Method for producing cyclic carbonate compound

Abstract

To provide a method for producing a cyclic carbonate compound that exhibits superior reaction efficiency.SOLUTION: The foregoing problem is solved by providing a method for producing a cyclic carbonate compound, the method including a reaction step for supplying carbon dioxide as bubbles having a diameter of 1 μm or less into a liquid containing an epoxy compound, and causing a reaction between the epoxy compound and the carbon dioxide.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a cyclic carbonate compound. [Background technology]

[0002] Cyclic carbonate compounds are used as raw materials for polycarbonate resins, etc. As a method for producing such a cyclic carbonate compound, a method of reacting an epoxy compound with carbon dioxide is known (Patent Document 1, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5403537 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the method described in Patent Document 1 has the drawback that the reaction efficiency is sometimes insufficient.

[0005] The present invention has been made in view of the above problems, and a main object of the present invention is to provide a method for producing a cyclic carbonate compound with excellent reaction efficiency. [Means for solving the problem]

[0006] The present inventors have found that excellent reaction efficiency can be achieved by supplying carbon dioxide in the form of bubbles having a predetermined diameter.

[0007] That is, the present disclosure provides a method for producing a cyclic carbonate compound, characterized by including a reaction step of supplying carbon dioxide as bubbles having a diameter of 1 μm or less to a reaction liquid containing an epoxy compound, and reacting the epoxy compound and carbon dioxide.

[0008] According to the present disclosure, excellent reaction efficiency can be achieved.

[0009] In the present disclosure, the epoxy compound is preferably a monofunctional epoxy compound, because the effect of excellent reaction efficiency can be more effectively exhibited.

[0010] In the present disclosure, the content of the epoxy compound in 100 parts by mass of the reaction liquid is preferably 60 parts by mass or more, because this allows the effect of excellent reaction efficiency to be more effectively exhibited. [Effects of the Invention]

[0011] According to the present disclosure, a method for producing a cyclic carbonate compound with excellent reaction efficiency can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present disclosure relates to a method for producing a cyclic carbonate compound. The method for producing the cyclic carbonate compound of the present disclosure will be described in detail below.

[0013] A. Method for producing cyclic carbonate compounds The method for producing a cyclic carbonate compound of the present disclosure is characterized by having a reaction step in which carbon dioxide is supplied to a reaction liquid containing an epoxy compound in the form of bubbles having a diameter of 1 μm or less, and the epoxy compound and carbon dioxide are reacted with each other.

[0014] According to the present disclosure, excellent reaction efficiency can be achieved.

[0015] The manufacturing method of the present disclosure includes a reaction step. Each step of the manufacturing method of the present disclosure will be described in detail below.

[0016] 1.Reaction process This step is a step in which carbon dioxide is supplied as bubbles having a diameter of 1 μm or less to a reaction liquid containing an epoxy compound, and the epoxy compound and carbon dioxide are reacted with each other.

[0017] (1) Carbon dioxide The carbon dioxide supplied to this step is supplied to the reaction solution as bubbles having a diameter of 1 μm or less. In this step, the diameter of the bubbles is preferably 0.01 μm or more and 1 μm or less, more preferably 0.02 μm or more and 0.5 μm or less, particularly preferably 0.03 μm or more and 0.3 μm or less, and most preferably 0.05 μm or more and 0.2 μm or less, because this allows the effect of excellent reaction efficiency to be more effectively exhibited. The diameter of the bubbles refers to the diameter of the bubbles when they are supplied into the reaction liquid. The diameter of such bubbles can be the same as the size of the supply port that comes into contact with the reaction liquid and through which carbon dioxide is supplied. For example, when carbon dioxide is supplied from a ceramic filter, the pore size of the ceramic filter can be selected according to the desired bubble diameter. The pore size of the ceramic filter can be obtained, for example, in accordance with the method for measuring the maximum pore size of a porous body according to the ASTM (American Society for Testing and Materials) standard (F316-86) described in Patent No. 5148044.

[0018] The supply rate of the carbon dioxide is preferably 0.01 L / min to 1 L / min per 100 g of the epoxy compound, more preferably 0.02 L / min to 0.5 L / min, and particularly preferably 0.03 L / min to 0.3 L / min, because this allows the effect of excellent reaction efficiency to be more effectively exhibited. The volume (L) of carbon dioxide in this disclosure, including the examples, is a value measured under conditions of 0°C, atmospheric pressure of 0.1013 MPa, and relative humidity of 0%.

