WO2015178463A1 - Procédé de production de carbonate de diphényle, carbonate de diphényle ainsi obtenu, polycarbonate produit à partir dudit carbonate de diphényle, catalyseur pour la production de carbonate de diphényle, procédé de production du catalyseur, et procédé de récupération et de réutilisation du catalyseur - Google Patents

Procédé de production de carbonate de diphényle, carbonate de diphényle ainsi obtenu, polycarbonate produit à partir dudit carbonate de diphényle, catalyseur pour la production de carbonate de diphényle, procédé de production du catalyseur, et procédé de récupération et de réutilisation du catalyseur Download PDF

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WO2015178463A1
WO2015178463A1 PCT/JP2015/064645 JP2015064645W WO2015178463A1 WO 2015178463 A1 WO2015178463 A1 WO 2015178463A1 JP 2015064645 W JP2015064645 W JP 2015064645W WO 2015178463 A1 WO2015178463 A1 WO 2015178463A1
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Prior art keywords
catalyst
diphenyl carbonate
reaction
adduct
chloride
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PCT/JP2015/064645
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English (en)
Japanese (ja)
Inventor
馨 内山
金丸　高志
敏光 井上
中村　誠
佐藤　崇
芳夫 古賀
俊雄 内堀
智 浦川
功一 早志
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三菱化学株式会社
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Priority claimed from JP2014144298A external-priority patent/JP6245097B2/ja
Priority claimed from JP2014144297A external-priority patent/JP6287655B2/ja
Priority claimed from JP2014219464A external-priority patent/JP6344196B2/ja
Priority claimed from JP2014219463A external-priority patent/JP6344195B2/ja
Application filed by 三菱化学株式会社 filed Critical 三菱化学株式会社
Priority to KR1020167032584A priority Critical patent/KR102206139B1/ko
Priority to CN201580026720.8A priority patent/CN106458834B/zh
Publication of WO2015178463A1 publication Critical patent/WO2015178463A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/08—Purification; Separation; Stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for producing diphenyl carbonate such as diphenyl carbonate and a carbonic acid diester obtained by the production method.
  • a method for producing a carbonic acid diester by decarbonylating a oxalic acid diester such as diphenyl oxalate in the presence of a catalyst an easy-to-handle catalyst is used to stabilize a highly pure diphenyl carbonate stably. It is an invention about providing a method which can be manufactured continuously.
  • the present invention is an invention relating to a high-purity polycarbonate which is obtained by using a carbonic acid diester produced by this method as a raw material and which is less colored. Furthermore, this invention is invention about the catalyst suitable for this carbonic acid diester manufacture, and its manufacturing method. The present invention also provides a method for recovering a high-purity catalyst efficiently from a reaction solution by a simple method, reusing it and stably producing a high-purity carbonic acid diester, and a solvent used for recovering the catalyst. Is also an invention about reuse.
  • Carbonic acid diester is known as a raw material compound in various chemical reactions.
  • 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 organic phosphorus compound (see Patent Document 1).
  • a decarbonylation catalyst such as an organic phosphorus compound
  • the reaction pressure it is disclosed that “the pressure is increased when the reaction temperature exceeds the boiling point of diaryl oxalate, but is usually normal pressure or reduced pressure”.
  • a pressure vessel is required for the pressure reaction, and a vacuum pump is required for the pressure reduction reaction, and the pressure must be controlled, so that the reaction is generally performed at normal pressure.
  • a method for producing a carbonic acid diester using an oxalic acid diester having a low content of an aromatic hydroxy compound or an alkylaryl oxalate as a raw material is also disclosed (see Patent Document 2).
  • diphenyl carbonate obtained by decarbonylation reaction of diphenyl oxalate contains light impurities such as furan compounds, it is distilled or pyrolyzed (heat treated at a temperature of 150 to 300 ° C. for about 0.05 to 10 hours.
  • there has been proposed a method of removing by thermal decomposition, condensation and / or thermal denaturation see Patent Document 3).
  • diaryl carbonate obtained by decarbonylation reaction of diaryl oxalate is a non-evaporated component containing a decarbonylation catalyst, a high boiling point substance, etc. by evaporating the decarbonylation reaction solution with an evaporator.
  • a product fraction obtained by separating the distillate and the evaporating component mainly containing the target diaryl carbonate and the starting material diaryl oxalate, and further purifying the evaporating component by distillation operation Mixing with furan compounds such as benzofuran-2,3-dione produced by fleece rearrangement of diaryl oxalate will cause the polycarbonate product produced using the diaryl carbonate to be colored.
  • Patent Document 4 also has problems such as requiring a large number of distillation steps for purification and very complicated operations, and further improvements in the purification of diphenyl carbonate. It was sought after.
  • 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 above-described catalyst recovery method is performed using an asymmetric tetraarylphosphonium halide and / or an asymmetric tetraarylphosphonium halide and a hydrogen halide.
  • the present invention provides a method for solving at least one of these problems, and an object thereof is to provide at least one of the following methods.
  • the first problem of the present invention is that a method for producing a carbonic acid diester by subjecting an oxalic acid diester to a decarbonylation reaction in the presence of a catalyst, and by using an easy-to-handle catalyst, the carbonic acid diester can be easily and efficiently stabilized.
  • a method that can be manufactured will be provided.
  • the second object of the present invention is to provide a method capable of stably producing a high-purity carbonic acid diester that does not easily cause coloration in a polycarbonate produced from the raw material without causing troubles such as clogging due to catalyst precipitation. I will do it.
  • the third problem of the present invention is that when an asymmetric tetraarylphosphonium halide and / or an adduct of an asymmetric tetraarylphosphonium halide and a hydrogen halide is used as a catalyst in the production of a carbonic acid diester by decarbonylation of an oxalic acid diester.
  • the present invention provides a method for efficiently recovering a high-purity catalyst from a reaction solution by a simple method, reusing it, and stably and continuously producing a high-purity carbonic acid diester.
  • the fourth problem of the present invention is that when tetraarylphosphonium halide and / or an adduct of tetraarylphosphonium halide and hydrogen halide is used as a catalyst for the production of carbonic acid diester by decarbonylation of oxalic acid diester, Provide a method for efficiently and stably producing a high-purity carbonic acid diester by reusing and reusing a high-purity catalyst efficiently and reusing the solvent used for catalyst recovery. I will do it.
  • the fifth object of the present invention is to produce a carbonic acid diester by decarbonylation reaction of an oxalic acid diester in the presence of a catalyst.
  • a simple method efficiently and stably produces a high-purity carbonic acid diester. We will provide a possible method.
  • a sixth problem of the present invention is that a carbonic acid diester is efficiently and industrially produced by a more simplified reaction apparatus and process for a method for producing a carbonic acid diester by decarbonylating a oxalic acid diester in the presence of a catalyst.
  • a method for continuous production shall be provided.
  • the present inventors have intensively studied to solve the above problems.
  • a method for producing diphenyl carbonate by decarbonylating diphenyl oxalate in the presence of a catalyst the catalyst is used as an adduct of an asymmetric tetraarylphosphonium halide and hydrogen halide.
  • it can be solved by supplying.
  • 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. .
  • the catalyst in the method for producing a carbonic acid diester by decarbonylating the oxalic acid diester in the presence of a catalyst, the catalyst is precipitated by using a catalyst soluble in the carbonic acid diester. And after conversion at a conversion rate of 96% or more, the amount of residual oxalic acid diester is reduced by evaporating 50% by weight or more of the carbonic acid diester contained in the reaction solution, and the by-product of furan compounds during evaporation of the carbonic acid diester is produced. It became possible to suppress and found out that this could be solved.
  • the present inventors diligently studied a method for recovering an adduct body of asymmetric tetraarylphosphonium halide and / or asymmetric tetraarylphosphonium halide and hydrogen halide.
  • a high purity catalyst is efficiently recovered as a precipitate by bringing a polar organic solvent and hydrogen chloride into contact with the remaining liquid obtained from the reaction solution containing a component containing carbonic acid diester, and then bringing water into contact therewith. It was found that can be solved.
  • the present inventors diligently studied a method for recovering a tetraarylphosphonium halide and / or an adduct of a tetraarylphosphonium halide and a hydrogen halide.
  • a high purity catalyst can be efficiently recovered by contacting a polar organic solvent with hydrogen chloride gas and / or hydrochloric acid in the residual liquid obtained from the reaction liquid containing a component containing carbonic acid diester, It has been found that this can be solved by reusing the residual liquid after catalyst recovery as the polar organic solvent.
  • the present inventors have found that this can be solved by supplying the catalyst dissolved in the carbonic acid diester when reusing the catalyst after the reaction. Further, the present inventors have found that a high-purity carbonic acid diester can be efficiently produced by using an oxalic acid diester containing a specific amount of a specific impurity as a raw material. And it discovered that highly pure diphenyl carbonate could be manufactured efficiently and stably by performing decarbonylation reaction of an oxalic acid diester under specific pressure conditions. Further, the present inventors have found that the thermal decomposition of a furan compound is promoted by contacting with a basic compound, and the furan compound contained in the produced carbonic acid diester is brought into contact with the basic compound. It has been found that a high-purity carbonic acid diester can be produced efficiently by removing the above.
  • the present inventors stir the reaction solution by performing a decarbonylation reaction while supplying a small amount of a gas inert to the decarbonylation reaction from the bottom of the decarbonylation reactor.
  • the present inventors have found that carbonic acid diesters can be produced efficiently by removing impurities such as phenol by-produced during the decarbonylation reaction.
  • the present invention is as follows. 1. 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. 2. 2. The method for producing diphenyl carbonate according to item 1, wherein the average particle size of the adduct body is 50 ⁇ m or more and 1 mm or less. 3. 3. 3.
  • the inert gas in the decarbonylation reaction is carried out the decarbonylation reaction while supplying from the lower part of the decarbonylation reactor below superficial linear velocity 0.00001M ⁇ s -1 or 0.01 m ⁇ s -1, item 1
  • the catalyst is soluble in diphenyl carbonate, and after the decarbonylation reaction is carried out at a conversion rate of 96% or more, the reaction remaining after removing 50% by weight or more of diphenyl carbonate contained in the reaction solution 8.
  • Diphenyl oxalate contains 0.076 weight% or more and 10 weight% or less of carboxylic acid phenylester represented by following General formula (5).
  • n 1 or 2.
  • 1st process The process of manufacturing diphenyl carbonate by the manufacturing method of diphenyl carbonate of any one of the preceding clauses 1 thru
  • 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 reactor of the first step.
  • a method for recovering a catalyst used in the production of diphenyl carbonate by decarbonylation of diphenyl oxalate wherein the catalyst is an asymmetric tetraarylphosphonium halide and / or an adduct of an asymmetric tetraarylphosphonium halide and a hydrogen halide,
  • the catalyst is recovered as a precipitate obtained by bringing a polar organic solvent and a hydrogen halide gas into contact with the residual liquid obtained from the reaction liquid after the decarbonylation reaction and containing a component containing diphenyl carbonate, and then contacting with water.
  • a method for recovering a catalyst used in the production of diphenyl carbonate by decarbonylation of diphenyl oxalate wherein the catalyst is a tetraarylphosphonium halide and / or an adduct of a tetraarylphosphonium halide and a hydrogen halide, After contacting the residual liquid obtained from the reaction liquid after the carbonyl reaction with diphenyl carbonate component with a polar organic solvent and hydrogen halide, the catalyst contained in the residual liquid is recovered (catalyst recovery step) and the polar A method for recovering a catalyst, comprising recovering an organic solvent and reusing it in the catalyst recovery step. 15. 15.
  • a process for producing diphenyl carbonate by decarbonylation of diphenyl oxalate wherein the catalyst recovered by the recovery method according to item 13 or 14 is used as a catalyst.
  • 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. 17.
  • 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. 18. 16.
  • the first effect of the present invention is that a method for producing diphenyl carbonate by subjecting diphenyl oxalate to a decarbonylation reaction in the presence of a catalyst, using an easy-to-handle catalyst, easily and efficiently stabilizing high-purity diphenyl carbonate. It can be manufactured continuously.
  • 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.
  • the second effect of the present invention is that a method for producing a carbonic acid diester by decarbonylation of an oxalic acid diester is simple and efficient, and stably produces a high-purity carbonic acid diester without causing troubles such as clogging due to catalyst precipitation. Is what you can do. Moreover, by using this carbonic acid diester as a raw material, it is possible to obtain a high-purity polycarbonate that hardly causes coloring.
  • the third effect of the present invention is that when an asymmetric tetraarylphosphonium halide and / or an adduct of an asymmetric tetraarylphosphonium halide and a hydrogen halide is used as a catalyst in the production of a carbonic acid diester by decarbonylation of an oxalic acid diester.
  • the high-purity catalyst can be efficiently recovered from the reaction solution by a simple method and reused, and a high-purity carbonic acid diester can be stably and continuously produced. Further, by using this high-purity carbonic acid diester as a raw material, a high-purity polycarbonate can be obtained.
  • the fourth effect of the present invention is that when a tetraarylphosphonium halide and / or an adduct of tetraarylphosphonium halide and hydrogen halide is used as a catalyst in the production of a carbonic acid diester by decarbonylation of an oxalic acid diester, Efficient and stable production of high-purity carbonic acid diesters by efficiently recovering and reusing high-purity catalysts from liquids and reusing solvents used for catalyst recovery It is possible to do. Further, by using this high-purity carbonic acid diester as a raw material, a high-purity polycarbonate can be obtained.
  • the fifth effect of the present invention is that a method for producing a carbonic acid diester by decarbonylation reaction of an oxalic acid diester in the presence of a catalyst is a simple and efficient method for stably and stably producing a high-purity carbonic acid diester. It is possible to provide a method that can. Further, by using this high-purity carbonic acid diester as a raw material, a high-purity polycarbonate can be obtained.
  • the sixth effect of the present invention is that the method for producing a carbonic acid diester by decarbonylation reaction of oxalic acid diester in the presence of a catalyst enables diphenyl carbonate to be efficiently and industrially produced by a more simplified reaction apparatus and process. It is possible to provide a method for continuous production.
  • the oxalic acid diester is decarbonylated in the presence of a catalyst (hereinafter sometimes referred to as “decarbonylation reaction according to the present invention” or simply “decarbonylation reaction”). Carbonic acid diester is produced.
  • a catalyst hereinafter sometimes referred to as “decarbonylation reaction according to the present invention” or simply “decarbonylation reaction”. Carbonic acid diester is produced.
  • the decarbonylation reaction according to the present invention is performed according to the following reaction formula (1).
  • two Rs are each independently a hydrocarbon group which may have a substituent.
  • the oxalic acid diester in the reaction formula (1) (hereinafter sometimes referred to as “oxalic acid diester according to the present invention” or simply “oxalic acid diester”) is a raw material in the method for producing the carbonic acid diester of the present invention.
  • the carbonic acid diester according to the present invention obtained from the oxalic acid diester according to the present invention as a raw material is thermally stable and suitable as a polycarbonate raw material.
  • the oxalic acid diester according to the present invention is usually an oxalic acid diester having the same type of hydrocarbon group (R) as the target carbonic acid diester.
  • the hydrocarbon group in the oxalic acid diester according to the present invention may be aliphatic or aromatic. That is, the hydrocarbon groups possessed by the oxalic acid diester may be both alkyl groups, one alkyl group and one aromatic ring group, or both aromatic ring groups.
  • both of them are preferably aromatic ring groups because the leaving group can be easily recovered.
  • hydrocarbon group of the oxalic acid diester according to the present invention is an alkyl group, it may be linear, branched or cyclic.
  • the aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the carbonic acid diester of the present invention is easily detached when used as a raw material for producing a polycarbonate, an aromatic hydrocarbon ring group is preferred.
  • a single ring is preferable because the leaving group can be easily recovered and the leaving group is stable.
  • aromatic hydrocarbon ring group examples include a 5- or 6-membered monocyclic ring or a 2-5 condensed ring having one free valence.
  • free valence refers to those that can form bonds with other free valences as described in Organic Chemistry / Biochemical Nomenclature (above) (Revised 2nd edition, Nankodo, 1992). Say.
  • aromatic hydrocarbon ring group examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene having one free valence. Ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • a benzene ring (phenyl group) having one free valence is particularly preferable since the leaving group is stable when the carbonic acid diester of the present invention is used as a raw material for producing polycarbonate or the like.
  • the oxalic acid diester according to the present invention is preferably a compound in which both R in the carbonic acid diester produced in the above reaction formula (1) is an aromatic ring group, and both R are aromatic hydrocarbon ring groups. Some compounds are more preferred, and diphenyl oxalate in which both R are phenyl groups is particularly preferred.
  • the oxalic acid diester according to the present invention is preferably diphenyl oxalate (hereinafter sometimes referred to as “diphenyl oxalate according to the present invention” or simply “diphenyl oxalate”), and the carbonic acid diester of the present invention.
  • the carbonic acid diester produced by this production method is preferably diphenyl carbonate (hereinafter sometimes referred to as “diphenyl carbonate according to the present invention” or simply “diphenyl carbonate”).
  • the decarbonylation reaction of the oxalic acid diester is preferably performed according to the following reaction formula (2).
  • two Ph's are each independently a phenyl group optionally having a substituent.
  • the aromatic heterocyclic group may be a 5- or 6-membered monocyclic ring having 2 free valences or 2 To 4 condensed rings.
  • aromatic heterocyclic group examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole ring having one free valence.
