CN106458834B

CN106458834B - Diphenyl carbonate and its manufacturing method, catalyst and its manufacture recycling and reusing method, polycarbonate

Info

Publication number: CN106458834B
Application number: CN201580026720.8A
Authority: CN
Inventors: 内山馨; 金丸高志; 井上敏光; 中村诚; 佐藤崇; 古贺芳夫; 内堀俊雄; 浦川智; 早志功一
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Rayon Co Ltd
Priority date: 2014-05-23
Filing date: 2015-05-21
Publication date: 2019-10-25
Anticipated expiration: 2035-05-21
Also published as: CN106458834A; KR20170012247A; KR102206139B1; WO2015178463A1

Abstract

It is an object of the invention to, manufacturing method about the diphenyl carbonate carried out and making phenostal carry out de-carbonyl reaction in the presence of a catalyst, use maneuverable catalyst, the diphenyl carbonate for manufacturing to simple and effective, steady and continuous high-purity will not generate the obstacle of occlusion caused by catalyst is precipitated etc..Furthermore, it is therefore intended that by easy method from reaction solution, efficiently recycle, recycle the catalyst of high-purity.The present invention relates to the manufacturing methods of diphenyl carbonate, it is the method for manufacturing diphenyl carbonate and making phenostal carry out de-carbonyl reaction in the presence of a catalyst, it is characterized in that, being supplied the catalyst as the adduct of asymmetric four aryl halogenation phosphine and hydrogen halides.

Description

Diphenyl carbonate and its manufacturing method, catalyst and its manufacture recycling and reusing Method, polycarbonate

Technical field

The present invention is to be related to the manufacturing method of the carbonic diester of diphenyl carbonate etc. and obtained by the manufacturing method The invention of carbonic diester.Specifically a kind of following invention: about by being catalyzed the oxalate diester of phenostal etc. De-carbonyl reaction is carried out in the presence of agent to the method that manufactures carbonic diester, provide using maneuverable catalyst, can be easy Efficiently, the method for high-purity diphenyl carbonate is manufactured to steady and continuous.

In addition, the present invention be related to carbonic diester to be manufactured by this method it is less as the obtained coloring of raw material and The invention of high-purity polycarbonate.Further, the present invention relates to the catalyst for being suitable for carbonic diester manufacture and its manufactures The invention of method.In addition, the present invention relates to easy method high efficiente callback high purity catalyst is passed through from reaction solution, by it Recycle, at the same steady and continuous manufacture high purity carbon acid diesters method, and will be used for catalyst recovered solvent also into The invention that row recycles.

Background technique

Carbonic diester is known as the raw material compound in various chemical reactions, specifically, it is known that diphenyl carbonate Polycarbonate can be manufactured by the polycondensation reaction with dihydroxylic aromatic compound.

Carbonic diester can be by taking off oxalate diester in the presence of the de- carbonylic catalyst of organic phosphorus compound etc. Carbonyl reaction and obtain (referenced patent document 1).Herein, about reaction pressure, although disclosing, " reaction temperature is more than oxalic acid two Pressurize when the boiling point of aryl ester, but usually normal pressure or decompression ", but as embodiment is reaction under normal pressure, due to pressurization Vacuum pump respectively must be with the required above control pressure when pressure vessel, Depressor response when reaction, thus reacts generally in normal pressure Lower progress.

A kind of manufacturing method of carbonic diester is also disclosed, and this method is by aromatic hydroxy compound and oxalic acid alkylaryl The less oxalate diester of the content of ester etc. uses (referenced patent document 2) as raw material.In addition, proposing that there are as below methods: in grass Diphenyl carbonate obtained in the decarbonylated reaction of diphenyl phthalate due to the light impurities containing furans based compound etc., By distill or thermally decompose (by 150~300 DEG C at a temperature of be heat-treated about 0.05~10 hour, be allowed to thermally decompose, contract Conjunction and/or heat modification) and remove (referenced patent document 3).

In addition, about by making oxalate diester carry out de-carbonyl reaction in the presence of the catalyst of tetraphenylphosphonium chloride etc. Obtained carbonic diester, it was also proposed that have method for making its high purity etc. (referenced patent document 4).

In addition, being also reported (referenced patent document 5) following situation: obtained by the de-carbonyl reaction by oxalic acid diaryl Diaryl carbonate, even if by the way that de-carbonyl reaction liquid is evaporated operation in vaporising device, its decarbonylation base is anti- It answers liquid and mainly contains the diaryl carbonates for not evaporating ingredient and target product containing de- carbonylic catalyst and high boiling substance etc. The evaporation ingredient of the diaryl esters of oxalic acid of ester and raw material separates, and then purifies the evaporation ingredient using by distillation procedure etc. When obtained product cut, due to the benzo furan of the generations such as Fu Laisi (Fries) rearrangement reaction by diaryl esters of oxalic acid The furans based compound of -2,3- diketone etc. of muttering is mixed into, and the polycarbonate article manufactured using the diaryl carbonate can colour, It thus needs to separate and recover flashing to containing diaryl carbonate from and de-carbonyl reaction liquid is evaporated operation Point, then by the way that the evaporation ingredient is carried out distillation procedure, successively removes low-boiling point material and high boiling substance and obtain carbonic acid Furans system impurity is removed in the thick fraction of diaryl ester.

Conversion ratio when about in the presence of tetraphenylphosphonium chloride by phenostal generation diphenyl carbonate, in order to press down The precipitation of catalyst processed needs to carry out de-carbonyl reaction (referenced patent document 6) in 95% or less conversion ratio.

About the recycling for de-carbonyl reaction phosphonium salt catalyst, proposition has by " being added with into reaction solution Machine polar solvent adds hydrogen halides while dilution, to make phosphonium salt or phosphonium salt ingredient remaining in the reaction mixture as halogen Change hydrogen adduct to be precipitated, separate " and the method (referenced patent document 7) of recycling.

Existing technical literature

Patent document

Patent document 1: the flat 8-333307 bulletin of Japanese Patent Laid-Open

Patent document 2: the flat 11-152252 bulletin of Japanese Patent Laid-Open

Patent document 3: Japanese Patent Laid-Open 2003-226751 bulletin

Patent document 4: Japanese Patent Laid-Open 2002-53657 bulletin

Patent document 5: Japanese Patent Laid-Open 2002-47251 bulletin

Patent document 6: the flat 11-246489 bulletin of Japanese Patent Laid-Open

Patent document 7: Japanese Patent Laid-Open 2002-45704 bulletin

Summary of the invention

Subject to be solved by the invention

But the method recorded about above patent document 4, purification are also required to many distillation process, have operation very numerous Miscellaneous equal problem, the high purity etc. about diphenyl carbonate need further to improve.In addition, the present inventors is about non-right Claim that the operability of tetraphenylphosphonium chloride studied as a result, distinguished that the substance is easy to disperse since partial size is smaller, hygroscopicity It is higher, therefore used as catalyst, when carrying out the de-carbonyl reaction of phenostal, due to the water of diphenyl carbonate Solution is easy by-product phenol.

About above-mentioned catalyst recovery method, can not say centainly can be with high efficiente callback high purity catalyst, the present invention The result that the method that people record above patent document 7 is studied in detail, it is thus understood that phenostal contained in catalyst liquid It can be decomposed in preservation and generate by-product.In addition, it is used to contain in the organic polar solvent of recycling hydrogen halides and water, but about By its one thing of recycling and reusing, without any research.

Therefore, the present inventors exists about what the recovery method of Zhong Zhong phosphonium salt catalyst was studied as a result, being especially Above-mentioned catalyst recovery method is suitable for the adduct of asymmetric four aryl halogenation phosphine and/or four aryl halogenation phosphines and hydrogen halides Recycling when, can not high efficiente callback high concentration catalyst.

In addition, it is contemplated that since the de-carbonyl reaction of oxalate diester is the endothermic reaction, for industrial continuous manufacture, instead It answers the medium-and-large-sized stirring wing of device to be necessary, needs the simplification of reaction unit and process.

Problem of the present invention is that providing at least wantonly 1 method solved these problems, below at least wantonly 1 is provided A method etc..

That is, the 1st project of the invention is, about by making oxalate diester carry out de-carbonyl reaction in the presence of a catalyst To the method that manufactures carbonic diester, provide by using maneuverable catalyst, can simple and effective steadily manufacture carbonic acid The method of diester.

2nd project of the invention is that the case where failure of caused occlusion etc. is precipitated by catalyst will not be generated by providing Under steadily manufacture the method for carbonic diester, which be difficult on the polycarbonate manufactured using carbonic diester as raw material Generate the carbonic diester of the high-purity of the degree of coloring.

3rd project of the invention is, provides: by asymmetric four aryl halogenation phosphine and/or asymmetric four aryl halogenation phosphine with The adduct of hydrogen halides uses in the manufacture for the carbonic diester that the de-carbonyl reaction by oxalate diester carries out as catalyst When, with the catalyst of easy method high efficiente callback high-purity from reaction solution, recycled, while steady and continuous manufacture The method of the carbonic diester of high-purity.

4th project of the invention is, provides: by four aryl halogenation phosphines and/or four aryl halogenation phosphines and hydrogen halides plus Object is closed, as catalyst in use, passing through use in the manufacture for the carbonic diester that the de-carbonyl reaction by oxalate diester carries out The method high efficiente callback of simplicity and the catalyst for recycling high-purity, while it will be also used for catalyst recovered solvent recycling, Thus the method for efficiently and stably manufacturing the carbonic diester of high-purity.

5th project of the invention is, and about de-carbonyl reaction is carried out in the presence of a catalyst by making oxalate diester The method for manufacturing carbonic diester provides the side that the carbonic diester of high-purity can be continuously manufactured by with easy method efficient stable Method.

6th project of the invention is, and about de-carbonyl reaction is carried out in the presence of a catalyst by making oxalate diester The method for manufacturing carbonic diester, provides the reaction unit and process by more simplifying, industrially manufactures carbon to high-efficiency and continuous The method of acid diesters.

The means to solve the problem

The present inventors is concentrated on studies in order to solve the above problems.As a result, discovery: for above-mentioned 1st class Topic can be with about by making phenostal carry out the method that de-carbonyl reaction manufactures diphenyl carbonate in the presence of a catalyst It is solved and supplying the catalyst as the adduct of asymmetric four aryl halogenation phosphine and hydrogen chloride.It moreover has been found that: it should The adduct of asymmetric four aryl halogenation phosphine and hydrogen chloride, can be non-by will contact with hydrogen chloride and polar organic solvent Symmetrical four aryl halogenation phosphine crystallization is to easily obtain.

In addition, discovery: oxalate diester is made to carry out de-carbonyl reaction system in the presence of a catalyst above-mentioned 2nd project It makes in the method for carbonic diester, by using the catalyst for dissolving in carbonic diester, the precipitation of catalyst will not be caused, with conversion After 96% or more rate carries out, by evaporating the 50 weight % or more of contained carbonic diester in reaction solution, remaining can be reduced The amount of oxalate diester inhibits the by-product of furans based compound when carbonic diester evaporation, can be solved.

For above-mentioned 3rd project, the present inventors is about asymmetric four aryl halogenation phosphine and/or asymmetric four aryl halogenation The recovery method of the adduct of phosphine and hydrogen halides is concentrated on studies.Finally, it is found that: by making polar organic solvent and chlorine Change raffinate of the hydrogen contact after obtaining the ingredient containing carbonic diester in reaction solution, then contacts water, thus urging high-purity Agent can be solved as precipitate high efficiente callback.

For above-mentioned 4th project, the present inventors is about four aryl halogenation phosphines and/or four aryl halogenation phosphines and hydrogen halides The recovery method of adduct is concentrated on studies.Finally, it is found that: by make polar organic solvent and hydrogen chloride gas and/ Or hydrochloric acid contact from reaction solution obtain the ingredient containing carbonic diester after raffinate, can high efficiente callback high-purity catalyst, Further, it is recycled, can be solved as the polar organic solvent by the way that the raffinate after the catalyst will be recycled.

For above-mentioned 5th project, the present inventors's discovery: when by catalyst recycle after reaction, by by catalyst With the state supply being dissolved in carbonic diester, can be solved.In addition, the present inventors has found, by that will contain specific quantity The oxalate diesters of specific impurities used as raw material, can efficiently manufacture the carbonic diester of high-purity.Further, it was found that: pass through The de-carbonyl reaction that oxalate diester is carried out under specific pressurized conditions, can efficiently and stably manufacture the carbonic diester of high-purity. In addition, the present inventors has found, by contacting with alkali compounds, the thermal decomposition of furans based compound is promoted, and find logical Crossing makes furans based compound contained in the carbonic diester generated contact and remove with alkali compounds, thus can efficiently manufacture The carbonic diester of high-purity.

For above-mentioned 6th project, the present inventors's discovery: anti-from the lower part of de-carbonyl reaction device to decarbonylation base by one side Non-active gas should be supplied on a small quantity, carry out de-carbonyl reaction on one side, while being stirred to react liquid, pair when removing de-carbonyl reaction Thus the impurity of the phenol of production etc. can efficiently manufacture carbonic diester.

That is, the present invention is as described below.

1. a kind of manufacturing method of diphenyl carbonate is by making phenostal carry out decarbonylation base in the presence of a catalyst The method of reaction manufacture diphenyl carbonate, which is characterized in that using the catalyst as asymmetric four aryl halogenation phosphine (phosphonium) it is supplied with the adduct of hydrogen halides.

2. according to the manufacturing method for the diphenyl carbonate that preceding paragraph 1 is recorded, the average grain diameter of the adduct is 50 μm or more, 1mm or less.

3. the adduct is by making asymmetric four virtue according to the manufacturing method for the diphenyl carbonate that preceding paragraph 1 or 2 is recorded Base halogenation phosphine and hydrogen halides are dissolved in after polar organic solvent obtained from crystallization.

4. according to the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 3, the asymmetric four aryl halogenation Phosphine does not have benzylic protons.

5. the adduct is 4- 2-methyl-2-phenylpropane according to the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 4 The adduct of base triphenyl phosphine dichloride and hydrogen chloride.

6. exhausted when the de-carbonyl reaction according to the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 5 It is 0.105MPa or more, 10MPa or less to pressure.

7. according to the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 6, on one side from de-carbonyl reaction device Lower part is with 0.00001ms^-1The above 0.01ms^-1Superficial linear velocity below supplies nonactive gas to the de-carbonyl reaction Body carries out de-carbonyl reaction on one side.

8. according to the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 7, which is characterized in that the catalyst Diphenyl carbonate is dissolved in, after the de-carbonyl reaction is carried out with 96% or more conversion ratio, by making contained in reaction solution The 50 weight % or more of diphenyl carbonate evaporate after taking out, and the reaction solution of remaining is supplied to the de-carbonyl reaction.

9. according to the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 8, which is characterized in that by the catalysis Agent is supplied with the state for being dissolved in the diphenyl carbonate.

10. according to the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 8, which is characterized in that the oxalic acid Diphenyl ester contain 0.076 weight % or more, 10 weight % amounts below the following general formula (5) represented by carboxylic acid phenyl ester.

[changing 1]

(in formula, n is 1 or 2.)

11. according to the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 10, which is characterized in that make to pass through institute State the diphenyl carbonate and alkali compounds contact that decarbonylated reaction obtains.

12. a kind of manufacturing method of diphenyl carbonate, which is characterized in that successively contain following 1st~3 processes.

1st process: diphenyl carbonate is manufactured by the manufacturing method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 11 Process,

2nd process: the diphenyl carbonate manufactured in the 1st process is divided with containing the adduct and/or the adduct The process of the catalyst liquid separation for the adduct decomposition product that solution generates,

3rd process: the process that at least part of the catalyst liquid is supplied into the reactor to the 1st process.

13. a kind of recovery method of catalyst is for carrying out dipheryl carbonate by the de-carbonyl reaction of phenostal The recovery method of the catalyst of the manufacture of ester, which is characterized in that the catalyst is asymmetric four aryl halogenation phosphine and/or non-right The adduct for claiming four aryl halogenation phosphines and hydrogen halides, by make polar organic solvent and hydrogen halide with it is anti-from the decarbonylation base Raffinate contact after obtaining the ingredient containing diphenyl carbonate in reaction solution after answering, then contacts with water, and obtains precipitate, It is recycled catalyst as the precipitate.

14. a kind of recovery method of catalyst is for carrying out dipheryl carbonate by the de-carbonyl reaction of phenostal The recovery method of the catalyst of the manufacture of ester, which is characterized in that the catalyst is four aryl halogenation phosphines and/or four aryl halogenations The adduct of phosphine and hydrogen halides makes after obtaining the ingredient containing diphenyl carbonate in the reaction solution after the de-carbonyl reaction After raffinate contacts polar organic solvent and hydrogen halides, catalyst contained in the raffinate (catalyst recovery process) is recycled, together When, the polar organic solvent is recycled, the catalyst recovery process is reused in.

15. a kind of manufacturing method of diphenyl carbonate is to manufacture dipheryl carbonate by the de-carbonyl reaction of phenostal The method of ester, which is characterized in that as catalyst, the catalysis recycled using the recovery method recorded by preceding paragraph 13 or 14 Agent.

16. a kind of manufacturing method of the adduct of asymmetric four aryl halogenation phosphine and hydrogen halides, be four aryl halogenation phosphines and The manufacturing method of the adduct of hydrogen halides, which is characterized in that by making asymmetric four aryl halogenation phosphine and hydrogen halides be dissolved in pole Crystallization after property organic solvent, obtains the adduct of asymmetric four aryl halogenation phosphine and hydrogen halides.

17. a kind of diphenyl carbonate catalyst for producing is for carrying out carbon by the de-carbonyl reaction of phenostal The catalyst of the manufacture of diphenyl phthalate, which is characterized in that the catalyst is asymmetric four aryl halide without benzylic protons Change the adduct of phosphine and hydrogen halides.

18. a kind of manufacturing method of polycarbonate is by urging diphenyl carbonate and dihydroxy compounds in transesterification Polycondensation in the presence of agent and the method for manufacturing polycarbonate, which is characterized in that passing through wantonly 1 in preceding paragraph 1 to 12 and 15 After the manufacturing method for the diphenyl carbonate that item is recorded manufactures the diphenyl carbonate, with the dihydroxy compounds polycondensation.

19. a kind of diphenyl carbonate is the manufacture by the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 12 and 15 What method obtained.

20. a kind of polycarbonate is existed by the diphenyl carbonate for recording aromatic dihydroxy compound and preceding paragraph 19 Polycondensation obtains in the presence of ester exchange catalyst.

The effect of invention

1st effect of the invention is, and about de-carbonyl reaction is carried out in the presence of a catalyst by making phenostal The method for manufacturing diphenyl carbonate, using maneuverable catalyst, can simple and effective, manufacture to steady and continuous the carbon of high-purity Diphenyl phthalate.Herein, can by crystallization after making asymmetric four aryl halogenation phosphine and hydrogen halides be dissolved in polar organic solvent, thus Be easily obtained be suitable for the de-carbonyl reaction catalyst.In addition, by the way that the diphenyl carbonate of the high-purity is made as raw material With the polycarbonate of high-purity can be obtained.

2nd effect of the invention is the system about the diphenyl carbonate that the de-carbonyl reaction by phenostal carries out Make method, can simple and effective, will not generate by catalyst be precipitated caused by occlusion etc. failure, steadily manufacture high-purity carbon Acid diesters.In addition, the poly- carbonic acid for the high-purity for being difficult to generate coloring can be obtained by using using the carbonic diester as raw material Ester.

3rd effect of the invention is, by asymmetric four aryl halogenation phosphine and/or asymmetric four aryl halogenation phosphine and hydrogen halides Adduct, as catalyst in use, can in the manufacture of the carbonic diester carried out by the de-carbonyl reaction of oxalate diester With the catalyst of easy method high efficiente callback high-purity from reaction solution, recycled, at the same steady and continuous manufacture height The carbonic diester of purity.In addition, the poly- carbonic acid of high-purity can be obtained by using the carbonic diester of the high-purity as raw material Ester.

4th effect of the invention is, by four aryl halogenation phosphines and/or the adduct of four aryl halogenation phosphines and hydrogen halides, As catalyst in use, can be by with simplicity in the manufacture of the carbonic diester carried out by the de-carbonyl reaction of oxalate diester Method high efficiente callback recycles the catalyst of high-purity, while will also be used for catalyst recovered solvent recycling, efficient stable The carbonic diester of ground manufacture high-purity.In addition, high-purity can be obtained by using the carbonic diester of the high-purity as raw material Polycarbonate.

5th effect of the invention is, about by making oxalate diester carry out de-carbonyl reaction and system in the presence of a catalyst The method for making carbonic diester, it is possible to provide the side of the carbonic diester of high-purity can be continuously manufactured by with easy method efficient stable Method.In addition, the polycarbonate of high-purity can be obtained by using the carbonic diester of the high-purity as raw material.

6th effect of the invention is, about by making oxalate diester carry out de-carbonyl reaction and system in the presence of a catalyst The method for making carbonic diester, it is possible to provide by the reaction unit and process more simplified, industrially manufacture carbon to high-efficiency and continuous The method of acid diesters.

Specific embodiment

Hereinafter, the embodiment of the manufacturing method about carbonic diester of the invention is described in detail.

It is anti-by making oxalate diester carry out decarbonylation base in the presence of a catalyst in the manufacturing method of carbonic diester of the invention Answer (hereinafter, be sometimes referred to as " de-carbonyl reaction of the present invention " or be only called " de-carbonyl reaction ") manufacture carbonic diester.

De-carbonyl reaction of the present invention is carried out according to reaction equation (1) as shown below.

[changing 2]

In formula, 2 R are the alkyl that can have substituent group each independently.

[oxalate diester]

Oxalate diester in reaction equation (1) is (hereinafter, being sometimes referred to as " oxalate diester of the present invention " or being only called " grass Acid diesters ") it is raw material in the manufacturing method of carbonic diester of the invention.In addition, using oxalate diester of the present invention as The obtained carbonic diester of the present invention of raw material, due to hot upper stabilization, the raw material as polycarbonate is suitable.

Oxalate diester of the present invention, usually using the alkyl having with carbonic diester identical type as a purpose (R) oxalate diester.Alkyl in oxalate diester of the present invention can be aliphatic, be also possible to aromatic series.That is, oxalic acid Alkyl possessed by diester all can be alkyl with 2, all can also can also be fragrance with 2 with alkyl and fragrant each 1 of ring group Ring group.But the group due to being easily separated from, being detached from when using carbonic diester of the invention as the raw material of polycarbonate etc. Recycling be easy, preferably 2 are all fragrant ring groups.

When alkyl possessed by oxalate diester of the present invention is alkyl, it can be in straight chain, branch and ring type Any one.

When alkyl possessed by oxalate diester of the present invention is fragrant ring group, which can be aromatic ring Alkyl is also possible to aromatic heterocycle.But due to making carbonic diester of the invention as the raw material of manufacture polycarbonate Used time is easily separated from, optimization aromatic cyclic hydrocarbon radical.Further, since the recycling for the group being detached from is easy, the group of disengaging is stablized, excellent Menu ring.

As the aromatic ring alkyl, monocycle or 2~5 condensed ring of the 5- or 6-membered ring with 1 free valency etc. can be enumerated.This Outside, in the present invention, as organic chemistry biological chemical name method (on) (and revision second edition, Nan Jiangtang, 1992 issue) in Recorded, so-called free valency refers to can be with other free valency bondings.

As the concrete example of the aromatic ring alkyl, can enumerate phenyl ring with 1 free valency, naphthalene nucleus, anthracene nucleus, phenanthrene ring, Ring, aphthacene ring, pyrene ring, BaP ring,Ring, Sanya phenyl ring, acenaphthene ring, fluoranthene ring, fluorenes ring etc..

Wherein, since the group being detached from when using carbonic diester of the invention as the raw material of manufacture polycarbonate etc. is steady It is fixed, particularly preferably with the phenyl ring (phenyl) of 1 free valency.

Therefore, oxalate diester of the present invention, 2 R in carbonic diester preferably generated in above-mentioned reaction equation (1) It is the compound of fragrant ring group, more preferable 2 R are the compound of aromatic ring alkyl, and particularly preferred 2 R are phenyl Phenostal.

Therefore, the preferred phenostal of oxalate diester of the present invention is (hereinafter, sometimes referred to as " grass of the present invention Diphenyl phthalate " is only called " phenostal "), carbonic diester manufactured by the manufacturing method of carbonic diester through the invention It is preferred that diphenyl carbonate (hereinafter, be sometimes referred to as " diphenyl carbonate of the present invention " or be only called " diphenyl carbonate ").

In addition, the de-carbonyl reaction of oxalate diester is preferably carried out according to reaction equation (2) as shown below.

[changing 3]

In formula, 2 Ph are the phenyl that can have substituent group each independently.

When alkyl possessed by oxalate diester of the present invention is aromatic heterocycle, as the aromatic heterocycle, Monocycle or 2~4 condensed ring etc. of the 5- or 6-membered ring with 1 free valency can be enumerated.

As the concrete example of the aromatic heterocycle, furan nucleus, benzofuran ring, thiophene with 1 free valency can be enumerated Pheno ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazoles ring, indole ring, carbazole ring, pyrrolo- imidazole ring, pyrroles And pyrazole ring, pyrrolopyrrole ring, Thienopyrroles ring, thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thiophene Pheno and furan nucleus, benzo isozole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, Triazine ring, quinoline ring, isoquinolin ring, cinnolines ring, quinoxaline ring, phenanthridines ring, benzimidazole ring, perimidine ring, quinoline Oxazoline ring, quinazolinone ring, azulenes etc..

As substituent group possessed by alkyl possessed by oxalate diester of the present invention, as long as this will not substantially be interfered The excellent effect of invention, is just not particularly limited.But when obtained diphenyl carbonate is used for polycarbonate manufacture, preferably The boiling point of the by-product generated in polycarbonate manufacture is lower, is easy to be distilled off.

Therefore, and specifically, it is preferable to the alkyl of the carbon atom number 1~12 of methyl, ethyl etc.；The carbon of methoxyl group, ethyoxyl etc. The alkoxy of atomicity 1~12；Nitro；The halogen atom of fluorine atom, chlorine atom etc. and fragrant ring group etc..

In addition, the alkyl as substituent group, refers to the situation that alkyl is incorporated in fragrant ring group as substituent group, as taking The fragrant ring group of Dai Ji, such as refer to the situation etc. that aromatic heterocycle is incorporated on aromatic ring alkyl as substituent group.

Fragrant ring group with substituent group, according to the position of substituent group, there are various isomers, can be any number of.Example Such as, as the isomers of substituted-phenyl, 2-, 3- or 4- aminomethyl phenyl, 2- can be enumerated, 3- or 4- ethylphenyl etc. has carbon former 2-, 3- or the 4- alkyl phenyl of the alkyl of subnumber 1~12；2-, 3- or 4- methoxyphenyl, 2-, 3- or 4- ethoxyl phenenyl etc. The alkoxy with carbon atom number 1~12 2-, 3- or 4- alkoxyl phenyl；2-, 3- or 4- nitrobenzophenone；2-, 3- or 4- Fluorophenyl, 2-, 2-, 3- or the 4- halogenophenyl etc. with halogen atom of 3- or 4- chlorphenyl etc., can be therein any number of.

Carbon atom number possessed by alkyl possessed by oxalate diester of the present invention, based on by carbonic acid two of the invention It is preferably more in terms of the stability of the group of disengaging when ester is used as the raw material of manufacture polycarbonate etc., but it is based on disengaging Group recycling be easy aspect, it is preferably less.

Specifically, have substituent group when, include substituent group, preferably 1 or more, more preferably 2 or more, on the other hand, it is excellent 12 are selected as hereinafter, more preferably 10 or less.

Wherein, particularly, by obtained diphenyl carbonate be used for polycarbonate manufacture when etc., most preferably unsubstituted benzene Base.

Diaryl esters of oxalic acid (oxalate diester as alkyl with 2 fragrant ring groups), can be used such as following reaction equations (3) The shown substance etc. by the manufacture of the ester exchange reaction of dialkyl oxalate and aromatic hydroxy compound.

Herein, it as the dialkyl oxalate of raw material, can be used as shown in following reaction equations (4) by with an oxidation Carbon, oxygen and aliphatic alcohol are the substance etc. that the oxidation carbonylation of raw material manufactures.

[changing 4]

In formula, R indicates that alkyl, Ar indicate fragrant ring group.

[changing 5]

In formula, R indicates alkyl.

In the manufacturing method of carbonic diester of the invention, using phenostal as raw material in use, the phenostal Preferably comprise 0.076 weight % or more, the carboxylic acid phenyl ester that the following general formula (5) of 10 weight % amounts below indicates.In addition, careless The amount of carboxylic acid phenyl ester contained by diphenyl phthalate is preferably greater than 1 weight %.

In addition, the amount of carboxylic acid phenyl ester contained by phenostal refers to, the total amount and carboxylic acid relative to phenostal The total amount of the carboxylic acid phenyl ester of the total amount of the total amount of phenylester.

[changing 6]

In formula, n is 1 or 2.

As the carboxylic acid phenyl ester that above-mentioned general formula (5) indicate, due to being easy to reduce phenol, preferably: by phenostal It is reset by Fu Laisi (Fries) and the phenyl (to phenyloxycarbonyl phenyl) of general formula (6) expression of the generations such as polycondensation is careless Phenyl (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) that acid esters (PCPO) or general formula (7) indicate etc. phenyl (to (or It is adjacent) phenyloxycarbonyl phenyl) oxalate, and, it is given birth to by diphenyl carbonate by Fu Laisi (Fries) rearrangement and polycondensation etc. At general formula (8) indicate phenyl (to phenyloxycarbonyl phenyl) carbonic ester (PCPC) or general formula (9) indicate phenyl (adjacent benzene oxygen Base carbonyl phenyl) carbonic ester (OCPC) etc. phenyl (to (or adjacent) phenyloxycarbonyl phenyl) carbonic ester.

[changing 7]

Carboxylic acid phenyl ester is by-product when manufacturing phenostal by the ester exchange reaction of dialkyl oxalate and phenol. Therefore, the phenostal containing 0.076 weight % or more, the carboxylic acid phenyl ester of 10 weight % amounts below, can be by will be sharp With the obtained phenostal distilation of the ester exchange reaction of dialkyl oxalate and phenol, so that carboxylic acid phenyl ester becomes Above range, to obtain.

Herein, above-mentioned carboxylic acid phenyl ester is usually higher than phenostal boiling point.Therefore, can by from utilize oxalic acid dialkyl group The obtained phenostal of the ester exchange reaction of ester and phenol mainly only removes the substance than phenostal low boiling point and obtains It arrives.

In addition, when that will be purified by the obtained phenostal of ester exchange reaction of dialkyl oxalate and phenol, If accidentally the high ingredient of continued proportion phenostal boiling point also removes, there are the amounts of the carboxylic acid phenyl ester contained by phenostal It can become the situation fewer than above-mentioned lower limit.

[de- carbonylic catalyst]

Catalyst used in the manufacturing method of carbonic diester of the invention is (hereinafter, sometimes referred to as " of the present invention de- Carbonylic catalyst ", " de- carbonylic catalyst " or " catalyst "), the chemical valence that can enumerate phosphorus atoms is the organic of trivalent or 5 valences Phosphorus compound etc..The chemical valence of phosphorus atoms is the organic phosphorus compound of trivalent or 5 valences, preferably has at least one carbon-phosphorus (C-P) key Organic phosphorus compound, more preferably with the organic phosphorus compound of 3 or more carbon-phosphorus (C-P) key.

