CN106458834A

CN106458834A - Method for producing diphenyl carbonate, diphenyl carbonate obtained by said production method, polycarbonate produced from said diphenyl carbonate, catalyst for diphenyl carbonate production, method for producing said catalyst, catalyst recovery and reuse method

Info

Publication number: CN106458834A
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; 早志功一
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Rayon Co Ltd
Priority date: 2014-05-23
Filing date: 2015-05-21
Publication date: 2017-02-22
Anticipated expiration: 2035-05-21
Also published as: CN106458834B; WO2015178463A1; KR102206139B1; KR20170012247A

Abstract

The purpose of the present invention is a method for producing diphenyl carbonate by a decarbonylation reaction of diphenyl oxalate in the presence of a catalyst, wherein high-purity diphenyl carbonate is produced simply, efficiently, stably, and continuously using an easy-to-handle catalyst without problems such as clogging due to catalyst precipitation. Another purpose is to recover and reuse a high-purity catalyst efficiently by a simple method. The present invention pertains to a method for producing diphenyl carbonate by a decarbonylation reaction of diphenyl oxalate in the presence of a catalyst, wherein the method for producing diphenyl carbonate is characterized by supplying the catalyst as an adduct of an asymmetric tetraarylphosphonium halide and hydrogen halide.

Description

Diphenyl carbonate and its manufacture method, catalyst and its manufacture recycling Method, Merlon

Technical field

The present invention is the manufacture method of the diphenyl carbonate being related to diphenyl carbonate etc. and is obtained by this manufacture method Carbonic diester invention.Specifically a kind of following invention:With regard to being urged by making the oxalate diester of phenostal etc. Carry out de-carbonyl reaction in the presence of agent thus manufacturing the method for carbonic diester, provide using maneuverable catalyst, can letter Just the efficiently, method that steady and continuous ground manufactures high-purity diphenyl carbonate.

Additionally, the present invention to be coloring obtained by being related to the carbonic diester being manufactured by the method as raw material less and The invention of high-purity polycarbonate.Further, the present invention is the catalyst and its manufacture manufacturing with regard to suitably this carbonic diester The invention of method.Additionally, the present invention is with regard to passing through easy method high efficiente callback high purity catalyst from reactant liquor, by it Recycle, the method that Simultaneous Stabilization is continuously manufactured by high purity carbon acid diesters, and catalyst recovered solvent will be used for also to enter The invention that row recycles.

Background technology

Carbonic diester is known as the starting compound in a variety of chemical reactions, specifically, it is known that diphenyl carbonate Can be by the polycondensation reaction with dihydroxylic aromatic compound thus manufacturing Merlon.

Carbonic diester can be taken off in the presence of the de- carbonylic catalyst of organic phosphorus compound etc. by making oxalate diester Carbonyl reaction and obtain (referenced patent document 1).Herein, with regard to reaction pressure although disclosing that " reaction temperature exceedes oxalic acid two Pressurize during the boiling point of aryl ester, but usually normal pressure or decompression ", but as embodiment is reaction at ambient pressure, due to pressurization During reaction, when pressure vessel, Depressor response, vacuum pump respectively must be with required above control pressure, thus reaction is typically in normal pressure Under carry out.

A kind of manufacture method of carbonic diester is also disclosed, and the method is by aromatic hydroxy compound and oxalic acid alkylaryl The oxalate diester that the content of ester etc. is less uses (referenced patent document 2) as raw material.Additionally, propose there are as below methods：In grass The diphenyl carbonate obtaining in the decarbonylated reaction of diphenyl phthalate due to the light impurities containing furan based compound etc., therefore By distillation or thermal decomposition, (at a temperature of 150～300 DEG C, heat treatment about 0.05～10 hour, is allowed to thermally decompose, is condensed And/or heat modification) and remove (referenced patent document 3).

Additionally, with regard to carrying out de-carbonyl reaction in the presence of the catalyst of tetraphenylphosphonium chloride etc. by making oxalate diester Obtained carbonic diester is it was also proposed that there is method making its high purity etc. (referenced patent document 4).