[0019] The supply pressure of the carbon dioxide is preferably 0.1 MPa or more and 1.5 MPa or less, more preferably 0.5 MPa or more and 1.2 MPa or less, and particularly preferably 0.8 MPa or more and 1.1 MPa or less, because this allows the effect of excellent reaction efficiency to be more effectively exhibited.

[0020] The amount of carbon dioxide supplied is preferably 0.7 to 3 moles, more preferably 0.8 to 2 moles, and particularly preferably 0.9 to 1.5 moles, per mole of the epoxy compound, because this allows the effect of excellent reaction efficiency to be more effectively exhibited. The above supply amount refers to the total amount of carbon dioxide supplied relative to the total amount of epoxy compounds contained in the reaction liquid at the start of this step.

[0021] The carbon dioxide may be supplied by any method that can supply the carbon dioxide as bubbles of a desired diameter, and examples thereof include a method of passing the carbon dioxide through a ceramic filter. The carbon dioxide supply method may be a method of bubbling the carbon dioxide into the reaction solution in a batch-type reaction vessel, or a method of removing the reaction solution in the reaction vessel to the outside and supplying the carbon dioxide into the reaction solution in a circulation line that returns the reaction solution to the reaction vessel.

[0022] (2) Reaction solution The reaction liquid contains an epoxy compound and is in a liquid state. Here, being in a liquid state means that the carbon dioxide is in a liquid state at least when it is supplied.

[0023] (2-1) Epoxy compounds The epoxy compound is not particularly limited as long as it is a compound having at least one epoxy group in one molecule, and examples thereof include monofunctional epoxy compounds having one epoxy group; and polyfunctional epoxy compounds having two or more epoxy groups, such as bifunctional epoxy compounds having two epoxy groups. In this step, the epoxy compound is preferably a monofunctional epoxy compound, since this can more effectively exhibit the effect of excellent reaction efficiency.

[0024] As the monofunctional epoxy compound, a compound represented by the following general formula (1) can be used.

[0025] [ka]

[0026] (In the formula, R 1 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.

[0027] R 1 The aliphatic hydrocarbon group having 1 to 20 carbon atoms used in may be a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocyclic ring, and examples thereof include a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aliphatic ring-containing group having 3 to 20 carbon atoms. Examples of the chain aliphatic hydrocarbon group having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms and alkenyl groups having 2 to 20 carbon atoms. Examples of the aliphatic ring-containing group having 3 to 20 carbon atoms include a cycloalkyl group having 3 to 20 carbon atoms and a cycloalkylalkyl group having 4 to 20 carbon atoms.

[0028] The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, isoamyl, tert-amyl, hexyl, heptyl, and octyl. Examples of branched alkyl groups include isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, and octadecyl.

[0029] The alkenyl group having 2 to 20 carbon atoms may be linear or branched. It may be a terminal alkenyl group having an unsaturated bond at the terminal, or an internal alkenyl group having an internal unsaturated bond. Examples of terminal alkenyl groups include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl. Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienylallyl.

[0030] Examples of the cycloalkyl group having 3 to 20 carbon atoms include saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and groups having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups have been substituted with alkyl groups. Examples of the saturated monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. Examples of the saturated polycyclic alkyl group include an adamantyl group, a decahydronaphthyl group, an octahydropentalene group, and a bicyclo[1.1.1]pentanyl group. Examples of the alkyl group substituting a hydrogen atom in the ring of a saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified above as the alkyl group having 1 to 20 carbon atoms. Examples of groups in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group have been substituted with alkyl groups include a bornyl group.

[0031] The cycloalkylalkyl group having 4 to 20 carbon atoms refers to a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and a monocyclic cycloalkyl group include a cyclopropylmethyl group, a 2-cyclobutylethyl group, a 3-cyclopentylpropyl group, a 4-cyclohexylbutyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a 2-cyclononylethyl group, and a 2-cyclodecylethyl group. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and a polycyclic cycloalkyl group include a 3-3-adamantylpropyl group and a decahydronaphthylpropyl group.