As such organic phosphorus compound, example such as phosphonium salt system organic phosphorus compound (following, also referred to as phosphonium salt), phosphine can be lifted It is organic phosphorus compound, dihalide phosphine system's organic phosphorus compound and phosphine oxide system organic phosphorus compound etc..Wherein, as this hair The bright de- carbonylic catalyst being related to, it is excellent to select phosphonium salt system organic phosphorus compound.

Phosphonium salt system organic phosphorus compound general formula (A) Biao Shi phosphonium salt preferably below.

[changing 8]

In formula, R¹、R²、R³And R⁴Each independently represent fragrant ring group, aralkyl or the alkyl that there can be substituent group, X Indicate can Xing Cheng phosphonium salt ion balance atom or atomic group.

As the fragrant ring group of the general formula (A), the virtue of the carbon atom number 6~14 of phenyl, xenyl, naphthalene etc. can be enumerated The carbon atom number 4~16 containing sulphur atom, oxygen atom or nitrogen-atoms of fragrant race's alkyl and thienyl, furyl, pyridyl group etc. Aromatic heterocycle etc..

As the aralkyl, the carbon with unsaturated bond of benzyl, phenethyl, cinnamyl, menaphthyl etc. can be enumerated The aralkyl etc. of atomicity 7~15.

As the alkyl, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, cyclopropyl, ring can be enumerated Amyl, cyclohexyl, suberyl, cyclohexyl methyl, vinyl, acrylic, cyclobutenyl, 1,3- butadienyl etc. have ring knot The alkyl etc. of the carbon atom number 1~16 of structure or unsaturated bond.

The R of the general formula (A)¹~R⁴Including various isomers, there can be 1 or more substituent group.

As the substituent group, can illustrate as (preferably carbon is former for alkoxy (preferably carbon atom number 1~12), thio alkoxy Subnumber 1~12), aralkoxy (preferably carbon atom number 7~13), aryloxy group (preferably carbon atom number 6~16), thio-aryloxy (preferably carbon atom number 6~16), acyl group (preferably carbon atom number 1~12), alkoxy carbonyl (preferably carbon atom number 2~16), carboxylic Base, amino, alkyl-substituted amino (preferably carbon atom number 2~16), nitro, cyano, hydroxyl, halogen atom (fluorine, chlorine, bromine etc.) Deng.In addition, these substituent groups can further have substituent group that can enumerate halogen atom etc. as its substituent group.

In addition, the R of the general formula (A)¹~R⁴When for phenyl with substituent group, there are various isomers.It is different as these Structure body, can illustrate as 2- (or 3-, 4-) aminomethyl phenyl, 2- (or 3-, 4-) ethylphenyl, 2,3- (or 3,4-) 3,5-dimethylphenyl, The alkyl or halogen of the carbon atom number 1~12 of 2,4,6- trimethylphenyl, 4- trifluoromethyl, 3,5- bis trifluoromethyl phenyl etc. Change alkyl and is incorporated in the alkyl phenyl on phenyl；The carbon atom number 1~12 of 3- methoxyphenyl, 2,4,6- trimethoxyphenyl etc. Alkoxy be incorporated in the alkoxyl phenyl on phenyl；The halogen atom of 3- (or 4-) chlorphenyl, 3- fluorophenyl etc. is incorporated in phenyl On halogenophenyl etc..

The R of the general formula (A)¹~R⁴When for fragrant ring group, they, can be on its ring as taking except the substituent group Dai Ji has 1 or more alkyl (preferably carbon atom number 1~12), which can have ring knot Structure (containing heterocycle) or unsaturated bond.In addition, R¹~R⁴When for aromatic heterocycle, they, can be miscellaneous at its except the substituent group There is 1 or more aromatic ring alkyl (preferably carbon atom number 6~16) as substituent group on ring.

The R of the general formula (A)¹~R⁴Mutually it may be the same or different.In addition, can be between 2 groups Key or crosslinking.But based on dissolubility aspect, R¹~R⁴Any 1 group preferably and any of other 3 groups All different groups.Herein, different groups refers to, includes the case where that the presence or absence of substituent group, type, the position of substitution are different, phase Mutually any different group.In addition, in the present invention, like this by R¹~R⁴At least any 1 group and other 3 groups At least the different situation of any one group is known as " asymmetric ".

Ion balance X as the general formula (A)^-, the halogen ion and two of chloride ion, bromide ion, iodide ion etc. can be enumerated The halogenation hydride ion etc. of chlorination hydrogen ion, dibrominated hydrogen ion, diiodinating hydrogen ion, chlorine bromination hydrogen ion etc..Wherein, this hair In the bright de-carbonyl reaction being related to, since the catalyst as high activity is easy to work, the preferred halogen ion of X, more preferable chlorine from Son.

As You Xuan phosphonium salt system organic phosphorus compound, specifically, the compound that can be exemplified below.That is, as described logical The R of formula (A)¹~R⁴All it is the organic chloride phosphine of unsubstituted aromatic hydrocarbyl, tetraphenylphosphonium chloride can be enumerated, to xenyl three Tetraphenylphosphonium chloride phosphine, 1- naphthalene triphenyl phosphine dichloride, 2- naphthalene triphenyl phosphine dichloride etc..

R as the general formula (A)¹~R⁴For unsubstituted aromatic hydrocarbyl or aromatic hydrocarbyl with substituent group Organic chloride phosphine can enumerate o-methyl-phenyl triphenyl phosphine dichloride, aminomethyl phenyl triphenyl phosphine dichloride, p-methylphenyl triphen Base phosphonium chloride, p-isopropyl phenyl triphenyl phosphine dichloride, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, m-trifluoromethylphenyl triphenyl The compound with the aromatic hydrocarbyl containing alkyl of phosphonium chloride, 2,4,6- trimethylphenyl triphenyl phosphine dichloride etc.；To chlorobenzene The compound of the aromatic hydrocarbyl with halogen atom of base triphenyl phosphine dichloride etc.；M-methoxyphenyl triphenyl phosphine dichloride, P-methoxyphenyl triphenyl phosphine dichloride has the aromatic hydrocarbyl containing alkoxy to ethoxyl phenenyl triphenyl phosphine dichloride etc. Compound；The compound with amino-containing aromatic hydrocarbyl of p-aminophenyl triphenyl phosphine dichloride etc.；Between cyano-phenyl Triphenyl phosphine dichloride, to the compound of the aromatic hydrocarbyl with cyano-containing of cyano-phenyl triphenyl phosphine dichloride etc. and to nitre The compound etc. with the aromatic hydrocarbyl containing nitro of base phenyl-three-p-methylphenyl phosphonium chloride etc..

R as the general formula (A)¹~R⁴All be the organic chloride phosphine of aralkyl, can enumerate benzyl triphenyl phosphonium chloride phosphine with And phenethyl triphenyl phosphine dichloride etc..R as the general formula (A)¹~R⁴All it is the organic chloride phosphine of alkyl, tetrem can be enumerated Base phosphonium chloride, tetrabutylphosphonium chloride, cetyltributylphosphonium phosphonium chloride etc..

R as the general formula (A)¹~R⁴For aromatic hydrocarbyl or the organic chloride phosphine of alkyl, methyl triphenyl can be enumerated Phosphonium chloride, ethyltriphenyl phosphonium chloride phosphine, propyl triphenyl phosphine dichloride, butyltriphenylphosphonium chloride phosphine, hexyltriphenylphosphonium phosphonium chloride, heptan Base triphenyl phosphine dichloride, myristyl triphenyl phosphine dichloride, dimethyl diphenyl phosphonium chloride, allyl triphenyl phosphine dichloride etc. Alkyl triphenyl phosphonium phosphonium chloride；The alkyl triaryl phosphonium chloride with ring structure alkyl of cyclopropyl triphenyl phosphine dichloride etc.； The compound etc. with the alkyl containing unsaturated bond of 1,3- butadienyl triphenyl phosphine dichloride etc..In addition, as the general formula (A) R¹~R⁴For aromatic hydrocarbyl or the organic chloride phosphine of the alkyl with substituent group, (1,3- dioxolane-can be enumerated 2- yl) methyl triphenyl phosphonium chloride, 2- (1,3- dioxolane -2- base) ethyltriphenyl phosphonium chloride phosphine, 2- (1,3- dioxy six Ring -2- base) ethyltriphenyl phosphonium chloride phosphine etc. the compound with the alkyl containing heterocycle；Bromomethyl triphenyl phosphine dichloride etc. The compound of alkyl with halogen atom；4- carboxybutyl triphenyl phosphine dichloride, 2- carboxyallyl triphenyl phosphine dichloride etc. The compound with carboxylic alkyl；4- ethoxycarbonylbutyl triphenyl phosphine dichloride etc. has containing alkoxy carbonyl The compound of alkyl；The compound with the alkyl containing alkyl-substituted amino of 2- dimethylaminomethyl triphenyl phosphine dichloride etc. And the compound etc. with the alkyl containing acyl group of phenacyl triphenyl phosphine dichloride etc..

R as the general formula (A)¹~R⁴For aromatic hydrocarbyl or the organic chloride phosphine of aralkyl, benzyl triphen can be enumerated Base phosphonium chloride, 4- ethoxy benzyl triphenyl phosphine dichloride, cinnamyl triphenyl phosphine dichloride etc..

It is particularly preferably described in this little phosphonium salt systems organic phosphorus compound as de- carbonylic catalyst of the present invention The R of general formula (A)¹~R⁴It is all fragrant ring group, more preferable R¹~R⁴It is all aromatic hydrocarbyl.And it is particularly preferred to asymmetric four virtue Base halogenation phosphine, most preferably 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride.

In addition, sometimes by the R of the general formula (A)¹~R⁴It is all that aromatic rings Ji phosphonium salt system organic phosphorus compound is known as " four aryl halogenation phosphine of the present invention " or it is only called " four aryl halogenation phosphines ".

In addition, in the four aryl halogenation phosphine of the present invention, sometimes by particularly preferred R¹~R⁴For asymmetrical four virtue Base halogenation phosphine is known as " asymmetric four aryl halogenation phosphine of the present invention " or is only called " asymmetric four aryl halogenation phosphine ".

It is below logical as the preferred four aryl halogenation phosphine of the present invention of de- carbonylic catalyst of the present invention The compound that formula (10) indicates.

[changing 9]

In formula, Ar¹、Ar²、Ar³And Ar⁴The fragrant ring group that there can be substituent group is each independently represented, X indicates that halogen is former Son.

As Ar¹~Ar⁴Fragrant ring group, the aromatic series of the carbon atom number 6~14 of phenyl, xenyl, naphthalene etc. can be enumerated The virtue of the carbon atom number 4~16 containing sulphur atom, oxygen atom or nitrogen-atoms of alkyl and thienyl, furyl, pyridyl group etc. Fragrant race's heterocycle etc..Wherein, since catalyst, optimization aromatic alkyl, more preferable phenyl can be manufactured inexpensively.

Ar¹~Ar⁴Comprising various isomers, each fragrance ring group can have 1 or more substituent group.As the substituent group, It can illustrate as (preferably carbon is former for alkyl (preferably carbon atom number 1~12), alkoxy (preferably carbon atom number 1~12), thio alkoxy Subnumber 1~12), aralkoxy (preferably carbon atom number 7~13), aryloxy group (preferably carbon atom number 6~16), thio-aryloxy (preferably carbon atom number 6~16), acyl group (preferably carbon atom number 1~12), alkoxy carbonyl (preferably carbon atom number 2~16), carboxylic Base, amino, alkyl-substituted amino (preferably carbon atom number 2~16), nitro, cyano, hydroxyl, halogen atom (fluorine, chlorine, bromine etc.) Deng.In addition, these substituent groups can further have substituent group that can enumerate fragrant ring group and halogen atom etc. as its substituent group.

Wherein, due to hot upper stabilization, thus optimizing alkyl, the alkyl of more preferable carbon atom number 1~12, further preferably The alkyl of the branch of carbon atom number 3~8.Further, since catalyst thermostabilization, anti-as decarbonylation base of the invention using the substituent group Applications catalyst using when be difficult to decompose, thus the substituent group does not preferably have benzylic protons.That is, the particularly preferred carbon of the substituent group The alkyl without benzylic protons of atomicity 3~8, most preferably tert-butyl.

In addition, Ar¹~Ar⁴When for fragrant ring group with substituent group, there are various isomers, but Ar¹~Ar⁴It can be It is wherein any number of.As these isomers, such as Ar¹~Ar⁴When for phenyl with substituent group, 2- (or 3-, 4-) first can be enumerated Base phenyl, 2- (or 3-, 4-) ethylphenyl, 2,3- (or 3,4-) 3,5-dimethylphenyl, 2,4,6- trimethylphenyl, 4- trifluoromethyl The alkyl or halogenated alkyl of the carbon atom number 1~12 of phenyl, 3,5- bis trifluoromethyl phenyl etc. are incorporated in the alkylbenzene on phenyl Base；The alkoxy of the carbon atom number 1~12 of 3- methoxyphenyl, 2,4,6- trimethoxyphenyl etc. is incorporated in the alcoxyl on phenyl Base phenyl；2- (or 3-, 4-) nitrobenzophenone；The halogen atom of 3- (or 4-) chlorphenyl, 3- fluorophenyl etc. is incorporated in the halogen on phenyl For phenyl etc..

Ar¹~Ar⁴It can be mutual bonding or crosslinking between 2 groups.

In four aryl halogenation phosphine of the present invention, Ar¹~Ar⁴At least any 1 group it is preferably and 3 other At least any one different group of group.That is, asymmetric four aryl halogenation phosphine of the present invention is above-mentioned general formula (10) The compound of expression is Ar¹、Ar²、Ar³And Ar⁴For asymmetrical compound.

When four aryl halogenation phosphine of the present invention is asymmetric, due to Ar¹~Ar⁴At least any 1 group be and its At least any one different group of his 3 groups, thus dissolubility is excellent.

When four aryl halogenation phosphine of the present invention is asymmetric, Ar¹~Ar⁴Remaining 3 groups mutually can be identical, It can also be different.As asymmetric four aryl halogenation phosphine of the present invention, due to being easy to stabilize on hot, thus preferably Ar¹~Ar⁴It is all fragrant ring group, more preferable Ar¹~Ar⁴Any 1 be the fragrant ring group with substituent group, and be left 3 bases Group is unsubstituted fragrant ring group, particularly preferred Ar¹~Ar⁴At least any 1 be the aryl with substituent group, and it is remaining Group is unsubstituted aryl, most preferably Ar¹~Ar⁴Any 1 for substituent group phenyl, and remaining 3 groups are without taking The phenyl in generation.

The halogen atom X of general formula (10) is the halogen atom of chlorine atom, bromine atom, iodine atom etc..Wherein, of the present invention de- In carbonyl reaction, since the catalyst as high activity is easy to work, thus preferred chlorine atom.That is, of the present invention four Aryl halogenation phosphine preferably (can have substituent group) tetraphenylphosphonium chloride.In addition, four aryl halogenation phosphine of the present invention is preferred Without benzylic protons.That is, not having the asymmetric four aryl phosphonium chloride of benzylic protons particularly preferably.

As the preferred concrete example of four aryl halogenation phosphine of the present invention, following compound can be enumerated.That is, conduct Ar¹~Ar⁴It is unsubstituted aromatic hydrocarbyl, tetraphenylphosphonium chloride can be enumerated, to xenyl triphenyl phosphine dichloride, 1- naphthalene Triphenyl phosphine dichloride, 2- naphthalene triphenyl phosphine dichloride etc..

As Ar¹~Ar⁴For unsubstituted aromatic hydrocarbyl or the organic chloride phosphine of the aromatic hydrocarbyl with substituent group, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, m-benzotrifluoride base triphenyl phosphine dichloride etc. can be enumerated does not have benzylic protons and has The compound of aromatic hydrocarbyl containing alkyl；The aromatic hydrocarbyl with halogen atom of rubigan triphenyl phosphine dichloride etc. Compound；M-methoxyphenyl triphenyl phosphine dichloride, p-methoxyphenyl triphenyl phosphine dichloride, to ethoxyl phenenyl triphenyl chlorine Change the compound with the aromatic hydrocarbyl containing alkoxy of phosphine etc.；Having for p-aminophenyl triphenyl phosphine dichloride etc. contains amino Aromatic hydrocarbyl compound；Between cyano-phenyl triphenyl phosphine dichloride, to cyano-phenyl triphenyl phosphine dichloride etc. have contain The compound of the aromatic hydrocarbyl of cyano and p-nitrophenyl-three-p-methylphenyl phosphonium chloride etc. have the fragrance containing nitro The compound etc. of race's alkyl.

Wherein, four aryl halogenation phosphine of the present invention can preferably have the tetraphenylphosphonium chloride of substituent group.Furthermore it is preferred that Asymmetric four aryl phosphonium chloride (in above compound, compound) other than tetraphenylphosphonium chloride, particularly preferred 4- 2-methyl-2-phenylpropane base Triphenyl phosphine dichloride.

In addition, catalyst used in the manufacturing method of carbonic diester of the invention, particularly preferably above-mentioned asymmetric four virtue Base halogenation phosphine and hydrogen halides adduct (hereinafter, sometimes referred to as " asymmetric adduct of the present invention " or be only called it is " non-right Claim adduct ").In addition, sometimes referred to as the hydrogen halides be " hydrogen halides of the present invention ", the adduct be referred to as " the present invention relates to Adduct " or be only called " adduct ".

As hydrogen halides of the present invention, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide can be enumerated.It is of the present invention The halogen of hydrogen halides, due to be used for de-carbonyl reaction catalyst when etc., the type of by-product if the type increase of halogen Increase, reaction system is easy to complicate, therefore preferably identical with the above-mentioned halogen of four aryl halogenation phosphine of the present invention Halogen.

That is, hydrogen halides of the present invention, preferably hydrogen chloride, adduct of the present invention, preferably tetraphenylphosphonium chloride With the adduct of hydrogen chloride, the adduct of more preferable asymmetric tetraphenylphosphonium chloride and hydrogen chloride, particularly preferred 4- 2-methyl-2-phenylpropane base The adduct of triphenyl phosphine dichloride and hydrogen chloride.

In addition, adduct is normally used as meaning the term of addition product crystallization and using.Adduct of the present invention leads to On Chang Si aryl halogenation phosphine addition have the solid of hydrogen halides or the substance after its melting or dissolved substance etc. also by comprising In adduct of the present invention.In general, relative to 1 mole of four aryl halogenation phosphine, adduction in adduct of the present invention There is 0.01~1.0 mole of hydrogen halides.That is, in adduct of the present invention, usually with molar ratio computing, relative to 100 part four Aryl halogenation phosphine, addition have 1~100 part of hydrogen halides.

In addition, about as the most preferred asymmetric adduct of the present invention of de- carbonylic catalyst of the present invention Preparation method, partial size and hygroscopicity etc., will be aftermentioned.

The type of de- carbonylic catalyst, can pass through elemental microanalysis method, mass analysis, nuclear magnetic resonance spectrometry and liquid phase The well known method of chromatography etc. is analyzed.Specifically, when such as the case where 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, pass through and utilize member Plain analytic approach, mass analysis and NMR spectrum are analyzed, and can confirm it is 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride.

In addition, the liquid chromatogram of the substance of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is identified as by measurement, benefit With liquid chromatography, can more easily confirm.About the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, firstly, It carries out as described above, confirmation contains 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, then, dense by chlorine contained by measurement adduct Degree, can calculate is and the adduct of hydrogen chloride and its adduction rate.

De- carbonylic catalyst of the present invention, is preferably soluble in carbonic diester.The reason for this is that because, carbon of the invention In the manufacturing method of acid diesters, by using the catalyst for dissolving in carbonic diester, the precipitation of catalyst can not be caused, turned with height Rate steadily carries out de-carbonyl reaction, reduces remaining oxalate diester amount, can inhibit the furan of the by-product when evaporating carbonic diester It mutters the generation of based compound.

In addition, supplied by state that catalyst is dissolved in carbonic diester, the unreacted oxalate diester after reaction compared with Less, contain the recycling of the catalyst liquid of carbonic diester with high concentration, thus the Fu Laisi (Fries) of oxalate diester, which is reset, generates The by-product of object bring phenol etc. is difficult to happen, and the carbonic diester of high-purity can be obtained.

It in the present invention, dissolves in carbonic diester and refers to, at 150 DEG C, for carbonic diester 100g, catalyst usually dissolves 10g or more, preferably dissolution 50g or more.In addition, the solubility the high the more preferred, but it is usually limited to 1000g thereon.Dissolve in carbonic acid The catalyst of diester can simply be selected by measuring it for the solubility of carbonic diester to above-mentioned de- carbonylic catalyst.

In addition, in general, with 1 or more alkyl Si Fang Ji phosphonium salt, since the solubility for carbonic diester is higher, because This is preferred.The quantity preferably 1 or more, 3 or less of alkyl possessed by Si Fang Ji phosphonium salt with 1 or more alkyl.Herein, Si Fang Ji phosphonium salt with 2 or more alkyl, can have 1 fragrance for containing 2 or more alkyl as substituent group Ring group, it is possible to have 2 fragrant ring groups for containing 1 or more alkyl as substituent group are easy, preferably due to synthesizing The latter.

In addition, asymmetric four aryl halogenation phosphine of the present invention, due to returning by aftermentioned catalyst of the invention Receiving method is easy the catalyst high efficiente callback of high-purity, thus preferably for the solubility of polar organic solvent and water compared with It is low.

On the other hand, asymmetric adduct of the present invention is held due to the recovery method of catalyst through the invention Easily by the catalyst high efficiente callback of high-purity, therefore, dissolution for water higher preferably for the solubility of polar organic solvent It spends lower.

Therefore, specifically, for the meltage of the aftermentioned polar organic solvent 100g of the present invention at 40 DEG C, It is preferred that asymmetric adduct of the present invention 0.5g or more more than asymmetric four aryl halogenation phosphine of the present invention, more preferably More 1.0g or more, particularly preferred more 1.5g or more.

That is, asymmetric four aryl halogenation phosphine of the present invention, at 40 DEG C, for aftermentioned polarity of the present invention Organic solvent 100g will not preferably dissolve 2.0g or more, will not more preferably dissolve 1.5g or more.

On the other hand, asymmetric adduct of the present invention, at 40 DEG C, for aftermentioned polarity of the present invention Organic solvent 100g, preferably dissolution 2.5g or more, more preferably dissolve 3.0g or more.

In addition, asymmetric four aryl halogenation phosphine of the present invention and asymmetric adduct of the present invention, 40 At DEG C, for pure water 100g, 2.5g or more will not be preferably dissolved, will not more preferably dissolve 2.0g or more.

About the relationship between these dissolubilities and catalyst recycling, in the preferred manufacturing method of aftermentioned carbonic diester In the 3rd process in be described in detail.

Furthermore, thus it is speculated that asymmetric adduct of the present invention, in the manufacturing method of carbonic diester of the invention, dissolution In the reaction solution of de-carbonyl reaction, while hydrogen halides is free, and asymmetric four aryl halogenation phosphine works as catalyst.Cause This, in the recovery method of aftermentioned catalyst of the invention, can similarly recycle asymmetric four aryl phosphonium chloride and its and chlorination The adduct of hydrogen.

The amount that carbonylic catalyst is taken off used in the manufacturing method of carbonic diester of the invention, in terms of being based on production efficiency, Reaction speed is easy to accelerate aspect, preferably more, but based on manufacturing cost and the catalyst in the purification process of carbonic diester It is difficult to that aspect is precipitated, it is preferably less.

Therefore, and specifically, it is preferable to be 1.0 weight % or more, more preferably 2.0 weight % or more, particularly preferably 3.0 weights Measure % or more, in addition, on the other hand, preferably 15.0 weight % hereinafter, more preferably 10.0 weight % hereinafter, more preferably 8.0 weight % or less.

In addition, taking off carbonylic catalyst relative to 1 mole of oxalate diester it is preferable to use 0.001 mole or more, more preferably using 0.01 mole or more, in addition, on the other hand, it is preferable to use 1 mole hereinafter, more preferably use 0.5 mole or less.

100 moles of total mole of de- carbonylic catalyst relative to oxalate diester and carbonic diester in reactor Preferably 0.001 mole or more of amount, more preferably 0.1 mole or more, in addition, on the other hand, preferably 50 moles hereinafter, more excellent It is selected as 20 moles or less.

In addition, catalyst can be used alone, with arbitrary ratio and can also be applied in combination a variety of, using more When kind, above-mentioned it is preferable to use amounts to indicate its total amount.In addition, referring to adduct and the adduct point when using adduct The total amount of solution and four aryl halogenation phosphines of generation.

In addition, supplying in the manufacturing method of carbonic diester of the invention to the phenostal and four aryl halides of reactor Change phosphine total amount relative quantity, due to the total amount of reactor medium-height grass diphenyl phthalate and four aryl halogenation phosphines easily become it is above-mentioned Preferred range, therefore relative to 100 moles of phenostal, preferably set the total amount of four aryl halogenation phosphines as 0.1 mole with On, it is more preferably set as 1 mole or more, in addition, on the other hand, being preferably set to 50 moles hereinafter, being more preferably set as 20 moles or less.

[halogen compounds]

It is excellent due to being easy to maintain de-carbonyl reaction with high selectivity in the manufacturing method of carbonic diester of the invention Choosing is used together halogen compounds (hereinafter sometimes referred to " halogen compounds of the present invention ") with de- carbonylic catalyst.

When using phosphine or phosphine oxide particularly as organic phosphorus compound, or use other than halide and dihalide hydrogen When phosphonium salt, or using low concentration halogenation phosphine or dihalide hydrogen phosphine when, preferably there is halogen compounds.

As halogen compounds of the present invention, following inorganic halogen compounds and/or organic halogen can be enumerated Close object etc..In these halogen compounds, preferably chlorine compound or bromine compounds, wherein particularly preferred chlorine compound.

Halogen compounds can use in the following way: relative to de- carbonylic catalyst, molar ratio (halogen compounds/de- Carbonylic catalyst) it is usually 0.0001 or more, preferably 0.001 or more, more preferable 0.01 or more, particularly preferred 0.1 or more, this Outside, on the other hand, usually 300 hereinafter, it is preferred that 100 hereinafter, more preferable 3.00 hereinafter, particularly preferred 1.00 or less.In addition, halogen Plain compound can be used alone, can also by a variety of arbitrary ratio and to be applied in combination, using it is a variety of when, it is above-mentioned It is preferable to use amounts to indicate its total amount.

As inorganic halogen compounds, the halide for such as aluminium of aluminium chloride, aluminium bromide that can illustrate；Platinum chloride, chloroplatinic acid, The halide of the platinum group metal of ruthenic chloride, palladium chloride etc.；Phosphorus trichloride, phosphorus pentachloride, phosphorous oxychloride, phosphorus tribromide, pentabromo- Change the halide of the phosphorus of phosphorus, phosphorus oxybromide etc.；The hydrogen halides of hydrogen chloride, hydrogen bromide etc.；Thionyl chloride, sulfonic acid chloride, dichloride The halide of the sulphur of sulphur, disulphur dichloride etc.；Halogen monomer of chlorine, bromine etc. etc..

As organohalogen compound, can enumerate by carbon atom, chlorine atom, bromine atom etc. halogen atom and from hydrogen atom, The compound etc. that at least one kind of atom selected in oxygen atom, nitrogen-atoms, sulphur atom and silicon atom is constituted.

As such organohalogen compound, it is preferable to use for example with the structure for being combined with halogen atom in saturated carbon (C-Hal), be combined in carbonyl carbon the structure (- CO-Hal) of halogen atom, be combined on the silicon atoms halogen atom structure (- C-Si-Hal) or on sulphur atom it is combined with the structure (CSO of halogen atom₂- Hal) organohalogen compound.Wherein, Hal Indicate the halogen atom of chlorine atom, bromine atom etc..These structures, such as it is expressed as general formula (a), (b), (c), (d).

[changing 10]

In formula, Hal indicates the halogen atom of chlorine atom, bromine atom etc., n¹Integer, n for 1~4²Indicate 1~3 integer.

It, can concrete example compound as follows as organohalogen compound.

As organic halogen with structure as represented by general formula (a), to be combined in saturated carbon halogen atom Plain compound can enumerate the alkyl halide of chloroform, carbon tetrachloride, 1,2- dichloroethanes, chlorobutane, chlorinated dodecane base etc.；Chloromethane The araalkyl of the bromo- ortho-xylene of benzene, benzotrichloride, triphenylchloromethane, α-etc.；The halogen of β-chloroethyl nitrile, γ-chlorobutyronitrile etc. Replace aliphatic nitrile；The halogen of monoxone, bromoacetic acid, chloropropionic acid etc. replaces aliphatic carboxylic acid etc..

As having structure organic halogen as general formula (b) indicates, to be combined in carbonyl carbon halogen atom Object is closed, chloroacetic chloride, ethanedioly chloride, propionyl chloride, stearyl chloride, chlorobenzoyl chloride, 2- naphthalene-carboxylic acid acyl chlorides, 2-Thiophene Carboxylic Acid acyl can be enumerated The acyl halide of chlorine etc., the Haloacetaldehydes acid aryl ester of oxalyl chloride phenyl ester etc., halogen formate aromatic ester of phenyl chloroformate etc. etc..

As at least having with 1 structure as general formula (c) indicates, being combined with halogen atom on the silicon atoms Machine halogen compounds can enumerate the halogenated silane etc. of diphenyl dichlorosilane, tri-phenyl chloride etc..

As the organic halogen with structure as general formula (d) indicates, to be combined on sulphur atom halogen atom Compound can enumerate the sulfonyl halide etc. of paratoluensulfonyl chloride, 2- naphthalene sulfonyl chloride etc..

As organohalogen compound, in addition, the hydrogen halides of the salt containing nitrogen-atoms or phosphorus atoms can be enumerated Addition product etc..Specifically, ammonium salt hydrogen halides addition product, phosphonium salt hydrogen halides addition product etc. can be enumerated.

Wherein, it is easy aspect, preferably hydrogen chloride and organohalogen compound based on starting with, more preferably there is general formula (a) The organohalogen compound of the structure that halogen atom is combined in saturated carbon indicated, particularly preferred alkyl halide, most preferably chloroform.

In addition, based in terms of the by-product that can inhibit from halogen compounds, preferred inorganic halogen compounds, more preferable halogen Change hydrogen, particularly preferred hydrogen chloride.Further, since the type of by-product increases when the type of existing halogen increases in reaction system Add, reaction system is easy to complicate, therefore the halogen of preferably halogen compounds of the present invention is and halogen of the present invention Change the identical halogen of halogen of the halogen and adduct of the present invention of hydrogen.

That is, particularly preferred adduct of the present invention is the adduct of four aryl phosphonium chlorides and hydrogen chloride, the present invention is related to And halogen compounds be hydrogen chloride.Moreover, adduct most preferably of the present invention is asymmetric four aryl phosphonium chloride and chlorine Change the adduct of hydrogen, halogen compounds of the present invention is hydrogen chloride.

[de-carbonyl reaction]

De-carbonyl reaction in the manufacturing method of carbonic diester of the invention is (hereinafter, sometimes referred to as " of the present invention de- Carbonyl reaction " is only called " de-carbonyl reaction ") preferably carried out by liquid phase reactor.In addition, using carbonic diester is dissolved in When catalyst, catalyst preferably is supplied to be dissolved in the state of carbonic diester, is more preferably supplied with the state for being dissolved in carbonic diester To reactor, particularly preferably catalyst contained by the reaction solution after reaction is directly carried out with the state for being dissolved in carbonic diester It recycles.