Additionally, being also reported (referenced patent document 5) following situation：Obtained by de-carbonyl reaction by oxalic acid diaryl Diaryl carbonate, even if by by de-carbonyl reaction liquid be evaporated in vaporising device operate, will be anti-for its decarbonylation base The diaryl carbonates not evaporating composition and target product answered liquid and mainly contain containing de- carbonylic catalyst and high boiling substance etc. The evaporation composition of the diaryl esters of oxalic acid of ester and raw material separates, and then purifies this evaporation composition using by distillation procedure etc. During obtained product cut, due to the benzo furan by generations such as Fu Laisi (Fries) rearrangement reactions of diaryl esters of oxalic acid Mutter-being mixed into of the furan based compound of 2,3- diketone etc., the polycarbonate article using this diaryl carbonate manufacture can colour, So that from by being evaporated operating and separation and recovery flashing to containing diaryl carbonate de-carbonyl reaction liquid Point, then by this evaporation composition is carried out distillation procedure, remove low-boiling point material and high boiling substance successively and obtain carbonic acid Furan system impurity is removed in the thick fraction of diaryl ester.

With regard to conversion ratio during diphenyl carbonate being generated by phenostal in the presence of tetraphenylphosphonium chloride, in order to press down The precipitation of catalyst processed, needs to carry out de-carbonyl reaction (referenced patent document 6) below 95% in conversion ratio.

With regard to the recovery of the salt catalyst for de-carbonyl reaction, proposition has by " adding in reactant mixture Add hydrogen halides while organic polar solvent dilution, so that the salt of remaining or salt component conduct in this reactant mixture Hydrogen halides adduct separates out, separates " and the method (referenced patent document 7) of recovery.

Prior art literature

Patent documentation

Patent documentation 1：Japanese Patent Laid-Open flat 8-333307 publication

Patent documentation 2：Japanese Patent Laid-Open flat 11-152252 publication

Patent documentation 3：Japanese Patent Laid-Open 2003-226751 publication

Patent documentation 4：Japanese Patent Laid-Open 2002-53657 publication

Patent documentation 5：Japanese Patent Laid-Open 2002-47251 publication

Patent documentation 6：Japanese Patent Laid-Open flat 11-246489 publication

Patent documentation 7：Japanese Patent Laid-Open 2002-45704 publication

Content of the invention

Invention problem to be solved

But, the method recorded with regard to above-mentioned patent documentation 4, purification is also required to many distillation process, has operation very numerous The problem of miscellaneous grade, with regard to the high purity etc. of diphenyl carbonate, needs to improve further.Additionally, the present inventors is with regard to non-right The result claiming the operability of tetraphenylphosphonium chloride to be studied, has distinguished that this material easily disperses because particle diameter is less, hygroscopicity Higher, therefore as catalyst use, carry out phenostal de-carbonyl reaction when, due to the water of diphenyl carbonate Solution, easy by-product phenol.

With regard to above-mentioned catalyst recovery method, nor say necessarily can be with high efficiente callback high purity catalyst, the present invention The result of method that people record to above-mentioned patent documentation 7 research in detail is it is thus understood that phenostal contained in catalyst liquid Preservation can be decomposed and produce by-product.Additionally, containing hydrogen halides and water in the organic polar solvent of recovery, but with regard to By its recycling one thing, there is no any research.

Therefore, the present inventors, with regard to the result studied of recovery method of a variety of salt catalysts, distinguishes:Especially Be by above-mentioned catalyst recovery method be applied to asymmetric four aryl halogenation phosphines and/or four aryl halogenation phosphines and hydrogen halides plus It is impossible to the catalyst of high efficiente callback high concentration during the recovery of compound.

In addition, it is contemplated that because the de-carbonyl reaction of oxalate diester is the endothermic reaction, for industrial continuous manufacture, instead Answer the medium-and-large-sized agitator of device to be necessary, need the simplification of reaction unit and operation.

The problem of the present invention is, the method providing solve these problems at least wantonly 1, provides following at least wantonly 1 Individual method etc..

That is, the 1st problem of the present invention is, with regard to carrying out de-carbonyl reaction in the presence of a catalyst by making oxalate diester Thus the method manufacturing carbonic diester, provide by using maneuverable catalyst, simple and effective can stably manufacture carbonic acid The method of diester.

