Preparation method of a cyclic ethylene carbonate compound

Abstract

The present invention relates to the technical fields of organic synthesis and new material synthesis, and particularly relates to a preparation method of a cyclic ethylene carbonate that can be used as an additive for lithium ion battery electrolytes. The preparation method includes the following experimental steps: mixing an ethylene oxide compound shown by formula (II) with a polyoxometalate catalyst and a tetrabutyl halide, and reacting in a CO 2 atmosphere to obtain a cyclic ethylene carbonate shown by formula (I). The yield of the product can reach over 98% after single distillation, and the purity is over 99.0%.

Description

Technical Field

[0001] The present invention relates to the technical fields of organic synthesis and new material synthesis, and particularly relates to a preparation method of cyclic ethylene carbonate which can be used as an additive for lithium-ion battery electrolytes. Background Art

[0002] Carbonates are a type of organic solvents with relatively high boiling points. Due to their advantages such as good biodegradability, solubility, low toxicity, and low corrosiveness, they are widely used in many fields such as material synthesis, plastics, textiles, battery electrolytes, and metal extractants (Green Chem. 2010, 12, 1514). Carbonate compounds are also excellent additives for lithium-ion battery electrolytes. In recent years, with the rapid development of new energy vehicles and the energy storage industry, the market demand for carbonate products will increase rapidly.

[0003] The preparation methods of cyclic ethylene carbonate mainly include phosgene method, transesterification method, epoxy cycloaddition method, urea method, etc. Among them, directly catalytically cycloadding using epoxides such as propylene oxide (PO) and ethylene oxide (EO) and carbon dioxide (CO2) as raw materials to prepare carbonates such as PC and EC is regarded as an environmentally friendly and atom-economical process route. Currently, various different homogeneous and heterogeneous catalysts have been reported for CO 2The cycloaddition reaction with epoxides includes amides, tetradentate Schiff base metal complexes, organic polymers, nitrogen-containing heterocyclic quaternary ammonium salts, ionic liquids, etc. The catalysts used are as follows: (1) Amides. Patent CN100999514 reported that a homogeneous catalytic reaction system with amide RCONR'R" as the catalyst and water as the cocatalyst achieved the addition reaction of epoxides with carbon dioxide to synthesize cyclic carbonates. (2) Tetradentate Schiff base metal complexes. Patent CN101270113 reported the preparation of optically active cyclic carbonates by the cycloaddition reaction of racemic epoxides and carbon dioxide catalyzed by a chiral two-component catalyst. The main catalyst used was a chiral bidentate tetradentate Schiff base metal complex, and the cocatalyst used was a tetra-substituted tribromide or quaternary ammonium salt; the catalyst used in Patent CN103170365 was a tetradentate Schiff base aluminum complex, and the molecule contained more than one quaternary ammonium salt or quaternary phosphonium salt group. When chiral epoxides were used as reactants, the optical purity of the product was completely maintained. (3) Organic polymers. Patent CN107840954 reported that an ionic polymer catalyst was an organic polymer containing triazine groups and quaternary ammonium salt ionic groups, which could achieve efficient catalytic conversion of carbon dioxide to prepare cyclic carbonates under atmospheric pressure; Patent CN110746602 reported a metal cobalt porphyrin-based porous organic polymer as a catalyst for the cycloaddition reaction of carbon dioxide and cyclic carbonates. (4) Nitrogen-containing heterocyclic quaternary ammonium salts. The main catalyst in Patent CN108440487 was a nitrogen-containing heterocyclic quaternary ammonium salt, and the cocatalyst was an inorganic salt. In the absence of organic solvents, it catalyzed the cycloaddition reaction of carbon dioxide and cyclic carbonates, etc.

[0004] The preparation of cyclic carbonates by the cycloaddition reaction of carbon dioxide as a raw material and epoxides is an atom-economical green chemical reaction. However, there are many types of catalysts reported in the current literature and patents, and basically all of them have problems such as difficult catalyst synthesis, high cost, low efficiency, incomplete raw material conversion, high required temperature and pressure, and difficult catalyst recovery. Therefore, screening catalysts with mild reaction conditions, green and efficient, low cost, and easy to synthesize has important practical value for the current preparation of cyclic carbonate compounds by the cycloaddition reaction of carbon dioxide and epoxides. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an efficient, green, and environmentally friendly method for preparing ethylene carbonate, and also provide a new way to chemically utilize the greenhouse gas carbon dioxide resources. This method is suitable for large-scale industrial production and can achieve obvious economic and social benefits.

[0006] To achieve the purpose of this invention, the present invention adopts the following technical solutions:

[0007] The present invention provides a new method for preparing ethylene carbonate using a polyoxometalate (POMs) catalyst. The preparation method includes the following steps:

[0008] Mix the ethylene oxide compound shown in formula (II) with a polyoxometalate catalyst and a tetrabutyl halide, and react in a CO 2 atmosphere to obtain the ethylene carbonate shown in formula (I);

[0009] The chemical reaction formula is as follows:

[0010]

[0011] Wherein, R 1 、R 2 、R 3 、R 4 are independently selected from any one of H, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C6-C12 aryl, halogen, substituted or unsubstituted C1-C12 alkoxy, and C1-C12 alkylamine.

[0012] In some embodiments of the present invention, after the reaction is completed, the polyoxometalate (POMs) is recovered by filtration, and the filtrate is purified to obtain the ethylene carbonate shown in formula (I).

[0013] In some embodiments of the present invention, the reaction can be carried out continuously or intermittently in the presence or absence of an organic solvent; when a solvent is required for the reaction, the reaction can be carried out in an organic solvent; the solvent is selected from any one or a combination of at least two of dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, tetrahydrofuran, acetonitrile, dimethyl carbonate, etc.

[0014] In some embodiments of the present invention, R 1 、R 2 、R 3 、R 4 are independently selected from any one of H, C1-C4 alkyl, halogenated C1-C4 alkyl, substituted or unsubstituted C2-C5 alkenyl, substituted or unsubstituted C6-C12 aryl, halogen, and substituted or unsubstituted C1-C6 alkoxy.

