Eco-friendly method for preparing alkylene carbonate

Abstract

The present invention relates to an eco-friendly method for preparing an alkylene carbonate and, specifically, comprises a step of reacting a first reaction mixture comprising a C2-7 halogenated monohydric or dihydric alcohol, an organic base and CO2, thereby synthesizing an alkylene carbonate represented by chemical formula 1. The organic base is any one or a combination of at least two selected from the group consisting of an amine represented by chemical formula 2, a bi- or polycyclic amine compound and a salt thereof. In addition, an organic base-CO2 absorbate is formed as a solid precipitate so as to be easily transferred, and is advantageous in terms of the purity of reactants and raw materials. Furthermore, a step of reacting, with an alkylene oxide, an amine salt formed as a by-product of the reaction, so as to regenerate same as an alcohol and an organic base is additionally performed, and thus a preparation cycle ensuring eco-friendliness and economic feasibility can be formed.

Description

Method for producing environmentally friendly alkylene carbonate

[0001] The present invention relates to a method for producing an environmentally friendly alkylene carbonate.

[0002] Global warming has recently become a serious problem, necessitating a global effort to reduce fossil fuel use and carbon dioxide emissions. One way to reduce carbon dioxide emissions is through technologies that use carbon dioxide as a raw material to produce new compounds, and extensive research is underway in this area. Key elements of these carbon dioxide capture technologies include the development of effective catalysts, optimization of reaction conditions, and international cooperation. These efforts are expected to contribute to protecting the global environment and reducing greenhouse gas emissions.

[0003] As an example of a technology that produces new compounds using carbon dioxide as a raw material, ethylene carbonate can be produced starting from ethylene oxide or halogenated alcohols in the presence of a solvent and an inorganic catalyst under a high-pressure carbon dioxide atmosphere. However, these conventional technologies have low yields, require highly toxic solvents such as DMSO or DMF, incur enormous costs for recovery and solvent disposal, and require complex reaction equipment to achieve demanding high-pressure, high-temperature reaction conditions. Consequently, these technologies pose many limitations for commercialization when considering operational efficiency and economic feasibility.

[0004] Carbon dioxide is also produced in large quantities as an industrial byproduct. To capture this carbon dioxide, a separate absorbent is typically used to absorb it, followed by a separate process to separate the carbon dioxide and the absorbent. However, conventional technologies suffer from various problems, including exothermic reactions with carbon dioxide, deterioration and corrosion during carbon dioxide desorption, and the uneconomical use of high renewable energy sources.

[0005] The purpose of the present invention to solve the problems of the past is to provide an eco-friendly method for producing alkylene carbonate with economic and environmental advantages by using an organic base as an absorbent for carbon dioxide and at the same time as a raw material in the production of alkylene carbonate, thereby significantly reducing process and installation costs.

[0006] In addition, another object of the present invention is to provide an environmentally friendly method for producing alkylene carbonate with a high yield under milder conditions than the prior art, specifically, under room temperature and pressure conditions.

[0007] In addition, another object of the present invention is to provide a method for producing a solid organic base-carbon dioxide precipitate from an organic base and CO2.

[0008] In addition, another object of the present invention is to provide an environmentally friendly method for producing alkylene carbonate, which can recycle a by-product generated during the production of alkylene carbonate according to one embodiment into a raw material for the synthesis of alkylene carbonate by reacting it with alkylene oxide.

[0009] The inventors of the present invention have continuously researched to achieve the above-mentioned purpose, and as a result, C 2-7 When synthesizing an alkylene carbonate by reacting a reaction mixture containing a halogenated monohydric or dihydric alcohol, an organic base, and CO2, the organic base is used as both an absorbent for carbon dioxide and a raw material for producing an alkylene carbonate, thereby significantly reducing process and installation costs, thereby improving economic and environmental benefits, and finding that an alkylene carbonate can be produced in a high yield without using toxic solvents such as DMSO or DMF, the present invention has been completed. Furthermore, it has been confirmed that when a by-product generated during the production of the alkylene carbonate is reacted with an alkylene oxide, it can be recycled as a raw material for the synthesis of an alkylene carbonate, thereby ensuring both excellent environmental friendliness and economic feasibility.

[0010] The present invention (S1) C2-7 A step of synthesizing an alkylene carbonate represented by the following chemical formula 1 by reacting a first reaction mixture containing a halogenated monohydric or dihydric alcohol, an organic base, and CO2;

[0011] The above organic base provides a method for producing an environmentally friendly alkylene carbonate, wherein the organic base is one or a combination of two or more selected from the group consisting of amines, bicyclic or polycyclic amine compounds and salts thereof represented by the following chemical formula 2.

[0012] [Chemical Formula 1]

[0013]

[0014] [Chemical Formula 2]

[0015]

[0016] In the above chemical formulas 1 and 2,

[0017] R 11 Silver hydrogen, straight or branched chain C 1-10 Alkyl, (C 3-20 Aryl)-(C 1-10 alkyl), C 3-20 Aryl or (C 1-10 alkyl)-(C 3-20 Aryl),

[0018] Optionally, any one of the carbons of the above alkyl may be replaced by one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2 and Si atoms,

[0019] R 12 is hydrogen, methyl or halogen,

[0020] R2 to R4 are independently hydrogen, straight or branched chain C 1-7 Alkyl, C 1-10 Hydroxyalkyl, C 3-20 An aryl or anion exchange resin-derived residue, wherein R2 to R4 are not all hydrogen.

[0021] According to one embodiment of the present invention, the CO2 may be an industrial byproduct generated in an industrial process.

[0022] According to one embodiment of the present invention, the step (S1) comprises (S1-1) C 2-7 It may be a method of synthesizing an alkylene carbonate represented by the chemical formula 1 by injecting CO2 into a mixture containing a halogenated monohydric or dihydric alcohol and an organic base and reacting the mixture.

[0023] According to one embodiment of the present invention, the reaction may be carried out by stirring an organic base with a monohydric or dihydric alcohol under a CO2 gas atmosphere.

[0024] According to one embodiment of the present invention, the reaction may be carried out by passing a monohydric or dihydric alcohol through an organic base column under a CO2 gas atmosphere.

[0025] According to one embodiment of the present invention, the step (S1) comprises: (S1-2) an organic base-CO2 absorbent formed from an organic base and CO2; and C 2-7 It may be a method of synthesizing an alkylene carbonate represented by the following chemical formula 1 by reacting a second reaction mixture containing a halogenated monohydric or dihydric alcohol.

[0026] According to one embodiment of the present invention, the organic base may be in contact with CO2 in the presence of a solvent.

[0027] According to one embodiment of the present invention, the organic base-CO2 absorbent may be a precipitate formed from an organic base and CO2.

[0028] According to one embodiment of the present invention, the organic base-CO2 absorbent

[0029] (1) Formed in an external reactor and separately injected into a second reaction mixture, or

[0030] (2) Organic base, CO2 and C 2-7formed in a second reaction mixture containing a halogenated monohydric or dihydric alcohol, or

[0031] (3) C without separate separation immediately after formation in the same reactor 2-7 It may react with a halogenated monohydric or dihydric alcohol.

[0032] According to one embodiment of the present invention, a process of injecting CO2 gas into the second reaction mixture during the reaction may be further performed.

[0033] According to one embodiment of the present invention, the monohydric or dihydric alcohol may be represented by the following chemical formula 3.

[0034] [Chemical Formula 3]

[0035]

[0036] In the above chemical formula 3, X is halogen, and R 11 Silver hydrogen, straight or branched chain C 1-10 Alkyl, (C 3-20 Aryl)-(C 1-10 alkyl), C 3-20 Aryl or (C 1-10 alkyl)-(C 3-20 Aryl),

[0037] Optionally, any one of the carbons of the above alkyl may be replaced by one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2 and Si atoms,

[0038] R 12 is hydrogen, methyl or halogen.

[0039] According to one embodiment of the present invention, in the chemical formula 3, X may be I, Br or Cl.

[0040] According to one embodiment of the present invention, in the above chemical formula 2, R2 to R4 are each independently hydrogen, straight chain or branched chain C 1-3 Alkyl, C 1-3Hydroxyalkyl or anion exchange resin-derived residues, which may not all be hydrogen.

[0041] According to one embodiment of the present invention, the organic base may be included in an amount of 0.5 to 3 moles per mole of the monohydric or dihydric alcohol.

[0042] According to one embodiment of the present invention, the anion exchange resin may be in the form of beads having an average particle size of 0.1 to 5.0 mm.

[0043] According to one embodiment of the present invention, the anion exchange resin may have a uniformity coefficient of 1.5 or less.

[0044] According to one embodiment of the present invention, the anion exchange resin may have an exchange capacity of 1.5 eq / L or more.

[0045] According to one embodiment of the present invention, the anion exchange resin may have a pH of 9 or less.

[0046] According to one embodiment of the present invention, when R2 is a residue derived from an anion exchange resin, the organic base may be included in an amount of 30 to 90 parts by weight based on 10 parts by weight of the monohydric or dihydric alcohol.

[0047] According to one embodiment of the present invention, the bi- or polycyclic amine compound may be a secondary or tertiary amine.

[0048] According to one embodiment of the present invention, the bicyclic or polycyclic amine compound may be included in an amount of 1 to 30 wt% based on the total weight of the organic base.

[0049] According to one embodiment of the present invention, the amine may further comprise a weak acid.

[0050] According to one embodiment of the present invention, the reaction may be performed under atmospheric pressure or pressurized conditions.

[0051] According to one embodiment of the present invention, the reaction may be performed under pressure conditions of normal pressure to 20 bar.

[0052] According to one embodiment of the present invention, the reaction may be performed under temperature conditions of 0 to 80°C.

[0053] According to one embodiment of the present invention, the first reaction mixture may further comprise a solvent.

[0054] According to one embodiment of the present invention, the solvent may have a dielectric constant of 10 to 35.

[0055] According to one embodiment of the present invention, the solvent may be included in an amount of 10 to 200 parts by weight based on 10 parts by weight of the monohydric or dihydric alcohol.

[0056] According to one embodiment of the present invention, the alkylene carbonate may include at least one selected from the group consisting of ethylene carbonate, 4-halogen ethylene carbonate, propylene carbonate, 4-butyl ethylene carbonate, 4-ethoxymethyl ethylene carbonate, 4-allyloxymethyl ethylene carbonate, 4-aryl ethylene carbonate, and 4-aryloxymethyl ethylene carbonate.

[0057] According to one embodiment of the present invention, a step of recovering a salt of an amine represented by the following chemical formula 4 formed as a by-product of the above reaction may be further performed.

[0058] [Chemical Formula 4]

[0059]

[0060] In the above chemical formula 4,

[0061] R5 to R7 are independently hydrogen, straight or branched chain C 1-5 Alkyl, C 1-5 Hydroxyalkyl, C 3-20 A residue derived from an aryl or anion exchange resin, wherein R2 to R4 are not all hydrogen,

[0062] X is a halogen.

[0063] According to one embodiment of the present invention, a step of regenerating alcohol and organic base may be further performed by reacting a third reaction mixture including a salt of the recovered amine and an alkylene oxide represented by the following chemical formula 5.

[0064] [Chemical Formula 5]

[0065]

[0066] In the above chemical formula 5, R 81 R of the above chemical formula 1 11 is identical to the definition of R 82 is R of the above chemical formula 1 12 is identical to the definition of .

[0067] According to one embodiment of the present invention, the third reaction mixture may further comprise a solvent, a catalyst, or a mixture thereof.

[0068] According to one embodiment of the present invention, the regenerated organic base may be used as a raw material for the reaction.

[0069] According to one embodiment of the present invention, the percentage (yield) of the amount of alkylene carbonate produced with respect to the amount of monovalent or divalent alcohol input may be 80% or more.

[0070] The present invention can provide an alkylene carbonate manufactured from the above-described method for manufacturing an environmentally friendly alkylene carbonate.