2nd problem of the present invention is, provides the situation that will not produce the fault being separated out the obturation leading to etc. by catalyst Under stably manufacture the method for carbonic diester, this carbonic diester is to be difficult on carbonic diester for the Merlon of raw material manufacture Produce the highly purified carbonic diester of the degree of coloring.

3rd problem of the present invention is, provides：By asymmetric four aryl halogenation phosphines and/or asymmetric four aryl halogenation phosphines with The adduct of hydrogen halides, is used as catalyst in the manufacture of the carbonic diester being carried out by the de-carbonyl reaction of oxalate diester and uses When, with the easy highly purified catalyst of method high efficiente callback from reactant liquor, recycled, Simultaneous Stabilization is continuously manufactured by The method of highly purified carbonic diester.

4th problem of the present invention is, provides：By four aryl halogenation phosphines and/or four aryl halogenation phosphines and hydrogen halides plus Compound, when being used as catalyst in the manufacture of the carbonic diester carrying out by the de-carbonyl reaction of oxalate diester and using, by with Easy method high efficiente callback simultaneously recycles highly purified catalyst, also will be used for catalyst recovered solvent simultaneously and recycle, Thus the method efficiently and stably manufacturing highly purified carbonic diester.

5th problem of the present invention is, with regard to by making oxalate diester carry out de-carbonyl reaction in the presence of a catalyst and The method manufacturing carbonic diester, provides the method efficient stable of available simplicity to be continuously manufactured by the side of highly purified carbonic diester Method.

6th problem of the present invention is, with regard to by making oxalate diester carry out de-carbonyl reaction in the presence of a catalyst and The method manufacturing carbonic diester, provides the reaction unit by more simplification and operation, and industrially high-efficiency and continuous ground manufactures carbon The method of acid diesters.

Means to solve the problem

The present inventors is concentrated on studies to solve above-mentioned problem.As a result, finding：For above-mentioned 1st class Topic is with regard to carrying out, by making phenostal, the method that de-carbonyl reaction manufactures diphenyl carbonate in the presence of a catalyst, permissible By described catalyst is solved as the adduct supply of asymmetric four aryl halogenation phosphines and hydrogen chloride.It moreover has been found that：Should Asymmetric four aryl halogenation phosphines and the adduct of hydrogen chloride, can pass through will be non-with what hydrogen chloride and polar organic solvent contacted Symmetrical four aryl halogenation phosphine crystallizes are thus easily obtain.

Additionally, for above-mentioned 2nd problem, finding：Carry out de-carbonyl reaction system making oxalate diester in the presence of a catalyst Make the precipitation that catalyst by using dissolving in the catalyst of carbonic diester, will not be caused in the method for carbonic diester, to convert After rate more than 96% is carried out, evaporated by making more than 50 weight % of contained carbonic diester in reactant liquor, it is possible to decrease remaining The amount of oxalate diester, the by-product of furan based compound during suppression carbonic diester evaporation, can be solved.

For above-mentioned 3rd problem, the present inventors is with regard to asymmetric four aryl halogenation phosphines and/or asymmetric four aryl halogenations The recovery method of phosphine and the adduct of hydrogen halides is concentrated on studies.As a result, finding：By making polar organic solvent and chlorine Change hydrogen contact and obtain the residual liquid after the composition containing carbonic diester from reactant liquor, then contact water, thus urge highly purified Agent, as precipitate high efficiente callback, can be solved.

For above-mentioned 4th problem, the present inventors is with regard to four aryl halogenation phosphines and/or four aryl halogenation phosphines and hydrogen halides The recovery method of adduct is concentrated on studies.As a result, finding：By make polar organic solvent and hydrogen chloride gas and/ Or hydrochloric acid contact obtains the residual liquid after the composition containing carbonic diester from reactant liquor, can the highly purified catalyst of high efficiente callback, Further, by recycling the residual liquid reclaiming after described catalyst as described polar organic solvent, can be solved.