  • the substituent which the hydrocarbon group of the oxalic acid diester according to the present invention has is not particularly limited as long as the excellent effect of the present invention is not significantly prevented.
  • 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.
  • an alkyl group having 1 to 12 carbon atoms such as a methyl group or an ethyl group
  • an alkoxy group having 1 to 12 carbon atoms such as a methoxy group or an ethoxy group
  • a nitro group such as a halogen such as a fluorine atom or a chlorine atom Atoms and aromatic ring groups are preferred.
  • the alkyl group as a substituent refers to the case where an alkyl group is bonded as a substituent to an aromatic ring group, and the aromatic ring group as a substituent is, for example, an aromatic heterocyclic group to an aromatic heterocyclic group.
  • bonds as a substituent etc. is said.
  • the aromatic ring group having a substituent has various isomers depending on the position of the substituent, and any of them may be used.
  • 2-, 3- having an alkyl group having 1 to 12 carbon atoms such as 2-, 3- or 4-methylphenyl group, 2-, 3- or 4-ethylphenyl group Or 4-alkylphenyl group; 2-, 3- or 4- having an alkoxy group having 1 to 12 carbon atoms such as 2-, 3- or 4-methoxyphenyl group, 2-, 3- or 4-ethoxyphenyl group 2-, 3- or 4-nitrophenyl having a halogen atom such as 2-, 3- or 4-nitrophenyl; 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl Examples thereof include 4-halophenyl group, and any of these may be used.
  • the number of carbon atoms of the hydrocarbon group of the oxalic acid diester according to the present invention is preferably large in terms of the stability of the leaving group when the carbonic acid diester of the present invention is used as a raw material for producing polycarbonate, It is preferable that the number of leaving groups is small in view of easy recovery.
  • substituent when it has a substituent, it is preferably 1 or more including the substituent, more preferably 2 or more, and on the other hand, it is preferably 12 or less, and is 10 or less. More preferably.
  • an unsubstituted phenyl group is most preferred particularly when the obtained diphenyl carbonate is used for polycarbonate production.
  • Diaryl oxalate (oxalate diester having two aromatic ring groups as a hydrocarbon group) is produced by transesterification of dialkyl oxalate and aromatic hydroxy compound as shown in the following reaction formula (3). Can be used.
  • dialkyl oxalate used as a raw material as produced by the following reaction formula (4), those produced by an oxidative carbonylation reaction using carbon monoxide, oxygen and an aliphatic alcohol as raw materials can be used.
  • R represents an alkyl group
  • Ar represents an aromatic ring group
  • R represents an alkyl group.
  • the diphenyl oxalate when diphenyl oxalate is used as a raw material, the diphenyl oxalate contains 0.076 wt% or more and 10 wt% or less of a carboxylic acid phenyl ester represented by the following general formula (5). It is preferable to contain the amount of.
  • the amount of carboxylic acid phenyl ester contained in diphenyl oxalate is preferably more than 1% by weight.
  • the amount of carboxylic acid phenyl ester contained in diphenyl oxalate refers to the total amount of carboxylic acid phenyl ester relative to the total amount of diphenyl oxalate and total carboxylic acid phenyl ester.
  • n 1 or 2.
  • the carboxylic acid phenyl ester represented by the general formula (5) since the phenol is easily reduced, the phenyl (p-phenoxy) represented by the general formula (6) produced from diphenyl oxalate by Fries rearrangement and condensation polymerization is used.
  • Phenyl (p- (or o-) phenyloxycarbonylphenyl) oxalate and diphenyl carbonate such as carbonylphenyl) oxalate (PCPO) or phenyl (o-phenoxycarbonylphenyl) oxalate (OCPO) represented by general formula (7)
  • Phenyl, such as preparative (OCPC) (p- (or o-) phenyloxycarbonyl phenyl) carbonate is preferred.
  • Carboxylic acid phenyl ester is produced as a by-product when diphenyl oxalate is produced by transesterification of dialkyl oxalate with phenol. Therefore, diphenyl oxalate containing 0.076 wt% or more and 10 wt% or less of carboxylic acid phenyl ester is obtained by converting the diphenyl oxalate obtained by the transesterification reaction between dialkyl oxalate and phenol into carboxylic acid phenyl ester. It can be obtained by distillation purification so as to be in the above range.
  • the carboxylic acid phenyl ester usually has a boiling point higher than that of diphenyl oxalate. Therefore, it can be obtained mainly by removing only the low boiling point from diphenyl oxalate from diphenyl oxalate obtained by the transesterification reaction between dialkyl oxalate and phenol.
  • the carboxylic acid contained in diphenyl oxalate may be less than the above lower limit.
  • the catalyst used in the method for producing a carbonic acid diester of the present invention (hereinafter sometimes referred to as “decarbonylation catalyst according to the present invention”, “decarbonylation catalyst” or “catalyst”) has a trivalent valence of phosphorus atoms of Examples include pentavalent organic phosphorus compounds.
  • the organophosphorus compound in which the valence of the phosphorus atom is trivalent or pentavalent is preferably an organophosphorus compound having at least one carbon-phosphorus (CP) bond, and three or more carbon-phosphorus ( More preferred are organophosphorus compounds having a CP) bond.
  • organic phosphorus compounds examples include phosphonium salt organic phosphorus compounds (hereinafter also referred to as phosphonium salts), phosphine organic phosphorus compounds, phosphine dihalide organic phosphorus compounds, and phosphine oxide organic phosphorus compounds. .
  • phosphonium salt organic phosphorus compounds hereinafter also referred to as phosphonium salts
  • phosphine organic phosphorus compounds phosphine dihalide organic phosphorus compounds
  • phosphine oxide organic phosphorus compounds examples include phosphonium salt organic phosphorus compounds (hereinafter also referred to as phosphonium salts), phosphine organic phosphorus compounds, phosphine dihalide organic phosphorus compounds, and phosphine oxide organic phosphorus compounds.
  • a phosphonium salt-based organophosphorus compound is preferable as the decarbonylation catalyst according to the present invention.
  • the phosphonium salt-based organic phosphorus compound is preferably a phosphonium salt represented by the following general formula (A).
  • R 1 , R 2 , R 3 and R 4 each independently represent an optionally substituted aromatic ring group, aralkyl group or alkyl group, and X forms a counter ion of the phosphonium salt. Represents a possible atom or atomic group.
  • aromatic ring group of the general formula (A) examples include aromatic hydrocarbon groups having 6 to 14 carbon atoms such as phenyl group, biphenyl group and naphthyl group, sulfur atoms such as thienyl group, furyl group and pyridyl group, oxygen atom Alternatively, an aromatic heterocyclic group having 4 to 16 carbon atoms containing a nitrogen atom can be used.
  • aralkyl group examples include an aralkyl group having 7 to 15 carbon atoms which may have an unsaturated bond such as a benzyl group, a phenethyl group, a cinnamyl group, and a naphthylmethyl group.
  • alkyl group examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylmethyl, and vinyl.
  • a cyclic structure such as a propenyl group, a butenyl group, a 1,3-butadienyl group, or an alkyl group having 1 to 16 carbon atoms which may have an unsaturated bond.
  • R 1 to R 4 in the general formula (A) include various isomers and may have one or more substituents.
  • substituents examples include an alkoxy group (preferably 1 to 12 carbon atoms), a thioalkoxy group (preferably 1 to 12 carbon atoms), an aralkyloxy group (preferably 7 to 13 carbon atoms), an 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 An amino group, an alkyl-substituted amino group (preferably having 2 to 16 carbon atoms), a nitro group, a cyano group, a hydroxy group, a halogen atom (fluorine, chlorine, bromine, etc.) and the like. Further, these substituents may further have a substituent, and examples of the substituent include a halogen atom.
  • R 1 to R 4 in the general formula (A) are phenyl groups having a substituent
  • various isomers exist. Examples of these isomers include 2- (or 3-, 4-) methylphenyl group, 2- (or 3-, 4-) ethylphenyl group, 2,3- (or 3,4-) dimethylphenyl Group, a 2,4,6-trimethylphenyl group, a 4-trifluoromethylphenyl group, a 3,5-bistrifluoromethylphenyl group or the like, or an alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group is bonded to the phenyl group.
  • R 1 to R 4 in the general formula (A) are aromatic ring groups
  • these may be an alkyl group which may have a ring structure (including a heterocyclic ring) or an unsaturated bond in addition to the substituent. (Preferably having 1 to 12 carbon atoms) may be present on the ring as one or more substituents.
  • R 1 to R 4 are aromatic heterocyclic groups
  • these may be substituted with an aromatic hydrocarbon ring group (preferably having 6 to 16 carbon atoms) as a substituent on the heterocyclic ring. You may have two or more.
  • R 1 to R 4 in the general formula (A) may be the same as or different from each other. Further, the two groups may be bonded to each other or crosslinked. However, from the viewpoint of solubility, any one of R 1 to R 4 is preferably a group different from any of the other three groups.
  • 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 at least any one of R 1 to R 4 is different from at least one of the other three groups is referred to as “asymmetric”.
  • the counter ion X ⁇ in the general formula (A) includes halogen ions such as chlorine ion, bromine ion and iodine ion, hydrogen dichloride ion, hydrogen dibromide ion, hydrogen diiodide ion and hydrogen dibromide chloride. Examples thereof include hydrogen halide ions such as ions.
  • X is preferably a halogen ion, and more preferably a chlorine ion, since it easily acts as a highly active catalyst in the decarbonylation reaction according to the present invention.
  • preferable phosphonium salt-based organic phosphorus compounds include the following compounds. That is, examples of the organic phosphonium chloride in which R 1 to R 4 in the general formula (A) are all unsubstituted aromatic hydrocarbon groups include tetraphenylphosphonium chloride, p-biphenyltriphenylphosphonium chloride, 1-naphthyltrichloride. Examples thereof include phenylphosphonium chloride and 2-naphthyltriphenylphosphonium chloride.
  • Examples of the organic phosphonium chloride in which R 1 to R 4 in the general formula (A) are an unsubstituted aromatic hydrocarbon group or an aromatic hydrocarbon group having a substituent include o-methylphenyltriphenylphosphonium chloride, m- Methylphenyltriphenylphosphonium chloride, p-methylphenyltriphenylphosphonium chloride, p-isopropylphenyltriphenylphosphonium chloride, 4-t-butylphenyltriphenylphosphonium chloride, m-trifluoromethylphenyltriphenylphosphonium chloride, 2,4 Compounds having an aromatic hydrocarbon group having an alkyl group such as 1,6-trimethylphenyltriphenylphosphonium chloride; halogen atoms such as p-chlorophenyltriphenylphosphonium chloride; A compound having an aromatic hydrocarbon group such as m-methoxyphenyltriphenylphosphonium chlor
  • Examples of the organic phosphonium chloride in which R 1 to R 4 in the general formula (A) are aralkyl groups include benzyltriphenylphosphonium chloride and phenethyltriphenylphosphonium chloride.
  • Examples of the organic phosphonium chloride in which R 1 to R 4 in the general formula (A) are all alkyl groups include tetraethylphosphonium chloride, tetrabutylphosphonium chloride, hexadecyltributylphosphonium chloride, and the like.
  • Examples of the organic phosphonium chloride in which R 1 to R 4 in the general formula (A) are an aromatic hydrocarbon group or an alkyl group include methyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium chloride, butyltriphenyl. Ring structures such as phosphonium chloride, hexyltriphenylphosphonium chloride, heptyltriphenylphosphonium chloride, tetradecyltriphenylphosphonium chloride, dimethyldiphenylphosphonium chloride, allyltriphenylphosphonium chloride, and the like; cyclopropyltriphenylphosphonium chloride, etc.
  • Examples of the organic phosphonium chloride in which R 1 to R 4 in the general formula (A) are an aromatic hydrocarbon group or an alkyl group having a substituent include (1,3-dioxolan-2-yl) methyltriphenylphosphonium.
  • alkyl group having a heterocyclic group such as chloride, 2- (1,3-dioxolan-2-yl) ethyltriphenylphosphonium chloride, 2- (1,3-dioxan-2-yl) ethyltriphenylphosphonium chloride, etc.
  • Compound Compound having an alkyl group having a halogen atom such as bromomethyltriphenylphosphonium chloride; Compound having an alkyl group having a carboxyl group such as 4-carboxybutyltriphenylphosphonium chloride, 2-carboxyallyltriphenylphosphonium chloride; 4 -D Compounds having an alkyl group having an alkoxycarbonyl group, such as xyloxybutyltriphenylphosphonium chloride; compounds having an alkyl group having an alkyl-substituted amino group, such as 2-dimethylaminomethyltriphenylphosphonium chloride, and phenacyltriphenylphosphonium chloride And compounds having an alkyl group having an acyl group.
  • a halogen atom such as bromomethyltriphenylphosphonium chloride
  • Compound having an alkyl group having a carboxyl group such as 4-carboxybutyltriphenylphosphonium
  • Examples of the organic phosphonium chloride in which R 1 to R 4 in the general formula (A) are an aromatic hydrocarbon group or an aralkyl group include benzyltriphenylphosphonium chloride, 4-ethoxybenzyltriphenylphosphonium chloride, cinnamyltriphenylphosphonium chloride. Etc.
  • R 1 to R 4 in the general formula (A) are all aromatic ring groups, and R 1 to R More preferably, all 4 are aromatic hydrocarbon groups.
  • Asymmetric tetraarylphosphonium halide is particularly preferred, and 4-t-butylphenyltriphenylphosphonium chloride is most preferred.
  • tetraarylphosphonium halide The phosphonium salt organic phosphorus compound in which R 1 to R 4 in the general formula (A) are all aromatic ring groups is referred to as “tetraarylphosphonium halide according to the present invention” or simply “tetraarylphosphonium halide”. There is a case.
  • tetraarylphosphonium halides according to the present invention particularly preferred tetraarylphosphonium halides in which R 1 to R 4 are asymmetric are referred to as “asymmetric tetraarylphosphonium halides according to the present invention” or simply “asymmetric tetraarylphosphonium halides”. May be said.
  • the tetraarylphosphonium halide according to the present invention which is preferable as a decarbonylation catalyst according to the present invention, is a compound represented by the following general formula (10).
  • 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.
  • Examples of the aromatic ring group represented by Ar 1 to Ar 4 include aromatic hydrocarbon groups having 6 to 14 carbon atoms such as phenyl group, biphenyl group, and naphthyl group, sulfur atoms such as thienyl group, furyl group, pyridyl group, oxygen atom, 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.
  • substituents 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 Is an aryloxy group (preferably 6 to 16 carbon atoms), a thioaryloxy group (preferably 6 to 16 carbon atoms), an acyl group (preferably 1 to 12 carbon atoms), an alkoxycarbonyl group (Preferably having 2 to 16 carbon atoms), carboxyl group, amino group, alkyl-substituted amino group (preferably having 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
  • an alkyl group is preferable because it is thermally stable, an alkyl group having 1 to 12 carbon atoms is more preferable, and a branched alkyl group having 3 to 8 carbon atoms is more preferable.
  • the substituent does not have a benzyl proton because the catalyst becomes thermally stable and hardly decomposes when used as the catalyst for 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.
  • Ar 1 to Ar 4 are aromatic ring groups having a substituent
  • various isomers exist, and Ar 1 to Ar 4 may be any of them.
  • These isomers include, for example, when Ar 1 to Ar 4 are a phenyl group having a substituent, 2- (or 3-, 4-) methylphenyl group, 2- (or 3-, 4-) ethyl 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
  • Ar 1 to Ar 4 may be bonded to each other or bridged between two groups.
  • the asymmetric tetraarylphosphonium halide according to the present invention is a compound represented by the above general formula (10), wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 are asymmetric.
  • the tetraarylphosphonium halide according to the present invention is asymmetric, at least any one group of Ar 1 to Ar 4 is a group different from at least one of the other three groups, so that the solubility is excellent.
  • the remaining three groups of Ar 1 to Ar 4 may be the same or different from each other.
  • Ar 1 to Ar 4 are preferably aromatic ring groups because they are likely to be thermally stable, and any one of Ar 1 to Ar 4 has a substituent. It is more preferable that the remaining three groups in the aromatic ring group have an unsubstituted aromatic ring group, and at least any one of Ar 1 to Ar 4 is an aryl group having a substituent and the remaining group is an unsubstituted aryl group.
  • a group is particularly preferred, and any one of Ar 1 to Ar 4 is most preferably a phenyl group having a substituent and the remaining three groups being an unsubstituted phenyl group.
  • the halogen atom X in the general formula (10) is a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom.
  • a chlorine atom is preferable because it easily acts as a highly active catalyst in the decarbonylation reaction according to the present invention.
  • the tetraarylphosphonium halide according to the present invention is preferably tetraphenylphosphonium chloride (which may have a substituent).
  • the tetraarylphosphonium halide according to the present invention preferably has no benzyl proton. That is, an asymmetric tetraarylphosphonium chloride having no benzyl proton is particularly preferred.
  • tetraarylphosphonium halide include the following compounds. That is, Ar 1 to Ar 4 are all unsubstituted aromatic hydrocarbon groups such as tetraphenylphosphonium chloride, p-biphenyltriphenylphosphonium chloride, 1-naphthyltriphenylphosphonium chloride, 2-naphthyltriphenylphosphonium chloride, etc. Is mentioned.
  • Examples of the organic phosphonium chloride in which Ar 1 to Ar 4 are an unsubstituted aromatic hydrocarbon group or an aromatic hydrocarbon group having a substituent 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
  • the tetraarylphosphonium halide according to the present invention is preferably tetraphenylphosphonium chloride which may have a substituent.