[0071] The environmentally friendly alkylene carbonate manufacturing method of the present invention can significantly reduce process and installation costs, thereby providing economic and environmental advantages, and can manufacture alkylene carbonate at a high yield without using toxic solvents such as DMSO or DMF.

[0072] In addition, when forming an organic base-CO2 absorbent from an organic base and CO2 using a specific solvent, it can be formed as a solid precipitate, which is advantageous in terms of easier transport and purity of raw materials or reactants.

[0073] Furthermore, by reacting the byproducts generated during the production of the above-mentioned alkylene carbonate with alkylene oxide can be regenerated as a raw material for the synthesis of alkylene carbonate, thereby ensuring both excellent environmental friendliness and economic feasibility. The alkylene carbonate produced through this method is superior to conventional technologies in both economic efficiency and environmental friendliness, and can be used as an organic solvent, an electrolyte for secondary batteries, an extractant, a foaming agent, and a lubricant stabilizer.

[0074] Figure 1 is a process diagram schematically showing a chemical formula for an eco-friendly alkylene carbonate manufacturing method according to one embodiment of the present invention. Referring to Figure 1, an organic base represented by Chemical Formula 2 is adsorbed with CO2 to form an organic base-CO2 absorbent, and an organic base-CO2 absorbent and C represented by Chemical Formula 3 are adsorbed. 2-7 It shows a step of synthesizing an alkylene carbonate represented by chemical formula 1 by reacting a halogenated monohydric or dihydric alcohol. Then, the synthesized alkylene carbonate is separated, and the salt of the amine represented by chemical formula 4 obtained as a byproduct can be recovered and reacted with an alkylene oxide represented by chemical formula 5. Through the reaction, an organic base represented by chemical formula 2 and a halogenated monohydric or dihydric alcohol can be obtained again and regenerated in a subsequent reaction, and at this time, the alcohol is C represented by chemical formula 3 used as the raw material. 2-7 The halogenated monohydric or dihydric alcohol may be the same or different and may vary depending on the alkylene oxide being introduced. In Figure 1, C represented by chemical formula 3 2-7 The substituent of the alkylene oxide represented by the formula 5 is the same as the substituents of the formulas 1 and 3 so as to obtain the same product as the halogenated monohydric or dihydric alcohol of R of the formula 5.81 R 11 R of chemical formula 5 82 to R 12 It was described as follows. Through this, the method for manufacturing an eco-friendly alkylene carbonate according to one embodiment can provide a more eco-friendly process by regenerating the by-product of the reaction back into a raw material.

[0075] The present invention is further described in detail below through specific examples or embodiments, including the attached drawings. However, the following specific examples or embodiments are merely references for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

[0076] Additionally, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of describing specific embodiments only and is not intended to be limiting.

[0077] Additionally, the singular forms used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0078] In addition, units used in this specification without special mention are based on weight, and for example, units of % or ratio mean weight% or weight ratio, and weight% means the weight% that any one component of the entire composition occupies in the composition unless otherwise defined.

[0079] Additionally, when a part in this specification is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0080] Additionally, the numerical ranges used herein may include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specifically defined in the present specification, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0081] In addition, in this specification, it is a broad concept that includes both “~ polymer / polymer / copolymer” and “~ polymer / polymer / copolymer derivatives.”

[0082] In addition, in this specification, “residue” means the remaining portion of a polymer excluding a specific structure or functional group, and the type of the polymer is not particularly limited.

[0083] Additionally, in this specification, “weak acid” means a compound having a pKa of 2 to 6 as measured according to a conventionally known method.

[0084] Additionally, in this specification, “weakly basic” means a compound having a pKa of 8 to 12 as measured according to a conventionally known method.

[0085] Additionally, in this specification, “room temperature” means a temperature of 25±3℃.

[0086] Additionally, in this specification, “normal pressure” means 1 atm, which is atmospheric pressure, and means a state in which the gauge pressure inside the reactor is 0 bar.

[0087] In addition, the term 'Hansen solubility factor' in this specification means the Hansen solubility parameter (proposed by Dr. C. Hansen in 1967) calculated by considering three factors of the degree of bonding within a substance: nonpolar dispersion bonding, polar bonding due to permanent dipoles, and hydrogen bonding.

[0088] Additionally, in this specification, “precipitate” means a solid form of reactant formed due to interaction between raw materials of a reaction.

[0089] Additionally, as used herein, "aryl" refers to a carbon ring aromatic group containing 5 to 10 ring atoms. Representative examples include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. Furthermore, aryl also includes heteroaryl in which the carbon ring aromatic group and the group are connected by alkylene or alkenylene, or by one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2, and Si atoms.

[0090] Additionally, in this specification, “alkylaryl” means an alkyl-substituted aryl group.

[0091] Additionally, in this specification, “arylalkyl” means an aryl-substituted alkyl group.

[0092] In addition, when naming a compound having the following structure in this specification, it is named as 'substituent 3-R2, 4-R1 ethylene carbonate' except when the substituent R1 or R2 is methyl. For example, when R1 is butyl, it is named as butyl ethylene carbonate, when R1 is halogen, it is named as halo ethylene carbonate, when R1 is allyloxymethyl, it is named as 4-allyloxymethyl ethylene carbonate, and when R1 is halomethyl and R2 is methyl, it is named as 3-methyl 4-halomethyl ethylene carbonate. In this case, the halo may be fluoro (F), iodo (I), chloro (Cl), or bromo (Br).

[0093] [structure]

[0094]

[0095] In this specification, R of chemical formula 1 11 and R of chemical formula 311 Silver and / or R of formula 5 81 may be the same or different, and R of chemical formula 1 12 and R of chemical formula 3 12 and / or R of chemical formula 5 82 may be the same or different. In addition, R2 to R4 of Chemical Formula 2 and R5 to R7 of Chemical Formula 4 may be the same or different. (In order)

[0096] Hereinafter, a method for producing an environmentally friendly alkylene carbonate according to one embodiment of the present invention will be described in more detail.

[0097] The present invention (S1) C 2-7 The present invention provides a method for producing an environmentally friendly alkylene carbonate, comprising the step of reacting a first reaction mixture containing a halogenated monohydric or dihydric alcohol, an organic base, and CO2 to synthesize an alkylene carbonate represented by the following chemical formula 1.

[0098] The above reaction may be performed at room temperature and pressure, but is not limited thereto, and may of course also include both high pressure and high temperature. Those skilled in the art will appreciate that performing the reaction under conditions of temperature and pressure higher than room temperature or pressure can result in higher yields.

[0099] However, what the present invention seeks to achieve is that a reaction that was previously performed at high temperature and high pressure can be performed at a high yield even under room temperature and pressure conditions, thereby effectively solving the problem of a very low yield at room temperature and pressure in the past.

[0100] A manufacturing method according to one embodiment comprises C as a starting material 2-7By using a halogenated monohydric or dihydric alcohol and an organic base having a specific structure, the handling and transportation of raw materials are improved compared to the conventional technology, and the reaction can be performed under high efficiency, low energy, environmentally friendly, and mild conditions, while at the same time achieving a higher yield under room temperature and pressure.

[0101] [Chemical Formula 1]

[0102]

[0103] In the above chemical formula 1, R 11 Silver hydrogen, straight or branched chain C 1-10 Alkyl, (C 3-20 Aryl)-(C 1-10 alkyl), C 3-20 Aryl or (C 1-10 alkyl)-(C 3-20 Aryl), and optionally, any one of the carbon atoms of the alkyl may be substituted with one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2 and Si atoms, and R 12 is hydrogen, methyl or halogen. Or in the above formula 1, R 11 Silver hydrogen, straight chain C 1-7 Alkyl, (C 3-12 Aryl)-(C 1-7 alkyl), C 3-12 Aryl or (C 1-7 alkyl)-(C 3-12 aryl), and optionally any one of the carbons of the alkyl may be substituted with one or more heteroatoms selected from O, N and C(=O), etc., and R 12 may be hydrogen, methyl or halogen. Or in the above formula 1, R 11 Silver hydrogen or straight chain C 1-5 or C 1-3 It can be alkyl and R 12 may be hydrogen, methyl or halogen. When the above structure is satisfied, the effect aimed at in the present invention can be achieved, which is preferable.

[0104] According to one embodiment of the present invention, the step (S1) comprises (S1-1) C 2-7 It may be a method of synthesizing an alkylene carbonate represented by the chemical formula 1 by injecting CO2 into a mixture containing a halogenated monohydric or dihydric alcohol and an organic base and reacting the mixture.

[0105] Specifically, the above step (S1-1) may include (a) a step of preparing a mixture including an organic base and a monohydric or dihydric alcohol; (b) a step of supplying carbon dioxide to the mixture (reactant); and (c) a step of reacting the mixture to prepare an alkylene carbonate.

[0106] According to one embodiment of the present invention, step (a) may be performed by first introducing a monohydric or dihydric alcohol and then introducing an organic base. Specifically, step (a) may be performed by first introducing a solvent and a monohydric or dihydric alcohol, and then adding the organic base dropwise and stirring to prepare a mixture.

[0107] According to another embodiment of the present invention, step (a) may be performed by first introducing an organic base and then introducing a monohydric or dihydric alcohol. When the organic base is an anion exchange resin, a step of first introducing a solvent and anion exchange resin and swelling the anion exchange resin in the solvent may be further performed. After performing the swelling step for 10 minutes or more or 20 minutes or more, the monohydric or dihydric alcohol may be introduced and stirred to prepare a mixture.

[0108] According to one embodiment of the present invention, step (b) may inject carbon dioxide gas into the reactor or the column described below via an external gas line. The gas injection method may use a conventional or known method, and as a non-limiting example, carbon dioxide gas may be continuously injected during the reaction to constantly control the pressure inside the reactor or column, or a carbon dioxide gas atmosphere may be formed only once before the start of the reaction and then the supply may be stopped, but is not limited thereto.

[0109] According to one embodiment of the present invention, the reaction in step (c) may be performed by stirring an organic base with a monohydric or dihydric alcohol under a CO2 gas atmosphere, but is not limited thereto.

[0110] According to another embodiment of the present invention, the step (S1-1) may include a step of manufacturing a column containing an organic base, forming a CO2 gas atmosphere within the column, and then passing a monohydric or dihydric alcohol through the column to cause a reaction. When the organic base is an anion exchange resin, a step of manufacturing a column containing anion exchange resin beads and continuously flowing a solvent through the column to cause the anion exchange resin to swell in the solvent may be further performed. Subsequently, after performing the swelling step for 10 minutes or more or 20 minutes or more, a reaction may be performed by flowing a monohydric or dihydric alcohol through the column. At this time, the formation of a carbon dioxide (CO2) gas atmosphere and the reaction may be performed in the same manner as the gas supply and reaction conditions described below.

[0111] According to another embodiment of the present invention, the step (S1) comprises: (S1-2) an organic base-CO2 absorbent formed from an organic base and CO2; and C 2-7 It may be a method of synthesizing an alkylene carbonate represented by the following chemical formula 1 by reacting a second reaction mixture containing a halogenated monohydric or dihydric alcohol.

[0112] According to one embodiment of the present invention, a step of producing an organic base-CO2 absorbent (hereinafter, absorbent) may be first performed prior to the step (S1-2). The organic base-CO2 absorbent may be formed from an organic base and CO2, and specifically, when CO2 is injected into the organic base, the CO2 may be adsorbed to form the absorbent.

[0113] According to one embodiment of the present invention, the organic base-CO2 absorbent in the step (S1-2) may be produced by any one of the following methods selected from (1) to (3).

[0114] (1) The organic base-CO2 absorbent may be formed in an external reactor and separately introduced into a second reaction mixture. Specifically, the organic base-CO2 absorbent may be formed by introducing an organic base and CO2 gas into an external reactor, and then introduced into the second reaction mixture through a separate means such as a supply line. In other words, the absorbent formation process and the alkylene carbonate reaction process may be performed in separate reactors.

