Method for producing carbonate compound

Abstract

The purpose of the present invention is to provide a method for efficiently producing a carbonate compound from a halogenated hydrocarbon having 2 or more carbon atoms. This method for producing a carbonate compound is characterized by comprising: an oxidative photodecomposition step for obtaining an oxidative photodecomposition product of a C2-4 halogenated hydrocarbon by irradiating the C2-4 halogenated hydrocarbon having one or more halogenated groups selected from the group consisting of chlorine groups, bromine groups, and iodine groups with light in the presence of oxygen; an alcohol compound reaction step for reacting the oxidative photolysis product with an alcohol compound; and a base addition step in which an inorganic base is added after the alcohol compound reaction step, or an organic base is added at least after the oxidative photodecomposition step.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for safely and efficiently producing carbonate compounds. BACKGROUND

[0002] Tetrachloroethylene is in a liquid state at ordinary temperature and is used as a general-purpose organic solvent having high chemical stability. In addition, it is produced and consumed in large amounts worldwide for dry cleaning fluid, cleaning of metals, and the like. However, tetrachloroethylene is known to paralyze the central nervous system, cause liver damage and carcinogenesis, and in addition, sometimes causes skin inflammation by dissolving the fatty components of the skin. In addition, tetrachloroethylene has been used in large amounts as a dry cleaning solvent for a long time, but its demand is decreasing year by year due to the above-mentioned toxicity and the like.

[0003] Halogenated hydrocarbons other than tetrachloroethylene have also been used as dry cleaning solvents and degreasing solvents in the field of electronics.

[0004] It is known that if tetrachloroethylene is irradiated with ultraviolet light in an oxygen atmosphere, it is decomposed into carbon oxides such as phosgene, carbon monoxide, chlorine, trichloroacetyl chloride (TCAC), and the like. Since these compounds have high chemical reactivity, they are harmful to the human body and the environment if released into the atmosphere. However, on the other hand, due to the high chemical reactivity, they are expected to be used as extremely useful C1 and C2 building blocks and the like in the field of synthetic chemistry.

[0005] The present inventors and others have developed various technologies for performing photoirradiation on halogenated hydrocarbons in the presence of oxygen and utilizing the resulting oxidative photodecomposition products for chemical synthesis. For example, Patent Literature 1 discloses a method for producing a halogenated carboxylate, characterized by performing photoirradiation on a mixture containing a halogenated hydrocarbon and an alcohol in the presence of oxygen, and discloses an example of producing hexyl trichloroacetate from tetrachloroethylene (1,1,2,2-tetrachloroethylene).

[0006] However, among carbonate compounds, aliphatic carbonates have been used as solvents and the like, and in particular in recent years, as non-aqueous solvents for electrolytes of lithium ion secondary batteries, the production amount has been increasing. In addition, polycarbonates, which are condensates of carbon dioxide and bisphenol compounds, are widely used as engineering plastics excellent in transparency and impact resistance.

[0007] Carbonate compounds are generally produced from phosgene and alcohol compounds. However, phosgene reacts easily with water to produce hydrogen chloride, or has a history of being used as a toxic gas, and is a very toxic substance. Furthermore, although there are methods for reacting carbon monoxide, alcohol, and oxygen, there is a problem that toxic carbon monoxide must be used under high pressure. Therefore, safe production methods for various carbonate compounds are being studied.

[0008] The present inventors have developed a technique for safely and efficiently producing a carbonate compound using a halogenated hydrocarbon. For example, Patent Literature 2 discloses a method for producing a carbonate derivative, which includes a step of subjecting a composition containing a halogenated hydrocarbon, a compound containing a nucleophilic functional group, and a base to light irradiation in the presence of oxygen. Patent Literature 3 discloses a method for producing a polycarbonate, which includes a step of subjecting a composition containing a halogenated hydrocarbon, a diol compound, and a specific base to light irradiation in the presence of oxygen.

[0009] Prior Art Documents

[0010] Patent Literature

[0011] Patent Literature 1: International Publication No. 2015 / 156245

[0012] Patent Literature 2: International Publication No. 2018 / 211952

[0013] Patent Literature 3: International Publication No. 2020 / 100975 SUMMARY

[0014] As described above, the present inventors have developed various techniques for using an oxidative photolyzate of a halogenated hydrocarbon for chemical synthesis, and have also developed a method for producing a carbonate compound. In these techniques, chloroform is mainly used as the halogenated hydrocarbon.

[0015] However, the present inventors have found through experiments that, in the case of using a halogenated hydrocarbon having 2 or more carbon atoms, even if a mixture containing the halogenated hydrocarbon, an alcohol compound, and a base is subjected to high-energy light irradiation, the desired carbonate compound is not sufficiently produced.

[0016] Therefore, an object of the present application is to provide a method for efficiently producing a carbonate compound from a halogenated hydrocarbon having 2 or more carbon atoms.

[0017] The present inventors have conducted intensive studies in order to solve the above-described problems. As a result, it has been found that, if a mixture containing a halogenated hydrocarbon compound having 2 or more carbon atoms, an alcohol compound, and a base is subjected to high-energy light irradiation, the desired carbonate compound is not obtained, but by adjusting the timing of addition of the base, the desired carbonate compound can be efficiently produced from a halogenated hydrocarbon having 2 or more carbon atoms, thereby completing the present application.

[0018] Hereinafter, the present application will be described.

[0019] [1] A method for producing a carbonate compound, characterized by comprising:

[0020] an oxidative photolysis step of subjecting a halogenated hydrocarbon having a halogen group selected from one or more of a chlorine group, a bromine group, and an iodine group to light irradiation in the presence of oxygen to obtain a C 2-4 a carbonate compound.2-4 a process of oxidizing and photolyzing a halogenated hydrocarbon,

[0021] an alcohol compound reaction process of reacting the oxidized and photolyzed product with an alcohol compound,

[0022] a base addition process of adding an inorganic base after the alcohol compound reaction process, or at least adding an organic base after the oxidizing and photolyzing process.

[0023] [2] The method according to the above [1], wherein the C 2-4 a halogenated hydrocarbon and the alcohol compound are subjected to light irradiation.

[0024] [3] The method according to the above [1] or [2], wherein the inorganic base is added after the alcohol compound reaction process.

[0025] [4] The method according to any one of the above [1] to [3], wherein tetrachloroethylene is used as the C 2-4 halogenated hydrocarbon.

[0026] [5] The method according to any one of the above [1] to [4], wherein the light irradiated to the C 2-4 halogenated hydrocarbon has a peak wavelength included in a range of 180 nm to 500 nm.

[0027] The method of the present application provides a new use of a C 2-4 halogenated hydrocarbon, which is consumed in large amounts for dry cleaning and the like, but the demand for which is decreasing year by year. In addition, by the method of the present application, a carbonate compound can be produced without using a highly toxic compound such as phosgene or carbon monoxide, and a high-priced catalyst as a raw material compound. Therefore, the method of the present application is extremely useful in industry as a technology capable of safely and efficiently producing a useful carbonate compound. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is a schematic view showing one example of a configuration of a reaction apparatus used in the method of the present application.

[0029] Figure 2 is a schematic view showing one example of a configuration of a reaction apparatus used in the method of the present application. DETAILED DESCRIPTION

[0030] The method of producing a carbonate compound of the present application includes an oxidizing and photolyzing process, an alcohol compound reaction process, and a base addition process. Hereinafter, the present application will be described by each process together with preferred examples and specific examples, but the present application is not limited to the following preferred examples and specific examples.