For above-mentioned 5th problem, the present inventors finds：During by reacted catalyst recycle, by by catalyst With the state supply being dissolved in carbonic diester, can be solved.Additionally, the present inventors finds, by containing specified quantitative The oxalate diester of specific impurities use as raw material, can efficiently manufacture highly purified carbonic diester.Further, it was found that：Pass through Carry out the de-carbonyl reaction of oxalate diester under specific pressurized conditions, can efficiently and stably manufacture highly purified carbonic diester. Additionally, the present inventors finds, by contacting with alkali compoundss, promote the thermal decomposition of furan based compound, and find to lead to Cross contained furan based compound in the carbonic diester make generation to contact with alkali compoundss and remove, thus can efficiently manufacture Highly purified carbonic diester.

For above-mentioned 6th problem, the present inventors finds：By while anti-to decarbonylation base from the bottom of de-carbonyl reaction device Non-active gas should be supplied on a small quantity, carry out de-carbonyl reaction, while stirring reaction liquid, pair when removing de-carbonyl reaction The impurity of the phenol producing etc., thus can efficiently manufacture carbonic diester.

That is, the present invention is as described below.

1. a kind of manufacture method of diphenyl carbonate, is to carry out de-carbonyl reaction in the presence of a catalyst by making phenostal The method manufacturing diphenyl carbonate is it is characterised in that using described catalyst as asymmetric four aryl halogenation phosphines (phosphonium) and hydrogen halides adduct supply.

2. the manufacture method of the diphenyl carbonate recorded according to preceding paragraph 1, the mean diameter of described adduct is more than 50 μm, 1mm Below.

3. the manufacture method of the diphenyl carbonate recorded according to preceding paragraph 1 or 2, described adduct is by making asymmetric four aryl halides Change phosphine and hydrogen halides to be dissolved in obtained from crystallize after polar organic solvent.

4. the manufacture method of the diphenyl carbonate of wantonly 1 record according to preceding paragraph 1 to 3, described asymmetric four aryl halogenation phosphines are not There are benzylic protons.

5. the manufacture method of the diphenyl carbonate of wantonly 1 record according to preceding paragraph 1 to 4, described adduct is 4- 2-methyl-2-phenylpropane base three Tetraphenylphosphonium chloride phosphine and the adduct of hydrogen chloride.

6. the manufacture method of the diphenyl carbonate of wantonly 1 record according to preceding paragraph 1 to 5, absolute pressure during described de-carbonyl reaction Power is more than 0.105MPa, below 10MPa.

7. the manufacture method of the diphenyl carbonate of wantonly 1 record according to preceding paragraph 1 to 6, from the bottom of de-carbonyl reaction device With 0.00001m s^-1Above 0.01m s^-1Following superficial linear velocity to described de-carbonyl reaction supply non-active gas, one While carrying out de-carbonyl reaction.

8. the manufacture method of the diphenyl carbonate of wantonly 1 record according to preceding paragraph 1 to 7 is it is characterised in that described catalyst soluble In diphenyl carbonate, after described de-carbonyl reaction is carried out with conversion ratio more than 96%, by making contained carbonic acid in reactant liquor More than 50 weight % of diphenyl ester evaporate and after taking-up, remaining reactant liquor is supplied to described de-carbonyl reaction.

9. according to preceding paragraph 1 to 8 wantonly 1 record diphenyl carbonate manufacture method it is characterised in that by described catalyst with It is dissolved in the state supply of described diphenyl carbonate.

10. the manufacture method of the diphenyl carbonate of wantonly 1 record according to preceding paragraph 1 to 8 is it is characterised in that described diphenyl oxalate Ester contains the carboxylic acid phenyl ester represented by following formulas (5) of more than 0.076 weight %, amount below 10 weight %.

[changing 1]

(in formula, n is 1 or 2.)

The manufacture method of 11. diphenyl carbonates according to wantonly 1 record of preceding paragraph 1 to 10 is it is characterised in that make by described de- The diphenyl carbonate that carbonylation obtains contacts with alkali compoundss.

A kind of 12. manufacture methods of diphenyl carbonate are it is characterised in that contain following 1st～3 operations successively.

