JP2016000727A - Production method of diphenyl carbonate, diphenyl carbonate obtained by the production method, polycarbonate produced from the diphenyl carbonate, catalyst for production of diphenyl carbonate, and production method of the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of diphenyl carbonate by a decarbonylation reaction of diphenyl oxalate in the presence of a catalyst, in which high-purity diphenyl carbonate can be simply, efficiently, stably and continuously produced by using an easy-to-handle catalyst.SOLUTION: In the production method of diphenyl carbonate, a catalyst is supplied as an adduct of an asymmetric tetraarylphosphonium halide and hydrogen halide. Diphenyl carbonate is obtained by the production method of diphenyl carbonate. The catalyst used is preferably an adduct obtained by crystallizing an asymmetric tetraarylphosphonium halide in contact with a hydrogen halide acid and a solvent. The asymmetric tetraarylphosphonium halide is preferably an asymmetric tetraarylphosphonium chloride having no benzyl proton; and the hydrogen halide is preferably hydrogen chloride. The asymmetric tetraarylphosphonium chloride is more preferably 4-t-butylphenyltriphenylphosphonium chloride. The catalyst preferably has an average particle diameter of 50 μm or more and 1 mm or less.

Description

  The present invention relates to a method for producing diphenyl carbonate and diphenyl carbonate obtained by the production method. Specifically, with regard to a method for producing diphenyl carbonate by decarbonylation reaction of diphenyl oxalate in the presence of a catalyst, a simple, efficient, and highly stable diphenyl carbonate can be stably and continuously produced using an easy-to-handle catalyst. It is an invention about providing a method. Further, the present invention relates to a catalyst suitable for the production of diphenyl carbonate and a production method thereof.

Carbonic acid diesters are known as raw material compounds in various chemical reactions. In particular, it is known that diphenyl carbonate can produce a polycarbonate by a polycondensation reaction with a divalent hydroxyaromatic compound.
Carbonic acid diester can be obtained by decarbonylation reaction of oxalic acid diester in the presence of a decarbonylation catalyst such as an organophosphorus compound (see Patent Document 1). Carbonic acid diesters can also be obtained by decarbonylating oxalic acid diesters in the presence of a catalyst such as tetraphenylphosphonium chloride. However, since the carbonic acid diester obtained by this method has low purity, a method for purifying it has been proposed (see Patent Document 2).

JP-A-8-333307 JP 2002-53657 A

  However, the method described in Patent Document 2 also has problems such as a large number of distillation steps required for purification and a very complicated operation. In addition, as a result of investigations on the handleability of asymmetric tetraphenylphosphonium chloride by the present inventors, the substance is easily scattered due to its small particle size and has high hygroscopicity. It was found that when decarbonylation of acid diphenyl was carried out, phenol was easily produced as a by-product due to hydrolysis of diphenyl carbonate.

  The present invention solves these problems and provides a method for producing diphenyl carbonate by subjecting diphenyl oxalate to a decarbonylation reaction in the presence of a catalyst. It is an object of the present invention to provide a method that can efficiently and stably produce high-purity diphenyl carbonate.

The present inventor has intensively studied to solve the above problems. As a result, regarding a method for producing diphenyl carbonate by reacting diphenyl oxalate in a reactor in the presence of a catalyst, the catalyst is supplied as an adduct of an asymmetric tetraarylphosphonium halide and hydrogen halide. The present inventors have found that the above problems can be solved. It was also found that the adduct of this asymmetric tetraarylphosphonium halide and hydrogen halide can be easily obtained by crystallizing the asymmetric tetraarylphosphonium halide in contact with the hydrogen halide and polar organic solvent. .

  That is, the first gist of the present invention is a method for producing diphenyl carbonate by subjecting diphenyl oxalate to a decarbonylation reaction in the presence of a catalyst in a reactor, wherein the catalyst is converted to an asymmetric tetraarylphosphonium halide and a halogenated salt. It exists in the manufacturing method of diphenyl carbonate characterized by supplying as an adduct body with hydrogen. The second gist of the present invention resides in the method for producing diphenyl carbonate described in the first gist, wherein the adduct body has an average particle size of 50 μm or more and 1 mm or less. The third gist of the present invention is the method for producing diphenyl carbonate described in the first or second gist, wherein the adduct is obtained by dissolving an asymmetric tetraarylphosphonium halide and a hydrogen halide in a polar organic solvent. It exists in the manufacturing method of diphenyl carbonate which is obtained by crystallization later. A fourth aspect of the present invention is a method for producing diphenyl carbonate according to any one of the first to third aspects, wherein the asymmetric tetraarylphosphonium halide does not have a benzyl proton. Exist. A fifth gist of the present invention is the method for producing diphenyl carbonate according to any one of the first to fourth gist, wherein the adduct is composed of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride. And a method for producing diphenyl carbonate, which is an adduct body.

  Moreover, the 6th summary of this invention exists in the manufacturing method of diphenyl carbonate, Comprising: It has the following 1st-3rd steps in this order, It exists in the manufacturing method of diphenyl carbonate characterized by the above-mentioned. 1st process: The process of manufacturing diphenyl carbonate by the manufacturing method of diphenyl carbonate as described in any one 1st thru | or 5th summary. Second step: A step of separating diphenyl carbonate produced in the first step from a catalyst solution containing the adduct body and / or an adduct body decomposition product generated by decomposing the adduct body. Third step: A step of supplying at least a part of the catalyst solution to the first step.

  A seventh aspect of the present invention is the method for producing diphenyl carbonate according to the sixth aspect, wherein a liquid having a higher boiling point than the diphenyl carbonate is removed from the catalyst liquid separated in the second step, And an adduct of an asymmetric tetraarylphosphonium halide and a hydrogen halide is supplied to the first step in the third step.

  The eighth aspect of the present invention is a method for producing an adduct of tetraarylphosphonium halide and hydrogen halide, wherein the asymmetric tetraarylphosphonium halide and hydrogen halide are dissolved in a polar organic solvent, In the method for producing an adduct of asymmetric tetraarylphosphonium halide and hydrogen halide, an adduct of asymmetric tetraarylphosphonium halide and hydrogen halide is obtained.

A ninth aspect of the present invention is an adduct of tetraarylphosphonium halide and hydrogen halide, wherein the tetraarylphosphonium halide is an asymmetric tetraarylphosphonium halide having no benzyl proton. In adducts of asymmetric tetraarylphosphonium halides and hydrogen halides.
A tenth aspect of the present invention is a catalyst for producing diphenyl carbonate by decarbonylation of diphenyl oxalate, wherein the catalyst is an adduct of an asymmetric tetraarylphosphonium halide having no benzyl proton and a hydrogen halide. It exists in the catalyst for diphenyl carbonate manufacture characterized by these.

The eleventh aspect of the present invention resides in diphenyl carbonate obtained by the method for producing diphenyl carbonate described in any one of the first to seventh aspects. A twelfth aspect of the present invention resides in a polycarbonate obtained by polycondensation of an aromatic dihydroxy compound and diphenyl carbonate described in the eleventh aspect in the presence of a transesterification catalyst.

  According to the present invention, a method for producing diphenyl carbonate by subjecting diphenyl oxalate to a decarbonylation reaction in the presence of a catalyst, using a catalyst that is easy to handle, is simple and efficient, and high-purity diphenyl carbonate is stably and continuously produced. Can be manufactured. Here, a catalyst suitable for the decarbonylation reaction can be easily obtained by dissolving an asymmetric tetraarylphosphonium halide and a hydrogen halide in a polar organic solvent and then crystallization. Further, by using this high purity diphenyl carbonate as a raw material, a high purity polycarbonate can be obtained.

Hereinafter, embodiments of the method for producing diphenyl carbonate of the present invention will be described in detail. In the method for producing diphenyl carbonate of the present invention, diphenyl oxalate is decarbonylated in the presence of a catalyst (hereinafter sometimes referred to as “decarbonylation reaction according to the present invention” or simply “decarbonylation reaction”). Diphenyl carbonate is produced.
The decarbonylation reaction of diphenyl oxalate is performed according to the following reaction formula (1).

(In the formula, two Ph's are each independently a phenyl group optionally having a substituent.)

[Diphenyl oxalate]
In the method for producing diphenyl carbonate of the present invention, diphenyl oxalate (hereinafter sometimes referred to as “diphenyl oxalate according to the present invention” or simply “diphenyl oxalate”) is diphenyl carbonate (hereinafter referred to as “according to the present invention”). It may be referred to as “diphenyl carbonate” or simply “diphenyl carbonate”. The diphenyl carbonate according to the present invention obtained from the diphenyl oxalate according to the present invention as a raw material is thermally stable and suitable as a raw material for polycarbonate.

  The substituent that the phenyl group of diphenyl oxalate may have is not particularly limited as long as the excellent effects of the present invention are not significantly hindered. However, when the obtained diphenyl carbonate is used for the production of polycarbonate, it is preferable that the by-product produced in the production of the polycarbonate has a low boiling point and is easily removed by distillation. Therefore, specifically, an alkyl group having 1 to 12 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 12 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a halogen such as a fluorine atom and a chlorine atom Atoms and aromatic ring groups are preferred. In addition, the alkyl group as a substituent means the case where an alkyl group couple | bonds with a phenyl group as a substituent.

The phenyl group having a substituent has various isomers depending on the position of the substituent, and any of them may be used. For example, a 2-, 3- or 4-alkylphenyl group having an alkyl group having 1 to 12 carbon atoms such as a 2-, 3- or 4-methylphenyl group, a 2-, 3- or 4-ethylphenyl group; 2 2-, 3- or 4-alkoxyphenyl groups having an alkoxy group having 1 to 12 carbon atoms such as-, 3- or 4-methoxyphenyl group, 2-, 3- or 4-ethoxyphenyl group; -Or 4-nitrophenyl group; 2-, 3- or 4-halophenyl group having a halogen atom such as 2-, 3- or 4-fluorophenyl group, 2-, 3- or 4-chlorophenyl group However, any of these may be used.

Of these, an unsubstituted phenyl group is preferred particularly when the obtained diphenyl carbonate is used for the production of polycarbonate.
As diphenyl oxalate, one produced by transesterification of dialkyl oxalate and an aromatic hydroxy compound as shown in the following reaction formula (2) can be used. Here, as the dialkyl oxalate used as a raw material, as produced by the following reaction formula (3), those produced by an carbonylation reaction using carbon monoxide, oxygen and an aliphatic alcohol as raw materials can be used.

(In the formula, R represents an alkyl group, and Ar represents an aromatic ring group.)

(In the formula, R represents an alkyl group.)

[Decarbonylation catalyst]
The catalyst used in the method for producing diphenyl carbonate of the present invention is supplied as an adduct of an asymmetric tetraarylphosphonium halide and a hydrogen halide. Here, the catalyst is usually supplied to the reactor. The asymmetric tetraarylphosphonium halide is “the asymmetric tetraarylphosphonium halide according to the present invention”, the hydrogen halide is “the hydrogen halide according to the present invention”, and the adduct is “the adduct according to the present invention”. Or they may be simply referred to as “adduct bodies”.
The asymmetric tetraarylphosphonium halide according to the present invention is a compound represented by the following general formula (4).

(In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aromatic ring group which may have a substituent, and X represents a halogen atom.)
As the aromatic ring group of Ar ^{1 to} Ar ^4, an aromatic hydrocarbon group having 6 to 14 carbon atoms such as a phenyl group, a biphenyl group, and a naphthyl group, a sulfur atom such as a thienyl group, a furyl group, and a pyridyl group, an oxygen atom, or Examples thereof include an aromatic heterocyclic group having 4 to 16 carbon atoms containing a nitrogen atom. Of these, an aromatic hydrocarbon group is preferable because a catalyst can be produced at low cost, and a phenyl group is more preferable.