[0031] 1. Oxidizing and photolyzing process

[0032] In the present process, a C 2-4 halogenated hydrocarbon is subjected to oxidative photolysis in the presence of oxygen, whereby a C 2-4 halogenated hydrocarbon is subjected to oxidative photolysis in the presence of oxygen, whereby a C

[0033] The C 2-4 halogenated hydrocarbon is a hydrocarbon having a carbon number of 2 to 4, and has one or more halogenated groups selected from chlorine, bromine, and iodine. The C 2-4 The halogenated hydrocarbon is roughly decomposed in the presence of oxygen and irradiation light to be converted into a carbonyl halide or a carbonyl halide-like compound.

[0034] As described above, it is considered that in the present application, the C 2-4 The halogenated hydrocarbon is decomposed in the presence of irradiation light and oxygen to generate a carbonyl halide or a carbonyl halide-like compound that functions as a carbonyl halide. Hereinafter, the carbonyl halide includes the carbonyl halide-like compound. As the C 2-4 The halogenated hydrocarbon is preferably a C2halogenated hydrocarbon, more preferably a halogenated ethane and a halogenated ethene. In order to make the decomposition more easily proceed, the C 2-4 The halogenated hydrocarbon is preferably an olefin or an alkyne having one or more unsaturated bonds. As the C 2-4 The halogenated hydrocarbon is more preferably a C2halogenated hydrocarbon, and further more preferably a halogenated ethane and a halogenated ethene. 2-4 The halogenated hydrocarbon is more preferably a C2halogenated hydrocarbon, and further more preferably a halogenated ethane and a halogenated ethene. 2-4 The halogenated hydrocarbon is more preferably a C2halogenated hydrocarbon, and further more preferably a halogenated ethane and a halogenated ethene. 2-4 The halogenated group possessed by the halogenated hydrocarbon is preferably chlorine and / or bromine, and more preferably chlorine. In addition, from the viewpoint of cost and the like, the C 2-4 The halogenated hydrocarbon is more preferably a C2halogenated hydrocarbon, and further more preferably a halogenated ethane and a halogenated ethene. 2-3 The halogenated hydrocarbon is more preferably a C2halogenated hydrocarbon, and further more preferably a halogenated ethane and a halogenated ethene.

[0035] As a specific C 2-4 The halogenated hydrocarbon can be exemplified by, for example, halogenated ethanes such as 1,1,2-trichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane, and the like; halogenated ethenes such as 1,1,2-trichloroethene, 1,1,2-tribromoethene, and the like; halogenated propanes such as 1,1,1,3-tetrachloropropane, and the like; perhalogenated alkanes such as hexachloroethane, hexabromoethane, and the like; perhalogenated ethenes such as tetrachloroethene, tetrabromoethene, and the like.

[0036] The C 2-4 The halogenated hydrocarbon can be appropriately selected depending on the target chemical reaction and the desired product, and one kind can be used alone or two or more kinds can be used in combination. In addition, one kind of the C2-4 halogenated hydrocarbon. C 2-4 Among halogenated hydrocarbons, from the viewpoint of cost and the like, C 2-4 halogenated hydrocarbons.

[0037] As the C 2-4 halogenated hydrocarbons used in the method of the present application, those industrially used for the purpose of chemical fibers, metal cleaning, and the like can be used, and in addition, tetrachloroethylene (Cl2C=CCl2) produced as a byproduct in other chemical synthesis processes can be preferably used. For example, C 2-4 halogenated hydrocarbons temporarily used as a solvent can be recovered and reused. At this time, if a large amount of impurities, water, and the like are contained, the reaction can be hindered, and thus purification to some extent is preferable. For example, after water, water-soluble impurities, and the like are removed by water washing, dehydration is performed using anhydrous sodium sulfate, anhydrous magnesium sulfate, or the like. However, even if water of about 1 mass% or more is contained, the reaction is considered to proceed, and thus excessive purification that reduces the productivity is not necessary. As the water content, 0.5 mass% or less, further 0.2 mass% or less, and still further 0.1 mass% or less is more preferable. As the water content, 0 mass% or less or the detection limit is preferable. In addition, the reused C 2-4 halogenated hydrocarbons can also contain C 2-4 decomposition products of the C

[0038] In particular, in the case of C 2-4 halogenated hydrocarbons that are not liquid at normal temperature and normal pressure or are difficult to vaporize, the C 2-4 halogenated hydrocarbons can also be used together with a solvent. In addition, the solvent can also promote the decomposition of the C 2-4 halogenated hydrocarbons. Furthermore, the solvent can also inhibit the decomposition of the carbonyl halide produced by the oxidative photodecomposition of the C 2-4 halogenated hydrocarbons. As the solvent, a substance that can moderately dissolve the C 2-4 halogenated hydrocarbons and does not hinder the decomposition of the C 2-4 halogenated hydrocarbons is preferable. As the solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as n-hexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzonitrile; ether-based solvents such as diethyl ether, tetrahydrofuran, and dioxane; and nitrile-based solvents such as acetonitrile can be exemplified.

[0039] When a solvent is used together, the amount of the solvent used can be appropriately adjusted, and for example, the C 2-4 halogenated hydrocarbons can be used in an amount of 1 to 100 parts relative to 1 part of the C 2-4The ratio of the halogenated hydrocarbon to the solvent is adjusted to 50 mass% or more. As the ratio, 60 mass% or more, or 70 mass% or more is preferable, and 80 mass% or more, or 90 mass% or more is more preferable. As the ratio, 100 mass% or less is preferable, and 100 mass%, if possible, is preferable, i.e., no solvent is used.

[0040] A stabilizer such as an alcohol, which hinders the decomposition of the halogenated hydrocarbon, is contained in the general halogenated hydrocarbon product. In the present application, in order to decompose the C 2-4 halogenated hydrocarbon, the stabilizer is removed from the C 2-4 halogenated hydrocarbon. By using the C 2-4 halogenated hydrocarbon from which the stabilizer is removed, a lower energy light can be used, or the irradiation time of the light can be reduced, and it is possible to more efficiently decompose the C 2-4 halogenated hydrocarbon. From the C 2-4 halogenated hydrocarbon from which the stabilizer is removed, a lower energy light can be used, or the irradiation time of the light can be reduced, and it is possible to more efficiently decompose the C 2-4 halogenated hydrocarbon. From the C

[0041] In the present application, the C 2-4 halogenated hydrocarbon is irradiated with light in the presence of oxygen. As the oxygen source used, a gas containing oxygen is sufficient, and, for example, air, purified oxygen can be used. The purified oxygen can also be used in a mixture with a non-reactive gas such as nitrogen, argon, etc. From the aspects of cost and ease, air can also be used. In the case where air is used as the oxygen source, it is possible that the air components other than oxygen absorb excessive high energy light, and decomposition of the phosgene generated can be suppressed. From the viewpoint of improving the efficiency of the decomposition of the C 2-4 halogenated hydrocarbon based on the irradiation of high energy light, the oxygen content ratio in the oxygen-containing gas used as the oxygen source is preferably about 15 volume% to 100 volume%. In addition, other than unavoidable impurities, it is preferable to use only oxygen substantially. The oxygen content ratio can be appropriately determined depending on the kind of the C 2-4 halogenated hydrocarbon, etc. For example, in the case where a chlorinated hydrocarbon such as tetrachloroethylene is used as the C 2-4 halogenated hydrocarbon described above, the oxygen content ratio is preferably 15 volume% to 100 volume%, and in the case where a brominated hydrocarbon compound is used, the oxygen content ratio is preferably 90 volume% to 100 volume%. Note that even in the case where oxygen (oxygen content ratio 100 volume%) is used, the oxygen content ratio can be controlled within the range described above by adjusting the oxygen flow rate into the reaction system.

