For CO 2 Catalyst composition for producing cyclic carbonate from olefins

Abstract

The present invention relates to a catalyst composition for preparing cyclic carbonate from CO2 and olefin using a halohydrin reagent as a coreactant under mild conditions, wherein the catalyst composition can effectively catalyze the synthesis of cyclic carbonate and provides good selectivity for cyclic carbonate, wherein the catalyst composition comprises: a) a metal complex as shown in structure (I): #imgabs0#Structural formula (I), wherein M represents a transition metal atom; R1, R2 and R3 represent groups independently selected from hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, amine groups, phenyl groups, benzyl groups, cyclic hydrocarbon groups containing heteroatoms, perfluoroalkyl groups or nitro groups; R4 represents a group selected from alkylene groups, cycloalkylene groups or phenylene groups; X represents a group selected from halogen atoms, acetate groups or trifluoromethylsulfonate groups; b) a halohydrin reagent in at least one solvent; and c) at least one base.

Description

Technical Field

[0001] The present invention relates to the field of science, in particular to the use of 2 A catalyst composition for producing cyclic carbonates from olefins. Background Art

[0002] Cyclic carbonate is a kind of valuable chemical, and is of vital importance in these two fields of chemical and polymer industry.In chemical industry, cyclic carbonate is generally used as polar aprotic solvent, and wherein commonly used cyclic carbonate is ethylene carbonate and propylene carbonate.Cyclic carbonate is used to replace polar aprotic solvent such as dimethylformamide, hexamethylphosphoramide, N-methyl-2-pyrrolidone, dimethylacetamide etc.This is because cyclic carbonate has low toxicity, low vapor pressure, high flash point, and is more environmentally friendly.In addition, in downstream chemical industry such as dyestuff, medicine and cosmetics, particularly in personal care products, cyclic carbonate is regarded as the medium that is generally used for making or synthesizing these downstream chemicals.

[0003] In the polymer industry, cyclic carbonates are important precursors for the manufacture of polymers such as polycarbonate and polyurethane, including polycarbonate diols (PCDL) used in the manufacture of polyurethanes, which are required to have special properties such as better elasticity and mechanical properties, weather resistance and fungus resistance, oxidation resistance and UV protection. At the same time, cyclic carbonates are also important substances for the manufacture of important chemicals used in the polymer industry, such as 1,4-bis(2-hydroxyethoxy)benzene (HQEE) synthesized from ethylene carbonate, which is used as a spacer in the manufacture of chemically resistant and heat-resistant high-strength polyurethanes for the manufacture of vehicle tires, or 1,3,5-tris(2-hydroxyethyl)isocyanurate (THEIC) synthesized from ethylene carbonate, which is used as a crosslinker in the manufacture of corrosion-resistant polyester resins suitable for covering cables. In addition to the use of cyclic carbonates in the manufacture of chemicals in the polymer industry, cyclic carbonates are also commonly used for direct addition to polymers to improve polymer properties.

[0004] For the synthesis of this cyclic carbonate, in the past, phosgene could be used as a precursor in the synthesis, for example, ethylene carbonate was synthesized from phosgene and ethylene glycol. However, the synthetic method is quite dangerous, and because phosgene has high toxicity, it also affects the environment. Therefore, a method for synthesizing cyclic carbonates by replacing phosgene with other precursors has been developed. At present, the carbon source that is used as a precursor and obtains attention when manufacturing valuable chemicals including fuels is carbon dioxide, because carbon dioxide has low toxicity, low cost and has the ability to reuse renewable resources, so it is an important C1 structural unit. Therefore, carbon dioxide has been used as a precursor for synthesizing cyclic carbonates, particularly the first disclosed cyclic carbonate synthesized by the reaction between carbon dioxide and epoxide in patent documentation DE 740,366. The advantage of this synthetic method is that the atomic efficiency of the chemical process conversion of this reaction is 100%. This means that all atoms of the precursor become products, thereby making it possible to effectively capture and store carbon dioxide in the form of cyclic carbonate products by the synthetic method of this reaction.

[0005] Yet most of epoxides are made from olefins.Therefore, developed and invented the method that uses olefins to make cyclic carbonates together with carbon dioxide as precursor, rather than using epoxide to make cyclic carbonates together with carbon dioxide as precursor, thereby reduced the step of making epoxides by olefins and the separation step of the epoxides brought by said method, thereby further used for cyclic carbonate manufacturing.Due to compared with the manufacture method that uses epoxides as precursor, the precursor cost used in the method that is made cyclic carbonates by olefins and carbon dioxide is low, easily obtainable and toxicity is less, so this method is of great concern.The method that is made cyclic carbonates by olefins and carbon dioxide can be divided into following two modes:

[0006] The first mode is oxidative carboxylation reaction, wherein in the first step, as the precursor of alkene and oxidant reaction to form epoxide by epoxidation, then this epoxide and carbon dioxide reaction to form cyclic carbonate by carboxylation.Example is the manufacturing of cyclic carbonate disclosed in patent documentation US 3,025,305, wherein said disclosed method is the reaction between the following two: pressure is the alkene and carbon dioxide of at least 500psig and operating temperature is 200 ° F to 400 ° F gas with oxygen-containing molecules as component, and use comprises the catalyst system of the cobalt organic salt oxidation catalyst and the cocatalyst of quaternary ammonium compound.But, because the alkene in the first step and oxidant reaction also produce oxidative by-product (such as benzaldehyde and benzoic acid) except epoxide, therefore the manufacturing of this cyclic carbonate has the shortcoming that selectivity is low and cyclic carbonate yield is low.This causes the yield of manufactured epoxide to be lower and also causes the yield of cyclic carbonate to be lower.

[0007] The second method is the hydroxyhalogenation-carboxylation reaction, in which in the first step, an olefin precursor is reacted with a halohydrin reagent such as N-bromosuccinimide (NBS) or bromide ion / hydrogen peroxide (Br - / H 2 O 2 ) thereby forms the intermediate as halohydrin by hydroxyl halogenation, thereby forms cyclic carbonate by carboxylation with carbonic acid gas reaction then.Compare with first way, this mode of making cyclic carbonate has better efficiency, wherein discloses the method for making cyclic carbonate by hydroxyl halogenation-carboxylation and by the synthetic halohydrin of olefin in the following document.