[0115] (2) The above organic base-CO2 absorbent is an organic base, CO2 and C 2-7 It can be formed in the second reaction mixture containing a halogenated monohydric or dihydric alcohol. Specifically, an organic base and C 2-7 It may be possible to simultaneously introduce all halogenated monohydric or dihydric alcohols and supply CO2 gas to form an organic base-CO2 absorbent while simultaneously reacting the organic base-CO2 absorbent and the halogenated monohydric or dihydric alcohol.

[0116] (3) The above organic base-CO2 absorbent is formed in the same reactor immediately after C without separate separation. 2-7 It may react with a halogenated monohydric or dihydric alcohol. Specifically, by injecting an organic base and CO2 gas, an organic base-CO2 absorbent is formed, and then C is added to the same reactor without separate separation. 2-7The reaction can be carried out by introducing a halogenated monohydric or dihydric alcohol. In other words, the absorbent formation process and the alkylene carbonate reaction process can be performed in the same reactor.

[0117] According to one embodiment of the present invention, the organic base may be in contact with CO2 in the presence of a solvent when forming an organic base-CO2 absorbent. Depending on the type of the solvent, the absorbent may be dissolved in the solvent or may be precipitated as a solid organic base-CO2 precipitate. Without limitation, the solvent may include a combination of any one or more selected from the group consisting of water, acetone, methyl ethyl ketone, methyl iso-butyl ketone, acetonitrile, tetrahydrofuran, tetrahydrofuran (THF), dichloromethane (DCM), propylene carbonate, N-methyl-2-pyrrolidone (NMP), ethyl acetate, and N,N-dimethylacetamide (DMAc).

[0118] According to another embodiment of the present invention, the organic base-CO2 absorbent may be a precipitate formed from an organic base and CO2. The organic base may contact CO2 in the presence of a solvent to form a solid organic base-CO2 precipitate. At this time, the solvent may be used without significant limitation as long as it is a solvent in which the organic base-CO2 precipitate can be precipitated, and may be easily changed depending on the type of the organic base. The solvent may be polar and may be water, an organic base, or a mixture thereof. If the organic base includes DBU, the solvent may have a δP representing the polarity among the Hansen solubility factors of 5 MPa^0.5 or more, 7 MPa^0.5 or more, or 7 to 20 MPa^0.5, but is not limited thereto.

[0119] According to one embodiment of the present invention, the solvent may be included in an amount of 1 to 200 parts by weight, 1 to 150 parts by weight, 2 to 100 parts by weight, 5 to 80 parts by weight, or 10 to 70 parts by weight, relative to 10 parts by weight of the organic base when forming an organic base-CO2 absorbent or precipitate. Alternatively, the solvent input volume (㎖) may be included in a concentration of 1 to 50 ㎖ / g, 1 to 30 ㎖ / g, or 2 to 20 ㎖ / g relative to the weight (g) of the organic base input, but is not limited thereto.

[0120] According to one embodiment of the present invention, the contacting of the organic base with CO2 can be performed by injecting CO2 gas or forming a CO2 gas atmosphere as described in the specification. At this time, when forming the organic base-CO2 precipitate, the temperature condition may be performed under a temperature condition of 0 to 50°C, or 0 to 40°C, 0 to 35°C, 0 to 30°C, 0 to 25°C, or less than 45°C, or less than 35°C, less than 30°C, or less than 28°C, but is not limited thereto.

[0121] According to one embodiment of the present invention, when forming an organic base-CO2 absorbent or precipitate, the pressure condition may be performed under atmospheric pressure or pressurized conditions, and at this time, the pressure of the reaction may be based on the gauge pressure of the reactor, and may be the same as or different from the pressure condition of the reaction described below. Alternatively, the pressure condition may be a balloon pressure, and the balloon pressure may have the same meaning as commonly used in academic circles.

[0122] According to one embodiment of the present invention, in the step (S1-2), the reaction may be carried out by stirring the second reaction mixture under a CO2 gas atmosphere, but is not limited thereto. In addition, a process of injecting CO2 gas into the second reaction mixture during the reaction may be further performed. The process may inject carbon dioxide gas into the inside of the reactor or the inside of the column described below through an external gas line, as in a typical CO2 gas injection method. The gas injection method may use a typical or known method, and as a non-limiting example, carbon dioxide gas may be continuously injected during the reaction to constantly control the pressure inside the reactor or the column, or a carbon dioxide gas atmosphere may be formed only once before the start of the reaction and the supply may be stopped, but is not limited thereto.

[0123] According to one embodiment of the present invention, in the step (S1), the first reaction mixture (or mixture or second reaction mixture) may further include a solvent as described above. Since the solvent is not a toxic organic solvent such as DMSO or DMF, the manufacturing method according to one embodiment can satisfy both economical and environmental friendliness in that unnecessary treatments such as a recovery process after the completion of the reaction are not required. In addition, the solvent may be used without significant restrictions as long as it is a solvent in which the organic base can be dissolved.

[0124] According to one embodiment of the present invention, the solvent may be water or an aprotic polar solvent, or a mixture thereof, and specifically, the solvent may have a dielectric constant of 5 to 40, 10 to 35, 15 to 25, or 18 to 22. Non-limiting examples of the solvent include water, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, dichloromethane (DCM), propylene carbonate, ethyl acetate, and N,N-dimethylacetamide (DMAc), but acetone is preferably used.

[0125] According to one embodiment of the present invention, the solvent may be a ketone solvent, specifically C 1-5 Ketone solvent, C 1-4 Ketone solvent, or C 1-3 It may be a ketone solvent. Examples of the ketone solvent include acetone, 2-butanone (methyl ethyl ketone), 3-methyl-2-butanone (methyl-iso-propyl ketone), methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl iso-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, and acetophenone, but acetone is preferably used.

[0126] According to one embodiment of the present invention, the solvent may be included in an amount of 5 to 400 parts by weight, 10 to 200 parts by weight, 50 to 350 parts by weight, 50 to 200 parts by weight, or 100 to 200 parts by weight, based on 10 parts by weight of the monohydric or dihydric alcohol. Alternatively, the solvent input volume (mL) may be included in a concentration of 1 to 50 mL / g, 5 to 30 mL / g, or 15 to 25 mL / g based on the weight (g) of the monohydric or dihydric alcohol input, but is not limited thereto.

[0127] According to another embodiment of the present invention, the solvent may be included in an amount of 5 to 400 parts by weight, 10 to 350 parts by weight, 30 to 200 parts by weight, or 40 to 150 parts by weight, based on 10 parts by weight of the monohydric or dihydric alcohol. Alternatively, the solvent input volume (mL) may be included in a concentration of 1 to 50 mL / g, 2 to 30 mL / g, or 3 to 20 mL / g based on the weight (g) of the monohydric or dihydric alcohol input, but is not limited thereto.

[0128] According to one embodiment of the present invention, the step of preparing the absorbent of step (S-2) or the alkylene carbonate synthesis reaction of step (S1) may be performed under a temperature condition of 0 to 80°C, or may be performed under a temperature condition of 0 to 60°C, 0 to 50°C, 0 to 45°C, 0 to 40°C, 0 to 35°C, 0 to 30°C, or less than 45°C, or less than 35°C, less than 30°C, or less than 28°C, but is not limited thereto.

[0129] According to one embodiment of the present invention, the step of preparing the absorbent of step (S-2) or the alkylene carbonate synthesis reaction of step (S1) may be performed under a temperature condition of room temperature to 80°C, or may be performed under a temperature condition of room temperature to 60°C, room temperature to 50°C, room temperature to 45°C, room temperature to 40°C, room temperature to 35°C, room temperature to 30°C, or less than 45°C, or less than 35°C, less than 30°C, less than 28°C, or room temperature, but is not limited thereto.

[0130] Although it is common sense to those skilled in the art that a higher yield can be achieved by performing the reaction at a higher temperature, the manufacturing method according to one embodiment has the advantage of being able to achieve an excellent yield even at room temperature rather than at high temperature.

[0131] According to one embodiment of the present invention, the step of producing the absorbent in step (S-2) or the alkylene carbonate synthesis reaction in step (S1) may be performed under normal pressure or pressurized conditions. At this time, the pressure of the reaction is based on the gauge pressure of the reactor. The reaction may be performed under a condition of normal pressure (atmospheric pressure) without pressurizing the inside of the reactor, in which case the gauge pressure inside the reactor may be 0 bar. For example, the normal pressure reaction may be a reaction in which CO2 gas is continuously injected into the reactant without sealing the reactor. At this time, the concentration of the injected CO2 gas may be controlled by adjusting the flow rate valve of the CO2 gas supply line. Alternatively, the pressure condition may be a balloon pressure, and the balloon pressure may have the same meaning as commonly used in academic circles.

[0132] Alternatively, the step of producing the absorbent of the step (S-2), or the alkylene carbonate synthesis reaction of the step (S1), may be performed under pressurized conditions. For example, the reactor may be sealed (closed system) and CO2 gas may be injected into the reactants. The reaction may be performed under pressurized conditions in which the pressure within the reactor, i.e., the gauge pressure of the reactor, is greater than 0, 40 bar or less, 20 bar or less, 10 bar or less, 5 bar or less, 3 bar or less, or 2 bar or less, or the gauge pressure is 0.1 to 20 bar, 0.1 to 15 bar, 0.1 to 10 bar, 0.1 to 5 bar, 0.1 to 3 bar, or 0.1 to 2 bar. At this time, the concentration of CO2 gas may be controlled by controlling the flow valve of the CO2 gas supply line, but is not limited thereto. When the above reaction is performed under pressurized conditions, the pressure (gauge pressure) inside the reactor can be controlled according to the flow rate of the supplied CO2 gas.

[0133] According to one embodiment of the present invention, the step of producing the absorbent in step (S-2) or the alkylene carbonate synthesis reaction in step (S1) may be performed under a pressure condition of a gauge pressure of 0 bar to 20 bar, 15 bar to 10 bar, 5 bar to 3 bar, or 2 bar to 5 bar.

[0134] Although it is common sense to those skilled in the art that a higher yield can be achieved by performing the reaction at a higher pressure, the manufacturing method according to one embodiment has the advantage of being able to achieve an excellent yield even under atmospheric pressure or lower pressure conditions than before, rather than under high pressure conditions.

[0135] According to one embodiment of the present invention, the CO2 may be an industrial byproduct generated during an industrial process. This may be carbon dioxide gas recovered from industries that emit large amounts of greenhouse gases, such as carbon dioxide (CO2), during their production processes. The CO2 may be supplied externally via a transport method such as a pipeline, but is not limited thereto. By utilizing the carbon dioxide from the industrial byproduct, a more environmentally friendly process can be realized.

[0136] According to one embodiment of the invention, the organic base is characterized by being one or a combination of two or more selected from the group consisting of amines, bi- or polycyclic amine compounds, and salts thereof represented by the following chemical formula 2. The organic base may be one or a combination of two or more selected from the group consisting of amines, bi- or polycyclic amine compounds, and salts thereof represented by the above chemical formula 2. Specifically, the organic base may include one or more selected from the group consisting of an amine represented by the above chemical formula 2; a salt of an amine represented by the above chemical formula 2; a bi- or polycyclic amine compound; and a salt of a bi- or polycyclic amine compound; and the like. In addition, the organic base is preferably a non-metal base that does not contain a metal, and when it contains a metal or is an inorganic base, the reaction is undesirable because it occurs in a low yield at room temperature and pressure.

[0137] [Chemical Formula 2]

[0138]

[0139] In the above chemical formula 2, R2 to R4 are each independently hydrogen, straight chain or branched chain C 1-7 Alkyl, C 1-10 Hydroxyalkyl, C 3-20 An aryl or anion exchange resin-derived residue, wherein R2 to R4 are not all hydrogen.

[0140] The amine represented by the above chemical formula 2 may be a primary amine, a secondary amine, or a tertiary amine. In the above chemical formula 2, if two of R2 to R4 are hydrogen, the amine is a primary amine, if one of R2 to R4 is hydrogen, the amine is a secondary amine, and if not all of R2 to R4 are hydrogen, the amine may be a tertiary amine.