[0042] As the oxygen source, dry air that has passed through a desiccant such as silica gel can also be used, but even air containing water vapor does not excessively hinder the reaction, and thus air that has not been adjusted in terms of water vapor content can also be used. Note that the oxygen concentration in air is approximately 21 vol%, and the oxygen concentration with respect to the oxygen source can also be adjusted to 20 ± 5 vol%. As this ratio, 20 ± 2 vol% is preferable. In the case where air is used as the oxygen source, it is possible that an air component other than oxygen absorbs excessively high-energy light, and decomposition of the generated carbonyl halide can be suppressed.

[0043] "under the presence of oxygen" can be C 2-4 the state in which the halogenated hydrocarbon is contacted with oxygen, or in C 2-4 the halogenated hydrocarbon or the composition containing C 2-4 any one of the states in which oxygen is present in the composition of the halogenated hydrocarbon. Thus, the light irradiation can be performed under a gas stream of an oxygen-containing gas, but from the viewpoint of improving the yield of the oxidized photo-decomposition product, it is preferable to blow an oxygen-containing gas into C 2-4 the halogenated hydrocarbon or the composition containing C 2-4 the halogenated hydrocarbon.

[0044] The amount of the oxygen-containing gas can be appropriately determined in accordance with C 2-4 The amount of the halogenated hydrocarbon, the shape of the reaction vessel, and the like can be appropriately determined. For example, it is preferable to make the amount of the oxygen supplied to the reaction vessel per minute with respect to the C 2-4 The amount of the oxygen supplied to the reaction vessel per minute with respect to the halogenated hydrocarbon is 1 volume-fold to 500 volume-folds. If this ratio is 1 volume-fold or more, C 2-4 the halogenated hydrocarbon is oxidized and photo-decomposed. If this ratio is 500 volume-folds or less, C 2-4 the halogenated hydrocarbon is volatilized. As this ratio, 2 volume-folds or more is more preferable, 5 volume-folds or more is further more preferable, and 250 volume-folds or less is more preferable, and 150 volume-folds or less is further more preferable.

[0045] As the light irradiated to C 2-4 The light irradiated to the halogenated hydrocarbon preferably contains short-wavelength light, and more preferably contains ultraviolet light, and more specifically, light containing light having a wavelength of 180 nm to 500 nm, and light having a peak wavelength included in 180 nm to 500 nm. Note that the wavelength of the irradiated light can be appropriately determined, and more preferably 400 nm or less, and further more preferably 300 nm or less, and light having a peak wavelength included in these ranges is also preferable. In the case where the irradiated light contains light in the above-described wavelength range, C 2-4The halocarbon is efficiently photooxidized. For example, light containing UV-B of 280 nm to 315 nm and / or UV-C of 180 nm to 280 nm can be used, preferably light containing UV-C of 180 nm to 280 nm is used, and also preferably light having a peak wavelength within these ranges is used.

[0046] For example, in the case of using a C 2-4 halocarbon without a stabilizer, or in the case of using a radical generating material as described later, even lower energy light can be able to photooxidize the C 2-4 halocarbon. As lower energy light, light having a peak wavelength within the visible light wavelength region can be given. As this visible light wavelength region, 350 nm to 830 nm can be given, preferably 380 nm or more, more preferably 400 nm or more, and also preferably 800 nm or less, more preferably 780 nm or less, and further more preferably 500 nm or less.

[0047] As a means for light irradiation, there is no particular limitation as long as light having the above-described wavelength can be irradiated, and as a light source of light having such a wavelength range within the wavelength region, for example, sunlight, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light, a metal halide lamp, an LED lamp, and the like can be given. From the aspects of reaction efficiency and cost, it is preferable to use a low-pressure mercury lamp.

[0048] As conditions such as the intensity of the irradiated light, it is appropriate to set according to the C 2-4 halocarbon, and the like, for example, as the desired intensity of light at the shortest distance position from the light source to the C 2-4 halocarbon, although it also depends on the scale of implementation and the wavelength of the irradiated light, and the like, it is preferably 1 mW / cm 2 or more, and more preferably 10 mW / cm 2 or more. For example, in the case of a shorter wavelength of the irradiated light, as this light intensity, it is more preferably 100 mW / cm 2 or more, and further more preferably 20 mW / cm 2 or more. In the case of a longer wavelength of the irradiated light, as this light intensity, it is more preferably 10 mW / cm 2 or more, and further more preferably 20 mW / cm 2 or more. In the case of a longer wavelength of the irradiated light, as this light intensity, it is more preferably 10 mW / cm 2 or more, and further more preferably 20 mW / cm 2 or more. In the case of a longer wavelength of the irradiated light, as this light intensity, it is more preferably 10 mW / cm 2 or more. In addition, as the distance between the light source and the C 2-4The shortest distance of the halogenated hydrocarbon is preferably less than 1m, more preferably less than 50cm, and further preferably less than 10cm or less than 5cm. The lower limit of the shortest distance is not particularly limited and can be 0cm, that is, the light source can be present at C 2-4 Halogenated hydrocarbons may contain C 2-4 In the composition of halogenated hydrocarbons.

[0049] By addition to C 2-4 In addition to halogenated hydrocarbons and oxygen, free radical generating substances can coexist, which may promote C 2-4 Decomposition of halogenated hydrocarbons. The free radical generating substance that can be used in the present invention is a substance that generates free radicals by light irradiation. Examples of the free radical generating substance include one or more halogen elements selected from chlorine (Cl2), bromine (Br2) and iodine (I2); hydrochloric acid and its salts; chlorous acid and its salts; hypochlorous acid and its salts; perchloric acid and its salts; bromic acid and its salts; bromous acid and its salts; hypobromous acid and its salts; perbromic acid and its salts; iodic acid and its salts; iodous acid and its salts; hypoiodous acid and its salts; periodic acid and its salts; organic peroxides such as benzoyl peroxide; and azo compounds such as azobisisobutyronitrile (AIBN). Examples of the counter cations constituting the above-mentioned salts include alkali metal ions such as lithium ions, sodium ions, and potassium ions, and ions of group IIA elements such as magnesium ions and calcium ions.

[0050] Chlorine is a gas at room temperature and pressure, so it can be introduced as a mixed gas with oxygen or separately from oxygen. 2-4 Halogenated hydrocarbons may contain C 2-4 In the composition of halogenated hydrocarbons. Chlorine can be generated in another reaction vessel and introduced into the reaction solution after drying, or a chlorine gas bottle can be used. On the other hand, bromine is liquid and iodine is solid at room temperature and pressure. Therefore, bromine and iodine can be mixed in C 2-4 Halogenated hydrocarbons may contain C 2-4 Other free radical generating substances that are solid or liquid at room temperature and pressure can also be mixed in the C 2-4 Halogenated hydrocarbons may contain C 2-4 In the composition of halogenated hydrocarbons.

[0051] The amount of the free radical generating substance used can be adjusted appropriately. For example, 2-4 The halogenated hydrocarbon is 0.1 mol% to 10 mol% of a radical generating substance.