1st operation：Manufacture the work of diphenyl carbonate by the manufacture method of the diphenyl carbonate of wantonly 1 record of preceding paragraph 1 to 11 Sequence,

2nd operation：The diphenyl carbonate manufacturing in 1st operation is produced with decomposing containing described adduct and/or described adduct The detached operation of catalyst liquid of adduct analyte of life,

3rd operation：At least a portion of described catalyst liquid is supplied the operation of the reactor to the 1st operation.

A kind of 13. recovery methods of catalyst, are for carrying out diphenyl carbonate by the de-carbonyl reaction of phenostal The recovery method of the catalyst manufacturing is it is characterised in that described catalyst is asymmetric four aryl halogenation phosphines and/or asymmetric four The adduct of aryl halogenation phosphine and hydrogen halides, by make polar organic solvent and hydrogen halide with after described de-carbonyl reaction Reactant liquor in obtain the contact of the residual liquid after the composition containing diphenyl carbonate, then contact with water, and obtain precipitate, will urge Agent reclaims as described precipitate.

A kind of 14. recovery methods of catalyst, are for carrying out diphenyl carbonate by the de-carbonyl reaction of phenostal The recovery method of the catalyst manufacturing it is characterised in that described catalyst be four aryl halogenation phosphines and/or four aryl halogenation phosphines with The adduct of hydrogen halides, makes the residual liquid after obtaining the composition containing diphenyl carbonate from the reactant liquor after described de-carbonyl reaction After contact polar organic solvent and hydrogen halides, reclaim contained catalyst (catalyst recovery process) in described residual liquid, return meanwhile Receive described polar organic solvent, be reused in described catalyst recovery process.

A kind of 15. manufacture methods of diphenyl carbonate, are to manufacture diphenyl carbonate by the de-carbonyl reaction of phenostal Method it is characterised in that as catalyst, using the catalyst being reclaimed by the recovery method that preceding paragraph 13 or 14 is recorded.

The manufacture method of the adduct of a kind of 16. asymmetric four aryl halogenation phosphines and hydrogen halides, is four aryl halogenation phosphines and halogenation The manufacture method of the adduct of hydrogen is it is characterised in that being dissolved in polarity and have by making asymmetric four aryl halogenation phosphines and hydrogen halides Crystallize after machine solvent, obtains the adduct of asymmetric four aryl halogenation phosphines and hydrogen halides.

A kind of 17. diphenyl carbonate catalyst for producing, are for carrying out carbonic acid two by the de-carbonyl reaction of phenostal The catalyst of the manufacture of phenyl ester is it is characterised in that described catalyst is the asymmetric four aryl halogenation phosphines without benzylic protons Adduct with hydrogen halides.

A kind of 18. manufacture methods of Merlon, are by making diphenyl carbonate and dihydroxy compounds in ester exchange catalyst In the presence of polycondensation and manufacture Merlon method it is characterised in that by preceding paragraph 1 to 12 and 15 wantonly 1 note After the manufacture method of the diphenyl carbonate carrying manufactures described diphenyl carbonate, with described dihydroxy compounds polycondensation.

A kind of 19. diphenyl carbonates, are the manufacture methods of the diphenyl carbonate of wantonly 1 record by preceding paragraph 1 to 12 and 15 Obtain.

A kind of 20. Merlon, are to be handed in ester by making aromatic dihydroxy compound and the diphenyl carbonate of preceding paragraph 19 record In the presence of catalyst changeout, polycondensation obtains.

The effect of invention

1st effect of the present invention is, with regard to by making phenostal carry out de-carbonyl reaction in the presence of a catalyst and The method manufacturing diphenyl carbonate, using maneuverable catalyst, can simple and effective, the highly purified carbon of steady and continuous ground manufacture Diphenyl phthalate.Herein, can by making asymmetric four aryl halogenation phosphines and hydrogen halides are dissolved in crystallize after polar organic solvent, thus Easily obtain the catalyst of suitably this de-carbonyl reaction.Additionally, by making this highly purified diphenyl carbonate as raw material With can get highly purified Merlon.