The reaction temperature of de-carbonyl reaction, based on preferably high temperature, but the purity based on carbonic diester in terms of reaction speed Aspect is preferably low temperature.Therefore, when normal pressure, preferable reaction temperature is usually 100 DEG C or more, especially 160 DEG C or more, especially 180 DEG C or more.In addition, on the other hand, usually 450 DEG C hereinafter, it is preferred that 400 DEG C hereinafter, more preferable 350 DEG C hereinafter, further The boiling point of preferable oxalate diester hereinafter, and specifically, it is preferable to 340 DEG C hereinafter, particularly preferred 320 DEG C hereinafter, most preferably 300 DEG C with Under.

Pressure when reaction is determined by the important document in process.But the by-product based on impurity is difficult to happen, and is held It is easy to get to the carbonic diester of high-purity, therefore is preferably carried out under specific pressurized conditions.That is, it is preferred that make de-carbonyl reaction than It is reacted under normal pressure (absolute pressure 0.109MPa) condition of high voltage.

And specifically, it is preferable to which absolute pressure is 0.105MPa or more, 10MPa or less.In addition, more preferably 0.110MPa with On, further preferably 0.130MPa or more, particularly preferably 0.150MPa or more, in addition, on the other hand, preferably 8MPa with Under, particularly preferably 5MPa or less.In addition, decompression is lower when carrying out de-carbonyl reaction, be typically due to maintain decompression state and Using vacuum pump, therefore absolute pressure is usually 0.990MPa or less.

The control of pressure when reaction preferably passes through the adjustment of the discharge rate of the carbon monoxide of by-product in de-carbonyl reaction It carries out.That is, one being aoxidized by this it is preferred that at least part of the carbon monoxide of by-product in de-carbonyl reaction is discharged from reactor The discharge rate of carbon, adjust de-carbonyl reaction when absolute pressure control.

Specifically, such as by pressure-control valve etc. it controls, so that the discharge pressure of carbon monoxide is relative to above-mentioned decarbonylation Pressure when base reacts is 0.9 times~1.1 times or so.In addition, discharged carbon monoxide is preferably from reaction solution gas-liquid naturally Separation.

In addition, discharged carbon monoxide, original when preferably as by nitrous acid ester and carbon monoxide manufacture oxalate diester Material utilizes.(for example, referring to the method for the records such as the flat 10-152457 bulletin of Japanese Laid-Open).

That is, it is preferred that by least part of the carbon monoxide of by-product in de-carbonyl reaction, as by nitrous acid ester and an oxygen Raw material when changing carbon manufacture oxalate diester uses, and more preferably sets using the carbon monoxide of the by-product as oxalic acid two manufactured by raw material Manufacture raw material of the ester as carbonic diester.

It is preferred that on one side from the lower part of reactor with superficial linear velocity 0.00001ms^-1The above 0.01ms^-1It is following to de- Carbonyl reaction supply non-active gas is (hereinafter, sometimes referred to as " non-active gas of the present invention " or be only called that " present invention relates to And gas "), carry out de-carbonyl reaction on one side.

The inert gas, nitrogen, carbon monoxide etc. of argon etc. can be used in non-active gas.When using carbon monoxide, preferably make With the carbon monoxide of by-product in de-carbonyl reaction of the present invention.In addition, it is anti-to carry out decarbonylation base with multi-groove type flow reactor At once, the carbon monoxide generated in the reactor of leading portion can be supplied together with reaction solution to the reactor of back segment.

Herein, when by the way that phenol, carbon dioxide, hydrogen halides will be contained in carbon monoxide obtained from reaction solution gas-liquid separation Deng impurity when, it is preferable to use absorption tower or washer etc. purification after use.Furthermore it is preferred that non-active gas uses air blower etc. It is recycled, more efficiently.

It since de-carbonyl reaction of the present invention is the endothermic reaction, preferably stirs on one side, so that fast in reactor Speed and equably heat, reacted on one side.Therefore, in de-carbonyl reaction of the present invention, by by non-active gas from The lower part of reactor supplies, and thus the time of contact between gas and reaction solution is elongated, while effectively stirring, can make to take off The phenol of by-product gasifies and removes when carbonyl reaction.

That is, by by non-active gas from the supply of the lower part of reactor, stirring, can be without stirring wing or with smaller In stirring wing stirred reactor.Additionally it is believed that: by remove by-product phenol, can be improved the reaction speed of de-carbonyl reaction with And conversion ratio.

In addition, reactor lower part, typically refers to more lower compared to the central part in the short transverse of the reaction solution in reactor Side.Further, it from the supply of the gas of reactor lower part, is preferably supplied from the position near the central part of reactor lower part.

The supply of reaction raw materials from the position near the central part of reactor lower part it is also preferred that supply.Because pair can be passed through The carbon monoxide of production effectively stirs the raw material oxalate diester locally got higher near the supply mouth of reaction raw materials.In addition, in court To in the supply mouth of the gas of reactor lower part, check-valves etc. is preferably provided with so that liquid is difficult to leak out.The amount of the gas of supply, Based on while being stirred to react liquid, the phenol in reaction solution is easy gasification aspect together, preferably more.

In addition, the present inventors has found that in de-carbonyl reaction of the present invention, hydrogen halides can be from general formula (10) sometimes It volatilizees in the four aryl halogenation phosphines indicated；If carrying out de-carbonyl reaction under reduced pressure, which increases；And if halogen Measure less, the then conversion ratio reduction of the phenostal in de-carbonyl reaction.

When therefore, based on the higher halogen compounds of volatility for using hydrogen chloride etc., it is difficult to the aspect that gasified together, It is preferred that the amount of the gas supplied is less.Therefore, when supply gas, preferably with superficial linear velocity 0.00001ms^-1More than 0.01m·s^-1It supplies below.Supply amount is more preferably 0.0001ms^-1More than, particularly preferably 0.005ms^-1Below.

In addition, gas internal circulating load (3~30 times of appearances of the carbon monoxide of generation in Japanese Laid-Open flat No. 11-246487 280NL/hr in amount and embodiment 1), if being scaled superficial linear velocity, the internal volume based on estimating device is 1 liter of appearance Amount, internal diameter 100mm or so are estimated as 0.018ms^-1Left and right.

In addition, when by making oxalate diester carry out de-carbonyl reaction in the presence of a catalyst to manufacture carbonic diester, Usually the oxalic acid as reaction raw materials is supplied from the top of reactor as flat No. 10-158222 Fig. 1~3 of Japanese Laid-Open Diester.

But in de-carbonyl reaction of the present invention, if by non-active gas together with reaction raw materials under reactor Portion's supply, then more efficiently.In addition, the gas of supply and the carbonic diester of manufacture, preferably take out from reactor top.

Based on high-efficiency stirring and it is easy to carry out the gasification aspect of phenol, the bubble diameter of gas is preferably smaller, and specifically, it is preferable to For 50mm hereinafter, more preferably 10mm or less.Gas sparger or mixer etc. can be used to carry out for the control of bubble diameter. Aperture at this time, preferably 10mm are hereinafter, more preferably 5mm or less.

De-carbonyl reaction can be batch reactions, be also possible to successive reaction, industrially, preferred successive reaction, due to holding It is easy to do into high conversion, is more preferably reacted and is carried out with continuous multi-stage, particularly preferably supplies non-active gas as described above on one side, Its at least one reaction is carried out on one side.About the conventional method of successive reaction, the flat 10-109962 public affairs of Japanese Laid-Open can be used Methods of records such as report, the flat 10-109963 bulletin of Japanese Laid-Open and Japanese Laid-Open 2006-89416 bulletin etc..

When being reacted with the temperature more than fusing point for the substance of reaction, what de-carbonyl reaction did not use solvent must The aprotic polar solvent wanting, but also can be properly used sulfolane, N-Methyl pyrrolidone, methylimidazole alkanone etc., Hydrocarbon solvent, aromatic hydrocarbon solvents etc..

The material of reactor, without special as long as the de-carbonyl reaction that can be related to through the invention generates carbonic diester Limitation.Due in side reaction, generating the aromatic monohydroxy compound of phenol etc., therefore the gold of preferably acid resistance material sometimes Belong to container or enamel container.The form of reactor, as long as the de-carbonyl reaction that can be related to through the invention makes carbonic acid two Ester generates, and any type of reactor can use.As such reactor, such as the complete of 1 slot or multi-groove type can be used Full hybrid reactor (stirred tank), tower reactor etc..

In de-carbonyl reaction of the present invention, based on being difficult to generate the impurity as caused by the side reaction of oxalate diester, anti- The excellent aspect of efficiency is answered, the conversion ratio of oxalate diester is preferably higher.Specifically, the conversion ratio of oxalate diester is preferably set to 96 weights % or more is measured, 97 weight % or more is more preferably set as, is further preferably set as 98 weight % or more, is particularly preferably set as 99 weights Measure % or more.In addition, the upper limit of the conversion ratio of oxalate diester, according to the solubility for carbonic diester of catalyst etc., not It can cause suitably select in the range of occluding as caused by the precipitation of catalyst etc., but most preferably 100 weight %.

In addition, herein, the conversion ratio of oxalate diester can calculate as described below.

Firstly, setting the conversion ratio of oxalate diester as the amount of the reaction solution after x [%], reaction is y [g], oxalate diester and carbon Total charge of acid diesters and catalyst is sum [g].

Herein, the amount [g] of the carbon monoxide generated in de-carbonyl reaction is " charge [mole] of oxalate diester " × " x [%]/100 " × " molecular weight of carbon monoxide ".

In addition, the amount y [g] of the reaction solution after reaction is " sum [g] "-" production quantity [g] of carbon monoxide ".

Therefore, y [g]=(" sum [g] ")-(" charge [mole] of oxalate diester " × " x [%]/100 " × " oxidation The molecular weight of carbon ").

In addition, the amount [g] of the oxalate diester after reaction is, " y [g] " × " concentration [weight of the oxalate diester after reaction Measure %]/100 "=" charge [g] of oxalate diester " × (100-x [%])/100.

It is as described below if merging two calculating formulas.

(" sum [g] "-" charge [mole] of oxalate diester " × " x [%]/100 " × " molecular weight of carbon monoxide ") × " concentration [weight %]/100 of the oxalate diester after reaction "=" charge [g] of oxalate diester " × (100-x [%])/ 100

It is as described below if both sides are multiplied by 100.

(" sum [g] "-" charge [mole] of oxalate diester " × " x [%]/100 " × " molecular weight of carbon monoxide ") × " concentration [weight %] of the oxalate diester after reaction "=" additive amount [g] of oxalate diester " × (100-x [%])

It is as described below if the formula is unfolded.

" sum [g] " × " concentration [weight %] of the oxalate diester after reaction "-" charge [mole] of oxalate diester " × " x [%]/100 " × " molecular weight of carbon monoxide " × " concentration [weight %] of the oxalate diester after reaction "=" oxalate diester Charge [g] " × 100- " charge [g] of oxalate diester " × " x [%] ")

It herein, is as described below if being solved about x [%].

" sum [g] " × " concentration [weight %] of the oxalate diester after reaction "-" charge [g] of oxalate diester " × 100 =" charge [mole] of oxalate diester " × " x [%]/100 " × " molecular weight of carbon monoxide " × " oxalic acid two after reaction The concentration [weight %] of ester "-" charge [g] of oxalate diester " × " x [%] "

X [%]=(" sum [g] " × " concentration [weight %] of the oxalate diester after the reaction "-" charge of oxalate diester [g] " × 100) ÷ " charge [mole] of oxalate diester " × " x [%]/100 " × " molecular weight of carbon monoxide " × " reaction The concentration [weight %] of oxalate diester afterwards "-" charge [g] of oxalate diester ")

[taking-up of carbonic diester]

By above-mentioned de-carbonyl reaction, carbonic diester corresponding with raw material oxalate diester can be made to generate.Carbon of the invention Acid diesters, 2 R in carbonic diester preferably generated in above-mentioned reaction equation (1) are the compound of fragrant ring group, more preferably 2 R are the compound of aromatic ring alkyl, and particularly preferred 2 R are the diphenyl carbonate of phenyl.

In the manufacturing method of carbonic diester of the invention, preferably by steaming carbonic diester contained by the reaction solution after reacting It sends out (hereinafter, be sometimes referred to as " evaporation of the present invention " or be only called " evaporation ") and takes out.If evaporating carbonic diester, When containing high boiling substance in the reaction solution after de- carbonylic catalyst and reaction, it can also remain in reaction solution together.Cause This, is taken out and evaporating carbonic diester from the reaction solution after reaction, can make carbonic diester and de- carbonylic catalyst and height Boilers separation.

In terms of improving the rate of recovery of carbonic diester, obtaining the catalyst liquid of high concentration, the enrichment factor of carbonic diester (steams Hair rate) it is preferably higher.Herein, as catalyst of the present invention, when using the catalyst for dissolving in carbonic diester, even if making A large amount of carbonic diester evaporation is also difficult to be precipitated.It is therefore preferable that the 50 weight % by making carbonic diester contained in reaction solution It evaporates and takes out above.

The distillation of diphenyl carbonate separates, and can carry out in the reactor for carrying out de-carbonyl reaction, can also be by reaction solution Move to vaporising device progress.It is not particularly limited about vaporising device (method of evaporating) as long as above-mentioned purpose can be reached.

As vaporising device, due to being easy to separate in a short time, thus preferably for example using downward film evaporator, film Formula evaporator etc. carries out.In addition, bumping is slowlyed with being preferably difficult to happen bumping while stirring to be subtracted when evaporating in reactor Pressure, is allowed to evaporate on one side.

Time required for separating also is influenced by the shape of heat transfer efficiency and separation vessel, but is based on being difficult to cause impurity By-product in terms of, preferably carry out in a short time, preferably 20 hours hereinafter, more preferable 15 hours hereinafter, particularly preferred 10 hours Below.

In terms of based on the by-product for being difficult to happen impurity, preferably carried out under low-temp low-pressure.Pressure is preferably evaporated under reduced pressure, Specifically, the preferred 0.1kPaA or more of pressure, more preferable 0.2kPaA or more, on the other hand, preferably 50kPaA is hereinafter, more preferably 20kPaA or less.

Further, it is carried out below reaction temperature of the temperature preferably in de-carbonyl reaction.Specifically, it is usually preferred to 100 DEG C or more, particularly preferred 160 DEG C or more, particularly preferred 180 DEG C or more, furthermore, it is usually preferred to which 450 DEG C hereinafter, particularly preferred 400 DEG C hereinafter, particularly preferred 350 DEG C or less.

[purification of carbonic diester]

Contain carbonic diester, de- carbonylic catalyst and unreacted oxalate diester in reaction solution after de-carbonyl reaction. In addition, existing also other than it containing rearrangement, the decomposition, reaction by oxalate diester, carbonic diester, de- carbonylic catalyst etc. Deng and generate by-product etc. a possibility that.

As by-product, the aromatic monohydroxy compound for such as phenol that can illustrate, passes through oxalic acid at 4- chlorobenzoic acid phenyl ester The Fu Laisi (Fries) of diphenyl ester resets the carboxylic acid phenyl ester generated and the decarbonylated reaction by reaction equation below (11) The furans based compound etc. of the benzofuran -2,3- diketone of generation etc..

In addition, can also enumerate the aromatic monohydroxy compound of phenol etc., 4- chlorobenzoic acid phenyl ester etc..Use above-mentioned halogen When plain compound, there is also contain the halogen compounds or its by-product.As the carboxylic acid phenyl ester of by-product, can lift Phenyl (to the phenyloxycarbonyl phenyl) carbonic ester (PCPC) etc. that above-mentioned formula (8) indicates out.

[changing 11]

Therefore, the carbonic diester obtained by above-mentioned carbonyl reaction, in order to be made into purity corresponding with purposes and form, Suitably purified.

In addition, in de-carbonyl reaction by-product carbon monoxide, preferably from reaction solution naturally gas-liquid separation, discharge.In addition, Raw material when carbon monoxide is also used as by nitrous acid ester and carbon monoxide manufacture oxalate diester is recycled.(for example, ginseng According to the method for the records such as the flat 10-152457 bulletin of Japanese Laid-Open).

Herein, when impurity containing phenol, carbon dioxide, hydrogen halides etc. in carbon monoxide, preferably by absorption tower or After the purifying plant of washer etc., it is used in the raw material etc. of oxalate diester.

In de-carbonyl reaction of the present invention, using adduct of the present invention as catalyst in use, thinking anti- Answer the amount of phenol contained in liquid less.Think the reason for this is that, be since adduct hygroscopicity is lower, by water as described later The by-product of phenol caused by solving is difficult to happen.

Further, since phenol becomes the Obstacle Factors of de-carbonyl reaction of the present invention, thus in carbonic acid of the invention In the manufacturing method of diester, using adduct of the present invention as catalyst in use, easy method can be used, efficiently To the carbonic diester of high-purity.

Additionally it is believed that when carrying out de-carbonyl reaction using the oxalate diester containing carboxylic acid phenyl ester, contained in reaction solution Phenol amount is also less.Think the reason for this is that becoming diphenyl carbonate or diphenyl oxalate due to carboxylic acid phenyl ester and phenol reactant Ester.Since phenol is with as four aryl chlorination phosphine reactions of catalyst, four as Fu Laisi (Fries) rearrangement catalyst are formed Phenylphosphine phenolate, thus become the Obstacle Factors of de-carbonyl reaction of the present invention.

Therefore, in the manufacturing method of carbonic diester of the invention, about using the phenostal containing carboxylic acid phenyl ester When being reacted, it is also possible to which easy method is efficiently obtained the carbonic diester of the less high-purity of content of phenol.

When further, about de-carbonyl reaction of the present invention is carried out under an increased pressure, it is believed that carboxylic acid phenyl ester By-product be difficult to happen, the carbonic diester of the less high-purity of content of carboxylic acid phenyl ester can be obtained.

Its reason is considered due to thus decomposing when de-carbonyl reaction by carrying out de-carbonyl reaction under an increased pressure Fu Laisi (Fries) rearrangement of oxalate diester caused by catalyst is difficult to happen.Specifically, it is believed that: for example by general formula (10) The four aryl halogenation phosphines indicated are as catalyst in use, being broken down into four benzene by the four aryl halogenation phosphines that general formula (10) indicate Base phosphine phenolate and halogen compounds, the tetraphenyl phosphine phenolate and oxalate diester carry out Fu Laisi (Fries) rearrangement reaction, by This causes the generation of phenyl (to phenyloxycarbonyl phenyl) carbonic ester (PCPC).

Furthermore, it is believed that: the halogen compounds of by-product together with the tetraphenyl phosphine phenolate, with by-product in de-carbonyl reaction Carbon monoxide is distillated from reaction solution together, thereby promotes the decomposition reaction of the catalyst.

However, it is believed that: if carrying out de-carbonyl reaction under an increased pressure, due to four aryl halides indicated by general formula (10) Change halogen compounds caused by the decomposition of phosphine to become difficult to distillate from reaction solution, so inhibiting phenyl (to phenyloxycarbonyl Phenyl) carbonic ester (PCPC) generation.That is, in the manufacturing method of carbonic diester of the invention, can by under an increased pressure into Easy method as row de-carbonyl reaction, efficiently and stably obtains the carbonic diester of high-purity.

Even if supplying non-active gas from the lower part of de-carbonyl reaction device to de-carbonyl reaction about one side, taken off on one side The case where carbonyl reaction, also thinks that phenol etc. is gasified together together with non-active gas, thus phenol contained in reaction solution Amount it is less.

Particularly, when catalyst is the four aryl halogenation phosphine of general formula (10), as with caused by the reacting of the phenol of by-product The obstruction of de-carbonyl reaction is difficult to happen caused by generation of tetraphenyl phosphine phenolate etc., thus carbonic diester of the invention In manufacturing method, carbonic diester can be efficiently obtained with easy method.

If remaining a large amount of oxalate diester in reaction solution, heating when existing through evaporation generates furans system chemical combination A possibility that object.Such as there is Fu Laisi (Fries) the rearrangement generation by reaction equation below (12) in diphenyl oxalate esters A possibility that benzofuran -2,3- diones and phenols.

Particularly, since benzofuran -2,3- diketone is to become the coloring of carbonic diester sometimes in orange compound Reason, therefore the amount of benzofuran -2,3- diketone in preferred carbonic acid diester is less.

But in the manufacturing method of carbonic diester of the invention, using the catalyst for dissolving in carbonic diester, with conversion ratio When 96% or more progress de-carbonyl reaction, remaining oxalate diester is less, furans system caused by heating when can inhibit evaporation Close the by-product of object.

Specifically, the amount of furans based compound contained in the carbonic diester of evaporation, although also will receive de-carbonyl reaction In oxalate diester conversion ratio influence, but usually can be set to 1ppm hereinafter, being preferably set to 0.1ppm or less.

[changing 12]

In formula, R is identical with the R in reaction equation (1).

In addition, in the manufacturing method of above-mentioned preferred carbonic diester of the invention, when evaporating carbonic diester, evaporation 70 weight % or more, preferably 80 weight % or more, more preferable 90 weight % or more, further preferred 97 weight are usually contained in fraction Measure the carbonic diester of % or more, particularly preferred 98 weight % or more.In addition, its upper limit, usually 100 weight %.

When containing oxalate diester in the fraction, usually 0.001 weight % or more, preferably 0.01 weight % or more, more excellent 0.1 weight % or more is selected, in addition, on the other hand, usually 3 weight % are hereinafter, it is preferred that 2 weight % are hereinafter, more preferable 1 weight % Hereinafter, more preferable 0.5 weight % or less.But most preferably 0 weight %.

In addition, content when containing ingredient except them, 100 weight of total amount relative to carbonic diester and oxalate diester Part is measured, usually 1 parts by weight are hereinafter, it is preferred that below 0.5 parts by weight, below more preferable 0.1 parts by weight.Contain ionic chlorine etc. When content, usually 0.0001 weight % hereinafter, it is preferred that 0.00001 weight % hereinafter, more preferable 0.000001 weight % with Under.

The phenyl contained in the fraction (to phenyloxycarbonyl phenyl) carbonic ester (PCPC), usually 0.35 weight % Hereinafter, it is preferred that 0.30 weight % hereinafter, more preferable 0.10 weight % hereinafter, more preferable 0.08 weight % hereinafter, particularly preferably 0.05 weight % or less.

As the ingredient except them, sometimes with the aromatic monohydroxy compound etc. of phenol etc., but content at this time Usually 1 weight % is hereinafter, it is preferred that 0.5 weight % is hereinafter, more preferable 0.3 weight % or less.

In addition, the content of the furans based compound of benzofuran -2,3- diketone etc. contained in the fraction is usually 10 weights Ppb or more, preferably 100 weight ppb or more, more preferable 1000 weight ppb or more are measured, in addition, on the other hand, usually 2 weight % is measured hereinafter, it is preferred that 1 weight % is hereinafter, more preferable 0.5 weight % or less.

The carbonic diester of evaporation is used directly for the purposes of polycarbonate manufacture etc., but can be as needed purity etc. into One step is purified.Further, it is also possible to the evaporation of above-mentioned carbonic diester be carried out by distillation, by that will boil respectively than carbonic diester The high ingredient of point from tower bottom side, by carbonic diester from middle section, by the ingredient than carbonic diester low boiling point from tower top it is side-draw go out, thus Obtain the carbonic diester of high-purity.

When further purifying, it can be carried out by distilling and adsorbing etc..And specifically, it is preferable to use the theory with 5~50 layers The plate column of layer and the vaporising device of packed tower etc. carry out distilation.

In the manufacturing method of carbonic diester of the invention, using the catalyst for dissolving in carbonic diester, with conversion ratio 96% When the above progress de-carbonyl reaction, it is suppressed that the by-product of furans based compound, thus furans is removed from the carbonic diester of evaporation Based compound operation can not as desired purity design even.That is, compared to the rear work for removing furans based compound Sequence is necessary previous method, can obtain to simple and effective the carbonic diester of high-purity.

As the ingredient higher than carbonic diester boiling point, the decarbonylation base of oxalate diester, oxalic acid aminomethyl phenyl phenyl ester etc. can be enumerated In the raw material and its raw material of reaction in the evaporation of mixed high boiling substance, de-carbonyl reaction and its reaction solution by-product to chloro The organohalogen compounds generated when benzoic acid phenyl ester, phenyl salicylate, its polymer, de-carbonyl reaction are (to chloro benzoic acid Phenyl ester etc.) etc..

It is preferably obtained by the decarbonylated reaction of oxalate diester by making in the manufacturing method of carbonic ester of the invention Carbonic diester is contacted with alkali compounds, thus decomposes furans based compound contained in the carbonic diester, easy in this way Method, the carbonic diester of efficient stable and the less high-purity of the content for being continuously manufactured by furans based compound.

[alkali compounds]

As the alkali compounds for removing furans based compound, for example, hydrogen-oxygen can be enumerated as alkali metal compound Change the hydroxide of the alkali metal of lithium, sodium hydroxide, potassium hydroxide, cesium hydroxide etc.；Lithium bicarbonate, sodium bicarbonate, bicarbonate The bicarbonate alkali metal salt of potassium, caesium bicarbonate etc.；The carbonate of the alkali metal of lithium carbonate, sodium carbonate, potassium carbonate etc.；Lithium acetate, The acetate of the alkali metal of sodium acetate, potassium acetate, cesium acetate etc.；Lithium stearate, odium stearate, potassium stearate, stearic acid caesium etc. Stearic alkali metal salt；The alkali metal salt of the boron hydride of lithium borohydride, sodium borohydride, potassium borohydride, hydroboration caesium etc.；Peace The benzoate of the alkali metal of the fragrant sour lithium of breath, sodium benzoate, benzoic acid potassium, benzoic acid caesium etc.；Lithium dihydrogen phosphate, phosphorus The dihydric phosphate of the alkali metal of acid dihydride sodium, potassium dihydrogen phosphate, cesium dihydrogen phosphate etc.；Two lithium of phosphenylic acid, phosphenylic acid two The phenyl microcosmic salt of the alkali metal of sodium, phosphenylic acid dipotassium, two caesium of phosphenylic acid etc.；Lithium, sodium, potassium, caesium alkoxide；Lithium, sodium, potassium, The phenates of caesium；Dilithium salt, disodium salt, di-potassium, two cesium salts of bisphenol-A etc..

As alkali earth metallic compound, the alkali of calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide etc. can be enumerated The hydroxide of great soil group metal；The bicarbonate alkali earth metal salt of calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate etc.； The carbonate of the alkali metal of calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate etc.；Calcium acetate, barium acetate, magnesium acetate, strontium acetate etc. The acetate of alkaline-earth metal；The stearic alkaline-earth metal of calcium stearate, barium stearate, magnesium stearate, strontium stearate etc. Salt etc..

As organoboron compound, tetramethyl canopy, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl can be enumerated Boron, trimethyl benzyl boron, trimethylphenyl boron, triethyl methyl boron, triethylbenzyl boron, triethyl group phenyl boron, tributyl benzyl The hydroxide of base boron, tributyl phenyl boron, tetraphenyl boron, benzyltriphenyl phosphonium boron, methyl triphenyl boron, butyl triphenyl boron etc. Deng.

As organic phosphorus compound, triethyl phosphine, three-n-propyl phosphines, tri isopropyl phosphine, three-normal-butyl phosphines, three can be enumerated Phenylphosphine, tributylphosphine or quaternary alkylphosphonium salt etc..

As organic ammonium salt, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, four fourths can be enumerated Base ammonium hydroxide, trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, triethyl group first Base ammonium hydroxide, triethylbenzyl ammonium hydroxide, triethyl group phenyl ammonium hydroxide, tributyl benzyl ammonium hydroxide, tributyl benzene Base ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyltriphenyl phosphonium ammonium hydroxide, methyl triphenyl ammonium hydroxide, butyl triphenyl hydrogen Amine-oxides etc..

As pyridine compounds, 4-aminopyridine, 2-aminopyridine, N, N- dimethyl -4-aminopyridine, 4- bis- can be enumerated Ethylamino pyridine, 2 hydroxy pyrimidine, 2- methoxypyridine, 4-methoxypyridine etc..As imidazolium compounds, 2- bis- can be enumerated Methylamino imidazoles, 2- methoxyl group imidazoles, imidazoles, 2- mercaptoimidazole, 2-methylimidazole etc..In addition, can also enumerate aminoquinoline Deng.

Wherein, since volatility is lower, preferred as alkali compound and alkali earth metallic compound, more preferable alkali metal Compound.

Alkali compounds, as long as can be contacted with the impurity of furans based compound etc. contained in carbonic diester, in the present invention Carbonic diester manufacturing method in can arbitrarily supply.By the decarbonylated reaction institute convenient for passing through oxalate diester to storage The supply such as the groove tank of obtained carbonic diester or its purifying column, thus preferred alkali compounds.

As the groove tank of storage carbonic diester, specifically, storage can be enumerated from the decarbonylated reaction for passing through oxalate diester Obtained reaction solution removes the groove tank of the ingredient of catalyst liquid.In addition, the purifying column as carbonic diester, can enumerate such as Japan The destilling tower etc. distilled with being recorded in state's special open 2002-322130 Publication.

Alkali compounds can only alkali compounds state supply, can also be dissolved in solvent etc. state supply.? It is preferably higher for the solubility of diphenyl carbonate as phenol when supplying alkali compounds to be dissolved in the state of solvent Solvent.

Decomposition based on furans based compound is easy to happen aspect, and the amount of the alkali compounds supplied to carbonic diester is preferred It is more, but the decomposition based on carbonic diester is difficult to happen aspect, it is preferably less.Accordingly, with respect to 100 parts by weight of carbonic diester, Usually more than 0.0000001 parts by weight, it is more than preferably 0.000001 parts by weight, it is more than more preferable 0.00001 parts by weight, this Outside, on the other hand, usually 1 parts by weight are hereinafter, it is preferred that 0.1 parts by weight are hereinafter, below more preferable 0.01 parts by weight.

The decomposition of furans based compound, high temperature is more easy to happen, but the decomposition side of being difficult to happen based on carbonic diester Face preferably carries out at low temperature.Therefore, it is usually carried out in 100 DEG C or more, preferably 130 DEG C or more, more preferable 150 DEG C or more. In addition, on the other hand, usually being carried out in 300 DEG C or less, preferably 280 DEG C or less, more preferable 250 DEG C or less.

The removing of furans based compound, usually to containing from passing through the obtained carbonic acid of decarbonylated reaction of oxalate diester The ingredient that the carbonic diester after catalyst liquid is removed in diester carries out.

[recycling of de- carbonylic catalyst]

It is anti-carrying out decarbonylation base using the catalyst for dissolving in carbonic diester in the manufacturing method of carbonic diester of the invention At once, even if being reacted with high conversion, remaining catalyst generally also dissolves in the reaction solution after evaporating carbonic diester In the carbonic diester for remaining in reaction solution.

It is therefore preferable that at least part of the catalyst is taken out from residual liquid, supply to de-carbonyl reaction is recycled. That is, it is preferred that by the way that at least part of catalyst contained in the residual liquid is used as catalyst, by catalyst to dissolve It supplies in the state of carbonic diester to reactor.

The viewpoint of accumulation based on the higher-boiling compound prevented in reaction system, the recycling of catalyst preferably will be from making Liquid after removing the compound higher than carbonic diester boiling point in reaction solution after carbonic diester evaporation is supplied to reactor.

As the ingredient being removed by the process, the grass of phenostal (334 DEG C of boiling point under 1 air pressure) etc. can be enumerated The high boiling substance of acid diesters and 4- Para Hydroxy Benzoic Acid phenyl ester (boiling point is higher than phenostal under 1 air pressure) etc..It can pass through Method well known to distillation, extraction, crystallization etc. removes higher-boiling compound.

Specifically, it such as can be separated with the method etc. of Japanese Laid-Open 2002-45704 bulletin record.In addition, phenyl Boiling point of (to the phenyloxycarbonyl phenyl) carbonic ester (PCPC) under 1 air pressure is 340 DEG C, thus is contained in higher boiling chemical combination Object.