[0052] When a halogen element is used as a radical generating substance, the halogen element constituting the halogen element and the halogen element constituting the C 2-4The halogen elements of the halogenated groups of the halogenated hydrocarbons may be different, but are preferably the same. It is believed that when the two halogen elements are the same, the generated carbonyl halide or carbonyl halide compound is single, the generation of by-products is also suppressed, and the reproducibility of the reaction is improved. For example, when chlorine is used as C 2-4 Halogenated hydrocarbons, preferably C substituted with chlorine 2-4 Chlorohydrocarbons, more preferably C2 chlorinated hydrocarbons are used.

[0053] Light irradiation conditions as long as according to C 2-4 Halogenated hydrocarbons etc. can be appropriately set. For example, the temperature during light irradiation can be adjusted to be above 0°C and below 0°C. 2-4 The boiling point of the halogenated hydrocarbon. This temperature is preferably 10°C or higher, more preferably 20°C or higher or 30°C or higher, further preferably 50°C or higher or 60°C or higher, and preferably 100°C or lower, more preferably 80°C or lower. The light irradiation time is as long as C 2-4 The halogenated hydrocarbon may be sufficiently decomposed to obtain an oxidative photodecomposition product, and the time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 5 hours.

[0054] The method of light irradiation is not particularly limited, and can be 2-4 Any of the following methods may be used: a method of continuously irradiating light from the start to the end of the oxidative photodecomposition reaction of the halogenated hydrocarbon; a method of alternately repeating light irradiation and light non-irradiation; a method of irradiating light only for a predetermined time from the start of the oxidative photodecomposition reaction; and a method of continuously irradiating light from the start to the end of the oxidative photodecomposition reaction.

[0055] 2. Alcohol compound reaction process

[0056] In this step, the oxidative photodecomposition product obtained in the oxidative photodecomposition step is reacted with an alcohol compound.

[0057] As the alcohol compound, for example, the alcohol compound of formula R 1 (OH) m (Where R 1 represents an m-valent organic group, where m represents an integer of 1 to 5). As m, it is preferably 4 or less or 3 or less, and more preferably 1 or 2. When m is 1, a symmetrical chain carbonate is mainly obtained. When m is 2, a symmetrical chain carbonate or an asymmetrical chain carbonate may also be obtained. However, if the reaction proceeds sufficiently, a cyclic carbonate or a polycarbonate is obtained.

[0058] R in alcohol compound (I) 1 represents an m-valent organic group. Hereinafter, a monovalent organic group will be described as a representative example. 1 The monovalent organic group of1-10 Monovalent chain aliphatic hydrocarbon group, C 3-10 Monovalent cyclic aliphatic hydrocarbon group, C 6-15 a monovalent aromatic hydrocarbon group, and a monovalent organic group in which 2 to 5 of these groups are bonded together.

[0059] “C 1-10 "Monovalent chain aliphatic hydrocarbon group" refers to a linear or branched monovalent saturated aliphatic hydrocarbon group or a monovalent unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. For example, as C 1-10 Monovalent chain aliphatic hydrocarbon groups include C 1-10 Alkyl, C 2-10 Alkenyl and C 2-10 Alkynyl.

[0060] As C 1-10 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2,2-dimethylethyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl. 1-8 Alkyl or C 1-6 Alkyl, more preferably C 1-4 Alkyl or C 1-2 The alkyl group is more preferably a methyl group.

[0061] As C 2-10 Alkenyl, for example, vinyl (vinyl), 1-propenyl, 2-propenyl (allyl), butenyl, hexenyl, octenyl, decenyl, etc. Preferably C 2-8 Alkenyl, more preferably C 2-6 Alkenyl or C 2-4 The alkenyl group is more preferably vinyl (vinyl) or 2-propenyl (allyl). In addition, examples of the monohydric alcohol compound having a C2-10 alkenyl group include rhodiol, geraniol, nerol, and linalool.

[0062] As C 2-10 Alkynyl, for example, ethynyl, propynyl, butynyl, hexynyl, octynyl, pentadecynyl, etc. Preferably C 2-8 Alkynyl, more preferably C 2-6 Alkynyl or C 2-4 Alkynyl.

[0063] “C 3-10 The term "monovalent cyclic aliphatic hydrocarbon group" refers to a cyclic monovalent saturated aliphatic hydrocarbon group or a monovalent unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms. For example, C 3-10 Cycloalkyl, C 3-10 Cycloalkenyl and C 3-10 Cycloalkynyl. As C 3-10Cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl groups. 3-10 Cycloalkenyl groups include, for example, cyclopropenyl, cyclobutenyl, cyclopentadienyl, and cyclohexenyl groups. 3-10 Cycloalkynyl groups include, for example, cyclobutenynyl groups.

[0064] "C 6-15 A monovalent aromatic hydrocarbon group refers to a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Examples include phenyl, indenyl, naphthyl, biphenyl, phenalenyl, phenanthryl, anthryl, and the like, and a C 6-12 A monovalent aromatic hydrocarbon group, more preferably a phenyl group.

[0065] As the m-valent organic group selected from C 1-10 A monovalent chain aliphatic hydrocarbon group, C 3-10 A monovalent cyclic aliphatic hydrocarbon group, and C 6-15 A monovalent organic group in which 2 to 5 groups selected from C 3-10 A monovalent cyclic aliphatic hydrocarbon group - C 1-10 A monovalent chain aliphatic hydrocarbon group, C 1-10 A monovalent chain aliphatic hydrocarbon group - C 3-10 A monovalent cyclic aliphatic hydrocarbon group, C 6-15 A monovalent aromatic hydrocarbon group - C 1-10 A monovalent chain aliphatic hydrocarbon group, C 1-10 A monovalent chain aliphatic hydrocarbon group - C 6-15 A monovalent aromatic hydrocarbon group, C 1-10 A monovalent chain aliphatic hydrocarbon group - C 3-10 A divalent cyclic aliphatic hydrocarbon group - C 1-10 A monovalent chain aliphatic hydrocarbon group, C 3-10 A monovalent cyclic aliphatic hydrocarbon group - C 1-10 A divalent chain aliphatic hydrocarbon group - C 3-10 A monovalent cyclic aliphatic hydrocarbon group, and C 1-10 A monovalent chain aliphatic hydrocarbon group - C 6-15 A divalent aromatic hydrocarbon group - C 1-10 A monovalent group obtained by removing one hydrogen atom from a monovalent chain aliphatic hydrocarbon group.

[0066] The m-valent organic group in the alcohol compound (I) can also be substituted with a substituent. As the C 1-10 A substituent α of the m-valent chain aliphatic hydrocarbon group includes, for example, one or more substituents selected from C 1-6 Alkoxy, halogeno, ether (-0-), thioether (-S-), carbonyl (-C(=0)-), and tri(C 1-6 Alkyl)silyl groups, as C 3-10 A substituent β of the m-valent cyclic aliphatic hydrocarbon group includes, for example, one or more substituents selected from C 1-6alkyl, C 1-6 alkoxy, halo, ether, thioether, carbonyl and tri(C 1-6 alkyl)silyl groups. As the C 6-15 alkyl group, one or more substituents selected from the group consisting of C 1-6 alkyl, C 1-6 alkoxy and halo. It should be noted that ether, thioether and carbonyl groups are substituted in the form of carbon-carbon bonds entering the hydrocarbon chain. In addition, as the tri(C 1-6 alkyl)silyl group, for example, trimethylsilyl group can be mentioned.

[0067] The number of substituents of the m-valent organic group is not particularly limited as long as it can be substituted, and for example, it can be 1 to 10. As the number, it is preferably 8 or less, or 6 or less, more preferably 5 or less, 4 or less, or 3 or less, and still more preferably 1 or 2.