[0008] Patent document US 3,884,984 discloses a method for synthesizing a halohydrin such as chlorohydrin or bromohydrin, which is carried out by reacting an olefin such as ethylene with water and chlorine or bromine ions in the presence of a thallium salt. Patent document US 3,923,842 discloses a method for preparing a cyclic carbonate having 3 to 31 carbon atoms by reacting a halohydrin with carbon dioxide in the presence of an amine compound.

[0009] Patent document US Pat. No. 4,325,874 discloses a method for producing an alkylene carbonate such as ethylene carbonate by a reaction between an olefin and carbon dioxide in the presence of iodine or an iodine compound and a thallium oxide compound or a weakly acidic salt of thallium.

[0010] Patent document WO 2008 / 034265 A1 discloses a method for manufacturing cyclic carbonates in aqueous solution by alkene and carbon dioxide via an intermediate in the form of halohydrins such as bromohydrins. The manufacture of the cyclic carbonate disclosed in the document is a reaction between alkene and carbon dioxide in aqueous solution, in the presence of a halogen compound and a base with an amine group, or a reaction between alkene and carbon dioxide in aqueous solution, in the presence of a halogen compound, a base with an amine group and an oxidant. Examples of halogen compounds are N-bromosuccinimide (NBS), tetrabutylammonium bromide (TBAB), potassium bromide (KBr) or sodium bromide (NaBr) etc. Examples of bases with an amine group are 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) etc. Examples of oxidants are hydrogen peroxide (H 2 O 2 ) etc. It was found that the preparation method can be effectively carried out under mild conditions.

[0011] Jia-Ning Xie et al. (Journal of CO 2Utilization, 2016, 16, 313-317) discloses the direct synthesis of cyclic carbonates from olefins and carbon dioxide under mild conditions, i.e., carbon dioxide pressure of 3 MPa and temperature of 60°C. Potassium persulfate (K 2 S 2 O 8 ) is used as an oxidant, and sodium bromide (NaBr) is used as a reactant for the bromination reaction for the early stages of the hydroxyhalogenation of olefins. Then, potassium carbonate (K 2 CO 3 ) as the deprotonation reactant together with polyethylene glycol (PEG) by carboxylation, olefin and carbon dioxide are reacted to form cyclic carbonate. Find under described operating conditions, this method can manufacture cyclic carbonate.Yet, in described manufacture method, use polyethylene glycol to have shortcomings in the separation of cyclic carbonate product and polyethylene glycol.In addition, this building-up process also needs longer operating time.

[0012] Therefore, the present invention is directed to the preparation of a novel alkyl ester for preparing a alkyl ester from CO using a halohydrin reagent as a coreactant under mild conditions. 2 The invention discloses a catalyst composition for preparing cyclic carbonate from olefins, which can effectively catalyze the synthesis of cyclic carbonate and has good selectivity for cyclic carbonate. Summary of the invention

[0013] The present invention relates to a method for preparing a novel catalytic reaction of CO using a halogenated alcohol reagent as a coreactant under mild conditions. 2 A catalyst composition for producing cyclic carbonate from olefins and olefins, the catalyst composition can effectively catalyze the synthesis of cyclic carbonate and provide good selectivity for cyclic carbonate, wherein the catalyst composition comprises:

[0014] a) a metal complex as shown in structure (I):

[0015]

[0016] in,

[0017] M represents a transition metal atom;

[0018] R 1 , R 2 and R 3 represents a group independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amine group, a phenyl group, a benzyl group, a cyclic hydrocarbon group containing a heteroatom, a perfluoroalkyl group or a nitro group;

[0019] R 4 represents a group selected from an alkylene group, a cycloalkylene group or a phenylene group;

[0020] X represents a group selected from a halogen atom, an acetate group or a trifluoromethylsulfonate group;

[0021] b) a halohydrin reagent in at least one solvent; and

[0022] c) at least one base. DETAILED DESCRIPTION

[0023] The present invention relates to a method for producing CO under mild conditions 2 A catalyst composition for producing cyclic carbonates from olefins and olefins, wherein the catalyst according to the present invention can effectively catalyze the synthesis of cyclic carbonates and has good selectivity for cyclic carbonates, wherein the catalyst according to the present invention can be described according to the following embodiments.

[0024] Unless otherwise stated, any aspect described herein is also intended to include application to the other aspects of the invention.

[0025] Unless otherwise defined, technical or scientific terms used herein have the same definitions as understood by one of ordinary skill in the art.

[0026] Any tools, equipment, methods or chemicals mentioned herein refer to tools, equipment, methods or chemicals operated or commonly used by those skilled in the art, unless otherwise specified that they are only specific tools, equipment, methods or chemicals in the present invention.

[0027] The use of a singular noun or singular pronoun with "comprising" or "including" in the claims or the specification means "one" and also includes "one or more", "at least one" and "one or more than one".

[0028] All compositions and / or methods disclosed and claimed in this application are intended to cover such embodiments: although not specifically set forth in the claims, embodiments obtained by any operation, performance, modification or adjustment of any element that can be obtained by a person of ordinary skill in the art without conducting any experiment significantly different from the present invention, and that has the same utility purpose and result as the present embodiment. Therefore, the purposes that the present embodiment can replace or are similar to (including any minor modifications or adjustments that are obvious to those skilled in the art) should be interpreted as belonging to the spirit, scope and concept of the present invention appearing in the appended claims.

[0029] Throughout this application, the term "about" refers to any number shown or illustrated herein which may vary or deviate due to any error in the equipment, method or individual using the equipment or method.

[0030] Hereinafter, embodiments of the present invention are illustrated without any intention of limiting any scope of the present invention.

[0031] The present invention relates to a method for using a halogenated alcohol reagent as a coreactant to produce CO under mild conditions. 2 A catalyst composition for producing cyclic carbonates from olefins and olefins, the catalyst composition can effectively catalyze the synthesis of cyclic carbonates and has good selectivity for cyclic carbonates, wherein the catalyst composition comprises:

[0032] a) a metal complex as shown in structure (I):

[0033]

[0034] in,

[0035] M represents a transition metal atom;

[0036] R 1 , R 2 and R 3 represents a group independently selected from a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amine group, a phenyl group, a benzyl group, a cyclic hydrocarbon group containing a heteroatom, a perfluoroalkyl group or a nitro group;

[0037] R 4 represents a group selected from an alkylene group, a cycloalkylene group or a phenylene group;

[0038] X represents a group selected from a halogen atom, an acetate group or a trifluoromethylsulfonate group;

[0039] b) a halohydrin reagent in at least one solvent; and

[0040] c) at least one base.