Moreover, when recycling residual liquid containing catalyst, carbonic diester contained in the residual liquid and carbonic diester it The total amount of the by-product of outer de-carbonyl reaction, relative to the total amount of the ingredient other than catalyst, preferably 85~100 weights Measure %.

When recycling catalyst, the catalyst of recycling can be used only, can also mix in the catalyst of recycling does not make Catalyst etc. and use.Further, it is also possible to further supply the molten of carbonic diester in the residual liquid to reactor supply Liquid.In addition, with the higher-boiling compound is removed, catalyst and catalyst be decomposed and a part of decomposition product for generating also by Remove etc., thus the catalyst of whole amount may not be reused.It is therefore preferable that adjustment catalytic amount, so that de- Carbonyl Catalysis The amount of agent becomes above-mentioned preferred range.

The adjustment of catalytic amount, preferably by will divide with the catalyst and catalyst being removed together with higher-boiling compound Solve object total mole same degree mole catalyst, with remove higher-boiling compound after liquid together with supply to It is carried out in the reactor of de-carbonyl reaction.Herein, when using adduct of the present invention as catalyst, the catalyst It is decomposed and the decomposition product that generates refers to the decomposition product of adduct.

Also, it is preferred that with remove higher-boiling compound after liquid together with, by with four aryl as adduct decomposition product The adduct of the mole of total mole same degree of halogenation phosphine is supplied to the reactor of de-carbonyl reaction.Same degree Mole, the catalyst relative to be removed together with higher-boiling compound, catalyst and four aryl halogenation phosphines etc. decompose 1 mole of the total amount of object, preferably 0.7 mole or more, more preferably 0.8 mole or more, particularly preferably 0.9 mole or more, In addition, on the other hand, preferably 2 moles hereinafter, more preferably 1.4 moles hereinafter, particularly preferably 1.1 moles or less.

When de- carbonylic catalyst in residual liquid is supplied to de-carbonyl reaction, preferably by above-mentioned halogen compounds and remaining Liquid is supplied together to de-carbonyl reaction.It is preferred that the amount of the halogen compounds supplied is, relative to de- in the presence of reactor The total amount of carbonylic catalyst (Te Bie Shi phosphonium salt catalyst), the halogen compounds in the presence of reactor are 0.01~100 to rub You are % (equimolar).

When by catalyst recycle, become the carboxylic acid phenyl ester in catalyst liquid also containing by-product in de-carbonyl reaction sometimes Deng high boiling substance state.In addition, becoming in catalyst liquid sometimes when using phenostal containing carboxylic acid phenyl ester Contain its state.

Therefore, in de-carbonyl reaction, using the carboxylic acid phenyl ester containing specific quantity phenostal when, pay the utmost attention to this The amount of carboxylic acid phenyl ester contained in catalyst liquid, the content for being adjusted to carboxylic acid phenyl ester contained in phenostal become mesh Scalar.

[preparation method of preferred carbonic diester]

As the manufacturing method of carbonic diester of the invention, particularly preferably successively contain the side of the 1st~3 process below Method.

1st process: the process that carbonic diester is manufactured by above-mentioned de-carbonyl reaction of the present invention,

2nd process: the carbonic diester that will be manufactured in the 1st process is decomposed generation with containing catalyst and/or catalyst The process of the catalyst liquid separation of decomposition product,

3rd process: it will be supplied by least part of isolated catalyst liquid to the reactor of the 1st process in the 2nd process Process.

1st process obtains the fraction containing non-active gas preferably from reactor, its at least part is supplied to anti- The process for answering device.The acquirement of fraction containing the non-active gas, such as can be by from simplicity such as reactor top gas bleedings Ground carries out.

Herein, the gasification together based on phenol caused by non-active gas is easy to happen aspect, the oxalic acid two in reaction solution The concentration of phenyl ester is preferably lower.Therefore, specifically, the concentration of the phenostal in reaction solution be preferably 30 weight % hereinafter, More preferably 10 weight % are hereinafter, particularly preferably 5 weight % or less.

Further, since the obstruction to de-carbonyl reaction is difficult to happen, the concentration of the phenol in reaction solution is preferably lower, specifically Ground, the molar ratio (phenol/catalyst) relative to catalyst be preferably 2 hereinafter, more preferably 1 hereinafter, particularly preferably 0.5 with Under.

It is recycling if supplying at least part of the fraction containing non-active gas to reactor in 1st process Non-active gas, while the carbon monoxide that effective use generates in de-carbonyl reaction.Herein, evaporating containing non-active gas Point, it can be directly fed to reactor, but preferably supply part of it to reactor.By the fraction containing non-active gas It, preferably will be other than the non-active gas of phenol contained in the fraction containing non-active gas etc. when a part supply to reactor Ingredient by distillation etc. remove after resupply.

In 2nd process, by the carbonic diester manufactured in the 1st process and urging containing catalyst and/or catalyst decomposition product The separation of agent liquid.Separation in 2nd process can be carried out with the well known method of distillation, extraction, crystallization etc..Of the present invention four Aryl halogenation phosphine and adduct of the present invention are usually higher boiling, thus using these compounds as catalyst in use, Separation in 2nd process, it is easier by distilling the method that carbonic diester separates, it is preferred.

It is preferably contained in the reaction solution after de-carbonyl reaction by making that is, in the manufacturing method of carbonic diester of the invention Carbonic diester evaporation and takes out, thus obtain the catalyst liquid that the decomposition product of generation is decomposed containing catalyst and/or catalyst.

In addition, Fu Laisi (Fries) weight in reaction solution after de-carbonyl reaction containing oxalate diester and carbonic diester When arranging the high boiling substance of compound etc., these substances, which also become to be contained in, decomposes generation containing catalyst and/or catalyst State in the catalyst liquid of decomposition product.

In addition, as described above, it is preferred to making to be contacted by isolated carbonic diester with alkali compounds in the 2nd process.In addition, can Purity etc. as needed before contacting with alkali compounds and/or after contact, is distilled diphenyl carbonate further progress or is inhaled It is attached etc..

In 3rd process, at least part of catalyst liquid obtained in the 2nd process is supplied to the reactor of the 1st process. In this way, recycling de- carbonylic catalyst.The carbonic diester of 2nd process distillation separation and the 3rd process catalyst again It utilizes, is preferably carried out by the above method and condition.

In the manufacturing method of carbonic diester of the invention, as described above, even if the catalyst for being used for de-carbonyl reaction is returned It receives and recycles, it is also difficult to generate by-product, the diphenyl carbonate of high-purity can be efficiently obtained with easy method.

[recovery method of catalyst]

As de- carbonylic catalyst, uses (there can be substituent group) four aryl halogenation phosphine and/or (there can be substituent group ) adduct of four aryl halogenation phosphines and hydrogen chloride when, can be by the following method (hereinafter, sometimes referred to as " catalysis of the invention The recovery method of agent "), the catalyst of high-purity is recycled to simple and effective from reaction solution.In addition, by recycling the catalysis Agent can manufacture to steady and continuous the carbonic diester of high-purity.

The recovery method of catalyst of the invention will be used for the catalyst of above-mentioned de-carbonyl reaction, from by de-carbonyl reaction Raffinate (hereinafter, sometimes referred to as " catalyst liquid ") recycling after obtaining the ingredient containing carbonic diester in reaction solution afterwards.Specifically, The recovery method of catalyst of the invention has the process for making polar organic solvent and hydrogen halides contact the raffinate.

The recovery method for estimating catalyst of the invention is proceed as follows, and is recycled and is taken off Carbonyl Catalysis contained in catalyst liquid Agent.

In de-carbonyl reaction, it is somebody's turn to do using four aryl halogenation phosphines as catalyst agent in use, containing in catalyst liquid Four aryl halogenation phosphines.In addition, in de-carbonyl reaction, it is believed that about using the adduct of four aryl halogenation phosphines and hydrogen chloride as catalysis Agent is in use, also containing the four aryl halogenation phosphines for separating out hydrogen halides from the adduct middle reaches in catalyst liquid.

Further, in catalyst liquid contain symmetrical four aryl halogenation phosphine when, the symmetrical four aryl halogenation phosphine by with halogen The contact for changing hydrogen, becomes the adduct of the symmetrical four aryl halogenation phosphine and hydrogen halides.The symmetrical four aryl halogenation phosphine and hydrogen halides Adduct, it is lower generally for the solubility of polar organic solvent.

Therefore, if contacting the catalyst liquid and polar organic solvent, remaining carbonic diester in usual catalyst liquid It is dissolved in polar organic solvent with impurity etc., but symmetrical four aryl halogenation phosphine of the present invention can be precipitated.It then, can be by taking The precipitate is obtained, de- carbonylic catalyst is recycled.

On the other hand, when containing asymmetric four aryl halogenation phosphine in catalyst liquid, which passes through Contact with hydrogen halides becomes the adduct of the asymmetric four aryl halogenation phosphine and hydrogen halides.Herein, asymmetric four aryl halogenation Phosphine, it is lower generally for the solubility of polar organic solvent.

In addition, the adduct of itself and hydrogen halides, higher generally for the solubility of polar organic solvent, but for the molten of water Xie Du is lower.Therefore, if contacting the catalyst liquid with polar organic solvent, remaining carbonic diester in usual catalyst liquid It is dissolved in polar organic solvent with impurity etc., and asymmetric four aryl halogenation phosphine of the present invention is due to organic for polarity molten The solubility of agent is lower, thus is precipitated, which is slurry.

In addition, when asymmetric four aryl halogenation phosphine contained in the catalyst liquid and hydrogen halides contact, become and hydrogen halides Adduct, due to for polar organic solvent solubility improve, thus dissolve.Further, due to asymmetric four aryl The adduct of halogenation phosphine is lower for the solubility of water, therefore is precipitated by the contact with water, and the usual catalyst liquid is again As slurry.

Therefore, de- carbonylic catalyst can be recycled by obtaining the precipitate.That is, de- carbonylic catalyst is asymmetric four virtue When the adduct of base halogenation phosphine and/or asymmetric four aryl halogenation phosphine and hydrogen halides, catalyst contained in the raffinate, by connecing After touching polar organic solvent and hydrogen halides, water is contacted, thus can be used as precipitate recycling.

The recovery method of catalyst of the invention, by asymmetric four aryl halogenation phosphine and/or asymmetric four aryl halogenation phosphine With the adduct of hydrogen halides, catalyst is used as in the manufacture of the diphenyl carbonate of the de-carbonyl reaction progress by phenostal In use, so implementing, the catalyst of high-purity can be efficiently recycled by easy method from reaction solution.

In the recovery method of catalyst of the invention, contact of the polar organic solvent with hydrogen chloride to the raffinate can be simultaneously It carries out, contacts another party again after either party can also be made first to contact.That is, polar organic solvent and hydrogen halides connect raffinate Touching is contacted with hydrogen halides again after raffinate and polar organic solvent can be made to dissolve contact.In addition, polar organic solvent and hydrogen halides pair The contact of raffinate makes it contact raffinate after polar organic solvent and hydrogen halides can be made to contact.

But based on the catalyst for being easy efficiently to recycle high-purity in terms of, preferably by using absorbing hydrogen halides Thus polar organic solvent etc. is allowed to contact simultaneously, or with polar organic solvent contact after again with hydrogen halides contact, more preferably and It is contacted again with hydrogen halides after polar organic solvent contact.

The reason is that, thinking: if hydrogen halides first contacts the raffinate, passing through point of carbonic diester contained in the raffinate Solution generates phenol, there is a possibility that causing four aryl halogenation phosphines to become the reaction of tetraphenyl phosphine phenolate, thus passes through and polarity Organic solvent contacts simultaneously, or first contacts polar organic solvent, can make that the reaction is caused to become difficult.

Moreover, the manufacturing method of carbonic diester of the invention, preferably using the precipitate of the recycling as de-carbonyl reaction Catalyst is recycled, and is more preferably used the precipitate of the recycling as the catalyst of de-carbonyl reaction, and is allowed to carry out Successive reaction.

The polar organic solvent of recovery method for catalyst of the invention, preferably for few contained in catalyst liquid The carbonic diester and by-product high boiling substance of amount and the intermiscibility of water are higher, be easy to make four aryl halogenation phosphines and hydrogen halides plus It closes object dissolution, be easy the solvent that four aryl halogenation phosphines are precipitated.As the preference of polar organic solvent, ketone, ether can be enumerated Class, halogenated hydrocarbon and esters etc..

As ketone, can illustrate such as dimethyl ketone, metacetone, methyl ethyl ketone, methyl n-propyl ketone, isopropyl methyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl isoamyl ketone, ethyl n-propyl ketone, ethylisopropyl The low alkyl group ketone and cyclohexanone, ring penta of the carbon atom number 1~15 of base ketone, ethyl normal-butyl ketone, ethyl isobutylo ketone etc. Cyclic annular ketone of carbon atom number 3~10 of ketone etc. etc..

As ethers, can illustrate such as dimethyl ether, Anaesthetie Ether, methyl ethyl ether, methyl n-propyl ether, isopropyl methyl Ether, methyl n-butyl ether, methyl-isobutyl ether, methyl n-amyl ether, methyl isoamyl ether, ethyl n-propyl ether, ethylisopropyl The carbon atom number 2~10 of base ether, ethyl n-butyl ether, ethyl isobutyl ether, dimethoxy-ethane, diethoxyethane etc. it is low Grade alkyl ether；The diaryl ethers etc. of the ring-type ethers of tetrahydrofuran etc. and diphenyl ether etc..

As halogenated hydrocarbon, can illustrate such as monochloro methane, methylene chloride, chloroform, 1- chloroethanes, 1,2-, bis- chloroethene Alkane, 1,1- dichloroethanes, 1,1,2- trichloroethanes, n-propyl chloride, 2 cbloropropane isopropyl chloride, 1,2- dichloropropane, 1,1- dichloropropane, 2, The halogenated hydrocarbon etc. of the carbon atom number 1~6 of 2- dichloropropane etc..

As esters, can illustrate such as alkyl fatty race carboxylate, alkylcarbonic acid diester, alkyl oxalate diester and ethylene glycol Aliphatic ester etc..

As alkyl fatty race carboxylate, formic acid methyl ester, formic acid ethyl, formic acid n-propyl, formic acid isopropyl ester, ant can be enumerated The low alkyl group formate of sour N-butyl, formic acid isobutyl etc.；Methyl acetate, ethyl acetate, n-propyl acetate, acetic acid isopropyl Low alkyl group acetate and methyl propionate, ethyl propionate, the n propyl propionate, third of ester, n-butyl acetate, isobutyl acetate etc. Low alkyl group aliphatic carboxylic acid esters of the low alkyl group propionic ester of isopropyl propionate, n-butyl propionate, isobutyl propionate etc. etc. etc..Make For alkylcarbonic acid diester, the lower alkyl of dimethyl carbonate, diethyl carbonate, butyl carbonate, methyl ethyl ester etc. can be enumerated Base carbonic diester etc..

As alkyl oxalate diester, low alkyl group oxalate diester of dimethyl oxalate, diethy-aceto oxalate etc. etc. can be enumerated.Make For glycol acetate, ethyl acetate, propyl acetate, butyl acetate etc. can be enumerated.

As the aliphatic ester of ethylene glycol, glycol acetate etc. can be enumerated.

Wherein, preferably carbon atom number possessed by polar organic solvent be 3~15 polar organic solvent, more preferable 3~ 10 polar organic solvent.Furthermore it is preferred that structure is asymmetrical pole as methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK) Property organic solvent.Further, it is preferable to ketone, more preferable alkyl ketone.

Therefore, in particular it is preferred to alkyl ketone, the alkyl ketone that more preferable total number of carbon atoms are 3~10, most preferably such as Methyl isopropyl Ketone and the such ground structure of methyl iso-butyl ketone (MIBK) are asymmetrical alkyl ketone.

The amount (weight) of the polar organic solvent contacted with catalyst liquid, based on being difficult to cause carbonic diester and by-product high boiling It is preferably more in terms of the precipitation of point substance and the solidification of raffinate, in addition, on the other hand, the rate of recovery and pole based on catalyst The less aspect of energy required for the separation and recovery of property organic solvent, it is preferably less.

Therefore, specifically, relative to catalyst liquid, preferably 0.5 times or more, more preferably 1 times or more, in addition, another Aspect, preferably 10 times hereinafter, more preferably 5 times hereinafter, particularly preferably 3 times or less.

The amount of water in polar organic solvent, if more, the solubility of the hydrogen chloride adduct of four aryl halogenation phosphines becomes It is small, and the phenol of by-product with diphenyl carbonate reaction contained in catalyst liquid is easy to become with four aryl halogenation phosphine reactions At tetraphenyl phosphine phenolate, thus the weight relative to polar organic solvent, usually 2.0 weight % are hereinafter, it is preferred that 1.0 weights % is measured hereinafter, more preferable 0.5 weight % is hereinafter, particularly preferred 0.2 weight % or less.

When de- carbonylic catalyst is adduct, the hydrogen halides contacted with catalyst liquid is preferably the hydrogen halides phase with adduction Same hydrogen halides.In addition, when de- carbonylic catalyst is four aryl halogenation phosphine, it is preferably former with halogen contained by the four aryl halogenation phosphine The hydride of the identical halogen atom of son.

Further, due to de- carbonylic catalyst of the present invention preferably (can have substituent group) four aryl phosphonium chloride And the adduct of (can have substituent group) four aryl phosphonium chloride and hydrogen chloride, therefore used in the method recycled The preferred hydrogen chloride of hydrogen halides.

The hydrogen halides contacted with catalyst liquid, when the catalyst contained in catalyst liquid is symmetrical four aryl halogenation phosphine, By the contact with polar organic solvent, adduct is precipitated, and this point does not change, thus can be gas, liquid, can also be with It is the aqueous solution of hydrogen halides.That is, hydrogen halides used herein, preferably hydrogen chloride gas, liquid hydrogen chloride or hydrochloric acid, due to being easy Operation, more preferable hydrogen chloride gas or hydrochloric acid.

On the other hand, when catalyst contained in catalyst liquid is asymmetric four aryl halogenation phosphine, if using hydrogen halides Aqueous solution, then adduct becomes difficult to be dissolved in polar organic solvent, thus the hydrogen halides contacted with catalyst liquid, usually gas Body or liquid, preferably gas.That is, hydrogen halides used herein, preferably hydrogen chloride gas or liquid hydrogen chloride, due to being easy behaviour Make, more preferable hydrogen chloride gas.

Hydrogen halides is to add four aryl halogenation phosphines contained in catalyst liquid as the hydrogen halides of four aryl halogenation phosphines It closes object and uses.Therefore, the amount of the hydrogen halides contacted with catalyst liquid, relative to four aryl halogenation contained in catalyst liquid 1 mole of phosphine, preferably 1 mole or more, more preferably 1.1 moles or more, in addition, on the other hand, preferably 5 moles hereinafter, more Preferably 2 moles or less.

After contacting catalyst liquid and polar organic solvent, then when contacting with hydrogen halide, catalyst liquid is difficult to Solidification, therefore contacted preferably more than the fusing point of carbonic diester, below the boiling point of polar organic solvent with hydrogen halide.

In addition, the recovery efficiency based on catalyst be easy improve aspect, the temperature of the hydrogen halide of contact and with contain The temperature of the polar organic solvent containing hydrogen halides when thering is the polar organic solvent of hydrogen chloride to contact, it is preferably lower.Specifically, Preferably 50 DEG C hereinafter, more preferably 40 DEG C hereinafter, particularly preferably 30 DEG C or less.The reason is that, if carbonic diester and by-product High boiling substance is contacted with hydrogen chloride, then has a possibility that water contained in polar organic solvent etc. hydrolyzes and generates phenol.

It is anti-by recycling above-mentioned recycling catalyst to carry out decarbonylation base in the manufacturing method of carbonic diester of the invention It answers, thus can manufacture to steady and continuous the carbonic diester of high-purity.Successive reaction by using recycling catalyst is obtained The purity of carbonic diester, usually 99 weight % or more, preferably 99.3 weight % or more, more preferably 99.5 weight % with On.When containing impurity, sometimes with ionic chlorine etc., but content at this time is usually 1 weight ppm hereinafter, preferably 0.1 weight Ppm is measured hereinafter, more preferably 0.01 weight ppm or less.

In addition, de- carbonylic catalyst be asymmetric four aryl halogenation phosphine or asymmetric four aryl halogenation phosphine and hydrogen halides plus When closing object, the amount of the water contacted in order to which the adduct of the asymmetric four aryl halogenation phosphine and hydrogen halides is precipitated, based on non-right The hydrogen halides adduct of four aryl halogenation phosphines is claimed to be easy to be precipitated, the rate of recovery improves aspect, and it is preferably more, in addition, on the other hand, base It is difficult to be precipitated in carbonic diester and by-product high boiling substance, it is preferably less in terms of the catalyst for being easy recycling high-purity.

Therefore, specifically, amount (weight ratio) of the amount of water relative to polar organic solvent, preferably 0.001 times or more, more Preferably 0.01 times or more, particularly preferably 0.02 times or more, in addition, on the other hand, preferably 0.5 times hereinafter, more preferably 0.2 times hereinafter, particularly preferably 0.1 times or less.

The temperature of the water of contact, preferably 50 DEG C hereinafter, more preferably 40 DEG C hereinafter, particularly preferably 30 DEG C or less.Base In terms of being easy in the catalyst of recycling to get higher purity, the contact with water is preferably slowly time-consumingly carried out.That is, with whole water one are made Secondary contact is compared, and preferably separates water, or a small amount of contact every time.

That is, de- carbonylic catalyst is the adduction of asymmetric four aryl halogenation phosphine or asymmetric four aryl halogenation phosphine and hydrogen halides When object, the 3rd process in the manufacturing method of above-mentioned carbonic diester of the invention, preferably successively have following 3A processes and 3B process is more preferably carried out the manufacturing method of carbonic diester of the invention as successive reaction.

3A process: by make at least part of the catalyst liquid separated in the 2nd process and polar organic solvent and After hydrogen halides contact, contact water, the process for obtaining precipitate,

3B process: it is supplied at least part of precipitate obtained in the 3rd process as the catalyst of de-carbonyl reaction To the process to the 1st process.

In 3A process, by make at least part and the polar organic solvent of the catalyst liquid separated in the 2nd process with And after hydrogen halides contact, water is contacted, precipitate is thus obtained.In 3A process, by keeping the catalyst liquid and polarity organic molten After agent and hydrogen halides contact, water is contacted, precipitate is thus obtained, is estimated this is because generating caused by phenomenon as described above 's.

In 3B process, using at least part urging as de-carbonyl reaction of precipitate obtained in above-mentioned 3A process Agent is supplied to above-mentioned 1st process.Slurries obtained in 3A process keep the solid by being separated by solid-liquid separation dry, And supply to the reactor of de-carbonyl reaction, it can be used as catalyst recycle accordingly.But based on the storage for preventing high boiling substance Long-pending viewpoint, slurries obtained in 3A process preferably remove after the ingredient higher than carbonic diester boiling point supply to the 1st process.

As the ingredient being removed herein, can illustrate such as to Para Hydroxy Benzoic Acid phenyl ester or phenyl (adjacent phenyloxycarbonyl benzene Base) carbonic ester (PCPC) etc. by-product high boiling substance.Separation of solid and liquid can be carried out by pressure filtration etc..In addition, drying is logical The solid made is crossed at about 80~220 DEG C, 0.1~50kPa, it is about 1~10 hour dry, it thus can be organic molten except depolarization Agent and water.

The recovery method of catalyst of the invention, by by above-mentioned 1st process, the 2nd process, 3A process and 3B work Sequence is sequentially carried out continuously with this, is using asymmetric four aryl halogenation phosphine or its hydrogen halides adduct as de- carbonylic catalyst When, it efficiently and stably can continuously manufacture the diphenyl carbonate of high-purity.

But in above-mentioned 3A process, returned even if the catalyst liquid of the whole amount obtained in the 2nd process carries out catalyst Receipts processing, is sometimes associated with the processing of removing of by-product high boiling substance etc., a part of catalyst can be also removed.Therefore, Carry out successive reaction when, as described above, it is preferred to by supplied while recycling catalyst asymmetric four aryl halogenation phosphine and/or The adduct of asymmetric four aryl halogenation phosphine and hydrogen halides adjusts catalytic amount, so that asymmetric four aryl halogenation in reactor The total amount of phosphine becomes above-mentioned preferred range.

[recycling of polar organic solvent]

The recovery method of catalyst of the invention preferably has polar organic solvent of the recycling for catalyst recycling, and The process for being reused in catalyst recovery process.That is, de- carbonylic catalyst be four aryl halogenation phosphines and/or four aryl halogenation phosphines with When the adduct of hydrogen halides, can by from reaction solution obtain the ingredient containing carbonic diester after raffinate contained in catalyst, It is recycled using polar organic solvent, at the same time, also polar organic solvent of the recycling for catalyst recycling, is reused in and urges Agent recycling.

Specifically, keep polarity organic molten when the 3rd process in the manufacturing method of above-mentioned carbonic diester of the invention has The process that agent is contacted with hydrogen halides at least part of catalyst liquid obtained in the 2nd process, and make institute in the catalyst liquid When the catalyst contained is precipitated, preferably recycling is used for the polar organic solvent of catalyst recycling and is recycled.

Catalyst in the 3rd process is estimated to be precipitated by phenomenon as described above.In addition, being contacted about with catalyst liquid Polar organic solvent type and amount (weight), the amount of hydrogen chloride, contact hydrogen chloride temperature or pole containing hydrogen chloride The temperature of property organic solvent, amount and temperature when contacting water, also as described in the recovery method about catalyst.

But when de- carbonylic catalyst be four aryl halogenation phosphines and/or adduct, the pole of the recycling of the catalyst will be used for Property organic solvent recycle when, hydrogen chloride contact with raffinate can be used as hydrochloric acid supply.

The recovery method of catalyst of the invention, preferably by by (A) process below and (B) process with this sequentially into Row, thus polar organic solvent of the recycling for catalyst recycling, is reused in catalyst recovery process.

(A) process: being evaporated by using the polar organic solvent recycled in the catalyst, in the Liquid liquid Separation for being packed into water It is distillated in device, make the polar organic solvent of the Liquid liquid Separation device is mutually back to the raffinate side, removes institute in the raffinate At least part of process of the hydrogen chloride contained,

(B) process: the process that liquid obtained in (A) process is distilled.

(A) in process, make to recycle the raffinate evaporation after catalyst as precipitate as described above, in Liquid liquid Separation device It distillates.Herein, due in Liquid liquid Separation device be equipped with water, thus in Liquid liquid Separation device polar organic solvent phase (upper layer) and water Phase (lower layer) separated, but hydrogen chloride contained in polar organic solvent, compared with polar organic solvent, in aqueous phase side More easily dissolve.Therefore, it is mutually back to raffinate side by make polar organic solvent, can removed contained in polar organic solvent Hydrogen chloride.

(A) distilling apparatus used in process (method of evaporating) is not particularly limited as long as it can reach above-mentioned purpose. It is separated in a short time as vaporising device, such as downward film evaporator, thin-film evaporator etc. because being easy, thus is preferred 's.In addition, slowlying while stirring with being preferably difficult to happen bumping and depressurizing, be allowed to evaporate on one side when being evaporated in reactor.

The time required for hydrogen chloride contained in polar organic solvent is removed, by the shape of heat transfer efficiency and separation vessel It influences, but based on the by-product aspect for being difficult to happen impurity, preferably carries out in a short time, preferably 20 hours hereinafter, more preferable 15 Hour is hereinafter, particularly preferred 10 hours or less.

In terms of the by-product for being difficult to happen impurity, evaporation is preferably carried out under low temperature, low-pressure, and pressure is preferably normal Pressure or the lower evaporation of decompression, the temperature that the preferred hydrogen chloride of temperature distillates.

Specifically, the preferred 1kPaA or more of pressure, more preferable 2kPaA or more.In addition, on the other hand, preferably 100kPaA with Under, more preferable 80kPaA or less.Moreover, temperature is usually 50 DEG C or more, and preferably 60 DEG C or more, particularly preferred 70 DEG C or more, this Outside, on the other hand, usually 200 DEG C hereinafter, it is preferred that 190 DEG C hereinafter, particularly preferred 180 DEG C or less.

The amount and temperature for the water being packed into Liquid liquid Separation device, as long as the polar organic solvent and hydrogen chloride that distillate are by liquid liquid point From being just not particularly limited.The amount of water present in Liquid liquid Separation device is preferably set to after the recovery using catalyst as precipitate The 1 weight % or more of raffinate, more preferably 2 weight % or more, on the other hand, preferably 50 weight % are hereinafter, more preferably 30 Weight % or less.

Due to be easy Liquid liquid Separation, the temperature of Liquid liquid Separation device be preferably set to 60 DEG C hereinafter, more preferably be set as 50 DEG C hereinafter, In addition, on the other hand, being therefore preferably set to 0 DEG C or more, more preferable 5 DEG C or more since water phase is difficult to solidify.

It when carrying out (A) process under the conditions of such preferred, is back in the phase of the polar organic solvent of raffinate side, leads to Often contain 70 weight % of polar organic solvent or more, preferably 80 weight % or more, more preferable 90 weight % or more.In addition, thereon Limit is usually 100 weight %.In addition, be back to hydrogen chloride contained in the phase of the polar organic solvent of raffinate side, usually 1 weight % is measured hereinafter, preferably 0.5 weight % is hereinafter, more preferably 0.3 weight % or less.

(B) in process, liquid obtained in (A) process is distilled.By distillation, can be removed from polar organic solvent Water.(B) distilling apparatus used in process (method of evaporating) can be implemented in the same manner as (A) process.In addition, distillation condition, as long as Energy separating polar organic solvent and water are just not particularly limited.It is organic molten based on can be easily separated polarity but about vapo(u)rizing temperature Agent and water, preferably high temperature, but the higher-boiling compound of phenol based on by-product in de-carbonyl reaction etc. is difficult to be mixed into polarity and has In solvent, preferably low temperature.

The recovery method of catalyst of the invention so can recycle high-purity by easy method high efficiente callback Catalyst at the same time, high efficiente callback be used for catalyst recycling polar organic solvent, by the polar organic solvent of high-purity It is recycled.Moreover, can be stablized by recycling the catalyst recycled by the recovery method of catalyst of the invention The diphenyl carbonate of ground manufacture high-purity.

[manufacturing method of polycarbonate]

One of purposes of carbonic diester manufactured in the present invention, i.e. polycarbonate, can be by making to be manufactured by above-mentioned method Carbonic diester, especially diaryl carbonate, and using bisphenol-A as the aromatic series of representative or aliphatic dihydroxy compounds, Ester exchange reaction is carried out in the presence of alkali metal compound and/or alkali earth metallic compound and is manufactured.

Above-mentioned ester exchange reaction can suitably select well known method to carry out.Herein, the two of transesterification is carried out with carbonic diester Hydroxy compounds can be aromatic dihydroxy compound, be also possible to aliphatic dihydroxy compounds, but optimization aromatic two Hydroxy compounds.Hereinafter, explanation is using diphenyl carbonate and bisphenol-A as an example of raw material.

In the manufacturing method of above-mentioned polycarbonate, preferably diphenyl carbonate uses the amount relative to bisphenol-A surplus.Relatively Less, the thermal stability of polymer in terminal hydroxyl in the amount for the diphenyl carbonate that bisphenol-A uses, the polycarbonate based on manufacture Excellent aspect, it is preferably more, in addition, the polycarbonate side of easy to manufacture desired molecular weight fast based on ester exchange reaction speed Face, it is preferably less.And specifically, it is preferable to using for example relative to 1 mole of bisphenol-A, usually 1.001 moles or more, preferably 1.02 Mole or more, usually 1.3 moles hereinafter, it is preferred that 1.2 moles or less.