[0068] "C 1-6 alkyl" means a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl and the like are mentioned. C 1-4 alkyl is preferred, and C 1-2 alkyl is more preferred, and methyl is most preferred.

[0069] "C 1-6 alkoxy" means a linear or branched saturated aliphatic hydrocarbon oxy group having 1 to 6 carbon atoms. For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexyloxy and the like are mentioned, and C 1-4 alkoxy is preferred, and C 1-2 alkoxy is more preferred.

[0070] As the halo group, one or more halo groups selected from the group consisting of fluorine, chlorine, bromine and iodine can be mentioned.

[0071] Further, as the monovalent organic group of R 1 in the alcohol compound (I), a monovalent organic group represented by the formula R 12 — [— X— R 11 — ] r — (X represents O or S, preferably O, R 11 represents C 2-8 alkyldiyl, R 12 represents C 1-6 alkyl, and r represents an integer of 1 to 180) can be mentioned.

[0072] R 11Ethylene (-CH2CH2-), propylene [-CH2CH2CH2-, -CH(CH3)CH2- or -CH2CH(CH3)-] and tetramethylene (-CH2CH2CH2CH2-) can be given as examples.

[0073] As r, it is preferable to be 5 or more, more preferable to be 10 or more, further more preferable to be 20 or more, and, on the other hand, it is preferable to be 160 or less, more preferable to be 150 or less, further more preferable to be 2 or less.

[0074] In the case where m in the alcohol compound (I) is 2 or more, the above monovalent organic group including the exemplifications is replaced by an m-valent organic group. For example, in the case where m is 2, C 1-10 alkyl is replaced by C 1-10 alkyldiyl, in the case where m is 3, C 1-10 alkyl is replaced by C 1-10 alkyl is replaced by C 12 -[ -X -R 11 -] r - In the case where m is 2, it can be of the formula -[ -X -R 11 -]r-.

[0075] As the alcohol compound (I) where m is 2, for example, diol compounds such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polycarbonate glycol, etc.; dihydroxybenzene compounds such as o-dihydroxybenzene, m-dihydroxybenzene, etc.; dihydroxyheteroaryl compounds such as 4,6-dihydroxy-2-methylpyrimidine, 3,6-dihydroxy-4-methylpyridazine, etc.; bisphenol compounds such as bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol TMC, bisphenol Z, etc.; sugar alcohol dehydrates such as isosorbide, isomannide, etc. can be given. As the alcohol compound (I) where m is 3, for example, glycerol can be given, as the alcohol compound (I) where m is 4, for example, erythritol, pentaerythritol, ribose can be given, and as the alcohol compound (I) where m is 5 or more, glucose, galactose, ketose, lactose, sucrose, etc. can be given.

[0076] The amount of the alcohol compound to be used can be appropriately adjusted, and for example, it can be 0.5 times mole or more and 20 times mole or less relative to C 2-4 The initial amount of the halogenated hydrocarbon can be 0.5 times mole to 20 times mole. As the ratio, it is preferable to be 10 times mole or less, more preferable to be 5 times mole or less, further more preferable to be 2 times mole or less. Also, an alcohol compound which is equimolar or approximately equimolar to C 2-4 halogenated hydrocarbon can be given. Equimolar or approximately equimolar means that the alcohol compound is equimolar or approximately equimolar to C 2-4The molar ratio of the halogenated hydrocarbon is 0.8 to 1.2. The ratio is preferably 0.9 or more, more preferably 0.95 or more, and preferably 1.1 or less, more preferably 1.05 or less. 2-4 In the case of an equimolar or approximately equimolar amount of a halogenated hydrocarbon and an alcohol compound, the alcohol compound has C 2-4 Advantages include suppressing the inhibition of oxidative photodecomposition of halogenated hydrocarbons, suppressing the formation of chain carbonates other than the target carbonate, and increasing the molecular weight of the polycarbonate.

[0077] In this step, after the oxidative photodecomposition step, that is, after the light irradiation, C 2-4 An alcohol compound is added to the halogenated hydrocarbon. During the addition of the alcohol compound and the reaction between the oxidative photodecomposition product and the alcohol compound, light irradiation may be continued or stopped. However, in order to suppress photodecomposition of the alcohol compound, the oxidative photodecomposition product, and the reaction product, light irradiation is preferably stopped after the addition of the alcohol compound.

[0078] In addition, the oxidative photodecomposition step and the alcohol compound reaction step can also be carried out simultaneously. 2-4 The composition of halogenated hydrocarbon and alcohol compound is subjected to light irradiation, and the C 2-4 The alcohol compound is added during the photoirradiation of the halogenated hydrocarbon, and then the photoirradiation is continued. 2-4 A portion of the oxidative photodecomposition products of halogenated hydrocarbons is generally gaseous at room temperature and pressure. If they do not react quickly with alcohol compounds, they may be released outside the system. Therefore, it is preferred to 2-4 The composition of the halogenated hydrocarbon and the alcohol compound is subjected to light irradiation.

[0079] The conditions of this step can be adjusted in the same manner as the oxidative photolysis step. For example, the reaction temperature of the oxidative photolysis product and the alcohol compound can be adjusted to be above 0°C and below 0°C. 2-4 The boiling points of the halogenated hydrocarbon and the alcohol compound. This temperature is preferably 10°C or higher, more preferably 20°C or higher or 30°C or higher, and even more preferably 50°C or higher or 60°C or higher. It is also preferably 100°C or lower, and more preferably 80°C or lower. The reaction time of this step can be set to a time sufficient for the oxidative photodecomposition product and the alcohol compound to react fully. For example, it is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 5 hours. It should be noted that the conditions of the oxidative photodecomposition step and this step do not need to be the same, except when performed simultaneously, but they may be the same.

[0080] In this step, although the target carbonate compound may be generated by the reaction of the oxidative photodecomposition product with the alcohol compound, a sufficient amount of the target carbonate compound is not generated. The main product of this step is not particularly limited, but is considered to be a precursor of the target carbonate compound.

[0081] 3. Base addition step

[0082] In this step, after the alcohol compound reaction step, an inorganic base is added to the reaction liquid of the oxidative photolysis product of the halogenated hydrocarbon and the alcohol compound, or at least after the oxidative photolysis step, the reaction liquid after the oxidative photolysis of the halogenated hydrocarbon is subjected to the C 2-4 An inorganic base is added to the reaction liquid of the oxidative photolysis product of the halogenated hydrocarbon and the alcohol compound, or at least after the oxidative photolysis step, the reaction liquid after the oxidative photolysis of the halogenated hydrocarbon is subjected to the C 2-4 An organic base is added to the reaction liquid after the oxidative photolysis of the halogenated hydrocarbon. As described above, the amount of the target carbonate obtained in the reaction of the oxidative photolysis product and the alcohol compound is insufficient, but it is considered that the reaction from the target carbonate precursor to the target carbonate compound is sufficiently performed by the addition of the base.