  • asymmetric tetraarylphosphonium chloride (a compound other than tetraphenylphosphonium chloride among the above compounds) is preferable, and 4-t-butylphenyltriphenylphosphonium chloride is particularly preferable.
  • the catalyst used in the method for producing a carbonic acid diester of the present invention is an adduct body of the above-mentioned asymmetric tetraarylphosphonium halide and hydrogen halide (hereinafter referred to as “asymmetric adduct body according to the present invention” or simply “asymmetric adduct body”). Is particularly preferred.
  • the hydrogen halide may be referred to as “hydrogen halide according to the present invention”, and the adduct body may be referred to as “adduct body according to the present invention” or simply “adduct body”.
  • Examples of the hydrogen halide according to the present invention include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.
  • 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 tetraarylphosphonium halide is preferred.
  • the hydrogen halide according to the present invention is preferably hydrogen chloride
  • the adduct according to the present invention is preferably an adduct of tetraphenylphosphonium chloride and hydrogen chloride, and an adduct of asymmetric tetraphenylphosphonium chloride and hydrogen chloride. Is more preferable, and an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride is particularly preferable.
  • 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 hydrogen halide is added to tetraarylphosphonium halide, a melted or dissolved substance thereof, and the like.
  • 0.01 to 1.0 mol of hydrogen halide is usually added to 1 mol of tetraarylphosphonium halide. That is, the adduct according to the present invention usually has 1 to 100% of hydrogen halide added to the asymmetric tetraarylphosphonium halide 100 in a molar ratio.
  • the type of decarbonylation catalyst 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, 4-t-butylphenyltriphenylphosphonium chloride is analyzed by elemental analysis, mass spectrometry, and nuclear magnetic resonance spectrum. I can confirm that.
  • the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride first, it was confirmed that 4-t-butylphenyltriphenylphosphonium chloride was contained as described above, and then 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 decarbonylation catalyst 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 and the production of furan-based compounds by-produced when the carbonic acid diester is evaporated can be suppressed.
  • the catalyst can be supplied in a state dissolved in a carbonic acid diester, and the Fries rearrangement product of the oxalic acid diester is obtained by reusing a catalyst solution containing a small amount of the unreacted oxalic acid diester after the reaction and containing a high concentration of the carbonic acid diester.
  • By-products such as phenol are hardly generated, and a high-purity carbonic acid diester can be obtained.
  • being soluble in a carbonic acid diester means that the catalyst usually dissolves 10 g or more, preferably 50 g or more, in 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 above-mentioned decarbonylation catalyst in the carbonic acid diester.
  • tetraarylphosphonium salts having one or more alkyl groups are preferred because of their high solubility in carbonic acid diesters.
  • the number of alkyl groups contained in the tetraarylphosphonium salt having one or more alkyl groups is preferably 1 or more and 3 or less.
  • the tetraarylphosphonium salt having two or more alkyl groups has an aromatic group having one or more alkyl groups as a substituent even if it has one aromatic ring group having two or more alkyl groups as substituents. Although it may have two ring groups, the latter is preferable because of easy synthesis.
  • the asymmetric tetraarylphosphonium halide according to the present invention preferably has low solubility in a polar organic solvent and water because a high-purity catalyst can be efficiently efficiently recovered by the catalyst recovery method of the present invention described later.
  • the asymmetric adduct according to the present invention preferably has a high solubility in a polar organic solvent and a low solubility in water, because a high-purity catalyst can be efficiently recovered efficiently by the catalyst recovery method of the present invention.
  • the amount of asymmetric adducts according to the present invention dissolved in 100 g of the polar organic solvent according to the present invention described later at 40 ° C. is more than 0.5 g more than the asymmetric tetraarylphosphonium halide according to the present invention. Is more preferable, more preferably 1.0 g or more, and particularly preferably 1.5 g or more.
  • the asymmetric tetraarylphosphonium halide according to the present invention preferably does not dissolve 2.0 g or more and further does not dissolve 1.5 g or more with respect to 100 g of the polar organic solvent according to the present invention described later at 40 ° C. preferable.
  • the asymmetric adduct according to the present invention is preferably dissolved at 2.5 g or more, more preferably at least 3.0 g, at 40 ° C. with respect to 100 g of the polar organic solvent according to the present invention described later.
  • the asymmetric tetraarylphosphonium halide according to the present invention and the asymmetric adduct according to the present invention preferably do not dissolve 2.5 g or more, and do not dissolve 2.0 g or more with respect to 100 g of pure water at 40 ° C. Further preferred.
  • the asymmetric adduct according to the present invention is 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. It is estimated that Therefore, in the catalyst recovery method of the present invention described later, the asymmetric tetraarylphosphonium chloride and its adduct with hydrogen chloride can be recovered in the same manner.
  • the amount of the decarbonylation catalyst used in the method for producing a carbonic acid diester of the present invention is preferably large from the viewpoint of production efficiency in that the reaction rate tends to be high, but the catalyst is difficult to precipitate during the production cost and the carbonic acid diester purification process. It is preferable that there is little in terms.
  • it is preferably 1.0% by weight or more, more preferably 2.0% by weight or more, particularly preferably 3.0% by weight or more, It is preferably 15.0% by weight or less, more preferably 10.0% by weight or less, and further preferably 8.0% by weight or less.
  • the decarbonylation catalyst is preferably used in an amount of 0.001 mol or more, more preferably 0.01 mol or more, and more preferably 1 mol or less, based on 1 mol of oxalic acid diester. More preferably, 5 mol or less is used.
  • the amount of the decarbonylation catalyst with respect to 100 mol of the total molar amount of oxalic acid diester and carbonic acid diester in the reactor is preferably 0.001 mol or more, more preferably 0.1 mol or more, It is preferably 50 mol or less, and more preferably 20 mol or less.
  • a catalyst 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.
  • disassembled is said.
  • the relative amount of the total amount of diphenyl oxalate and tetraarylphosphonium halide supplied to the reactor is the total amount of diphenyl oxalate and tetraarylphosphonium halide in the reactor. Since it is easy to be in the above preferred range, the total amount of tetraarylphosphonium halide is preferably 0.1 mol or more, more preferably 1 mol or more, relative to 100 mol of diphenyl oxalate, The amount is preferably 50 mol or less, and more preferably 20 mol or less.
  • Halogen compounds In the method for producing a carbonic acid diester of 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.
  • phosphine or phosphine oxide is used as the organic phosphorus compound, or when a phosphonium salt other than halide and hydrogen dihalide is used, or a low concentration of phosphonium halide or phosphonium hydrogen dihalide is used. In some cases, a halogen compound is preferably present.
  • halogen compound according to the present invention examples include the following inorganic halogen compounds and / or organic halogen compounds.
  • these halogen compounds a chlorine compound or a bromine compound is preferable, and a chlorine compound is particularly preferable among them.
  • the halogen compound has a molar ratio relative to the decarbonylation catalyst (halogen compound / decarbonylation catalyst) of 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, particularly preferably 1.00 or less.
  • 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.
  • 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.
  • 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 tribro
  • organic halogen compound examples 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.
  • Hal represents halogen atoms, such as a chlorine atom and a bromine atom.
  • Hal represents a halogen atom such as a chlorine atom or a bromine atom
  • n 1 represents an integer of 1 to 4
  • n 2 represents an integer of 1 to 3.
  • organic halogen compound examples 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.
  • halogen-substituted aliphatics such as ⁇ -chloropropionitrile and ⁇ -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, arylhaloglyoxylates such as phenyl chloroglyoxylate, and arylhalogenates 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.
  • organic halogen compounds include hydrogen halide adducts of onium salts containing nitrogen atoms or phosphorus atoms. Specific examples include ammonium salt hydrogen halide adducts and phosphonium salt hydrogen halide adducts.
  • hydrogen chloride and organic halogen compounds are preferable in terms of easy availability, and organic halogen compounds having a structure in which a halogen atom is bonded to the saturated carbon represented by the general formula (a) are more preferable.
  • Alkyl is particularly preferred and chloroform is most preferred.
  • the halogen of the halogen compound according to the present invention is the halogen of the hydrogen halide according to the present invention. And it is preferable that it is the same halogen as the halogen of the adduct body according to the present invention.
  • the adduct body according to the present invention is an adduct body of tetraarylphosphonium chloride and hydrogen chloride
  • the halogen compound according to the present invention is hydrogen chloride.
  • the adduct body according to the present invention is an adduct body of asymmetric tetraarylphosphonium chloride and hydrogen chloride
  • the halogen compound according to the present invention is most preferably hydrogen chloride.
  • 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 the reaction rate, but is preferably low in terms of the purity of the carbonic acid diester. 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 can be determined from process requirements. However, it is preferable to carry out the reaction under specific pressure conditions because impurities by-products hardly occur and high-purity carbonic acid diester is easily obtained. That is, it is preferable to carry out the decarbonylation reaction under conditions higher than normal pressure (absolute pressure 0.109 MPa).
  • the absolute pressure is preferably 0.105 MPa or more and 10 MPa or less. Further, it is more preferably 0.110 MPa or more, further preferably 0.130 MPa or more, particularly preferably 0.150 MPa or more, and on the other hand, preferably 8 MPa or less, preferably 5 MPa or less. It is particularly preferred that In the case where the decarbonylation reaction is carried out under reduced pressure, a vacuum pump is usually used to maintain the reduced pressure state, so that the absolute pressure is usually 0.990 MPa or less.
  • the pressure during the reaction is preferably controlled by adjusting the emission amount of carbon monoxide by-produced in the decarbonylation reaction. That is, it is preferable that at least a part of carbon monoxide by-produced in the decarbonylation reaction is discharged from the reactor, and the control of the absolute pressure during the decarbonylation reaction is adjusted by the amount of carbon monoxide discharged.
  • the discharge pressure of carbon monoxide is controlled by a pressure control valve or the like so as to be about 0.9 to 1.1 times the pressure during the decarbonylation reaction.
  • the discharged carbon monoxide is naturally gas-liquid separated from the reaction solution.
  • the discharged carbon monoxide as a raw material when producing an oxalic acid diester from nitrite and carbon monoxide.
  • the discharged carbon monoxide as a raw material when producing an oxalic acid diester from nitrite and carbon monoxide.
  • the oxalic acid diester produced using as a raw material is used as the raw material for producing the carbonic acid diester.
  • a gas inert to the decarbonylation reaction (hereinafter sometimes referred to as “inert gas according to the present invention” or simply “gas according to the present invention”) is emptied from the bottom of the reactor. it is preferably performed while supplying a linear velocity 0.00001M ⁇ s -1 or 0.01 m ⁇ s -1 or less.
  • an inert gas such as argon, nitrogen, carbon monoxide, or the like can be used.
  • carbon monoxide it is preferable to use carbon monoxide by-produced in the decarbonylation reaction according to the present invention.
  • carbon monoxide generated in the former reactor may be supplied to the latter reactor together with the reaction solution.
  • carbon monoxide obtained by gas-liquid separation of the reaction solution contains impurities such as phenol, carbon dioxide, hydrogen halide, etc.
  • impurities such as phenol, carbon dioxide, hydrogen halide, etc.
  • the decarbonylation reaction according to the present invention is an endothermic reaction, it is preferably carried out with stirring so that the inside of the reactor is heated quickly and uniformly. Therefore, in the decarbonylation reaction according to the present invention, by supplying an inert gas from the lower part of the reactor, the contact time between the gas and the reaction solution becomes longer, and the stirring is performed efficiently and at the time of the decarbonylation reaction. By-product phenol can be vaporized and removed.
  • the lower part of the reactor usually refers to a part below the central part in the height direction of the reaction liquid in the reactor. And it is preferable to supply the gas from the reactor lower part from the position near the center part of the reactor lower part.
  • reaction raw material it is preferable to supply the reaction raw material from a position close to the center of the lower part of the reactor. This is because the raw material oxalic acid diester locally increased in the vicinity of the reaction raw material supply port can be efficiently stirred by by-product carbon monoxide. Moreover, it is preferable to attach a check valve or the like to the gas supply port to the lower part of the reactor so that the liquid does not easily leak.
  • the amount of gas to be supplied is preferably large in that the reaction liquid is stirred and the phenol in the reaction liquid is easily vaporized.
  • hydrogen halide may be volatilized from the tetraarylphosphonium halide represented by the general formula (10), and the decarbonylation reaction is performed under reduced pressure. It has been found that the amount of volatilization increases and the conversion of diphenyl oxalate in the decarbonylation reaction decreases when the amount of halogen is small.
  • the amount of gas to be supplied is small in that it is difficult to vaporize it. Therefore, superficial linear velocity in the case of supplying a gas, it is preferable to supply at 0.00001M ⁇ s -1 or 0.01 m ⁇ s -1 or less.
  • the feed rate further preferably 0.0001 m ⁇ s -1 or more, and particularly preferably 0.005 m ⁇ s -1 or less.
  • gas circulation rate (3 to 30 times the volume of produced carbon monoxide and 280 NL / hr in Example 1) in Japanese Patent Application Laid-Open No. 11-246487 is calculated as follows. Since it is a 1-liter scale and is estimated to have an inner diameter of around 100 mm, it is estimated to be about 0.018 m ⁇ s ⁇ 1 .
  • the oxalic acid diester that is a reaction raw material is usually as shown in FIGS. 1 to 3 of Japanese Patent Laid-Open No. 10-158222. Supplied from the top of the reactor.
  • the decarbonylation reaction it is more efficient to supply an inert gas together with the reaction raw material from the lower part of the reactor. Further, the supplied gas and the produced carbonic acid diester are preferably extracted from the upper part of the reactor.
  • the gas bubble diameter is preferably small from the viewpoint of efficient stirring and vaporization of phenol, specifically 50 mm or less, more preferably 10 mm or less.
  • the bubble diameter can be controlled using a gas sparger or a mixer.
  • the hole diameter is preferably 10 mm or less, and more preferably 5 mm or less.
  • the decarbonylation reaction may be a batch reaction or a continuous reaction.
  • a continuous reaction is preferable, and since it is easy to achieve a high conversion rate, it is more preferable to carry out a continuous multistage reaction, and at least one of the reactions is as described above. It is particularly preferable to carry out the process while supplying an inert gas.
  • the general method of the continuous reaction the methods described in Japanese Patent Application Laid-Open No. 10-109962, Japanese Patent Application Laid-Open No. 10-109963, Japanese Patent Application Laid-Open No. 2006-89416, etc. may be used. it can.
  • 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.
  • 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 the carbonic acid diester can be generated by the decarbonylation reaction according to the present invention. Since aromatic monohydroxy compounds such as phenol may be generated by side reaction, acid-resistant metal containers and glass-lined containers are preferred. Any type of reactor can be used as long as the carbonic acid diester 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.
  • the conversion rate of the oxalic acid diester is high in terms of excellent reaction efficiency because impurities are hardly generated due to side reaction of the oxalic acid diester.
  • the conversion rate of the oxalic acid diester is preferably 96% by weight or more, more preferably 97% by weight or more, still more preferably 98% by weight or more, and particularly preferably 99% by weight or more.
  • the upper limit of the conversion rate of the oxalic acid diester may be appropriately selected in accordance with the solubility of the catalyst or the like in the carbonic acid diester so long as the clogging due to precipitation of the catalyst or the like does not occur, but 100% by weight is most preferable.
  • the conversion rate of the oxalic acid diester can be calculated as follows. First, the conversion rate of the oxalic acid diester is x [%], the amount of the reaction solution after the reaction is y [g], and the total charge of the oxalic acid diester, the carbonic acid diester and the catalyst is sum [g].
  • the amount [g] of carbon monoxide generated by the decarbonylation reaction is “amount of oxalic acid diester charged [mol]” ⁇ “x [%] / 100” ⁇ “molecular weight of carbon monoxide”.
  • the amount y [g] of the reaction solution after the reaction is “sum [g]“ ⁇ ”the amount of carbon monoxide produced [g]”.
  • y [g] (“sum [g]”) ⁇ (“amount of oxalic acid diester [mol]” ⁇ “x [%] / 100” ⁇ “molecular weight of carbon monoxide”).
  • the sum of both formulas is as follows.
  • the carbonic acid diester of the present invention is preferably a compound in which both R in the carbonic acid diester produced in the above reaction formula (1) is an aromatic ring group, and further a compound in which both R are aromatic hydrocarbon ring groups. Particularly preferred is diphenyl carbonate in which both R are phenyl groups.
  • the carbonic acid diester contained in the reaction solution after the reaction is removed by evaporation (hereinafter sometimes referred to as “evaporation according to the present invention” or simply “evaporation”). Is preferred.
  • evaporation according to the present invention or simply “evaporation”.
  • the carbonic acid diester is evaporated, if a high-boiling point substance is contained in the decarbonylation catalyst and the reaction solution after the reaction, these also remain in the reaction solution. Therefore, the carbonic acid diester can be separated from the decarbonylation catalyst and the high-boiling substance by evaporating and removing the carbonic acid diester from the reaction solution after the reaction.
  • the concentration rate (evaporation rate) of the carbonic acid diester is preferably high in terms of increasing the carbonic acid diester recovery rate and obtaining a high concentration catalyst solution.
  • a catalyst soluble in carbonic acid diester is used as the catalyst according to the present invention, it is difficult to deposit even if a large amount of carbonic acid diester is evaporated. Therefore, it is preferable to take out 50% by weight or more of the carbonic acid diester contained in the reaction solution by evaporation.