2nd effect of the present invention is, the system of the diphenyl carbonate with regard to being carried out by the de-carbonyl reaction of phenostal Make method, can simple and effective, will not produce and separated out the fault of the obturation that leads to etc., stably manufactured highly purified carbon by catalyst Acid diesters.Additionally, by using this carbonic diester as raw material, the highly purified poly- carbonic acid being difficult to produce coloring can be obtained Ester.

3rd effect of the present invention is, by asymmetric four aryl halogenation phosphines and/or asymmetric four aryl halogenation phosphines and hydrogen halides Adduct, when being used as catalyst in the manufacture of the carbonic diester carrying out by the de-carbonyl reaction of oxalate diester and using, can With the easy highly purified catalyst of method high efficiente callback from reactant liquor, recycled, Simultaneous Stabilization is continuously manufactured by height The carbonic diester of purity.Additionally, by using this highly purified carbonic diester as raw material, can get highly purified poly- carbonic acid Ester.

4th effect of the present invention is, by the adduct of four aryl halogenation phosphines and/or four aryl halogenation phosphines and hydrogen halides, When being used as catalyst in the manufacture of the carbonic diester carrying out by the de-carbonyl reaction of oxalate diester and using, can be by with easy Method high efficiente callback recycles highly purified catalyst, also will be used for catalyst recovered solvent simultaneously and recycle, efficient stable Ground manufactures highly purified carbonic diester.Additionally, by using this highly purified carbonic diester as raw material, can get high-purity Merlon.

5th effect of the present invention is, with regard to being made by making oxalate diester carry out de-carbonyl reaction in the presence of a catalyst The method making carbonic diester, it is possible to provide the side of highly purified carbonic diester can be continuously manufactured by with easy method efficient stable Method.Additionally, by using this highly purified carbonic diester as raw material, can get highly purified Merlon.

6th effect of the present invention is, with regard to being made by making oxalate diester carry out de-carbonyl reaction in the presence of a catalyst The method making carbonic diester, it is possible to provide by reaction unit and the operation of more simplification, industrially high-efficiency and continuous ground manufacture carbon The method of acid diesters.

Specific embodiment

Hereinafter, the embodiment with regard to the manufacture method of the carbonic diester of the present invention is described in detail.

In the manufacture method of the carbonic diester of the present invention, anti-by making oxalate diester carry out decarbonylation base in the presence of a catalyst (below, sometimes referred to as " de-carbonyl reaction according to the present invention " or be only called " de-carbonyl reaction ") carbonic diester should be manufactured.

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

[changing 2]

In formula, 2 R are the alkyl can with substituent group independently of one another.

[oxalate diester]

Oxalate diester in reaction equation (1) is (below, sometimes referred to as " oxalate diester according to the present invention " or be only called " oxalic acid two Ester ") be the present invention the manufacture method of carbonic diester in raw material.Additionally, using oxalate diester according to the present invention as raw material Obtained carbonic diester according to the present invention, due to hot stable, the raw material as Merlon is suitable.

Oxalate diester according to the present invention, is usually used the alkyl having with the carbonic diester identical type as purpose (R) oxalate diester.Alkyl in oxalate diester according to the present invention can be aliphatic or aromatic series.That is, oxalic acid The alkyl that diester has can be all alkyl with 2 it is also possible to alkyl and fragrant ring group each 1 it is also possible to 2 is all fragrance Ring group.But, due to the group being easily separated from, departing from when using the carbonic diester of the present invention as the raw material of Merlon etc. Recovery easily, preferably 2 is all fragrant ring group.

When the alkyl that oxalate diester according to the present invention has is alkyl, can be in straight chain, side chain and ring type Any one.

When the alkyl that oxalate diester according to the present invention has is fragrant ring group, this fragrant ring group can be aromatic ring Alkyl or aromatic heterocycle.But, due to the carbonic diester of the present invention being made as the raw material manufacturing Merlon Used time is easily separated from, optimization aromatic cyclic hydrocarbon radical.Further, since the recovery of the group departing from is easily, the group of disengaging is stable, excellent Menu ring.

As this aromatic ring alkyl, can enumerate and there are monocyclic or 2～5 condensed ring of 5 or 6 yuan of rings of 1 free valency etc..This Outward, in the present invention, as organic chemistry biological chemical name method (on) (and revision second edition, Nan Jiangtang, 1992 distribution) in Described, so-called free valency refers to can be with other free valency bondings.