[0015] In some embodiments of the present invention, R 1 、R 2 、R 3 、R 4 are independently selected from groups such as H, chloromethyl, bromomethyl, hydroxymethyl, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, vinyl, phenyl, fluorine, chlorine, or bromine.

[0016] In some embodiments of the present invention, the polyoxometalates (POMs) are selected from (NH 4 ) 3 [CoMo 6 O 18 (OH) 6 , (NH4) 3 [CrMo 6 O 18 (OH) 6 , (NH 4 ) 3 [FeMo 6 O 18 (OH) 6 , (NH 4 ) 4 [CuMo 6 O 18 (OH) 6 .5H 2 O, (NH 4 ) 2 [Mo 6 O 19 , (NH 4 ) 5 [IMo 6 O 24 and the like, or a combination of one or more of them.

[0017] In some embodiments of the present invention, the molar ratio of the polyoxometalate (POMs) catalyst to the epoxide represented by formula (II) is 0.0002 to 0.10:1.

[0018] In some embodiments of the present invention, the tetrabutyl halide is a combination of one or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, and tetrabutylphosphonium bromide.

[0019] In some embodiments of the present invention, the molar ratio of the tetrabutyl halide to the epoxide represented by formula (II) is 0.005 to 0.10:1.

[0020] In some embodiments of the present invention, the reaction temperature is 25 - 150 °C. Preferably, the reaction temperature is 25 - 100 °C.

[0021] In some embodiments of the present invention, the carbon dioxide pressure is 0.1 - 5.0 MPa. Preferably, the carbon dioxide pressure is 0.1 MPa - 2 MPa.

[0022] The purification operation by vacuum distillation includes: removing the solvent in the reaction system by atmospheric distillation to obtain a crude product, and then performing vacuum distillation treatment. The vacuum distillation temperature is 20 - 300 °C.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The preparation method of the cyclic ethylene carbonate compound of the present invention uses polyoxometalates (POMs) and tetrabutylammonium halide to catalyze the reaction of ethylene oxide compound with CO 2 to directly react to form a carbon cyclic ethylene carbonate compound. The preparation method is simple, the reaction conditions are mild, the process steps are few, and the yield is high, the product purity is high, there is no pollution, it is environmentally friendly, and the polyoxometalates (POMs) can be recycled and reused, greatly reducing the synthesis cost. The yield is as high as 98.8%, and the purity is as high as 99.9%. Detailed Embodiments

[0025] Hereinafter, embodiments of a method for preparing a cyclic ethylene carbonate specifically disclosed in the present application will be described in detail.

[0026] The inventors of the present invention have found through a large number of experiments that the ethylene oxide compound (Formula II) can be converted into cyclic ethylene carbonate (Formula I) by a catalytic method, and complete conversion can be achieved, and high-purity cyclic ethylene carbonate can be conveniently prepared, which can meet the requirements for high purity, quality and production capacity of cyclic ethylene carbonate when used as an additive for lithium ion battery electrolytes. On this basis, the present invention has been completed.

[0027] Term Definition

[0028] Unless otherwise specified, the following words, phrases and symbols used in this specification generally have the meanings described below.

[0029] Generally, the nomenclature used herein (e.g., IUPAC nomenclature) and the laboratory procedures described below (including those for cell culture, organic chemistry, analytical chemistry, pharmacology, etc.) are those well known and commonly used in the art. Unless otherwise defined, all scientific and technical terms used herein in connection with the present disclosure described herein have the same meaning as commonly understood by those skilled in the art. Additionally, in the claims and / or the specification, when the term "a" or "an" is used in conjunction with the term "comprising" or a noun, its meaning may be "one", but it is also consistent with the meanings of "one or more", "at least one" and "one or more than one". Similarly, the term "another" or "other" may mean at least a second or more.

[0030] It should be understood that whenever an aspect is described herein using the term "comprising" or "including", other similar aspects described by "consisting of" and / or "consisting essentially of" are also provided.

[0031] As used herein, the term "substituted or unsubstituted", used alone or in combination, means substituted with one or more substituents selected from the following: deuterium, halogen, cyano, nitro, hydroxy, mercapto, carbonyl, ester, imide, amino, phosphine oxide group, oxo, alkoxy, trifluoromethoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamino, aralkylamino, heteroarylamino, arylamino, arylphosphino and heteroaryl, acenaphthyl, or unsubstituted; or substituted with a substituent that connects two or more of the substituents exemplified above, or unsubstituted. For example, the "substituent that connects two or more substituents" may include biphenyl, i.e., biphenyl may be an aryl or a substituent that connects two phenyl groups.

[0032] As used herein, the term "alkyl", used alone or in combination, may be straight-chain or branched-chain, and the number of carbon atoms may be, for example, C1-C12, C1-C10, C1-C9, C1-C8, C1-C7, C1-C5, C1-C4, C1-C3, C1-C2, etc. By way of example, alkyl includes, but is not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. In the present disclosure, the "alkyl" is optionally substituted, and the substituting substituents are optionally selected from, for example, halogen (such as fluorine, chlorine, bromine or iodine), trifluoromethyl, hydroxy, cyano, C1-C3 alkoxy, deuterium, amino, mercapto, nitro, carbonyl, ester, oxo, imide, phosphine oxide group, trifluoromethoxy and any combination thereof.

[0033] As used herein, the term "halo C1-C4 alkyl" means that one or more hydrogen atoms in the alkyl are each replaced by a halogen atom. "Halo C1-C4 alkyl" includes, but is not limited to, -CF 3 , -CHF 2 , -CH 2 F, -CH 2 -CF 3 , -CH 2 -CHF 2 , -CH 2 -CH 2 F, --CH 2 CF 2 CF 2 H, -CH(CF 3 ) 2 , -CCl 3 , -CHCl2 , -CH 2 Cl, -CH 2 -CCl 3 , -CH 2 -CHCl 2 , -CH 2 -CH 2 Cl, etc. Here, the alkyl group is as defined above.