  • Distillation separation of diphenyl carbonate may be performed in a reactor in which decarbonylation reaction has been performed, 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.
  • the evaporation apparatus for example, it is preferable to use a falling film evaporator, a thin film evaporator or the like because it is easy to separate 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 viewpoint that impurities are not easily produced as a by-product.
  • the pressure is preferably evaporated under reduced pressure.
  • 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.
  • the temperature below the reaction temperature in the decarbonylation reaction 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.
  • the reaction solution after the decarbonylation reaction contains a carbonic acid diester, a decarbonylation catalyst, and an unreacted oxalic acid diester.
  • a decarbonylation catalyst for reacting carbonic acid diester with carbonic acid diester with carbonic acid diester and decarbonylation catalyst.
  • By-products include, for example, aromatic monohydroxy compounds such as phenol, phenyl 4-chlorobenzoic acid, carboxylic acid phenyl ester formed by Fries rearrangement of diphenyl oxalate, and decarbonylation reaction of the following reaction formula (11).
  • aromatic monohydroxy compounds such as phenol, phenyl 4-chlorobenzoic acid, carboxylic acid phenyl ester formed by Fries rearrangement of diphenyl oxalate, and decarbonylation reaction of the following reaction formula (11).
  • furan-based compounds such as benzofuran-2,3-dione.
  • aromatic monohydroxy compounds such as phenol, phenyl 4-chlorobenzoic acid and the like can be mentioned.
  • the halogen compound or its by-products may be contained.
  • by-product carboxylic acid phenyl ester include phenyl (p-phenyloxycarbonylphenyl) carbonate (PCPC) represented by the above formula (8).
  • the carbonic acid diester obtained by the carbonyl reaction is appropriately purified in order to obtain a purity and form suitable for the intended use.
  • carbon monoxide by-produced in the decarbonylation reaction is naturally gas-liquid separated from the reaction solution and discharged.
  • Carbon monoxide can also be reused as a raw material in the production of oxalic acid diester from nitrite and carbon monoxide. (For example, see the method described in Japanese Patent Laid-Open No. 10-152457, etc.).
  • carbon monoxide contains impurities such as phenol, carbon dioxide, and hydrogen halide
  • it is preferably used as a raw material for oxalic acid diester after passing through a purification apparatus such as an absorption tower or a scrubber.
  • the adduct body according to the present invention when used 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.
  • the amount of phenol contained in the reaction solution is considered to be small.
  • carboxylic acid phenyl ester reacts with phenol to become diphenyl carbonate or oxalate diphenyl.
  • Phenol reacts with tetraarylphosphonium chloride, which is a catalyst, to form tetraarylphosphonium phenolate, which is a fleece rearrangement catalyst, and is thus an inhibitor of the decarbonylation reaction according to the present invention.
  • a high-purity carbonic acid diester with a low phenol content is obtained by a simple method even when the reaction is carried out using diphenyl oxalate containing a carboxylic acid phenyl ester. be able to.
  • the reason is considered to be that the fleece rearrangement of the oxalic acid diester by the catalyst decomposed during the decarbonylation reaction is less likely to occur when the decarbonylation reaction is performed under a pressurized condition.
  • a tetraarylphosphonium halide represented by the general formula (10) is used as a catalyst, the tetraarylphosphonium halide represented by the general formula (10) is converted into a tetraarylphosphonium phenolate and a halogen compound.
  • PCPC phenyl (p-phenyloxycarbonylphenyl) carbonate
  • the halogen compound produced as a by-product with the tetraarylphosphonium phenolate is distilled from the reaction solution together with the carbon monoxide produced as a by-product in the decarbonylation reaction, thereby promoting the decomposition reaction of the catalyst. It is done.
  • the catalyst is a tetraarylphosphonium halide represented by the general formula (10), it is difficult to inhibit the decarbonylation reaction due to the formation of tetraarylphosphonium phenolate by the reaction with by-product phenol.
  • a carbonic acid diester can be obtained efficiently by a simple method.
  • a furan compound may be generated by heating during evaporation.
  • diphenyl oxalates may produce benzofuran-2,3-diones and phenols by the Fries rearrangement of the following reaction formula (12).
  • benzofuran-2,3-dione is an orange-colored compound and may cause coloring of the carbonic acid diester
  • the amount of benzofuran-2,3-dione in the carbonic acid diester is preferably small.
  • the method for producing a carbonic acid diester of the present invention when a decarbonylation reaction is carried out at a conversion rate of 96% or more using a catalyst soluble in the carbonic acid diester, the residual oxalic acid diester is small and it is caused by heating during evaporation. By-products of furan compounds can be suppressed.
  • the amount of the furan compound contained in the evaporated carbonic acid diester is affected by the conversion rate of the oxalic acid diester in the decarbonylation reaction, but is usually 1 ppm or less, preferably 0.1 ppm or less. Is possible.
  • R is the same as R in the reaction formula (1).
  • the carbonic acid diester when the carbonic acid diester is evaporated, is usually 70% by weight or more, preferably 80% by weight or more, more preferably in the evaporated fraction. It is 90% by weight or more, more preferably 97% by weight or more, and particularly preferably 98% by weight or more.
  • the upper limit is usually 100% by weight.
  • this fraction contains an oxalic acid diester, 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.
  • it is preferably 2% by weight or less, more preferably 1% by weight or less, and further preferably 0.5% by weight or less.
  • 0% by weight is most preferable.
  • the content is usually 1 part by weight or less, preferably 0.5 parts by weight or less, more preferably 0. 1 part by weight or less.
  • the content is usually 0.0001% by weight or less, preferably 0.00001% by weight or less, and more preferably 0.000001% by weight or less.
  • the phenyl (p-phenyloxycarbonylphenyl) carbonate (PCPC) contained in this fraction is usually 0.35% by weight or less, preferably 0.30% by weight or less, more preferably 0.10% by weight or less, Preferably it is 0.08 weight% or less, Most preferably, it is 0.05 weight% or less.
  • aromatic monohydroxy compounds such as phenol may be included, but the content in that case is usually 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0%. .3% by weight or less.
  • the content of a furan compound such as benzofuran-2,3-dione contained in this fraction is usually 10 wt ppb or more, preferably 100 wt ppb or more, more preferably 1000 wt ppb or more. In general, it is 2% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less.
  • the evaporated carbonic acid diester may be used as it is for the production of polycarbonate or the like, but may be further purified according to the required purity.
  • 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 stage, 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 evaporator such as a plate column or packed column having 5 to 50 theoretical plates.
  • an evaporator such as a plate column or packed column having 5 to 50 theoretical plates.
  • a decarbonylation reaction when a decarbonylation reaction is performed at a conversion rate of 96% or more using a catalyst soluble in the carbonic acid diester, by-product formation of a furan compound is suppressed.
  • the operation of removing the furan compound from the carbonic acid diester may not be provided depending on the required purity. That is, it becomes possible to obtain a carbonic acid diester having high purity, which is simple and efficient, as compared with the conventional method in which a post-process for removing the furan compound is essential.
  • Components having a higher boiling point than carbonic acid diester include raw materials for decarbonylation reaction such as oxalic acid diester and methylphenylphenyl oxalate, and high-boiling substances mixed in the raw material, decarbonylation reaction and evaporation of the reaction liquid. Examples include by-product phenyl p-chlorobenzoate, phenyl salicylate, polymers thereof, and organic halides (such as phenyl parachlorobenzoate) produced during the decarbonylation reaction.
  • a simple method of decomposing a furan compound contained in the carbonic acid diester by contacting the carbonic acid diester obtained by the decarbonylation reaction of the oxalic acid diester with a basic compound Therefore, it is preferable to produce a high-purity carbonic acid diester with a low content of a furan compound efficiently, stably and continuously.
  • Examples of basic compounds used for the removal of furan compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; lithium hydrogen carbonate, carbonic acid Alkali metal hydrogen carbonates such as sodium hydrogen, potassium hydrogen carbonate and cesium hydrogen carbonate; Alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; Alkali metal such as lithium acetate, sodium acetate, potassium acetate and cesium acetate Acetic acid salt; alkali metal salt of stearic acid such as lithium stearate, sodium stearate, potassium stearate, cesium stearate; hydrogenation such as lithium borohydride, sodium borohydride, potassium borohydride, cesium borohydride Boron Alkali metal salts; benzoates of alkali metals such as lithium benzoate, sodium benzoate, potassium benzoate, cesium benzoate; lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium
  • Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide and other alkaline earth metal hydroxides; calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, etc.
  • organic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributyl.
  • hydroxides such as phenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl triphenyl boron, and butyl triphenyl boron.
  • organic boron compound examples include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salt.
  • Organic ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium Hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyrate Triphenyl ammonium hydroxide and the like.
  • Examples of the pyridine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine and the like.
  • Examples of the imidazole compound include 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole and the like. Moreover, aminoquinoline etc. are mentioned.
  • alkali metal compounds and alkaline earth metal compounds are preferred because of their low volatility, and alkali metal compounds are more preferred.
  • the basic compound may be supplied in any manner in the method for producing a carbonic acid diester of the present invention as long as it can be brought into contact with impurities such as a furan compound contained in the carbonic acid diester. It is convenient and preferable to supply the basic compound to a tank for storing a carbonic acid diester obtained by decarbonylation reaction of an oxalic acid diester or a purification tower thereof.
  • the tank for storing the carbonic acid diester examples include a tank for storing a component obtained by removing the catalyst liquid from the reaction liquid obtained by the decarbonylation reaction of the oxalic acid diester.
  • the carbonic acid diester purification column examples include a distillation column for distillation as described in Japanese Patent Application Laid-Open No. 2002-322130.
  • the basic compound may be supplied in the state of only the basic compound or in the state of being dissolved in a solvent.
  • the solvent with high solubility with respect to diphenyl carbonate like phenol is preferable.
  • the amount of the basic compound supplied to the carbonic acid diester is preferably large from the viewpoint that decomposition of the furan compound is likely to occur, but is preferably small from the viewpoint that decomposition of the carbonic acid diester is difficult to occur. Therefore, it is usually 0.0000001 parts by weight or more, preferably 0.000001 parts by weight or more, more preferably 0.00001 parts by weight or more, and usually 1 part by weight or less with respect to 100 parts by weight of carbonic acid diester. The amount is preferably 0.1 parts by weight or less, more preferably 0.01 parts by weight or less.
  • the decomposition of the furan compound is more likely to occur at a higher temperature, but it is preferably performed at a low temperature from the viewpoint that the decomposition of the carbonic acid diester hardly occurs. Therefore, it is usually performed at 100 ° C. or higher, preferably 130 ° C. or higher, more preferably 150 ° C. or higher. On the other hand, the temperature is usually 300 ° C. or lower, preferably 280 ° C. or lower, more preferably 250 ° C. or lower.
  • the removal of the furan compound is usually performed on the component containing the carbonic acid diester obtained by removing the catalyst solution from the carbonic acid diester obtained by the decarbonylation reaction of the oxalic acid diester.
  • At least a part of the catalyst is taken out from the remaining liquid, supplied to the decarbonylation reaction, and reused. That is, by using at least a part of the catalyst contained in the residual liquid as a catalyst, it is preferable to supply the catalyst to the reactor in a state dissolved in the carbonic acid diester.
  • Recycling the catalyst is to supply the reactor with a liquid from which the compound having a higher boiling point than the carbonic acid diester is removed from the reaction liquid after the carbonic acid diester is evaporated, from the viewpoint of preventing the accumulation of high-boiling compounds in the reaction system. Is preferred.
  • Components removed by this step include high-boiling substances such as oxalic acid diesters such as diphenyl oxalate (boiling point 334 ° C. at 1 atm) and phenyl 4-hydroxybenzoate (boiling point higher than diphenyl oxalate at 1 atm). It is done.
  • the removal of the high boiling point compound can be performed by a known method such as distillation, extraction, or crystallization.
  • Phenyl (p-phenyloxycarbonylphenyl) carbonate has a boiling point of 340 ° C. at 1 atm, and is therefore included in the high boiling point compound.
  • the total amount of by-products of the decarbonylation reaction other than the carbonic acid diester and the carbonic acid diester contained in the residual liquid is 85 to 100 with respect to the total amount of components other than the catalyst. It is preferable that it is weight%.
  • the recovered catalyst When reusing the catalyst, only the recovered catalyst may be used, or an unused catalyst may be mixed with the recovered catalyst. Further, a solution obtained by adding carbonic acid diester to the remaining liquid may be supplied to the reactor. In addition, the catalyst may not be reused due to the removal of the high-boiling point compound and a part of the decomposition product generated by the decomposition of the catalyst and the catalyst. 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 catalyst amount is adjusted by supplying a catalyst having a molar amount equivalent to the total molar amount of the catalyst removed together with the high boiling point compound and the catalyst decomposition product together with the liquid excluding the high boiling point compound to the reactor for the decarbonylation reaction. It is preferable to carry out by.
  • the decomposition product generated by the decomposition of the catalyst refers to the decomposition product of the adduct body.
  • the molar amount of the same degree is preferably 0.7 mol or more with respect to 1 mol of the total amount of the catalyst and catalyst decomposition products such as tetraarylphosphonium halide removed together with the high boiling point compound, More preferably, it is more preferably 0.9 mol or more. On the other hand, it is preferably 2 mol or less, more preferably 1.4 mol or less, and 1.1 mol. It is particularly preferred that
  • the halogen compound When supplying the decarbonylation catalyst in the remaining liquid to the decarbonylation reaction, it is preferable to supply the halogen compound to the decarbonylation reaction together with the remaining liquid.
  • the amount of the halogen compound to be supplied is 0.01 to 100 mol% (equal mol) of the halogen compound present in the reactor with respect to the total amount of the decarbonylation catalyst (particularly the phosphonium salt catalyst) present in the reactor. It is preferable to become.
  • a high boiling point substance such as carboxylic acid phenyl ester by-produced in the decarbonylation reaction may be included in the catalyst solution. Further, when diphenyl oxalate containing carboxylic acid phenyl ester is used, it may be in a state of being contained in the catalyst solution.
  • the amount of carboxylic acid phenyl ester contained in the catalyst solution is taken into account, and the carboxylic acid phenyl ester contained in diphenyl oxalate is taken into account. It is preferable to adjust the amount so that the target amount is included.
  • [Preferred production method of carbonic acid diester] As the method for producing the carbonic acid diester of the present invention, a method comprising the following first to third steps in this order is particularly preferable.
  • 1st process The process of manufacturing a carbonic acid diester by the decarbonylation reaction which concerns on said this invention
  • Second step A step of separating the carbonic acid diester produced in the first step from the catalyst and / or a catalyst solution containing a decomposition product generated by decomposing the catalyst
  • Third step A step of supplying at least a part of the catalyst liquid separated in the second step to the reactor in the first step.
  • the first step is preferably a step of obtaining a fraction containing an inert gas from the reactor and supplying at least a part thereof to the reactor.
  • the fraction containing the inert gas can be easily obtained by, for example, extracting the gas from the upper part of the reactor.
  • the concentration of diphenyl oxalate in the reaction solution is low in that phenol entrainment vaporization by an inert gas is likely to occur. Therefore, specifically, the concentration of diphenyl oxalate in the reaction solution is preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
  • the concentration of phenol in the reaction solution is preferably low because inhibition of decarbonylation reaction is unlikely to occur.
  • the molar ratio to the catalyst is preferably 2 or less. More preferably, it is more preferably 0.5 or less.
  • the inert gas when at least a part of the fraction containing the inert gas is supplied to the reactor, the inert gas can be reused and the carbon monoxide generated by the decarbonylation reaction can be effectively used. it can.
  • the fraction containing an inert gas may be supplied to the reactor as it is, but it is preferable to supply a part thereof to the reactor.
  • the carbonic acid diester produced in the first step is separated from the catalyst liquid containing the catalyst and / or catalyst decomposition product. Separation in the second step can be performed by a known method such as distillation, extraction, or crystallization. Since the tetraarylphosphonium halide according to the present invention and the adduct according to the present invention usually have a high boiling point, when these compounds are used as a catalyst, the separation in the second step is simple by separating the carbonic diester by distillation. preferable.
  • a catalyst solution containing a catalyst and / or a decomposition product generated by decomposing the catalyst by evaporating and removing the carbonic acid diester contained in the reaction solution after the decarbonylation reaction It is preferable to obtain
  • reaction liquid after the decarbonylation reaction contains a high boiling point substance such as an oxalic acid diester or a fleece rearrangement compound of carbonic acid diester, these are also decomposed products generated by the decomposition of the catalyst and / or the catalyst. It will be in the state contained in the catalyst liquid which contains.
  • the carbonic acid diester separated in the second step is preferably contacted with a basic compound.
  • diphenyl carbonate may be further distilled or adsorbed before and / or after contacting with the basic compound.
  • 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.
  • the decarbonylation catalyst can be reused.
  • the distillation separation of the carbonic diester in the second step and the reuse of the catalyst in the third step are preferably carried out by the method and conditions described above.
  • Catalyst recovery method When using a tetraarylphosphonium halide (which may have a substituent) and / or an adduct of a tetraarylphosphonium halide (which may have a substituent) and a hydrogen halide as the decarbonylation catalyst, A high-purity catalyst can be easily and efficiently recovered from the reaction solution by the following method (hereinafter sometimes referred to as “the catalyst recovery method of the present invention”). Further, by reusing this recovered catalyst, a high-purity carbonic acid diester can be stably and continuously produced.