[0083] In detail, it is considered that the base promotes the reaction from the target carbonate precursor produced by the reaction of the oxidative photolysis product of the halogenated hydrocarbon and the alcohol compound to the target carbonate compound. In addition, in the oxidative photolysis reaction of the halogenated hydrocarbon, the reaction of the carbonyl halide or the carbonyl halide compound and the alcohol compound, halogenated hydrogen such as hydrogen chloride is produced as a by-product. The base also has a possibility of promoting the generation of the target carbonate compound by neutralizing the halogenated hydrogen. 2-4 In detail, it is considered that the base promotes the reaction from the target carbonate precursor produced by the reaction of the oxidative photolysis product of the halogenated hydrocarbon and the alcohol compound to the target carbonate compound. In addition, in the oxidative photolysis reaction of the halogenated hydrocarbon, the reaction of the carbonyl halide or the carbonyl halide compound and the alcohol compound, halogenated hydrogen such as hydrogen chloride is produced as a by-product. The base also has a possibility of promoting the generation of the target carbonate compound by neutralizing the halogenated hydrogen. 2-4 In detail, it is considered that the base promotes the reaction from the target carbonate precursor produced by the reaction of the oxidative photolysis product of the halogenated hydrocarbon and the alcohol compound to the target carbonate compound. In addition, in the oxidative photolysis reaction of the halogenated hydrocarbon, the reaction of the carbonyl halide or the carbonyl halide compound and the alcohol compound, halogenated hydrogen such as hydrogen chloride is produced as a by-product. The base also has a possibility of promoting the generation of the target carbonate compound by neutralizing the halogenated hydrogen.

[0084] The base is generally classified into an inorganic base and an organic base. The inorganic base refers to a base composed only of inorganic components, and the organic base refers to a base among the bases containing carbon, other than the inorganic base classified as an alkali carbonate or the like. As the inorganic base, for example, carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; carbonates of Group IIA metals such as magnesium carbonate, calcium carbonate, barium carbonate; bicarbonates of alkali metals such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide; hydroxides of Group IIA metals such as magnesium hydroxide, calcium hydroxide; fluoride salts of alkali metals such as lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and the like can be given, and the carbonate or bicarbonate of an alkali metal or Group IIA metal having low hygroscopicity and deliquescence is preferable, and the carbonate of an alkali metal is more preferable. As the organic base, from the viewpoint of low reactivity with the product produced by the photoreaction of tetrahaloethylene, for example, trimethylamine, triethylamine, diisopropylethylamine, and the like can be used. The amount of the base to be added is not particularly limited, but is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, relative to 1 mol of the target carbonate compound. 1-4alkoxide; sodium tert-butoxide, potassium tert-butoxide, and the like; alkali metal salts of tertiary amines such as triethylamine, diisopropylethylamine, and the like; non-nucleophilic organic bases such as diazabicycloundecene, lithium diisopropylamide, lithium tetramethylpiperidide, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,1,3,3-tetramethylguanidine (TMG), and N-methylmorpholine; and low-nucleophilic organic bases such as pyridine, 2,6-lutidine, and the like. In addition, the above-mentioned bases can be used in combination.

[0085] As the base, an inorganic base is preferred because it is inexpensive compared to organic bases and is easier to remove after the reaction.

[0086] The amount of the base used is appropriately adjusted within a range in which the reaction proceeds well, for example, 0.01 to 10 mol, relative to 1 mol of the halogenated hydrocarbon. 2-4 The amount of the halogenated hydrocarbon can be 0.01 to 10 mol, relative to 1 mol of the alcohol compound. As the ratio, 0.05 mol or more or 0.1 mol or more is preferred, and 0.15 mol or more or 0.2 mol or more is more preferred. In addition, 5 mol or less or 2 mol or less is preferred, and 1 mol or less or 0.5 mol or less is more preferred.

[0087] In the present process, the inorganic base is added after the alcohol compound reaction step, or at least the organic base is added after the oxidative photolysis step. In the oxidative photolysis step, if the alcohol compound coexists with the inorganic base, there is a concern that water is generated by a side reaction in which the inorganic base participates, a carboxylate or the like is generated from the target carbonate precursor by the water and the inorganic base, the target carbonate precursor and the inorganic base are deactivated, and the reaction from the target carbonate precursor to the target carbonate does not sufficiently proceed. Therefore, in the present process, the inorganic base is added after the alcohol compound reaction step, or at least the organic base is added after the oxidative photolysis step. 2-4 The reaction from the target carbonate precursor to the target carbonate is sufficiently promoted by adding the inorganic base after the oxidative photolysis product of the halogenated hydrocarbon sufficiently reacts with the alcohol compound. Therefore, in the present process, the inorganic base is added after the alcohol compound reaction step, or at least the organic base is added after the oxidative photolysis step. 2-4 The reaction liquid of the oxidative photolysis product of the halogenated hydrocarbon is added with the alcohol compound and allowed to sufficiently react, and then the inorganic base is added.

[0088] In the case where the organic base is used as the base, a side reaction in which the inorganic base participates does not occur. However, if light, particularly high-energy light, is irradiated to the organic base, there is a concern that a colored decomposition product is generated, the reaction of the halogenated hydrocarbon is hindered, and the reaction of the alcohol compound is hindered. 2-4 The oxidative photolysis reaction of the halogenated hydrocarbon. Therefore, in the case where the organic base is used as the base, the organic base is added at least after the oxidative photolysis step. For example, the organic base can be added after the oxidative photolysis step to the reaction liquid containing the oxidative photolysis product of the halogenated hydrocarbon. 2-4The reaction solution of the oxidative photodecomposition product of the halogenated hydrocarbon is added with an alcohol compound and allowed to react sufficiently, and then an organic base is added. Alternatively, the alcohol compound and the organic base can be mixed after the oxidative photodecomposition step, and then added to the reaction solution containing C 2-4 The reaction solution of the oxidative photodecomposition product of the halogenated hydrocarbon is added with an alcohol compound and allowed to react sufficiently, and then an organic base is added. Alternatively, the alcohol compound and the organic base can be mixed after the oxidative photodecomposition step, and then added to the reaction solution containing C 2-4 The reaction solution of the oxidative photodecomposition product of the halogenated hydrocarbon is added with an alcohol compound and allowed to react sufficiently, and then an organic base is added. Alternatively, the alcohol compound and the organic base can be mixed after the oxidative photodecomposition step, and then added to the reaction solution containing C

[0089] The inorganic base or the organic base can be added at once, or added little by little, or added dropwise little by little continuously. Alternatively, the inorganic base or the organic base can be dissolved or dispersed in a solvent, and the resulting solution or dispersion can be added. Hereinafter, the inorganic base or the organic base is collectively referred to as a base.

[0090] The conditions at the time of addition of the base and the conditions after addition of the base can be adjusted as appropriate. For example, the temperature can be adjusted to be higher than or equal to 0°C and lower than the lowest boiling point among the boiling points of the respective components. As the temperature, it is preferable to be higher than or equal to 10°C, more preferable to be higher than or equal to 20°C, and further more preferable to be higher than or equal to 30°C, and on the other hand, it is preferable to be lower than or equal to 100°C or lower than or equal to 80°C, and more preferable to be lower than or equal to 60°C or lower than or equal to 40°C. The reaction time of the present step can be set to be a time sufficient for generating the target carbonate, and for example, it is preferable to be from 1 hour to 50 hours.

[0091] As a reaction apparatus that can be used in the production method of the present application, a photo reaction apparatus provided with a light irradiation means in a reaction vessel can be given. The photo reaction apparatus can further be provided with a stirring apparatus, a temperature control means. Figure 1 One mode of a photo reaction apparatus that can be used in the production method of the present application is shown. Figure 1 The photo reaction apparatus shown has a light irradiation means 1 in a photo reaction vessel 5. In the photo reaction vessel 5, at least C 2-4 A halogenated hydrocarbon, a gas containing oxygen is supplied to the photo reaction vessel 5, or C 2-4 A halogenated hydrocarbon or a composition containing C 2-4 The composition of the halogenated hydrocarbon is bubbled with a gas containing oxygen (not shown), and at the same time, C 2-4 The halogenated hydrocarbon is oxidative photodecomposed. In the case where the above light irradiation means 1 is covered with a sleeve 2 or the like, the sleeve is preferably made of a material that transmits the above irradiation light. Alternatively, the light irradiation can be performed from the outside of the reaction vessel, in which case, the photo reaction vessel is preferably made of a material that transmits the irradiation light. As the material that transmits the irradiation light, for example, quartz glass or the like can be given.