[0141] According to one embodiment of the present invention, in the above chemical formula 2, R2 to R4 are each independently hydrogen, straight chain or branched chain C 1-5 Alkyl, C 1-7 Hydroxyalkyl, C 3-20 An aryl or anion exchange resin-derived residue, wherein R2 to R4 are not all hydrogen. Specifically, in the above chemical formula 2, R2 to R4 are each independently hydrogen, straight-chain or branched C 1-3 Alkyl, C 1-3 A hydroxyalkyl or anion exchange resin-derived residue, and not all of which may be hydrogen. If the above structure is satisfied, the desired effect of the present invention can be achieved, which is preferable.

[0142] According to one embodiment of the present invention, in the above chemical formula 2, R2 to R4 are each independently hydrogen, straight chain or branched chain C 1-5 Alkyl, and all of R2 to R4 may not be hydrogen. Or R2 to R4 may be independently hydrogen, straight-chain or branched C 1-5 Alkyl, and at least one or two of R2 to R4 may be hydrogen. Or R2 to R4 are each independently a straight or branched chain C 1-5 It could be an alkyl.

[0143] According to one embodiment of the present invention, in the above chemical formula 2, R2 to R4 are each independently hydrogen, straight chain or branched chain C 1-5 Alkyl, and two of the above R2 to R4 may be hydrogen. Or R2 to R4 are each independently hydrogen, branched chain C 3-5Alkyl, and two of the R2 to R4 may be hydrogen. The alkyl may be a branched chain alkyl, and may be at least one selected from, but is not limited to, a tert-butyl group, a 2-ethylhexyl group, a 3-methylpentyl group, a 2,2-dimethylpropyl group, a 2-methylbutyl group, a 3-ethylheptyl group, a 2-methylpentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, and a 3-methylheptyl group.

[0144] According to one embodiment of the present invention, in the above chemical formula 2, R2 to R4 are each independently hydrogen or straight or branched chain C 1-3 Alkyl, and all of R2 to R4 may not be hydrogen. Or R2 to R4 may be independently hydrogen or straight or branched chain C 1-3 It is alkyl, and only one of R2 to R4 can be hydrogen.

[0145] According to one embodiment of the present invention, in the above chemical formula 2, R2 to R4 are each independently a straight chain or branched chain C 1-3 It may be alkyl, or the above R2 to R4 are each independently a straight chain C 1-3 It may be an alkyl. If it satisfies the above structure, it is preferable to achieve the effect aimed at in the present invention. The alkyl may be methyl, ethyl, propyl, or isopropyl.

[0146] Non-limiting examples of amines satisfying the above chemical formula 2 include monomethanolamine (MMA), monoethanolamine (MEA), methylamine, ethylamine, isopropylamine, t-butylamine, dimethylamine, diethylamine, diisopropylamine, trimethylamine, triethylamine, tripropylamine, N,N-Diisopropylethylamine, Tri-n-butylamine, triphenylamine, N,N-dimethylaniline, N,N-diisopropylaniline, N,N-diethylaniline, Examples include N,N,N',N'-tetramethylethylenediamine (TMEDA, N,N,N',N'-Tetramethylethylenediamine) and 4-dimethylaminopyridine (DMAP, 4-Dimethylaminopyridine), but they can be used without significant restrictions as long as they satisfy the above chemical formula 2.

[0147] According to another embodiment of the present invention, in the above chemical formula 2, R2 to R4 are each independently hydrogen or C 3-7 Hydroxyalkyl and may not all be hydrogen. If the above structure is satisfied, the effect aimed at in the present invention can be achieved, which is preferable.

[0148] The above hydroxy alkyl may be a straight or branched chain alkyl containing a hydroxyl group at the terminal. Non-limiting examples thereof include, but are not limited to, one or more selected from a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyethyl group, a hydroxynonyl group, a hydroxydecyl group, a 2-methyl-hydroxypropyl group, a 2-methyl-hydroxybutyl group, a 2-methyl-hydroxy-t-butyl group, a 3-methyl-hydroxybutyl group, a 2-ethyl-hydroxybutyl group, a 2-methyl-hydroxypentyl group, a 3-methyl-hydroxypentyl group, a 4-methyl-hydroxypentyl group, a 2-ethyl-hydroxypentyl group, a 3-ethyl-hydroxypentyl group, and a 2,2-dimethyl-hydroxybutyl group.

[0149] According to one embodiment of the present invention, the amine may include an alkanolamine, and non-limiting examples of the amine satisfying the chemical formula 2 include 2-aminoethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 1-amino-2-methyl-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 3-(dimethylamino)-1-propanol, 2-(diethylamino)ethanol, 1-amino-2-butanol, 3-amino-2-methyl-1-propanol, 2-amino-3-methyl-1-butanol, 2-amino-2-ethyl-1-propanol, Examples include 4-amino-2-methyl-1-butanol, 3-amino-3-methyl-1-butanol, 2-(isopropylamino)ethanol, and 2-(tert-butylamino)ethanol.

[0150] According to one embodiment of the present invention, the salt of the amine may be represented by the following chemical formula 6.

[0151] [Chemical Formula 6]

[0152] [R 64 ] - [N(R 61 )(R 62 )(R63 )H] +

[0153] In the above chemical formula 6, R 61 Inland R 63 are independently linear or branched C 1-5 Alkyl or C 3-20 Aryl, R 64 is an anion of a weak acid. The anion of the weak acid refers to the form of an anion that is the result of a weak acid forming a salt with an amine, as described below. In addition, N(R) of the chemical formula 6 61 )(R 62 )(R 63 ) may have the same structure as the chemical formula 2 described above, and for example, in the definition, R of the chemical formula 6 61 may be the same as R2 of the above chemical formula 2, and R of the above chemical formula 6 62 and R 63 may be the same as R3 and R4 of the above chemical formula 2, but is not limited thereto.

[0154] According to one embodiment of the present invention, the salt of the amine may be a salt of the amine represented by the above-described chemical formula 2 and the weak acid described below.

[0155] According to one embodiment of the present invention, the amine may further comprise a weak acid. The above weak acid may be one or a combination of two or more selected from the group consisting of aliphatic weak acids, alicyclic weak acids, and aromatic weak acids, and non-limiting examples thereof include formic acid, acetic acid, propionic acid, butyric acid, iso-butyric acid, valeric acid, hexanecarboxylic acid, adipic acid, azelaic acid, sebacic acid, sorbic acid, acrylic acid, methacrylic acid, isovaleric acid, furan-2-carboxylic acid, crotonic acid, glyoxylic acid, lactic acid, vinylacetic acid, pivelinic acid, 2-ethylbutyric acid, and the like; the above alicyclic weak acids include cyclopentanecarboxylic acid, cyclopropanecarboxylic acid, and the like; and the above aromatic weak acids include benzoic acid, nitrobenzoic acid, 3,5-dinitrobenzoic acid, acetylsalicylic acid, 4-aminobenzoic acid, Examples include, but are not limited to, 5-aminoisophthalic acid.

[0156] According to another embodiment of the present invention, in the above chemical formula 2, at least one of R2 to R4 is an anion exchange resin-derived residue and the rest are independently linear or branched C 1-3 It may be alkyl, or at least one of R2 to R4 is an anion exchange resin-derived residue, and the rest are independently straight chain C 1-3 It may be alkyl. The anion exchange resin is the same as described below.

[0157] For organic bases satisfying the above range, a significantly improved yield can be achieved even under conditions of room temperature and pressure.

[0158] According to one embodiment of the present invention, when at least one of R2 to R4 in the above chemical formula 2 is an anion exchange resin-derived residue, the organic base is an anion exchange resin, and the anion exchange resin may be a FB (Free Base) type weakly basic anion exchange resin including a secondary or tertiary amine group. Specifically, the anion exchange resin is a weakly basic anion exchange resin in which a specific cation is not pre-bonded to a secondary or tertiary amine and then, under a specific environment, a weakly acidic cation (H + ) may be combined with, if the anion exchange resin contains a halogen, it is not preferred because the reactivity with the monohydric or dihydric alcohol is low and the yield at room temperature and pressure is insufficient.

[0159] For example, the anion exchange resin may be a commercially available weakly basic anion exchange resin, and any one or more selected from products of Samyang Corporation such as TRILITE AW90, AW80, AW30, AW30C AW30L, Pure Resin products such as PA300 PA301, PA503, PA511, and DuPont products such as AmberLite FPA51, FPA52, FPA661, HPR9700, HPR9500, HPR7000, and the like.

[0160] According to one embodiment of the present invention, the anion exchange resin may be an acrylic resin (polymer), a styrene resin (polymer), or a copolymer thereof, and may be a copolymer copolymerized with another additional monomer (e.g., a crosslinking monomer), but is not limited thereto. As long as the repeating unit of the anion exchange resin is such, any known or conventional anion exchange resin, specifically a weakly basic anion exchange resin, may be used without significant limitation.

[0161] According to one embodiment of the present invention, the weakly basic anion exchange resin may be in the form of beads having an average particle size of 0.1 to 5.0 mm, 0.1 to 2.0 mm, 0.1 to 1.0 mm, or 0.2 to 0.6 mm. The average particle size was measured by a particle size analyzer.

[0162] According to one embodiment of the present invention, the weakly basic anion exchange resin may have a uniformity coefficient of 1.7 or less, 1.5 or less, or 1.2 or less, or 0.5 or more. The uniformity coefficient was measured according to a conventional method.

[0163] According to one embodiment of the present invention, the weakly basic anion exchange resin may have an exchange capacity of 1.2 eq / L or more, 1.5 eq / L or more, or 1.6 eq / L or more, or 10 eq / L or less. The exchange capacity was measured according to a conventional method.

[0164] According to one embodiment of the present invention, the weakly basic anion exchange resin may have a pH of 9 or less, or 7 to 9.

[0165] According to one embodiment of the present invention, when at least one of R2 to R4 is an anion exchange resin-derived residue, the organic base may be included in an amount of 5 to 100 parts by weight, 30 to 90 parts by weight, or 30 to 60 parts by weight, based on 10 parts by weight of the monohydric or dihydric alcohol.

[0166] According to one embodiment of the present invention, the bi- or polycyclic amine compound is an amine compound containing two or more ring structures, and may be a secondary or tertiary amine. The ring structures may be 3 to 30-membered rings, 3 to 20-membered rings, or 4 to 10-membered rings, and the bi- or polycyclic amine compound may contain 2 or more, 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2, or 3 ring structures. When the above structures are satisfied, the desired effect of the present invention can be achieved, which is preferable.

[0167] According to one embodiment of the present invention, the bi- or polycyclic amine compound may be a secondary or tertiary amine, and non-limiting examples thereof include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene), and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD).

[0168] According to one embodiment of the present invention, the bicyclic or polycyclic amine compound may be included in an amount of 0.5 to 60 wt%, 1 to 30 wt%, or 5 to 15 wt% based on the total weight of the organic base.

[0169] According to one embodiment of the present invention, the organic base may include a mixture of an amine represented by the above chemical formula 2 and a bi- or polycyclic amine compound. In this case, the equivalent ratio of the amine to the bi- or polycyclic amine compound may be 0.1 to 50:1, 1 to 30:1, or 3 to 20:1. In the case of an organic base satisfying the above range, a significantly improved yield can be achieved even under conditions of room temperature and pressure.

[0170] According to one embodiment of the present invention, the organic base may be included in an amount of 0.1 to 5 mol, 0.5 to 3 mol, 0.8 to 2.0 mol, or 1.0 to 1.5 mol per mol of the monohydric or dihydric alcohol.

[0171] According to another embodiment of the present invention, the organic base may be an organic superbase. The definition of the organic superbase may refer to an academically accepted or known definition, and may be an organic compound having a pKa of 15 or more or 20 or more, and examples thereof include, but are not limited to, bicyclic or polycyclic amine compounds such as DBU and TBD described above. When the organic base is a superbase, the organic base-CO2 absorbent may be a solid organic base-CO2 precipitate. Specifically, the organic superbase may come into contact with CO2 to form a solid organic base-CO2 precipitate.