Ar ^{1 to} Ar ⁴ include various isomers, and each aromatic ring group may have one or more substituents. Examples of the substituent include an alkyl group (preferably 1 to 12 carbon atoms), an alkoxy group (preferably 1 to 12 carbon atoms), a thioalkoxy group (preferably 1 to 12 carbon atoms), an aralkyloxy group (preferably Has 7 to 13 carbon atoms, aryloxy group (preferably 6 to 16 carbon atoms), thioaryloxy group (preferably 6 to 16 carbon atoms), acyl group (preferably 1 to 12 carbon atoms), alkoxycarbonyl group (Preferably 2 to 16 carbon atoms), carboxyl group, amino group, alkyl-substituted amino group (preferably 2 to 16 carbon atoms), nitro group, cyano group, hydroxy group, halogen atom (fluorine, chlorine, bromine, etc.), etc. Is mentioned. Further, these substituents may further have a substituent, and examples of the substituent include an aromatic ring group and a halogen atom. Among these, since it is thermally stable, an alkyl group is preferable, a C1-C12 alkyl group is more preferable, and a C3-C8 branched alkyl group is still more preferable. In addition, it is preferable that the substituent does not have a benzyl proton because the adduct according to the present invention is thermally stable and hardly decomposes when used as the catalyst for the decarbonylation reaction of the present invention. That is, the substituent is particularly preferably an alkyl group having 3 to 8 carbon atoms having no benzyl proton, and most preferably a t-butyl group.

In addition, when Ar < ¹ > -Ar < ⁴ > is an aromatic ring group which has a substituent, although various isomers exist, Ar < ¹ > -Ar < ⁴ > may be any of them. Examples of these isomers include 2- (or 3-, 4-) methylphenyl group, 2- (or 3-, 4-) ethyl when Ar ^{1 to} Ar ⁴ are a phenyl group having a substituent. 1 carbon number such as phenyl group, 2,3- (or 3,4-) dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group An alkylphenyl group in which an alkyl group of -12 or a halogenated alkyl group is bonded to a phenyl group; an alkoxy group having 1-12 carbon atoms such as a 3-methoxyphenyl group or a 2,4,6-trimethoxyphenyl group; Alkoxyphenyl group bonded to the group; 2- (or 3-, 4-) nitrophenyl group; halogen source such as 3- (or 4-) chlorophenyl group, 3-fluorophenyl group There like halophenyl group attached to the phenyl group.

Ar ^{1 to} Ar ⁴ may be bonded to each other or bridged between two groups.
In the asymmetric tetraarylphosphonium halide according to the present invention, at least any one group of Ar ^{1 to} Ar ⁴ is a group different from at least one of the other three groups. Here, different groups refer to groups different in any one, including those having different substituents, different types, and different substitution positions. In the present invention, the fact that any one group of Ar ¹ to Ar ⁴ is different from at least one of the other three groups is referred to as “asymmetric”. The asymmetric tetraarylphosphonium halide according to the present invention is excellent in solubility because any one group of Ar ^{1 to} Ar ⁴ is different from at least one of the other three groups.

The remaining three groups of Ar ^{1 to} Ar ⁴ may be the same as or different from each other. The asymmetric tetra aryl phosphonium halide according to the present invention, it is preferable that Ar ¹ to Ar ⁴ since apt to be thermally stable are both an aromatic ring group, either one of the substituents of Ar ¹ to Ar ⁴ More preferably, the remaining three groups of the aromatic ring group are unsubstituted aromatic ring groups, and at least ^one of Ar ^{1 to} Ar ⁴ is an aryl group having a substituent and the remaining group is an unsubstituted aryl It is particularly preferable that any one of Ar ^{1 to} Ar ⁴ is a phenyl group having a substituent, and the remaining three groups are most preferably an unsubstituted phenyl group.

  The halogen atom X in the general formula (4) is a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. Among these, a chlorine atom is preferable because it easily acts as a highly active catalyst in the decarbonylation reaction according to the present invention. That is, the asymmetric tetraarylphosphonium halide according to the present invention is preferably an asymmetric tetraphenylphosphonium chloride, and more preferably an asymmetric tetraphenylphosphonium chloride having no benzyl proton.

Preferable specific examples of the asymmetric tetraarylphosphonium halide according to the present invention include the following compounds. That is, examples of the aromatic hydrocarbon group in which Ar ^{1 to} Ar ⁴ are all unsubstituted include p-biphenyltriphenylphosphonium chloride, 1-naphthyltriphenylphosphonium chloride, 2-naphthyltriphenylphosphonium chloride, and the like. Examples of the organic phosphonium chloride in which Ar ^{1 to} Ar ⁴ are an unsubstituted aromatic hydrocarbon group or a substituted aromatic hydrocarbon group include 4-t-butylphenyltriphenylphosphonium chloride, m-trifluoromethylphenyltri Compounds having an aromatic hydrocarbon group having an alkyl group and having no benzyl proton such as phenylphosphonium chloride; Compounds having an aromatic hydrocarbon group having a halogen atom such as p-chlorophenyltriphenylphosphonium chloride; m-methoxyphenyl Compounds having an aromatic hydrocarbon group having an alkoxy group such as triphenylphosphonium chloride, p-methoxyphenyltriphenylphosphonium chloride, p-ethoxyphenyltriphenylphosphonium chloride; p-aminophenyl Compounds having an aromatic hydrocarbon group having an amino group, such as triphenylphosphonium chloride; Compounds having an aromatic hydrocarbon group having a cyano group, such as m-cyanophenyltriphenylphosphonium chloride and p-cyanophenyltriphenylphosphonium chloride And a compound having an aromatic hydrocarbon group having a nitro group, such as p-nitrophenyl-tri-p-tolylphosphonium chloride. Of these, the asymmetric tetraarylphosphonium halide according to the present invention is particularly preferably 4-t-butylphenyltriphenylphosphonium chloride.

  Examples of the hydrogen halide according to the present invention include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide. When the halogen of the hydrogen halide according to the present invention is used as a catalyst for decarbonylation reaction or the like, if the number of halogens increases, the types of by-products increase and the reaction system tends to become complicated. The same halogen as that of the asymmetric tetraarylphosphonium halide is preferred. That is, the hydrogen halide according to the present invention is preferably hydrogen chloride, and the adduct according to the present invention is preferably an adduct of asymmetric tetraphenylphosphonium chloride and hydrogen chloride, and 4-t-butylphenyltriphenylphosphonium chloride and An adduct with hydrogen chloride is particularly preferred.

  The adduct body is usually used as a term meaning an adduct crystal. The adduct body according to the present invention usually includes a solid in which a hydrogen halide is added to an asymmetric tetraarylphosphonium halide, a melted or dissolved product thereof, and the like. In the adduct according to the present invention, 0.01 to 1.0 mole of hydrogen halide is usually added to 1 mole of asymmetric tetraarylphosphonium halide. That is, in the adduct according to the present invention, 1 to 100% of hydrogen halide is usually added to the asymmetric tetraarylphosphonium halide 100 in a molar ratio.

In addition, the manufacturing method of the adduct body which concerns on this invention, a particle size, hygroscopicity, etc. are mentioned later.
The type of the adduct according to the present invention can be analyzed by known methods such as elemental analysis, mass spectrometry, nuclear magnetic resonance spectroscopy, and liquid chromatography. Specifically, for example,
In the case of 4-t-butylphenyltriphenylphosphonium chloride, it can be confirmed that it is 4-t-butylphenyltriphenylphosphonium chloride by analyzing by elemental analysis, mass spectrometry and nuclear magnetic resonance spectrum. Further, by measuring a liquid chromatogram of a substance that has been confirmed to be 4-t-butylphenyltriphenylphosphonium chloride, it can be confirmed more easily by liquid chromatography. For the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride, first, as described above, it was confirmed that 4-t-butylphenyltriphenylphosphonium chloride was contained, By measuring the concentration of chlorine contained in the adduct body, the adduct body with hydrogen chloride and the adduct ratio thereof can be calculated.

  The adduct body according to the present invention is preferably soluble in a carbonic acid diester. The reason for this is that, in the method for producing a carbonic acid diester of the present invention, by using a catalyst soluble in the carbonic acid diester, the decarbonylation reaction is stably carried out at a high conversion rate without causing catalyst precipitation, and the residual oxalic acid diester This is because the amount can be reduced. In the present invention, “soluble in a carbonic acid diester” means that the catalyst usually dissolves 10 g or more, preferably 50 g or more, with respect to 100 g of the carbonic acid diester at 150 ° C. The higher the solubility, the better, but the upper limit is usually 1000 g. The catalyst soluble in the carbonic acid diester can be easily selected by measuring the solubility of the adduct according to the present invention in the carbonic acid diester.

The adduct according to the present invention is presumed to be dissolved in the reaction solution for the decarbonylation reaction in the method for producing diphenyl carbonate of the present invention, hydrogen halide is liberated, and the asymmetric tetraarylphosphonium halide functions as a catalyst. Is done.
In the method for producing diphenyl carbonate according to the present invention, the amount of the adduct body in the reactor and / or the amount of the asymmetric tetraarylphosphonium halide produced by the decomposition of the adduct body is large in that the production efficiency and the reaction rate are likely to increase. However, it is preferable that the catalyst is less in terms of production cost and difficulty in precipitating the catalyst during the purification process of diphenyl carbonate. Therefore, specifically, it is preferably 1.0% by weight or more in total, more preferably 2.0% by weight or more, particularly preferably 3.0% by weight or more, It is preferably 15% by weight or less, more preferably 10% by weight or less, and further preferably 8% by weight or less.

In addition, the total amount of the adduct or the asymmetric tetraarylphosphonium halide (generated by decomposition of the adduct) is preferably 0.001 mol or more, and 0.01 mol or more with respect to 1 mol of the oxalic acid diester. More preferably, it is preferably 1 mol or less, more preferably 0.5 mol or less.
A total of 100 mol of diphenyl oxalate and diphenyl carbonate in the reactor is 0.001 mol or more in total of adduct or asymmetric tetraarylphosphonium halide (generated by decomposition of the adduct). Preferably, it is 0.1 mol or more, and on the other hand, it is preferably 50 mol or less, more preferably 20 mol or less. In addition, an adduct body may be used individually by 1 type, or multiple types may be used by arbitrary ratios and combinations, and said preferable usage-amount in the case of using multiple types represents the total amount.

Further, in the method for producing diphenyl carbonate of the present invention, the relative amount of diphenyl oxalate and adduct body supplied to the reactor is such that the amount of diphenyl oxalate and adduct body in the reactor tends to be in the above preferred range. The adduct is preferably 0.1 mol or more, more preferably 1 mol or more, and more preferably 50 mol or less, and 20 mol or less with respect to 100 mol of diphenyl oxalate. More preferably.

[Halogen compounds]
In the method for producing diphenyl carbonate according to the present invention, since a decarbonylation reaction is easily maintained with high selectivity, a halogen compound (hereinafter sometimes referred to as “halogen compound according to the present invention”) is used together with a decarbonylation catalyst. Is preferred.
Examples of the halogen compound according to the present invention include the following inorganic halogen compounds and / or organic halogen compounds. Of these halogen compounds, chlorine compounds are preferred. The molar ratio of the halogen compound to the adduct body (halogen compound / adduct body) is usually 0.0001 or more, preferably 0.001 or more, more preferably 0.01 or more, particularly preferably 0.1 or more. On the other hand, it is usually used so that it is 300 or less, preferably 100 or less, more preferably 3.00 or less, and particularly preferably 1.00 or less. In addition, a halogen compound may be used individually by 1 type, or multiple types may be used by arbitrary ratios and combinations, and said preferable usage-amount in the case of using multiple types represents the total amount.

  Examples of inorganic halogen compounds include aluminum halides such as aluminum chloride and aluminum bromide; platinum group metal halides such as platinum chloride, chloroplatinic acid, ruthenium chloride, and palladium chloride; phosphorus trichloride, phosphorus pentachloride, Phosphorus halides such as phosphorus oxychloride, phosphorus tribromide, phosphorus pentabromide and phosphorus oxybromide; hydrogen halides such as hydrogen chloride and hydrogen bromide; thionyl chloride, sulfuryl chloride, sulfur dichloride, dichloride dichloride Sulfur halides such as sulfur; Halogen alone such as chlorine and bromine.

Examples of the organic halogen compound include a compound composed of a carbon atom, a halogen atom such as a chlorine atom or a bromine atom, and at least one atom selected from a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom. Is mentioned. Examples of such an organic halogen compound include a structure in which a halogen atom is bonded to saturated carbon (C-Hal), a structure in which a halogen atom is bonded to carbonyl carbon (-CO-Hal), and a halogen to a silicon atom. An organic halogen compound having a structure in which atoms are bonded (—C—Si—Hal) or a structure in which a halogen atom is bonded to a sulfur atom (CSO ₂ —Hal) is preferably used. However, H
al represents a halogen atom such as a chlorine atom or a bromine atom. These structures are represented by, for example, general formulas (a), (b), (c), and (d), respectively.