[0041] Preferably, in the metal complex in a), M represents a transition metal atom selected from chromium, cobalt or iron. More preferably, M is a chromium metal atom.

[0042] In one aspect of the present invention, in the metal complex in a), R 1 , R 2 and R 3 represents a group independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an alkynyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amine group, a phenyl group, a benzyl group, a cycloalkyl group containing a heteroatom, a perfluoroalkyl group or a nitro group.

[0043] In one aspect of the present invention, in the metal complex in a), R 1 , R 2 and R 3represents a group independently selected from (but not limited to) a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a methoxy group, an ethoxy group, an isopropoxy group, a n-butoxy group, a tert-butoxy group, a phenyl group, a benzyl group, a trifluoromethyl group or a nitro group. Preferably, in the metal complex in a), R 1 , R 2 and R 3 A hydrogen atom.

[0044] In one aspect of the present invention, in the metal complex in a), R 4 represents a group selected from an alkylene group having 2 to 3 carbon atoms, a cycloalkylene group having 6 carbon atoms, or a phenylene group.

[0045] In one aspect of the present invention, in the metal complex in a), R 4 represents a group selected from (but not limited to) ethylene, 1,3-propylene, 1,2-cyclohexylene or 1,2-phenylene. Preferably, in the metal complex in a), R 4 represents a group selected from 1,2-phenylene.

[0046] In one aspect of the present invention, in the metal complex in a), X represents a group selected from (but not limited to) a chlorine atom, a bromine atom, an iodine atom, an acetate group or a trifluoromethylsulfonate group.

[0047] In one aspect of the present invention, the metal complex in a) is selected from N-N'-bis(ethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(ethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(ethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(ethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride,

[0048] N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl,5-tert-butylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, 5-trifluoromethylethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-methoxyethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-nitrosalicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-chloroethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride,

[0049] N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-propane-1,3-diamino metal(III) chloride 1,3-diaminometal(III) chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-trifluoromethylethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-methoxyethylidene salicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-nitrosalicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-chloroethylidene salicylidene)-propane-1,3-diaminometal(III)chloride,

[0050] N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, 5-trifluoromethylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methoxyethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-nitrosalicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-chloroethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-methoxyethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-nitrosalicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-chloroethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride,

[0051] N-N'-bis(3,5-di-tert-butylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-trifluoromethylethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-methoxyethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-nitrosalicylidene)-cyclohexane-1,2-diaminometal(III) chloride or N-N'-bis(3-methyl, 5-chloroethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride.

[0052] In one aspect of the present invention, the metal complex in a) can be synthesized by a reaction between a metal salt precursor and N-N'-bis(ethylene salicylidene)-diamine ligand and its derivatives, wherein the molar ratio of the reaction between the metal salt and the ligand is in the range of 1:1 to 1:2.

[0053] In one aspect of the present invention, the chromium metal salt precursor of the metal complex in a) of the present invention can be selected from (but not limited to) chromium (III) chloride (CrCl 3 ), chromium(III) chloride (CrCl 3 (THF)3 ), chromium(II) chloride (CrCl 2 ), chromium(III) chloride hexahydrate (CrCl 3 6H 2 O), chromium (III) bromide (CrBr 3 ), chromium (III) iodide (CrI 3 ), chromium(III) acetate (Cr(C 2 H 3 O 2 ) 3 ) or chromium(III) trifluoromethanesulfonate (Cr(CF 3 SO 3 ) 3 Preferably, the chromium metal salt precursor of the metal complex in a) of the present invention is selected from tetrahydrofuran chromium (III) chloride (CrCl 3 (THF) 3 ) or chromium(II) chloride (CrCl 2 ).

[0054] In one aspect of the present invention, the cobalt metal salt precursor of the metal complex in a) of the present invention can be selected from (but not limited to) cobalt (II) chloride (CoCl 2 ), cobalt(II) chloride hexahydrate (CoCl 2 6H 2 O), cobalt(II) bromide (CoBr 2 ), cobalt(II) iodide (CoI 2 ), cobalt(II) acetate (Co(CH 3 CO 2 ) 2 ) or cobalt(II) trifluoromethanesulfonate (Co(CF 3 SO 3 ) 2 Preferably, the cobalt metal salt precursor of the metal complex in a) of the present invention is selected from cobalt (II) chloride (CoCl 2 ).

[0055] In one aspect of the present invention, the iron metal salt precursor of the metal complex in a) of the present invention can be selected from (but not limited to) iron (III) chloride (FeCl 3 ), iron(III) chloride hexahydrate (FeCl 3 6H 2 O), iron(III) bromide (FeBr 3 ), iron(III) iodide (FeI 3 ), iron(III) acetate (Fe(C 2 H 3 O 2 )3 ) or iron(III) trifluoromethanesulfonate (Fe(CF 3 SO 3 ) 3 Preferably, the iron metal salt precursor of the metal complex in a) of the present invention is selected from iron (III) chloride (FeCl 3 ).

[0056] In one aspect of the present invention, the N-N'-bis(ethylene salicylidene)-diamine ligand and its derivatives are selected from (but not limited to) N-N'-bis(ethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(ethylene salicylidene)-propane-1,3-diamine, N-N'-bis(ethylene salicylidene)-benzene-1,2-diamine, N-N'-bis(ethylene salicylidene)-cyclohexane-1,2-diamine,

[0057] N-N'-bis(3,5-di-tert-butylethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(3,5-dimethylethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-methylethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(5-methylethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-tert-butylethylene salicylidene)-ethane-1,2-diamine 1,2-diamine, N-N'-bis(5-tert-butylethylidene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-ethane-1,2-diamine, 5-trifluoromethylethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methoxyethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-nitrosalicylidene)-ethane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-chloroethylene salicylidene)-ethane-1,2-diamine, N-N' -Bis(3-methyl, 5-trifluoromethylethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-methyl, 5-methoxyethylene salicylidene)-ethane-1,2-diamine, N-N'-bis(3-methyl, 5-nitrosalicylidene)-ethane-1,2-diamine, N-N'-bis(3-methyl, 5-chloroethylene salicylidene)-ethane-1,2-diamine,