As the supply method of raw material, bisphenol-A and diphenyl carbonate can be supplied with solid, but preferably make one of them or The two melting is supplied with liquid condition.

When manufacturing polycarbonate with the ester exchange reaction of diphenyl carbonate and bisphenol-A, usually using catalyst.Above-mentioned is poly- This point of minute of carbonic ester, as the ester exchange catalyst, it is preferable to use alkali metal compound and/or alkaline-earth metal chemical combination Object.They can be used a kind, can also by two or more in any combination and ratio use.On practical, preferred as alkali Close object.

Relative to 1 moles of bisphenol A or diphenyl carbonate, usually more than 0.05 micromole, preferably 0.08 micro- rubs catalyst More than you, it is more than more preferable 0.10 micromole, in addition, on the other hand, usually 5 micromoles hereinafter, it is preferred that 4 micromoles hereinafter, More preferable 2 micromole range below uses.

Within the above range by the usage amount of catalyst, it is easy to get needed for the polycarbonate for manufacturing desired molecular weight The polymerization activity wanted, also, polymer form and aspect are excellent, and not will do it the branch of excessive polymer, are easy to get molding When the excellent polycarbonate of mobility.

As alkali metal compound, preferably cesium compound.Preferred cesium compound is cesium carbonate, caesium bicarbonate, hydroxide Caesium.

Polycarbonate is manufactured by the above method, preferably continuously supply two kinds of above-mentioned raw materials to raw material mixing channel It gives, obtained mixture and ester exchange catalyst is continuously supplied to polymerization tank.

In manufacture by the polycarbonate of ester-interchange method progress, in general, existing to two kinds of raw materials that raw material mixing channel supplies After uniform stirring, it is supplied to the polymerization tank of addition catalyst, produces polymer.

[polycarbonate]

As noted previously, as the obtained carbonic diester purity of manufacturing method through the invention is very high, by make by The obtained carbonic diester of the manufacturing method of the present invention and aliphatic dihydroxy compounds or aromatic dihydroxy compound are in ester The polycarbonate of high-purity can be obtained in polycondensation in the presence of exchange catalysts.

Particularly, the carbon of the less high-purity of by-product phenol can be obtained in the manufacturing method of carbonic diester through the invention Acid diesters, thus the polycarbonate of high-quality can be obtained with it.In addition, in the manufacturing method of carbonic diester of the invention, when It can inhibit furans system chemical combination when carrying out de-carbonyl reaction with 96% or more conversion ratio using the catalyst for dissolving in carbonic diester The by-product of object, thus can obtain colouring the polycarbonate of less high-quality.

In the manufacturing method of carbonic diester of the invention, even if about absolute pressure when making de-carbonyl reaction 0.105MPa or more, 10MPa or less and when reacting, the less high-purity of by-product of aromatic monohydroxy compound also can be obtained Diphenyl carbonate, thus it can be used to obtain the polycarbonate resin of high-quality.In addition, even if about make generate carbonic diester and When alkali compounds contacts, the diphenyl carbonate of the less high-purity of furans based compound also can be obtained, thus it can be used to obtain The polycarbonate of high-quality.

[adduct of asymmetric four aryl halogenation phosphine and hydrogen halides]

As recorded in Japanese Laid-Open flat No. 9-328492, four aryl halogenation phosphines can be by making triaryl phosphine and aryl halide exist It reacts and obtains in the presence of metal halogen compound catalyst and water soluble high boiling point solvent.

Moreover, being recorded in Japanese Laid-Open 2013-82695, by being catalyzed to containing aryl halide, metal halogen compound The liquid of agent and water soluble high boiling point solvent separates or continuously adds triaryl phosphine, thus can high yield, in high selectivity Manufacture asymmetric four aryl halogenation phosphine.In addition, being recorded in Japanese Laid-Open 2013-82695, by obtained asymmetric four Aryl bromide phosphine is transformed to chloride.

The present inventor is about the de-carbonyl reaction for using the obtained asymmetric four aryl halogenation phosphine as catalyst It is studied in detail.As a result, distinguished using the above-mentioned asymmetric tetraphenyl halogenation phosphine obtained like that as with hydrogen halides When adduct (asymmetric adduct of the present invention) carries out de-carbonyl reaction for catalyst, by-product phenol can be reduced Amount.

As described later, reason is considered since adduct hygroscopicity is lower, thus the by-product of the phenol caused by hydrolyzing It is difficult to happen.That is, crystallinity is lower, easily becomes since asymmetric four aryl halogenation phosphine is symmetry lower structure Micro mist disperses.Additionally it is believed that if being used using the higher asymmetric four aryl halogenation phosphine of hygroscopicity as catalyst, due to urge Agent is supplied together to the moisture of reaction system, carbonic diester and oxalate diester hydrolysis, can generate phenol.On the other hand, recognize For due to adduct partial size of the present invention it is bigger, so hygroscopicity is lower, it is difficult to occur by carbonic diester and oxalic acid two The by-product of phenol caused by ester hydrolysis.

Asymmetric adduct of the present invention, since partial size is larger, hygroscopicity is lower, it is difficult to disperse, easily become and be easy The solid of operation.Therefore, as the catalyst of de-carbonyl reaction in use, can by catalyst in a short time, before moisture absorption It is packed into reactor, the by-product of phenol tails off, and can be readily derived the carbon of high-purity with high conversion, high selectivity by oxalate diester Diphenyl phthalate.

The partial size of asymmetric adduct of the present invention, it is specifically preferably 50 μm or more, more preferable 60 μm or more, more excellent Select 80 μm or more, particularly preferred 100 μm or more.In addition, the upper limit of the partial size of asymmetric adduct of the present invention is usually 1mm。

In addition, the partial size of asymmetric adduct of the present invention, can be used as using methyl iso-butyl ketone (MIBK) as decentralized medium, makes It is measured with Nikkiso Company Limited's マイ Network ロトラッ Network (Microtrac) particle size distribution device " MT3300EXII " Meso-position radius (D50) and obtain.

In addition, the hygroscopicity of asymmetric adduct of the present invention, it can be by comparing in 15~20 DEG C of temperature, humidity 40 It is evaluated under~45% atmosphere from the time required for defined moisture content moisture absorption to defined moisture content.

Specifically, for example, about 20g adduct, can be increased to needed for 0.5 weight % with by moisture content from 0.2 weight % The Time evaluation wanted.Herein, the measurement of moisture content, can be by four aryl halogenation phosphine moisture meter (capital of a country Electronics Industry Company systems " MKS-500 ") measurement.

The dissolubility of asymmetric adduct of the present invention, is usually soluble in carbonic diester.Due to of the present invention Asymmetric adduct dissolves in carbonic diester, therefore in the manufacturing method of carbonic diester of the invention, can not cause catalyst Precipitation, steadily with high conversion carry out de-carbonyl reaction, reduce remaining oxalate diester amount, can inhibit makes carbonic diester The generation of the furans based compound of by-product when evaporation.

Further, since asymmetric adduct of the present invention dissolves in carbonic diester, therefore turn phenostal height It reacts to rate for even if carbonic diester is concentrated in high concentration, catalyst will not be precipitated in raffinate after carbonic diester, thus It is easy to recycle catalyst contained in raffinate.

Further, since asymmetric adduct of the present invention dissolves in carbonic diester, can by catalyst with Be dissolved in carbonic diester state supply, by reaction after unreacted oxalate diester it is less, carbonic diester is contained with high concentration Catalyst liquid recycling, it is difficult to occur to reset phenol etc. caused by product as the Fu Laisi (Fries) of oxalate diester The carbonic diester of high-purity can be obtained in by-product.

Asymmetric adduct of the present invention, can by elemental microanalysis method, mass analysis, nuclear magnetic resonance spectrometry with And the well known method analysis of liquid chromatography etc..Specifically, such as in the case where 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, pass through Using elemental microanalysis method, mass analysis and nuclear magnetic resonance spectroscopy, it can confirm it is 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride.

In addition, being confirmed to be the liquid chromatogram of the substance of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride by measurement, utilize Liquid chromatography can more easily confirm.

About the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, firstly, implementing as described above, confirmation contains There is 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, then, by cl concn contained by measurement adduct, can calculate is added with hydrogen chloride Close object and its adduction rate.

The composition analysis carried out using liquid chromatography can be carried out according to sequence below and condition.

Device: Shimadzu Seisakusho Ltd. LC-2010, Imtakt Cadenza 3mm CD-C18 250mm × 4.6mmID.It is low Press gradient method.30 DEG C of temperature of analysis.Alternatively, substituting above-mentioned chromatographic column using Shimadzu Seisakusho Ltd.'s system " ODS3VID ".Eluent group At: A liquid acetonitrile: 0.5 weight % biphosphate sodium water solution of water=7.2:1.0 weight %/weight %, B liquid.Analysis time 0 divides Clock~12 minute.A liquid: B liquid=65:35 (volume ratio, same as below).In 12~35 minutes analysis times, form eluent Slowly varying is A liquid: B liquid=92:8, in 35~40 minutes analysis times, maintains A liquid: B liquid=92:8,1 ml/min of flow velocity Clock.

In addition, making measure object about with milli-Q water and being extracted in toluene of the cl concn less than 1 weight ppb Liquid be dissolved as uniform solution after, add ultrapure water, obtained water phase be sufficiently stirred, by the chromatography of ions with below Sequence and condition measure cl concn.

Device: DIONEX corporation ION CHROMATOGRAPH, IonPac AS12A.Eluent use is into ultrapure water Sodium bicarbonate is added to 0.3 mM of dm^-3, make 2.7 mMs of dm of sodium carbonate^-3Liquid.

[manufacturing method of adduct of the present invention]

Adduct of the present invention, can be by asymmetric four aryl halide that will be manufactured with well known method as described above Change phosphine together with hydrogen halides crystallization and obtain.It specifically, can be by making asymmetric four aryl halogenation phosphine and hydrogen halides be dissolved in pole Property organic solvent after crystallization, take out obtain.(hereinafter, the method for obtaining the adduct is known as sometimes " of the present invention to add Close the manufacturing method of object ").Moreover, adduct of the present invention, it is preferable to use the adduct being related to through the invention manufacture The obtained adduct of method.

In the manufacturing method of adduct of the present invention, by using organic solvent, asymmetric four aryl halogenation can be made Phosphine dissolution, in addition, hydrogen halides can be made to dissolve by using polar solvent.

Further, in the manufacturing method of adduct of the present invention, using asymmetric four aryl halogenation phosphine with it is non- Poor solubility between the hydrogen halides adduct of symmetrical four aryl halogenation phosphine, makes adduct crystallization and obtains.Then, so in fact Apply, since partial size is larger, hygroscopicity is lower, thus it is available be difficult to disperse, maneuverable solid.

Polar organic solvent used in the manufacturing method of adduct of the present invention is (hereinafter, sometimes have the polarity Solvent is known as " polar organic solvent that the manufacturing method of adduct of the invention is related to " or " manufacture for adduct Polar organic solvent ") while preferably there is sufficient solubility to asymmetric four aryl halogenation phosphine and hydrogen halides to adduction Object shows insoluble organic solvent.

Herein, the hydrogen halides used in the manufacturing method of adduct of the present invention, usually as the water of hydrogen halides Solution uses.That is, will have sufficient solubility to be known as with polarity aqueous solution of hydrogen halide.

There is sufficient solubility to refer to hydrogen halides, usually at 25 DEG C, in organic solvent 100g, hydrogen halides dissolution 1g or more.Polar organic solvent used in the manufacturing method of adduct of the present invention is preferably with aqueous solution of hydrogen halide in height The lower organic solvent in uniform state of temperature.High temperature refers to, usually 50 DEG C or more, preferably 60 DEG C or more, more preferable 70 DEG C or more.

Crystallization can be carried out by cooling adduct, can also be carried out and contacting with poor solvent, but pass through cooling The method of precipitation is easy, is preferred.

The preference of polar organic solvent as the manufacture for adduct can enumerate alcohols, ketone, ethers, halogenated Hydro carbons, esters etc..

As alcohols, can illustrate as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, Alkyl alcohols of carbon atom number 1~5 of isoamyl alcohol etc. etc..

As ketone, can illustrate such as dimethyl ketone, metacetone, methyl ethyl ketone, methyl n-propyl ketone, isopropyl methyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl isoamyl ketone, ethyl n-propyl ketone, ethylisopropyl The low alkyl group ketone and cyclohexanone, ring penta of the carbon atom number 1~10 of base ketone, ethyl normal-butyl ketone, ethyl isobutylo ketone etc. Cyclic annular ketone of carbon atom number 3~10 of ketone etc. etc..

As esters, such as alkyl formate of can illustrating, alkyl acetates, alkyl propionate lower aliphatic carboxylic acid Ester；The alkylene carbonate of dimethyl carbonate, diethyl carbonate, methyl ethyl ester, carbonic acid dibutyl ester etc.；Oxalic acid The oxalate diester of dimethyl esters, diethyl oxalate etc.；Acetic acid ethyl ester, acetic acid propyl diester, acetic acid butyl ester, ethylene glycol acetic acid The acetate etc. of the aliphatic ester of ester and ethylene glycol etc..

Wherein, the polar organic solvent being related to as the manufacturing method of adduct of the invention, preferably methyl isopropyl Ketone And methyl iso-butyl ketone (MIBK) is such, structure is the alkyl ketone that asymmetric, alkyl total number of carbon atoms are 3~15, more preferably The alkyl ketone that the total number of carbon atoms of alkyl are 3~10.

In addition, becoming the adduct with asymmetric four aryl halogenation phosphine in the manufacturing method of adduct of the present invention Hydrogen halides, usually as hydrogen halides aqueous solution use.That is, adduct of the present invention, by making the water with hydrogen halides The asymmetric four aryl halogenation phosphine crystallization of the liquid condition of solution contact, taking-up obtain.

Specifically, such as when obtaining the adduct with hydrogen chloride hydrochloric acid (hydrochloride aqueous solution) can be used, obtaining Hydrobromic acid (aqueous solution of hydrogen bromide) can be used when with the adduct of hydrogen bromide, can make when obtaining the adduct with hydrogen iodide It is obtained with hydroiodic acid (aqueous solution of hydrogen iodide).Aqueous solution as hydrogen halides, wherein particularly preferred hydrochloric acid.

Next, the sequence about the manufacturing method for implementing adduct of the present invention, lifts preferred an example explanation.

Firstly, contacting asymmetric four aryl halogenation phosphine with polar organic solvent and halogen acids.

Asymmetric four aryl halogenation phosphine is easy dissolution aspect when herein, based on heating, the amount of polar organic solvent preferably compared with It is more, but be easy that aspect is sucked out based on adduct when cooling down, it is preferably less.

Therefore, the amount of polar organic solvent, relative to asymmetric four aryl halogenation phosphine, with weight ratio meter, it is preferable to use 0.15 times or more, more preferably use 0.2 times or more, in addition, on the other hand, it is preferable to use 2 times hereinafter, more preferably using 1 times with Under.

In addition, the production rate based on adduct is easy to improve aspect, the amount of hydrogen halides contained by halogen acids is preferably more, but Asymmetric four aryl halogenation phosphine is easy that aspect is precipitated when, cooling less based on water contained by halogen acids, preferably less.

Therefore, the amount of hydrogen halides contained by halogen acids, relative to asymmetric four aryl halogenation phosphine, with weight ratio meter, preferably Using 0.5 times or more, in addition, on the other hand, it is preferable to use 2.0 times hereinafter, more preferably use 1.5 times or less.

The relative quantity of water relative to polar organic solvent, when due to heating asymmetric four aryl halogenation phosphine be easy dissolution, Adduct is easy to be precipitated when cooling, thus preferred 2 times or more, in addition, on the other hand, preferably 20 times hereinafter, more preferable 15 times with Under.

Next, dissolving asymmetric four halogenations phosphine by the way that the liquid heats up.During until dissolution, liquid is preferably stirred Body.Liquid temperature after heating, forms according to liquid, and preferred temperature is different, but is based on being easy that asymmetric four halogenations phosphine is made to exist Dissolution aspect, preferably high temperature in short time, but be based on being difficult to happen boiling aspect, preferably low temperature.Particularly, different using methyl When butyl ketone is easy the polar organic solvent of azeotrope with water like that, it is preferably set to lower.It is therefore preferable that 50 DEG C or more, it is more excellent 60 DEG C or more are selected, in addition, on the other hand, preferably 95 DEG C hereinafter, more preferable 90 DEG C or less.

Then, can be cooling by the way that the solution of asymmetric four aryl halogenation phosphine will be dissolved with, thus make asymmetric four aryl halide The adduct for changing phosphine and hydrogen halides is precipitated.

In terms of being difficult to happen the solidification of solution itself, the preferred high temperature of temperature when adduct is precipitated, but based on plus Close the yield aspects of object, preferably low temperature.Therefore it is usually preferred to 5 DEG C or more, more preferable 10 DEG C or more, particularly preferred 20 DEG C or more, In addition, on the other hand, preferably 70 DEG C hereinafter, more preferable 60 DEG C or less.

The cooling rate being precipitated from the state of heating to adduct, based on be precipitated in a short time with skinny device aspect, it is excellent Choosing is very fast, but based on hygroscopicity is lower, be difficult to disperse and be easy that easy-operating big crystallization is precipitated in terms of, it is preferably relatively slow.Therefore, cool down Preferably 0.1~2 DEG C per minute of speed.

About the adduct of organic chloride phosphine and hydrogen chloride, flat No. 9-328491 record of Japanese Laid-Open can also be passed through Method obtains.But the document is the document recorded about the method by organic bromide phosphine manufacture organic chloride phosphine, this article In offering, organic dichloride hydrogen phosphine is recorded merely as single intermediate for obtaining organic chloride phosphine, wherein should Organic chloride phosphine as various reactions catalyst (alternate moving catalyst, polymerization catalyst, halide halogen exchange reaction urge Agent etc.) it is useful.

In addition, method documented by the document makes organic dichloro by the way that the dissolved hydrochloric acid of organic bromide phosphine will be made cooling Change after hydrogen phosphine is precipitated, heating removes hydrogen halides, synthesize accordingly tetraphenyl dichloride hydrogen phosphine (symmetrical four aryl phosphine and hydrogen chloride Adduct.Embodiment 1) or benzyltriphenyl phosphonium dichloride hydrogen phosphine and benzyl triphenyl phosphonium chloride phosphine mixture (containing asymmetric The compound of the adduct of organic phosphine and hydrogen chloride.Embodiment 9) etc..

Herein, asymmetric four aryl halogenation phosphine of the present invention, preferably 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride etc. are such The lower substance of hydrophily due to not dissolving in hydrochloric acid, thus is unable to get adduct in this way.In addition, comparison as be described hereinafter Shown in example 1, the method recorded by the document is unable to get adduct of the present invention.

Embodiment

By the following examples and comparative example, the present invention is further illustrated, but the present invention is without departing from its main idea, Just do not limited by embodiment below.

[raw materials and reagents]

Phenostal is used through the substance after purifying the 1 grade of reagent simple distillation of Tokyo chemical conversion industry corporation.It should The purity for distilling obtained phenostal is 99 weight % or more, 50 weight ppm of water, 200 weight ppm of phenol, methyl ethyl oxalate 10 weight ppm of base phenylester, phenol (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) be Monitoring lower-cut (1 weight ppm) below.

The method synthesis that 4- 2-methyl-2-phenylpropane base triphenylphosphinebromide is recorded by Japanese Laid-Open 2013-82695 bulletin.

The method synthesis that 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is recorded by the flat 11-217393 bulletin of Japanese Laid-Open. The 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 66.67g, is dissolved in diphenyl carbonate 100g at 150 DEG C.

Methyl iso-butyl ketone (MIBK), n-butyl alcohol, hydrochloric acid, chlorocarbonic acid phenyl ester, tetrahydrofuran, pyridine, toluene, to hydroxybenzoate perfume Acid phenenyl ester, sodium bicarbonate, anhydrous magnesium sulfate, sodium chloride, sodium hydroxide, sodium nitrite, sulfuric acid, active carbon, ethyl acetate, heptane And phosphorus pentoxide uses the product of Wako Pure Chemical Industries, Ltd..

In addition, the water concentration in methyl iso-butyl ketone (MIBK) is divided with moisture meter (capital of a country Electronics Industry Company system " MKS-500 ") It is 500 weight ppm when analysis.

Tetraphenylphosphonium chloride uses the product of Tokyo chemical conversion industry company.Diphenyl carbonate and phenol use Mitsubishi Chemical The product of Co., Ltd..In addition, sodium phenate uses the product of Alfa Aesar company.Isatin uses Tokyo chemical conversion industry strain formula meeting The product of society.Hydrogen chloride gas uses the product of Sumitomo Seika Co., Ltd.

The method synthesis that 4- aminomethyl phenyl triphenyl phosphine dichloride is recorded by the flat 8-333307 bulletin of Japanese Laid-Open.

[analysis]

Composition analysis is to be carried out by high performance liquid chromatography with sequence below and condition.

Device: Shimadzu Seisakusho Ltd. LC-2010A, Imtakt Cadenza 3mm CD-C18 250mm × 4.6mmID.It is low Press gradient method.30 DEG C of temperature of analysis.Alternatively, substituting above-mentioned chromatographic column using Shimadzu Seisakusho Ltd.'s system " ODS3VID ".Eluent group At: A liquid acetonitrile: 0.5 weight % biphosphate sodium water solution of water=7.2:1.0 weight %/weight %, B liquid.Analysis time 0 divides Clock~12 minute.A liquid: B liquid=65:35 (volume ratio, same as below).In 12~35 minutes analysis times, form eluent Slowly varying is A liquid: B liquid=92:8, in 35~40 minutes analysis times, maintenance A liquid: and B liquid=92:8,1 ml/min of flow velocity, It analyzes accordingly.

Quantifying for benzofuran -2,3- diketone is to be carried out by high performance liquid chromatography with sequence below and condition.

Device: Shimadzu Seisakusho Ltd. LC-2010A, 18,3 μm of Scherzo SM-C, 250mm × 4.6mmID.Low pressure gradient Method.40 DEG C of temperature of analysis.Eluent composition: A liquid acetic acid: acetonitrile: water=0.1 volume %:10 volume %:90 volume %, B liquid 0.2 weight % ammonium acetate aqueous solution: acetonitrile=90 volume %:10 volume %.In 0~20 minute analysis time, with A liquid: B liquid= 60:40 fixes (volume ratio, same as below).In 20~25 minutes analysis times, keep eluent composition slowly varying for A liquid: B liquid =85:5, in 25~35 minutes analysis times, maintain A liquid: B liquid=60:40,0.85 ml/min of flow velocity are analyzed accordingly.

Quantifying for methyl iso-butyl ketone (MIBK) is to be carried out by gas chromatography with sequence below and condition.Device uses island Saliva manufacturing company system " GC-2014 ".Chromatographic column uses Agilent Technologies' system " DB-17 " (internal diameter 0.53mm, column length Spend 60m, 1 μm of film thickness).Carrier gas is helium, and flow is set as 7.34cm per minute³, linear velocity is set as 50.7cm per second.If injection Mouth temperature is 220 DEG C, if detector temperature is 260 DEG C.The heating mode of chromatographic column is, after first being kept for 3 minutes at 75 DEG C, with 10 DEG C per minute are warming up to 220 DEG C, keep 10 minutes at 220 DEG C, then, are warming up to 250 DEG C with 40 DEG C per minute, keep 10 Minute, it is analyzed.

The adduction of the adduct and tetraphenylphosphonium chloride and hydrogen halides of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen halides The adduction rate of object, by using the potential difference titration outfit (capital of a country Electronics Industry Company system " AT-610 ") for utilizing silver nitrate to measure Cl concn calculates.

The measurement of moisture content uses moisture meter (capital of a country electronics work by four aryl halogenation phosphines to be placed on the state on disk Industry society system " MKS-500 ") measurement.The test of dry difficulty is by the way that sample to be fitted into 100 milliliters of eggplant type flask, by it It is mounted on the rotary evaporator for having oil bath, heats and by oil bath heating to 100 DEG C, at pressure 10Torr, compare It is carried out from defined moisture content is dry to the time required for defined moisture content.In addition, hygroscopic test is to pass through 15~20 DEG C of temperature, humidity 40~45% atmosphere under, compare from needed for defined moisture content moisture absorption to defined moisture content Time for wanting and carry out.

Partial size is to use Nikkiso Company Limited's マイ Network ロトラッ Network grain using methyl iso-butyl ketone (MIBK) as decentralized medium The meso-position radius (D50) that degree distribution measurement device " MT3300EXII " is measured.

Quantifying for bromide ion is measured using DIONEX corporation ion chromatography device " ION CHROMATOGRAPH " 's.Chromatographic column uses DIONEX corporation separation chromatography column " IonPac AS12A ".Eluent is prepared in ultrapure water, so that carbon Sour sodium is 2.7 mMs of dm^-3And sodium bicarbonate is 0.3 mM of dm^-3。

About with milli-Q water and being extracted in toluene of the cl concn less than 1 weight ppb, make the liquid of measure object After being dissolved as uniform solution, add ultrapure water, obtained water phase is sufficiently stirred, by chromatography of ions sequence below with The measurement of condition progress cl concn.

Device: DIONEX corporation ION CHROMATOGRAPH, IonPac AS12A.Eluent use is into ultrapure water Addition sodium carbonate is to becoming 2.7 mMs of dm^-3And sodium bicarbonate is added to becoming 0.3 mM of dm^-3Liquid.

[synthesis example 1]

Into 500 milliliters of a full set of tubular type of detachable flask for having thermometer and blender, it is packed into tetraphenylphosphonichloride chloride Phosphine 50g (0.13 mole), 28 weight % hydrochloric acid 400g, are heated to 90 DEG C in a nitrogen atmosphere.

Then, detachable flask is cooled to room temperature, which is filtered by glass filter, the solid that will be obtained Move to eggplant type flask.By the way that eggplant type flask to be placed on the rotary evaporator for having oil bath, by oil bath heating to 100 DEG C, pressing It is 2 hours dry under power 10Torr, obtain 42g solid.By the cl concn of the solid potential difference of capital of a country Electronics Industry Company Titration outfit " AT-610 " analysis the result is that 17 weight %.

Therefore, the amount of chlorine contained in the solid is 42g × 0.17=7g (0.192 mole).Herein, if by the amount of the chlorine It is considered as the amount of chlorine contained in tetraphenylphosphonium chloride contained in solid and (ignores with the total amount of the amount of the hydrogen chloride of its adduction Hydrogen timesharing contained by hydrogen chloride), then the amount of tetraphenyl phosphine contained by the solid is that (0.100 rubs 42g × (1-0.192)=34g You), the amount of chlorine contained by the solid is 0.192 mole -0.100 mole=0.092 mole.

It is thus identified that obtained solid is the tetraphenylphosphonium chloride of adduction rate 92% and the adduct of hydrogen chloride.

[embodiment 1]

Into 500 milliliters of a full set of tubular type of detachable flask for having thermometer and blender, it is packed into 4- 2-methyl-2-phenylpropane base Triphenyl phosphine dichloride 70g (0.162 mole), methyl iso-butyl ketone (MIBK) 18g and 28 weight % hydrochloric acid 263g, under nitrogen atmosphere plus Heat makes to 90 DEG C in uniform solution.Then, by being cooled to room temperature detachable flask to obtain slurries.

The slurries are filtered by glass filter, obtained solid is moved into eggplant type flask.By by the eggplant type flask It is mounted on the rotary evaporator for having oil bath, it is 2 hours dry at pressure 10Torr by oil bath heating to 100 DEG C, it obtains 75g solid.The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 14.6 weight %.

Therefore, the amount of chlorine contained by the solid is 75g × 0.146=11g (0.309 mole).Herein, if by the amount of the chlorine It is considered as the amount (ignoring hydrogen timesharing contained by hydrogen chloride) of hydrogen chloride contained by adduct, 4- 2-methyl-2-phenylpropane base triphen contained by the solid The amount of base phosphine is 75g × (1-0.146)=64g (0.162 mole), and the amount of chlorine contained by the hydrogen chloride of adduct is rubbed for 0.309 You have -0.162 mole=0.147 mole, thus confirms that the solid is adduction rate 91% (0.147 mole of ÷ 0.162 mole × 100) 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride adduct.In addition, the yield for calculating adduct is 0.162 mole of ÷ 0.162 × 100=100%.

In the three-necked flask for having thermometer and stirrer, it is packed into phenostal 300g (1.238 moles), by making The three-necked flask is immersed in 230 DEG C of oil bath and heats, and dissolves phenostal.It will obtained uncle 4- as described above Adduct (adduction rate 91%) 20g (0.043 mole) of butylbenzene base triphenyl phosphine dichloride and hydrogen chloride, is 4mm with bottom bore Funnel supply into the three-necked flask.After terminating 30 minutes from the supply of adduct, one of the liquid in three-necked flask is taken out Part carries out composition analysis by high performance liquid chromatography.

As a result, 0.5 weight % of phenol, 29.5 weight % of phenostal, 54.7 weight % of diphenyl carbonate.Herein, The conversion ratio of phenostal is 71%.

About tetraphenylphosphonium chloride, its obtained adduct of synthesis example 1,4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and reality Its obtained adduct of example 1 is applied, its character, volume density, partial size, dry difficulty (are reduced moisture content from 2 weight % To drying time required for 0.5 weight %) and hygroscopicity (moisture content is increased to required for 0.5 weight % from 0.2 weight % Time) be summarised in table 1.

If table 1 is expressed, specify by the way that 4- 2-methyl-2-phenylpropane base triphenyl chlorine is made in 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride The adduct for changing phosphine and hydrogen chloride, can become easy to operate, be easy drying, reduce hygroscopicity.

[table 1]

Moisture content (is reduced to 0.5 weight from 2 weight % by character, volume density, partial size, the dry difficulty of each catalyst Measure drying time required for %) and hygroscopicity (moisture content is increased to the time required for 0.5 weight % from 0.2 weight %)

※ for DPC solubility ... at 150 DEG C, the amount that is dissolved in diphenyl carbonate 100g.

※ TPPC ... tetraphenylphosphonichloride chloride phosphorus.

The adduct of ※ TPPCHCl ... tetraphenylphosphonichloride chloride phosphorus and hydrogen chloride.

※ tBu-TPPC ... 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride.

The adduct of ※ tBu-TPPCHCl ... 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.

[comparative example 1]

Into 500 milliliters of a full set of tubular type of detachable flask for having thermometer and blender, it is packed into 4- 2-methyl-2-phenylpropane base Triphenyl phosphine dichloride 50g (0.116 mole), 28 weight % hydrochloric acid 200g, are heated to 90 DEG C in a nitrogen atmosphere, but not in uniform State, and it is in slurry condition.Then, detachable flask is cooled to room temperature, which is filtered by glass filter, it will Obtained solid moves to eggplant type flask.

By the way that eggplant type flask to be placed on the rotary evaporator for having oil bath, by oil bath heating to 100 DEG C, in pressure It is 2 hours dry under 10Torr, obtain 45g micro mist.The cl concn of the micro mist potential difference of capital of a country Electronics Industry Company is dripped Determine device " AT-610 " analysis the result is that 8.0 weight %.

8.2 weight % of theoretical value than the cl concn of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is low, thus confirmation obtain it is micro- Powder becomes the adduct with hydrogen chloride.In addition, the micro mist is white particle, volume density 0.23gcm^-3, partial size is 31μm。

Next, using micro mist as catalyst, implement the de-carbonyl reaction of phenostal.Specifically, in addition to It is real similarly to Example 1 other than which is used as catalyst as catalyst in the de-carbonyl reaction of embodiment 1 It applies, carries out de-carbonyl reaction.After terminating 30 minutes from the supply of adduct, a part of the liquid in three-necked flask is taken out, Composition analysis is carried out by high performance liquid chromatography.