(In the formula, Hal represents a halogen atom such as a chlorine atom or a bromine atom, n ¹ represents an integer of ¹ to 4, and n ² represents an integer of 1 to ^3. )
Specific examples of the organic halogen compound include the following compounds.
Examples of the organic halogen compound having a structure in which a halogen atom is bonded to saturated carbon as represented by the general formula (a) include chloroform, carbon tetrachloride, 1,2-dichloroethane, butyl chloride, and dodecyl chloride. Alkyl halides, aralkyl halides such as benzyl chloride, benzotrichloride, triphenylmethyl chloride, α-bromo-o-xylene, and halogen-substituted aliphatics such as β-chloropropionitrile and γ-chlorobutyronitrile Examples include nitriles and halogen-substituted aliphatic carboxylic acids such as chloroacetic acid, bromoacetic acid, and chloropropionic acid.

  Examples of the organic halogen compound having a structure in which a halogen atom is bonded to the carbonyl carbon as represented by the general formula (b) include acetyl chloride, oxalyl chloride, propionyl chloride, stearoyl chloride, benzoyl chloride, and 2-naphthalenecarboxylic acid. Examples thereof include acid halides such as acid chloride and 2-thionephencarboxylic acid chloride, aryl halogenoglyoxylates such as phenyl chloroglyoxylate, and aryl halides such as phenyl chloroformate.

Examples of the organic halogen compound having at least one structure in which a halogen atom is bonded to a silicon atom as represented by the general formula (c) include halogenated silanes such as diphenyldichlorosilane and triphenylchlorosilane. .
Examples of the organic halogen compound having a structure in which a halogen atom is bonded to a sulfur atom as represented by the general formula (d) include sulfonyl halides such as p-toluenesulfonic acid chloride and 2-naphthalenesulfonic acid chloride. Is mentioned.

  Of these, inorganic halogen compounds are preferred, hydrogen halides are more preferred, and hydrogen chloride is particularly preferred because by-products derived from halogen compounds can be suppressed. In addition, the halogen of the halogen compound according to the present invention is related to the present invention because the type of by-products increases and the reaction system tends to become complicated when the number of halogens increases when used for a catalyst for decarbonylation reaction. The halogen is preferably the same as the halogen of the hydrogen halide and the halogen of the adduct according to the present invention. That is, it is particularly preferable that the adduct body according to the present invention is an adduct body of asymmetric tetraarylphosphonium chloride and hydrogen chloride, and the halogen compound according to the present invention is hydrogen chloride.

[Decarbonylation reaction]
The decarbonylation reaction (hereinafter sometimes referred to as “carbonyl reaction according to the present invention” or simply “decarbonylation reaction”) in the method for producing a carbonic acid diester of the present invention is preferably carried out by a liquid phase reaction. Further, when a catalyst soluble in carbonic acid diester is used, the catalyst is preferably supplied in a state dissolved in carbonic acid diester, more preferably supplied to the reactor in a state dissolved in carbonic acid diester. It is particularly preferable to reuse the catalyst contained in the reaction solution while being dissolved in the carbonic acid diester.

The reaction temperature of the decarbonylation reaction is preferably high in terms of reaction rate, but is preferably low in terms of the purity of diphenyl carbonate. Therefore, in the case of normal pressure, the reaction temperature is usually 100 ° C. or higher, particularly 160 ° C. or higher, and particularly preferably 180 ° C. or higher. On the other hand, it is usually 450 ° C. or lower, preferably 400 ° C. or lower, more preferably 350 ° C. or lower, more preferably lower than the boiling point of the oxalic acid diester, specifically 340 ° C. or lower, preferably 320 ° C. or lower. Particularly preferred is 300 ° C. or less.
The pressure during the reaction may be determined from the process requirements.

  Although the decarbonylation reaction may be a batch reaction or a continuous reaction, industrially, a continuous reaction is preferable, and it is more preferable to carry out a continuous multistage reaction because it is easy to achieve a high conversion rate. As a general method for the continuous reaction, the methods described in JP-A-10-109962, JP-A-10-109963, JP-A-2006-89416 and the like can be used.

The decarbonylation reaction does not require the use of a solvent when the reaction is carried out at a temperature equal to or higher than the melting point of the substance used for the reaction, but an aprotic polar solvent such as sulfolane, N-methylpyrrolidone, dimethylimidazolidone, or a hydrocarbon solvent. Aromatic hydrocarbon solvents and the like can also be used as appropriate.
The material of the reactor is not particularly limited as long as diphenyl carbonate can be generated by the decarbonylation reaction according to the present invention. However, since phenol may be generated by a side reaction, an acid-resistant metal container or glass lining may be used. Made containers are preferred. Any type of reactor can be used as long as diphenyl carbonate can be produced by the decarbonylation reaction according to the present invention. As such a reactor, for example, a single tank or multi-tank type fully mixed reactor (stirring tank), a tower reactor, or the like can be used.

[Purification of diphenyl carbonate]
By the carbonyl reaction, diphenyl carbonate corresponding to the raw material diphenyl oxalate can be generated. The reaction solution after the decarbonylation reaction contains diphenyl carbonate, a decarbonylation catalyst, and unreacted diphenyl oxalate. In addition, there may be contained by-products generated by rearrangement, decomposition, reaction, etc. of diphenyl oxalate, diphenyl carbonate, decarbonylation catalyst, and the like. Examples of by-products include phenol and phenyl 4-chlorobenzoic acid. Moreover, when the above-mentioned halogen compound is used, this halogen compound or its by-product may be contained. Therefore, the diphenyl carbonate obtained by the carbonyl reaction is appropriately purified in order to obtain a purity and form corresponding to the application. However, since the decarbonylation reaction according to the present invention uses the adduct body according to the present invention as a catalyst, it is considered that the amount of phenol contained in the reaction solution is small. The reason is that, as will be described later, the adduct body has low hygroscopicity, so that it is difficult for by-production of phenol by hydrolysis. In addition, since phenol becomes an inhibitory factor for the decarbonylation reaction according to the present invention, in the method for producing diphenyl carbonate according to the present invention, highly pure diphenyl carbonate can be obtained efficiently by a simple method.

Carbon monoxide by-produced in the decarbonylation reaction is preferably gas-liquid separated from the reaction solution and discharged. Carbon monoxide can also be reused as a raw material for producing diphenyl oxalate from nitrite and carbon monoxide. (For example, see the method described in JP-A-10-152457, etc.). Here, when impurities such as phenol, carbon dioxide and hydrogen halide are contained in carbon monoxide, it is preferably used as a raw material for diphenyl oxalate after passing through a purification apparatus such as an absorption tower or a scrubber. As a manufacturing method of diphenyl carbonate of the present invention, a method having the following first to third steps in this order is particularly preferable.
1st process: The process which manufactures diphenyl carbonate by the decarbonylation reaction which concerns on said this invention, 2nd process: The adduct which the diphenyl carbonate manufactured at the 1st process, the adduct body, and / or the adduct body decomposed | disassembled produced Separating the catalyst solution containing the body decomposition product,
Third step: A step of supplying at least a part of the catalyst liquid separated in the second step to the first step.

  In the second step, diphenyl carbonate produced in the first step is separated from the catalyst liquid containing the adduct body and / or the adduct body decomposition product. Separation in the second step can be performed by a known method such as distillation, extraction, or crystallization. Since the asymmetric tetraarylphosphonium halide according to the present invention and the adduct according to the present invention usually have a high boiling point, the separation in the second step is preferably a method in which diphenyl carbonate is separated by distillation. That is, in the method for producing diphenyl carbonate of the present invention, the diphenyl carbonate contained in the reaction solution after the decarbonylation reaction is evaporated and taken out to be separated from the catalyst solution containing the adduct body and / or the adduct body decomposition product. It is preferable. In addition, when a high boiling point substance such as diphenyl oxalate or fleece rearrangement compound of diphenyl carbonate is contained in the reaction solution after the decarbonylation reaction, these are also added to the catalyst solution containing the adduct body and / or the adduct body decomposition product. It will be included.

Distillation of diphenyl carbonate may be carried out in the reactor where the decarbonylation reaction has been carried out, or the reaction solution may be transferred to an evaporator. The evaporation apparatus (evaporation method) is not particularly limited as long as the above object can be achieved. As the evaporation apparatus, for example, it is preferable to use a falling film evaporator, a thin film evaporator or the like because separation is easy in a short time. Moreover, when evaporating in the reactor, it is preferable to evaporate while gradually reducing pressure while stirring so that bumping hardly occurs. The time required for the separation is also affected by the heat transfer efficiency and the shape of the separation container, but it is preferably performed in a short time from the point that impurities are not easily produced, preferably 20 hours or less, more preferably 15 hours or less, 10 hours or less is particularly preferable.

  Evaporation is preferably performed at a low temperature and a low pressure from the point that impurities are not easily produced. The pressure is preferably evaporated under reduced pressure. Specifically, the pressure is preferably 0.1 kPaA or more, more preferably 0.2 kPaA or more, on the other hand, 50 kPaA or less, more preferably 20 kPaA or less. And it is preferable to carry out temperature below the reaction temperature in a decarbonylation reaction. Specifically, it is preferably 100 ° C. or higher, particularly 160 ° C. or higher, particularly 180 ° C. or higher, and usually 450 ° C. or lower, particularly 400 ° C. or lower, especially 350 ° C. or lower.

  When distillation is performed under the above preferred conditions, diphenyl carbonate is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 97% by weight or more in the evaporated fraction. Particularly preferably, it is contained at 98% by weight or more. The upper limit is usually 100% by weight. When this fraction contains diphenyl oxalate, it is usually 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and on the other hand, usually 3% by weight. Hereinafter, it is preferably 2% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. However, 0% by weight is most preferable. Components other than these may include phenol and the like, but the content in that case is usually 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.3% by weight or less. .

The evaporated diphenyl carbonate may be used as it is for the production of polycarbonate or the like, but may be further purified according to the required purity. In addition, evaporation of the carbonic acid diester is carried out by distillation, and components having a higher boiling point than the carbonic acid diester are extracted from the column bottom side, carbonic acid diester is extracted from the middle, and components having a lower boiling point than the carbonic acid diester are extracted from the column top side. A pure carbonic acid diester may be obtained.
Further purification can be performed by distillation or adsorption.
Specifically, it is preferable to carry out distillation purification using an evaporation apparatus such as a plate column or packed column having 5 to 50 theoretical plates.

[Recovery of decarbonylation catalyst]
In the third step, at least a part of the catalyst liquid obtained in the second step is supplied to the reactor in the first step. In this way, the decarbonylation catalyst can be reused.
In the third step, from the viewpoint of preventing the accumulation of high-boiling compounds in the reaction system, a solution obtained by removing a compound having a higher boiling point than diphenyl carbonate from the catalyst solution obtained in the second step is supplied to the reactor in the first step. It is preferable to do. Components removed by this step include high-boiling substances such as diphenyl oxalate (boiling point 334 ° C. at 1 atm) and phenyl 4-hydroxybenzoate (boiling point higher than diphenyl oxalate at 1 atm). The removal of the high boiling point compound can be performed by a known method such as distillation, extraction, or crystallization. Specifically, for example, it can be separated by the method described in JP-A-2002-45704.

In addition, the adduct body according to the present invention and a part of the adduct body decomposition product are also removed along with the removal of the high boiling point compound, and therefore, the entire amount of the adduct body according to the present invention may not be reused. Therefore, it is preferable to adjust the catalyst amount so that the amount of the decarbonylation catalyst is within the above-mentioned preferable range. The adjustment of the amount of catalyst is obtained in the second step with an adduct having a molar amount equivalent to the total molar amount of the aduct tetraarylphosphonium halide which is the adduct and / or an adduct decomposition product removed in the second step. It is preferable to carry out by supplying to the reactor of the first step together with a solution obtained by removing the high boiling point compound from the catalyst solution. Here, the equivalent molar amount is 0.7 mol or more with respect to 1 mol of the total amount of asymmetric tetraarylphosphonium halide which is the adduct body and / or the adduct body decomposition product removed in the second step. Is preferably 0.8 mol or more, particularly preferably 0.9 mol or more, and on the other hand, it is preferably 2 mol or less, and 1.4 mol or less. More preferred is 1.1 mol or less.