  • the catalyst used for the decarbonylation reaction is a residual liquid obtained by obtaining a component containing a carbonic diester from the reaction liquid after the decarbonylation reaction (hereinafter sometimes referred to as “catalyst liquid”). Recover from.
  • the catalyst recovery method of the present invention includes a step of bringing the residual liquid into contact with a polar organic solvent and a hydrogen halide.
  • the catalyst recovery method of the present invention is estimated to recover the decarbonylation catalyst contained in the catalyst solution as follows.
  • the catalyst solution contains the tetraarylphosphonium halide. Also, in the case where an adduct of tetraarylphosphonium halide and hydrogen halide is used as a catalyst for the decarbonylation reaction, the catalyst solution contains tetraarylphosphonium halide in which hydrogen halide is liberated from the adduct. It is thought that there is.
  • the symmetric tetraarylphosphonium halide becomes an adduct with the hydrogen halide by contact with the hydrogen halide.
  • the adduct body of this symmetrical tetraarylphosphonium halide and hydrogen halide usually has low solubility in a polar organic solvent.
  • the carbonic acid diester and impurities remaining in the catalyst solution are usually dissolved in the polar organic solvent, but the symmetric tetraarylphosphonium halide according to the present invention is precipitated. And a decarbonylation catalyst is recoverable by acquiring this deposit.
  • the asymmetric tetraarylphosphonium halide becomes an adduct with the hydrogen halide by contact with the hydrogen halide.
  • the asymmetric tetraarylphosphonium halide usually has low solubility in a polar organic solvent.
  • the adduct with the hydrogen halide usually has high solubility in polar organic solvents, but low solubility in water. Therefore, when the catalyst solution is brought into contact with a polar organic solvent, the carbonic acid diester and impurities remaining in the catalyst solution are normally dissolved in the polar organic solvent, but the asymmetric tetraarylphosphonium halide according to the present invention is a polar organic solvent. Since the solubility with respect to is low, it precipitates and this catalyst liquid becomes a slurry form.
  • the asymmetric tetraarylphosphonium halide contained in the catalyst solution comes into contact with hydrogen halide, it becomes an adduct with hydrogen halide and dissolves because of its increased solubility in polar organic solvents. And since the adduct body of asymmetric tetraarylphosphonium halide has low solubility with respect to water, it precipitates by contact with water, and usually this catalyst liquid becomes a slurry again.
  • the decarbonylation catalyst can be recovered by obtaining this precipitate. That is, when the decarbonylation catalyst is an adduct of an asymmetric tetraarylphosphonium halide and / or an asymmetric tetraarylphosphonium halide and a hydrogen halide, the catalyst contained in the residual liquid contacts a polar organic solvent and a hydrogen halide. Then, it can be recovered as a precipitate by contacting with water.
  • the catalyst recovery method of the present invention is used when an asymmetric tetraarylphosphonium halide and / or an adduct of an asymmetric tetraarylphosphonium halide and a hydrogen halide is used as a catalyst in the production of diphenyl carbonate by decarbonylation of diphenyl oxalate.
  • a highly pure catalyst can be efficiently recovered from the reaction solution by a simple method.
  • the residual organic solvent and hydrogen halide may be contacted simultaneously with the remaining liquid, or one of them may be contacted first and then the other may be contacted.
  • the polar organic solvent and hydrogen halide may be brought into contact with the residual liquid after contacting the residual liquid with the polar organic solvent and then with the hydrogen halide.
  • the polar organic solvent and hydrogen halide may be brought into contact with the remaining liquid after the polar organic solvent and hydrogen halide are brought into contact with each other, and then the remaining liquid may be brought into contact therewith.
  • the method for producing a carbonic acid diester of the present invention is preferably carried out by reusing the recovered precipitate as a catalyst for the decarbonylation reaction, and continuously using the recovered precipitate as a catalyst for the decarbonylation reaction. It is more preferable to react.
  • the polar organic solvent used in the catalyst recovery method of the present invention is highly compatible with a small amount of carbonic diester, by-product high-boiling substances and water contained in the catalyst solution, and an adduct of tetraarylphosphonium halide and hydrogen halide is used. Solvents that are easy to dissolve and that easily precipitate tetraarylphosphonium halide are preferred.
  • the polar organic solvent include ketones, ethers, halogenated carbons, and esters.
  • ketones examples 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.
  • lower alkyl ketones having 1 to 15 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.
  • 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 It is done.
  • 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.
  • esters examples include alkyl aliphatic carboxylic acid esters, alkyl carbonic acid diesters, alkyl oxalic acid diesters, and ethylene glycol fatty acid esters.
  • alkyl aliphatic carboxylic acid esters examples include lower alkyl formates such as methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, and isobutyl formate; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate Lower alkyl acetates such as n-butyl acetate and isobutyl acetate and lower alkyl propionates such as methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate and isobutyl propionate, etc.
  • lower alkyl formates such as methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, and isobutyl format
  • alkyl carbonate diester examples include lower alkyl carbonate diesters such as dimethyl carbonate, diethyl carbonate, butyl carbonate, and methyl ethyl carbonate.
  • alkyl oxalic acid diesters examples include lower alkyl oxalic acid diesters such as dimethyl oxalate and diethyl oxalate.
  • Ethylene glycol acetate includes ethyl acetate, propyl acetate, butyl acetate and the like.
  • Examples of the fatty acid ester of ethylene glycol include ethylene glycol acetate.
  • polar organic solvents having 3 to 15 carbon atoms in the polar organic solvent are preferred, and polar organic solvents having 3 to 10 are more preferred.
  • a polar organic solvent having an asymmetric structure such as methyl isopropyl ketone and methyl isobutyl ketone is preferable.
  • ketones are preferable and alkyl ketones are more preferable.
  • alkyl ketones are particularly preferable, alkyl ketones having a total carbon number of 3 to 10 are more preferable, and alkyl ketones having an asymmetric structure such as methyl isopropyl ketone and methyl isobutyl ketone are most preferable.
  • the amount (weight) of the polar organic solvent to be brought into contact with the catalyst solution is preferably large in that precipitation of carbonic acid diesters and by-product high-boiling substances and solidification of the remaining liquid are difficult to occur. And it is preferable that the energy required for the separation and recovery of the polar organic solvent is small.
  • it is preferably 0.5 times or more with respect to the catalyst solution, more preferably 1 time or more, and on the other hand, it is preferably 10 times or less, and preferably 5 times or less. It is more preferable that it is 3 times or less.
  • the solubility of the hydrogen chloride adduct of tetraarylphosphonium halide is reduced, and phenol produced as a by-product by reaction with diphenyl carbonate contained in the catalyst solution is converted to tetraarylphosphonium halide. Since it reacts easily with tetraarylphosphonium phenoxide, it is usually 2.0% by weight or less, preferably 1.0% by weight or less, more preferably 0.5% by weight or less, based on the weight of the polar organic solvent. Especially preferably, it is 0.2 weight% or less.
  • the hydrogen halide to be brought into contact with the catalyst solution is preferably the same hydrogen halide as the adduct hydrogen halide.
  • the decarbonylation catalyst is a tetraarylphosphonium halide, it is preferably a hydride of the same halogen atom as the halogen atom contained in the tetraarylphosphonium halide.
  • the decarbonylation catalyst according to the present invention includes tetraarylphosphonium chloride (which may have a substituent) and an adduct of tetraarylphosphonium chloride (which may have a substituent) and hydrogen chloride. Since it is preferable, the hydrogen halide used in the method of recovering this is preferably hydrogen chloride.
  • the hydrogen halide to be brought into contact with the catalyst liquid is a gas because the adduct body is still deposited by contact with the polar organic solvent.
  • it may be a liquid or an aqueous solution of hydrogen halide. That is, the hydrogen halide used here is preferably hydrogen chloride gas, liquid hydrogen chloride, or hydrochloric acid, and more preferably hydrogen chloride gas or hydrochloric acid because it is easy to handle.
  • the catalyst contained in the catalyst solution is an asymmetric tetraarylphosphonium halide
  • the use of an aqueous solution of hydrogen halide makes it difficult for the adduct to dissolve in the polar organic solvent.
  • a gas or liquid preferably a gas. That is, the hydrogen halide used here is preferably hydrogen chloride gas or liquid hydrogen chloride, and more preferably hydrogen chloride gas because it is easy to handle.
  • the hydrogen halide is used to convert the tetraarylphosphonium halide contained in the catalyst solution into a hydrogen halide adduct of tetraarylphosphonium halide. Therefore, the amount of hydrogen halide brought into contact with the catalyst solution is preferably 1 mol or more, more preferably 1.1 mol or more, relative to 1 mol of tetraarylphosphonium halide contained in the catalyst solution, On the other hand, it is preferably 5 mol or less, and more preferably 2 mol or less.
  • the catalyst solution When the catalyst solution is brought into contact with the polar organic solvent and then brought into contact with the hydrogen halide gas, since the catalyst solution is difficult to solidify, it is brought into contact with the hydrogen halide gas at the melting point of the carbonic acid diester or more and below the boiling point of the polar organic solvent. It is preferable.
  • the temperature of the hydrogen halide gas to be contacted and the temperature of the polar organic solvent containing hydrogen halide when contacting with the polar organic solvent containing hydrogen chloride are preferably low. Specifically, it is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and particularly preferably 30 ° C. or lower. This is because when a carbonic acid diester or a by-product high-boiling substance comes into contact with hydrogen chloride, it may be hydrolyzed by water or the like contained in a polar organic solvent to produce phenol.
  • a high-purity carbonic acid diester can be stably and continuously produced by reusing the above-mentioned recovered catalyst for a decarbonylation reaction.
  • the purity of the carbonic acid diester obtained by the continuous reaction using the recovered catalyst is usually 99.0% by weight or more, preferably 99.3% by weight or more, and more preferably 99.5% by weight or more.
  • impurities ionic chlorine or the like may be included.
  • the content is usually 1 ppm by weight or less, preferably 0.1 ppm by weight or less, more preferably 0.01 ppm by weight. It is as follows.
  • the decarbonylation catalyst is an adduct of an asymmetric tetraarylphosphonium halide or an asymmetric tetraarylphosphonium halide and a hydrogen halide
  • contact is made to precipitate the adduct of the asymmetric tetraarylphosphonium halide and the hydrogen halide.
  • the amount of water is preferably large in that the hydrogen halide adduct of an asymmetric tetraarylphosphonium halide is precipitated and the recovery rate tends to be high.
  • carbonic acid diesters and by-product high-boiling substances are difficult to precipitate. In terms of easy recovery of a high-purity catalyst, a small amount is preferable.
  • the amount of water (weight ratio) with respect to the amount of the polar organic solvent is preferably 0.001 times or more, more preferably 0.01 times or more, and more preferably 0.02 times or more. On the other hand, it is preferably 0.5 times or less, more preferably 0.2 times or less, and particularly preferably 0.1 times or less.
  • the temperature of the water to be contacted is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and particularly preferably 30 ° C. or lower.
  • the contact with water is preferably performed slowly over time in that the recovered catalyst tends to be highly pure. That is, it is preferable to divide water or make small amounts contact rather than contacting the whole amount of water at once.
  • the third step in the above-described method for producing a carbonic acid diester of the present invention includes the following 3A step and It is preferable to have 3B process in this order, and it is still more preferable to perform the manufacturing method of the carbonic acid diester of this invention as a continuous reaction.
  • Step 3A a step of bringing a polar organic solvent and hydrogen halide into contact with at least a part of the catalyst solution separated in the second step, and then bringing a precipitate into contact with water;
  • Step 3B A step of supplying at least a part of the precipitate obtained in the third step to the first step as a catalyst for the decarbonylation reaction.
  • step 3A a polar organic solvent and hydrogen halide are brought into contact with at least a part of the catalyst liquid separated in step 2, and then a precipitate is obtained by bringing water into contact therewith.
  • Step 3A it is presumed that the precipitate is obtained by bringing the catalyst solution into contact with a polar organic solvent and hydrogen halide, and then bringing water into contact with the catalyst solution, due to the occurrence of the above phenomenon. Is done.
  • step 3B at least part of the precipitate obtained in step 3A is supplied to the first step as a catalyst for decarbonylation reaction.
  • the slurry obtained in step 3A can be reused as a catalyst by drying the solid obtained by solid-liquid separation and supplying it to the reactor for decarbonylation reaction.
  • the slurry obtained in the step 3A is preferably supplied to the first step after removing components having a higher boiling point than the carbonic acid diester.
  • Examples of the components removed here include by-product high-boiling substances such as phenyl p-hydroxybenzoate and phenyl (o-phenoxycarbonylphenyl) carbonate (PCPC).
  • Solid-liquid separation can be performed by pressure filtration or the like.
  • the polar organic solvent and water can be removed by drying the obtained solid at about 80 to 220 ° C. and 0.1 to 50 kPa for about 1 to 10 hours.
  • the first step, the second step, the third step A, and the third step B are sequentially performed in this order, whereby an asymmetric tetraarylphosphonium halide or a hydrogen halide thereof is used as a decarbonylation catalyst.
  • an asymmetric tetraarylphosphonium halide or a hydrogen halide thereof is used as a decarbonylation catalyst.
  • the catalyst recovery process is performed from the total amount of the catalyst liquid obtained in the second process in the above-mentioned 3A process, a part of the catalyst is also removed along with the process such as the removal of by-product high-boiling substances. May end up. Therefore, when performing the continuous reaction, as described above, the asymmetric tetraarylphosphonium halide and / or the asymmetric tetraarylphosphonium are used together with the recovered catalyst so that the total amount of the asymmetric tetraarylphosphonium halide is in the above-described preferable range in the reactor. It is preferable to adjust the amount of catalyst by supplying an adduct of halide and hydrogen halide.
  • the catalyst recovery method of the present invention preferably includes a step of recovering the polar organic solvent used for catalyst recovery and reusing it in the catalyst recovery step. That is, when the decarbonylation catalyst is a tetraarylphosphonium halide and / or an adduct of a tetraarylphosphonium halide and a hydrogen halide, the catalyst contained in the residual liquid obtained from the reaction liquid containing a component containing a carbonic acid diester is converted into a polar organic compound. While recovering using a solvent, the polar organic solvent used for catalyst recovery can also be recovered and reused for catalyst recovery.
  • the third step in the method for producing a carbonic acid diester of the present invention includes a step of bringing a polar organic solvent and a hydrogen halide into contact with at least a part of the catalyst liquid obtained in the second step, When precipitating the catalyst contained in the catalyst solution, it is preferable to collect and reuse the polar organic solvent used for catalyst recovery.
  • the catalyst is precipitated due to the above phenomenon. Also, the type and amount (weight) of the polar organic solvent to be contacted with the catalyst solution, the amount of hydrogen chloride, the temperature of the hydrogen chloride to be contacted or the temperature of the polar organic solvent containing hydrogen chloride, and the amount and temperature in the case of contacting water Is as described above for the catalyst recovery method.
  • the decarbonylation catalyst is a tetraarylphosphonium halide and / or an adduct, and the polar organic solvent used for the recovery of the catalyst is reused
  • the hydrogen chloride to be contacted with the residual liquid may be supplied as hydrochloric acid. Good.
  • the following steps (A) and (B) are preferably performed in this order to recover the polar organic solvent used for catalyst recovery and reused in the catalyst recovery step.
  • Step The polar organic solvent used for the catalyst recovery is evaporated and distilled into a liquid-liquid separator containing water, and the polar organic solvent phase of the liquid-liquid separator is moved to the residual liquid side. Removing at least part of the hydrogen chloride contained in the residual liquid by returning, (B) Process: The process of distilling the liquid obtained at the (A) process.
  • the residual liquid obtained by collecting the catalyst as a precipitate as described above is evaporated and distilled into a liquid-liquid separator.
  • a polar organic solvent phase upper phase
  • a water phase lower phase
  • Hydrogen chloride is more easily dissolved in the water phase than in the polar organic solvent phase. Therefore, the hydrogen chloride contained in the polar organic solvent can be removed by returning the phase of the polar organic solvent to the residual liquid side.
  • the distillation apparatus (evaporation method) used in the step (A) is not particularly limited as long as the above object can be achieved.
  • the evaporator for example, a falling film evaporator, a thin film evaporator and the like are preferable because they can be easily separated in a short time.
  • the time required to remove hydrogen chloride contained in the polar organic solvent is also affected by heat transfer efficiency and the shape of the separation vessel, but it is preferable to carry out in a short time from the point that impurities by-product hardly occurs, It is preferably 20 hours or shorter, more preferably 15 hours or shorter, and particularly preferably 10 hours or shorter.
  • Evaporation is preferably performed at a low temperature and low pressure from the viewpoint that impurities are not easily produced as a by-product.
  • the pressure is preferably evaporated at normal pressure or reduced pressure, and the temperature is preferably a temperature at which hydrogen chloride is distilled off.
  • the pressure is preferably 1 kPaA or more, and more preferably 2 kPaA or more. On the other hand, 100 kPaA or less is preferable, and 80 kPaA or less is more preferable.
  • the temperature is usually 50 ° C. or higher, preferably 60 ° C. or higher, particularly preferably 70 ° C. or higher. On the other hand, it is usually 200 ° C. or lower, preferably 190 ° C. or lower, particularly preferably 180 ° C. or lower.
  • the amount and temperature of water put into the liquid-liquid separator are not particularly limited as long as the distilled polar organic solvent and hydrogen chloride are subjected to liquid-liquid separation.