[0034] As used herein, the term "alkenyl" used alone or in combination includes straight-chain or branched alkenyl groups, the number of carbon atoms of which can be, for example, C2-C12, C2-C10, C3-C10, C2-C5, C2-C4, C2-C3, etc. By way of example, alkenyl includes, but is not limited to, vinyl, allyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. In the present disclosure, the "alkenyl" is an optionally substituted alkenyl. A substituted alkenyl means an alkenyl that is substituted one or more times (e.g., 1-4, 1-3, or 1-2 times) by a substituent, and the substituent can be, for example, a halogen (fluorine, chlorine, bromine, or iodine, etc.), trifluoromethyl, hydroxyl, cyano, C1-C3 alkoxy, C1-C3 alkyl, deuterium, amino, mercapto, nitro, carbonyl, ester group, oxo group, imide group, phosphine oxide group, trifluoromethoxy, and any combination thereof.

[0035] As used herein, the term "aryl" used alone or in combination refers to a monovalent carbocyclic aromatic group containing one or more fused rings, such as C6-C12, C6-C10 aryl, etc. The aryl group can be a monocyclic arylene or a polycyclic arylene. In some embodiments, the monocyclic aryl includes, but is not limited to, phenyl, biphenyl, etc. The polycyclic aryl includes, but is not limited to, naphthyl, etc. In the present disclosure, the "aryl" is an optionally substituted aryl. A substituted aryl means an aryl that is substituted one or more times (e.g., 1-4, 1-3, or 1-2 times) by a substituent, for example, the aryl is monosubstituted, disubstituted, or trisubstituted by the substituent, and the substituent is optionally selected from a halogen (fluorine, chlorine, bromine, or iodine, etc.), trifluoromethyl, hydroxyl, cyano, C1-C3 alkoxy, C1-C3 alkyl, deuterium, amino, mercapto, nitro, carbonyl, ester group, oxo group, imide group, phosphine oxide group, trifluoromethoxy, and any combination thereof.

[0036] As used herein, the term "halogen" used alone or in combination refers to fluorine, chlorine, bromine, or iodine.

[0037] As used herein, the term "alkoxy", used alone or in combination, refers to -O(alkyl). Optionally, the alkyl portion of the alkoxy may contain 1 to 6 (or 1 to 5, 1 to 4, or 1 to 3) carbon atoms. The alkoxy may include, for example, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 2-ethylbutoxy, and the like. In the present disclosure, the "alkoxy" is an optionally substituted alkoxy. A substituted alkoxy refers to an alkoxy that is substituted one or more times (e.g., 1 to 4, 1 to 3, or 1 to 2 times) by a substituent, such as an alkoxy that is mono-substituted, di-substituted, or tri-substituted by a substituent, where the substituent is optionally selected from, for example, a halogen (such as fluorine, chlorine, bromine, or iodine), trifluoromethyl, hydroxy, cyano, C1-C3 alkoxy, C1-C3 alkyl, deuterium, amino, mercapto, nitro, carbonyl, ester group, oxo group, imide group, phosphine oxide group, trifluoromethoxy, and any combination thereof.

[0038] As used herein, the term "alkylamino", used alone or in combination, may be, for example, methylamino, ethylamino, propylamino, isopropylamino, and the like.

[0039] As used herein, polyoxometalates (POMs) are produced by the condensation and dehydration of simple oxygen-containing salts under certain pH conditions. POMs obtained by the condensation and dehydration of only one oxygen-containing salt are called isopolyacids, while POMs formed by the dehydration between two or more oxygen-containing salts are called heteropolyacids. For example, it may be (NH 4 ) 3 [CoMo 6 O 18 (OH) 6 , (NH 4 ) 3 [CrMo 6 O 18 (OH) 6 , (NH 4 ) 3 [FeMo 6 O 18 (OH) 6 , (NH 4 ) 4 [CuMo 6 O 18 (OH) 6 .5H 2 O, (NH 4 ) 2 [Mo 6 O 19 , (NH 4 ) 5 [IMo6 O 24 etc.

[0040] The preparation method of the cyclic ethylene carbonate of the present invention is described below.

[0041] The present invention provides a preparation method of cyclic ethylene carbonate. The preparation route of the cyclic ethylene carbonate (Formula I) is as follows:

[0042] Mix the ethylene oxide compound shown in Formula (II) with a polyoxometalate and a tetrabutyl halide, and react in a CO 2 atmosphere to obtain the cyclic ethylene carbonate shown in Formula (I);

[0043] The chemical reaction formula is as follows:

[0044]

[0045] Among them, R 1 , R 2 , R 3 , R 4 are independently selected from any one of H, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C6-C12 aryl, halogen, and substituted or unsubstituted C1-C12 alkoxy.

[0046] In the present invention, further, R 1 , R 2 , R 3 , R 4 are independently selected from any one of C1-C12 alkyl, C2-C12 alkenyl, C6-C12 aryl, halogen, C1-C12 alkoxy, or C1-C12 alkylamino. Among them, C1-C12 means that the structure contains one carbon atom, two carbon atoms, three carbon atoms, etc., and so on, which will not be elaborated here.

[0047] In Formula (I) or (II) of the present invention, optionally, R 1 , R 2 , R 3 , R 4 are independently selected from H.

[0048] In Formula (I) or (II) of the present invention, R 1 , R 2 , R 3 , R 4 are independently selected from substituted or unsubstituted C1-C12 alkyl. In specific embodiments, R 1 , R 2 , R 3 , R 4Independently selected from substituted or unsubstituted (C1-C10, C1-C8, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2) alkyl. Further, R 1 , R 2 , R 3 , R 4 For example, can be independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, etc. Further, the alkyl can be substituted, and the substituents can be, for example, halogen (such as fluorine, chlorine, bromine or iodine), trifluoromethyl, hydroxyl, cyano, C1-C3 alkoxy, etc.

[0049] In the formula (I) or (II) of the present invention, R 1 , R 2 , R 3 , R 4 Independently selected from C2-C12 unsubstituted alkenyl. Optionally, R 1 , R 2 , R 3 , R 4 Each independently selected from substituted or unsubstituted (such as C2-C10, C2-C8, C2-C6, C2-C5, C2-C4, C2-C3) alkenyl, for example, can be vinyl, propenyl, 1-butenyl, 2-butenyl, etc. The alkenyl can be unsubstituted or substituted alkenyl, and the substituents can be, for example, halogen (such as fluorine, chlorine, bromine or iodine), trifluoromethyl, hydroxyl, cyano, C1-C3 alkoxy, etc.