[Diphenyl carbonate]
In the method for producing diphenyl carbonate according to the present invention, since the decarbonylation reaction is performed using the adduct according to the present invention as a catalyst, the decarbonylation reaction is hardly inhibited by by-product phenol, and high-purity diphenyl carbonate is produced. Can be obtained. Therefore, the purity of diphenyl carbonate obtained by the above-described method for producing diphenyl carbonate of the present invention is usually 99.0% by weight.
The above is preferably 99.3% by weight or more, more preferably 99.5% by weight or more. When impurities are included, ionic chlorine or the like may be included. In this case, the content is usually 0.0001% by weight or less, preferably 0.00001% by weight or less, more preferably 0.000001. % By weight or less.

[Production method of polycarbonate]
Polycarbonate, which is one of the uses of diphenyl carbonate produced in the present invention, comprises diphenyl carbonate produced by the above-described method, an aromatic or aliphatic dihydroxy compound represented by bisphenol A, an alkali metal compound and / or It can be produced by transesterification in the presence of an alkaline earth metal compound. The transesterification reaction can be carried out by appropriately selecting a known method. An example using diphenyl carbonate and bisphenol A as raw materials will be described below.

  In the above polycarbonate production method, diphenyl carbonate is preferably used in excess relative to bisphenol A. The amount of diphenyl carbonate used with respect to bisphenol A is preferably large in that the produced polycarbonate has few terminal hydroxyl groups and is excellent in the thermal stability of the polymer, and the transesterification reaction rate is high, and the polycarbonate having a desired molecular weight. It is preferable that the amount is small in that it is easy to manufacture. Specifically, for example, it is preferably used in an amount of usually 1.001 mol or more, preferably 1.02 mol or more, usually 1.3 mol or less, preferably 1.2 mol or less with respect to 1 mol of bisphenol A.

As a raw material supply method, bisphenol A and diphenyl carbonate can be supplied in solid form, but it is preferable to supply one or both in a liquid state by melting them.
When producing a polycarbonate by transesterification of diphenyl carbonate and bisphenol A, a catalyst is usually used. In the above polycarbonate production method, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound as the transesterification catalyst. These may be used alone, or two or more may be used in any combination and ratio. Practically, an alkali metal compound is desirable.

The catalyst is usually 0.05 μmol or more, preferably 0.08 μmol or more, more preferably 0.10 μmol or more, and usually 5 μmol or less, preferably 4 μmol, relative to 1 mol of bisphenol A or diphenyl carbonate. It is used in a range of not more than mol, more preferably not more than 2 μmol.
When the amount of the catalyst used is within the above range, it is easy to obtain the polymerization activity necessary for producing a polycarbonate having a desired molecular weight, and the polymer color is excellent, and excessive polymer branching does not progress. It is easy to obtain polycarbonate with excellent fluidity.

As the alkali metal compound, a cesium compound is preferable. Preferred cesium compounds are cesium carbonate, cesium bicarbonate, and cesium hydroxide.
In order to produce polycarbonate by the above method, it is preferable to continuously supply both the raw materials to the raw material mixing tank, and to continuously supply the obtained mixture and the transesterification catalyst to the polymerization tank.
In the production of polycarbonate by the transesterification method, both raw materials supplied to the raw material mixing tank are usually stirred uniformly and then supplied to a polymerization tank to which a catalyst is added to produce a polymer.

[Polycarbonate]
As described above, since diphenyl carbonate obtained by the production method of the present invention is very high in purity, polycondensation of diphenyl carbonate obtained by the production method of the present invention and an aromatic dihydroxy compound in the presence of a transesterification catalyst. By doing so, a high-purity polycarbonate can be obtained.
In particular, the method for producing diphenyl carbonate according to the present invention can provide high-purity diphenyl carbonate with a small amount of by-product phenol, so that it can be used to obtain a high-quality polycarbonate.

[Adduct of asymmetric tetraarylphosphonium halide and hydrogen halide]
The tetraarylphosphonium halide is obtained, for example, by reacting a triarylphosphine with an aryl halide in the presence of a metal halide compound catalyst and a water-soluble high-boiling solvent as described in JP-A-9-328492. be able to. JP-A-2013-82695 discloses that an asymmetric tetraarylphosphonium halide is increased by dividing or continuously adding triarylphosphine to a liquid containing an aryl halide, a metal halide compound catalyst, and a water-soluble high-boiling solvent. It describes that it can be produced with high yield and high selectivity. Japanese Patent Application Laid-Open No. 2013-82695 describes that the asymmetric tetraarylphosphonium bromide thus obtained is converted to chloride.

  The present inventor has examined in detail the decarbonylation reaction using the asymmetric tetraarylphosphonium halide thus obtained as a catalyst. As a result, it was found that the amount of by-product phenol can be reduced by performing a decarbonylation reaction using an adduct as a catalyst instead of the asymmetric tetraphenylphosphonium halide obtained as described above. The reason for this is that, as will be described later, the adduct body has low hygroscopicity, so that it is difficult for phenol to be a by-product due to hydrolysis. That is, since the asymmetric tetraarylphosphonium halide has a low symmetry structure, the crystallinity is low and the powder is likely to be scattered as a fine powder. In addition, when an asymmetric tetraarylphosphonium halide having high hygroscopicity is used as a catalyst, it is considered that phenol is generated by hydrolysis of diphenyl carbonate and diphenyl oxalate due to moisture supplied to the reaction system together with the catalyst. On the other hand, since the adduct body according to the present invention has a relatively large particle size, the hygroscopic property is low, and it is considered that the by-product of phenol due to hydrolysis of diphenyl carbonate or diphenyl oxalate hardly occurs.

Since the adduct body according to the present invention has a large particle size and low hygroscopicity, it tends to be a solid that is difficult to scatter and easy to handle. For this reason, when this is used as a catalyst for the decarbonylation reaction, the catalyst can be put into the reactor in a short time before being absorbed by moisture, resulting in less phenol by-product and high conversion from diphenyl oxalate, Diphenyl carbonate with high selectivity and high purity can be easily obtained. Specifically, the particle size of the adduct body according to the present invention is preferably 50 μm or more, more preferably 60 μm or more, further preferably 80 μm or more, and particularly preferably 100 μm or more. . Moreover, the upper limit of the particle size of the adduct body according to the present invention is usually 1 mm. The particle size of the adduct according to the present invention can be obtained as a median diameter (D50) measured using a microtrack particle size distribution measuring apparatus “MT3300EXII” manufactured by Nikkiso Co., Ltd. using methyl isobutyl ketone as a dispersion medium. In addition, the hygroscopicity of the adduct body according to the present invention is to compare the time required for moisture absorption from a predetermined moisture content to a predetermined moisture content in an atmosphere having an air temperature of 15 to 20 ° C. and a humidity of 40 to 45%. Can be evaluated. Specifically, for example, a 20 g adduct body can be evaluated in the time required to increase the moisture content from 0.2 wt% to 0.5 wt%. Here, the water content can be measured by measuring tetraarylphosphonium halide using a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.).

The type of adduct according to the present invention can be analyzed by known methods such as elemental analysis, mass spectrometry, nuclear magnetic resonance spectroscopy, and liquid chromatography, as described above.
The composition analysis by liquid chromatography can be performed according to the following procedures and conditions.
Apparatus: LC-2010A manufactured by Shimadzu Corporation, Imtakt Cadenza 3 mm CD-C18 250 mm × 4.6 mm ID. Low pressure gradient method. Analysis temperature 30 ° C. As the column, “ODS3VID” manufactured by Shimadzu Corporation was used. Eluent composition: A solution Acetonitrile: water = 7.2: 1.0 wt% / wt%, B solution 0.5 wt% sodium dihydrogen phosphate aqueous solution. Analysis time 0-12 minutes. Liquid A: Liquid B = 65: 35 (volume ratio, the same applies hereinafter). The analysis time is 12 to 35 minutes, the eluent composition is gradually changed to A liquid: B liquid = 92: 8, and the analysis time of 35 to 40 minutes is maintained at A liquid: B liquid = 92: 8, flow rate 1 ml / min. ).

In addition, the chlorine concentration is determined by dissolving the liquid to be measured in toluene that has been washed and extracted with ultrapure water until the chlorine concentration is less than 1 ppb, and then adding ultrapure water and stirring thoroughly. The aqueous phase thus obtained can be measured by ion chromatography under the following procedure and conditions.
Apparatus: ION CROMATOGRAPH, IonPac AS12A manufactured by DIONEX. As the eluent, a solution obtained by adding sodium hydrogen carbonate to 0.3 mmol · dm ⁻³ so that sodium carbonate becomes 2.7 mmol · dm ^{−3 in} ultrapure water is used.

[Method for producing adduct body according to the present invention]
The adduct according to the present invention can be obtained by crystallizing an asymmetric tetraarylphosphonium halide produced by a known method as described above together with a hydrogen halide. Specifically, it can be obtained by dissolving an asymmetric tetraarylphosphonium halide and a hydrogen halide in a polar organic solvent, followed by crystallization and taking out. (Hereinafter, the method for obtaining this adduct body may be referred to as “the method for producing an adduct body according to the present invention”). And it is preferable to use the adduct body obtained by the manufacturing method of the adduct body which concerns on this invention for the adduct body which concerns on this invention.

  In the method for producing an adduct according to the present invention, an asymmetric tetraarylphosphonium halide can be dissolved by using an organic solvent, and a hydrogen halide can be dissolved by using a polar solvent. And in the manufacturing method of the adduct body which concerns on this invention, it can obtain by crystallizing an adduct body using the solubility difference of the hydrogen halide adduct body of asymmetric tetraarylphosphonium halide and asymmetric tetraarylphosphonium halide. Thus, a solid that is difficult to scatter and easy to handle can be obtained because of its large particle size and low hygroscopicity.

The polar organic solvent used in the method for producing an adduct body according to the present invention is preferably an organic solvent having sufficient solubility with respect to the asymmetric tetraarylphosphonium halide and hydrogen halide and insoluble in the adduct body. Here, the hydrogen halide used in the method for producing an adduct body according to the present invention is usually used as an aqueous solution of hydrogen halide. That is, having sufficient solubility in an aqueous hydrogen halide solution is said to have polarity. Having sufficient solubility with respect to hydrogen halide is usually 100 g of organic solvent at 25 ° C.
Means that 1 g or more of hydrogen halide is dissolved. The polar organic solvent used in the method for producing an adduct body according to the present invention is preferably an organic solvent that is uniform with an aqueous hydrogen halide solution and at a high temperature. The high temperature is usually 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher.

Crystallization may be performed by cooling the adduct body or contacting it with a poor solvent, but a method of precipitation by cooling is simple and preferable.
Preferable examples of the polar organic solvent used for producing the adduct body include alcohols, ketones, ethers, halogenated hydrocarbons, esters and the like.
Examples of alcohols include alkyl alcohols having 1 to 5 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, and i-pentanol. And the like. Examples of ketones include dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, and ethyl n-propyl ketone. And lower alkyl ketones having 1 to 10 carbon atoms such as ethyl isopropyl ketone, ethyl n-butyl ketone and ethyl isobutyl ketone, and cyclic ketones having 3 to 10 carbon atoms such as cyclohexanone and cyclopentanone. Examples of ethers include dimethyl ether, diethyl ether, methyl ethyl ether, methyl n-propyl ether, methyl isopropyl ether, methyl n-butyl ether, methyl isobutyl ether, methyl n-pentyl ether, methyl isopentyl ether, ethyl n-propyl. C2-C10 lower alkyl ethers such as ether, ethyl isopropyl ether, ethyl n-butyl ether, ethyl isobutyl ether, dimethoxyethane, diethoxyethane; cyclic ethers such as tetrahydrofuran and diaryl ethers such as diphenyl ether be able to. Examples of the halogenated hydrocarbons include monochloromethane, dichloromethane, trichloromethane, 1-chloroethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,2-trichloroethane, 1-chloropropane, 2-chloropropane, Examples thereof include halogenated hydrocarbons having 1 to 6 carbon atoms such as 1,2-dichloropropane, 1,1-dichloropropane, and 2,2-dichloropropane. Examples of the esters include lower aliphatic carboxylic acid esters such as alkyl formate, alkyl acetate, and alkyl propionate; alkyl carbonate diesters such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and dibutyl carbonate; Examples thereof include oxalic acid diesters such as dimethyl oxalate and diethyl oxalate; and acetates such as ethyl acetate, propyl acetate, butyl acetate, ethylene glycol acetate and ethylene glycol fatty acid ester.