As a result, 1.50 weight % of phenol, 63.2 weight % of phenostal, 24.2 weight % of diphenyl carbonate.This Place, the conversion ratio of phenostal are 36%.

[embodiment 2]

Into 500 milliliters of a full set of tubular type of detachable flask for having thermometer and blender, it is packed into 4- 2-methyl-2-phenylpropane base Triphenylphosphinebromide 50g (0.105 mole), methyl iso-butyl ketone (MIBK) 13g and 28 weight % hydrochloric acid 188g, in addition to this, with reality It applies example 1 similarly to implement, obtains slurries.The slurries are filtered by glass filter, obtain solid.

It is detachable by moving to obtained solid together with methyl iso-butyl ketone (MIBK) 13g and 28 weight % hydrochloric acid 188g Flask is heated to 90 DEG C under nitrogen atmosphere, in after uniform solution, detachable flask is cooled to room temperature, slurries are become, led to It crosses and is filtered with a glass filter the slurries, obtain solid.

The solid is heated together with methyl iso-butyl ketone (MIBK) and hydrochloric acid, in after uniform solution, by the obtained slurries of cooling It filters and obtains the operation of solid and repeat 3 times and (4- 2-methyl-2-phenylpropane base triphenylphosphinebromide is transformed to 4- 2-methyl-2-phenylpropane base triphenyl Phosphonium chloride).

By the way that obtained solid is moved to eggplant type flask, eggplant type flask is mounted on the rotary evaporator for having oil bath, It is 2 hours dry at pressure 10Torr by oil bath heating to 120 DEG C, obtain 35g solid.

The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 13.3 weight %.Therefore, the amount of chlorine contained in the solid is 35g × 0.133=4.66g (0.132 mole).

Herein, if the amount of the chlorine to be considered as to the amount (ignoring hydrogen timesharing contained by hydrogen chloride) of hydrogen chloride contained by adduct, The amount of 4- 2-methyl-2-phenylpropane base triphenylphosphine contained by the solid is 35g × (1-0.133)=30g (0.077 mole), the chlorine of adduct The amount for changing chlorine contained by hydrogen is 0.132 mole -0.077 mole=0.055 mole, thus confirms that the solid is adduction rate 71% The adduct of 4- the 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride of (0.055 mole of ÷ 0.077 mole × 100).In addition, calculating The yield of adduct is 0.077 mole of ÷, 0.105 mole × 100=73%.

By bromide ion contained in the solid, with DIONEX corporation ion chromatography device " ION CHROMATOGRAPH " measurement as a result, being 0.5 mole of % or less.

[embodiment 3]

In embodiment 1, methyl iso-butyl ketone (MIBK) 18g is replaced using n-butyl alcohol 18g, replaced using 35 weight % hydrochloric acid 263g In addition to this 28 weight % hydrochloric acid 263g are implemented similarly to Example 1, obtain slurries.The slurries are passed through into glass filter Filtering, moves to eggplant type flask for obtained solid.It, will by the way that the eggplant type flask to be mounted on the rotary evaporator for having oil bath Oil bath heating is 2 hours dry at pressure 10Torr to 130 DEG C, obtains 72g solid.

The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 11.0 weight %.Therefore, the amount of chlorine contained in the solid is 72g × 0.110=7.9g (0.223 mole).

Herein, if the amount of the chlorine to be considered as to the amount (ignoring hydrogen timesharing contained by hydrogen chloride) of hydrogen chloride contained by adduct, The amount of 4- 2-methyl-2-phenylpropane base triphenylphosphine contained by the solid is 72g × (1-0.110)=64g (0.162 mole), the chlorine of adduct The amount for changing chlorine contained by hydrogen is 0.223 mole -0.162 mole=0.061 mole, thus confirms that the solid is adduction rate 38% The adduct of 4- the 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride of (0.061 mole of ÷ 0.162 mole × 100).In addition, calculating The yield of the adduct of 4- 2-methyl-2-phenylpropane base triphenylphosphine is 0.162 mole of ÷, 0.162 mole × 100=100%.

[embodiment 4]

By (0.011 mole) loading eggplant type flask of adduct 5g obtained in embodiment 3, it is placed on the rotation for having oil bath It is 2 hours dry at pressure 10Torr by oil bath heating to 180 DEG C on evaporator.

By its with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company analyze as a result, adduct Adduction rate is reduced to 2%.About Examples 1 to 3 and above-mentioned adduct, will measurement adduction rate and hygroscopicity (moisture content is from 0.2 Weight % rises to the time required for 0.5 weight %) result be summarized in table 2.

If table 2 is expressed, specify that adduction rate is higher, the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride Hygroscopicity is lower.

[table 2]

The hygroscopicity of the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride and the relationship of adduction rate

	Adduction rate	Hygroscopicity
			Embodiment 4	2%	5 minutes
Embodiment 3	38%	7 minutes
			Embodiment 2	71%	20 minutes
Embodiment 1	91%	50 minutes

[embodiment 5]

By having thermometer, blender, 500 milliliters of a full set of tubular type of detachable burning for distillating pipe and recipient In bottle, it is packed into adduct (adduction rate 91%) 11g of the obtained 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of embodiment 1 and hydrogen chloride (0.024 mole) and diphenyl carbonate 96g (0.448 mole), will be heated to 150 DEG C, makes adduct in detachable flask Dissolution.

It is 3 hours dry if pressure is 2kPa by the way that 185 DEG C will be heated in detachable flask, thus make water and carbonic acid Diphenyl ester is total to distillate 20g, makes dry in detachable flask.Phenostal 160g is added into the detachable flask (0.661 mole), by being heated to 150 DEG C, dissolves phenostal.

Further, it is blown into 0.012 mole of hydrogen chloride gas into the detachable flask, is warming up to 225 DEG C.In addition, When reaching 225 DEG C, a part of the liquid in detachable flask is taken out, composition analysis is carried out by high performance liquid chromatography When, it is 0.2 weight % of phenol, 55.1 weight % of phenostal, 40.0 weight % of diphenyl carbonate.

After reaching 225 DEG C in detachable flask, the carbon monoxide generated in reaction is removed with nitrogen under normal pressure on one side It goes to outside reaction system, is reacted 80 minutes in the state of being kept for 225 DEG C on one side.By a part of the liquid after reacting 80 minutes It takes out, is 0.2 weight % of phenol, 8.5 weight % of phenostal, carbon when carrying out composition analysis by high performance liquid chromatography 84.4 weight % of diphenyl phthalate.Herein, the conversion ratio of phenostal is 88%.

[comparative example 2]

In embodiment 5, using obtained in 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 10g (0.024 mole) alternate embodiment 1 In addition to this adduct 11g of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride is tested similarly to Example 5.

The composition analysis knot of the liquid in detachable flask when reaching 225 DEG C obtained by high performance liquid chromatography Fruit is 0.4 weight % of phenol, 54.8 weight % of phenostal, 40.1 weight % of diphenyl carbonate.

In addition, by the composition analysis of the liquid after reacting 80 minutes obtained by high performance liquid chromatography as a result, benzene 0.4 weight % of phenol, 22.2 weight % of phenostal, 72.4 weight % of diphenyl carbonate.Herein, the conversion ratio of phenostal It is 68%.

The result of embodiment 5 and comparative example 2 is summarized in table 3.It is confirmed by table 3, due to 4- 2-methyl-2-phenylpropane base triphenyl Phosphonium chloride hygroscopicity is higher, therefore the by-product quantitative change of the phenol as caused by phenostal and dipheryl carbonate ester hydrolysis is more, As a result, the conversion ratio of phenostal is lower, reactivity is reduced.

[table 3]

The liquid of embodiment 5 and comparative example 2 composition

[embodiment 6]

Having thermometer, blender, 500 milliliters of a full set of tubular type of detachable flask for distillating pipe and recipient In, after being packed into phenostal 300g (1.238 moles), by being heated to 150 DEG C, it is allowed to dissolve.In the detachable flask In, add adduct (adduction rate 91%) 15g of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride obtained in embodiment 1 After (0.032 mole) dissolution, it is warming up to 230 DEG C.

In addition, a part of the liquid in detachable flask is taken out when reaching 230 DEG C, pass through high performance liquid chromatography It is 0.2 weight % of phenol, 75.5 weight % of phenostal, 18.0 weight % of diphenyl carbonate when carrying out composition analysis.

After reaching 230 DEG C in detachable flask, the carbon monoxide generated in reaction is removed with nitrogen under normal pressure on one side It goes to outside reaction system, is reacted 6 hours in the state of being kept for 230 DEG C on one side.A part of liquid after reacting 6 hours is taken It out, is 92.7 weight % of diphenyl carbonate, 0.2 weight % of phenol, oxalic acid when carrying out composition analysis by high performance liquid chromatography 484.6 weight ppm, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of diphenyl ester, 5.0 weight %.Herein, the conversion ratio of phenostal is 99.9%.

In addition, the reaction solution (before the sample for taking out composition analysis) after reaction is 279g, 4- 2-methyl-2-phenylpropane base triphenyl chlorine The molecular weight for changing phosphine is 431.Therefore, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride contained in the reaction solution after calculating reaction is 279g × 0.05 ÷ 431=0.032 mole.

Herein, the charge weight of the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride is also 0.032 mole, thus The resolution ratio of the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride is 0%.

Then, pressure is slowly reduced to 10Torr, distillates thick diphenyl carbonate 230g.In addition, making thick diphenyl carbonate Raffinate 47g in detachable flask after distillating visually has dissolved at 200 DEG C.

Therefore, enrichment factor (evaporation rate) is 230g/ (230g+47g)=83%.In addition, being surveyed by high performance liquid chromatography It is 11 weight ppm when the concentration of benzofuran -2,3- diketone in fixed thick diphenyl carbonate.

[embodiment 7]

Raffinate in detachable flask obtained in embodiment 6 is being maintained to 150 DEG C of state, is taking out wherein 40g. Herein, the molecular weight of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is the adduction of 431,4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride The molecular weight of object is 467, thus in raffinate 40g, to be dissolved in the 4- 2-methyl-2-phenylpropane base triphen that the state of diphenyl carbonate contains Base phosphonium chloride is 15g × (431 ÷ 467) × (40 ÷ 47)=11.8g.

In the adduct (adduction that 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride obtained in embodiment 1 is wherein added Rate 91%) 0.3g (0.640 mM) and phenostal 267g (1.102 moles) are in uniform solution.Here, it further blows Enter hydrogen chloride 400cm³(0.0179 mole), is warming up to 230 DEG C.

In addition, a part of the liquid in detachable flask is taken out, high performance liquid chromatography is passed through when reaching 230 DEG C It is 59.6 weight % of phenostal, 33.67 weight % of diphenyl carbonate, 0.2 weight % of phenol when method carries out composition analysis.

After reaching 230 DEG C in detachable flask, the carbon monoxide generated in reaction is removed with nitrogen under normal pressure on one side It goes to outside reaction system, is reacted 6 hours in the state of being kept for 230 DEG C on one side.A part of liquid after reacting 6 hours is taken It out, is 92.7 weight % of diphenyl carbonate, 0.3 weight % of phenol, oxalic acid when carrying out composition analysis by high performance liquid chromatography 548.1 weight ppm of diphenyl ester.Herein, the conversion ratio of phenostal is 99.9%.

Then, pressure is slowly reduced to 10Torr, distillates thick diphenyl carbonate 200g.After distillating thick diphenyl carbonate Detachable flask in raffinate 36g, visually dissolved at 200 DEG C.

Therefore, enrichment factor (evaporation rate) is 200g/ (230g+36g) × 100=84.7%.In addition, passing through high-efficient liquid phase color It is 10 weight ppm when spectrometry measures the concentration of benzofuran -2,3- diketone in thick diphenyl carbonate.

[comparative example 3]

In embodiment 6, the charge weight of phenostal is reduced to 95g (0.392 mole) by 300g, uses synthesis example 1 Obtained in tetraphenylphosphonium chloride and hydrogen chloride adduct 5g replace 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride plus Object 15g is closed, the reaction time at 230 DEG C shortened to 1.3 hours from 6 hours, in addition to this, manufactures similarly to Example 6 Diphenyl carbonate.

The group of liquid after reaction 1.3 hours becomes, 59.8 weight % of diphenyl carbonate, 30.7 weight of phenostal Measure %, 0.2 weight % of phenol.Herein, the conversion ratio of phenostal is 70.2%.

In addition, thick diphenyl carbonate is made to distillate 38g.The raffinate in detachable flask after slightly diphenyl carbonate distillates 45g is visually in slurry at 200 DEG C.Therefore, enrichment factor (evaporation rate) is 38g/ (38g+45g) × 100=46%.In addition, It is 150 weight ppm when by the concentration of benzofuran -2,3- diketone in the thick diphenyl carbonate of high effective liquid chromatography for measuring.

[comparative example 4]

In embodiment 6, the charge weight of phenostal is reduced to 95g (0.392 mole) by 300g, uses tetraphenylphosphonichloride chloride Phosphine 5g replaces the adduct 15g of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, adds chlorine after dissolving tetraphenylphosphonium chloride Change hydrogen 300cm³, the reaction time at 230 DEG C was shortened to 1.3 hours from 6 hours, in addition to this, similarly to Example 6 Manufacture diphenyl carbonate.

The group of liquid after reaction 1.3 hours becomes, 57.8 weight % of diphenyl carbonate, 28.4 weight of phenostal Measure %, 0.2 weight % of phenol.Herein, the conversion ratio of phenostal is 72.5%.

In addition, thick diphenyl carbonate is made to distillate 66g.The raffinate in detachable flask after slightly diphenyl carbonate distillates 22g is visually in slurry at 200 DEG C.Therefore, enrichment factor (evaporation rate) is 66g/ (66g+22g) × 100=75%.In addition, It is 120 weight ppm when by the concentration of benzofuran -2,3- diketone in the thick diphenyl carbonate of high effective liquid chromatography for measuring.

The result of embodiment 6, comparative example 3 and comparative example 4 is summarized in table 4.It is confirmed by table 4,4- 2-methyl-2-phenylpropane base triphen Benzofuran -2 can be obtained compared with the adduct of tetraphenylphosphonium chloride and tetraphenylphosphonium chloride and hydrogen chloride in base phosphonium chloride, 3- diketone is less, high-purity diphenyl carbonate.

Furthermore, it was demonstrated that: due to 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, with tetraphenylphosphonium chloride and tetraphenylphosphonium chloride and The adduct of hydrogen chloride is compared, higher to the solubility of diphenyl carbonate, even if making phenostal with high conversion reaction After diphenyl carbonate, diphenyl carbonate is concentrated in high concentration, catalyst will not be precipitated in raffinate, thus be easy to recycle residual Catalyst contained in liquid.

[table 4]

The type and reaction achievement of catalyst

※ TPPC ... tetraphenylphosphonichloride chloride phosphorus.

※ DPO ... phenostal.

※ DPC ... diphenyl carbonate.

※ YF ... benzofuran -2,3- diketone.

[embodiment 8]

Into 500 milliliters of a full set of tubular type of detachable flask for having thermometer and blender, it is packed into 4- 2-methyl-2-phenylpropane base Triphenyl phosphine dichloride 20g (0.05 mole), n-butyl alcohol 5g and 28 weight % hydrochloric acid 75g, are heated to 90 DEG C under nitrogen atmosphere, In uniform solution.Then, slurries are obtained by the way that detachable flask is cooled to 10 DEG C.

The slurries are filtered by glass filter, obtained solid is moved into eggplant type flask.By by the eggplant type flask It is mounted on the rotary evaporator for having oil bath, it is 2 hours dry at pressure 10Torr by oil bath heating to 100 DEG C, it obtains 15g solid.

The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 15.8 weight %.Therefore, the amount of chlorine contained in the solid is 15g × 0.158=2.4g (0.068 mole).

Herein, if the amount that the amount of the chlorine is considered as hydrogen chloride contained by adduct (is ignored hydrogen contained in hydrogen chloride point When), the molecular weight of 4- tolyl triphenylphosphine is 353, thus 4- tolyl triphenylphosphine contained by the solid is 15g × (1- 0.158)=12.6g (0.036 mole), the amount of chlorine contained by the hydrogen chloride of adduct is 0.068 mole -0.036 mole= 0.032 mole.

It is thus identified that the solid is the 4- tolyl triphen of adduction rate 89% (0.032 mole of ÷ 0.036 mole × 100) The adduct of base phosphonium chloride and hydrogen chloride.In addition, the yield for calculating adduct is 0.036 mole of 0.05 × 100=72% of ÷.

[embodiment 9]

In embodiment 6, the adduct of 4- tolyl triphenyl phosphine dichloride and hydrogen chloride obtained in embodiment 8 is used 15g (0.035 mole) (adduction rate 89%) replaces the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, by 230 DEG C Under reaction time foreshortened to 3 hours by 6 hours, in addition to this similarly manufacture diphenyl carbonate with embodiment 6.

Liquid group when reaching 230 DEG C becomes, 66.2 weight % of phenostal, diphenyl carbonate 26.6 weight %, 4- 5.1 weight % of tolyl triphenyl phosphine dichloride, 1.5 weight % of phenol.

In addition, the group of the liquid after reaction 3 hours becomes, and 49.5 weight % of diphenyl carbonate, 39.5 weight of phenostal Measure %, 3.6 weight % of 4- tolyl triphenyl phosphine dichloride, 2.3 weight % of phenol.Herein, the conversion ratio of phenostal is 61%.

Herein, the reaction solution after reaction (before the sample for taking out composition analysis) is 265g, 4- tolyl benzyltriphenylphosphonium chloride The molecular weight of phosphine is 389.Therefore, calculate reaction after reaction solution contained in 4- tolyl triphenyl phosphine dichloride be 265g × 0.036 ÷ 389=0.025 mole.

Herein, since the charge weight of 4- tolyl triphenyl phosphine dichloride and the adduct of hydrogen chloride is 0.035 mole, The resolution ratio of the adduct of 4- tolyl triphenyl phosphine dichloride and hydrogen chloride is that (0.035 mole -0.025 mole) ÷ 0.035 rubs That × 100=29%.

Therefore, it is confirmed from the comparison of embodiment 6 and embodiment 9, the asymmetric four aryl halogenation phosphine without benzylic protons, That is the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, the high stability in de-carbonyl reaction are especially excellent Choosing.

[embodiment 10]

In the test tube for having stirrer and thermometer, it is packed into thick diphenyl carbonate obtained in embodiment 6 and (contains 11 weight Benzofuran -2,3- diketone of ppm) after 100g, with oil bath heating, making the interior temperature of the test tube is 100 DEG C.

Further heating, making the interior temperature of the test tube is 230 DEG C, adds 1 mole of dm^-3Sodium hydrate aqueous solution 1cm³ (as 1 mM of sodium hydroxide), after maintaining 230 DEG C, 120 minutes as former state, passes through its benzo of high effective liquid chromatography for measuring The concentration of furans -2,3- diketone.As a result, being 100 weight ppb.

Therefore, the resolution ratio of benzofuran -2,3- diketone is (11ppm-100ppb) ÷ 11ppm × 100=99.1%.

[synthesis example 2]

By method as shown below, synthesis of phenyl (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO).

By method identical with the method recorded in No. 5892091 specifications of U.S. Patent No., chloro oxalic acid benzene is synthesized Ester (PCO).

That is, being packed into phenostal 27.3g (0.11 mole) and third in 1 liter of conical flask for having magnetic stirring apparatus Ketone 600cm³.By in 50cm³Beaker in be packed into water 25cm³, it is slowly added to acetic acid 6.8g (0.11 mole) and carbonic acid thereto Potassium 7.8g (0.06 mole) is simultaneously mixed, and thus obtains acetic acid aqueous solutions of potassium.

The acetic acid aqueous solutions of potassium is packed into dropping funel, is stirred on one side into the acetone soln for the phenostal previously prepared It mixes, instilled within one side used time 4 hours.After instillation, futher stirs 2 hours, obtain slurries.It will be depressurized by the slurries The solid component arrived is suspended with acetone and is cleaned, and obtains the solid of white.By being dried under reduced pressure the solid component of the white, obtain Oxalic acid phenyl ester sylvite 20.1g (0.10 mole).

The oxalic acid phenyl ester sylvite is packed into 100cm³Eggplant type flask in, kept the temperature at 20 DEG C using water-bath.It is leaked to dropping liquid Thionyl chloride 17.5g (0.15 mole) is added in bucket, instills in the used time 30 minutes oxalic acid phenyl ester sylvite into eggplant type flask.

After instillation, return pipe is set in eggplant type flask, is warming up to 90 DEG C and reacts 1 hour.After reaction, by eggplant shape The return pipe of flask, which changes into, distillates pipe, distillates unreacted thionyl chloride.After thionyl chloride is distilled off, by depressurizing, Obtain chloro oxalic acid phenyl ester 15.5g (0.08 mole).

By the chloro oxalic acid phenyl ester and tetrahydrofuran 100cm³It is packed into 500cm together³Eggplant type flask in.Pass through the used time 10 Minute instills pyridine 6.6g (0.08 mole) thereto, obtains slurries.

By phenyl salicylate 18.0g (0.08 mole) and tetrahydrofuran 100cm³It is packed into 200cm³Beaker in, be added previous Slurries after, react 2 hours.After reaction, toluene 100cm is added³, further add water 100cm³, hydrolysis.

2 phase separating liquids of the hydrolysis are moved into separatory funnel, separate water.By adding saturated carbon into obtained organic phase Sour hydrogen sodium water solution 100cm³It is sufficiently mixed, neutralizes, after obtaining 2 phase separating liquids, separate water phase.

By the way that saturated sodium-chloride water solution 100cm is further added into obtained organic phase³, after dehydration, separate water phase. Obtained organic phase is moved into 500cm³Conical flask, be added magnesium sulfate 30g, further be dehydrated.

By filtering the organic phase, after filtering out magnesium sulfate, organic phase is moved into 500cm³Eggplant type flask, use under reduced pressure Evaporator distillates tetrahydrofuran.It is slowly added hexane into the liquid after distillating the tetrahydrofuran, when crystallization is precipitated, stops The addition of hexane, lets cool.

Obtained slurries are filtered under diminished pressure, the solid component of white is obtained.Solid component by making the white depressurizes dry It is dry, obtain phenyl (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) 10.2g (0.03 mole).

[embodiment 11]

Having thermometer, blender, a full set of tubular type 500cm for distillating pipe and recipient³Detachable flask in, It is fitted into phenostal 89g (0.367 mole), aftermentioned real applies the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and chlorine manufactured in example 25 Change the adduct 10g (0.021 mole) and phenyl (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) 1g of hydrogen) (0.003 rubs You) after, it will heat up in detachable flask.

After reaching 230 DEG C in detachable flask, the carbon monoxide that reaction generates is removed to outside reaction system on one side, 60 minutes de-carbonyl reactions are carried out in the state of being kept for 230 DEG C on one side.A part of the liquid of reaction after sixty minutes is taken It out, is 1.33 weight % of phenol, 20.36 weight % of phenostal, carbon when carrying out composition analysis by high performance liquid chromatography 64.92 weight % of diphenyl phthalate.

[embodiment 12]

In embodiment 11, phenostal is changed to 85g (0.351 mole) from 89g, phenyl (adjacent phenyloxycarbonyl benzene Base) oxalate (OCPO) from 1g is changed to 5g (0.014 mole), and in addition to this, implement similarly to Example 11, carries out decarbonylation base Its liquid of reaction after sixty minutes is analyzed in reaction.As a result, 1.19 weight % of phenol, 12.89 weight % of phenostal, 68.47 weight % of diphenyl carbonate.

[embodiment 13]

In embodiment 11, phenostal is increased into 90g (0.372 mole) from 89g, phenyl (adjacent phenoxy group is not used Carbonyl phenyl) oxalate (OCPO) in addition to this implemented similarly to Example 11, and de-carbonyl reaction is carried out, its reaction is analyzed Liquid after sixty minutes.As a result, 1.40 weight % of phenol, 21.98 weight % of phenostal, diphenyl carbonate 64.40 Weight %.

The result of embodiment 11~13 is summarized in table 5.

[table 5]

The result of embodiment 11~13

※ Monitoring lower-cut is 1 weight ppm or less

It is confirmed by table 5, by using the grass of phenyl (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) containing specific quantity Thus diphenyl phthalate efficiently and stably manufactures the amount reduction of phenol, the diphenyl carbonate of high-purity.

[embodiment 14]

In the tube sealing teat glass of wall thickness 5mm, it is fitted into the 4- 2-methyl-2-phenylpropane base triphen manufactured in aftermentioned embodiment 25 The adduct 0.03g (0.06 mM) of base phosphonium chloride and hydrogen chloride and phenostal 0.57g (2.35 mMs).Using true Sky pump closing, so as to be 10kPa in tube sealing teat glass, tube sealing volume becomes 30cm³.The tube sealing is set to be impregnated in 230 DEG C oil bath in the state of react 1 hour.

Reaction solution after reaction is taken out from tube sealing, composition analysis is carried out by high performance liquid chromatography.As a result, benzene 0.66 weight % of phenol, 34.13 weight % of phenostal, 58.81 weight % of diphenyl carbonate, phenyl is (to phenyloxycarbonyl benzene Base) 0.27 weight % of carbonic ester (PCPC).In addition, the conversion ratio of phenostal is 67%.

Herein, in de-carbonyl reaction, rise with the pressure in generation carbon monoxide correspondingly tube sealing, according to perfect gas Equation of state, the absolute pressure in tube sealing after reaction are as follows: yield × gas constant of carbon monoxide × temperature ÷ tube sealing Volume=(0.00235 mole × 0.67) × 8.314Pam³·K^-1× mole^-1×(230+273)K÷(0.000030m³)= 0.2MPa。

[embodiment 15]

In the tube sealing teat glass of wall thickness 5mm, it is fitted into the 4- 2-methyl-2-phenylpropane base triphen manufactured in aftermentioned embodiment 25 The adduct 0.10g (0.21 mM) of base phosphonium chloride and hydrogen chloride and phenostal 1.90g (7.84 mMs), with implementation Example 14 is similarly implemented, and reacts 1 hour.

Reaction solution after reaction is taken out from tube sealing, composition analysis is carried out by high performance liquid chromatography.As a result, benzene 0.65 weight % of phenol, 34.85 weight % of phenostal, 57.88 weight % of diphenyl carbonate, phenyl is (to phenyloxycarbonyl benzene Base) 0.27 weight % of carbonic ester (PCPC).In addition, the conversion ratio of phenostal is 66%.

Herein, in de-carbonyl reaction, correspondingly with generation carbon monoxide, the pressure in tube sealing rises, according to perfect gas Equation of state, the absolute pressure in tube sealing after reaction are as follows: yield × gas constant of carbon monoxide × temperature ÷ envelope Pipe volume=(0.00784 mole × 0.66) × 8.314Pam³·K^-1× mole^-1×(230+273)K÷(0.000030m³) =0.7MPa.

[embodiment 16]

In the tube sealing teat glass of wall thickness 5mm, it is packed into 4- 2-methyl-2-phenylpropane base benzyltriphenylphosphonium chloride similarly to Example 14 The adduct and phenostal of phosphine and hydrogen chloride make in tube sealing teat glass to be back to normal pressure (absolute pressure after 10kPa Power 0.10MPa), it is reacted 1 hour under the dress state in the oil bath for being impregnated in 230 DEG C as former state.

Reaction solution after reaction is taken out from tube sealing, composition analysis is carried out by high performance liquid chromatography.As a result, benzene 0.63 weight % of phenol, 34.61 weight % of phenostal, 58.33 weight % of diphenyl carbonate, phenyl is (to phenyloxycarbonyl benzene Base) 0.41 weight % of carbonic ester (PCPC).

The result of embodiment 14~16 is summarized in table 6.

[table 6]

The result of embodiment 14~16

After reaction	Embodiment 14	Embodiment 15	Embodiment 16
				Absolute pressure	0.2MPa	0.7MPa	0.10MPa
Diphenyl oxalate ester concentration	34.13 weight %	34.85 weight %	34.61 weight %
				Dipheryl carbonate ester concentration	58.81 weight %	57.88 weight %	58.33 weight %
PCPC concentration	0.27 weight %	0.27 weight %	0.41 weight %
				Phenol concentration	0.66 weight %	0.65 weight %	0.63 weight %

It is confirmed by table 6, by carrying out de-carbonyl reaction under specific pressurized conditions, can more efficient, more stably be manufactured The by-product of phenyl (to phenyloxycarbonyl phenyl) carbonic ester is less, higher purity diphenyl carbonate.

[embodiment 17]

Have thermometer, blender, distillate pipe, recipient and diameter 2mm glass tube a full set of tubular type 500cm³ Detachable flask in, be fitted into phenostal 185.8g, diphenyl carbonate 74.0g and aftermentioned embodiment 25 and manufacture 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride adduct 13.9g after, start the stirring carried out with stirring wing.Passing through will It is warming up to 150 DEG C in detachable flask, dissolves the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.

A part of the liquid is taken out, when calculating chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride molar ratio, is 1.225 (0.03660 mole/0.02988 moles).In addition, the amount of chlorine atom, passes through potential difference titration outfit (capital with silver nitrate All potential difference titration outfits " AT-610 " of Electronics Industry Company) measurement.In addition, the amount of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride Pass through high effective liquid chromatography for measuring.

The position for adjusting the front end of glass tube, makes the position of the front end of glass tube in the lower part of detachable flask (from liquid The downward 60mm in body upper surface becomes the center side of flask bottom surface from the upward 20mm in flask bottom), and then heats up, when detachable burning If reach 230 DEG C in bottle, by the glass tube with 0.08cm per minute³It is blown into nitrogen, starts to blister.Herein, relative to can The superficial linear velocity of the nitrogen of separate type flask is 0.00046ms^-1, the bubble diameter of nitrogen is about 7mm.

The gas of the nitrogen being blown into from the lower part of detachable flask etc. is removed from reactor top on one side, is being protected on one side The reaction was continued in the state of holding 230 DEG C.The a part for the liquid for reacting 1 hour is taken out, is carried out by high performance liquid chromatography When composition analysis, the diphenyl carbonate containing 0.33 weight % of phenol, 13.57 weight % of phenostal is obtained.In addition, this is anti- Chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride molar ratio in liquid after answering 1 hour is 1.051.

In the case where keeping the state, further continue reaction, after 3 hours, takes out reaction solution again since reaction A part, when carrying out composition analysis by high performance liquid chromatography, the concentration of phenostal is 0.77 weight %, and phenol is dense Degree is reduced to 0.30 weight %.In addition, chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride in liquid after the reaction 3 hours Molar ratio be reduced to 1.034.In addition, the conversion ratio of the phenostal between after reaction beginning 1~3 hour is 94.4%.

In the case where keeping the state, further continue reaction, takes out reaction solution after 5 hours since reaction A part, when carrying out composition analysis by high performance liquid chromatography, the concentration of phenostal is 1.53 weight %, phenol concentration It is further reduced as 0.29 weight %.In addition, chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl chlorine in liquid after the reaction 3 hours The molar ratio drop for changing phosphine is reduced to 1.028.

In addition, reaction start 3~5 hours after between phenostal conversion ratio be 98.0%, than reaction start 1~ It is improved after 3 hours.In addition, the conversion ratio of the phenostal between after reaction beginning 1~5 hour is 99.89%.