[0092] Alternatively, a reaction system shown can be used. Figure 2 The reaction system of the present application contains a flow type photo reaction apparatus 9. For example, a halogenated hydrocarbon 3, an alcohol compound 4, and an organic base 5 are mixed in a reaction vessel 6, and then the mixture is supplied to the photo reaction apparatus 9 using a syringe pump 7. The reaction system of the present application can be used in the production method of the present application. Figure 2 The reaction system of the present application contains a flow type photo reaction apparatus 9. For example, a halogenated hydrocarbon 3, an alcohol compound 4, and an organic base 5 are mixed in a reaction vessel 6, and then the mixture is supplied to the photo reaction apparatus 9 using a syringe pump 7. The reaction system of the present application can be used in the production method of the present application. 2-4A halogenated hydrocarbon and a prescribed flow of an oxygen-containing gas are supplied to a flow-type photoreactor 9 using a mass flow controller 8. A gas-liquid mixture containing C 2-4 The halogenated hydrocarbon and the oxygen-containing gas are irradiated with light while passing through the flow-type photoreactor 9, and an oxidation photodecomposition product of the halogenated hydrocarbon is obtained. 2-4 The reaction liquid of the oxidation photodecomposition product of the halogenated hydrocarbon. This reaction liquid is blown into at least a composition containing an alcohol compound in the reaction vessel 10. An alkali can not be added in the reaction vessel 10, and the oxidation photodecomposition product can be reacted with the alcohol compound first and then the alkali can be added, or a composition containing an alcohol compound and an organic alkali can be added from the beginning. The reaction liquid passing through the reaction vessel 10 is preferably supplied to the trap in the gas phase.

[0093] The configuration of the flow-type photoreactor 9 is not particularly limited, and for example, one or more reaction tubes can be disposed around a light source, or a light source can be inserted into a tube having a gas inlet and a gas outlet at both ends. Alternatively, the reaction tube can be wound around the light source in a coil shape.

[0094] After the reaction, general post-treatment can be performed. For example, C 2-4 The halogenated hydrocarbon is not soluble or hardly soluble in water, and thus, after the reaction, the reaction liquid is partitioned with a water-soluble solvent such as water, brine, a sodium bicarbonate aqueous solution, dilute hydrochloric acid, or the like, together with a water-insoluble organic solvent such as a halogenated hydrocarbon solvent. The obtained organic phase can be further washed with a water-soluble solvent, and alternatively, dried with anhydrous sodium sulfate or anhydrous magnesium sulfate. By distilling off the solvent from the obtained organic phase, a target carbonate compound is obtained. The target carbonate compound can be further purified by a conventional method such as distillation, column chromatography, recrystallization, or the like.

[0095] The type of the carbonate compound obtained in the method of the present application mainly depends on the alcohol compound. For example, in the case where the alcohol compound is a monohydric alcohol having only one hydroxyl group, the main carbonate compound is a chain carbonate. Alternatively, in the case where the alcohol compound is a dihydric alcohol, and the number of carbon atoms of the main chain R 1 is 2 or 3, and a stable ring structure such as a 5-membered ring or a 6-membered ring is formed, the main carbonate compound is a chain carbonate. In the case where the alcohol compound is a dihydric alcohol, and the number of carbon atoms of the main chain R 1 is large, and a stable ring structure is not formed, the main carbonate compound is a polycarbonate, but if the alcohol is excessively used, a chain carbonate can sometimes be dominant.

[0096]

[0097] The carbonate compound obtained in the production method of the present application is useful as a non-aqueous solvent or the like, and for example, can be used as an electrolyte for a lithium ion secondary battery. Alternatively, the polycarbonate is useful as an excellent engineering plastic.

[0098] Examples

[0099] The present application is described in more detail below by citing examples, but the present application can of course be implemented by appropriately changing it within the scope of the gist described above and below without being limited by the examples described below, and these are included in the technical scope of the present application.

[0100] Example 1

[0101]

[0102] A 1.0 L three-necked round bottom flask was equipped with a quartz glass jacket (diameter 30 mm, length 150 mm), and further, a low-pressure mercury lamp ("UVL20PH-6" manufactured by SEN Light Co., 20 W, 254 nm) was installed in the quartz glass jacket to construct a reaction system. A schematic diagram of the reaction system is shown in Figure 1 It should be noted that the irradiation light from the low-pressure mercury lamp contains UV-C of 254 nm, and the irradiance of the light of 254 nm at a position 5 mm from the wall of the jacket was 6.23 to 9.07 mW / cm 2 The temperature of the jacket was set to 0°C.

[0103] Into the photoreactor 5, tetrachloroethylene (TCE) and an equimolar amount of an alcohol compound were put and stirred to mix. While the reaction solution was stirred, 0.1 L / min of oxygen was bubbled at the temperature shown in Table 1. The high-energy light containing UV-C was irradiated for the time shown in Table 1 using a low-pressure mercury lamp. The gas that passed through the jacket was blown into the same alcohol compound, ethanol or propanol, in the reactor 6, and the gas that passed through the reactor 6 was blown into a saturated sodium bicarbonate solution in a trap for treatment. It should be noted that the gas that passed through the reactor 6 was an acidic gas containing HCI and the like generated in the reaction.

[0104] After the oxidative photodegradation reaction, the temperature of the bath 3 of the photoreactor 5 was adjusted to 60°C, and stirred for 1.5 hours. Next, the reaction solution was analyzed by 1 HNMR.

[0105] To the obtained reaction solution in the photoreactor 5, triethylamine or potassium carbonate was added in the amount shown in Table 1, and stirred at room temperature overnight. Acetonitrile was added to the reaction solution as an internal standard, and the yield of the cyclic carbonate as the target compound was calculated by analyzing it by 1 HNMR.

[0106] In addition, the yield of the carbonate in the reactor 6 was also calculated. The results are shown in Table 1.

[0107] [Table 1] ​

[0108]

[0109] As shown in the results in Table 1, even when a mixture of tetrachloroethylene and an alcohol compound containing no base is irradiated with high-energy light, only a small amount of carbonate is produced, or only a large amount of byproducts or intermediates is produced, the extent of which cannot be identified. However, the subsequent addition of a base significantly improves the carbonate yield.

[0110] Therefore, it was revealed that the target carbonate can be produced in high yield by first irradiating a mixture of tetrachloroethylene and an alcohol compound with high-energy light to oxidatively photodecompose the tetrachloroethylene and then adding a base.

[0111] Example 2

[0112]

[0113] As in Example 1, Figure 1 Tetrachloroethylene (TCE) and an equimolar amount of tetraethylene glycol (TEG) are placed in a photoreactor of the reaction system schematically shown in the figure and stirred to mix. While stirring the reaction solution, oxygen gas is bubbled in at a temperature shown in Table 2 at 0.1 L / min. A low-pressure mercury lamp is used to irradiate high-energy light including UV-C for the time shown in Table 2. The photodecomposed gas that has passed through the cooling tube is blown into the propanol in the reaction container 6, and the gas that has passed through the reaction container 6 is blown into a saturated sodium bicarbonate solution in a collector for treatment. It should be noted that the gas that has passed through the reaction container 6 is an acidic gas including HCl and the like generated during the reaction.