[0172] According to one embodiment of the present invention, the absorbent (or precipitate) may be included in an amount of 0.1 to 5 mol, 0.5 to 3 mol, 0.8 to 2.0 mol, or 1.0 to 1.5 mol per mol of the monohydric or dihydric alcohol.

[0173] According to another embodiment of the present invention, not only an organic base but also an organic-inorganic hybrid can be used as a CO2 absorbent, thereby forming an organic base-CO2 absorbent from the organic-inorganic hybrid and CO2.

[0174] The above organic-inorganic hybrid can selectively utilize chemical adsorption and / or physical adsorption processes through zeolite or activated carbon to perform CO2 absorption. As a non-limiting example of the above organic-inorganic hybrid, an alkyleneamine-carbon nano hybrid composite can be prepared by reacting 3-aminopropyltriethoxysilane (APTS) and an alkyleneamine with a mesoporous silicate. Alternatively, an alkyleneamine-zeolite hybrid composite can be prepared by modifying a zeolite with an alkyleneamine base. When the above alkyleneamine-zeolite hybrid composite is used as a CO2 absorbent, the limitations of zeolite in the presence of carbon dioxide and moisture and the weakness of the material of the alkyleneamine base polymer, which is vulnerable at high temperatures, can be effectively complemented, thereby significantly improving efficiency. Without being limited thereto, various organic-inorganic hybrids can be used as CO2 absorbents, including, for example, organic amines, basic resins, and organic amines immobilized on organic, inorganic, and organic-inorganic supports, through which low-energy monolithic absorbents with multifunctional properties of CO2 absorption and reaction can be manufactured.

[0175] According to one embodiment of the present invention, the monohydric or dihydric alcohol is C 2-7 Halogenated monohydric alcohol, C 2-7 halogenated dihydric alcohols or mixtures thereof. Or the monohydric or dihydric alcohol may be C 2-5 Halogenated monohydric alcohol, C 2-5 It may include a halogenated dihydric alcohol or a mixture thereof. The monohydric or dihydric alcohol (primary or secondary alcohol) may be represented by the following chemical formula 3. In this case, C 2-7 means the carbon number of the halogenated alcohol, and R below 11 and R 12 Excluding the carbon of the substituent.

[0176] [Chemical Formula 3]

[0177]

[0178] In the above chemical formula 3, X is halogen, and R 11 Silver hydrogen, straight or branched chain C 1-10 Alkyl, (C 3-20 Aryl)-(C 1-10 alkyl), C 3-20 Aryl or (C 1-10 alkyl)-(C 3-20 Aryl), and optionally, any one of the carbon atoms of the alkyl may be substituted with one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2 and Si atoms, and R 12 is hydrogen, methyl or halogen.

[0179] Or in the above chemical formula 3, X may be I, Cl or Br, and R 11 Silver hydrogen, straight chain C 1-7 Alkyl, (C 3-12 Aryl)-(C 1-7 alkyl), C 3-12 Aryl or (C 1-7 alkyl)-(C 3-12 aryl), and optionally any one of the carbons of the alkyl may be substituted with one or more heteroatoms selected from O, N and C(=O), etc., and R 12 can be hydrogen, methyl or halogen.

[0180] Or in the above chemical formula 3, X may be I, Br or Cl, and R 11 Silver hydrogen or straight chain C 1-5 or C 1-3 It can be alkyl and R 12 can be hydrogen, methyl or halogen.

[0181] When a compound satisfying the above range is used as a starting material, it has excellent reactivity with an organic base, so that an alkylene carbonate can be produced in a high yield under milder conditions than before. If a compound that does not satisfy the above chemical formula 3, for example, a compound that does not contain a diol or halogen, the reactivity with an organic base is low, so that the yield at room temperature and pressure is insufficient, and thus it is not preferred. In particular, in the case of a monohydric alcohol where X is Cl, the reactivity is very low in the prior art, but when produced according to a method for producing an alkylene carbonate according to an embodiment, there is an advantage of exhibiting significantly improved reactivity and yield.

[0182] According to one embodiment of the present invention, in the chemical formula 3, R 11 If this is hydrogen, the above monohydric or dihydric alcohol is C 2-7 is a halogenated monohydric alcohol, and R 11 This straight or branched chain C 1-5 If it is alkyl, the above monohydric or dihydric alcohol is C 2-7 It is a halogenated dihydric alcohol.

[0183] According to one embodiment of the present invention, the monohydric or dihydric alcohol may contain, but is not limited to, one or more, two or more, or three or more hydroxyl groups. In addition, the monohydric or dihydric alcohol may contain, but is not limited to, one or more, two or more, or three or more halogens. Non-limiting examples of the above monohydric or dihydric alcohols include, but are not limited to, 2-bromoethanol, 1-bromo-2-propanol, 2-bromo-1-butanol, 3-bromo-1-butanol, 4-bromo-1-butanol, 2-chloroethanol, 1-chloro-2-propanol, 2-chloro-1-butanol, 3-chloro-1-butanol, 4-chloro-1-butanol, 2-bromo-1-phenyl ethanol, 2-bromo-2-phenyl ethanol, 2,2-dichloro-1-ethanol, 3-bromo-1,2-propanediol, 3-chloro-1,2-propanediol, 2-bromo propanol, and the like.

[0184] According to one embodiment of the present invention, the percentage (yield) of the amount of alkylene carbonate produced with respect to the amount of monovalent or divalent alcohol input may be 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more.

[0185] The present invention can provide an alkylene carbonate produced from the above-described method for producing an alkylene carbonate. The alkylene carbonate can be represented by the above chemical formula 1. The alkylene carbonate can include at least one selected from the group consisting of ethylene carbonate, 4-halogen ethylene carbonate, propylene carbonate, butylene carbonate, 4-halomethyl ethylene carbonate, 4-hydroxymethyl ethylene carbonate, 4-butyl ethylene carbonate, 4-ethoxymethyl ethylene carbonate, 4-allyloxymethyl ethylene carbonate, 4-aryl ethylene carbonate, and 4-aryloxymethyl ethylene carbonate.

[0186] According to one embodiment of the present invention, as shown in FIG. 1, a step of recovering a salt of an amine represented by the following chemical formula 4 formed as a byproduct of the reaction may be further performed. The separation and recovery method may be performed by a conventional or known method, and an example of the method may include, but is not limited to, a filtration method. The reaction conditions of the step of recovering the salt of the amine may be any conventional or known reaction conditions without limitation.

[0187] [Chemical Formula 4]

[0188]

[0189] In the above chemical formula 4, R5 to R7 are each independently hydrogen, straight chain or branched chain C 1-7 Alkyl, C 1-10 Hydroxyalkyl, C 3-20An aryl or anion exchange resin-derived residue, wherein R5 to R7 are not all hydrogen, and X is halogen. Specifically, R5 to R7 are each independently hydrogen, straight-chain or branched C 1-3 Alkyl, C 1-3 A hydroxyalkyl or anion exchange resin-derived residue, not all of which are hydrogen, and X may be Br or Cl. R5R6 and R7 of the above chemical formula 4 may have the same definition as R2, R3 and R4 of the chemical formula 2, respectively.

[0190] According to one embodiment of the present invention, as shown in FIG. 1, a step of reacting a second reaction mixture comprising a salt of the recovered amine and an alkylene oxide represented by the following chemical formula 5 to regenerate an alcohol and an organic base may be further performed. Specifically, a step of reacting the second reaction mixture to produce an alcohol and an organic base and then separating the reacted alcohol and the organic base may be further performed.

[0191] [Chemical Formula 5]

[0192]

[0193] In the above chemical formula 5, R 81 R of the above chemical formula 1 11 can be the same as R 82 is R of the above chemical formula 1 12 can be identical to R. Specifically, R 81 Silver hydrogen, or straight or branched chain C 1-5 It can be alkyl and R 82 may be hydrogen, methyl or halogen, or R 81 Silver hydrogen or straight chain C 1-3 It can be alkyl and R 82 may be hydrogen.

[0194] According to one embodiment of the present invention, the second reaction mixture may further comprise a solvent, a catalyst, or a mixture thereof. The solvent may be the same as or different from the solvent of the first reaction mixture described above. In addition, the catalyst may be a catalyst typically used in an alkylene oxide reaction.

[0195] According to one embodiment of the present invention, as shown in FIG. 1, the regenerated alcohol is used as a raw material for the reaction, C 2-7 It may be used as a halogenated monohydric or dihydric alcohol. In addition, the regenerated organic base may be used as a raw material for the reaction.

[0196] The present invention can provide a method for producing carbon dioxide precipitate, which comprises a step of forming a solid organic base-CO2 precipitate from an organic base and CO2, wherein the organic base is one or a combination of two or more selected from the group consisting of amines, bicyclic or polycyclic amine compounds, and salts thereof, represented by the following chemical formula 2. In this case, a specific description of the organic base and the organic base-CO2 precipitate is omitted as it is the same as described above.

[0197] [Chemical Formula 2]

[0198]

[0199] A detailed description of the above chemical formula 2 is omitted as it is the same as described above.

[0200] According to a manufacturing method according to one embodiment, not only can an alkylene carbonate be manufactured in a high yield, but also carbon dioxide, which is an industrial by-product, can be utilized, and the economic benefits are significantly improved by regenerating and reusing reaction by-products generated during the manufacturing process. In addition, since the above-described process can be performed continuously, the efficiency of the process is maximized, and energy use can be reduced, so environmental friendliness can also be easily secured.

[0201] The present invention will be described in more detail based on the following examples and comparative examples. However, the following examples and comparative examples are merely illustrative examples for further explaining the present invention, and the present invention is not limited by the following examples and comparative examples.

[0202] [Example 1]

[0203]

[0204] 2-Bromoethanol (10 g, 80.025 mmol) was dissolved in 100 mL of acetone in a reactor, and triethylamine (TEA) (16.9 mL, 120.038 mmol, 1.5 eq.) was added dropwise and stirred. After degassing with carbon dioxide three times in the reactor, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure in the reactor at 0.5 atm (bar), and the mixture was stirred and reacted at room temperature for 24 hours. After completion of the reaction, the reactor was vented, stirred for 10 minutes, diethyl ether (100 mL) was added, stirred for 30 minutes, and the reactant was filtered. The filtered solid was removed, and the filtrate was concentrated under reduced pressure, and finally ethylene carbonate was obtained in a yield of 98%. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0205] Specifically, the yield was calculated by the following equation 1.