[0058] N-N'-bis(3,5-di-tert-butylethylene salicylidene)-propane-1,3-diamine, N-N'-bis(3,5-dimethylethylene salicylidene)-propane-1,3-diamine, N-N'-bis(3-methylethylene salicylidene)-propane-1,3-diamine, N-N'-bis(5-methylethylene salicylidene)-propane-1,3-diamine, N-N'-bis(3-tert-butylethylene salicylidene)-propane-1,3-diamine 1,3-diamine, N-N'-bis(5-tert-butylethylidene salicylidene)-propane-1,3-diamine, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-propane-1,3-diamine, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-propane-1,3-diamine, N-N'-bis(3-tert-butyl, 5-trifluoromethylethylidene salicylidene)-propane-1,3-diamine, N-N'-bis(3-tert-butyl, 5-methoxyethylidene salicylidene)-propane-1,3-diamine, N-N'-bis(3-tert-butyl, 5-nitrosalicylidene)-propane-1,3-diamine, N-N'-bis(3-tert-butyl, 5-chloroethylidene salicylidene)-propane-1,3-diamine, N-N' -Bis(3-methyl, 5-trifluoromethylethylene salicylidene)-propane-1,3-diamine, N-N'-bis(3-methyl, 5-methoxyethylene salicylidene)-propane-1,3-diamine, N-N'-bis(3-methyl, 5-nitrosalicylidene)-propane-1,3-diamine, N-N'-bis(3-methyl, 5-chloroethylene salicylidene)-propane-1,3-diamine,

[0059] N-N'-bis(3,5-di-tert-butylethylene salicylidene)-benzene-1,2-diamine, N-N'-bis(3,5-dimethylethylene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-methylethylene salicylidene)-benzene-1,2-diamine, N-N'-bis(5-methylethylene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-tert-butylethylene salicylidene)-benzene-1,2-diamine 1,2-diamine, N-N'-bis(5-tert-butylethylidene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-benzene-1,2-diamine, 5-trifluoromethylethylidene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methoxyethylidene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-tert-butyl, 5-nitrosalicylidene)-benzene-1,2-diamine, N-N'-bis(3-tert-butyl, 5-chloroethylidene salicylidene)-benzene-1,2-diamine, N-N' -Bis(3-methyl, 5-trifluoromethylethylene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-methyl, 5-methoxyethylene salicylidene)-benzene-1,2-diamine, N-N'-bis(3-methyl, 5-nitrosalicylidene)-benzene-1,2-diamine, N-N'-bis(3-methyl, 5-chloroethylene salicylidene)-benzene-1,2-diamine,

[0060] N-N'-bis(3,5-di-tert-butylethylene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3,5-dimethylethylene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-methylethylene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(5-methylethylene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-tert-butylethylene salicylidene)-cyclohexane-1,2-diamine 1,2-diamine, N-N'-bis(5-tert-butylethylidene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-trifluoromethylethylidene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-methoxyethylidene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-nitrosalicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-tert-butyl, 5-chloroethylidene salicylidene)-cyclohexane-1,2-diamine, N-N' -Bis(3-methyl, 5-trifluoromethylethylene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-methyl, 5-methoxyethylene salicylidene)-cyclohexane-1,2-diamine, N-N'-bis(3-methyl, 5-nitrosalicylidene)-cyclohexane-1,2-diamine or N-N'-bis(3-methyl, 5-chloroethylene salicylidene)-cyclohexane-1,2-diamine.

[0061] In one aspect of the present invention, the halohydrin reagent in b) is a halogen compound selected from the group consisting of 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 2 ), bromine (Br 2 ) or a mixture thereof. Preferably, the halohydrin reagent in b) is a halogen compound selected from N-bromosuccinimide

[0062] In one aspect of the present invention, the halohydrin reagent in b) further comprises an oxidizing agent selected from the group consisting of potassium persulfate (K 2 S 2 O 8 ), hydrogen peroxide (H 2 O 2 ), tert-butyl hydroperoxide, calcium hypochlorite (Ca(OCl) 2 ), benzoyl peroxide, potassium nitrate (KNO3 ) or a mixture thereof.

[0063] In one aspect of the present invention, at least one solvent is selected from (but not limited to) water, acetone, dichloromethane, hexane, benzene, toluene, dimethylformamide, acetonitrile or a mixture thereof. Preferably, the solvent is a mixture of water and acetone.

[0064] In one aspect of the present invention, at least one base is selected from potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), sodium bicarbonate (NaHCO 3 ), cesium carbonate (Ce 2 CO 3 ), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or a mixture thereof.

[0065] In one aspect of the present invention, the present invention relates to a method comprising: 2 A method for producing a cyclic carbonate from olefins, the method comprising reacting the above catalyst composition with CO 2 and contacting with a mixture of olefins.

[0066] In another aspect of the present invention, the present invention relates to a method comprising: 2 A method for preparing a cyclic carbonate from olefins, the method comprising the following steps:

[0067] i) contacting an olefin with a halohydrin reagent in at least one solvent; and

[0068] ii) subjecting the mixture obtained in step i) and CO 2 and at least one base are contacted with a metal complex catalyst selected from the metal complexes described above.

[0069] In one aspect of the present invention, the metal complex catalyst further comprises an organic compound selected from the group consisting of a nitrogen-containing compound, a quaternary ammonium salt compound or an iminium salt compound as a co-catalyst.

[0070] In one aspect of the present invention, the metal complex catalyst further comprises an organic compound as a co-catalyst selected from (but not limited to) the following: 4-dimethylaminopyridine (DMAP), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), tetrabutylammonium iodide (TBAI), imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine)imine bromide, bis(triphenylphosphine)imine chloride, bis(triphenylphosphine)imine iodide or a mixture thereof.

[0071] In one aspect of the present invention, the olefin is selected from ethylene, propylene, butene, 1,4-butadiene, styrene, 1-hexene or 1-octene. Preferably, the olefin is ethylene.

[0072] In one aspect of the present invention, the halohydrin reagent in step i) is a halogen compound selected from the group consisting of 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 2 ), bromine (Br 2 ) or a mixture thereof. Preferably, the halohydrin reagent in step i) is a halogen compound selected from N-bromosuccinimide.