[0114] After the oxidation photodecomposition reaction, the temperature of the bath 3 in the photoreactor 5 was adjusted to 60°C and stirred for 1.5 hours. 1 The reaction solution was analyzed by H NMR.

[0115] The reaction solution in the photoreactor 5 was added with potassium carbonate in the amount shown in Table 2, and stirred at room temperature overnight, and then at 50°C for 72 hours. Acetonitrile was added as an internal standard to the reaction solution. 1 The yield of the polycarbonate in the reaction vessel 6 was similarly determined. The results are shown in Table 2.

[0116] Methylene chloride and water were then added to the reaction mixture for separation. The organic phase was dried over anhydrous sodium sulfate, and the solvent was distilled off to isolate the polycarbonate as a viscous liquid. The resulting polycarbonate was analyzed by HPLC to determine its molecular weight. The results are shown in Table 3.

[0117] [Table 2]

[0118]

[0119] ND: not detected

[0120] [Table 3]

[0121] Mw Mn Mw / Mn 2,200 1,400 1.6

[0122] As shown in the results shown in Table 2 and Table 3, it was clarified that in the production of polycarbonate, even if a high-energy light is irradiated to the mixture of tetrachloroethylene and diol, polycarbonate is not generated, and by adding an alkali after the oxidative photodecomposition reaction, polycarbonate can be obtained at a high yield.

[0123] Comparative Example 1

[0124]

[0125] In the light reaction vessel of the reaction system schematically shown in Figure 1 tetrachloroethylene (TCE), ethylene glycol, and calcium carbonate were put in and mixed with stirring. While the reaction solution was stirred, 0.1 L / min of oxygen was bubbled at 60°C. High-energy light containing UV-C was irradiated for 2 hours using a low-pressure mercury lamp. The photodecomposition gas that passed through the cooling tube was blown into propanol in reaction vessel 6, and the gas that passed through reaction vessel 6 was blown into a saturated sodium hydrogencarbonate solution in a gas trap for treatment. Note that the gas that passed through reaction vessel 6 was an acidic gas containing HCI and the like that was generated in the reaction.

[0126] After the oxidative photodecomposition reaction, the temperature of bath 3 of light reaction vessel 5 was adjusted to 60°C, and stirring was performed for 1.5 hours. Next, the reaction solution was stirred overnight at ordinary temperature.

[0127] The obtained reaction solution was added with potassium carbonate in the amount shown in Table 4, and stirred for 3 days at ordinary temperature.

[0128] Using 1 The reaction solutions in light reaction vessel 5 and reaction vessel 6 were subjected to H NMR with 0.1 L / min of oxygen, and the generated compounds were identified. The results are shown in Table 4.

[0129] [Table 4]

[0130]

[0131] As shown in the results shown in Table 4, even if an inorganic base is added to the mixture of tetrachloroethylene and ethylene glycol from the very beginning and the mixture is irradiated with high-energy light, the target cyclic carbonate is not fully generated, but a similar amount of by-products are generated. The reason for this is not clear, but it is believed that when tetrachloroethylene, ethylene glycol, and an inorganic base coexist from the very beginning of the reaction, water is generated by a side reaction involving the inorganic base. This water and the inorganic base generate carboxylates and the like from the precursor of the target carbonate, thereby deactivating the precursor of the target carbonate and the inorganic base.

[0132] Example 3

[0133]

[0134] use Figure 2 Specifically, a low-pressure mercury lamp (SUV40D, manufactured by SEN Light, 40W, 10W) ​​was placed in a quartz glass tube with a diameter of 30 mm and a length of 320 mm. The cylindrical flow-type photoreaction apparatus 9 includes a 185-nm wavelength (185-600 nm, peak wavelengths at 184.9 nm and 253.7 nm) and is surrounded by twelve 1.033 mL quartz tubes with an inner diameter of 2.1 mm and a length of 320 mm. The total volume of the cylindrical flow-type photoreaction apparatus 9, including the joints, is 13.3 mL. Furthermore, the illuminance of light with a wavelength of 185 nm at a position 5 mm from the center of the low-pressure mercury lamp is 3.93 mW / cm 2 The illuminance of light with a wavelength of 254nm is 11.02mW / cm 2 .

[0135] Tetrachloroethylene was fed into a PTFE tube (inner diameter: 1 mm) at a flow rate shown in Table 5 using a syringe pump 7, mixed with oxygen whose flow rate was adjusted by a mass flow controller 8, and fed into the above-mentioned flow photoreaction device 9 at room temperature.

[0136] The product produced by the oxidative photodecomposition of a mixture of liquid tetrachloroethylene and oxygen was blown into a dichloromethane solution containing ethylene glycol in a connected reaction vessel 10 over two hours at room temperature while stirring. Unreacted gas was introduced into a connected alkali trap and treated to prevent toxic gas leakage. Next, potassium carbonate or triethylamine was added to the resulting reaction solution in reaction vessel 10 in the amounts shown in Table 5, and the mixture was stirred overnight at room temperature.

[0137] Acetonitrile was added as an internal standard to the reaction solution in the reaction vessel 10. 1 The product was identified and quantified by H NMR. The results are summarized in Table 5. It should be noted that the yields in Table 5 are relative to the tetrachloroethylene used.

[0138] [Table 5]

[0139]

[0140] As shown in the results shown in Table 5, even if the gas-liquid mixture containing liquid tetrachloroethylene and oxygen is continuously supplied to the light reaction device, tetrachloroethylene is photo-oxidized and decomposed. In addition, it was confirmed that if the base is not added, the yield of the carbonate compound is low, but by subsequently adding the base, the yield of the carbonate is significantly improved.

[0141] In the case where equimolar amounts of tetrachloroethylene and ethylene glycol are used, no chain carbonate is detected, and only a cyclic carbonate is produced. Therefore, it is considered that the reason why the yield of the chain carbonate is still high in Items 1 and 2 although a divalent alcohol is used is because an excess amount of ethylene glycol is used with respect to tetrachloroethylene.

[0142] Explanation of symbols

[0143] 1: Light irradiation means, 2: Jacket, 3: Constant temperature bath

[0144] 4: Stirrer, 5: Light reaction vessel, 6: Reaction vessel

[0145] 7: Syringe pump, 8: Mass flow controller,

[0146] 9: Flow type light reaction device, 10: Reaction vessel

Claims

1. A method for producing a carbonate compound, characterized by, comprises: Oxidative photolysis step: C 2-4 halogenated hydrocarbon is subjected to photoirradiation to obtain C 2-4 Oxidative photolysis product of halogenated hydrocarbon an alcohol compound reaction step of reacting the oxidized photolyzate with an alcohol compound, an alkali addition step of adding an inorganic alkali after the alcohol compound reaction step, or at least an organic alkali after the oxidized photolysis step.

2. The method of claim 1, wherein, The C 2-4 The composition of halogenated hydrocarbon and the alcohol compound is subjected to light irradiation.

3. The method of claim 1 or 2, wherein, the inorganic alkali is added after the alcohol compound reaction step.

4. The method according to any one of claims 1 to 3, wherein, tetrafluoroethylene as said C 2-4 halogenated hydrocarbon.

5. The method according to any one of claims 1 to 4, wherein, The C 2-4 The peak wavelength of the light of the halocarbon irradiation is comprised in the range of 180 nm to 500 nm.

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