  • the amount of water present in the liquid-liquid separator is preferably 1% by weight or more, more preferably 2% by weight or more of the residual liquid obtained by collecting the catalyst as a precipitate, but on the other hand, 50% by weight. It is preferable that the amount be 30% by weight or less.
  • the temperature of the liquid-liquid separator is preferably 60 ° C. or lower because it is easy to perform liquid-liquid separation, and more preferably 50 ° C. or lower. On the other hand, since the aqueous phase is difficult to solidify, The temperature is preferably 0 ° C or higher, more preferably 5 ° C or higher.
  • the polar organic solvent is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% in the phase of the polar organic solvent returned to the residual liquid side. Containing more than% by weight. The upper limit is usually 100% by weight. Further, hydrogen chloride contained in the phase of the polar organic solvent returned to the residual liquid side is usually 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.3% by weight or less.
  • step (B) the liquid obtained in step (A) is distilled. Distillation can remove water from the polar organic solvent.
  • the distillation apparatus (evaporation method) used in the step (A) can be carried out in the same manner as in the step (A).
  • the distillation conditions are not particularly limited as long as the polar organic solvent and water can be separated.
  • the distillation temperature is preferably high in terms of easy separation of the polar organic solvent and water, but in terms of difficulty in mixing high-boiling compounds such as phenol by-produced by the decarbonylation reaction into the polar organic solvent. It is preferable that the temperature is low.
  • the catalyst recovery method of the present invention efficiently recovers and reuses a high-purity catalyst by a simple method, and efficiently recovers the polar organic solvent used for catalyst recovery. New polar organic solvents can be reused. By reusing the catalyst recovered by the catalyst recovery method of the present invention, it is possible to efficiently produce high-purity diphenyl carbonate stably.
  • Polycarbonate which is one of the uses of the carbonic acid diester produced in the present invention, is obtained by converting a carbonic acid diester produced by the above-described method, particularly a diaryl carbonate, and an aromatic or aliphatic dihydroxy compound typified by bisphenol A into an alkali metal. It can be produced by transesterification in the presence of a compound and / or an alkaline earth metal compound.
  • the transesterification reaction can be performed by appropriately selecting a known method.
  • the dihydroxy compound to be transesterified with the carbonic acid diester may be an aromatic dihydroxy compound or an aliphatic dihydroxy compound, but an aromatic dihydroxy compound is preferred.
  • An example using diphenyl carbonate and bisphenol A as raw materials will be described below.
  • 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.
  • bisphenol A and diphenyl carbonate can be supplied in solid form, but it is preferable that one or both of them be melted and supplied in a liquid state.
  • a catalyst is usually used.
  • 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 ⁇ mol or more, preferably 0.08 ⁇ mol or more, more preferably 0.10 ⁇ mol or more, and usually 5 ⁇ mol or less, preferably 4 ⁇ mol, 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 ⁇ mol.
  • 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.
  • a cesium compound is preferable.
  • Preferred cesium compounds are cesium carbonate, cesium bicarbonate, and cesium hydroxide.
  • both raw materials supplied to the raw material mixing tank are uniformly stirred and then supplied to a polymerization tank to which a catalyst is added to produce a polymer.
  • the carbonic acid diester obtained by the production method of the present invention has a very high purity
  • the carbonic acid diester obtained by the production method of the present invention and an aliphatic dihydroxy compound or an aromatic dihydroxy compound are converted into a transesterification catalyst.
  • a high-purity polycarbonate can be obtained by polycondensation in the presence.
  • the carbonic acid diester production method of the present invention can provide a high-purity carbonic acid diester with less by-product phenol, it can be used to obtain a high-quality polycarbonate. Further, in the method for producing a carbonic acid diester of the present invention, when a decarbonylation reaction is performed at a conversion rate of 96% or more using a catalyst soluble in the carbonic acid diester, by-product formation of a furan compound can be suppressed, so that coloring is small A high-quality polycarbonate can be obtained.
  • Tetraarylphosphonium halides are prepared 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, for example, Japanese Patent Application Laid-Open No. 9-328492. Can be obtained.
  • JP-A-2013-82695 discloses an asymmetric tetraarylphosphonium halide by dividing or continuously adding a triarylphosphine to a liquid containing an aryl halide, a metal halide compound catalyst, and a water-soluble high-boiling solvent. 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.
  • the asymmetric tetraphenylphosphonium halide obtained as described above was used as a catalyst as an adduct with hydrogen halide (asymmetric adduct according to the present invention) as a catalyst, the amount of byproduct phenol was reduced. It turns out that it can be reduced.
  • the adduct body has low hygroscopicity, and it is considered that phenol by-product is hardly generated by 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. Further, when an asymmetric tetraarylphosphonium halide having a high hygroscopic property is used as a catalyst, it is considered that phenol is generated by hydrolysis of a carbonic acid diester or an oxalic acid diester due to moisture supplied to the reaction system together with the catalyst.
  • the adduct body according to the present invention since the adduct body according to the present invention has a relatively large particle size, it is considered that the hygroscopic property is low and phenol by-product is hardly generated by hydrolysis of carbonic acid diester or oxalic acid diester.
  • the asymmetric adduct body according to the present invention has a large particle diameter and low hygroscopicity, so that it is difficult to scatter and is easily solid. For this reason, when this is used as a catalyst for decarbonylation reaction, the catalyst can be put into the reactor in a short time before being absorbed, and phenol by-product is reduced, with high conversion from oxalic acid diester, Diphenyl carbonate with high selectivity and high purity can be easily obtained.
  • the particle diameter of the asymmetric adduct according to the present invention is preferably 50 ⁇ m or more, more preferably 60 ⁇ m or more, further preferably 80 ⁇ m or more, and particularly preferably 100 ⁇ m or more. preferable.
  • the upper limit of the particle size of the asymmetric adduct body according to the present invention is usually 1 mm.
  • the particle size of the asymmetric 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. .
  • the hygroscopicity of the asymmetric adduct body according to the present invention is compared with the time required for moisture absorption from a predetermined moisture content to a predetermined moisture content in an air atmosphere at a temperature of 15 to 20 ° C. and a humidity of 40 to 45%. Can be evaluated.
  • the water content can be measured by measuring tetraarylphosphonium halide using a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.).
  • the solubility of the asymmetric adduct according to the present invention is usually soluble in carbonic acid diester. Since the asymmetric adduct according to the present invention is soluble in the carbonic acid diester, in the method for producing the carbonic acid diester of the present invention, the decarbonylation reaction is stably performed at a high conversion rate without causing catalyst precipitation, and It becomes possible to reduce the amount of the acid diester, and to suppress the production of a furan compound produced as a by-product when the carbonic acid diester is evaporated.
  • the asymmetric adduct according to the present invention is soluble in carbonic acid diester, even if diphenyl oxalate is reacted with carbonic acid diester at a high conversion rate, the carbonic acid diester is concentrated to a high concentration, and the catalyst remains in the residual liquid. Therefore, the catalyst contained in the residual liquid can be easily reused.
  • the asymmetric adduct according to the present invention is soluble in the carbonic acid diester, the catalyst can be supplied in a state dissolved in the carbonic acid diester, and the amount of unreacted oxalic acid diester after the reaction is small and the carbonic acid diester is increased.
  • the catalyst solution contained at a concentration By reusing the catalyst solution contained at a concentration, by-products such as phenol are hardly caused by the fleece rearrangement product of the oxalic acid diester, and a highly pure carbonic acid diester can be obtained.
  • the asymmetric 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.
  • elemental analysis mass spectrometry
  • nuclear magnetic resonance spectroscopy nuclear magnetic resonance spectroscopy
  • liquid chromatography Specifically, for example, in the case of 4-t-butylphenyltriphenylphosphonium chloride, 4-t-butylphenyltriphenylphosphonium chloride is analyzed by elemental analysis, mass spectrometry, and nuclear magnetic resonance spectrum. I can confirm that.
  • 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.
  • ODS3VID manufactured by Shimadzu Corporation was used.
  • Liquid A: Liquid B 65: 35 (volume ratio, the same applies hereinafter).
  • 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.
  • 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.
  • 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.
  • an asymmetric tetraarylphosphonium halide can be dissolved by using an organic solvent, and a hydrogen halide can be dissolved by using a polar solvent.
  • the adduct body production method according to the present invention can be obtained by crystallizing an adduct body using the difference in solubility between the asymmetric tetraarylphosphonium halide and the hydrogen halide adduct body of the asymmetric tetraarylphosphonium halide.
  • a solid that is difficult to scatter and easy to handle can be obtained because of its large particle size and low hygroscopicity.
  • Polar organic solvent used in the method for producing an adduct body according to the present invention Is preferably an organic solvent that has sufficient solubility in asymmetric tetraarylphosphonium halides and hydrogen halides and is insoluble in adducts.
  • 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 in hydrogen halide” means that 1 g or more of hydrogen halide is dissolved in 100 g of an organic solvent at 25 ° C.
  • 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.
  • Preferred examples of the polar organic solvent used in the production of the adduct body include alcohols, ketones, ethers, halogenated hydrocarbons, esters and the like.
  • alcohols examples 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.
  • ketones examples 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.
  • 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.
  • 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.
  • 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.
  • esters examples 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.
  • alkyl carbonate diesters such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and dibutyl carbonate
  • oxalic acid diesters such as dimethyl oxalate and diethyl oxalate
  • acetates such as ethyl acetate, propyl acetate, but
  • an alkyl ketone having an asymmetric structure such as methyl isopropyl ketone and methyl isobutyl ketone and having 3 to 15 total carbon atoms in the alkyl group is used.
  • Alkyl ketones in which the total number of carbon atoms in the alkyl group is 3 to 10 are more preferable.
  • the hydrogen halide to be an adduct body with the 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.
  • hydrochloric acid aqueous hydrogen chloride
  • hydrobromic acid aqueous hydrogen bromide
  • hydrochloric acid is particularly preferred as the aqueous solution of hydrogen halide.
  • an asymmetric tetraarylphosphonium halide is contacted with a polar organic solvent and hydrohalic acid.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a polar organic solvent that easily azeotropes with water such as methyl isobutyl ketone
  • the temperature at which the adduct body is precipitated is preferably a high temperature in that the solution itself is unlikely 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.
  • 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 lowering 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 Japanese Patent Application Laid-Open No. 9-328491.
  • this document is a document describing a method for producing an organic phosphonium chloride from an organic phosphonium bromide.
  • 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.
  • 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
  • benzyltriphenylphosphonium hydrogen dichloride and benzyltriphenylphosphonium chloride (a mixture containing an adduct of asymmetric organic phosphonium and hydrogen chloride) Example 9) is synthesized.
  • 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.
  • adduct body based on this invention cannot be obtained by the method described in this literature.
  • Diphenyl oxalate used was a purified first grade reagent manufactured by Tokyo Chemical Industry Co., Ltd. by simple distillation. The purity of diphenyl oxalate obtained by this distillation is 99% by weight or more, 50 ppm by weight of water, 200 ppm by weight of phenol, 10 ppm by weight of methyl phenyl oxalate, phenyl (o-phenoxycarbonylphenyl) oxalate (OCPO) It was below the lower limit of detection (1 ppm by weight).
  • 4-t-butylphenyltriphenylphosphonium chloride was synthesized by the method described in Japanese Patent Application Laid-Open No. 11-217393. This 66.67 g of 4-t-butylphenyltriphenylphosphonium chloride was dissolved in 100 g of diphenyl carbonate at 150 ° C.
  • the water concentration in methyl isobutyl ketone was analyzed by a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 500 ppm by weight.
  • Tetraphenylphosphonium chloride was a product of Tokyo Chemical Industry Co., Ltd. Diphenyl carbonate and phenol used products of Mitsubishi Chemical Corporation. Moreover, the product of Alfa Aesar was used for sodium phenoxide. Isatin used a product of Tokyo Chemical Industry Co., Ltd. The hydrogen chloride gas used was a product of Sumitomo Seika Co., Ltd.
  • 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.
  • ODS3VID manufactured by Shimadzu Corporation was used.
  • Liquid A: Liquid B 65: 35 (volume ratio, the same applies hereinafter).
  • Methyl isobutyl ketone was quantified by gas chromatography under the following procedure and conditions.
  • GC-2014 manufactured by Shimadzu Corporation was used.
  • column “DB-17” (inner diameter 0.53 mm, column length 60 m, film thickness 1 ⁇ m) manufactured by Agilent Technologies was used.
  • the carrier gas was helium, the flow rate was 7.34 cm 3 / min, and the linear velocity was 50.7 cm / sec.
  • the inlet temperature was 220 ° C and the detector temperature was 260 ° C.
  • the temperature rising pattern of the column was first held at 75 ° C. for 3 minutes, then heated to 10 ° C./minute to 220 ° C., held at 220 ° C. for 10 minutes, and then heated to 40 ° C./minute to 250 ° C. And held for 10 minutes for analysis.
  • 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 potentiometric titration using silver nitrate (“AT- 610 ”) and calculated from the chlorine concentration.
  • the water content was measured using a moisture meter (“MKS-500” manufactured by Kyoto Denshi Kogyo Co., Ltd.) with tetraarylphosphonium halide placed on a petri dish.
  • MKS-500 manufactured by Kyoto Denshi Kogyo Co., Ltd.
  • 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.
  • the hygroscopicity test was performed by comparing the time required to absorb moisture from a predetermined moisture content to a predetermined moisture content in an air atmosphere at a temperature of 15 to 20 ° C. and a humidity of 40 to 45%.
  • the particle diameter was the median diameter (D50) measured using a microtrack particle size distribution measuring device “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.
  • ION CHROMATOGRAPH 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.
  • 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.
  • the separable flask was cooled to room temperature, the 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.
  • a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd. it was 17% by weight.
  • 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.
  • the obtained solid was an adduct of tetraphenylphosphonium chloride and hydrogen chloride having an adduct ratio 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-tert-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.
  • the 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.
  • 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).
  • Tetraphenylphosphonium chloride, its adduct obtained in Synthesis Example 1, 4-t-butylphenyltriphenylphosphonium chloride and its adduct obtained in Example 1 were analyzed for properties, bulk density, particle size, and drying. 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
  • 4-t-butylphenyltriphenylphosphonium chloride is made to be an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride, so that it is easy to handle and easy to dry. It was revealed that the hygroscopicity can be lowered.
  • 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.
  • the chlorine concentration of the fine powder was analyzed by a potentiometric titrator “AT-610” manufactured by Kyoto Electronics Industry Co., Ltd. As a result, it was 8.0% by weight.
  • decarbonylation reaction of diphenyl oxalate was carried out using the fine powder as a catalyst.
  • 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.
  • Example 2 Except that 50 g (0.105 mol) of 4-t-butylphenyltriphenylphosphonium bromide, 13 g of methyl isobutyl ketone and 188 g of 28% by weight hydrochloric acid were placed in a full-jacketed 500 ml separable flask equipped with a thermometer and a stirrer. A slurry was obtained in the same manner as in Example 1. 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. .
  • 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.
  • 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. .
  • Example 5 An adduct body of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride obtained in Example 1 was added to a full-jacketed 500 ml separable flask equipped with a thermometer, a stirrer, a distillation tube and a receiver ( 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., dried at 3 kPa under a pressure of 2 kPa, thereby distilling 20 g of water and diphenyl carbonate in total to dry the inside of the separable flask.
  • 160 g (0.661 mol) of diphenyl oxalate was added and heated to 150 ° C. to dissolve the diphenyl oxalate.
  • the reaction was carried out while maintaining the temperature at 225 ° C. for 80 minutes while removing carbon monoxide generated by the reaction from the reaction system with nitrogen under 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%. *
  • Example 5 In Example 5, 10 g (0.024 mol) of 4-t-butylphenyltriphenylphosphonium chloride was used instead of 11 g of the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride obtained in Example 1. The experiment was performed in the same manner as in Example 5 except that.
  • 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. .
  • composition analysis results of the liquid reacted for 80 minutes by high performance liquid chromatography were 0.4% by weight of phenol, 22.2% by weight of diphenyl oxalate, and 72.4% by weight of diphenyl carbonate.
  • the conversion rate of diphenyl oxalate was 68%.
  • 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-product due to hydrolysis of diphenyl oxalate and diphenyl carbonate increases, and as a result, the conversion rate of diphenyl oxalate increases. It was confirmed that the reaction activity was low.
  • 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 an adduct (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.
  • the reaction was carried out for 6 hours while maintaining at 230 ° C. while removing carbon monoxide generated by the reaction from the reaction system with nitrogen under normal 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%.
  • 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%.
  • 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.
  • 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, dissolved in diphenyl carbonate.
  • the reaction was carried out for 6 hours while maintaining at 230 ° C. while removing carbon monoxide generated by the reaction from the reaction system with nitrogen under normal 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%.
  • the concentration of benzofuran-2,3-dione in the crude diphenyl carbonate was measured by high performance liquid chromatography and found to be 10 ppm by weight.
  • 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.
  • the conversion rate of diphenyl oxalate was 70.2%.
  • 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.
  • the conversion rate of diphenyl oxalate was 72.5%.
  • Table 4 summarizes the results of Example 6, Comparative Example 3, and Comparative Example 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.
  • 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-tert-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.
  • 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.
  • 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.
  • the conversion rate of diphenyl oxalate was 61%.
  • Example 10 In a test tube equipped with a stirrer and a thermometer, 100.0 g of the crude diphenyl carbonate obtained in Example 6 (containing 11 wt ppm of benzofuran-2,3-dione) was added, and the oil bath was used to It heated so that the internal temperature of a test tube might be 100 degreeC.
