of cyclic lyst Olefins agent lyst:olefins olefins carbonate None styrene NaBr/ 0:1:100 95 49 K.sub.2S.sub.2O.sub.8 B styrene NaBr/ 1:1:100 91 57 K.sub.2S.sub.2O.sub.8 None styrene NaI/ 0:1:100 71 58 K.sub.2S.sub.2O.sub.8 B styrene NaI/ 1:1:100 90 84 K.sub.2S.sub.2O.sub.8 B 1-hexene NaI/ 1:1:100 100 84 K.sub.2S.sub.2O.sub.8

BEST MODE OR PREFERRED EMBODIMENT OF THE INVENTION

[0108] Best mode or preferred embodiment of the invention is as provided in the description of the invention.