[0032] In the present disclosure, the above R 1is preferably a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, and among these, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 3 to 15 carbon atoms is particularly preferred, and among these, an alkyl group having 3 to 10 carbon atoms is particularly preferred, because the effect of excellent reaction efficiency can be more effectively exhibited. Above R 1 The alkyl group used may be linear or branched, but is preferably branched, since this allows the effect of excellent reaction efficiency to be more effectively exhibited.

[0033] In this step, the melting point of the epoxy compound is preferably 200°C or lower, more preferably 120°C or lower, particularly preferably 80°C or lower, particularly preferably 50°C or lower, particularly preferably 30°C or lower, because this allows the effect of excellent reaction efficiency to be more effectively exhibited.

[0034] The content of the epoxy compound is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, more preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and more preferably 95 parts by mass or more in 100 parts by mass of the reaction liquid, because this allows the effect of excellent reaction efficiency to be more effectively exhibited.

[0035] (2-2) Solvent The reaction liquid may contain a solvent in addition to the epoxy compound. Such a solvent may be any solvent capable of dissolving an epoxy compound, and examples thereof include organic solvents such as amide-based solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; alcohol-based solvents such as methanol, ethanol, propanol, ethylene glycol, and propylene glycol; and ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran.

[0036] In this step, the amount of the solvent used is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less, particularly preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less, particularly preferably 1 part by mass or less, particularly preferably 0 parts by mass, i.e., it is preferable to use the epoxy compound as the solvent, since this can more effectively exhibit the effect of excellent reaction efficiency.

[0037] (2-3) Catalyst The reaction liquid may contain a catalyst that promotes the reaction between the epoxy compound and carbon dioxide. The catalyst may be used in a state of being dissolved in the reaction liquid, or may be used as an immobilized catalyst supported on an insoluble carrier. Examples of such catalysts include inorganic halogen compounds such as lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, and sodium iodide; quaternary ammonium salts; and quaternary phosphonium salts. In this step, the catalyst is preferably an inorganic halogen compound, and among these, lithium iodide or sodium iodide is preferred, and sodium iodide is particularly preferred, because the effect of excellent reaction efficiency can be more effectively exhibited. The amount of the catalyst used is preferably 0.1 to 50 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the epoxy compound, because this allows the effect of excellent reaction efficiency to be more effectively exhibited.

[0038] (3) Reaction conditions The temperature of the reaction solution is preferably 0°C or higher and 200°C or lower, more preferably 30°C or higher and 180°C or lower, particularly preferably 50°C or higher and 150°C or lower, and more preferably 80°C or higher and 120°C or lower, because this allows the effect of excellent reaction efficiency to be more effectively exhibited.

[0039] 2. Other processes The production method of the present disclosure includes the reaction steps described above, but may also include other steps as necessary. Such other steps include a filtration step of filtering the reaction liquid after the reaction step, and a catalyst removal step of removing the catalyst and the like from the reaction liquid after the reaction step.

[0040] B. Other The present disclosure includes the following aspects. [1] A method for producing a cyclic carbonate compound, comprising a reaction step of supplying carbon dioxide as bubbles having a diameter of 1 μm or less to a reaction solution containing an epoxy compound, and reacting the epoxy compound and carbon dioxide. [2] The method for producing a cyclic carbonate compound according to [1], wherein the epoxy compound is a monofunctional epoxy compound. [3] The method for producing a cyclic carbonate compound according to [1] or [2], wherein the content of the epoxy compound in 100 parts by mass of the reaction liquid is 60 parts by mass or more.

[0041] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiment that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included within the technical scope of the present disclosure. [Example]

[0042] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited to these examples.