  • test tube Internal temperature of the test tube is heated further so as to be 230 ° C., it was added 1 mol ⁇ dm aqueous sodium hydroxide solution 1 cm 3 of 3 (1 mmol of sodium hydroxide), was maintained as it 120 min 230 ° C.
  • concentration of the benzofuran-2,3-dione was measured by high performance liquid chromatography. As a result, it was 100 weight ppb.
  • This potassium acetate aqueous solution was placed in a dropping funnel and added dropwise to the previously prepared acetone solution of diphenyl oxalate over 4 hours with stirring. After completion of dropping, the mixture was further stirred for 2 hours to obtain a slurry. The solid content obtained by filtering the slurry under reduced pressure was washed with acetone to obtain a white solid content. This white solid was dried under reduced pressure to obtain 20.1 g (0.10 mol) of phenyl potassium oxalate.
  • the potassium phenyl oxalate was placed in a 100 cm 3 eggplant type flask and kept at 20 ° C. using a water bath. 17.5 g (0.15 mol) of thionyl chloride was placed in a dropping funnel and added dropwise to phenyl potassium oxalate in an eggplant type flask over 30 minutes.
  • the eggplant-shaped flask was equipped with a reflux tube, heated to 90 ° C., and reacted for 1 hour. After completion of the reaction, the reflux tube of the eggplant type flask was replaced with a distillation tube, and unreacted thionyl chloride was distilled off. After distilling off thionyl chloride, 15.5 g (0.08 mol) of phenyl chlorooxalate was obtained by reducing the pressure.
  • This phenyl chlorooxalate was put into a 500 cm 3 eggplant type flask together with 100 cm 3 of tetrahydrofuran. To this, 6.6 g (0.08 mol) of pyridine was dropped over 10 minutes to obtain a slurry.
  • the hydrolyzed two-phase separated liquid was transferred to a separatory funnel to separate water.
  • the obtained organic phase was neutralized by adding 100 cm 3 of a saturated aqueous sodium hydrogen carbonate solution and mixing well to obtain a two-phase separated solution, and then the aqueous phase was separated.
  • the resulting organic phase was further dehydrated by adding 100 cm 3 of a saturated aqueous sodium chloride solution, and then the aqueous phase was separated.
  • the obtained organic phase was transferred to a 500 cm 3 Erlenmeyer flask, and 30 g of magnesium sulfate was added for further dehydration.
  • the organic phase was filtered to remove magnesium sulfate, and then the organic phase was transferred to a 500 cm 3 eggplant type flask, and tetrahydrofuran was distilled off using an evaporator under reduced pressure. Hexane was gradually added to the liquid obtained by distilling tetrahydrofuran, and when crystals were precipitated, the addition of hexane was stopped and the mixture was allowed to cool.
  • Example 11 In a fully jacketed 500 cm 3 separable flask equipped with a thermometer, stirrer, distillation tube and receiver, 89 g (0.367 mol) of diphenyl oxalate, 4-t-butylphenyl produced in Example 25 described later After adding 10 g (0.021 mol) of an adduct of triphenylphosphonium chloride and hydrogen chloride and 1 g (0.003 mol) of phenyl (o-phenoxycarbonylphenyl) oxalate (OCPO), the temperature inside the separable flask was raised. did.
  • the carbon monoxide generated by the reaction was removed from the reaction system, and the decarbonylation reaction was performed while maintaining the temperature at 230 ° C. for 60 minutes. A part of the liquid reacted for 60 minutes was extracted and subjected to composition analysis by high performance liquid chromatography. As a result, it was 1.33% by weight of phenol, 20.36% by weight of diphenyl oxalate, and 64.92% by weight of diphenyl carbonate. .
  • Example 12 In Example 11, except that diphenyl oxalate was changed from 89 g to 85 g (0.351 mol) and phenyl (o-phenoxycarbonylphenyl) oxalate (OCPO) was changed from 1 g to 5 g (0.014 mol).
  • the decarbonylation reaction was carried out in the same manner as in Example 11, and the solution after the reaction for 60 minutes was analyzed. As a result, it was 1.19% by weight of phenol, 12.89% by weight of diphenyl oxalate, and 68.47% by weight of diphenyl carbonate.
  • Example 13 In Example 11, the amount of diphenyl oxalate was increased from 89 g to 90 g (0.372 mol), and phenyl (o-phenoxycarbonylphenyl) oxalate (OCPO) was not used. A carbonyl reaction was performed, and the liquid after the reaction for 60 minutes was analyzed. As a result, they were 1.40% by weight of phenol, 21.98% by weight of diphenyl oxalate, and 64.40% by weight of diphenyl carbonate.
  • OCPO o-phenoxycarbonylphenyl
  • Example 14 To a glass test tube for a sealed tube having a thickness of 5 mm, 0.03 g (0.06 mmol) of an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride produced in Example 25 described later and diphenyl oxalate 0 .57 g (2.35 mmol) was added. The inside of the glass test tube for sealed tubes was set to 10 kPa using a vacuum pump, and the sealed tube volume was sealed to 30 cm 3 . The sealed tube was allowed to react for 1 hour while immersed in an oil bath at 230 ° C.
  • the reaction solution after the reaction was taken out from the sealed tube and subjected to composition analysis by high performance liquid chromatography. As a result, it was 0.66% by weight of phenol, 34.13% by weight of diphenyl oxalate, 58.81% by weight of diphenyl carbonate, and 0.27% by weight of phenyl (p-phenyloxycarbonylphenyl) carbonate (PCPC). The conversion rate of diphenyl oxalate was 67%.
  • the pressure in the sealed tube is increased by the amount of carbon monoxide generated, and the absolute pressure in the sealed tube after the reaction is generated from the equation of state of the ideal gas.
  • Example 15 To a glass test tube for a sealed tube having a thickness of 5 mm, 0.10 g (0.21 mmol) of an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride produced in Example 25 described later and diphenyl oxalate 1 .90 g (7.84 mmol) was added and reacted in the same manner as in Example 14 for 1 hour.
  • the reaction solution after the reaction was taken out from the sealed tube and subjected to composition analysis by high performance liquid chromatography. As a result, it was 0.65% by weight of phenol, 34.85% by weight of diphenyl oxalate, 57.88% by weight of diphenyl carbonate, and 0.27% by weight of phenyl (p-phenyloxycarbonylphenyl) carbonate (PCPC).
  • the conversion rate of diphenyl oxalate was 66%.
  • the pressure in the sealed tube is increased by the amount of carbon monoxide generated, and the absolute pressure in the sealed tube after the reaction is generated from the equation of state of the ideal gas.
  • Example 16 In the same manner as in Example 14, an adduct body of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride and diphenyl oxalate were placed in a sealed glass test tube having a thickness of 5 mm, and the inside of the sealed glass test tube was 10 kPa. After that, the pressure was returned to normal pressure (absolute pressure 0.10 MPa) and reacted for 1 hour in a state where it was immersed in an oil bath at 230 ° C. as it was.
  • the reaction solution after the reaction was taken out from the sealed tube and subjected to composition analysis by high performance liquid chromatography. As a result, it was 0.63% by weight of phenol, 34.61% by weight of diphenyl oxalate, 58.33% by weight of diphenyl carbonate, and 0.41% by weight of phenyl (p-phenyloxycarbonylphenyl) carbonate (PCPC).
  • Example 17 In a full-jacketed 500 cm 3 separable flask equipped with a thermometer, a stirrer, a distilling tube, a receiver and a glass tube having a diameter of 2 mm, diphenyl oxalate 185.8 g, diphenyl carbonate 74.0 g and Example 25 described later After adding 13.9 g of the adduct body of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride produced, stirring with a stirring blade was started. The temperature in the separable flask was raised to 150 ° C. to dissolve the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride.
  • the reaction was continued in a state maintained at 230 ° C. while removing a gas such as nitrogen gas blown from the lower part of the separable flask from the upper part of the reactor.
  • a part of the liquid reacted for 1 hour was extracted and subjected to composition analysis by high performance liquid chromatography.
  • diphenyl carbonate containing 0.33% by weight of phenol and 13.57% by weight of diphenyl oxalate was obtained.
  • the molar ratio of chlorine atom / 4-t-butylphenyltriphenylphosphonium chloride in the liquid reacted for 1 hour was 1.051.
  • the reaction was further continued in this state, and after 3 hours from the start of the reaction, a part of the reaction solution was extracted again and subjected to composition analysis by high performance liquid chromatography.
  • the diphenyl oxalate concentration was 0.77% by weight.
  • the phenol concentration was reduced to 0.30% by weight.
  • the molar ratio of chlorine atom / 4-tert-butylphenyltriphenylphosphonium chloride in the liquid reacted for 3 hours was reduced to 1.034.
  • the conversion rate of diphenyl oxalate during 1 to 3 hours after the start of the reaction was 94.4%.
  • the reaction was further continued in this state, and after 5 hours from the start of the reaction, a part of the reaction solution was extracted and subjected to composition analysis by high performance liquid chromatography.
  • the diphenyl oxalate concentration was 1.53% by weight, The phenol concentration was further reduced to 0.29% by weight.
  • the molar ratio of chlorine atom / 4-t-butylphenyltriphenylphosphonium chloride in the liquid reacted for 3 hours was reduced to 1.028.
  • the conversion rate of diphenyl oxalate during 3 to 5 hours after the start of the reaction was 98.0%, which was improved from 1 to 3 hours after the start of the reaction.
  • the conversion rate of diphenyl oxalate during 1 to 5 hours after the start of the reaction was 99.89%.
  • Example 18 In Example 17, the nitrogen gas blowing rate was increased to 0.3 cm 3 / min (the nitrogen gas superficial linear velocity for the separable flask was 0.00170 m ⁇ s ⁇ 1 , and the bubble diameter of the nitrogen gas was about 7 mm). Except for the above, diphenyl carbonate was produced in the same manner as in Example 17, and the composition of the liquid after the reaction was analyzed.
  • the amount of phenol contained in the diphenyl carbonate after the reaction is reduced to 0.30% by weight after 1 hour reaction, 0.25% by weight after 3 hours reaction, and 0.22% by weight phenol after 5 hours reaction. It was.
  • the molar ratio of chlorine atom / 4-t-butylphenyltriphenylphosphonium chloride in the liquid after the reaction was 1.031 after the reaction for 1 hour, 1.019 after the reaction for 3 hours, and after the reaction for 5 hours. It was 1.009, and gradually decreased.
  • the amount of diphenyl oxalate contained in the diphenyl carbonate after the reaction was 16.54% by weight after the reaction for 1 hour, 1.05% by weight after the reaction for 3 hours, and 0.001% by weight after the reaction for 5 hours. .
  • the conversion rate of diphenyl oxalate was 93.7% between 1 and 3 hours after the start of the reaction, and 98.0% between 3 and 5 hours after the start of the reaction.
  • the conversion rate of diphenyl oxalate during 1 to 5 hours after the start of the reaction was 99.99%.
  • Example 19 In Example 17, except that nitrogen gas was not blown, diphenyl carbonate was produced in the same manner as in Example 17, and the composition of the liquid after the reaction was analyzed. The amount of phenol contained in the diphenyl carbonate after the reaction decreased so much as 0.39% by weight after the reaction for 1 hour, 0.36% by weight after the reaction for 3 hours, and 0.37% by weight after the reaction for 5 hours. It wasn't.
  • the molar ratio of chlorine atom / 4-t-butylphenyltriphenylphosphonium chloride in the liquid after the reaction was 1.250 after the reaction for 5 hours and gradually decreased.
  • the amount of diphenyl oxalate contained in the diphenyl carbonate after the reaction was 17.04% by weight after the reaction for 1 hour, 0.71% by weight after the reaction for 3 hours, and 0.042% by weight after the reaction for 5 hours. .
  • the conversion rate of diphenyl oxalate was 95.9% between 1 and 3 hours after the start of the reaction and 94.1% between 3 and 5 hours after the start of the reaction, which was lower than that after 1 to 3 hours after the start of the reaction.
  • the conversion rate of diphenyl oxalate during 1 to 5 hours after the start of the reaction was 99.76%, which was higher in Examples 17 and 18.
  • Table 7 summarizes the linear velocity of the nitrogen gas, the phenol concentration, the reaction conversion rate, and the molar ratio of chlorine atom / 4-t-butylphenyltriphenylphosphonium chloride in Examples 17 to 19.
  • Table 7 confirmed that by supplying a specific amount of nitrogen from the lower part of the reactor, the amount of phenol in the reaction solution was reduced, and diphenyl carbonate could be produced more efficiently and stably. Further, it was proved that the chlorine contained in the catalyst easily volatilizes as the supply amount of nitrogen gas increases.
  • the moisture concentration in the solid was analyzed by a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 6.5% by weight.
  • the composition of the solid was analyzed by high performance liquid chromatography. As a result, 73.0% by weight of 4-t-butylphenyltriphenylphosphonium chloride, 10.9% by weight of methyl isobutyl ketone, and 9.6% by weight of other components were obtained. (Excluding 6.5% by weight of water).
  • Example 20 In a 200 cm 3 eggplant-shaped flask equipped with a stir bar, 102 g (421 mmol) of diphenyl oxalate, an adduct (molecular weight 467) of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride produced in Example 25 described later. ) 20 g was put and immersed in an oil bath at 230 ° C. and reacted for 2 hours (the conversion rate of diphenyl oxalate was 99.99%).
  • the moisture concentration in the solid was analyzed by a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 7.2% by weight.
  • the composition of this solid was analyzed by high performance liquid chromatography. As a result, 73.0% by weight of 4-t-butylphenyltriphenylphosphonium chloride, 10.1% by weight of methyl isobutyl ketone, and 9.7% by weight of other components were obtained. % (Excluding 7.2% by weight of water).
  • Reference Example 2 In Reference Example 1, instead of methyl isobutyl ketone (including 500 ppm by weight of water), Reference Example 1 was used except that methyl isobutyl ketone having a water content of 3500 ppm by weight was added to the methyl isobutyl ketone. 1. A kettle obtained by dicarbonylating diphenyl oxalate in the presence of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride gas and distilling a mixture of diphenyl carbonate and phenol in the same manner as in 1. From the residue, 26 g of a solid containing 4-t-butylphenyltriphenylphosphonium chloride was obtained. However, when the filterability of the solid under reduced pressure filtration was compared with the filterability of the solid of Reference Example 1, the filterability of the solid of Reference Example 1 was better.
  • the moisture concentration in the solid was analyzed by a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 7.2% by weight.
  • the composition of this solid was analyzed by high performance liquid chromatography. As a result, 69.0% by weight of 4-t-butylphenyltriphenylphosphonium chloride, 13.0% by weight of methyl isobutyl ketone, and 10.8% by weight of other components % (Excluding 7.2% by weight of water).
  • composition of this solid was analyzed by high performance liquid chromatography. As a result, 26.0% by weight of 4-t-butylphenyltriphenylphosphonium chloride, 65.1% by weight of methyl isobutyl ketone, 6.9% by weight of diphenyl carbonate, and other components 2 0.0% by weight.
  • the water concentration in the solid was analyzed by a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 10.2% by weight.
  • the composition of the solid was analyzed by high performance liquid chromatography. As a result, 71.0% by weight of 4-t-butylphenyltriphenylphosphonium chloride, 17.6% by weight of methyl isobutyl ketone, and 1.2% by weight of other components % (Excluding 10.2% by weight of water).
  • Example 21 In a 500 cm 3 eggplant-shaped flask equipped with a stirrer, 250 g (1032 mmol) of diphenyl oxalate, an adduct (molecular weight 467) of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride produced in Example 25 described later. ) 66 g was put and immersed in an oil bath at 230 ° C. and reacted for 2 hours (the conversion rate of diphenyl oxalate was 99.99%).
  • the moisture concentration in the solid was analyzed by a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 6.7% by weight. Further, the hydrogen chloride concentration in the solid was analyzed by a potentiometric titrator using silver nitrate (“AT-610” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 7.2% by weight.
  • composition of this solid was analyzed by high performance liquid chromatography.
  • 75.0% by weight of 4-t-butylphenyltriphenylphosphonium chloride, 8.9% by weight of methyl isobutyl ketone, 0.2% by weight of diphenyl carbonate, and others The component was 2.0% by weight (excluding 6.7% by weight of water and 7.2% by weight of hydrogen chloride).
  • Methyl isobutyl ketone 53 g was added to a part (23 g) of methyl isobutyl ketone having a hydrogen chloride concentration of 6.6% by weight to prepare 76 g of methyl isobutyl ketone having a hydrogen chloride concentration of 2.0% by weight.
  • the water concentration in the solid was analyzed by a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 18.9% by weight. Further, the hydrogen chloride concentration in the solid was analyzed by a potentiometric titrator using silver nitrate (“AT-610” manufactured by Kyoto Electronics Industry Co., Ltd.) and found to be 6.7% by weight.
  • composition of this solid was analyzed by high performance liquid chromatography. As a result, 60.1% by weight of 4-t-butylphenyltriphenylphosphonium chloride, 9.7% by weight of methyl isobutyl ketone, 3.5% by weight of diphenyl carbonate, and other The component was 1.1 wt% (excluding 18.9 wt% water and 6.7 wt% hydrogen chloride).
  • Table 8 summarizes the properties and recovery rates of the catalysts recovered in Examples 20-22, Comparative Examples 5-6, and Reference Examples 1-2.