Among these, as the polar organic solvent according to the method for producing an adduct body of the present invention, an alkyl ketone having an asymmetric structure such as methyl isopropyl ketone and methyl isobutyl ketone and having a total carbon number of 3 to 15 alkyl groups. Are preferred, and alkyl ketones having a total carbon number of 3 to 10 are more preferred.
In the method for producing an adduct body according to the present invention, the hydrogen halide that forms an adduct with an asymmetric tetraarylphosphonium halide is usually used as an aqueous solution of hydrogen halide. That is, the adduct body according to the present invention is obtained by crystallizing and taking out a liquid-state asymmetric tetraarylphosphonium halide in contact with an aqueous solution of hydrogen halide. Specifically, for example, when an adduct with hydrogen chloride is obtained, hydrochloric acid (aqueous hydrogen chloride) is used. When an adduct with hydrogen bromide is obtained, hydrobromic acid (aqueous hydrogen bromide) is used. When obtaining an adduct with hydrogen, it can be obtained by using hydriodic acid (hydrogen iodide aqueous solution). Of these, hydrochloric acid is particularly preferred as the aqueous solution of hydrogen halide.

Next, a preferred example of the procedure for carrying out the method for manufacturing an adduct body according to the present invention will be described.
First, an asymmetric tetraarylphosphonium halide is contacted with a polar organic solvent and hydrohalic acid.
Here, the amount of the polar organic solvent is preferably large in that the asymmetric tetraarylphosphonium halide is easily dissolved when the temperature is raised, but is small in that the adduct is likely to precipitate when the temperature is lowered. preferable. Therefore, the amount of the polar organic solvent is preferably 0.15 times or more, more preferably 0.2 times or more by weight ratio with respect to the asymmetric tetraarylphosphonium halide, and more preferably 2 times or less. It is preferable to use 1 times or less.

  In addition, the amount of hydrogen halide contained in hydrohalic acid is preferably large in terms of the tendency of the adduct body formation rate to be high, but the amount of water contained in hydrohalic acid is small, and asymmetry occurs when the temperature is lowered. It is preferable that the number of tetraarylphosphonium halides is small in that they are likely to precipitate. Therefore, the amount of hydrogen halide contained in the hydrohalic acid is preferably 0.5 times or more by weight ratio with respect to the asymmetric tetraarylphosphonium halide, and on the other hand, preferably 2.0 times or less. More preferably, 1.5 times or less is used.

The relative amount of water with respect to the polar organic solvent is preferably 2 times or more because the asymmetric tetraarylphosphonium halide is easily dissolved when the temperature is raised, and the adduct is easily precipitated when the temperature is lowered. On the other hand, it is preferably 20 times or less, and more preferably 15 times or less.
Next, the liquid is heated to dissolve the asymmetric tetraphosphonium halide. It is preferable to stir the liquid until it is dissolved. The preferred temperature of the liquid temperature after the temperature rise is slightly different depending on the liquid composition, but a high temperature is preferable in that the asymmetric tetraphosphonium halide is easily dissolved in a short time, but a low temperature is preferable in that boiling does not easily occur. In particular, when a polar organic solvent that easily azeotropes with water, such as methyl isobutyl ketone, is used, it is preferable to set a low value. Therefore, 50 ° C. or higher is preferable, 60 ° C. or higher is more preferable, and 95 ° C. or lower is preferable, and 90 ° C. or lower is more preferable.

  Then, by cooling the solution in which the asymmetric tetraarylphosphonium halide is dissolved, an adduct body of the asymmetric tetraarylphosphonium halide and hydrogen halide can be deposited. The temperature at which the adduct body is precipitated is preferably a high temperature in that the solution itself is difficult to solidify, but a low temperature is preferable in terms of the yield of the adduct body. Therefore, it is usually preferably 5 ° C. or higher, more preferably 10 ° C. or higher, particularly preferably 20 ° C. or higher. On the other hand, 70 ° C. or lower is preferable, and 60 ° C. or lower is more preferable.

It is preferable that the temperature-decreasing rate from when the temperature is raised until the adduct body is precipitated is high in terms of being able to be deposited in a short time with small equipment, but it precipitates large crystals that have low hygroscopicity and are difficult to scatter. It is preferable that it is slow in that it is easy to do. Therefore, the temperature decreasing rate is preferably 0.1 to 2 ° C. per minute.
The adduct of organic phosphonium chloride and hydrogen chloride can also be obtained by the method described in JP-A-9-328491. However, this document is a document describing a method for producing an organic phosphonium chloride from an organic phosphonium bromide. In this document, the organic phosphonium hydrogen dichloride is a catalyst for various reactions (phase transfer catalyst, polymerization catalyst, halide). It is merely described as an intermediate for obtaining an organic phosphonium chloride useful as a halogen exchange reaction catalyst. Further, the method described in this document is a method in which hydrochloric acid in which organic phosphonium bromide is dissolved is cooled, and hydrogen chloride is removed by heating after precipitation of organic phosphonium hydrogen dichloride, thereby producing tetraphenylphosphonium. Hydrogen dichloride (adduct of symmetric tetraarylphosphonium and hydrogen chloride, Example 1) and a mixture of benzyltriphenylphosphonium hydrogen dichloride and benzyltriphenylphosphonium chloride (a mixture containing an adduct of asymmetric organic phosphonium and hydrogen chloride) Example 9) is synthesized. Here, the asymmetric tetraarylphosphonium halide according to the present invention preferably has a low hydrophilicity such as 4-t-butylphenyltriphenylphosphonium chloride and does not dissolve in hydrochloric acid, so that an adduct is obtained by this method. It is not possible. In addition, it is as having shown to the comparative example 1 mentioned later that the adduct body based on this invention cannot be obtained by the method described in this literature.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited by a following example, unless the summary is exceeded.

[Raw materials and reagents]
Diphenyl oxalate used was a purified first grade reagent manufactured by Tokyo Chemical Industry Co., Ltd. by simple distillation.
4-t-butylphenyltriphenylphosphonium bromide was synthesized by the method described in JP2013-82695A.
4-t-butylphenyltriphenylphosphonium chloride was synthesized by the method described in JP-A-11-217393. 66.67 g of this 4-t-butylphenyltriphenylphosphonium chloride was dissolved in 100 g of diphenyl carbonate at 150 ° C.
4-methylphenyltriphenylphosphonium chloride was synthesized by the method described in JP-A-8-333307.

[analysis]
The composition analysis was performed by high performance liquid chromatography under the following procedure and conditions.
Apparatus: LC-2010A manufactured by Shimadzu Corporation, Imtakt Cadenza 3 mm CD-C18 250 mm × 4.6 mm ID. Low pressure gradient method. Analysis temperature 30 ° C. As the column, “ODS3VID” manufactured by Shimadzu Corporation was used. Eluent composition: A solution Acetonitrile: water = 7.2: 1.0 wt% / wt%, B solution 0.5 wt% sodium dihydrogen phosphate aqueous solution. Analysis time 0-12 minutes. Liquid A: Liquid B = 65: 35 (volume ratio, the same applies hereinafter). The analysis time is 12 to 35 minutes, the eluent composition is gradually changed to A liquid: B liquid = 92: 8, and the analysis time of 35 to 40 minutes is maintained at A liquid: B liquid = 92: 8, flow rate 1 ml / min. ).

Quantification of benzofuran-2,3-dione was performed by high performance liquid chromatography under the following procedure and conditions.
Apparatus: LC-2010A manufactured by Shimadzu Corporation, Scherzo SM-C 18, 3 μm, 250 mm × 4.6 mm ID. Low pressure gradient method. Analysis temperature 40 ° C. Eluent composition: Liquid A Acetic acid: Acetonitrile: Water = 0.1% by volume: 10% by volume: 90% by volume, Liquid B: 0.2% by weight Ammonium acetate aqueous solution: Acetonitrile = 90% by volume: 10% by volume The analysis time 0 to 20 minutes is fixed at A liquid: B liquid = 60: 40 (volume ratio, the same applies hereinafter). The analysis time is 20-25 minutes, the eluent composition is gradually changed to A liquid: B liquid = 85: 5, and the analysis time 25-35 minutes is maintained at A liquid: B liquid = 60: 40, flow rate 0.85 ml. / Min).

The adduct ratio of adducts of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride and of adducts of tetraphenylphosphonium chloride and hydrogen chloride was determined by a potentiometric titration apparatus using silver nitrate (“AT- 610 ") and calculated from the chlorine concentration.
The moisture content was measured using a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.) with the tetraarylphosphonium halide placed on the petri dish. The test for easiness of drying was carried out by placing a sample in a 100 ml eggplant-shaped flask, attaching it to a rotary evaporator equipped with an oil bath, heating the oil bath to 100 ° C., and under a pressure of 10 Torr, This was carried out by comparing the time required for drying from a predetermined moisture content to a predetermined moisture content. Moreover, the hygroscopicity test was performed by comparing the time required for moisture absorption from a predetermined moisture content to a predetermined moisture content in an atmosphere with an air temperature of 15 to 20 ° C. and a humidity of 40 to 45%.

The particle diameter was a median diameter (D50) measured using a microtrack particle size distribution measuring apparatus “MT3300EXII” manufactured by Nikkiso Co., Ltd. using methyl isobutyl ketone as a dispersion medium.
The quantification of bromine ions was measured using an ion chromatography measuring device “ION CHROMATOGRAPH” manufactured by DIONEX. As the column, a separation column “IonPac AS12A” manufactured by DIONEX was used. The eluent was prepared in ultrapure water so that sodium carbonate was 2.7 mmol · dm ⁻³ and sodium bicarbonate was 0.3 rimole · dm ⁻³ .

Chlorine concentration is measured by dissolving the liquid to be measured in toluene that has been washed and extracted with ultrapure water until the chlorine concentration is less than 1 ppb, and then adding ultrapure water and stirring thoroughly. The aqueous phase thus obtained was subjected to the following procedure and conditions by ion chromatography.
Apparatus: ION CROMATOGRAPH, IonPac AS12A manufactured by DIONEX. As an eluent, a solution obtained by adding sodium hydrogen carbonate to 0.3 mmol · dm ⁻³ so that sodium carbonate was 2.7 mmol · dm ^{−3 in} ultrapure water was used.

[Synthesis Example 1]
A full-jacketed 500 ml separable flask equipped with a thermometer and a stirrer was charged with 50 g (0.13 mol) of tetraphenylphosphonium chloride and 400 g of 28 wt% hydrochloric acid and heated to 90 ° C. in a nitrogen atmosphere. Thereafter, the separable flask was cooled to room temperature, this slurry was filtered through a glass filter, and the obtained solid was transferred to an eggplant type flask. The eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath, and the oil bath was heated to 100 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 42 g of a solid. As a result of analyzing the chlorine concentration of this solid with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 17% by weight. Therefore, the amount of chlorine contained in this solid is 42 g × 0.17 = 7 g (0.192 mol). Here, if this amount of chlorine is regarded as the total amount of chlorine contained in tetraphenylphosphonium chloride contained in the solid and the amount of hydrogen chloride adducted to this, the amount of hydrogen contained in hydrogen chloride is ignored. Then, the amount of tetraphenylphosphonium contained in the solid was 42 g × (1−0.192) = 34 g (0.100 mol), and the amount of chlorine contained in the solid was 0.192 mol−0.100. Mole = 0.092 mol. Thus, it was confirmed that the obtained solid was an adduct of tetraphenylphosphonium chloride and hydrogen chloride with an adduct rate of 92%.

[Example 1]
A full-jacketed 500 ml separable flask equipped with a thermometer and a stirrer was charged with 70 g (0.162 mol) of 4-t-butylphenyltriphenylphosphonium chloride, 18 g of methyl isobutyl ketone and 263 g of 28 wt% hydrochloric acid, and a nitrogen atmosphere. Under heating to 90 ° C. to make a homogeneous solution. Thereafter, the separable flask was cooled to room temperature to obtain a slurry. This slurry was filtered through a glass filter, and the resulting solid was transferred to an eggplant type flask. The eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath, and the oil bath was heated to 100 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 75 g of a solid.