[0050] In the formula (I) or (II) of the present invention, R 1 , R 2 , R 3 , R 4 Independently selected from substituted or unsubstituted C6-C12 aryl, for example, can be phenyl, naphthyl, biphenyl, etc. The aryl can be unsubstituted or substituted aryl, and the substituents can be, for example, halogen (such as fluorine, chlorine, bromine or iodine), trifluoromethyl, hydroxyl, cyano, C1-C3 alkoxy, etc.

[0051] In the formula (I) or (II) of the present invention, R 1 , R 2 , R 3 , R 4 Independently selected from substituted or unsubstituted C1-C12 alkoxy. Optionally, R 1 , R 2 , R 3 , R 4Independently selected from substituted or unsubstituted (C1-C10, C1-C8, C1-C6, C1-C5, C1-C4, C1-C3, or C1-C2) alkoxy groups. Unsubstituted C1-C12 alkoxy groups can be, for example, methoxy, ethoxy, propoxy, isopropoxy, etc. The alkoxy group can also be further substituted, and the substituents can be, for example, halogen (fluorine, chlorine, bromine, iodine, etc.), trifluoromethyl, hydroxyl, cyano, C1-C3 alkoxy groups, etc.

[0052] In formula (Ⅰ) or (Ⅱ) of the present invention, unsubstituted C1-C12 alkylamino groups can be, for example, methylamino, ethylamino, propylamino, isopropylamino, etc.

[0053] In formula (Ⅰ) or (Ⅱ) of the present invention, halogen can be, for example, fluorine, chlorine, bromine, iodine, etc.

[0054] In a preferred embodiment, R 1 , R 2 , R 3 , R 4 are independently selected from groups such as H, chloromethyl, bromomethyl, hydroxymethyl, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, vinyl, phenyl, fluorine, chlorine, or bromine.

[0055] More specifically, the cyclic ethylene carbonate shown in formula (Ⅰ) can be, for example, chloromethyl dioxolane-2-one, bromomethyl dioxolane-2-one, n-butyl dioxolane-2-one, phenyl dioxolane-2-one, 4-(hydroxymethyl)-1,3-dioxolan-2-one, trifluoromethyl dioxolane-2-one, 4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolan-2-one, etc.

[0056] In the method for preparing the cyclic ethylene carbonate provided by the present invention, the reaction of the present invention can be carried out in the presence or absence of a solvent. The reaction effects are similar. When the reaction is carried out in the presence of a solvent, the chemical reaction formula is:

[0057]

[0058] When the reaction is carried out in the presence of a solvent, the solvent is an organic solvent, and the solvent is selected from any one or a combination of at least two of dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, tetrahydrofuran, acetonitrile, dimethyl carbonate, etc.

[0059] In the method for preparing cyclic ethylene carbonate provided by the present invention, the molar ratio of the polyoxometalate (POMs) catalyst to the epoxide represented by formula (II) is 0.0002 to 0.10:1. In specific embodiments, the molar ratio of the polyoxometalate to the epoxide represented by formula (II) can also be 0.0002 to 0.01:1, 0.01 to 0.10:1, 0.0002 to 0.0005:1, (0.0005 to 0.002):1, (0.002 to 0.01):1, (0.01 to 0.05):1, or (0.05 to 0.10):1, etc. In a preferred embodiment, the molar ratio of the polyoxometalate catalyst to the epoxide represented by formula (II) can also be (0.0005 to 0.002):1. Within the above range, the amount of catalyst used is small and the catalytic efficiency is high.

[0060] In the method for preparing cyclic ethylene carbonate provided by the present invention, the polyoxometalate is selected from (NH 4 ) 3 [CoMo 6 O 18 (OH) 6 , (NH 4 ) 3 [CrMo 6 O 18 (OH) 6 , (NH 4 ) 3 [FeMo 6 O 18 (OH) 6 , (NH 4 ) 4 [CuMo 6 O 18 (OH) 6 .5H 2 O, (NH 4 ) 2 [Mo 6 O 19 , (NH 4 ) 5 [IMo 6 O 24 , etc., or a combination of one or more of them. The advantage of selecting these polyoxometalates is that the raw materials are simple and easy to obtain and are easy to prepare.

[0061] In the method for preparing cyclic ethylene carbonate provided by the present invention, the tetrabutyl halide is one or several of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, and tetrabutylphosphonium bromide.

[0062] In the method for preparing cyclic ethylene carbonate provided by the present invention, the molar ratio of tetrabutyl halide to the epoxy compound shown in formula (II) is (0.01 - 0.10):1. In specific embodiments, the molar ratio of tetrabutyl halide to the epoxy compound shown in formula (II) can be (0.01 - 0.05):1, (0.05 - 0.10):1, (0.01 - 0.03):1, (0.03 - 0.05):1, (0.05 - 0.08):1, or (0.08 - 0.10):1, etc. Within the above range, the epoxy compound can be completely converted, and the reaction reproducibility is good.

[0063] In the method for preparing cyclic ethylene carbonate provided by the present invention, the reaction is carried out at a certain temperature, and the reaction temperature is 25 - 150 °C. In specific embodiments, the reaction temperature can be 25 - 80 °C, 80 - 100 °C, 25 - 100 °C, or 100 - 125 °C, etc. Preferably, the reaction temperature is 25 - 100 °C. More preferably, the reaction temperature is 25 - 80 °C. Within the above range, the reaction conditions are mild, the energy consumption is low, and it is easy to control.

[0064] In the method for preparing cyclic ethylene carbonate provided by the present invention, the carbon dioxide pressure is 0.1 - 5.0 MPa; in specific embodiments, the carbon dioxide pressure is 0.1 MPa - 2 MPa, or 2 MPa - 5 MPa, etc. Preferably, the carbon dioxide pressure is 0.1 MPa - 2 MPa. Within the above range, the pressure is relatively low, the requirements for equipment are not high, the safety is good, and the reaction proceeds completely.

[0065] In the method for preparing cyclic ethylene carbonate provided by the present invention, the reaction time is based on the complete conversion of the control raw material in each compound.