[0043] [Example 1] 400 g of 2-ethylhexyl glycidyl ether (trade name: Denacol EX-121, Nagase ChemteX Corporation) with an epoxy equivalent weight of 187 and 8.1 g of sodium iodide (Fujifilm Wako Pure Chemical Industries, Ltd.) were charged into a 500 mL four-neck flask. The mixture was then heated to 100°C with stirring. After the temperature was raised to 100°C, carbon dioxide was continuously supplied at a flow rate of 0.2 L / min with 0.1 μm bubbles through a porous ceramic ultrafine bubble generator placed inside the four-neck flask for 4 hours while maintaining the temperature at 100°C with continued stirring. The epoxy compound, 2-ethylhexyl glycidyl ether, and carbon dioxide were allowed to react for 4 hours from the start of the carbon dioxide supply. After 4 hours of reaction, a sample was taken and dissolved in deuterated chloroform. 1 HNMR was measured. 1 The disappearance of the raw materials and the production of the target cyclic carbonate compound represented by the following formula (1-1) were confirmed by HNMR. In addition, the production of the compound represented by the following formula (1-2) as a by-product was also confirmed. The reaction rate was 95% or more. The by-product production rate was 0.7%. The amount of carbon dioxide supplied, calculated from the reaction time and flow rate, was 1.1 moles per mole of epoxy raw material. After the temperature was returned to room temperature, filtration was carried out, and 10 parts of Kyoward (registered trademark) 500SH (Kyowa Chemical Industry Co., Ltd.) were added to remove the catalyst, thereby obtaining the target product. The loss of raw materials is1 This was confirmed by HNMR to confirm that the peak of the epoxy group in the epoxy compound charged as a raw material had disappeared. The volume of carbon dioxide (L) is the value under the conditions of 0°C, atmospheric pressure of 0.1013 MPa, and relative humidity of 0%. The reaction rate refers to the ratio of the number of moles of the synthesized target product to 1 mole of the epoxy compound charged as a raw material (= number of moles of the target product / number of moles of the epoxy compound charged as a raw material (%)). The ratio of the number of moles of the target product to 1 mole of the epoxy compound is as follows: 1 Determined by HNMR. The production rate of by-products refers to the ratio of the number of moles of synthesized by-products to 1 mole of epoxy compound charged as a raw material (= number of moles of by-products / number of moles of epoxy compound charged as a raw material (%)). The ratio of the number of moles of by-products to 1 mole of epoxy compound is as follows: 1 Determined by HNMR.

[0044] [ka]

[0045] [Comparative Example 1] 400 g of 2-ethylhexyl glycidyl ether (trade name: Denacol EX-121, Nagase ChemteX Corporation) with an epoxy equivalent weight of 187 and 8.1 g of sodium iodide (Fujifilm Wako Pure Chemical Industries, Ltd.) were charged into a 500 mL four-neck flask. The mixture was then heated to 100 °C with stirring. After the temperature was raised to 100 °C, carbon dioxide was continuously supplied through a porous glass bubble generator placed in the four-neck flask with 5.0 μm bubbles at a flow rate of 0.2 L / min for 6 hours while maintaining the temperature at 100 °C. The epoxy compound, 2-ethylhexyl glycidyl ether, and carbon dioxide were reacted for 6 hours from the start of carbon dioxide supply. Sampling was performed 4 hours and 6 hours after the start of carbon dioxide supply. After 4 hours of reaction, the sample was dissolved in deuterated chloroform. 1HNMR measurement revealed that the reaction rate was 88%, and 6.7% by mass of the raw material epoxy compound remained at the time of charging. In the sample taken after 6 hours of reaction, 1 The disappearance of the raw materials and the production of the target cyclic carbonate represented by the above formula (1-1) were confirmed by HNMR. The production of the compound represented by the above formula (1-2) as a by-product was also confirmed. The reaction rate was 95% or higher. The by-product production rate was 0.7%. The amount of carbon dioxide supplied, calculated from the reaction time and flow rate, was 1.65 moles per mole of epoxy raw material. After the temperature was returned to room temperature, filtration was performed, and 10 parts of Kyoward (registered trademark) 500SH (Kyowa Chemical Industry Co., Ltd.) were added to remove the catalyst, yielding the target product.

[0046] It was confirmed that the reaction proceeded in a shorter time in the production method of the example than in the comparative example. From this result, it was confirmed that the production method of the present disclosure has excellent reaction efficiency.

Claims

1. A method for producing a cyclic carbonate compound, comprising a reaction step of supplying carbon dioxide as bubbles having a diameter of 1 μm or less to a reaction liquid containing an epoxy compound, and reacting the epoxy compound with the carbon dioxide.

2. The method for producing a cyclic carbonate compound according to claim 1, wherein the epoxy compound is a monofunctional epoxy compound.

3. 3. The method for producing a cyclic carbonate compound according to claim 1, wherein the content of the epoxy compound in 100 parts by mass of the reaction liquid is 60 parts by mass or more.

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