  As a result of analyzing the solid chlorine concentration by a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 14.6% by weight. Therefore, the amount of chlorine contained in this solid is 75 g × 0.146 = 11 g (0.309 mol). Here, when this amount of chlorine is regarded as the amount of hydrogen chloride contained in the adduct body (ignoring the hydrogen content contained in hydrogen chloride), the amount of 4-t-butylphenyltriphenylphosphonium contained in this solid Is 75 g × (1−0.146) = 64 g (0.162 mol), and the amount of chlorine contained in the hydrogen chloride of the adduct body is 0.309 mol−0.162 mol = 0.147 mol, This solid was confirmed to be an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride having an adduct ratio of 91% (0.147 mol / 0.162 mol × 100). Moreover, the yield of the adduct body was calculated as 0.162 mol / 0.162 × 100 = 100%.

  In a three-necked flask equipped with a thermometer and a stirrer, 300 g (1.238 mol) of diphenyl oxalate was placed and heated by immersing the three-necked flask in an oil bath at 230 ° C. to melt the diphenyl oxalate. In this three-necked flask, 20 g (0.043 mol) of an adduct (adduct ratio 91%) of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride obtained as described above was added, and the foot diameter was 4 mm. The funnel was fed. 30 minutes after the supply of the adduct body was completed, a part of the liquid in the three-necked flask was withdrawn, and composition analysis was performed by high performance liquid chromatography. As a result, they were 0.5% by weight of phenol, 29.5% by weight of diphenyl oxalate, and 54.7% by weight of diphenyl carbonate. Here, the conversion rate of diphenyl oxalate was 71%.

  About tetraphenylphosphonium chloride, its adduct obtained in Synthesis Example 1, 4-t-butylphenyltriphenylphosphonium chloride and its adduct obtained in Example 1, its properties, bulk density, particle size, dried Expresses ease (drying time required to reduce moisture content from 2% to 0.5% by weight) and hygroscopicity (time required to increase moisture content from 0.2% to 0.5% by weight). 1 As is clear from Table 1, 4-t-butylphenyltriphenylphosphonium chloride is easily handled and dried by making it an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride. It was revealed that the hygroscopicity can be lowered.

[Comparative Example 1]
A full-jacketed 500 ml separable flask equipped with a thermometer and a stirrer was charged with 50 g (0.116 mol) of 4-t-butylphenyltriphenylphosphonium chloride and 200 g of 28% by weight hydrochloric acid at 90 ° C. under a nitrogen atmosphere. Although heated, it did not become a uniform state but became a slurry state. Thereafter, the separable flask was cooled to room temperature, this slurry was filtered through a glass filter, and the obtained solid was transferred to an eggplant type flask. The eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath, and the oil bath was heated to 100 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 45 g of fine powder. As a result of analyzing the chlorine concentration of the fine powder by a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 8.0% by weight. Since the theoretical chlorine concentration of 4-t-butylphenyltriphenylphosphonium chloride was lower than 8.2% by weight, it was confirmed that the obtained fine powder was not an adduct with hydrogen chloride. Moreover, this fine powder was a white granule, the bulk density was 0.23 g * cm < ³ >, and the particle size was 31 micrometers.

  Next, decarbonylation reaction of diphenyl oxalate was carried out using the fine powder as a catalyst. Specifically, the decarbonylation reaction of Example 1 was carried out in the same manner as in Example 1 except that this fine powder was used as a catalyst. 30 minutes after the supply of the adduct body was completed, a part of the liquid in the three-necked flask was withdrawn, and composition analysis was performed by high performance liquid chromatography. As a result, it was 1.50% by weight of phenol, 63.2% by weight of diphenyl oxalate, and 24.2% by weight of diphenyl carbonate. Here, the conversion rate of diphenyl oxalate was 36%.

[Example 2]
A full-jacketed 500 ml separable flask equipped with a thermometer and a stirrer was charged with 50 g (0.105 mol) of 4-t-butylphenyltriphenylphosphonium bromide, 13 g of methyl isobutyl ketone and 188 g of 28 wt% hydrochloric acid. Example 1
In the same manner, a slurry was obtained. This slurry was filtered through a glass filter to obtain a solid. The obtained solid was transferred to a separable flask together with 13 g of methyl isobutyl ketone and 188 g of 28% by weight hydrochloric acid, and heated to 90 ° C. under a nitrogen atmosphere to obtain a homogeneous solution, and then the slurry was cooled to room temperature. The slurry was filtered through a glass filter to obtain a solid. The solid was heated together with methyl isobutyl ketone and hydrochloric acid to obtain a homogeneous solution, and the operation of obtaining a solid by filtering the slurry obtained by cooling was repeated three more times (4-t-butylphenyltriphenylphosphonium bromide was added). Converted to 4-t-butylphenyltriphenylphosphonium chloride). The obtained solid was transferred to an eggplant-shaped flask, the eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath, the oil bath was heated to 120 ° C., and dried at a pressure of 10 Torr for 2 hours to obtain 35 g of a solid. .

As a result of analyzing the chlorine concentration of this solid with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 13.3% by weight. Therefore, the amount of chlorine contained in this solid is 35 g × 0.133 = 4.66 g (0.132 mol). Here, when this amount of chlorine is regarded as the amount of hydrogen chloride contained in the adduct body (ignoring the hydrogen content contained in hydrogen chloride), the amount of 4-t-butylphenyltriphenylphosphonium contained in this solid Is 35 g × (1−0.133) = 30 g (0.077 mol), and the amount of chlorine contained in the hydrogen chloride of the adduct body is 0.132 mol−0.077 mol = 0.055 mol, This solid was confirmed to be an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride having an adduct ratio of 71% (0.055 mol / 0.077 mol × 100). Moreover, the yield of the adduct body was calculated as 0.077 mol ÷ 0.105 mol × 100 = 73%.
As a result of measuring bromide ions contained in this solid using an ion chromatography measuring apparatus “ION CHROMATOGRAPH” manufactured by DIONEX, it was 0.5 mol% or less.

[Example 3]
A slurry was obtained in the same manner as in Example 1 except that 18 g of 1-butanol was used instead of 18 g of methyl isobutyl ketone and 263 g of 35 wt% hydrochloric acid was used instead of 263 g of 28 wt% hydrochloric acid. The solid obtained by filtering this slurry through a glass filter was transferred to an eggplant type flask. The eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath, and the oil bath was heated to 130 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 72 g of a solid.

  As a result of analyzing the chlorine concentration of this solid with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 11.0% by weight. Therefore, the amount of chlorine contained in this solid is 72 g × 0.110 = 7.9 g (0.223 mol). Here, when this amount of chlorine is regarded as the amount of hydrogen chloride contained in the adduct body (ignoring the hydrogen content contained in hydrogen chloride), the amount of 4-t-butylphenyltriphenylphosphonium contained in this solid Is 72 g × (1−0.110) = 64 g (0.162 mol), and the amount of chlorine contained in the adduct hydrogen chloride is 0.223 mol−0.162 mol = 0.061 mol, This solid was confirmed to be an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride having an adduct rate of 38% (0.061 mol ÷ 0.162 mol × 100). Further, the yield of 4-t-butylphenyltriphenylphosphonium adduct was calculated as 0.162 mol ÷ 0.162 mol × 100 = 100%.

[Example 4]
5 g (0.011 mol) of the adduct obtained in Example 3 was placed in an eggplant-shaped flask, attached to a rotary evaporator equipped with an oil bath, the oil bath was heated to 180 ° C., and dried at a pressure of 10 Torr for 2 hours. . This is a potentiometric titrator “AT-61” manufactured by Kyoto Electronics Industry Co., Ltd.
As a result of “0” analysis, the adduct ratio of the adduct body was reduced to 2%. The results of measuring adduct rate and hygroscopicity (time required to increase the moisture content from 0.2 wt% to 0.5 wt%) for Examples 1 to 3 and the adduct body are summarized in Table 2. As is apparent from Table 2, it was revealed that the hygroscopicity of the adduct body of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride decreases as the adduct ratio increases.

[Example 5]
In a full-jacketed 500 ml separable flask equipped with a thermometer, a stirrer, a distillation tube and a receiver, an adduct body of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride obtained in Example 1 ( 11 g (0.024 mol) of adduct ratio 91% and 96 g (0.0448 mol) of diphenyl carbonate were added, and the inside of the separable flask was heated to 150 ° C. to dissolve the adduct body. The inside of the separable flask was heated to 185 ° C., and the pressure was set to 2 kPa and dried for 3 hours, thereby distilling 20 g of water and diphenyl carbonate in total to dry the inside of the separable flask. To this separable flask, 160 g (0.661 mol) of diphenyl oxalate was added and heated to 150 ° C. to dissolve the diphenyl oxalate. Further, 0.012 mol of hydrogen chloride gas was blown into the separable flask, and the temperature was raised to 225 ° C. When the temperature reached 225 ° C., a part of the liquid in the separable flask was extracted and subjected to composition analysis by high performance liquid chromatography. As a result, phenol 0.2% by weight, diphenyl oxalate 55.1% by weight, diphenyl carbonate It was 40.0% by weight.

  After the inside of the separable flask reached 225 ° C., the reaction was carried out while maintaining the temperature at 225 ° C. for 80 minutes while removing carbon monoxide generated by the reaction with nitrogen under the normal pressure. A part of the liquid reacted for 80 minutes was extracted and subjected to composition analysis by high performance liquid chromatography. As a result, phenol was 0.2% by weight, diphenyl oxalate was 8.5% by weight, and diphenyl carbonate was 84.4% by weight. . Here, the conversion rate of diphenyl oxalate was 88%.

[Comparative Example 2]
In Example 5, instead of 11 g of the adduct body of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride obtained in Example 1, 10 g of 4-t-butylphenyltriphenylphosphonium chloride (0.024 mol) The experiment was performed in the same manner as in Example 5 except that. The composition analysis results of the liquid in the separable flask when the temperature reached 225 ° C. were 0.4% by weight of phenol, 54.8% by weight of diphenyl oxalate, and 40.1% by weight of diphenyl carbonate. . Moreover, the compositional analysis result of the liquid reacted for 80 minutes was 0.4% by weight of phenol, 22.2% by weight of diphenyl oxalate, and 72.4% by weight of diphenyl carbonate. Here, the conversion rate of diphenyl oxalate was 68%.

  The results of Example 5 and Comparative Example 2 are summarized in Table 3. From Table 3, since 4-t-butylphenyltriphenylphosphonium chloride has high hygroscopicity, the amount of phenol by-produced by hydrolysis of diphenyl oxalate and diphenyl carbonate increases, and as a result, the conversion rate of diphenyl oxalate It was confirmed that the reaction activity decreased.

[Example 6]
After putting 300 g (1.238 mol) of diphenyl oxalate into a full-jacketed 500 ml separable flask equipped with a thermometer, a stirrer, a distillation tube and a receiver, the mixture was dissolved by heating to 150 ° C. After adding 15 g (0.032 mol) of the adduct body (adduct ratio 91%) of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride obtained in Example 1 to the separable flask and dissolving them. The temperature was raised to 230 ° C. When 230 ° C. was reached, a part of the liquid in the separable flask was extracted and subjected to composition analysis by high performance liquid chromatography. As a result, phenol 0.2% by weight, diphenyl oxalate 75.5% by weight, diphenyl carbonate 18.0 wt%.

  After the inside of the separable flask reached 230 ° C., the reaction was carried out while maintaining the temperature at 230 ° C. for 6 hours while removing the carbon monoxide generated by the reaction from the reaction system with nitrogen under atmospheric pressure. A part of the liquid reacted for 6 hours was extracted and subjected to composition analysis by high performance liquid chromatography. As a result, 92.7% by weight of diphenyl carbonate, 0.2% by weight of phenol, 484.6% by weight of diphenyl oxalate, 4- The amount was 5.0% by weight of t-butylphenyltriphenylphosphonium chloride. Here, the conversion of diphenyl oxalate was 99.9%. Moreover, the reaction liquid after reaction (before extracting the sample for composition analysis) is 279 g, and the molecular weight of 4-t-butylphenyltriphenylphosphonium chloride is 431. Therefore, 4-t-butylphenyltriphenylphosphonium chloride contained in the reaction solution after the reaction is calculated as 279 g × 0.05 ÷ 431 = 0.032 mol. Here, since the charged amount of the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride was also 0.032 mol, the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride was used. The decomposition rate of the body was 0%.