[0066] In the method for preparing cyclic ethylene carbonate provided by the present invention, after the reaction is completed, the polyoxometalate can be recovered by filtration, and the filtrate is purified to obtain the cyclic ethylene carbonate shown in formula (I). The purification method is, for example, distilling the filtrate.

[0067] In specific embodiments, the epoxyethane compound shown in formula (II), a catalytic amount of polyoxometalate (POMs), and a mixture of tetrabutyl halide are placed in a pressure-resistant device, and 0.1 - 5.0 MPa CO 2 gas is introduced. The reaction mixture is placed at room temperature or slowly heated to 25 - 150 °C and stirred for reaction, and the reaction progress is tracked by GC until the reaction is complete, and a mixture mainly composed of cyclic carbonate (formula I) can be obtained. The catalyst is recovered by filtration, the solvent is recovered from the filtrate by vacuum distillation, and finally, cyclic ethylene carbonate (formula I) can be obtained by refining. The yield of the product by single distillation can reach more than 98%, and the purity is more than 99.0%.

[0068] On the other hand, the present invention provides a cyclic ethylene carbonate prepared by the method of the first aspect of the present invention.

[0069] On the other hand, the present invention provides the use of cyclic ethylene carbonate as an additive in the electrolyte of a lithium-ion battery.

[0070] The technical solutions of the present application will be clearly and completely described below in conjunction with the embodiments of the present invention. It is necessary to point out here that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention still fall within the protection scope of the present invention.

[0071] In the following embodiments, the reagents, materials, and instruments used can be obtained commercially without special instructions.

[0072] In the following examples, the yield calculation method is actual yield / theoretical yield × 100%, and the purity determination method is gas chromatography. The chromatographic column is SK-5, the column temperature is 50 °C, the retention time is 2 min, the temperature is raised to 150 °C at a rate of 10 °C / min, and then to 300 °C at a rate of 20 °C / min, and the final temperature retention time is 10 min.

[0073] Example 1

[0074] This example provides a preparation method of chloromethyldioxolane, and the specific steps are as follows:

[0075] Add 30.0 g (324 mmol, 1.0 e.q.) of epichlorohydrin to a 100 mL high-pressure reactor, add a catalyst (NH 4 ) 3 [CoMo 6 O 18 (OH) 6 174 mg (0.162 mmol, 0.5‰), and add 1.0 g (3.24 mmol, 1.0%) of tetrabutylammonium bromide. After replacing CO 2 three times, raise the temperature to 80 °C and react at a pressure of 0.3 MPa for 5 h. After detecting the reaction by GC and obtaining the product in quantitative yield. The reaction solution is filtered to recover the catalyst, and the crude product is subjected to vacuum distillation to obtain 43.4 g of a colorless liquid product with a yield of 98.1%. The product purity is 99.9%.

[0076] The characterization data is as follows:

[0077] 1 H NMR (400 MHz, CDCl 3δ 5.01 - 4.95 (m, 1H), 4.56 (t, J = 8.0 Hz, 1H), 4.37 (dd, J = 8.0 Hz, 4.0 Hz, 1H), 3.80 (dd, J = 12.0 Hz, 8.0 Hz, 1H), 3.70 (dd, J = 8.0 Hz, 4.0 Hz, 1H). 13 C NMR (400 MHz, CDCl 3 ):δ 154.5, 74.5, 67.0, 44.1. EIMS: m / z (rel intensity) 136 (M + , 1), 87 (100), 49 (8), 43 (30), 27 (7).

[0078] Example 2

[0079] This example provides a method for preparing chloromethyl dioxolane - 2 - one, and the specific steps are as follows:

[0080] Add 30.0 g (324 mmol, 1.0 e.q.) of epichlorohydrin to a 100 mL high - pressure reactor, add the catalyst (NH 4 ) 3 [CrMo 6 O 18 (OH) 6 174 mg (0.162 mmol, 0.5‰), and add 1.0 g (3.24 mmol, 1.0%) of tetrabutylammonium bromide. After replacing with CO 2 three times, heat up to 80 °C and react under a pressure of 0.3 MPa for 9 h. GC detection shows that the raw material content is 0.3%, the content of other impurities is 0.7%, and the product content is 99.0%. Filter the reaction solution to recover the catalyst, and conduct vacuum distillation on the crude product. 41.6 g of colorless liquid product is obtained by distillation, with a yield of 94.0%. The product purity is 99.9%.

[0081] Example 3

[0082] This example provides a method for preparing chloromethyl dioxolane - 2 - one, and the specific steps are as follows:

[0083] Add 30.0 g (324 mmol, 1.0 e.q.) of epichlorohydrin to a 100 mL high - pressure reactor, add the catalyst (NH 4 ) 3 [FeMo 6 O 18 (OH) 6 174 mg (0.162 mmol, 0.5‰), and add 1.0 g (3.24 mmol, 1.0%) of tetrabutylammonium bromide. After replacing with CO 2After three replacements, the temperature was raised to 80 °C, and the reaction was carried out at a pressure of 0.3 MPa for 5 h. The GC detection showed that the raw materials were completely converted, the content of other impurities was 0.5%, and the content of the product was 99.5%. The reaction solution was filtered to recover the catalyst, and the crude product was subjected to vacuum distillation. 43.6 g of a colorless liquid product was obtained by distillation, and the yield was 98.6%. The purity of the product was 99.9%.

[0084] Example 4

[0085] This example provides a method for preparing chloromethyl dioxolane-2-one, and the specific steps are as follows:

[0086] Add 30.0 g (324 mmol, 1.0 e.q.) of epichlorohydrin to a 100 mL high-pressure reactor, add a catalyst (NH 4 ) 4 [CuMo 6 O 18 (OH) 6 .5H2O 174 mg (0.162 mmol, 0.5‰), and add 1.0 g (3.24 mmol, 1.0%) of tetrabutylammonium bromide. CO 2 After three replacements, the temperature was raised to 80 °C, and the reaction was carried out at a pressure of 0.3 MPa for 12 h. The GC detection showed that the raw materials were completely converted, the content of other impurities was 0.4%, and the purity of the product was 99.6%. The reaction solution was filtered to recover the catalyst, and the crude product was subjected to vacuum distillation. 43.0 g of a colorless liquid product was obtained by distillation, and the yield was 97.2%. The purity of the product was 99.9%.