[embodiment 18]

In embodiment 17, the amount of being blown into of nitrogen is increased into 0.3cm³(the void tower of the nitrogen relative to detachable flask Linear velocity is 0.00170ms^-1, the bubble diameter of nitrogen is about 7mm), in addition to this, carbonic acid two is carried out similarly to Example 17 The manufacture of phenyl ester, the composition analysis of the liquid after carrying out its reaction.

The amount of phenol contained in diphenyl carbonate after reaction is reduced to 0.30 weight % after reaction 1 hour, anti- It is reduced to 0.25 weight % after answering 3 hours, is reduced to 0.22 weight % of phenol after reaction 5 hours.In addition, the liquid after reaction Chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride molar ratio, reaction 1 hour after be slowly reduced to 1.031, reaction 3 1.019 are slowly reduced to after hour, is slowly reduced to 1.009 after reaction 5 hours.

The amount of phenostal contained in diphenyl carbonate after reaction is 16.54 weight % after reaction 1 hour, It is 1.05 weight % after reaction 3 hours, is 0.001 weight % after reaction 5 hours.The conversion ratio of phenostal is opened in reaction It is 93.7% between after beginning 1~3 hour, reacting between after starting 3~5 hours is 98.0%, after starting 1~3 hour than reaction It improves.In addition, the conversion ratio of the phenostal between after reaction beginning 1~5 hour is 99.99%.

[embodiment 19]

In embodiment 17, it is not blown into nitrogen, in addition to this, carries out the system of diphenyl carbonate similarly to Example 17 It makes, the composition analysis of the liquid after carrying out its reaction.

The amount of phenol contained in diphenyl carbonate after reaction is not reduced substantially, is 0.39 weight after reaction 1 hour % is measured, is after 3 hours of reaction 0.36 weight %, phenol is 0.37 weight % after reaction 5 hours.

In addition, chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride molar ratio of the liquid after reaction is slowly reduced, 5 It is 1.250 after hour reaction.The amount of phenostal contained in diphenyl carbonate after reaction, reaction 1 hour after be 17.04 weight % are 0.71 weight % after reaction 3 hours, are 0.042 weight % after reaction 5 hours.

The conversion ratio of phenostal is 95.9% between after reaction beginning 1~3 hour, and reaction starts 3~5 hours It is 94.1% between afterwards, is reduced after starting 1~3 hour than reaction.In addition, the diphenyl oxalate between after reaction beginning 1~5 hour The conversion ratio of ester is 99.76%, and embodiment 17 and 18 is higher.

By the superficial linear velocity of the nitrogen in embodiment 17~19, phenol concentration, reaction conversion ratio and chlorine atom/uncle 4- The molar ratio of butylbenzene base triphenyl phosphine dichloride is summarized in table 7.

[table 7]

Superficial linear velocity, phenol concentration, reaction conversion ratio and the tertiary fourth of chlorine atom/4- of nitrogen in embodiment 17~19 The molar ratio of phenyl triphenyl phosphine dichloride

It is confirmed by table 7, by the way that nitrogen is supplied specific quantity from reactor lower part, the phenol amount in reaction solution is reduced, can be more Efficiently, diphenyl carbonate is more stably manufactured.Furthermore, it was demonstrated that: the supply amount of nitrogen is more, and chlorine contained in catalyst is easier Volatilization.

[reference example 1]

In the 200cm for having stirrer³Eggplant type flask in, be packed into phenostal 100g (413 mMs), the tertiary fourth of 4- Phenyl triphenyl phosphine dichloride (molecular weight 431) 20g, is impregnated in 150 DEG C of oil bath.Make hydrogen chloride gas (molecular weight 36) wherein After 560 milliliters of (23 mMs) blisterings, the temperature of oil bath is warming up to 230 DEG C, is reacted 2 hours.

After reaction, installation distillates pipe on the eggplant type flask, makes diphenyl carbonate and phenol under full vacuum with diaphragm pump Mixture 56g distillate.After obtained stillage residue is cooled to 100 DEG C, when methyl iso-butyl ketone (MIBK) 100g is added, white slurry Liquid.

The slurries are cooled to room temperature (about 30 DEG C), when making (60 mMs) of 1450 milliliters of hydrogen chloride gas blisterings, absorbing (relative to 1 mole of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, supplying 1.3 moles=0.060 ÷ of hydrogen chloride (20 ÷ 431)), obtains It is visually in uniform liquid.

In the liquid, when 30 minutes used times addition water 5g, white slurry again.By the way that the slurries were depressurized After filter, is suspended and cleaned with methyl iso-butyl ketone (MIBK) 20g, obtain 26g solid.In addition, the filterability in being filtered under diminished pressure of the solid is good It is good.

It is when being analyzed with moisture meter (capital of a country Electronics Industry Company system " MKS-500 ") by the moisture concentration in the solid 6.5 weight %.In addition, being 4- 2-methyl-2-phenylpropane base benzyltriphenylphosphonium chloride when the composition of the solid is passed through high-efficient liquid phase chromatogram technique analysis 9.6 weight % of 73.0 weight % of phosphine, 10.9 weight % of methyl iso-butyl ketone (MIBK) and other compositions (in addition to 6.5 weight % of water).This Outside, the rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (26g × 0.730) ÷ (20g) × 100=95%.

[embodiment 20]

In the 200cm for having stirrer³Eggplant type flask in, be packed into phenostal 102g (421 mMs), aftermentioned Adduct (molecular weight 467) 20g of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride manufactured in embodiment 25, is impregnated in In 230 DEG C of oil bath, reaction 2 hours (conversion ratio of phenostal is 99.99%).

After reaction, installation distillates pipe on the eggplant type flask, makes diphenyl carbonate and phenol under full vacuum with diaphragm pump Mixture 56g distillate that (amount of liquid before distillating is 110g, thus the enrichment factor (evaporation rate) of diphenyl carbonate is 56g/110g =51%).After obtained stillage residue is cooled to 100 DEG C, when methyl iso-butyl ketone (MIBK) 100g is added, white slurry.

The slurries are cooled to room temperature (about 30 DEG C), when making (56 mMs) of 1330 milliliters of hydrogen chloride gas blisterings, absorbing (relative to 1 mole of adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, supply 1.3 moles=0.056 ÷ of hydrogen chloride (20 ÷ 467)), it obtains visually in uniform liquid.

In the liquid, when 30 minutes used times addition water 5g, white slurry again.By the way that the slurries were depressurized After filter, is suspended and cleaned with methyl iso-butyl ketone (MIBK) 21g, obtain 25g solid.In addition, the filterability in being filtered under diminished pressure of the solid is good It is good.

It is 7.2 when moisture concentration in the solid is analyzed with moisture meter (capital of a country Electronics Industry Company system " MKS-500 ") Weight %.In addition, being 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride when the composition of the solid is passed through high-efficient liquid phase chromatogram technique analysis 9.7 weight % of 73.0 weight %, 10.1 weight % of methyl iso-butyl ketone (MIBK) and other compositions (in addition to 7.2 weight % of water).

Further, since the molecular weight of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride be 431,4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and The molecular weight of the adduct of hydrogen chloride is 467, so the rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is the (÷ of 25g × 0.730 431) ÷ (20 ÷ 467) × 100=99%.

[reference example 2]

In reference example 1, keep the methyl of 3500 weight ppm of water content different using adding water in the methyl iso-butyl ketone (MIBK) Butyl ketone substitutes methyl iso-butyl ketone (MIBK) (water containing 500 weight ppm), in addition to this, in 4- 2-methyl-2-phenylpropane base in the same manner as reference example 1 After the de-carbonyl reaction for carrying out phenostal in the presence of triphenyl phosphine dichloride and hydrogen chloride gas, make diphenyl carbonate and benzene The mixture of phenol distillates, and the solid of the 26g base triphenyl phosphine dichloride of 2-methyl-2-phenylpropane containing 4- is obtained from obtained stillage residue.But if By the filterability in being filtered under diminished pressure of the solid compared with the filterability of the solid of reference example 1, then the filtering of the solid of reference example 1 Property is be more good.

It is 7.2 when moisture concentration in the solid is analyzed with moisture meter (capital of a country Electronics Industry Company system " MKS-500 ") Weight %.In addition, being 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride when the composition of the solid is passed through high-efficient liquid phase chromatogram technique analysis 10.8 weight % of 69.0 weight %, 13.0 weight % of methyl iso-butyl ketone (MIBK) and other compositions (in addition to 7.2 weight % of water).This Outside, the rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (26g × 0.690) ÷ (20g) × 100=90%.

[comparative example 5]

In the 200cm for having stirrer³Eggplant type flask in, be packed into phenostal 102g (421 mMs), aftermentioned The 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 22g (51 mMs) manufactured in embodiment 25, is impregnated in 150 DEG C of oil bath.At it In make (26 mMs) of 574 milliliters of hydrogen chloride gas blisterings after, the temperature of oil bath is warming up to 230 DEG C, is reacted 2 hours.

After reaction, installation distillates pipe on the eggplant type flask, makes diphenyl carbonate and phenol under full vacuum with diaphragm pump Mixture 57g distillate.After obtained stillage residue is cooled to 100 DEG C, when methyl iso-butyl ketone (MIBK) 110g is added, white slurry Liquid.

When the slurries are cooled to room temperature (about 30 DEG C), mobility disappears, in the state that can not be filtered.Therefore, pass through liter Temperature improves mobility and filters, thus obtain 45g solid to 80 DEG C.In addition, being filtered under diminished pressure for the solid is time-consuming.

In addition, being 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride when passing through the composition of the high-efficient liquid phase chromatogram technique analysis solid 2.0 weight % of 26.0 weight %, 65.1 weight % of methyl iso-butyl ketone (MIBK), 6.9 weight % of diphenyl carbonate and other compositions. In addition, the rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (45g × 0.260) ÷ (22g) × 100=53%.

[comparative example 6]

Oxalic acid two is carried out in the presence of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride gas in the same manner as reference example 1 It is by distillating the mixture of diphenyl carbonate and phenol, obtained stillage residue is cooling after the de-carbonyl reaction of phenyl ester, addition Thus methyl iso-butyl ketone (MIBK) obtains white slurries.

The slurries are cooled to room temperature (about 30 DEG C), when adding 28 weight % hydrochloric acid 2580mg and stirring, precipitate agglutination. The precipitate of the agglutination is scraped with scraper broken, after being filtered under diminished pressure, is cleaned by being suspended with methyl iso-butyl ketone (MIBK) 20g, thus obtained 21g solid.In addition, being filtered under diminished pressure for the solid is time-consuming.

When moisture concentration in the solid is analyzed with moisture meter (capital of a country Electronics Industry Company system " MKS-500 "), it is 10.2 weight %.In addition, being 4- 2-methyl-2-phenylpropane base benzyltriphenylphosphonium chloride when the composition of the solid is passed through high-efficient liquid phase chromatogram technique analysis 1.2 weight % of 71.0 weight % of phosphine, 17.6 weight % of methyl iso-butyl ketone (MIBK) and other compositions (in addition to 10.2 weight % of water). In addition, the rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (21g × 0.710) ÷ (20g) × 100=75%.

[embodiment 21]

In the 500cm for having stirrer³Eggplant type flask in, be packed into phenostal 250g (1032 mMs), aftermentioned Embodiment 25 in adduct (molecular weight 467) 66g of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride for manufacturing, be impregnated in In 230 DEG C of oil bath, reaction 2 hours (conversion ratio of phenostal is 99.99%).

After reaction, installation distillates pipe on the eggplant type flask, makes diphenyl carbonate and phenol under full vacuum with diaphragm pump Mixture 117g distillate that (amount of liquid before distillating is 287g, thus the enrichment factor (evaporation rate) of diphenyl carbonate is 117g/ 287g=40.8%).By the way that obtained stillage residue is cooled to 100 DEG C, catalyst liquid 170g is obtained.The composition of the liquid is led to When crossing liquid chromatography confirmation, the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride containing 36.8 weight %.

A part (78g) of the liquid is moved into other 500cm³Eggplant type flask in, add methyl iso-butyl ketone (MIBK) 166g When, white slurry.The slurries are cooled to room temperature (about 30 DEG C), make (83 mMs) of 2000 milliliters of hydrogen chloride gas to rise Bubble (relative to 1 mole of adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, supplies 1.3 moles of hydrogen chloride when absorbing =0.083 ÷ { (66 ÷ 467) × (78 ÷ 170) }), it obtains visually in uniform liquid.

In the liquid, when 30 minutes used times addition water 3g, white slurry again.By the way that the slurries were depressurized After filter, is suspended and cleaned with methyl iso-butyl ketone (MIBK) 46g, obtain 36g solid.In addition, the filterability in being filtered under diminished pressure of the solid is good It is good.

It is 6.7 when moisture concentration in the solid is analyzed with moisture meter (capital of a country Electronics Industry Company system " MKS-500 ") Weight %.In addition, potential difference titration outfit (capital of a country Electronics Industry Company system " the AT-610 ") analysis by using silver nitrate should It is 7.2 weight % when hydrogen cloride concentration in solid.

It further, is 4- 2-methyl-2-phenylpropane base triphenyl chlorine when the composition of the solid being passed through high-efficient liquid phase chromatogram technique analysis Change 75.0 weight % of phosphine, 8.9 weight % of methyl iso-butyl ketone (MIBK), 0.2 weight % of diphenyl carbonate and 2.0 weight of other compositions It measures % (in addition to water 6.7 weight % and 7.2 weight % of hydrogen chloride).The rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (36g × 0.750) (78g × 0.368)=94% ÷.

[formulation example 1]

In 500cm³Detachable flask in, be packed into methyl iso-butyl ketone (MIBK) 220g.Wherein, make hydrogen chloride gas on one side With 300cm per minute³Blistering supplies 30 minutes on one side.By the hydrogen cloride concentration in the methyl iso-butyl ketone (MIBK) after blistering by making It is 6.6 weight % when being analyzed with the potential difference titration outfit (capital of a country Electronics Industry Company system " AT-610 ") of silver nitrate.

Methyl-isobutyl is added in a part (23g) for the methyl iso-butyl ketone (MIBK) that the hydrogen cloride concentration is 6.6 weight % Ketone 53g prepares the methyl iso-butyl ketone (MIBK) 76g that hydrogen cloride concentration is 2.0 weight %.

[embodiment 22]

A part (90g) of catalyst liquid obtained in embodiment 21 is moved to the 100cm of a full set of tubular type³Dropping funel In, it is heated to 160 DEG C.In other 500cm³Eggplant type flask in, be fitted into the 2.0 weight % of containing hydrogen chloride configured in formulation example 1 Methyl iso-butyl ketone (MIBK) 180g after (relative to 1 mole of adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, supply chlorine Change 1.3 moles of hydrogen=(180 × 0.020 ÷ 36) ÷ { (66 ÷ 467) × (90 ÷ 170) }), which is impregnated in 30 DEG C Water-bath in.It is obtained from 1 hour dropping funel used time addition catalyst liquid 90g so that the interior temperature of the eggplant type flask maintains 30 DEG C To visually in uniform liquid.

In the liquid, when 20 minutes used times instillation 4g water, white slurry.By the way that the slurries are filtered under diminished pressure Afterwards, it is suspended and is cleaned with methyl iso-butyl ketone (MIBK) 20g, thus obtain 22g solid.In addition, the filterability in being filtered under diminished pressure of the solid Well.

When moisture concentration in the solid is analyzed with moisture meter (capital of a country Electronics Industry Company system " MKS-500 "), it is 18.9 weight %.In addition, by using the potential difference titration outfit (capital of a country Electronics Industry Company system " AT-610 ") point of silver nitrate It is 6.7 weight % when analysing the hydrogen cloride concentration in the solid.

It is 60.1 weight of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride when the composition of the solid is passed through high-efficient liquid phase chromatogram technique analysis %, 9.7 weight % of methyl iso-butyl ketone (MIBK), 3.5 weight % of diphenyl carbonate and 1.1 weight % of other compositions are measured (in addition to water 6.7 weight % of 18.9 weight % and hydrogen chloride).The rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (22g × 0.601) ÷ (38g × 0.368)=95%.

Character and recycling about the catalyst recycled in embodiment 20~22, comparative example 5~6 and reference example 1~2 Rate is summarized in table 8.By table 8 as a result, it was confirmed that the recovery method of catalyst through the invention, can simple and effective with height Catalyst of the purity recycling for the manufacture of the diphenyl carbonate of the de-carbonyl reaction progress by phenostal.

[table 8]

The character and the rate of recovery of the catalyst recycled in embodiment 20~22, comparative example 5~6 and reference example 1~2

	Cohesion	Filterability	The rate of recovery
				Reference example 1	Nothing	Well	95%
Embodiment 20	Nothing	Well	99%
				Reference example 2	Nothing	It may filter that	90%
Embodiment 21	Nothing	Well	94%
				Embodiment 22	Nothing	Well	95%
Comparative example 5	Have	Difference	53%
				Comparative example 6	Nothing	Difference	75%

[embodiment 23]

Solid intracorporal 15g obtained in embodiment 22 is packed into 100cm³Eggplant type flask in, be arranged in and have oil bath On rotary evaporator.It is 1 hour dry at pressure 10Toor by oil bath heating to 100 DEG C.Moisture in dry solid is dense When degree is analyzed with moisture meter (capital of a country Electronics Industry Company system " MKS-500 "), according to moisture meter (capital of a country Electronics Industry Company system " MKS-500 ") it is 0.3 weight %.

By the solid intracorporal 5g and phenostal 100g (413 mMs) of the drying, it is packed into 500cm³Eggplant type flask In, it is impregnated in 230 DEG C of oil bath.When composition from dipping after 1 hour is passed through high-efficient liquid phase chromatogram technique analysis, contain carbon 65.0 weight % of diphenyl phthalate, 29.6 weight %, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of phenostal, 5.0 weight %, phenol 0.4 weight %.

[embodiment 24]

In embodiment 23, with the adduct of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride that are manufactured in embodiment 25 (11 mMs) of 5g substitutions make the 5g after the drying of solid obtained in embodiment 22, carry out similarly to Example 23 1 hour De-carbonyl reaction.Composition after being reacted by high-efficient liquid phase chromatogram technique analysis.

As a result, 60.5 weight % of diphenyl carbonate, 34.0 weight %, 4- 2-methyl-2-phenylpropane base benzyltriphenylphosphonium chloride of phenostal 5.0 weight % of phosphine, 0.5 weight % of phenol.

Liquid composition after reaction in embodiment 23 and embodiment 24 is summarized in table 9.It is confirmed by table 9, by making With dipheryl carbonate being recycled by the recovery method of catalyst of the invention, for being carried out by the de-carbonyl reaction of phenostal The catalyst of the manufacture of ester can stablize the diphenyl carbonate of manufacture high-purity.

[table 9]

Liquid composition after reaction in embodiment 23 and 24

[embodiment 25]

By the following method, the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride is synthesized.

Firstly, the method recorded by Japanese Laid-Open 2013-82695 bulletin, synthesizes 4- 2-methyl-2-phenylpropane base triphen bromide Change phosphine.The method that the bromide is recorded by the flat 11-217393 bulletin of Japanese Laid-Open, is transformed to 4- 2-methyl-2-phenylpropane base triphen Base phosphonium chloride (chloride).

4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, butanol and the hydrochloric acid is packed into detachable flask, in nitrogen atmosphere Under be heated to 90 DEG C, make it in uniform solution.Then, by being cooled to room temperature detachable flask to obtain slurries.By the slurry Liquid is filtered by glass filter, and obtained solid is moved to eggplant type flask.By the way that eggplant type flask to be placed on to the rotation for having oil bath Turn on evaporator, it is 2 hours dry at pressure 10Torr by oil bath heating to 100 DEG C, obtain solid.

By potential difference titration outfit " AT-610 " analysis of the solid capital of a country Electronics Industry Company as a result, being 14.2 Weight %, thus confirmation is the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.In addition, with moisture meter (capital of a country electricity Sub- industrial group's system " MKS-500 ") measurement moisture content be 0.4 weight %.

[embodiment 26]

In the 2000cm for having stirrer³Eggplant type flask in, be packed into phenostal 271g (1.1 moles), embodiment Adduct (molecular weight 467) 160g of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride synthesized in 25, is impregnated in 240 DEG C In oil bath.The temperature of oil bath is warming up to 240 DEG C, reaction 2 hours (conversion ratio of phenostal is 99.99%).

After reaction, installation distillates pipe on the eggplant type flask, makes diphenyl carbonate and phenol under full vacuum with diaphragm pump Mixture 20g distillate that (amount of liquid before distillating is 400g, thus the enrichment factor (evaporation rate) of diphenyl carbonate is 20g/400g =5%).After obtained stillage residue is cooled to 100 DEG C, when methyl iso-butyl ketone (MIBK) 800g is added, white slurry.

The slurries are cooled to room temperature (about 20 DEG C), make hydrogen chloride gas (molecular weight 36) 0.01m³(relative to reaction solution Contained in 1 mole of triphenyl phosphine dichloride of 4- 2-methyl-2-phenylpropane base, hydrogen chloride is 1.2 moles) blistering, when absorbing, obtain visually in equal One liquid.When to 30 minutes liquid used times addition water 40g, white slurry again.By being depressurized to by the slurries The solid being obtained by filtration is suspended after cleaning with methyl iso-butyl ketone (MIBK) 100g, is filtered under diminished pressure and obtains filtrate 1100g and solid as a result, 167g。

Herein, by the concentration of methyl iso-butyl ketone (MIBK) contained in obtained filtrate by gas-chromatography standard measure as a result, It is 74.0 weight %.In addition, by the concentration of water contained in the filtrate by moisture meter measure as a result, being 3.5 weight %.It will The concentration of hydrogen chloride contained in the filtrate is quantitative as a result, being 0.3 weight % by potential difference titration outfit.

In addition, the filterability in being filtered under diminished pressure of obtained solid is good.In addition, the composition of the solid is passed through efficient liquid When GC headspace analysis, the concentration of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride (molecular weight 431) is 73 weight %.Therefore, it calculates and makees For solid recycling 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride the rate of recovery be (÷ 431 of 167g × 0.73) ÷ (160g ÷ 467) × 100=83%.

It will be by the bavin field science strain formula meeting for the tower diameter 32mm for having a full set of tubular type detachable flask, thermometer and blender The batch distillation column that society's system " Oldershaw " (plate column) and Liquid liquid Separation slot are constituted, is arranged to make detachable flask When interior filtrate is evaporated, evaporation liquid is supplied to the lower part of Liquid liquid Separation slot by plate column, at the same time, from Liquid liquid Separation slot Top overflow and return in plate column.In addition, being arranged to the plugging of connecting plate type tower and Liquid liquid Separation slot to fore-running Groove tank or main sluice tank substitute Liquid liquid Separation slot.

The 300g being fitted into detachable flask in above-mentioned filtrate.In addition, being packed into water 20cm in Liquid liquid Separation slot³ With methyl iso-butyl ketone (MIBK) 80cm³(64) g makes 15 DEG C of Liquid liquid Separation slot.By by board-like tower pressure interior force from atmospheric depressurized to The bottom temp of detachable flask is warming up to 60.4 DEG C from room temperature, is distilled by 133kPa.

The evaporation liquid distillated from Liquid liquid Separation slot is separated into using water by two-phase as the lower phase of principal component and with methyl tert-butyl Base ketone is the upper phase of principal component.Herein, lower phase is detained in Liquid liquid Separation slot, but upper phase is overflowed and is back in plate column.Companion It being evaporated with dampening and methyl iso-butyl ketone (MIBK), the interface of lower phase and upper phase slowly rises, and the tower top temperature of plate column rises, But the water relative to isobutyl ketone when shortly after, reaching 15 DEG C along with the ratio of the methyl iso-butyl ketone (MIBK) of evaporation and water is satisfied And solubility, the temperature of the tower top temperature of plate column rise nearby laten at 57.7 DEG C it is slow, at the same time, the boundary of lower phase and upper phase The rising in face also stops.

The pipeline of connecting plate type tower and Liquid liquid Separation slot is switched into fore-running groove tank from Liquid liquid Separation slot, along with flashing to Water concentration contained in point reduces, and is distillated to the tower top temperature of plate column 58.2 DEG C near entirely, and temperature, which rises, to laten slow, obtains Head fraction 57g.Herein, by the concentration of methyl iso-butyl ketone (MIBK) contained by head fraction by gas chromatography as a result, 98.0 weight %.

Make reflux ratio 2, by connecting plate type tower and the plugging of fore-running groove tank to main sluice tank, makes detachable flask Bottom temp heating, continue to distillate to 67.3 DEG C, obtain main distillate fraction 153g.By the dense of methyl iso-butyl ketone (MIBK) contained by main distillate fraction Degree is by gas chromatography analysis as a result, 99.9 weight %.

In addition, water contained in main distillate fraction, 0.1 weight % is calculated as according to moisture, hydrogen chloride contained in main distillate fraction, according to Potential difference titration outfit, below detection boundary.Therefore, the rate of recovery of methyl iso-butyl ketone (MIBK) is in calculating main distillate fraction, (153g × 0.999) ÷ (300g × 0.740+64g) × 100=53%.In addition, calculating the methyl iso-butyl ketone (MIBK) supplied it in head fraction Recycling component after full fraction in methyl iso-butyl ketone (MIBK) the rate of recovery be (57g × 0.980+153g × 0.999) ÷ (300g × 0.740+64g) × 100=92%.

[embodiment 27]

In embodiment 26, filtrate 300g is added in detachable flask, is reloaded into head fraction obtained in embodiment 26 57g, in addition to this embodiment 26 is maintained in Liquid liquid Separation slot by the state that liquid accumulates is evaporated makes detachable flask Bottom temp heating, continues to distillate to 67.3 DEG C, until obtaining the operation of main distillate fraction, be steamed similarly to Example 26 It evaporates.

Specifically, head fraction 57g obtained in above-mentioned filtrate 300g and embodiment 26 is packed into detachable flask. In addition, Liquid liquid Separation slot is made to keep being incorporated with the state in the accumulation evaporation liquid of embodiment 26, make 15 DEG C of Liquid liquid Separation slot.Pass through By board-like tower pressure interior force from atmospheric depressurized to 133kPa, the bottom temp of detachable flask is warming up to 60.4 DEG C from room temperature, It is distilled.

The evaporation liquid distillated from Liquid liquid Separation slot is separated into using water by two-phase as the lower phase of principal component and with methyl tert-butyl Base ketone is the upper phase of principal component.Herein, lower phase is detained in Liquid liquid Separation slot, but upper phase is overflowed, and is back in plate column.Lower phase Slowly rise with the interface of upper phase, after the tower top temperature of plate column rises, the temperature of the tower top temperature of plate column rises at 57 DEG C It nearby latens slow, at the same time, the rising at the interface of lower phase and upper phase also stops.

The pipeline of connecting plate type tower and Liquid liquid Separation slot is switched into fore-running groove tank from Liquid liquid Separation slot, is distillated entirely to adjoint Water concentration reduces, the tower top temperature of plate column is 58.2 DEG C near contained in evaporation ingredient, temperature, which rises, to laten slow, obtains Head fraction 60g.Herein, by the concentration of methyl iso-butyl ketone (MIBK) contained by head fraction by gas chromatography analysis as a result, 98.0 weight %.

Make reflux ratio 2, by connecting plate type tower and the plugging of fore-running groove tank to main sluice tank, makes detachable flask Bottom temp heating, continue to distillate to 67.3 DEG C, obtain main distillate fraction 202g.By the dense of methyl iso-butyl ketone (MIBK) contained by main distillate fraction Degree is by gas chromatography analysis as a result, 99.9 weight %.In addition, water contained in main distillate fraction, is calculated as 0.1 according to moisture Weight %, hydrogen chloride contained in main distillate fraction, according to potential difference titration outfit, below detection boundary.

Therefore, the rate of recovery for calculating methyl iso-butyl ketone (MIBK) in main distillate fraction is (202g × 0.999) ÷ (300g × 0.740+ 57g × 0.980) × 100=73%.In addition, after calculating the recycling component for supplying it methyl iso-butyl ketone (MIBK) in head fraction The rate of recovery of methyl iso-butyl ketone (MIBK) in full fraction be (60g × 0.980+202g × 0.999) ÷ (300g × 0.740+57g × 0.980) × 100=94%.

[embodiment 28]

In embodiment 26, the pipeline from plate column is connected to fore-running groove tank, in addition to this, similarly to Example 26 Batch distillation column is arranged in ground.

Above-mentioned filtrate 300g is packed into detachable flask.By making reflux ratio 2, by board-like tower pressure interior force from normal Pressure is decompressed to 133kPa, and the bottom temp of detachable flask is warming up to 60.4 DEG C from room temperature, is distilled.

It distillates to water and is evaporated together along with methyl iso-butyl ketone (MIBK) entirely, the tower top temperature of plate column rises, and evaporates ingredient Contained in water concentration reduce, at the same time, temperature rises nearby to laten slow at 58.2 DEG C, obtains head fraction 131g.Herein, will The concentration of methyl iso-butyl ketone (MIBK) contained by head fraction is by gas chromatography analysis as a result, 92.0 weight %.

It maintains the reflux for, by connecting plate type tower and the plugging of fore-running groove tank to main sluice tank, making detachable burning than being 2 The bottom temp heating of bottle, continues to distillate to 67.3 DEG C, obtains main distillate fraction 79g.By methyl iso-butyl ketone (MIBK) contained by main distillate fraction Concentration is by gas chromatography analysis as a result, 99.9 weight %.

In addition, water contained in main distillate fraction, 0.1 weight % is calculated as according to moisture, hydrogen chloride contained in main distillate fraction, according to Potential difference titration outfit, below detection boundary.Therefore, the rate of recovery for calculating the methyl iso-butyl ketone (MIBK) in main distillate fraction is (79g × 0.999) ÷ (300g × 0.740) × 100=36%.

Head fraction and main distillate fraction are mixed with ratio of the weight ratio meter head fraction 131 to main distillate fraction 79, as full distillate.Entirely Water contained in distillate is calculated as 5.0 weight % according to moisture, and hydrogen chloride contained in full distillate is titrated according to potential difference Device is 0.1 weight %.

By the rate of recovery of the methyl iso-butyl ketone (MIBK) (MIBK) in the composition of the main distillate fraction in embodiment 26~28, main distillate fraction with And the rate of recovery of the methyl iso-butyl ketone (MIBK) (MIBK) in full fraction is summarized in table 10.Table 10 as a result, it was confirmed that through the invention Catalyst recovery method, can will be used for by phenostal de-carbonyl reaction manufacture diphenyl carbonate catalyst return Polar organic solvent used in receiving, is recycled to simple and effective.

[table 10]

The composition of main distillate fraction in embodiment 26~28, methyl iso-butyl ketone (MIBK) (MIBK) in main distillate fraction the rate of recovery and The rate of recovery of methyl iso-butyl ketone (MIBK) (MIBK) in full fraction

	The water concentration of main distillate fraction	The hydrogen cloride concentration of main distillate fraction	The rate of recovery of MIBK in main distillate fraction
				Embodiment 26	0.1 weight %	Detect boundary or less	53 weight %
Embodiment 27	0.1 weight %	Detect boundary or less	73 weight %
				Embodiment 28	0.1 weight %	Detect boundary or less	36 weight %

[embodiment 29]

Using main distillate fraction obtained in embodiment 27, catalyst recycling is carried out.

Specifically, in the eggplant type flask for having stirrer, phenostal 27g (0.11 mole), embodiment 25 are packed into The 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of middle manufacture and adduct (molecular weight 467) 16g of hydrogen chloride, are impregnated in 240 DEG C of oil In bath.The temperature of oil bath is warming up to 240 DEG C, reaction 2 hours (conversion ratio of phenostal is 99.99%).