[0206] [Formula 1]

[0207] (Number of moles of ethylene carbonate obtained / Number of moles of monohydric or dihydric alcohol added) X 100

[0208] [Example 2]

[0209]

[0210] 2-Bromoethanol (10 g, 80.025 mmol) was dissolved in 100 mL of acetone in a reactor, and triethylammonium acetate (TEA·CH3CO2H) (16.3 g, 120.038 mmol, 1.5 eq.) was added and stirred. After degassing the reactor with carbon dioxide three times, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure inside the reactor at 0.5 atm, and the mixture was stirred and reacted at room temperature for 24 hours. After completion of the reaction, the reactor was vented, stirred for 10 minutes, diethyl ether (100 mL) was added, stirred for 30 minutes, and the reactant was filtered. The filtered solid was removed, the filtrate was concentrated under reduced pressure, the concentrate was dissolved in water (100 ml), and extracted 10 times with DCM (20 ml). The extracted organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure. Finally, ethylene carbonate was obtained in a yield of 91%. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0211] [Example 3]

[0212]

[0213] Anion resin (TRILITE AW90, Samyang Corporation) (80 g, 200 mmol, 1.6 eq.) was added to 200 mL of acetone in a reactor and stirred for 30 minutes to allow swelling. Subsequently, 2-bromoethanol (10 g, 80.025 mmol) was added to the reactor, and carbon dioxide degassing was performed three times. Then, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure in the reactor at 0.5 atm, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction was completed, the reactor was vented, stirred for 10 minutes, and the reactant was filtered. The anion resin used in the reaction was removed, and the filtrate was concentrated under reduced pressure, and finally ethylene carbonate was obtained in an 84% yield. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0214] [Example 4]

[0215]

[0216] 2-Chloroethanol (10 g, 124.192 mmol) was dissolved in 100 mL of acetone in a reactor, and then triethylamine (TEA) (26.2 mL, 186.289 mmol, 1.5 eq.) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (1.85 mL, 12.419 mmol, 0.1 eq.) were added together and stirred. After degassing the reactor with carbon dioxide three times, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure in the reactor at 0.5 atm, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction was completed, the reactor was evacuated, stirred for 10 minutes, 200 ml of diethyl ether was added, stirred for 30 minutes, and the reaction product was filtered. The filtered solid was removed, and the filtrate was concentrated under reduced pressure, and finally ethylene carbonate was obtained in 86% yield. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0217] [Example 5]

[0218]

[0219] 1-Chloro-2-propanol (10 g, 105.775 mmol) was dissolved in 100 mL of acetone in a reactor, and then triethylamine (TEA) (22.3 mL, 158.662 mmol, 1.5 eq.) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (1.58 mL, 10.577 mmol, 0.1 eq.) were added together and stirred. After degassing the reactor with carbon dioxide three times, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure in the reactor at 0.5 atm, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction was completed, the reactor was evacuated, stirred for 10 minutes, 200 ml of diethyl ether was added, stirred for 30 minutes, and the reaction product was filtered. The filtered solid was removed, and the filtrate was concentrated under reduced pressure, and finally ethylene carbonate was obtained in a yield of 96%. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0220] [Example 6]

[0221] To the reactor, 36.45 g (360.115 mmol, 1.5 eq) of triethylamine (TEA) and 9.1 g (㎖) of distilled water were added to prepare an 80% TEA aqueous solution, and then 30 g (240.076 mmol) of 2-bromoethanol was added dropwise and stirred. After performing carbon dioxide degassing three times in the reactor, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure inside the reactor at 1 atm, and the mixture was stirred and reacted at room temperature for 24 hours. After completion of the reaction, the reactor was exhausted, 50 ml of acetone was added, stirred for 30 minutes, and the reactant was filtered. The filtered solid was removed, extracted five times with dichloromethane (DCM) and water, the organic layer was separated and concentrated under reduced pressure, and finally ethylene carbonate was obtained with a yield of 90.3%. The product is 1 It was confirmed by H-NMR spectrum analysis.

[0222]

[0223] [Comparative Example 1]

[0224] In Example 3, instead of the anion resin, 1.1 equivalents (eq.) of NaHCO3 powder was dissolved in 10 ml of water and added to the alcohol, and only 100 ml of acetone was added, and the reaction was performed for 40 hours, except that the same procedure as Example 1 was followed. The yield was calculated to be 20%.

[0225] [Comparative Example 2]

[0226] The same procedure as in Example 1 was followed, except that TRILTE MA20, a strong basic anion exchange resin, was used instead of AW90 in Example 3. The yield was calculated to be 31%.

[0227]

[0228] The raw material monohydric or dihydric alcohol, type of organic base, solvent, and reaction conditions are described in Table 1 below, and the yield of ethylene carbonate obtained accordingly is also recorded.

[0229] AlcoholOrganic baseSolventCO2Atmospheric pressureReaction yieldExample 1Bromoethanol (10g)TEA (1.5 eq.)Acetone (100㎖)0.5 bar24 hours98%Example 2Bromoethanol (10g)TEA CH3CO2H (1.5 eq.)Acetone (100㎖)0.5 bar24 hours91%Example 3Bromoethanol (10g)AW90 (80g)Acetone (200㎖)0.5 bar24 hours84%Example 4Chloroethanol (10g)TEA+DBU(1.5+0.1eq.)Acetone (100㎖)0.5 bar24 hours86%Example 51-Chloro-2-propanol(10g)TEA+DBU(1.5+0.1eq.)Acetone(100㎖)0.5 bar24 hours96%Example 6Bromoethanol(10g)TEA(1.5eq.)Water(9㎖)1 bar24 hours90%Comparative Example 1Bromoethanol(10g)NaHCO3(1.1eq.)Acetone+Water(100+10㎖)0.5 bar40 hours20%Comparative Example 2Bromoethanol(10g)MA20(80g)Acetone(200㎖)0.5 bar24 hours31%

[0230] As shown in Table 1 above, the method for producing alkylene carbonates according to one embodiment exhibited a high yield at room temperature and pressure without using a toxic solvent. In particular, through comparison between the examples and Comparative Example 1, it was confirmed that when NaHCO3, an inorganic base containing a metal, was used, a lower yield was observed at room temperature and pressure than when an organic base was used.

[0231] In addition, through a comparison between Example 3 and Comparative Example 2, it was confirmed that the effect of a weakly basic anion resin was remarkable, and that a strongly basic anion resin had poor reactivity with bromoethanol.

[0232] In addition, through comparison of Examples 1 and 4, it was confirmed that when a certain amount of a bicyclic or polycyclic amine compound is added when an organic base is added, a significant yield improvement effect can be achieved.

[0233]

[0234] [Example 7]

[0235]

[0236] Triethylamine (TEA) (18.85 g, 186.289 mmol, 1.2 eq.), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (3.78 g, 12.419 mmol, 0.2 eq.), and 40 mL of acetone were charged into a high-pressure reactor, and high-purity CO2 gas was injected under normal pressure or pressure at room temperature for a sufficient time to prepare a TEA-DBU-CO2 absorbent.

[0237]

[0238] Next, the manufactured TEA-DBU-CO2 absorbent was transferred to a pressure reactor, and 2-chloroethanol (10 g, 124.193 mmol) was added. After degassing with carbon dioxide in the reactor three times, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure in the reactor at 3 atm (bar), and the reaction mixture was stirred and reacted at room temperature for 6 hours (reaction time). After completion of the reaction, the reactor was exhausted, and the conversion of ethylene carbonate was confirmed by gas chromatography. The conversion of the ethylene carbonate produced at this time was 99.9%.

[0239] Next, the reaction mixture was cooled to 0 to 5°C, stirred for 30 minutes, and the resulting TEA-DBU hydrochloride (TEA-DBU hydrochloride) was filtered using a filter. The amount of TEA-DBU hydrochloride obtained was 15.9 g (93% yield).

[0240] The above filtered filtrate was concentrated under reduced pressure and purified by distillation to obtain 10.39 g of ethylene carbonate with a yield of 95%. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0241] At this time, the yield of ethylene carbonate, which is an alkylene carbonate, was calculated by the following equation 2, and the yield of TEA-DBU hydrochloride, which is a salt of an amine, was calculated by the following equation 3.

[0242] [Formula 2]

[0243] (Number of moles of ethylene carbonate (alkylene carbonate) obtained / Number of moles of 2-chloroethanol (monohydric or dihydric alcohol) introduced) X 100

[0244] [Formula 3]

[0245] (Number of moles of TEA-DBU hydrochloride (amine salt) obtained / Number of moles of 2-chloroethanol (monohydric or dihydric alcohol) introduced) X 100

[0246]

[0247] [Example 8]

[0248] The same procedure as in Example 7 was performed except that in Example 7, 1.5 eq. of triethylamine (TEA) was added instead of 1.2 eq., 0.1 eq. of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was added instead of 0.2 eq., and 100 ml of acetone was added instead of 40 ml, the gauge pressure in the reactor was changed from 3 bar to 1 bar, and the reaction time was changed from 6 hours to 22 hours.

[0249] [Example 9]

[0250] The same procedure as Example 8 was followed, except that the gauge pressure in the reactor was changed from 1 bar to 2 bar and the reaction time was changed from 22 hours to 16 hours.

[0251] [Example 10]

[0252] The same procedure as Example 8 was followed, except that the gauge pressure in the reactor was changed from 1 bar to 3 bar and the reaction time was changed from 22 hours to 8 hours.

[0253] [Example 11]

[0254] 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) (22.7 g, 149.031 mmol, 1.2 eq.) and 100 mL of acetone were charged into a high-pressure reactor, and high-purity CO2 gas was injected under normal pressure or pressure at room temperature for a sufficient period of time to produce a DBU-CO2 absorbent.

[0255] Next, the manufactured DBU-CO2 absorbent was transferred to a pressure reactor, and 2-chloroethanol (10 g, 124.193 mmol) was added. After degassing with carbon dioxide in the reactor three times, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure in the reactor at 3 atm (bar), and the reaction mixture was stirred and reacted at room temperature for 6 hours (reaction time). After completion of the reaction, the reactor was exhausted, and the conversion of ethylene carbonate was confirmed by gas chromatography. The conversion of the ethylene carbonate produced at this time was 96.9%.

[0256] Next, the reaction mixture was cooled to 0 to 5°C, stirred for 30 minutes, and the resulting 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) hydrochloride (DBU·hydrochloride) was filtered using a filter. The amount of DBU hydrochloride obtained at this time was 20.4 g (88% yield).

[0257] The above filtrate was concentrated under reduced pressure and purified by distillation to obtain 10.06 g of ethylene carbonate with a yield of 92%. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0258] [Example 12]

[0259] The same procedure as Example 11 was followed, except that 50 ml of NMP (N-methyl-2-pyrrolidone) was used instead of 100 ml of acetone.

[0260] [Example 13]

[0261]

[0262] 50 ml of MEK (Methyl ethyl ketone) and 9.14 g (60.019 mmol, 1.5 eq) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were added to the reactor, the temperature was cooled to 15-20 ℃, and carbon dioxide gas (99.99% purity) was injected. The mixture was stirred for 3 hours to form a DBU-CO2 absorbent. Then, argon gas was injected to remove the remaining carbon dioxide gas. 5 g (40.013 mmol) of 2-bromoethanol was added dropwise and stirred at room temperature for 12 hours to react. After the reaction was completed, the reactant was filtered. The filtered solid (DBU·HBr, 8.2 g, 88% yield) was obtained, and the filtrate was concentrated under reduced pressure. The concentrate was dissolved in water (50 ml), extracted five times with DCM (20 ml), and the extracted organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure to finally obtain 3.4 g of ethylene carbonate with a yield of 97%. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0263] [Example 14]

[0264] 1.0 g (6.830 mmol, 0.55 eq) of 1,8-diazabicyclo[5,4,0]untec-7-ene (DBU) and 1 g (12.419 mmol) of 2-chloroethanol were charged into a reactor without solvent, carbon dioxide gas (99.99% purity) was injected, and the mixture was stirred for 1 hour to form a DBU-CO2 absorbent. Then, argon gas was injected to remove the remaining carbon dioxide gas, and the reaction solution was concentrated under reduced pressure. The concentrate was dissolved in 10 ml of water and extracted five times with 10 ml of DCM (Dichloromethane). The extracted lower organic layer was dried with MgSO4, filtered, and the filtrate was concentrated under reduced pressure to finally obtain 0.35 g of ethylene carbonate with a yield of 32%.

[0265] [Example 15]

[0266] In Example 13, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD, 16.7 g, 120.038 mmol, 1.5 eq.) was added instead of DBU, and 100 mL of acetone was added instead of MEK, and the mixture was stirred for 8 hours to form a TBD-CO2 absorbent, and 2-bromoethanol (2-bromoethanol) (10 g, 80.025 mmol) was added dropwise and stirred at room temperature for 24 hours to react, except that the same procedure as in Example 13 was repeated.

[0267] [Example 16]

[0268] Into an autoclave reactor, 16.2 g (160.051 mmol, 2.0 eq) of triethylamine (TEA) and 4 g of distilled water were charged, the temperature was cooled to 5-15 ℃, carbon dioxide gas (99.99% purity) was injected using balloon pressure, the mixture was suspended and stirred for 8 hours, and then argon gas was injected to remove the remaining carbon dioxide gas. 10 g (80.025 mmol) of 2-bromoethanol was added dropwise and transferred to the autoclave reactor. Carbon dioxide gas (99.99% purity) was injected into the autoclave reactor, degassing was performed three times, and the reaction was carried out by stirring at room temperature for 8 hours while maintaining the pressure gauge inside the autoclave at 3 atm. After the reaction was completed, the carbon dioxide gas was removed by degassing, and 50 ml of acetone was added and stirred for 30 minutes. After the reaction was completed, the reactant was filtered. The filtered solid (TEA_HBr, 13.0 g, 89% yield) was obtained and the filtrate was concentrated under reduced pressure. The concentrate was dissolved in 50 ml of water and extracted five times with 30 ml of DCM (Dichloromethane). The extracted lower organic layer was dried with MgSO4 and filtered, and the filtrate was concentrated under reduced pressure to finally obtain 6.1 g of ethylene carbonate with a yield of 86.6%.