[0087] Example 5

[0088] This example provides a method for preparing chloromethyl dioxolane-2-one, and the specific steps are as follows:

[0089] Add 30.0 g (324 mmol, 1.0 e.q.) of epichlorohydrin to a 100 mL high-pressure reactor, add a catalyst (NH 4 ) 2 [Mo 6 O 19 148 mg (0.162 mmol, 0.5‰), and add 1.0 g (3.24 mmol, 1.0%) of tetrabutylammonium bromide. CO 2 After three replacements, the temperature was raised to 80 °C, and the reaction was carried out at a pressure of 0.3 MPa for 5 h. The GC detection showed that the remaining content of the raw materials was 0.1%, the content of other impurities was 0.6%, and the content of the product was 99.3%. The reaction solution was filtered to recover the catalyst, and the crude product was subjected to vacuum distillation. 43.7 g of a colorless liquid product was obtained by distillation, and the yield was 98.8%. The purity of the product was 99.9%.

[0090] Example 6

[0091] This embodiment provides a preparation method of chloromethyl dioxolane-2-one, and the specific steps are as follows:

[0092] Add 30.0 g (324 mmol, 1.0 e.q.) of epichlorohydrin to a 100 mL high-pressure reactor, add the catalyst (NH4) 5 [IMo 6 O 24 191 mg (0.162 mmol, 0.5‰), and add 1.0 g (3.24 mmol, 1.0%) of tetrabutylammonium bromide. CO 2 After purging three times, heat up to 80 °C and react for 10 h under a pressure of 0.3 MPa. GC detection shows that the raw materials are completely converted, and the product purity is 99.9%. Filter the reaction solution to recover the catalyst, and perform vacuum distillation on the crude product. Distill to obtain 43.7 g of a colorless liquid product, with a yield of 98.8%. The product purity is 99.9%.

[0093] Example 7

[0094] This embodiment provides a preparation method of bromomethyl dioxolane-2-one, and the specific steps are as follows:

[0095] Add 30.0 g (219 mmol, 1.0 e.q.) of epibromohydrin to a 100 mL high-pressure reactor, add the catalyst (NH 4 ) 2 [Mo 6 O 19 100 mg (0.110 mmol, 0.5‰), and add 706 mg (2.19 mmol, 1.0%) of tetrabutylammonium bromide. CO 2 After purging three times, heat up to 80 °C and react for 10 h under a pressure of 0.3 MPa. GC detection shows that the raw materials are completely converted, the content of other impurities is 0.3%, and the product content is 99.7%. Filter the reaction solution to recover the catalyst, and perform vacuum distillation on the crude product. Distill to obtain 38.1 g of a colorless liquid product, with a yield of 96.1%. The product purity is 99.8%.

[0096] The characterization data are as follows:

[0097] 1 H NMR (400 MHz, CDCl 3 ): δ 4.98 - 4.92 (m, 1H), 4.59 (t, J = 8.0 Hz, 1H), 4.34 (dd, J = 8.0 Hz, 8.0 Hz, 1H), 3.61 (dd, J = 8.0 Hz, 4.0 Hz, 1H). 13 C NMR (400 MHz, CDCl 3):δ154.2,74.1,68.2,31.5.EIMS:m / z(rel intensity)180(M + ,11),106(2),87(100),57(8),43(20),27(8).

[0098] Example 8

[0099] This example provides a preparation method of n-butyl dioxolane-2-one, and the specific steps are as follows:

[0100] Add 30.0 g (300 mmol, 1.0 e.q.) of butyl ethylene oxide to a 100 mL high-pressure reactor, and add a catalyst (NH 4 ) 2 [Mo 6 O 19 137 mg (0.150 mmol, 0.5‰), and add 967 mg (3.0 mmol, 1.0%) of tetrabutylammonium bromide. After displacing with CO 2 three times, heat up to 80 °C and react for 15 h under a pressure of 0.5 MPa. GC detection shows that the raw materials are completely converted, the content of other impurities is 0.7%, and the content of the product is 99.3%. Filter the reaction solution to recover the catalyst, and distill the crude product under reduced pressure. 41.6 g of colorless liquid product is obtained by distillation, and the yield is 96.2%. The purity of the product is 99.9%.

[0101] The characterization data are as follows:

[0102] 1 1H NMR (400 MHz, CDCl 3 ):δ4.75 - 4.68 (m, 1H), 4.54 (t, J = 8.0 Hz, 1H), 4.08 (dd, J = 4.0 Hz, 4.0 Hz, 1H), 1.86 - 1.77 (m, 1H), 1.74 - 1.65 (m, 1H), 1.50 - 1.32 (m, 4H), 0.93 (t, J = 8.0 Hz, 3H). 13 13C NMR (400 MHz, CDCl 3 ):δ155.1, 69.4, 62.1, 33.5, 26.4, 22.2, 13.8. EIMS: m / z (rel intensity) 145 [(M + H) + , 1], 87(77), 67(39), 58(64), 43(100), 29(23).

[0103] Example 9

[0104] This example provides a preparation method of phenyl dioxolane-2-one, and the specific steps are as follows:

[0105] 30.0 g (250 mmol, 1.0 e.q.) of phenyloxirane was added to a 100 mL high-pressure reactor, and the catalyst (NH 4 ) 2 [Mo 6 O 19 114 mg (0.125 mmol, 0.5‰) was added, and 806 mg (2.5 mmol, 1.0%) of tetrabutylammonium bromide was added. After three replacements with CO 2 , the temperature was raised to 80 °C, and the reaction was carried out at 0.5 MPa for 15 h. The remaining content of the raw material detected by GC was 0.3%, the content of other impurities was 0.3%, and the content of the product was 99.4%. The reaction solution was hot-filtered to recover the catalyst, and the crude product was subjected to vacuum distillation to obtain 39.7 g of a white solid product with a yield of 96.7%. The purity of the product was 99.7%.