[0073] In one aspect of the present invention, the halohydrin reagent in step i) further comprises an oxidizing agent selected from the group consisting of potassium persulfate (K 2 S 2 O 8 ), hydrogen peroxide (H 2 O 2 ), tert-butyl hydroperoxide, calcium hypochlorite (Ca(OCl) 2 ), benzoyl peroxide, potassium nitrate (KNO 3 ) or a mixture thereof.

[0074] In one aspect of the present invention, the at least one solvent in step i) is selected from water, acetone, dichloromethane, hexane, benzene, toluene, dimethylformamide, acetonitrile or a mixture thereof. Preferably, the solvent in step i) is a mixture of water and acetone.

[0075] In one aspect of the present invention, the at least one base in step ii) is selected from potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), sodium bicarbonate (NaHCO 3 ), cesium carbonate (Ce 2 CO 3 ), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or a mixture thereof.

[0076] In one aspect of the present invention, step ii) is carried out in the presence of an organic solvent selected from the group consisting of dichloromethane, hexane, benzene, toluene, dimethylformamide or a mixture thereof.

[0077] 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.

[0078] In one aspect of the present invention, the molar ratio of the metal complex to the olefin is in the range of 1:10 to 1:10000, and the CO 2 The pressure ranges from 15 psi to 600 psi.

[0079] According to the present invention, CO 2 The preparation of cyclic carbonate with olefin may further include a drying step (if necessary), wherein the step may be selected from but not limited to stirring drying or vacuum drying and the like.

[0080] In one aspect, the process of producing CO according to the present invention can be carried out in a reactor. 2 The invention relates to a method for producing cyclic carbonates by using olefins, but the reactor is not limited to a fixed bed reactor. The operation can be carried out in a batch or continuous manner.

[0081] The following examples are only used to illustrate one aspect of the present invention and are not intended to limit the scope of the present invention in any way.

[0082] Example 1: Synthesis of N-N'-bis(ethylene salicylidene)-diamine ligand and its derivatives used in the synthesis of metal complex catalyst containing N-N'-bis(ethylene salicylidene)-diamine ligand

[0083] Synthesis of ligand used in the synthesis of catalyst A

[0084] An ethanol solution of 7-hydroxy-1-indanone with a concentration of 0.67M was prepared by dissolving 0.30 g (2 mmol) of 7-hydroxy-1-indanone in 3 mL of ethanol. Then, 1,2-ethylenediamine was added to the solution. The molar ratio of 7-hydroxy-1-indanone to 1,2-ethylenediamine was 2:1. Then, about 1 to 2 drops of acetic acid were added. The resulting mixture was heated under stirring until refluxed for 48 hours. Then, the resulting mixture was filtered to separate the solid. The resulting solid was washed 3 times with 10 mL of ether. N-N'-bis(ethylene salicylidene)-ethane-1,2-diamine ligand was obtained as a yellow solid.

[0085] Synthesis of ligand used in synthesis of catalyst B

[0086] The synthesis of the ligand used in the synthesis of Catalyst B was prepared in the same manner as the synthesis of the ligand used in the synthesis of Catalyst A.

[0087] Synthesis of ligand used in the synthesis of catalyst C

[0088] An ethanol solution of 4,6-di-tert-butyl-7-hydroxy-2,3-dihydro-1-indanone with a concentration of 0.67M was prepared by dissolving 0.52g (2mmol) of 4,6-di-tert-butyl-7-hydroxy-2,3-dihydro-1-indanone in 3mL of ethanol. Then, 1,2-ethylenediamine was added to the solution. The molar ratio of 4,6-di-tert-butyl-7-hydroxy-2,3-dihydro-1-indanone to 1,2-ethylenediamine was 2:1. Then, about 1 to 2 drops of acetic acid were added. The resulting mixture was heated under stirring until refluxed for 48 hours. Then, the resulting mixture was filtered to separate the solid. The resulting solid was washed 3 times with 10mL of ether. N-N'-bis(3,5-di-tert-butylethylene salicylidene)-ethane-1,2-diamine ligand was obtained as a yellow solid.

[0089] Synthesis of ligand used in the synthesis of catalyst D

[0090] An ethanol solution of 7-hydroxy-1-indanone with a concentration of 0.67M was prepared by dissolving 0.30 g (2 mmol) of 7-hydroxy-1-indanone in 3 mL of ethanol. Then, 1,2-phenylenediamine was added to the solution. The molar ratio of 7-hydroxy-1-indanone to 1,2-phenylenediamine was 2:1. Then, about 1 to 2 drops of acetic acid were added. The resulting mixture was heated under stirring until refluxed for 48 hours. Then, the resulting mixture was filtered to separate the solid. The resulting solid was washed 3 times with 10 mL of ether. N-N'-bis(ethylene salicylidene)-benzene-1,2-diamine ligand was obtained as a yellow solid.

[0091] Example 2: Synthesis of Metal Complexes Containing N-N'-Bis(ethylene salicylidene)-diamine Ligands and Derivatives thereof

[0092] Synthesis of Catalyst A

[0093] A toluene solution of N-N'-bis(ethylene salicylidene)-ethane-1,2-diamine ligand with a concentration of 0.062 M was prepared by dissolving 0.20 g (0.62 mmol) of N-N'-bis(ethylene salicylidene)-ethane-1,2-diamine ligand in 10 mL of toluene. Then, 0.10 g (0.62 mmol) of iron(III) chloride (FeCl) and 0.10 g (0.62 mmol) of iron(III) chloride (FeCl) were mixed. 3 ) and triethylamine. The molar ratio of N-N'-bis(ethylene salicylidene)-ethane-1,2-diamine ligand to iron(III) chloride and triethylamine is 1:1:2. Then, the resulting mixture is stirred and heated at a temperature of 100°C in a nitrogen atmosphere until reflux for 12 hours. The resulting mixture is filtered through celite. Then, the resulting solution is evaporated under vacuum. Catalyst A is obtained as a reddish brown solid.