  • the results in Table 8 confirmed that the catalyst used in the production of diphenyl carbonate by the decarbonylation reaction of diphenyl oxalate can be easily and efficiently recovered with high purity by the catalyst recovery method of the present invention.
  • Example 23 15 g of the solid obtained in Example 22 was placed in a 100 cm 3 eggplant-shaped flask and placed on a rotary evaporator equipped with an oil bath. The oil bath was heated to 100 ° C. and dried at a pressure of 10 Torr for 1 hour. When the moisture concentration in the dried solid was analyzed with a moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.), it was 0.3% by weight from the moisture meter (“MKS-500” manufactured by Kyoto Electronics Industry Co., Ltd.). there were.
  • MKS-500 manufactured by Kyoto Electronics Industry Co., Ltd.
  • Example 24 In Example 23, 5 g (11 mmol) of the adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride prepared in Example 25 was used instead of 5 g of the dried solid obtained in Example 22. ) was used for 1 hour in the same manner as in Example 23. The composition after the reaction was analyzed by high performance liquid chromatography.
  • Table 9 summarizes the liquid compositions after reaction in Example 23 and Reference Example 3. Table 9 confirms that high-purity diphenyl carbonate can be stably produced by using the catalyst used in the production of diphenyl carbonate by the decarbonylation reaction of diphenyl oxalate recovered by the catalyst recovery method of the present invention. It was.
  • Example 25 An adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride was synthesized by the following method.
  • 4-t-butylphenyltriphenylphosphonium bromide was synthesized by the method described in Japanese Patent Application Laid-Open No. 2013-82695. This bromide was converted to 4-t-butylphenyltriphenylphosphonium chloride (chloride) by the method described in Japanese Patent Application Laid-Open No. 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.
  • Example 26 In a 2000 cm 3 eggplant-shaped flask equipped with a stir bar, 271 g (1.1 mol) of diphenyl oxalate, an adduct of 4-t-butylphenyltriphenylphosphonium chloride synthesized in Example 25 and hydrogen chloride (molecular weight 467) ) 160 g was placed and immersed in an oil bath at 240 ° C. The temperature of the oil bath was raised to 240 ° C. and reacted for 2 hours (diphenyl oxalate conversion was 99.99%).
  • the concentration of methyl isobutyl ketone contained in the obtained filtrate was quantified by gas chromatography. As a result, it was 74.0% by weight.
  • the concentration of water contained in the filtrate was measured with a moisture meter and found to be 3.5% by weight.
  • the concentration of hydrogen chloride contained in the filtrate was quantified with a potentiometric titrator, and found to be 0.3% by weight.
  • a batch distillation column consisting of a full-jacketed separable flask, a 32 mm column equipped with a thermometer and a stirrer, Shibata Kagaku Co., Ltd.'s “Alder Show” (tray column) and a liquid-liquid separation tank is placed inside the separable flask.
  • the filtrate was evaporated
  • the evaporated liquid was supplied to the lower part of the liquid-liquid separation tank through the plate tower, and overflowed from the upper part of the liquid-liquid separation tank to return to the plate tower.
  • a line connecting the tray tower and the liquid-liquid separation tank was installed so that it could be switched to the initial distillation tank or the mainstream tank instead of the liquid-liquid separation tank.
  • the evaporated liquid distilled into the liquid-liquid separation tank was separated into two phases into a lower phase mainly composed of water and an upper phase mainly composed of methyl isobutyl ketone.
  • the lower phase stayed in the liquid-liquid separation tank, but the upper phase overflowed and returned to the tray column.
  • the interface between the lower phase and the upper phase gradually rises and the top temperature of the plate tower rises, but the ratio of methyl isobutyl ketone and water that evaporates eventually becomes 15
  • the saturation solubility of water in isobutyl ketone at 0 ° C. was reached, the temperature rise of the top temperature of the plate column became dull at around 57.7 ° C. and the rise of the interface between the lower phase and the upper phase also stopped.
  • the line connecting the column tower and the liquid-liquid separation tank is switched from the liquid-liquid separation tank to the first distillation tank, and as the concentration of water contained in the evaporating component decreases, the top temperature of the plate tower increases to 58.2 ° C. Distillation was continued until the temperature rise in the vicinity was slow, and 57 g of the first fraction was obtained.
  • concentration of methyl isobutyl ketone contained in the first fraction it was 98.0% by weight.
  • the line connecting the tray tower and the first distillation tank is switched to the main distillation tank, the bottom temperature of the separable flask is raised, and the distillation is continued until it reaches 67.3 ° C. Obtained.
  • the concentration of methyl isobutyl ketone contained in the main distillate was analyzed by gas chromatography and found to be 99.9% by weight.
  • Example 27 In Example 26, in addition to 300 g of filtrate in a separable flask, 57 g of the first fraction obtained in Example 26 was further added, and the evaporating liquid was retained in Example 26 in the liquid-liquid separation tank. Distillation was performed in the same manner as in Example 26 until the bottom temperature of the flask was raised and the distillation was continued until the temperature reached 67.3 ° C. to obtain a main distillation.
  • Example 26 300 g of the above filtrate and 57 g of the first fraction obtained in Example 26 were charged in a separable flask. Moreover, the liquid-liquid separation tank kept the evaporation liquid collected in Example 26, and the liquid-liquid separation tank was 15 degreeC. Distillation was performed by reducing the pressure in the plate column from normal pressure to 133 kPa and raising the bottom temperature of the separable flask from room temperature to 60.4 ° C.
  • the evaporated liquid distilled into the liquid-liquid separation tank was separated into two phases into a lower phase mainly composed of water and an upper phase mainly composed of methyl isobutyl ketone.
  • the lower phase stayed in the liquid-liquid separation tank, but the upper phase overflowed and returned to the tray column.
  • the temperature rise of the top temperature of the plate tower becomes dull at around 57.7 ° C.
  • the rise of the upper phase interface also stopped.
  • the line connecting the plate tower and the liquid-liquid separation tank is switched from the liquid-liquid separation tank to the first distillation tank, and the top temperature of the plate tower is around 58.2 ° C as the concentration of water contained in the evaporation component decreases.
  • the total distillation was carried out until the temperature rise slowed to obtain 60 g of the first fraction.
  • concentration of methyl isobutyl ketone contained in the first fraction it was 98.0% by weight.
  • the line connecting the column tower and the first distillation tank is switched to the main distillation tank, the bottom temperature of the separable flask is raised, and the distillation is continued until it reaches 67.3 ° C. Obtained.
  • the concentration of methyl isobutyl ketone contained in the main distillate was analyzed by gas chromatography and found to be 99.9% by weight.
  • the water contained in the main fraction was 0.1% by weight by the moisture meter, and the hydrogen chloride contained in the main fraction was below the detection limit by the potentiometric titrator.
  • Example 28 In Example 26, a batch distillation column was installed in the same manner as in Example 26, except that the line from the plate column was connected to the first distillation tank. The separable flask was charged with 300 g of the filtrate described above. Distillation was performed by setting the reflux ratio to 2, reducing the pressure in the plate column from normal pressure to 133 kPa, and raising the bottom temperature of the separable flask from room temperature to 60.4 ° C.
  • the first distillate and the main distillate were mixed by the first distillate 131 pair and the main distillate 79 in a weight ratio to obtain a total distillate.
  • the water contained in the total distillate was 5.0% by weight with a moisture meter, and the hydrogen chloride contained in the total distillate was 0.1% by weight with a potentiometric titrator.
  • Table 10 summarizes the composition of main fractions in Examples 26 to 28, the recovery rate of methyl isobutyl ketone (MIBK) in the main distillate, and the recovery rate of methyl isobutyl ketone (MIBK) in all distillates. From the results of Table 10, it was confirmed that the polar organic solvent used for recovering the catalyst used for the production of diphenyl carbonate by the decarbonylation reaction of diphenyl oxalate can be easily and efficiently recovered by the catalyst recovery method of the present invention. .
  • Example 29 Catalyst recovery was carried out using the main fraction obtained in Example 27. Specifically, in an eggplant-shaped flask equipped with a stir bar, 27 g (0.11 mol) of diphenyl oxalate, an adduct of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride produced in Example 25 ( 16 g of molecular weight 467) was added and immersed in an oil bath at 240 ° C. The temperature of the oil bath was raised to 240 ° C. and reacted for 2 hours (diphenyl oxalate conversion was 99.99%).
  • This slurry was cooled to room temperature (about 20 ° C.), and hydrogen chloride gas (molecular weight 36) 0.001 m 3 (0.1 mol of hydrogen chloride relative to 1 mol of 4-t-butylphenyltriphenylphosphonium chloride contained in the reaction solution). 04 mol) was bubbled and absorbed, and a visually uniform liquid was obtained. When 4 g of water was added to this solution over 30 minutes, a white slurry was formed again. The slurry obtained by filtering this slurry under reduced pressure was overwashed with 10 g of methyl isobutyl ketone, and then filtered under reduced pressure to obtain 18 g of a solid.
  • hydrogen chloride gas molecular weight 36
  • Example 30 In Example 29, catalyst recovery was performed in the same manner as in Example 29 except that 80 g of the total distillate obtained in Example 28 was used instead of 80 g of the main distillate obtained in Example 27. However, the white slurry to which all the distillate had been added was cooled to room temperature (about 20 ° C.) and absorbed by lubbling 1 liter of hydrogen chloride gas, but it did not become a uniform liquid visually.
  • Example 3 Water was added to methyl isobutyl ketone manufactured by Wako Pure Chemical Industries, Ltd. to prepare a water concentration of 0.3% by weight. In Example 29, catalyst recovery was performed in the same manner as in Example 29 except that methyl isobutyl ketone having a water concentration of 0.3% by weight was used instead of the main fraction obtained in Example 27.
  • Table 11 summarizes the water concentration in methyl isobutyl ketone (MIBK) used for catalyst recovery and the recovery rate of 4-t-butylphenyltriphenylphosphonium chloride in Examples 29 and 30 and Reference Example 3.
  • MIBK methyl isobutyl ketone
  • the polar organic solvent used for catalyst recovery preferably has a low water concentration, and particularly preferably has a water concentration of 0.3% by weight or less.
  • Example 31 Using the recovered catalyst obtained in Example 29, decarbonylation reaction was performed. First, 10 g of the solid obtained in Example 29 was placed in a 100 cm 3 eggplant-shaped flask, attached to a rotary evaporator equipped with an oil bath, and dried for 1 hour under a full vacuum with an oil bath temperature of 140 ° C. and a diaphragm pump.
  • the liquid composition after the reaction was analyzed by high performance liquid chromatography. As a result, 66.0% by weight of diphenyl carbonate, 28.6% by weight of diphenyl oxalate, 5.0% by weight of 4-t-butylphenyltriphenylphosphonium chloride, phenol 0 4% by weight was included.
  • Example 32 In Example 31, instead of the dried solid obtained in Example 29, 5 g of the adduct body of 4-t-butylphenyltriphenylphosphonium chloride and hydrogen chloride produced in Example 25 was used. The decarbonylation reaction was carried out in the same manner as in Example 31.
  • the liquid composition after the reaction was analyzed by high performance liquid chromatography. As a result, 65.4% by weight of diphenyl carbonate, 29.2% by weight of diphenyl oxalate, 5.0% by weight of 4-t-butylphenyltriphenylphosphonium chloride, phenol 0 .4% by weight.
  • the recovered catalyst can be reused and the solvent used for catalyst recovery can be reused to efficiently and stably produce high-purity diphenyl carbonate. It was supported.
  • the beaker was placed on a water bath and heated to 60 ° C. After maintaining at 60 ° C. for 1 hour, the temperature was lowered and 0.1 g of activated carbon was added, followed by filtration. The obtained filtrate was transferred to a separatory funnel and extracted with 30 cm 3 of ethyl acetate.
  • the obtained organic phase was transferred to a 500 cm 3 eggplant-shaped flask, and ethyl acetate was distilled off under reduced pressure using a rotary evaporator. To the resulting residue, with toluene 30 cm 3 heptane 20 cm 3, it was dissolved. Thereto, 1.5 g of diphosphorus pentoxide was added, and a Dimroth condenser was provided and refluxed for 30 minutes.
  • Table 12 summarizes the results of Reference Example 4 and Comparative Examples 7 and 8.
  • the decomposition rate of Reference Example 4 in which a liquid containing a high concentration of benzofuran-2,3-dione was heated for a short time was a comparative example in which a liquid containing a low concentration of benzofuran-2,3-dione was heated for a long time. Since the decomposition rate was higher than 7, it was confirmed that the presence of the basic substance promotes the decomposition of benzofuran-2,3-dione by heating.
  • the concentration of the benzofuran-2,3-dione was measured by high performance liquid chromatography and found to be 90 ppm by weight.
  • the decomposition rate was 55.9%.
  • the concentration of the benzofuran-2,3-dione was measured by high performance liquid chromatography and found to be 76 ppm by weight.
  • the decomposition rate was 70.0%.
  • the concentration of the benzofuran-2,3-dione was measured by high performance liquid chromatography and found to be 101 ppm by weight.
  • the decomposition rate was 27.9%.
  • Table 13 confirmed that the decomposition of benzofuran-2,3-dione by heating was accelerated by the presence of the basic substance.
  • Reference Example 7 using a low-concentration sodium hydroxide-phenol solution had a higher decomposition rate than Reference Example 5 using a high-concentration sodium hydroxide aqueous solution, Such a solvent having high solubility in diphenyl carbonate was considered preferable.
  • the reaction solution after the reaction for 6 hours was gradually reduced in pressure to 10 Torr, and maintained at a state where the bottom temperature of the separable flask was lowered to 180 ° C., thereby obtaining 217 g of crude diphenyl carbonate as a fraction. At this time, the liquid at the bottom of the separable flask was visually uniform.
  • the composition of the reaction solution and crude diphenyl carbonate after the previous 6 hours reaction was analyzed by high performance liquid chromatography.
  • the reaction solution after the reaction for 6 hours was 94% by weight of diphenyl carbonate and 400 ppm by weight of diphenyl oxalate (the conversion rate of diphenyl oxalate was 99.97%).
  • the crude diphenyl carbonate contained 7000 ppm by weight of phenol and 100 ppm by weight of diphenyl oxalate. In both solutions, benzofuran-2,3-dione was below the detection limit.
  • diphenyl carbonate was 94% by weight and diphenyl oxalate was 400 ppm by weight.
  • Example 33 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. under 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.
  • this solid was found to be 4-t-butylphenyltriphenylphosphonium chloride with 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 ⁇ m.
  • 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.
  • Example 34 30 g (0.46 mol) of the adduct body obtained in Example 33 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 130 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 25 g of a solid.
  • Example 35 30 g (0.06 mol) of the adduct body obtained in Example 33 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 150 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 25 g of a solid.
  • Example 36 30 g (0.06 mol) of the adduct body obtained in Example 33 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 200 ° C. and dried at a pressure of 10 Torr for 2 hours to obtain 25 g of a solid.
  • a decarbonylation reaction of diphenyl oxalate was carried out using this adduct having an adduct ratio of 7% as a catalyst.
  • 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.
  • Example 37 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 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.
  • decarbonylation reaction of diphenyl oxalate was carried out using this adduct having an adduct ratio of 87% as a catalyst.
  • 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.
  • 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.
  • Japanese Patent Application No. 2014-107284 Japanese patent application filed on July 14, 2014
  • Japanese Patent Application No. 2014-144298 Japanese patent application filed on May 14, 2014
  • Japanese Patent Application No. 2014-144297 Japanese patent application filed on October 28, 2014
  • Japanese Patent Application No. 2014-219463 Japanese application filed on October 28, 2014 It is based on a patent application (Japanese Patent Application No. 2014-219464), which is incorporated by reference in its entirety.

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Abstract

　L'objet de la présente invention est de pourvoir à un procédé de production de carbonate de diphényle par une réaction de décarbonylation d'un oxalate de diphényle en présence d'un catalyseur, qui permet d'obtenir un carbonate de diphényle de haute pureté de manière simple, efficace, stable, et en continu à l'aide d'un catalyseur facile à manipuler sans problèmes tels que l'engorgement dus à la précipitation du catalyseur. Un autre objet est de récupérer et de réutiliser efficacement le catalyseur de haute pureté par un procédé simple. La solution selon l'invention porte sur un procédé de production de carbonate de diphényle par une réaction de décarbonylation d'un oxalate de diphényle en présence d'un catalyseur, ledit procédé de production de carbonate de diphényle étant caractérisé par l'utilisation d'un catalyseur sous la forme du produit d'addition d'un halogénure de tétraarylphosphonium asymétrique et d'un halogénure d'hydrogène.
PCT/JP2015/064645 2014-05-23 2015-05-21 Procédé de production de carbonate de diphényle, carbonate de diphényle ainsi obtenu, polycarbonate produit à partir dudit carbonate de diphényle, catalyseur pour la production de carbonate de diphényle, procédé de production du catalyseur, et procédé de récupération et de réutilisation du catalyseur WO2015178463A1 (fr)

Priority Applications (2)

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KR1020167032584A KR102206139B1 (ko) 2014-05-23 2015-05-21 탄산디페닐의 제조 방법, 그 제조 방법에 의해 얻어지는 탄산디페닐, 그 탄산디페닐로부터 제조되는 폴리카보네이트, 탄산디페닐 제조용 촉매, 그 촉매의 제조 방법, 촉매의 회수·재이용 방법
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