[0269] [Example 17]

[0270] 2-Bromoethanol (10 g, 80.025 mmol) was dissolved in 100 mL of acetone in an autoclave, and triethylamine (TEA) (16.9 mL, 120.038 mmol, 1.5 eq.) was added dropwise and stirred. After degassing the reactor with carbon dioxide three times, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure inside the reactor at 1 atm (bar), and the reaction mixture was stirred at room temperature for 24 hours (reaction time). After completion of the reaction, the reactor was vented, stirred for 10 minutes, 100 mL of diethyl ether was added, stirred for 30 minutes, and the reactant was filtered.

[0271] The filtered solid triethylamine hydrobromide (TEA·HBr, 20.7 g, 95% yield) was obtained, and the filtrate was concentrated under reduced pressure, and finally 7 g of ethylene carbonate was obtained in 97% yield. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0272] [Example 18]

[0273] The same procedure as Example 17 was followed, except that diethylamine (DEA) (12.4 ml, 120.038 mmol, 1.5 eq.) was added instead of triethylamine.

[0274] Diethylamine hydrobromide (DEA·HBr, 16.6 g, 90% yield) as a filtered solid was obtained, and the filtrate was concentrated under reduced pressure, and finally 6.6 g of ethylene carbonate was obtained with a 94% yield. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0275] [Example 19]

[0276] The same procedure as Example 17 was followed, except that diisopropylamine (DIPA) (16.9 ml, 120.038 mmol, 1.5 eq.) was added instead of triethylamine.

[0277] Diisopropylamine hydrobromide (DIPA·HBr, 16.4 g, 75% yield) was obtained as a filtered solid, and the filtrate was concentrated under reduced pressure, and finally 5.4 g of ethylene carbonate was obtained with a 77% yield. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0278] [Example 20]

[0279] The same procedure as in Example 17 was followed, except that t-butylamine (tert-butylamine, t-BuNH2) (12.6 ml, 120.038 mmol, 1.5 eq.) was added instead of triethylamine to form a t-BuNH2-CO2 absorbent.

[0280] The filtered solid t-butylamine hydrobromide (t-BuNH2·HBr, 15.2 g, 82% yield) was obtained, and the filtrate was concentrated under reduced pressure, and finally 6.0 g of ethylene carbonate was obtained with 85% yield. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0281] [Example 21]

[0282] In the above Example 20, the same procedure as Example 20 was performed except that the gauge pressure inside the reactor was changed from 1 bar to 3 bar.

[0283] [Example 22]

[0284] Anion resin (TRILITE AW90, Samyang Corporation) (80 g, 200 mmol, 1.6 eq.) was added to 200 mL of acetone in a high-pressure reactor and stirred for 30 minutes to allow swelling. Then, 2-bromoethanol (10 g, 80.025 mmol) was added and stirred. After degassing the reactor with carbon dioxide three times, carbon dioxide gas (99.99% purity) was injected into the reactor to maintain the gauge pressure in the reactor at 1 atm (bar), and the reaction mixture was stirred and reacted at room temperature for 24 hours (reaction time). After completion of the reaction, the reactant was filtered, and the obtained resin (AW90) and resin salt (AW90-HBr) were dried to obtain 70 g. The filtrate was concentrated under reduced pressure, and 5.6 g of ethylene carbonate was finally obtained in a yield of 79%. The product was confirmed by 1H-NMR spectral analysis.

[0285]

[0286] The raw materials of the above examples, monohydric or dihydric alcohols, types of organic bases, solvents, and reaction conditions are described in Table 2 below, and the yield of the obtained amine salt (yield 1) and the yield of ethylene carbonate (yield 2) are recorded accordingly.

[0287] AlcoholOrganic baseSolventCO2AtmReaction yield1Yield2Example 7ChloroethanolTEA+DBUacetone3bar6hours93%95%Example 8ChloroethanolTEA+DBUacetone1bar22hours88%92%Example 9ChloroethanolTEA+DBUacetone2bar16hours90%94%Example 10ChloroethanolTEA+DBUacetone3bar8hours87%91%Example 11ChloroethanolDBUacetone3bar6hours88%92%Example 12BromoethanolDBUNMP3bar6hours-78%Example 13BromoethanolDBUMEKBalloonpressure12hours88%97%Example 14ChloroethanolDBU-Balloon Line pressure 1 hour - 32% Example 15 Bromoethanol TBD Acetone Balloon pressure 24 hours 90% 95% Example 16 Bromoethanol TEA Water 3 bar 8 hours 89% 87% Example 17 Bromoethanol TEA Acetone 1 bar 24 hours 95% 97% Example 18 Bromoethanol DEA Acetone 1 bar 24 hours 90% 94% Example 19 Bromoethanol DIPA Acetone 1 bar 24 hours 75% 77% Example 20 Bromoethanol t-BuNH 2 Acetone 1 bar 24 hours 82% 85% Example 21 Bromoethanol t-BuNH 2 Acetone 3 bar 24 hours 90% 94% Example 22 Bromoethanol AW 90 Acetone 1 bar 24 hours - 79%

[0288]

[0289] [Example 23]

[0290]

[0291] In a glass reactor equipped with a reflux condenser under an Ar atmosphere, triethylamine hydrobromide (37.6 g, 206.611 mmol, 4.0 eq.) prepared in Example 7 was dissolved in methanol (MeOH, 100 mL), and then propylene oxide (PO) (3 g, 51.652 mmol, 1.0 eq.) was added at room temperature and stirred. The second reaction mixture was stirred at 20 °C (reaction temperature) for 68 hours, and concentrated under reduced pressure (bath temperature during concentration: 20 °C) to remove MeOH. Dichloromethane (DCM) (50 mL) was added to the concentrate, stirred for 10 minutes, and then ether (10 mL) was added and filtered. Water (100 ml) was added to the filtrate, extracted 10 times (10 ml * 10) with DCM, the DCM organic layer was dried over MgSO4 and filtered, and the filtrate was concentrated under reduced pressure (bath temperature 20 °C during concentration), and the concentrate was further purified by distillation, to finally obtain 5.3 g of 1-bromopropan-2-ol with a yield of 74%. The product is 1 H - It was confirmed by NMR spectrum analysis.

[0292] [Example 24]

[0293] The same procedure as Example 23 was followed, except that dichloromethane instead of methanol was used and the reaction temperature was changed to 35°C. 1-bromopropan-2-ol was finally obtained in a yield of 63%.

[0294] [Example 25]

[0295] The same procedure as in Example 24 was followed, except that 2.0 eq. of triethylamine hydrobromide was added instead of 4.0 eq. and 80 ml of dichloromethane in the second reaction mixture was added instead of 100 ml. Finally, 1-bromopropan-2-ol was obtained in a yield of 62%.

[0296] At this time, the yield of 1-bromopropan-2-ol (yield 3) was calculated by the following equation 4.

[0297] [Formula 4]

[0298] (Number of moles of 1-bromopropan-2-ol (alcohol) obtained / Number of moles of propylene oxide (alkylene oxide) introduced) X 100

[0299] Salt of amine Catalyst Temperature Solvent Time Yield 3 Example 23 TEA·HBr 4.0 equivalents none 20 MeOH (100㎖) 68 hours 74% Example 24 TEA·HBr 4.0 equivalents none 35 DCM (100㎖) 24 hours 63% Example 25 TEA·HBr 2.0 equivalents none 35 DCM (80㎖) 24 hours 62%

[0300] As shown in Tables 2 and 3 above, the manufacturing method according to one embodiment can produce alkylene carbonates in high yields under relaxed conditions. In particular, both chloroethanol and bromoethanol were confirmed to exhibit high reactivity and yields in the presence of various organic bases. However, Example 14, a neat reaction without using a solvent, showed an inadequate yield.

[0301] In addition, in Examples 11 to 14, DBU was used alone as the organic base, but in Example 13, which used MEK as the solvent, Example 15, which used TBD as the organic base, and Examples 20 and 21, which used t-BuNH2 as the organic base, it was confirmed that the organic base-CO2 absorbent was formed as a solid precipitate. To find out more about this, the following experiment was performed, and the results are recorded in Table 4 below.

[0302] [Example 26]

[0303]

[0304] TBD (1,5,7-Triazabicyclo[4.4.0]dec-5-ene) (10 g, 71.839 mmol) as an organic base and 50 ml of THF (Tetrahydrofuran) as a solvent were charged into a reactor and cooled to 5-10°C. Then, CO2 gas was injected at room temperature for 4 hours under balloon pressure to form a precipitate. The precipitate was filtered, washed with the solvent, and dried to produce 11.5 g (yield: 92%) of a white solid TBD-CO2 precipitate.

[0305] [Example 27]

[0306]

[0307] Into the reactor, 10.9 g (59.498 mmol 1.5 equivalents) of the TBD-CO2 precipitate prepared in Example 26 and 50 ml of acetone were added, and then 5 g (40.013 mmol) of 2-bromoethanol was added dropwise, and the reaction was carried out at room temperature for 24 hours. After completion of the reaction, the reactor was vented, 50 ml of diethyl ether was added, stirred for 30 minutes, and the reactant was filtered. The filtered solid (TBD·HBr) was obtained, and the filtrate was concentrated under reduced pressure. The concentrate was dissolved in water (100 ml), extracted 10 times with 20 ml of DCM (Dichloromethane), and the extracted organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure, to finally obtain 3.27 g (yield: 93%) of ethylene carbonate.

[0308] [Example 28]

[0309] In Example 26, AMP (2-amino-2-methyl-1-propanol) (7.4 g, 83.019 mmol) was added in 30 mL of acetone as a solvent, and the temperature was maintained at room temperature, except that the injection was performed for 6 hours instead of 4 hours, thereby producing 8.6 g (yield: 85%) of a white solid AMP-CO2 precipitate.

[0310] [Example 29]

[0311] In Example 27, 7.9 g (60.019 mmol, 1.5 equivalents) of AMP-CO2 precipitate prepared in Example 9 was added instead of the TBD-CO2 precipitate prepared in Example 7, and the reaction was performed for 18 hours, and the same procedure as Example 27 was followed, to ultimately produce 2.46 g (yield: 70%) of ethylene carbonate.

[0312] [Example 30]

[0313] In the above Example 26, DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) (20 g, 131.37 mmol) was added instead of TBD, MEK 50 ml was added instead of THF, and the injection was performed for 8 hours instead of 4 hours, thereby obtaining a white solid DBU-CO2 precipitate.

[0314] In addition, in the above Example 27, 7 g (35.853 mmol, 1.5 equivalents) of the DBU-CO2 precipitate prepared above was added instead of the TBD-CO2 precipitate prepared in Example 26, and the same procedure as Example 27 was performed, to finally prepare 1.8 g of ethylene carbonate (yield: 90%).

[0315] [Example 31]

[0316] TBD16.7 g (120.038 mmol, 1.5 eq) and acetone 100 ml were charged into the reactor and cooled to 5-15℃. Then, CO2 gas was injected at room temperature with balloon pressure for 4 hours to form a precipitate. After completion, the reaction was cooled to 5-15℃, and 2-bromoethanol (2-bromoethanol) 10 g (80.025 mmol) was added dropwise and the reaction was carried out at room temperature for 12 hours. After completion of the reaction, the generated reactant was filtered, and the filtrate was concentrated under reduced pressure and subjected to GC analysis. The obtained concentrate was extracted with water and DCM (Dichloromethane), and the extracted organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure to finally obtain 6.7 g (95% yield) of ethylene carbonate.