[0094] Synthesis of Catalyst B

[0095] A tetrahydrofuran solution of N-N'-bis(ethylene salicylidene)-ethane-1,2-diamine ligand having a concentration of 0.031 M was prepared by dissolving 0.10 g (0.31 mmol) of N-N'-bis(ethylene salicylidene)-ethane-1,2-diamine ligand in 10 mL of tetrahydrofuran. Then, 0.015 g (0.62 mmol) of sodium hydride was mixed into the solution and stirred at room temperature for 1 hour. Then, the resulting mixture was mixed with 0.12 g (0.31 mmol) of tetrahydrofuran chromium (III) chloride (CrCl 3 (THF) 3 ) were mixed. The molar ratio of N-N'-bis(ethylene salicylidene)-ethane-1,2-diamine ligand to tetrahydrofuran chromium (III) chloride and sodium hydride was 1:1:2. Then, the resulting mixture was stirred at room temperature for 12 hours in a nitrogen atmosphere. The resulting mixture was filtered. The resulting solid was washed with a saturated sodium chloride solution and water, respectively. Then, the resulting solid was dried under vacuum conditions. Catalyst B was obtained as a light brown solid.

[0096] Synthesis of Catalyst C

[0097] A tetrahydrofuran solution of N-N'-bis(3,5-di-tert-butylethylene salicylidene)-ethane-1,2-diamine ligand having a concentration of 0.018 M was prepared by dissolving 0.10 g (0.18 mmol) of N-N'-bis(3,5-di-tert-butylethylene salicylidene)-ethane-1,2-diamine ligand in 10 mL of tetrahydrofuran. Then, 0.0088 g (0.37 mmol) of sodium hydride was mixed into the solution and stirred at room temperature for 1 hour. Then, the resulting mixture was mixed with 0.68 g (0.18 mmol) of tetrahydrofuran chromium (III) chloride (CrCl 3 (THF) 3 ). The molar ratio of N-N'-bis(3,5-di-tert-butylethylene salicylidene)-ethane-1,2-diamine ligand to tetrahydrofuran chromium (III) chloride and sodium hydride is 1:1:2. Then, the resulting mixture is stirred at room temperature for 12 hours in a nitrogen atmosphere. The resulting mixture is filtered. The resulting solid is washed with a saturated sodium chloride solution and water, respectively. Then, the resulting solid is dried under vacuum conditions. Catalyst C is obtained as a light brown solid.

[0098] Synthesis of Catalyst D

[0099] A tetrahydrofuran solution of N,N'-bis(ethylene salicylidene)-benzene-1,2-diamine ligand having a concentration of 0.027 M was prepared by dissolving 0.10 g (0.27 mmol) of N,N'-bis(ethylene salicylidene)-benzene-1,2-diamine ligand in 10 mL of tetrahydrofuran. Then, 0.013 g (0.54 mmol) of sodium hydride was mixed into the solution and stirred at room temperature for 1 hour. Then, the resulting mixture was mixed with 0.10 g (0.27 mmol) of tetrahydrofuran chromium (III) chloride (CrCl 3 (THF) 3 ) were mixed. The molar ratio of N-N'-bis(ethylene salicylidene)-benzene-1,2-diamine ligand: tetrahydrofuran chromium (III) chloride: sodium hydride was 1:1:2. Then, the resulting mixture was stirred at room temperature for 12 hours in a nitrogen atmosphere. The resulting mixture was filtered. The resulting solid was washed with a saturated sodium chloride solution and water, respectively. Then, the resulting solid was dried under vacuum conditions. Catalyst D was obtained as a light brown solid.

[0100] Example 3: CO 2 Preparation of cyclic carbonates by reaction between olefins and

[0101] The metal complex catalysts according to the invention comprising N-N'-bis(ethylene salicylidene)-diamine ligands and derivatives thereof (the catalysts according to the invention are catalysts A, B, C and D) were tested for the reaction of CO 2 Ability to produce cyclic carbonates through reactions with olefins:

[0102] The catalyst according to the present invention is used under the condition that a halogen compound is used as a halohydrin reagent and further contains an oxidizing agent. Capability test for manufacturing cyclic carbonates

[0103] The ability of the metal complex catalyst comprising N-N'-bis(ethylene salicylidene)-diamine ligand and its derivatives according to the present invention to produce cyclic carbonate under the conditions of a halogen compound as a halohydrin reagent and further comprising an oxidant can be tested according to the following steps.

[0104] Step i):

[0105] 1 mmol of olefin, 1 mmol of halogen compound (sodium iodide or sodium bromide), 1 mmol of oxidant (potassium persulfate) and 2 mL of water solvent are added to the reactor. The reactor is heated at a temperature of 60° C. for 2 to 5 hours; and

[0106] Step ii):

[0107] About 4.06mg to 7.30mg of metal complex catalyst, 1.30mg of organic compound (4-dimethylaminopyridine) as cocatalyst, 1mmol of alkali (potassium carbonate) and 2mL of organic solvent (dimethylformamide) are added in the reactor containing the mixture of step i).Then, with the pressure of 300psi, carbon dioxide gas is added in the reactor.The reactor is heated at a temperature of 60 ℃ for 1 hour to 5 hours.After reaching the reaction time, the reactor temperature is reduced to room temperature.The product gained is a cyclic carbonate, which can be identified by NMR spectrum technology.

[0108] The catalyst according to the present invention is used to produce cyclic carbonate under the condition that halogen compound is used as halohydrin reagent. Ability Test

[0109] The ability of the metal complex catalyst comprising N-N'-bis(ethylene salicylidene)-diamine ligand and its derivatives according to the present invention to produce cyclic carbonate under the condition of a halogen compound as a halohydrin reagent can be tested according to the following steps.

[0110] Step i):

[0111] 1 mmol of olefin, 1 mmol of halogen compound (N-bromosuccinimide (NBS)), 2 mL of acetone solvent and 2 mL of water solvent were added to the reactor. The reactor was heated at a temperature of 40° C. for 2 hours; and

[0112] Step ii):

[0113] About 4.06mg to 7.30mg of metal complex catalyst, 1.30mg of organic compound (4-dimethylaminopyridine) as cocatalyst and 1mmol of alkali (potassium carbonate) are added to the reactor containing the mixture of step i).Then, with the pressure of 300psi, carbon dioxide gas is added to the reactor.The reactor is heated at a temperature of 60 ℃ for 2 hours.After reaching the reaction time, the reactor temperature is reduced to room temperature.The product gained is a cyclic carbonate, which can be identified by NMR spectrum technology.

[0114] Under the condition that a halogen compound is used as a halohydrin reagent and an oxidant is further contained, the catalyst according to the present invention Test on the ability of one-step preparation of cyclic carbonates

[0115] Under the condition that a halogen compound is used as a halohydrin reagent and an oxidant is further contained, the ability test of the metal complex catalyst comprising N-N'-bis(ethylene salicylidene)diamine ligand and its derivatives according to the present invention to produce cyclic carbonate in one step can be carried out according to the following steps.