  Thereafter, the pressure was gradually reduced to 10 Torr, and 230 g of crude diphenyl carbonate was distilled off. Further, 47 g of the residual liquid in the separable flask after distilling the crude diphenyl carbonate was visually dissolved at 200 ° C. Therefore, the concentration rate (evaporation rate) was 230 g / (230 g + 47 g) = 83%. Moreover, it was 11 weight ppm when the density | concentration of the benzofuran-2,3-dione in crude diphenyl carbonate was measured by the high performance liquid chromatography.

[Example 7]
In the state which maintained the residual liquid in the separable flask obtained in Example 6 at 150 degreeC, 40g inside was extracted. Here, the molecular weight of 4-t-butylphenyltriphenylphosphonium chloride is 431, and the molecular weight of the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride is 467. 4-t-butylphenyltriphenylphosphonium chloride, 15 g × (431 ÷ 467) × (40 ÷ 47) = 11.8 g, contained in a state dissolved in diphenyl carbonate. To this, 0.3 g (0.640 mmol) of an adduct (adduct ratio 91%) of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride obtained in Example 1 and 267 g of diphenyl oxalate (1. 102 mol) was added to obtain a homogeneous solution. Further, 400 cm ³ (0.0179 mol) of hydrogen chloride was blown into this, and the temperature was raised to 230 ° C. When 230 ° C. was reached, a part of the liquid in the separable flask was extracted and subjected to composition analysis by high performance liquid chromatography. As a result, 59.6% by weight of diphenyl oxalate, 33.67% by weight of diphenyl carbonate, phenol It was 0.2% by weight.

  After the inside of the separable flask reached 230 ° C., the reaction was carried out while maintaining the temperature at 230 ° C. for 6 hours while removing the carbon monoxide generated by the reaction from the reaction system with nitrogen under atmospheric pressure. A part of the liquid reacted for 6 hours was extracted and subjected to composition analysis by high performance liquid chromatography. As a result, it was 92.7% by weight of diphenyl carbonate, 0.3% by weight of phenol, and 548.1% by weight of diphenyl oxalate. . Here, the conversion rate of diphenyl oxalate was 99.9%.

  Thereafter, the pressure was gradually reduced to 10 Torr, and 200 g of crude diphenyl carbonate was distilled off. 36 g of the remaining liquid in the separable flask after distilling the crude diphenyl carbonate was visually dissolved at 200 ° C. Therefore, the concentration rate (evaporation rate) was 200 g / (230 g + 36 g) × 100 = 84.7%. Moreover, it was 10 weight ppm when the density | concentration of the benzofuran-2,3-dione in crude diphenyl carbonate was measured by the high performance liquid chromatography.

[Comparative Example 3]
In Example 6, the amount of diphenyl oxalate charged was reduced from 300 g to 95 g (0.392 mol) and obtained in Synthesis Example 1 instead of 15 g of adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride. Diphenyl carbonate was produced in the same manner as in Example 6 except that 5 g of the adduct body of tetraphenylphosphonium chloride and hydrogen chloride was used and the reaction time at 230 ° C. was shortened from 6 hours to 1.3 hours.

The composition of the liquid reacted for 1.3 hours was 59.8% by weight of diphenyl carbonate, 30.7% by weight of diphenyl oxalate, and 0.2% by weight of phenol. Here, the conversion rate of diphenyl oxalate was 70.2%.
Moreover, 38 g of crude diphenyl carbonate was distilled. The residual liquid 45g in the separable flask after crude diphenyl carbonate distillation was 200 degreeC, and was a slurry form visually. Therefore, the concentration rate (evaporation rate) was 38 g / (38 g + 45 g) × 100 = 46%. Further, the concentration of benzofuran-2,3-dione in the crude diphenyl carbonate was measured by high performance liquid chromatography and found to be 150 ppm by weight.

[Comparative Example 4]
In Example 6, the amount of diphenyl oxalate charged was reduced from 300 g to 95 g (0.392 mol), and 5 g of tetraphenylphosphonium chloride was used instead of 15 g of adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride. Then, after dissolving tetraphenylphosphonium chloride, 300 cm ³ of hydrogen chloride was added, and diphenyl carbonate was produced in the same manner as in Example 6 except that the reaction time at 230 ° C. was shortened from 6 hours to 1.3 hours.

The composition of the liquid reacted for 1.3 hours was 57.8% by weight of diphenyl carbonate, 28.4% by weight of diphenyl oxalate, and 0.2% by weight of phenol. Here, the conversion rate of diphenyl oxalate was 72.5%.
Moreover, 66 g of crude diphenyl carbonate was distilled. The residual liquid 22g in the separable flask after distilling the crude diphenyl carbonate was 200 ° C. and was visually slurry. Therefore, the concentration rate (evaporation rate) was 66 g / (66 g + 22 g) × 100 = 75%. Moreover, it was 120 weight ppm when the density | concentration of the benzofuran-2,3-dione in crude diphenyl carbonate was measured by the high performance liquid chromatography.

  The results of Example 6, Comparative Example 3 and Comparative Example 4 are summarized in Table 4. From Table 4, 4-t-butylphenyltriphenylphosphonium chloride has less benzofuran-2,3-dione and high purity carbonic acid compared to tetraphenylphosphonium chloride and adducts of tetraphenylphosphonium chloride and hydrogen chloride. It was confirmed that diphenyl can be obtained. In addition, 4-t-butylphenyltriphenylphosphonium chloride has higher solubility in diphenyl carbonate than tetraphenylphosphonium chloride and adducts of tetraphenylphosphonium chloride and hydrogen chloride, so diphenyl oxalate is converted to diphenyl carbonate. After reacting at a high conversion rate, even if diphenyl carbonate was concentrated to a high concentration, the catalyst was not precipitated in the residual liquid, so it was proved that the catalyst contained in the residual liquid was easy to reuse.

[Example 8]
A full-jacketed 500 ml separable flask equipped with a thermometer and a stirrer was charged with 20 g (0.05 mol) of 4-t-butylphenyltriphenylphosphonium chloride, 5 g of 1-butanol and 75 g of 28 wt% hydrochloric acid, and a nitrogen atmosphere. Under heating to 90 ° C. to make a homogeneous solution. Thereafter, the separable flask was cooled to 10 ° C. to obtain a slurry. The solid obtained by filtering this slurry through a glass filter was transferred to an eggplant type flask. The eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath, and the oil bath was heated to 100 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 15 g of a solid.

  As a result of analyzing the solid chlorine concentration with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 15.8% by weight. Therefore, the amount of chlorine contained in this solid is 15 g × 0.158 = 2.4 g (0.068 mol). Here, when this amount of chlorine is regarded as the amount of hydrogen chloride contained in the adduct body (ignoring the hydrogen content contained in hydrogen chloride), the molecular weight of 4-methylphenyltriphenylphosphonium is 353. The amount of 4-methylphenyltriphenylphosphonium contained in the solid was 15 g × (1−0.158) = 12.6 g (0.036 mol), and the amount of chlorine contained in the adduct hydrogen chloride was 0.068. Mol-0.036 mol = 0.032 mol. Thus, it was confirmed that this solid was an adduct of 4-methylphenyltriphenylphosphonium chloride and hydrogen chloride having an adduct ratio of 89% (0.032 mol / 0.036 mol × 100). Moreover, the yield of the adduct body was calculated as 0.036 mol ÷ 0.05 × 100 = 72%.

[Example 9]
In Example 6, instead of the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride, 15 g of the adduct of 4-methylphenyltriphenylphosphonium chloride and hydrogen chloride obtained in Example 8 ( 0.035 mol) (adduct rate 89%) was used, and diphenyl carbonate was produced in the same manner as in Example 6 except that the reaction time at 230 ° C. was shortened from 6 hours to 3 hours.

When the temperature reached 230 ° C., the liquid composition was 66.2% by weight of diphenyl oxalate, 26.6% by weight of diphenyl carbonate, 5.1% by weight of 4-methylphenyltriphenylphosphonium chloride, and 1.5% by weight of phenol. It was.
The composition of the liquid reacted for 3 hours was 49.5% by weight of diphenyl carbonate, 39.5% by weight of diphenyl oxalate, 3.6% by weight of 4-methylphenyltriphenylphosphonium chloride, and 2.3% by weight of phenol. there were. Here, the conversion rate of diphenyl oxalate was 61%.

  Here, the reaction liquid after the reaction (before extracting a sample for composition analysis) is 265 g, and the molecular weight of 4-methylphenyltriphenylphosphonium chloride is 389. Therefore, 4-methylphenyltriphenylphosphonium chloride contained in the reaction solution after the reaction is calculated as 265 g × 0.036 ÷ 389 = 0.025 mol. Here, since the charge amount of the adduct of 4-methylphenyltriphenylphosphonium chloride and hydrogen chloride was 0.035 mol, the decomposition rate of the adduct of 4-methylphenyltriphenylphosphonium chloride and hydrogen chloride (0.035 mol-0.025 mol) ÷ 0.035 mol × 100 = 29%.

  Therefore, from the comparison between Example 6 and Example 9, the adduct of 4-t-butylphenyltriphenylphosphonium chloride, which is an asymmetric tetraarylphosphonium halide having no benzyl proton, and hydrogen chloride is stable in decarbonylation reaction. It was confirmed that the property is high and particularly preferable.

[Example 10]
An adduct body of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride was synthesized by the following method.
First, 4-t-butylphenyltriphenylphosphonium bromide was synthesized by the method described in JP2013-82695A. This bromide body was converted into 4-t-butylphenyltriphenylphosphonium chloride (chloride body) by the method described in JP-A-11-217393.

  The separable flask was charged with this 4-t-butylphenyltriphenylphosphonium chloride, butanol and hydrochloric acid, and heated to 90 ° C. in a nitrogen atmosphere to obtain a uniform solution. Thereafter, the separable flask was cooled to room temperature to obtain a slurry. The solid obtained by filtering this slurry through a glass filter was transferred to an eggplant type flask. The eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath, and the oil bath was heated to 100 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain a solid. As a result of analyzing this solid with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 14.2% by weight, so that an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride was obtained. It was confirmed that. Moreover, the moisture content measured using the moisture meter (Kyoto Electronics Industry Co., Ltd. "MKS-500") was 0.4 weight%.

[Example 11]
In a 2-liter eggplant-shaped flask, 200 g (0.46 mol) of 4-t-butylphenyltriphenylphosphonium chloride, 100 g of 1-butanol and 700 g of 28% by weight hydrochloric acid were added and heated to 90 ° C. in a nitrogen atmosphere to be uniform. Into solution. Thereafter, the eggplant-shaped flask was cooled to room temperature to obtain a slurry. This slurry was filtered through a glass filter to obtain 190 g of a solid.

30 g of the obtained crystals were transferred to a 500 cm ³ eggplant type flask. The eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath, and the oil bath was heated to 70 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 25 g of a solid.
As a result of analyzing the solid chlorine concentration with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 15.2% by weight. Therefore, the amount of chlorine contained in this solid is 25 g × 0.152 = 3.8 g (0.107 mol). Here, when this amount of chlorine is regarded as the total amount of chlorine and hydrogen chloride in 4-t-butylphenyltriphenylphosphonium chloride contained in the adduct body (ignoring the hydrogen content in hydrogen chloride), this The amount of 4-t-butylphenyltriphenylphosphonium contained in the solid was 25 g × (1-0.152) = 21.2 g (0.054 mol), and the amount of chlorine contained in the adduct hydrogen chloride was 0.00. Since 107 mol-0.054 mol = 0.053 mol, this solid was converted into 4-t-butylphenyltriphenylphosphonium chloride having an adduct ratio of 95% (0.053 mol ÷ 0.056 mol × 100). It was confirmed that it is an adduct body of hydrogen chloride. The obtained solid was a white granule having a bulk density of 0.48 g · cm ³ and a particle size of 180 μm.