[0106] The characterization data are as follows:

[0107] 1 H NMR (400 MHz, CDCl 3 ): δ 7.47 - 7.42 (m, 3H), 7.41 - 7.34 (m, 2H), 5.68 (t, J = 8.0 Hz, 1H), 4.80 (t, J = 8.0 Hz, 1H), 4.35 (t, J = 8.0 Hz, 1H). 13 C NMR (400 MHz, CDCl 3 ): δ 154.8, 135.8, 129.8, 129.3, 125.9, 78.0, 71.2. EIMS: m / z (rel intensity) 164 (M + , 100), 119 (14), 105 (27), 90 (90), 78 (52), 65 (12), 51 (12).

[0108] Example 10

[0109] This example provides a method for preparing 4-(hydroxymethyl)-1,3-dioxolan-2-one, and the specific steps are as follows:

[0110] 30.0 g (405 mmol, 1.0 e.q.) of glycidol was added to a 100 mL high-pressure reactor, and the catalyst (NH 4 ) 2 [Mo 6 O 19 114 mg (0.202 mmol, 0.5‰) was added, and 1.3 g (4.05 mmol, 1.0%) of tetrabutylammonium bromide was added. CO 2After three replacements, the temperature was raised to 80 °C, and the reaction was carried out for 15 h under a pressure of 0.5 MPa. The content of the raw material detected by GC was 0.8%, the content of other impurities was 0.5%, and the content of the product was 98.7%. The reaction solution was filtered to recover the catalyst, and the crude product was subjected to vacuum distillation to obtain 43.5 g of a colorless liquid product with a yield of 91.0%. The purity of the product was 99.6%.

[0111] The characterization data are as follows:

[0112] 1 H NMR(400MHz,CDCl 3 ): δ4.8-4.78(m,1H),4.52(t,J=8.0Hz,1H),4.46(dd,J=8.0Hz,4.0Hz,1H),3.98(dd,J=12.0Hz,4.0Hz,1H),3.70(dd,J=12.0Hz,4.0Hz,1H). 13 CNMR(400MHz,CDCl 3 ): δ155.5,65.8,61.6,29.7.EIMS:m / z(rel intensity)118(M + ,1),87(65),43(100),31(47).

[0113] Example 11

[0114] This example provides a method for preparing trifluoromethyl dioxolane-2-one, and the specific steps are as follows:

[0115] 30.0 g (268 mmol, 1.0 e.q.) of trifluoromethyloxirane was added to a 100 mL high-pressure reactor, and the catalyst (NH 4 ) 2 [Mo 6 O 19 123 mg (0.134 mmol, 0.5‰) was added, and 864 mg (2.68 mmol, 1.0%) of tetrabutylammonium bromide was added. CO 2 After three replacements, the temperature was raised to 50 °C, and the reaction was carried out for 15 h under a pressure of 0.5 MPa. The remaining raw material detected by GC was 0.3%, the content of other impurities was 0.3%, and the content of the product was 99.4%. The reaction solution was filtered to recover the catalyst, and the crude product was subjected to vacuum distillation to obtain 38.6 g of the product with a yield of 92.3%. The purity of the product was 99.9%.

[0116] The characterization data are as follows:

[0117] 1 H NMR(400MHz,CDCl 3): δ 5.04 - 4.96 (m, 1H), 4.67 (t, J = 8.0 Hz, 1H), 4.55 (dd, J = 8.0 Hz, 4.0 Hz, 1H). 13 C NMR (400 MHz, CDCl 3 ): δ 152.8, 122.0 (q, 1C), 71.8 (q, 1C), 63.8 (m, 1C). 19 F NMR (400 MHz, CDCl 3 ): δ -80.2. EIMS: m / z (rel intensity) 156 (M + , 4), 126 (4), 107 (3), 87 (100), 69 (21), 43 (26), 29 (17).

[0118] Example 12

[0119] This example provides a preparation method of 4-difluoromethyl-1,3-dioxolan-2-one, and the specific steps are as follows:

[0120] Add 30 g (319 mmol, 1.0 e.q.) of 2-difluoromethylethylene oxide into a 100 mL high-pressure reactor, add a catalyst (NH 4 ) 2 [Mo 6 O 19 146 mg (0.16 mmol, 0.5‰), and add 1.0 g (3.19 mmol, 1.0%) of tetrabutylammonium bromide. Heat up to 50 °C and react for 15 h under a pressure of 0.5 MPa. The content of the product detected by GC is 99.7%. Filter the reaction solution to recover the catalyst, and perform vacuum distillation on the crude product to obtain 42.9 g of the product, with a yield of 97.5% and a product purity of 99.8%.

[0121] The characterization data are as follows:

[0122] 1 H NMR (400 MHz, CDCl 3 ): δ 5.78 - 5.69 (m, 1H), 5.65 - 5.55 (m, 1H), 4.46 (dd, J = 8.0 Hz, 4.0 Hz, 1H), 4.01 (dd, J = 8.0 Hz, 4.0 Hz, 1H).

[0123] Example 13

[0124] This example provides a preparation method of 4-vinyl-1,3-dioxolan-2-one, and the specific steps are as follows:

[0125] 30 g (428 mmol, 1.0 e.q.) of 3,4-epoxy-1-butene was added to a 100 mL high-pressure reactor, and the catalyst (NH 4 ) 2 [Mo 6 O 19 196 mg (0.21 mmol, 0.5‰) was added, and 1.38 g (4.28 mmol, 1.0%) of tetrabutylammonium bromide was added. The temperature was raised to 50 °C, and the reaction was carried out at a pressure of 0.5 MPa for 15 h. The content of the product was detected by GC to be 99.7%. The reaction solution was filtered to recover the catalyst, and 701 inhibitor was added to the crude product, followed by vacuum distillation to obtain 46.9 g of the product, with a yield of 96.1% and a product purity of 99.7%.

[0126] The characterization data are as follows:

[0127] 1 1H NMR (400 MHz, CDCl 3 ):δ 5.86 - 5.76 (m, 1H), 5.38 - 5.28 (m, 2H), 4.86 - 4.75 (m, 1H), 4.33 (dd, J = 8.0 Hz, 4.0 Hz, 1H), 4.08 (dd, J = 8.0 Hz, 4.0 Hz, 1H).