[0317] [Example 32]

[0318] DBU 9.14 g (60.019 mmol, 1.5 eq) and MEK 50 ml were added to the reactor and cooled to 5-15°C. Then, CO2 gas was injected at room temperature for 3 hours using balloon pressure to form a precipitate. After completion, the reaction was cooled to 5-15°C, 2-bromoethanol 5 g (40.013 mmol) was added dropwise, and the reaction was carried out at room temperature for 12 hours, except that the same procedure as in Example 31 was performed, and 3.4 g (97% yield) of ethylene carbonate was finally obtained.

[0319] [Example 33]

[0320] The same procedure as in Example 31 was followed, except that t-BuNH2 was added in the same molar amount instead of TBD, to form a precipitate. After completion, the reaction was cooled to 5 to 15°C, and 10 g (80.025 mmol) of 2-bromoethanol was added dropwise, and the reaction was conducted at room temperature for 24 hours. The subsequent steps were followed in the same manner as in Example 31, and 6.9 g (98% yield) of ethylene carbonate was finally obtained.

[0321] [Example 34]

[0322] The same procedure as in Example 31 was repeated except that AMP was added in the same molar amount instead of TBD, resulting in the formation of a precipitate. It was confirmed that an excessive amount of white solid precipitate was formed to the extent that stirring was difficult. The reaction mixture was then cooled to 5-15°C, 10 g of 2-bromoethanol was added dropwise, and the reaction was allowed to proceed at room temperature for 24 hours. Subsequent steps were repeated as in Example 31, resulting in the final yield of 5.8 g (82% yield) of ethylene carbonate.

[0323] AlcoholOrganic baseSolventCO2Atmospheric pressureTemperatureTimeYieldExample 26-TBDTHFBalloon pressureRoom temperature4 hours92%Example 27BromoethanolTBD-CO2AcetoneAtmospheric pressureRoom temperature24 hours93%Example 28-AMPAcetoneBalloon pressureRoom temperature6 hours85%Example 29BromoethanolAMP-CO2AcetoneAtmospheric pressureRoom temperature18 hours70%Example 30BromoethanolDB U-CO2 acetone balloon pressure, room temperature, 24 hours, 90% Example 31 Bromoethanol TBD acetone balloon pressure, room temperature, 24 hours, 95% Example 32 Bromoethanol DBUMEK balloon pressure, room temperature, 12 hours, 98% Example 33 Bromoethanol t-BuNH2 acetone balloon pressure, room temperature, 24 hours, 98% Example 34 Bromoethanol AMP acetone balloon pressure, room temperature, 24 hours, 82%

[0324] As shown in Table 4 above, the organic base-CO2 absorbents manufactured according to Examples 26 to 34 were formed as solid precipitates, and ethylene carbonate was manufactured in high yields. It was confirmed that organic base-CO2 precipitates were formed by selecting a specific organic base or a specific solvent, and such solid precipitates have the advantage of improving the ease of transportation, so that the precipitates can be transferred to a separate reactor or stored for later use, and it was confirmed that there is an advantage of being able to selectively react and form high-purity precipitates even when using CO2, a by-product generated in an actual industrial process, rather than high-purity CO2.

[0325] As described above, the present invention has been described through specific matters and limited examples, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on this description.

[0326] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. (S1) C 2-7 A step of synthesizing an alkylene carbonate represented by the following chemical formula 1 by reacting a first reaction mixture containing a halogenated monohydric or dihydric alcohol, an organic base, and CO2; A method for producing an environmentally friendly alkylene carbonate, wherein the organic base is one or a combination of two or more selected from the group consisting of amines, bicyclic or polycyclic amine compounds and salts thereof represented by the following chemical formula 2. [Chemical Formula 1] [Chemical Formula 2] In the above chemical formulas 1 and 2, R 11 Silver hydrogen, straight or branched chain C 1-10 Alkyl, (C 3-20 Aryl)-(C 1-10 alkyl), C 3-20 Aryl or (C 1-10 alkyl)-(C 3-20 Aryl), Optionally, any one of the carbons of the above alkyl may be replaced by one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2 and Si atoms, R 12 is hydrogen, methyl or halogen, R2 to R4 are independently hydrogen, straight or branched chain C 1-7 Alkyl, C 1-10 Hydroxyalkyl, C 3-20 An aryl or anion exchange resin-derived residue, wherein R2 to R4 are not all hydrogen.

2. In paragraph 1, The above CO2 is a method for producing environmentally friendly alkylene carbonate, which is an industrial by-product generated in an industrial process.

3. In paragraph 1, The above step (S1) (S1-1) C 2-7 An environmentally friendly method for producing an alkylene carbonate, comprising injecting CO2 into a mixture containing a halogenated monohydric or dihydric alcohol and an organic base and reacting the mixture to synthesize an alkylene carbonate represented by the chemical formula 1.

4. In paragraph 3, The above reaction is a method for producing an alkylene carbonate by stirring an organic base with a monohydric or dihydric alcohol under a CO2 gas atmosphere.

5. In paragraph 3, The above reaction is a method for producing an alkylene carbonate by passing a monohydric or dihydric alcohol through an organic base column under a CO2 gas atmosphere.

6. In paragraph 1, The above step (S1) (S1-2) Organic base-CO2 absorbent formed from organic base and CO2; and C 2-7 An environmentally friendly method for producing an alkylene carbonate, comprising reacting a second reaction mixture containing a halogenated monohydric or dihydric alcohol to synthesize an alkylene carbonate represented by the following chemical formula 1.

7. In paragraph 6, A method for producing an environmentally friendly alkylene carbonate, wherein the organic base is brought into contact with CO2 in the presence of a solvent.

8. In paragraph 6, The above organic base-CO2 absorbent is a method for producing an environmentally friendly alkylene carbonate, which is a precipitate formed from an organic base and CO2.

9. In paragraph 6, The above organic base-CO2 absorbent is (1) Formed in an external reactor and separately injected into a second reaction mixture, or (2) Organic base, CO2 and C 2-7 formed in a second reaction mixture containing a halogenated monohydric or dihydric alcohol, or (3) C without separate separation immediately after formation in the same reactor 2-7 A method for producing an environmentally friendly alkylene carbonate by reacting with a halogenated monohydric or dihydric alcohol.

10. In paragraph 6, An environmentally friendly method for producing an alkylene carbonate, which further comprises a step of injecting CO2 gas into the second reaction mixture during the above reaction.

11. In paragraph 1, A method for producing an environmentally friendly alkylene carbonate, wherein the above monohydric or dihydric alcohol is represented by the following chemical formula 3. [Chemical Formula 3] In the above chemical formula 3, X is halogen, and R 11 Silver hydrogen, straight or branched chain C 1-10 Alkyl, (C 3-20 Aryl)-(C 1-10 alkyl), C 3-20 Aryl or (C 1-10 alkyl)-(C 3-20 Aryl), Optionally, any one of the carbons of the above alkyl may be replaced by one or more heteroatoms selected from B, O, N, C(=O), P, P(=O), S, S(=O)2 and Si atoms, R 12 is hydrogen, methyl or halogen.

12. In paragraph 11, A method for producing an environmentally friendly alkylene carbonate, wherein in the above chemical formula 3, X is I, Br or Cl.

13. In paragraph 1, In the above chemical formula 2, R2 to R4 are each independently hydrogen, straight chain or branched chain C 1-3 Alkyl, C 1-3 A method for producing an environmentally friendly alkylene carbonate, wherein the residue is derived from a hydroxy alkyl or anion exchange resin and is not all hydrogen.

14. In paragraph 1, A method for producing an environmentally friendly alkylene carbonate, wherein the organic base is included in an amount of 0.5 to 3 moles per mole of the monohydric or dihydric alcohol.

15. In paragraph 1, A method for producing an alkylene carbonate, wherein the above anion exchange resin is in the form of beads having an average particle size of 0.1 to 5.0 mm.

16. In paragraph 1, The above anion exchange resin is a method for producing an alkylene carbonate having a uniformity coefficient of 1.5 or less.

17. In paragraph 1, The above anion exchange resin is a method for producing an alkylene carbonate having an exchange capacity of 1.5 eq / L or more.

18. In paragraph 1, The above anion exchange resin is a method for producing an alkylene carbonate having a pH of 9 or less.

19. In paragraph 1, A method for producing an alkylene carbonate, wherein when the above R2 is a residue derived from an anion exchange resin, the organic base is included in an amount of 30 to 90 parts by weight based on 10 parts by weight of the monohydric or dihydric alcohol.

20. In paragraph 1, A method for producing an environmentally friendly alkylene carbonate wherein the above bicyclic or polycyclic amine compound is a secondary or tertiary amine.

21. In paragraph 1, A method for producing an alkylene carbonate, wherein the above bicyclic or polycyclic amine compound is included in an amount of 1 to 30 wt% based on the total weight of the organic base.

22. In paragraph 1, A method for producing an alkylene carbonate, wherein the above amine further contains a weak acid.

23. In paragraph 1, An environmentally friendly method for producing an alkylene carbonate, wherein the above reaction is performed under atmospheric pressure or pressurized conditions.

24. In paragraph 1, An environmentally friendly method for producing an alkylene carbonate, wherein the above reaction is performed under pressure conditions of normal pressure to 20 bar.

25. In paragraph 1, An environmentally friendly method for producing an alkylene carbonate, wherein the above reaction is performed under temperature conditions of 0 to 80°C.

26. In paragraph 1, A method for producing an environmentally friendly alkylene carbonate, wherein the first reaction mixture further comprises a solvent.

27. In paragraph 26, The above solvent is a method for producing an environmentally friendly alkylene carbonate having a dielectric constant of 10 to 35.

28. In paragraph 26, A method for producing an environmentally friendly alkylene carbonate, wherein the solvent is included in an amount of 10 to 200 parts by weight based on 10 parts by weight of the monohydric or dihydric alcohol.

29. In paragraph 1, A method for producing an environmentally friendly alkylene carbonate, wherein the alkylene carbonate comprises at least one selected from the group consisting of ethylene carbonate, 4-halogen ethylene carbonate, propylene carbonate, 4-butyl ethylene carbonate, 4-ethoxymethyl ethylene carbonate, 4-allyloxymethyl ethylene carbonate, 4-aryl ethylene carbonate, and 4-aryloxymethyl ethylene carbonate.

30. In paragraph 1, A method for producing an environmentally friendly alkylene carbonate, further comprising the step of recovering a salt of an amine represented by the following chemical formula 4 formed as a by-product of the above reaction. [Chemical Formula 4] In the above chemical formula 4, R5 to R7 are independently hydrogen, straight or branched chain C 1-5 Alkyl, C 1-5 Hydroxyalkyl, C 3-20 A residue derived from an aryl or anion exchange resin, wherein R2 to R4 are not all hydrogen, X is a halogen.

31. In paragraph 30, A method for producing an environmentally friendly alkylene carbonate, further comprising a step of reacting a third reaction mixture containing a salt of the recovered amine and an alkylene oxide represented by the following chemical formula 5 to regenerate an alcohol and an organic base. [Chemical Formula 5] In the above chemical formula 5, R 81 R of the above chemical formula 1 11 is identical to the definition of R 82 is R of the above chemical formula 1 12 is identical to the definition of .

32. In paragraph 31, A method for producing an environmentally friendly alkylene carbonate, wherein the third reaction mixture further comprises a solvent, a catalyst or a mixture thereof.

33. In paragraph 31, A method for producing an environmentally friendly alkylene carbonate, wherein the organic base regenerated above is used as a raw material for the reaction.

34. In paragraph 1, A method for producing an environmentally friendly alkylene carbonate, wherein the percentage (yield) of the amount of alkylene carbonate produced with respect to the amount of the above monovalent or divalent alcohol input is 80% or more.

35. An alkylene carbonate produced from a method for producing an environmentally friendly alkylene carbonate selected from any one of claims 1 to 34.

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