After reaction, installation distillates pipe on the eggplant type flask, makes diphenyl carbonate and phenol under full vacuum with diaphragm pump Mixture 2g distillate that (amount of liquid before distillating is 40g, thus the enrichment factor (evaporation rate) of diphenyl carbonate is 2g/40g= 5%).After obtained stillage residue is cooled to 100 DEG C, when main distillate fraction 80g obtained in embodiment 26 is added, white slurries Shape.

The slurries are cooled to room temperature (about 20 DEG C), make hydrogen chloride gas (molecular weight 36) 0.001m³(relative to reaction solution Contained in 1 mole of triphenyl phosphine dichloride of 4- 2-methyl-2-phenylpropane base, hydrogen chloride is 0.04 mole) blistering, when absorbing, obtain visually in equal One liquid.Into the liquid, when 30 minutes used times addition water 4g, white slurry again.By subtracting to by the slurries The solid that press filtration obtains is suspended after cleaning with methyl iso-butyl ketone (MIBK) 10g, is filtered under diminished pressure, thus obtains solid 18g.

Filterability in being filtered under diminished pressure of obtained solid is good.In addition, the composition of the solid is passed through high-efficient liquid phase color When chromatography, the concentration of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is 76 weight %.

Therefore, the rate of recovery for calculating as solid the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride (molecular weight 431) recycled is (÷ 431 of 18g × 0.76) ÷ (16g ÷ 467) × 100=93%.In addition, by high-efficient liquid phase chromatogram technique analysis, but phenol is being examined Survey boundary or less.

[embodiment 30]

In embodiment 29, main distillate fraction obtained in the full distillate 80g alternate embodiment 27 obtained in embodiment 28 80g, in addition to this, catalyst recycles similarly to Example 29.But the stock white liquid that whole distillates are added is cooled to Room temperature (about 20 DEG C) makes hydrogen chloride gas 1 rise bubble, absorb, but is not visually in uniform liquid.

[reference example 3]

Add water to the methyl iso-butyl ketone (MIBK) of Wako Pure Chemicals Co., Ltd., is configured to water solubility as 0.3 weight %.In reality It applies in example 29, main distillate fraction obtained in the methyl iso-butyl ketone (MIBK) alternate embodiment 27 with 0.3 weight % of the moisture concentration, except this it Outside, catalyst recycles similarly to Example 29.

But the stock white liquid that whole distillates are added is cooled to room temperature (about 20 DEG C), rise hydrogen chloride gas 1 Bubble absorbs, but is visually only the white slurries of the dissolved residue of visible solid.By to 30 minutes liquid used times addition water 4g Afterwards, it to the solid being filtered under diminished pressure, is suspended after cleaning with methyl iso-butyl ketone (MIBK) 10g, is filtered under diminished pressure, thus obtains solid 18g.

When the composition of obtained solid is passed through high-efficient liquid phase chromatogram technique analysis, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride it is dense Degree is 77 weight %.Therefore, the rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (÷ 431 of 18g × 0.77) ÷ (16g ÷ 467) × 100=94%.But when by the solid high-efficient liquid phase chromatogram technique analysis, the phenol detected is 3 weight %.

About the water being used in embodiment 29,30 and reference example 3 in the methyl iso-butyl ketone (MIBK) (MIBK) of catalyst recycling The rate of recovery of concentration and 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, is summarized in table 11.

It is confirmed by table 11, for the polar organic solvent of catalyst recycling, preferably water concentration is lower, particularly preferred water concentration For 0.3 weight % or less.

[table 11]

In embodiment 29,30 and reference example 3, for the water concentration in the methyl iso-butyl ketone (MIBK) (MIBK) of catalyst recycling And the rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride

	Water concentration in MIBK	The rate of recovery of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride
			Embodiment 29	0.1 weight %	93 weight %
Embodiment 30	5.0 weight %	It can not recycle
			Reference example 3	0.3 weight %	94 weight %

[embodiment 31]

Using catalyst is recycled obtained in embodiment 29, de-carbonyl reaction is carried out.

Firstly, solid 10g obtained in embodiment 29 is packed into 100cm³Eggplant type flask, be mounted on the rotation for having oil bath Turn on evaporator, 140 DEG C of oil bath temperature, is dried 1 hour under full vacuum with diaphragm pump.

In the 500cm for having stirrer³Eggplant type flask in, be packed into the solid 5g and phenostal 95g of the drying (0.4 mole), is impregnated in 230 DEG C of oil bath, reacts 1 hour.

When liquid composition after reaction is passed through high-efficient liquid phase chromatogram technique analysis, containing 66.0 weight % of diphenyl carbonate, 28.6 weight %, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of phenostal 5.0 weight %, 0.4 weight % of phenol.

[embodiment 32]

In embodiment 31, with the adduct of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride that are manufactured in embodiment 25 5g substitution makes the substance after the drying of solid obtained in embodiment 29, is carried out similarly de-carbonyl reaction with embodiment 31.

It is 65.4 weight % of diphenyl carbonate, grass when liquid composition after reaction is passed through high-efficient liquid phase chromatogram technique analysis 29.2 weight %, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of diphenyl phthalate 5.0 weight %, 0.4 weight % of phenol.

By comparing the liquid composition after the reaction in embodiment 31 and 32, it was demonstrated that the polarity for being used for catalyst recycling to have Solvent recycles, and carries out catalyst recycling, can also efficiently and stably manufacture the diphenyl carbonate of high-purity.

As described above, it was demonstrated that by recycling the same of recycling catalyst in the recovery method by catalyst of the invention When, it recycles and is used for catalyst recovered solvent, can efficiently and stably manufacture the diphenyl carbonate of high-purity.

[synthesis example 3]

According to the method recorded in Bull.Chem.Soc.Jpn.82 (2009) 475, benzofuran -2,3- diketone is synthesized.

In the 500cm for having magnetic stir bar³Beaker in, be added isatin 1.5g and 1 mole of dm^-3Sodium hydroxide water Solution 150cm³, dissolve, use water-bath cooling on one side, add sodium nitrite 0.7g on one side.It is slowly added 2.5 moles of dm thereto^-3Sulfuric acid 15cm³, stir 10 minutes.

Then, beaker is placed in water-bath, is warming up to 60 DEG C.It is maintained at 60 DEG C as former state after 1 hour, activity is added in cooling Charcoal 0.1g, is filtered later.Obtained filtrate is moved into separatory funnel, with ethyl acetate 30cm³Extraction.

Obtained organic phase is moved into 500cm³Eggplant type flask in, acetic acid is distilled off under reduced pressure with rotary evaporator Ethyl ester.Toluene 30cm is added to obtained residue³With heptane 20cm³, it is allowed to dissolve.Phosphorus pentoxide 1.5g, peace are added thereto Di Muluo cooling tube is filled, is flowed back 30 minutes.

The slurries being obtained by filtration, add heptane in obtained filtrate, and crystallization obtains benzofuran -2,3- diketone 0.6g.

[reference example 4]

After the phenostal of Tokyo chemical conversion Co. Ltd. system is purified by simple distillation, recrystallized with toluene.It will herein The amount of benzofuran -2,3- diketone contained in obtained phenostal by high effective liquid chromatography for measuring, but is detecting 10 weight ppb of boundary or less.

In the 500cm for having stirrer and thermometer³Three-necked flask in, be packed into diphenyl carbonate 200.0g and oxalic acid two After phenyl ester 0.2g, it is heated to 210 DEG C.In the three-necked flask, the benzofuran -2,3- synthesized in micro synthesis example 3 is added Diketone is 8000 weight ppb when measuring the concentration of its benzofuran -2,3- diketone by high performance liquid chromatography.

It further adds sodium phenate 0.2g in the three-necked flask, maintains 210 DEG C after 30 minutes, pass through high performance liquid chromatography Method is 100 weight ppb when measuring the concentration of its benzofuran -2,3- diketone.

[comparative example 7]

In the 500cm for having stirrer and thermometer³Three-necked flask in, be packed into diphenyl carbonate 200.1g and oxalic acid two After phenyl ester 0.2g, it is heated to 210 DEG C.In the three-necked flask, the benzofuran -2,3- synthesized in micro synthesis example 3 is added Diketone is 578 weight ppb when measuring the concentration of its benzofuran -2,3- diketone by high performance liquid chromatography.

The three-necked flask was maintained 210 DEG C after 120 minutes, by high performance liquid chromatography, measures its benzofuran -2, It is 174 weight ppb when the concentration of 3- diketone.

[comparative example 8]

In the 500cm for having stirrer and thermometer³Three-necked flask in, be packed into diphenyl carbonate 201.2g and oxalic acid two After phenyl ester 0.2g, it is heated to 210 DEG C.The hydrogen chloride being stored in the pulling bag of Taide is added with gastight syringe in the three-necked flask Gas 40cm³, it is 227 weight ppm when by its cl concn of high effective liquid chromatography for measuring.

In the three-necked flask, benzofuran -2, the 3- diketone synthesized in micro synthesis example 3 is further added, is passed through High performance liquid chromatography is 458 weight ppb when measuring the concentration of its benzofuran -2,3- diketone.The three-necked flask is maintained It is 547 weight when by the concentration of high effective liquid chromatography for measuring its benzofuran -2,3- diketone at 210 DEG C after 120 minutes ppb。

The result of reference example 4 and comparative example 7,8 is summarized in table 12.

[table 12]

The result of reference example 4 and comparative example 7,8

※ resolution ratio be by by " benzofuran -2,3- diketone concentration when loading "-" benzofuran -2 after heating, 3- diketone concentration " is as " benzofuran -2,3- diketone concentration of decomposition ", by it divided by " benzofuran -2,3- bis- when loading What ketone concentration " calculated.

It is confirmed in table 12, the reference example 4 that the liquid short time of benzofuran -2,3- diketone containing high concentration is heated Resolution ratio, it is higher than by the resolution ratio of the comparative example 7 of benzofuran -2,3- diketone liquid long-time heating containing low concentration, Thus by the presence of alkaline matter, promotes and decomposed caused by the heating of benzofuran -2,3- diketone.

In addition, by the comparison of comparative example 7 and 8, if also having distinguished has acidic materials to substitute alkaline matter, benzo The amount of furans -2,3- diketone will increase instead.

[reference example 5]

In the test tube for having stirrer and thermometer, after being packed into diphenyl carbonate 20.0g, it is with oil bath heating to interior temperature 200℃.The hydroxide of the benzofuran -2,3- diketone 4.1mg and 9.2 weight % that synthesize in synthesis example 3 are added in the test tube Sodium water solution 53.7mg (being 0.1 mM as sodium hydroxide).

The test tube was maintained 200 DEG C after 30 minutes, passes through its benzofuran -2,3- diketone of high effective liquid chromatography for measuring Concentration when, be 90 weight ppm.Resolution ratio is 55.9%.

[reference example 6]

In the test tube for having stirrer and thermometer, after being packed into diphenyl carbonate 20.0g, it is with oil bath heating to interior temperature 200℃.Benzofuran -2,3- diketone 5.1mg and sodium phenate 14.3mg (0.1 milli synthesized in synthesis example 3 is added in the test tube Mole).

The test tube was maintained 200 DEG C after 30 minutes, passes through its benzofuran -2,3- diketone of high effective liquid chromatography for measuring Concentration when, be 76 weight ppm.Resolution ratio is 70.0%.

[reference example 7]

Sodium hydroxide and phenol are heated up to 50 DEG C, prepare sodium hydroxide-phenol solution of 0.9 weight %.

In the test tube for having stirrer and thermometer, after being packed into diphenyl carbonate 20.0g, it is with oil bath heating to interior temperature 200℃。

In the test tube, the hydrogen-oxygen of benzofuran -2, the 3- diketone 5.5mg and 0.9 weight % that synthesize in synthesis example 3 are added Change sodium-phenol solution 0.6g (being 0.1 mM as sodium hydroxide).The test tube was maintained 200 DEG C after 30 minutes, is passed through It is 86 weight ppm when the concentration of its benzofuran -2,3- diketone of high effective liquid chromatography for measuring.Resolution ratio is 68.7%.

[comparative example 9]

In the test tube for having stirrer and thermometer, after being packed into diphenyl carbonate 20.0g, it is with oil bath heating to interior temperature 200℃.Benzofuran -2,3- diketone the 2.8mg synthesized in synthesis example 3 is added in the test tube.

The test tube was maintained 200 DEG C after 30 minutes, passes through its benzofuran -2,3- diketone of high effective liquid chromatography for measuring Concentration when, be 101 weight ppm.Resolution ratio is 27.9%.

The result of reference example 5~7 and comparative example 9 is summarized in table 13.

[table 13]

The result of reference example 5~7 and comparative example 9

It is confirmed by table 13, by the presence of alkaline matter, promotes and divide caused by the heating of benzofuran -2,3- diketone Solution.In addition, using sodium hydroxide-phenol solution of low concentration than the reference example 5 of the sodium hydrate aqueous solution using high concentration The resolution ratio of reference example 7 is higher, it is thus regarded that, when using solvent, preferably the such solubility to diphenyl carbonate of phenol compared with High solvent.

Confirmed in above-described embodiment, furans based compound contained in thick diphenyl carbonate, by with alkali compounds It contacts and reduces, thus the manufacturing method of diphenyl carbonate through the invention, it can be efficiently and stably continuous with easy method Manufacture the diphenyl carbonate of high-purity.

[reference example 8]

By having thermometer, blender, 500 milliliters of a full set of tubular type of detachable flask for distillating pipe and recipient In, it is packed into phenostal 250g (1 mole), 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 13g (30 mMs), by detachable burning 150 DEG C are heated in bottle, is made into uniform solution (visual).

Next, being blown into 12 mMs of hydrogen chloride gas into the detachable flask, heat up.If in detachable flask If reaching 230 DEG C, the carbon monoxide generated in detachable flask is squeezed out under normal pressure by nitrogen on one side, on one side with It is maintained at 230 DEG C of state response 6 hours.

By making the reaction solution after reaction in this 6 hours slowly be decompressed to 10Torr, by the bottom temperature of detachable flask Degree maintains in the state of being reduced to 180 DEG C, obtains thick diphenyl carbonate 217g as fraction.In addition, at this point, detachable flask Bottom liquid, visually be in uniform state.

By the composition of reaction solution and thick diphenyl carbonate after reactions in 6 hours before, pass through high performance liquid chromatography Analysis.As a result, 6 hours reaction after reaction solution in, diphenyl carbonate be 94 weight %, phenostal be 400 weight ppm (conversion ratio of phenostal is 99.97%).

In addition, being 7000 weight ppm containing phenol in thick diphenyl carbonate, phenostal is 100 weight ppm.It is all In liquid, benzofuran -2,3- diketone is all below detection boundary.

[reference example 9]

In 200 milliliters of a full set of tubular type for having nitrogen ingress pipe of dropping funel, it is packed into 4- 2-methyl-2-phenylpropane base triphenyl chlorine Change phosphine 13g (30 mMs) and Mitsubishi Chemical diphenyl carbonate 10g (47 mMs), nitrogen is supplied on one side, on one side 150 Uniform solution is made at DEG C.

In 500 milliliters of a full set of tubular type for having the dropping funel, thermometer and blender of detachable flask, dress Enter phenostal 150g (619 mMs), 150 DEG C will be heated in detachable flask.

Next, in the detachable flask, from the carbon of dropping funel supply 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride After diphenyl phthalate solution, 12 mMs of hydrogen chloride gas are blown into, is warming up to 230 DEG C.The oxidation that will be generated on one side by reaction Carbon is removed with nitrogen to outside reaction system under normal pressure, react within 5 hours to be maintained at 230 DEG C of state on one side.

A part of liquid after reaction is taken out, when carrying out composition analysis by high performance liquid chromatography, dipheryl carbonate Ester is 94 weight %, and phenostal is 400 weight ppm.

[embodiment 33]

In 2 liters of eggplant type flask, it is packed into 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 200g (0.46 mole), n-butyl alcohol 100g And 28 weight % hydrochloric acid 700g, it is heated to 90 DEG C under nitrogen atmosphere, is in uniform solution.Then, by the way that eggplant type flask is cold But slurries are obtained to room temperature.The slurries are filtered by glass filter, obtain solid 190g.

30g in obtained crystallization is moved into 500cm³Eggplant type flask in.Have by the way that the eggplant type flask to be mounted on It is 2 hours dry at pressure 10Torr by oil bath heating to 70 DEG C on the rotary evaporator of oil bath, obtain 25g solid.

The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 15.2 weight %.Therefore, the amount of chlorine contained in the solid is 25g × 0.152=3.8g (0.107 mole).

Herein, if the amount of the chlorine to be considered as to the amount and chlorination of the chlorine of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride contained by adduct Total (the ignoring hydrogen timesharing contained by hydrogen chloride) of hydrogen amount, then] amount of 4- 2-methyl-2-phenylpropane base triphenylphosphine contained by the solid is 25g × (1-0.152)=21.2g (0.054 mole), the amount of chlorine contained by the hydrogen chloride of adduct are 0.107 mole -0.054 mole =0.053 mole, thus confirm that the solid is the 4- 2-methyl-2-phenylpropane base of adduction rate 95% (0.053 mole of ÷ 0.056 mole × 100) The adduct of triphenyl phosphine dichloride and hydrogen chloride.

In addition, obtained solid is white particle, volume density 0.48gcm^-3, partial size is 180 μm.

Next, the adduct of the adduction rate 95% is used as catalyst, the decarbonylation base for carrying out phenostal is anti- It answers.Specifically, in the de-carbonyl reaction of embodiment 1, as catalyst, using the adduct of above-mentioned adduction rate 95% as catalysis Agent uses, and in addition to this, implements similarly to Example 1, carries out de-carbonyl reaction.Terminate 30 minutes from the supply of adduct Afterwards, a part of the liquid in three-necked flask is taken out, composition analysis is carried out by high performance liquid chromatography.

As a result, 0.5 weight % of phenol, 30.1 weight % of phenostal, 56.2 weight % of diphenyl carbonate.Herein, The conversion ratio of phenostal is 70%.

[embodiment 34]

The eggplant type flask that 30g (0.46 mole) in adduct obtained in embodiment 33 is moved to 500 milliliters, by the eggplant Shape flask is mounted on the rotary evaporator for having oil bath.By the way that oil bath heating to 130 DEG C, is dried 2 at pressure 10Torr Hour, obtain 25g solid.

The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 12.7 weight %.Therefore, the amount of chlorine contained in the solid is 25g × 0.127=3.2g (0.090 mole).

Herein, if the amount of the chlorine to be considered as to the amount (ignoring hydrogen timesharing contained by hydrogen chloride) of hydrogen chloride contained by adduct, The amount of 4- 2-methyl-2-phenylpropane base triphenylphosphine contained by the solid is 25g × (1-0.127)=21.8g (0.055 mole), adduct The amount of chlorine contained by hydrogen chloride is 0.090 mole -0.055 mole=0.035 mole, thus confirms that the solid is adduction rate 64% The adduct of 4- the 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride of (0.035 mole of ÷ 0.055 mole × 100).In addition, obtaining Solid be white particle, volume density 0.45gcm^-3, partial size is 142 μm.

Next, the adduct of the adduction rate 64% is used as catalyst, the decarbonylation base for implementing phenostal is anti- It answers.Specifically, in the de-carbonyl reaction of embodiment 1, as catalyst, using the adduct of above-mentioned adduction rate 64% as catalysis Agent uses, and in addition to this, implements similarly to Example 1, carries out de-carbonyl reaction.Terminate 30 minutes from the supply of adduct Afterwards, a part of the liquid in three-necked flask is taken out, composition analysis is carried out by high performance liquid chromatography.

As a result, 0.6 weight % of phenol, 31.2 weight % of phenostal, 55.6 weight % of diphenyl carbonate.Herein, The conversion ratio of phenostal is 69%.

[embodiment 35]

The eggplant type flask that 30g (0.06 mole) in adduct obtained in embodiment 33 is moved to 500 milliliters, by the eggplant Shape flask is mounted on the rotary evaporator for having oil bath.By the way that oil bath heating to 150 DEG C, is dried 2 at pressure 10Torr Hour, obtain 25g solid.

The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 10.2 weight %.Therefore, the amount of chlorine contained in the solid is 25g × 0.102=2.6g (0.073 mole).

Herein, if the amount of the chlorine to be considered as to the amount (ignoring hydrogen timesharing contained by hydrogen chloride) of hydrogen chloride contained by adduct, Then the amount of 4- 2-methyl-2-phenylpropane base triphenylphosphine contained by the solid is 25g × (1-0.102)=22.5g (0.057 mole), adduct Hydrogen chloride contained by chlorine amount be 0.073 mole -0.057 mole=0.016 mole, thus confirm the solid be adduction rate The adduct of 4- the 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride of 28% (0.016 mole of ÷ 0.057 mole × 100).In addition, Obtained solid is white particle, volume density 0.45gcm^-3, partial size is 134 μm.

Next, the adduct of the adduction rate 28% is used as catalyst, the decarbonylation base for implementing phenostal is anti- It answers.Specifically, in the de-carbonyl reaction of embodiment 1, as catalyst, using the adduct of above-mentioned adduction rate 28% as catalysis Agent uses, and in addition to this, implements similarly to Example 1, carries out de-carbonyl reaction.

After terminating 30 minutes from the supply of adduct, a part of the liquid in three-necked flask is taken out, efficient liquid is passed through Phase chromatography carries out composition analysis.As a result, 0.6 weight % of phenol, 30.2 weight % of phenostal, diphenyl carbonate 55.2 Weight %.Herein, the conversion ratio of phenostal is 70%.

[embodiment 36]

The eggplant type flask that 30g (0.06 mole) in adduct obtained in embodiment 33 is moved to 500 milliliters, by the eggplant Shape flask is mounted on the rotary evaporator for having oil bath.By the way that oil bath heating to 200 DEG C, is dried 2 at pressure 10Torr Hour, obtain 25g solid.

The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 8.6 weight %.Therefore, the amount of chlorine contained in the solid is 25g × 0.086=2.2g (0.062 mole).Herein, if The amount of the chlorine is considered as to the amount (ignoring hydrogen timesharing contained by hydrogen chloride) of hydrogen chloride contained by adduct, then 4- contained by the solid The amount of 2-methyl-2-phenylpropane base triphenylphosphine is 25g × (1-0.086)=22.9g (0.058 mole), chlorine contained by the hydrogen chloride of adduct Amount be 0.062 mole -0.058 mole=0.004 mole, thus confirm the solid be (the 0.004 mole of ÷ of adduction rate 7% 0.058 mole × 100) adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.In addition, obtained solid is white Particle, volume density 0.41gcm^-3, partial size is 110 μm.

Next, the adduct of the adduction rate 7% is used as catalyst, the decarbonylation base for implementing phenostal is anti- It answers.Specifically, in the de-carbonyl reaction of embodiment 1, as catalyst, using the adduct of above-mentioned adduction rate 7% as catalysis Agent uses, and in addition to this, implements similarly to Example 1, carries out de-carbonyl reaction.Terminate 30 minutes from the supply of adduct Afterwards, a part of the liquid in three-necked flask is taken out, composition analysis is carried out by high performance liquid chromatography.

As a result, 0.5 weight % of phenol, 29.6 weight % of phenostal, 58.3 weight % of diphenyl carbonate.Herein, The conversion ratio of phenostal is 71%.

[embodiment 37]

In 500 milliliters of heart-shaped flask, after being packed into 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 30g (0.070 mole), make chlorine Change hydrogen to circulate 1 hour to the flask, hydrogen chloride gas will be replaced into flask.So that the state of hydrogen chloride gas circulation, The flask is impregnated in the Dewar bottle for being incorporated with liquid nitrogen.Hydrogen chloride gas in flask is liquefied, and the ingredient in flask is in 100 The gonorrhoea slurry of milliliter.

The state is kept, makes after being maintained 2 hours there are the state of 100 milliliters of slurries of gonorrhoea, stops hydrogen chloride gas Circulation, makes nitrogen circulate, is to slowly warm up to room temperature on one side, when the hydrogen halides in flask is driven out of, obtain 25g solid on one side.

The knot that the cl concn of the solid is analyzed with the potential difference titration outfit " AT-610 " of capital of a country Electronics Industry Company Fruit is 14.5 weight %.Therefore, the amount of chlorine contained in the solid is 25g × 0.145=3.6g (0.101 mole).Herein, if The amount of the chlorine is considered as to the amount (ignoring hydrogen timesharing contained by hydrogen chloride) of hydrogen chloride contained by adduct, then 4- contained by the solid The amount of 2-methyl-2-phenylpropane base triphenylphosphine is 25g × (1-0.145)=21.4g (0.054 mole), chlorine contained by the hydrogen chloride of adduct Amount be 0.101 mole -0.054 mole=0.047 mole, thus confirm the solid be (the 0.047 mole of ÷ of adduction rate 87% 0.054 mole × 100) adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.In addition, obtained solid is white Powder, volume density 0.41gcm^-3, partial size is 45 μm.

Next, the adduct of the adduction rate 87% is used as catalyst, the decarbonylation base for implementing phenostal is anti- It answers.Specifically, in the de-carbonyl reaction of embodiment 1, as catalyst, using the adduct of above-mentioned adduction rate 87% as catalysis Agent uses, and in addition to this, implements similarly to Example 1, carries out de-carbonyl reaction.

After terminating 30 minutes from the supply of adduct, a part of the liquid in three-necked flask is taken out, efficient liquid is passed through Phase chromatography carries out composition analysis.As a result, 1.3 weight % of phenol, 51.2 weight % of phenostal, diphenyl carbonate 20.7 Weight %.Herein, the conversion ratio of phenostal is 48%.

The result of embodiment 33~37 and comparative example 1 is summarized in table 14.

[table 14]

The adduction rate of each catalyst, partial size, volume density, phenostal when carrying out de-carbonyl reaction conversion ratio, Liquid composition after reaction

It is unequivocally established by table 14, by the way that asymmetric four aryl halogenation phosphine is made into the adduct with hydrogen chloride, thus partial size It is larger, volume density is higher, easy to operate, and, as catalyst using carry out de-carbonyl reaction when, phenostal Conversion ratio it is higher, the by-product amount of phenol is less, and the amount of unreacted phenostal is less, the generation quantitative change of diphenyl carbonate It is more.

Particularly, also confirm that the biggish catalyst of partial size shows excellent reaction achievement.In addition, also confirming that with the present invention The asymmetric adduct of the manufacturing method manufacture for the adduct being related to, partial size is larger, shows excellent reaction achievement.

The present invention is described in detail with specific mode, but the intent and scope of the present invention can not departed from, carries out various The change and deformation of various kinds, this is very clear to those skilled in the art.In addition, the application is based on 2014 5 Japanese patent application (Patent 2014-107284) filed in months 23 days, Japanese patent application filed on July 14th, 2014 are (special Be willing to 2014-144298), Japanese patent application (Patent 2014-144297), October 28 in 2014 filed on July 14th, 2014 Japanese patent application (Patent 2014-219463), Japanese patent application (Patent filed on October 28th, 2014 filed in day 2014-219464), its whole is quoted by reference.

Claims

1. a kind of manufacturing method of diphenyl carbonate is by making phenostal carry out decarbonylation in the presence of a catalyst The method of base reaction manufacture diphenyl carbonate, which is characterized in that using the catalyst as asymmetric four aryl halogenation phosphine and halogen Change the adduct supply of hydrogen, the adduct is the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.

2. the manufacturing method of diphenyl carbonate according to claim 1, the average grain diameter of the adduct is 50 μm or more, 1mm or less.

3. the manufacturing method of diphenyl carbonate according to claim 1, the adduct is by making asymmetric four aryl Halogenation phosphine and hydrogen halides are dissolved in after polar organic solvent obtained from crystallization.

4. according to claim 1 or 3 manufacturing methods of diphenyl carbonate recorded, the absolute pressure when de-carbonyl reaction are 0.105MPa or more, 10MPa or less.

5. according to claim 1 or 3 record diphenyl carbonate manufacturing method, on one side from the lower part of de-carbonyl reaction device with 0.00001m·s^-1The above 0.01ms^-1Superficial linear velocity below supplies non-active gas to the de-carbonyl reaction, on one side Carry out de-carbonyl reaction.

6. according to claim 1 or 3 record diphenyl carbonate manufacturing method, which is characterized in that the catalyst soluble in Diphenyl carbonate, after the de-carbonyl reaction is carried out with 96% or more conversion ratio, by making carbonic acid two contained in reaction solution The 50 weight % or more of phenyl ester evaporate after taking out, and the reaction solution of remaining is supplied to the de-carbonyl reaction.

7. according to claim 1 or 3 record diphenyl carbonate manufacturing method, which is characterized in that by the catalyst with molten The state of diphenyl carbonate described in Xie Yu supplies.

8. according to claim 1 or 3 record diphenyl carbonate manufacturing method, which is characterized in that the phenostal contains Have 0.076 weight % or more, 10 weight % amounts below the following general formula (5) represented by carboxylic acid phenyl ester；

[changing 13]

In formula, n is 1 or 2.

9. according to claim 1 or 3 record diphenyl carbonate manufacturing method, which is characterized in that make through the decarbonylation base Change the diphenyl carbonate and alkali compounds contact that reaction obtains.

10. the manufacturing method of diphenyl carbonate according to claim 1, which is characterized in that the phenostal contains 0.076 weight % or more, 10 weight % amounts below the following general formula (5) represented by carboxylic acid phenyl ester；

[changing 13]

In formula, n is 1 or 2；

The catalyst is dissolved in the state supply of the diphenyl carbonate,

The absolute pressure when de-carbonyl reaction be 0.105MPa or more, 10MPa hereinafter,

After the de-carbonyl reaction is carried out with 96% or more conversion ratio, by make diphenyl carbonate contained in reaction solution 50 Weight % or more evaporates after taking out, and the reaction solution of remaining is supplied to the de-carbonyl reaction.

11. the manufacturing method of diphenyl carbonate according to claim 10, which is characterized in that make by described decarbonylated React obtained diphenyl carbonate and alkali compounds contact.

12. a kind of manufacturing method of diphenyl carbonate, which is characterized in that successively contain following 1st~3 processes；

1st process: diphenyl carbonate is manufactured by the manufacturing method of the diphenyl carbonate of wantonly 1 record of claim 1 to 11 Process,

2nd process: the diphenyl carbonate manufactured in the 1st process is decomposed into production with containing the adduct and/or the adduct The process of the catalyst liquid separation of raw adduct decomposition product,

13. a kind of recovery method of catalyst is for carrying out diphenyl carbonate by the de-carbonyl reaction of phenostal The recovery method of the catalyst of manufacture, which is characterized in that the catalyst be asymmetric four aryl halogenation phosphine and hydrogen halides plus Object is closed, by making polar organic solvent and hydrogen halide, contains carbon with obtaining from the reaction solution after the de-carbonyl reaction Raffinate contact after the ingredient of diphenyl phthalate, then contacts with water, and obtains precipitate, returns catalyst as the precipitate It receives；The adduct is the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.

14. the recovery method of catalyst according to claim 13, which is characterized in that recycle and urged contained in the raffinate Agent, meanwhile, the polar organic solvent is recycled, the catalyst recovery process is reused in.

15. a kind of manufacturing method of diphenyl carbonate is to manufacture diphenyl carbonate by the de-carbonyl reaction of phenostal Method, which is characterized in that as catalyst, the catalysis recycled using the recovery method recorded by claim 13 or 14 Agent.

It is by making diphenyl carbonate and dihydroxy compounds there are transesterifications to urge 16. a kind of manufacturing method of polycarbonate The method of polycondensation manufacture polycarbonate under conditions of agent, which is characterized in that passing through appointing in claim 1 to 12 and 15 After the manufacturing method of the diphenyl carbonate of 1 record manufactures the diphenyl carbonate, with the dihydroxy compounds polycondensation.