[0128] Example 14

[0129] This example provides a method for preparing 4,5-dimethyl-1,3-dioxolan-2-one, and the specific steps are as follows:

[0130] 30 g (416 mmol, 1.0 e.q.) of 1,2-dimethylethylene oxide was added to a 100 mL high-pressure reactor, and the catalyst (NH 4 ) 2 [Mo 6 O 19 190 mg (0.21 mmol, 0.5‰) was added, and 1.34 g (4.16 mmol, 1.0%) of tetrabutylammonium bromide was added. The temperature was raised to 50 °C, and the reaction was carried out at a pressure of 0.5 MPa for 15 h. The content of the product was detected by GC to be 99.7%. The reaction solution was filtered to recover the catalyst, and the crude product was subjected to vacuum distillation to obtain 47.0 g of the product, with a yield of 97.3% and a product purity of 99.9%, which was a mixture of cis-trans isomers.

[0131] The characterization data are as follows:

[0132] 1 1H NMR (400 MHz, MeOH-d4): (major) δ 4.46 - 4.39 (m, 2H), 1.45 - 1.40 (m, 6H).

[0133] Example 15

[0134] This example provides a method for preparing 4,5-difluoro-1,3-dioxolan-2-one, and the specific steps are as follows:

[0135] Add a solution of 10.0 g (125 mmol, 1.0 e.q.) of 1,2-difluoroethylene oxide dissolved in 30 mL of tetrahydrofuran to a 100 mL high-pressure reactor, and add a catalyst (NH 4 ) 2 [Mo 6 O 19 57 mg (0.06 mmol, 0.5‰), and add 403 mg (1.25 mmol, 1.0%) of tetrabutylammonium bromide. Heat up to 50 °C and react for 15 h under a pressure of 1.0 MPa. The content of the product detected by GC is 99.8%. After the reaction solution is desolvated, the catalyst is recovered by filtration. The crude product is subjected to atmospheric distillation to obtain 13.8 g of the product, with a yield of 89.4% and a product purity of 99.9%, which is a mixture of cis-trans isomers.

[0136] The characterization data are as follows:

[0137] 1 1H NMR (400 MHz, MeOH-d4): (major) δ 6.58 - 6.53 (m, 1H), 6.44 - 6.40 (m, 1H).

[0138] The above content fully proves that the method provided by the present invention can effectively realize the synthesis of cyclic ethylene carbonate compounds, and the product has a high yield and high purity; by comparing Examples 1 - 6, it can be found that the present invention uses six different polyoxometalates (POMs) to basically prepare the final product in a quantitative yield, the reaction is clean, and the purity is high; by comparing Examples 7 - 15, it can be found that the reaction conditions used in the present invention for preparing cyclic ethylene carbonate compounds are applicable to different types of epoxides and the yield is relatively high.

[0139] The applicant declares that the present invention uses the above examples to illustrate the preparation method of the cyclic ethylene carbonate compound of the present invention, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0140] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0141] In addition, it should be noted that, in the above specific embodiments, the various specific technical features described can be combined in any appropriate manner without conflict. To avoid unnecessary repetition, the present invention will not separately describe various possible combination manners.

Claims

1. A preparation method of cyclic ethylene carbonate, characterized in that, the preparation method comprises the following steps: Mix the ethylene oxide compound shown in formula (II) with a polyoxometalate catalyst and a tetrabutyl halide, and react in a CO 2 atmosphere to obtain the cyclic ethylene carbonate shown in formula (I); The chemical reaction formula is as follows: Among them, R 1 , R 2 , R 3 , R 4 are independently selected from any one of H, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C6-C12 aryl, halogen, substituted or unsubstituted C1-C12 alkoxy, and C1-C12 alkylamine; The polyoxometalate catalyst is selected from one or more of (NH 4 ) 3 [CoMo 6 O 18 (OH) 6 , (NH 4 ) 3 [FeMo 6 O 18 (OH) 6 , (NH 4 ) 4 [CuMo 6 O 18 (OH) 6 .5H 2 O, (NH 4 ) 2 [Mo 6 O 19 , (NH 4 ) 5 [IMo 6 O 24 . The molar ratio of the polyoxometalate catalyst to the epoxy compound shown in formula (II) is 0.0002 to 0.0005.

2. The preparation method of the cyclic ethylene carbonate compound according to claim 1, characterized in that, After the reaction, the polyoxometalate is recovered by filtration, and the filtrate is purified to obtain the cyclic ethylene carbonate shown in formula (I).

3. The preparation method of the cyclic ethylene carbonate compound according to claim 1, characterized in that, The reaction can be carried out continuously or intermittently in the presence or absence of an organic solvent; the reaction can be carried out in an organic solvent; the solvent includes any one or a combination of at least two of dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, tetrahydrofuran, acetonitrile, and dimethyl carbonate.

4. The preparation method of the cyclic ethylene carbonate compound according to claim 1, characterized in that, R 1 、R 2 、R 3 、R 4 are independently selected from any one of H, C1-C4 alkyl, halo C1-C4 alkyl, substituted or unsubstituted C2-C5 alkenyl, substituted or unsubstituted C6-C12 aryl, halogen, and substituted or unsubstituted C1-C6 alkoxy.

5. The preparation method of the cyclic ethylene carbonate compound according to claim 1, characterized in that, R 1 、R 2 、R 3 、R 4 are independently selected from any one of H, chloromethyl, bromomethyl, hydroxymethyl, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, vinyl, phenyl, fluorine, chlorine, or bromine.

6. The preparation method of the cyclic ethylene carbonate compound according to claim 1, characterized in that, The tetrabutyl halide is one or several of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, and tetrabutylphosphonium bromide.

7. The preparation method of the cyclic ethylene carbonate compound according to claim 1, characterized in that, The molar ratio of the tetrabutyl halide to the epoxy compound shown in formula (II) is 0.005 - 0.10:

1.

8. The preparation method of the cyclic ethylene carbonate compound according to claim 1, characterized in that, The reaction temperature is 25 - 150 °C; and / or, the carbon dioxide pressure is 0.1 - 5.0 MPa.

9. The preparation method of the cyclic ethylene carbonate compound according to claim 8, characterized in that, The reaction temperature is 25 - 100 °C; and / or, the carbon dioxide pressure is 0.1 MPa - 2 MPa.

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