  Next, using this adduct having an adduct ratio of 95% as a catalyst, decarbonylation of diphenyl oxalate was carried out. Specifically, in the decarbonylation reaction of Example 1, the decarbonylation reaction was performed in the same manner as in Example 1 except that the above-mentioned adduct having an adduct ratio of 95% was used as the catalyst. 30 minutes after the supply of the adduct body was completed, a part of the liquid in the three-necked flask was withdrawn, and composition analysis was performed by high performance liquid chromatography. As a result, they were 0.5% by weight of phenol, 30.1% by weight of diphenyl oxalate, and 56.2% by weight of diphenyl carbonate. Here, the conversion rate of diphenyl oxalate was 70%.

[Example 12]
30 g (0.46 mol) of the adduct body obtained in Example 11 was transferred to a 500 ml eggplant-shaped flask, and this eggplant-shaped flask was attached to a rotary evaporator equipped with an oil bath. The oil bath was heated to 130 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 25 g of a solid.

As a result of analyzing the solid chlorine concentration with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 12.7% by weight. Therefore, the amount of chlorine contained in this solid is 25 g × 0.127 = 3.2 g (0.090 mol). Here, when this amount of chlorine is regarded as the amount of chlorine hydrogen contained in the adduct body (ignoring the hydrogen content contained in hydrogen chloride), the amount of 4-t-butylphenyltriphenylphosphonium contained in this solid Is 25 g × (1−0.127) = 21.8 g (0.055 mol), and the amount of chlorine contained in the hydrogen chloride of the adduct body is 0.090 mol−0.055 mol = 0.035 mol. From this, it was confirmed that this solid was an adduct body of 4-t-butylphenyltriphenylphosphonium and hydrogen chloride having an adduct ratio of 64% (0.035 mol ÷ 0.055 mol × 100). Moreover, the obtained solid was a white granule, the bulk density was 0.45 g * cm < ³ >, and the particle size was 142 micrometers.

  Next, using this adduct having an adduct ratio of 64% as a catalyst, decarbonylation of diphenyl oxalate was carried out. Specifically, in the decarbonylation reaction of Example 1, the decarbonylation reaction was performed in the same manner as in Example 1 except that the above-mentioned adduct having an adduct ratio of 64% was used as the catalyst. 30 minutes after the supply of the adduct body was completed, a part of the liquid in the three-necked flask was withdrawn, and composition analysis was performed by high performance liquid chromatography. As a result, it was 0.6% by weight of phenol, 31.2% by weight of diphenyl oxalate, and 55.6% by weight of diphenyl carbonate. Here, the conversion rate of diphenyl oxalate was 69%.

[Example 13]
30 g (0.06 mol) of the adduct body obtained in Example 11 was transferred to a 500 ml eggplant type flask, and this eggplant type flask was attached to a rotary evaporator equipped with an oil bath. The oil bath was heated to 150 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 25 g of a solid.

The chlorine concentration of this solid was analyzed by a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd. As a result, it was 10.2% by weight. Therefore, the amount of chlorine contained in this solid is 25 g × 0.102 = 2.6 g (0.073 mol). Here, when this amount of chlorine is regarded as the amount of chlorine hydrogen contained in the adduct body (ignoring the hydrogen content contained in hydrogen chloride), the amount of 4-t-butylphenyltriphenylphosphonium contained in this solid Is 25 g × (1−0.102) = 22.5 g (0.057 mol), and the amount of chlorine contained in the hydrogen chloride of the adduct body is 0.073 mol−0.057 mol = 0.016 mol. From this, it was confirmed that this solid was an adduct of 4-t-butylphenyltriphenylphosphonium and hydrogen chloride having an adduct ratio of 28% (0.016 mol ÷ 0.057 mol × 100). Moreover, the obtained solid was a white granule, the bulk density was 0.45 g * cm < ³ >, and the particle size was 134 micrometers.

  Next, using this adduct having an adduct ratio of 28% as a catalyst, decarbonylation of diphenyl oxalate was carried out. Specifically, in the decarbonylation reaction of Example 1, the decarbonylation reaction was performed in the same manner as in Example 1 except that the adduct having the adduct rate of 28% was used as the catalyst. 30 minutes after the supply of the adduct body was completed, a part of the liquid in the three-necked flask was withdrawn, and composition analysis was performed by high performance liquid chromatography. As a result, it was 0.6% by weight of phenol, 30.2% by weight of diphenyl oxalate, and 55.2% by weight of diphenyl carbonate. Here, the conversion rate of diphenyl oxalate was 70%.

[Example 14]
30 g (0.06 mol) of the adduct body obtained in Example 11 was transferred to a 500 ml eggplant type flask, and this eggplant type flask was attached to a rotary evaporator equipped with an oil bath. The oil bath was heated to 200 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 25 g of a solid.

As a result of analyzing the solid chlorine concentration with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 8.6% by weight. Therefore, the amount of chlorine contained in this solid is 25 g × 0.086 = 2.2 g (0.062 mol). Here, when this amount of chlorine is regarded as the amount of chlorine hydrogen contained in the adduct body (ignoring the hydrogen content contained in hydrogen chloride), the amount of 4-t-butylphenyltriphenylphosphonium contained in this solid Is 25 g × (1-0.086) = 22.9 g (0.058 mol), and the amount of chlorine contained in the adduct hydrogen chloride is 0.062 mol−0.058 mol = 0.004 mol. From this, it was confirmed that this solid was an adduct of 4-t-butylphenyltriphenylphosphonium and hydrogen chloride having an adduct ratio of 7% (0.004 mol ÷ 0.058 mol × 100). Moreover, the obtained solid was a white granule, the bulk density was 0.41 g * cm < ³ >, and the particle size was 110 micrometers.

  Next, decarbonylation reaction of diphenyl oxalate was carried out using this adduct having an adduct ratio of 7% as a catalyst. Specifically, in the decarbonylation reaction of Example 1, the decarbonylation reaction was performed in the same manner as in Example 1 except that the above adduct having an adduct rate of 7% was used as the catalyst. 30 minutes after the supply of the adduct body was completed, a part of the liquid in the three-necked flask was withdrawn, and composition analysis was performed by high performance liquid chromatography. As a result, they were 0.5% by weight of phenol, 29.6% by weight of diphenyl oxalate, and 58.3% by weight of diphenyl carbonate. Here, the conversion rate of diphenyl oxalate was 71%.

[Example 15]
After putting 30 g (0.070 mol) of 4-t-butylphenyltriphenylphosphonium chloride into a 500 ml heart-shaped flask, hydrogen chloride gas was passed through the flask for 1 hour, and the inside of the flask was filled with hydrogen chloride gas. Replaced. The flask was immersed in a Dewar bottle containing liquid nitrogen with hydrogen chloride gas flowing. The hydrogen chloride gas in the flask was liquefied, and the components in the flask became 100 ml of a cloudy slurry. In this state, after maintaining the state in which 100 ml of the cloudy slurry was present for 2 hours, the hydrogen chloride gas was stopped and the temperature was slowly raised to room temperature while the nitrogen gas was supplied to drive out the hydrogen chloride in the flask. As a result, 25 g of a solid was obtained.

As a result of analyzing the chlorine concentration of this solid with a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd., it was 14.5% by weight. Therefore, the amount of chlorine contained in this solid is 25 g × 0.145 = 3.6 g (0.101 mol). Here, when this amount of chlorine is regarded as the amount of chlorine hydrogen contained in the adduct body (ignoring the hydrogen content contained in hydrogen chloride), the amount of 4-t-butylphenyltriphenylphosphonium contained in this solid Is 25 g × (1−0.145) = 21.4 g (0.054 mol), and the amount of chlorine contained in the adduct hydrogen chloride is 0.101 mol−0.054 mol = 0.047 mol. From this, it was confirmed that this solid was an adduct of 4-t-butylphenyltriphenylphosphonium and hydrogen chloride having an adduct ratio of 87% (0.047 mol ÷ 0.054 mol × 100). Further, the obtained solid was a white powder having a bulk density of 0.41 g · cm ³ and a particle size of 45 μm.

Next, decarbonylation reaction of diphenyl oxalate was carried out using this adduct having an adduct ratio of 87% as a catalyst. Specifically, in the decarbonylation reaction of Example 1, the decarbonylation reaction was performed in the same manner as in Example 1 except that the above-mentioned adduct having an adduct ratio of 87% was used as the catalyst. 30 minutes after the supply of the adduct body was completed, a part of the liquid in the three-necked flask was withdrawn, and composition analysis was performed by high performance liquid chromatography. As a result, it was 1.3 weight% of phenol, 51.2 weight% of diphenyl oxalate, and 20.7 weight% of diphenyl carbonate. Here, the conversion rate of diphenyl oxalate was 48%.
The results of Examples 11 to 15 and Comparative Example 1 are summarized in Table 5.

  As can be seen from Table 5, by using an asymmetric tetraarylphosphonium halide as an adduct with hydrogen chloride, the particle size is large, the bulk density is high, it is easy to handle, and this is used as a catalyst. It was confirmed that when the carbonyl reaction was performed, the conversion rate of diphenyl oxalate was high, the amount of phenol by-product was small, the amount of unreacted diphenyl oxalate was small, and the amount of diphenyl carbonate produced was large. In particular, it was confirmed that a catalyst having a large particle size exhibits excellent reaction results. It was also confirmed that the asymmetric adduct produced by the method for producing an adduct produced according to the present invention has a large particle size and exhibits excellent reaction results.

Claims (12)

  A process for producing diphenyl carbonate by decarbonylation of diphenyl oxalate in the presence of a catalyst, wherein the catalyst is supplied as an adduct of an asymmetric tetraarylphosphonium halide and a hydrogen halide. Production method.   It is a manufacturing method of the diphenyl carbonate of Claim 1, Comprising: The manufacturing method of the diphenyl carbonate whose average particle diameter of the said adduct body is 50 micrometers or more and 1 mm or less.   The method for producing diphenyl carbonate according to claim 1 or 2, wherein the adduct is obtained by crystallization after dissolving an asymmetric tetraarylphosphonium halide and a hydrogen halide in a polar organic solvent. The manufacturing method of diphenyl carbonate.   The method for producing diphenyl carbonate according to any one of claims 1 to 3, wherein the asymmetric tetraarylphosphonium halide does not have a benzyl proton.   The method for producing diphenyl carbonate according to any one of claims 1 to 4, wherein the adduct is an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride. Production method. A method for producing diphenyl carbonate, comprising the following first to third steps in this order.
1st process: The process of manufacturing diphenyl carbonate by the manufacturing method of diphenyl carbonate of any one of Claims 1 thru | or 5,
Second step: Separating diphenyl carbonate produced in the first step from the adduct body and / or a catalyst solution containing an adduct body decomposition product generated by decomposing the adduct body,
Third step: A step of supplying at least a part of the catalyst solution to the first step   The method for producing diphenyl carbonate according to claim 6, wherein a liquid having a higher boiling point than the diphenyl carbonate is removed from the catalyst liquid separated in the second step, and an asymmetric tetraarylphosphonium halide and hydrogen halide And supplying the adduct body to the first step in the third step.   A method for producing an adduct of a tetraarylphosphonium halide and a hydrogen halide, wherein the asymmetric tetraarylphosphonium halide and the hydrogen halide are dissolved in a polar organic solvent, and then crystallized to form an asymmetric tetraarylphosphonium halide and a hydrogen halide. A method for producing an adduct of an asymmetric tetraarylphosphonium halide and a hydrogen halide, comprising obtaining an adduct of a hydrogen halide.   An adduct of tetraarylphosphonium halide and hydrogen halide, wherein the tetraarylphosphonium halide is an asymmetric tetraarylphosphonium halide having no benzyl protons, and an asymmetric tetraarylphosphonium halide and halogenated Adduct body with hydrogen.   A catalyst for producing diphenyl carbonate by decarbonylation of diphenyl oxalate, wherein the catalyst is an adduct of an asymmetric tetraarylphosphonium halide having no benzyl proton and a hydrogen halide. Catalyst for diphenyl production. Diphenyl carbonate obtained by the method for producing diphenyl carbonate according to any one of claims 1 to 7.   A polycarbonate obtained by polycondensation of an aromatic dihydroxy compound and diphenyl carbonate according to claim 11 in the presence of a transesterification catalyst.