[0116] The metal complex catalyst of the organic compound (4-dimethylaminopyridine) as a cocatalyst comprising 1.30mg of 1mmol alkali (potassium carbonate) and about 4.06mg to 7.30mg of 1mmol alkali, 1mmol halogen compound (sodium iodide), 1mmol oxidant (potassium persulfate), 2mL water solvent, 1mL dimethylformamide solvent, 1mmol is added in the reactor.Then, with the pressure of 300psi, carbon dioxide gas is added in the reactor.The reactor is heated 10 hours at 60 ℃ temperature.After reaching the reaction times, the reactor temperature is reduced to room temperature.The product gained is a cyclic carbonate, which can be identified by NMR spectrum technology.

[0117] The structure of the catalyst according to the invention

[0118] The structures of the synthesized metal complex catalysts containing N-N'-bis(ethylene salicylidene)-diamine ligands and their derivatives are shown in Table 1.

[0119] Table 1: Structure of the metal complex catalyst comprising N-N'-bis(ethylene salicylidene)-diamine ligand and its derivatives according to the present invention

[0120]

[0121] Formation of cyclic carbonates

[0122] Tables 2 and 3 show the effects of the metal complex catalysts (catalysts A, B, C and D) comprising N-N'-bis(ethylene salicylidene)-diamine ligands and their derivatives according to the present invention on the reaction of CO with CO compared to non-catalytic conditions. 2 The catalytic ability to form cyclic carbonates with olefins.

[0123] Table 2: Catalytic ability of metal complex catalysts containing N-N'-bis(ethylene salicylidene)-diamine ligands and their derivatives according to the present invention for the formation of cyclic carbonates

[0124]

[0125] a The amount of the metal complex catalyst is 0.5 mol%

[0126] b The amount of the metal complex catalyst is 0.1 mol%

[0127] Table 3: Catalytic ability of metal complex catalysts containing N-N'-bis(ethylene salicylidene)-diamine ligands and their derivatives according to the present invention for the formation of cyclic carbonates

[0128]

[0129] Best Mode for Preferred Embodiments of the Invention

[0130] As provided in the description of the present invention is the best mode or preferred embodiment of the present invention.

Claims

1. A catalyst composition for producing a cyclic carbonate from CO2 and an olefin, wherein the catalyst composition comprises: a) a metal complex as shown in structure (I): in, M represents a transition metal atom selected from chromium, cobalt or iron; R1, R2 and R3 represent a group independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an alkynyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, a trifluoromethyl group or a nitro group; R4 represents a group selected from an alkylene group having 2 to 3 carbon atoms, a cycloalkylene group having 6 carbon atoms or a phenylene group; X represents a group selected from a halogen atom, an acetate group or a trifluoromethylsulfonate group; b) a halohydrin reagent in at least one solvent, wherein the halohydrin reagent is selected from sodium iodide, sodium bromide, sodium chloride, potassium iodide, potassium bromide, tetrabutylammonium iodide, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, iodine, bromine or mixtures thereof; and c) at least one base; Wherein, the halohydrin reagent in b) further comprises an oxidant selected from the following: potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, calcium hypochlorite, benzoyl peroxide, potassium nitrate or a mixture thereof.

2. The catalyst composition according to claim 1, wherein in the metal complex in a), M is a chromium metal atom.

3. The catalyst composition according to claim 1, wherein in the metal complex in a), R1, R2 and R3 represent a group independently selected from a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a methoxy group, an ethoxy group, an isopropoxy group, a n-butoxy group, a tert-butoxy group, a phenyl group, a benzyl group, a trifluoromethyl group or a nitro group.

4. The catalyst composition according to claim 1, wherein in the metal complex in a), R1, R2 and R3 are hydrogen atoms.

5. The catalyst composition according to claim 1, wherein in the metal complex in a), R4 represents a group selected from ethylene, 1,3-propylene, 1,2-cyclohexylene or 1,2-phenylene.

6. The catalyst composition according to claim 5, wherein in the metal complex in a), R4 is 1,2-phenylene.

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

8. The catalyst composition according to claim 1, wherein the metal complex in a) is selected from N-N'-bis(ethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(ethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(ethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(ethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl,5-tert-butylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, 5-trifluoromethylethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-methoxyethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-nitrosalicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-chloroethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-propane-1,3-diamino metal(III) chloride 1,3-diaminometal(III) chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-trifluoromethylethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-methoxyethylidene salicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-nitrosalicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-chloroethylidene salicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, 5-trifluoromethylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methoxyethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-nitrosalicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-chloroethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-methoxyethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-nitrosalicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-chloroethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3,5-di-tert-butylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-trifluoromethylethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-methoxyethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-nitrosalicylidene)-cyclohexane-1,2-diaminometal(III) chloride or N-N'-bis(3-methyl, 5-chloroethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride.

9. The catalyst composition of claim 1, wherein the halohydrin reagent is N-bromosuccinimide.

10. The catalyst composition of claim 1, wherein the at least one solvent is selected from water, acetone, dichloromethane, hexane, benzene, toluene, dimethylformamide, acetonitrile or mixtures thereof.

11. The catalyst composition according to claim 10, wherein the solvent is a mixture of water and acetone.

12. The catalyst composition of claim 1, wherein the at least one base is selected from potassium carbonate, sodium carbonate, sodium bicarbonate, cesium carbonate, 1,8-diazabicyclo[5.4.0]undec-7-ene, or mixtures thereof.

13. A method for producing a cyclic carbonate from CO2 and an olefin, the method comprising the following steps: i) contacting an olefin with a halohydrin reagent in at least one solvent, wherein the halohydrin reagent is selected from sodium iodide, sodium bromide, sodium chloride, potassium iodide, potassium bromide, tetrabutylammonium iodide, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, iodine, bromine or a mixture thereof; wherein the halohydrin reagent in step i) further comprises an oxidant selected from the group consisting of potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, calcium hypochlorite, benzoyl peroxide, potassium nitrate or a mixture thereof; and ii) contacting the mixture obtained in step i), CO2 and at least one base with a metal complex catalyst represented by structure (I): in, M represents a transition metal atom selected from chromium, cobalt or iron; R1, R2 and R3 represent a group independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an alkynyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, a trifluoromethyl group or a nitro group; R4 represents a group selected from an alkylene group having 2 to 3 carbon atoms, a cycloalkylene group having 6 carbon atoms or a phenylene group; and X represents a group selected from a halogen atom, an acetate group or a trifluoromethylsulfonate group. 14 . The method for producing a cyclic carbonate according to claim 13 , wherein in the metal complex catalyst, M is a chromium metal atom.

15. The method for manufacturing cyclic carbonate according to claim 13, wherein in the metal complex catalyst, R1, R2 and R3 represent a group independently selected from hydrogen atom, chlorine atom, methyl, ethyl, isopropyl, n-butyl, tert-butyl, methoxyl group, ethoxyl group, isopropoxy, n-butoxy, tert-butoxy, phenyl, benzyl, trifluoromethyl or nitro.

16. The method for producing a cyclic carbonate according to claim 13, wherein in the metal complex catalyst, R1, R2 and R3 are hydrogen atoms.

17. The method for producing a cyclic carbonate according to claim 13, wherein in the metal complex catalyst, R4 represents a group selected from ethylene, 1,3-propylene, 1,2-cyclohexylene or 1,2-phenylene.

18. The method for producing a cyclic carbonate according to claim 17, wherein in the metal complex catalyst, R4 is 1,2-phenylene.

19. The method for producing a cyclic carbonate according to claim 13, wherein in the metal complex catalyst, X represents a group selected from a chlorine atom, a bromine atom, an iodine atom, an acetate group or a trifluoromethylsulfonate group.

20. The method for producing a cyclic carbonate according to claim 13, wherein the metal complex catalyst is selected from N-N'-bis(ethylene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis(ethylene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis(ethylene salicylidene)-benzene-1,2-diamino metal (III) chloride, N-N'-bis(ethylene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-ethane-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl,5-tert-butylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methylethylidene salicylidene)-ethane-1,2-diaminometal(III)chloride, 5-trifluoromethylethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-ethane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-ethane-1,2-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-methoxyethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-nitrosalicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-bis(3-methyl, 5-chloroethylidene salicylidene)-ethane-1,2-diamino metal(III) chloride, N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-propane-1,3-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-propane-1,3-diamino metal(III) chloride 1,3-diaminometal(III) chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-propane-1,3-diaminometal(III) chloride, N-N'-bis(3-tert-butyl, 5-trifluoromethylethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-propane-1,3-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-propane-1,3-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-methoxyethylidene salicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-nitrosalicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-chloroethylidene salicylidene)-propane-1,3-diaminometal(III)chloride, N-N'-Bis(3,5-di-tert-butylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-benzene-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, 5-trifluoromethylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-methoxyethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-nitrosalicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl,5-chloroethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-methoxyethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-nitrosalicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-Bis(3-methyl, 5-chloroethylidene salicylidene)-benzene-1,2-diaminometal(III)chloride, N-N'-bis(3,5-di-tert-butylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3,5-dimethylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3-methylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(5-methylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, N-N'-bis(3-tert-butylethylene salicylidene)-cyclohexane-1,2-diamino metal(III) chloride, 1,2-diaminometal(III)chloride, N-N'-bis(5-tert-butylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-methyl, 5-tert-butylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-methylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III)chloride, N-N'-bis(3-tert-butyl, 5-trifluoromethylethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-methoxyethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-nitrosalicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N'-bis (3-tert-butyl, 5-chloroethylidene salicylidene)-cyclohexane-1,2-diamino metal (III) chloride, N-N' -Bis(3-methyl, 5-trifluoromethylethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-methoxyethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride, N-N'-bis(3-methyl, 5-nitrosalicylidene)-cyclohexane-1,2-diaminometal(III) chloride or N-N'-bis(3-methyl, 5-chloroethylidene salicylidene)-cyclohexane-1,2-diaminometal(III) chloride.

21. The method for producing a cyclic carbonate according to claim 13, wherein the metal complex catalyst further comprises an organic compound selected from nitrogen-containing compounds as a co-catalyst.

22. The method for producing a cyclic carbonate according to claim 21, wherein the nitrogen-containing compound is a quaternary ammonium salt compound or an imide salt compound.

23. The method for manufacturing cyclic carbonate according to claim 21, wherein the organic compound as a cocatalyst is selected from 4-dimethylaminopyridine, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, imidazolium bromide, imidazolium chloride, imidazolium iodide, bis(triphenylphosphine)imine bromide, bis(triphenylphosphine)imine chloride, bis(triphenylphosphine)imine iodide or a mixture thereof.

24. The method for producing a cyclic carbonate according to claim 13, wherein the olefin is selected from ethylene, propylene, butene, 1,4-butadiene, styrene, 1-hexene or 1-octene.

25. The method for producing a cyclic carbonate according to claim 24, wherein the olefin is ethylene.

26. The method for producing a cyclic carbonate according to claim 13, wherein the halohydrin reagent is N-bromosuccinimide.

27. The method for producing a cyclic carbonate according to claim 13, wherein the at least one solvent in step i) is selected from water, acetone, dichloromethane, hexane, benzene, toluene, dimethylformamide, acetonitrile or a mixture thereof.

28. The method for producing a cyclic carbonate according to claim 13 or 27, wherein the solvent in step i) is a mixture of water and acetone.

29. The method for producing a cyclic carbonate according to claim 13, wherein the at least one base in step ii) is selected from potassium carbonate, sodium carbonate, sodium bicarbonate, cesium carbonate, 1,8-diazabicyclo[5.4.0]undec-7-ene or a mixture thereof.

30. The method for producing a cyclic carbonate according to claim 13, wherein step ii) is performed in the presence of an organic solvent selected from the group consisting of dichloromethane, hexane, benzene, toluene, dimethylformamide, or a mixture thereof.

31. The method for producing a cyclic carbonate according to claim 13, wherein the temperature in step i) is in the range of 30°C to 80°C.

32. The method for producing a cyclic carbonate according to claim 13, wherein the temperature in step ii) is in the range of 50°C to 120°C.

33. The method for producing a cyclic carbonate according to claim 13, wherein a molar ratio of the metal complex to the olefin is in the range of 1:10 to 1:10000.

34. The method for producing cyclic carbonate according to claim 13, wherein the CO2 pressure in step ii) is in the range of 15 psi to 600 psi.

Images