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

Wherein, the group due to departing from when using the carbonic diester of the present invention as the raw material manufacturing Merlon etc. is steady Fixed, particularly preferably there is the phenyl ring (phenyl) of 1 free valency.

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

Therefore, preferred phenostal (below, the sometimes referred to as " grass according to the present invention of oxalate diester according to the present invention Diphenyl phthalate " or be only called " phenostal "), by the carbonic diester manufactured by the manufacture method of the carbonic diester of the present invention Preferably diphenyl carbonate (below, sometimes referred to as " diphenyl carbonate according to the present invention " or be only called " diphenyl carbonate ").

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

[changing 3]

In formula, 2 Ph are the phenyl can with substituent group independently of one another.

When the alkyl that oxalate diester according to the present invention has is aromatic heterocycle, as this aromatic heterocycle, Can enumerate and there are monocyclic or 2～4 condensed ring of 5 or 6 yuan of rings of 1 free valency etc..

As the concrete example of this aromatic heterocycle, can enumerate and there is the furan nucleuss of 1 free valency, benzofuran ring, thiophene Fen 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, furo pyrrole ring, furo furan nucleuss, thiophene Fen furan nucleuss, benzo isozole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine 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..

The substituent group that the alkyl having as oxalate diester according to the present invention has, as long as this will not significantly be hindered The excellent effect of invention, is just not particularly limited.But, when the diphenyl carbonate obtaining is used for Merlon manufacture, preferably The boiling point of the by-product that Merlon produces in manufacturing is relatively low, is easily distilled off.

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

Additionally, as the alkyl of substituent group, referring to the situation that alkyl combines in fragrant ring group as substituent group, as taking The fragrant ring group of Dai Ji, for example, refer to that aromatic heterocycle combines situation on aromatic ring alkyl etc. as substituent group.

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

The carbon number that the alkyl that oxalate diester according to the present invention has has, based on by the carbonic acid two of the present invention The stability aspect of the group of disengaging when ester uses as the raw material manufacturing Merlon etc., preferably more, but based on disengaging Group the easy aspect of recovery, preferably less.

Specifically, when there is substituent group, comprise substituent group, preferably more than 1, more preferably more than 2, on the other hand, excellent Elect less than 12, more preferably less than 10 as.

Wherein, especially, the diphenyl carbonate obtaining is used for when Merlon manufactures etc., most preferably unsubstituted benzene Base.

Diaryl esters of oxalic acid (has the oxalate diester of 2 fragrant ring groups) as alkyl, can be using as following reaction equations (3) Material that the shown ester exchange reaction by dialkyl oxalate and aromatic hydroxy compound manufactures etc..

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

[changing 4]

In formula, R represents alkyl, and Ar represents fragrant ring group.

[changing 5]

In formula, R represents alkyl.

In the manufacture method of the carbonic diester of the present invention, using phenostal as raw material use when, this phenostal Preferably comprise more than 0.076 weight %, carboxylic acid phenyl ester that following formulas (5) of amount below 10 weight % represent.Additionally, it is careless The amount of the carboxylic acid phenyl ester contained by diphenyl phthalate is preferably greater than 1 weight %.

Additionally, the amount of the carboxylic acid phenyl ester contained by phenostal refers to, with respect to total amount and the carboxylic acid of 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.

The carboxylic acid phenyl ester representing as above-mentioned formula (5), due to easily making phenol reduce, preferably：By phenostal Phenyl (to the phenyloxycarbonyl phenyl) grass that the formula (6) being generated by Fu Laisi (Fries) rearrangement and polycondensation etc. is represented Phenyl (the adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) that acid esters (PCPO) or formula (7) represent etc. phenyl (to (or Adjacent) phenyloxycarbonyl phenyl) oxalate, and, given birth to by Fu Laisi (Fries) rearrangement and polycondensation etc. by diphenyl carbonate Phenyl (the adjacent benzene oxygen that phenyl (to the phenyloxycarbonyl phenyl) carbonic ester (PCPC) that represents of formula (8) becoming or formula (9) represent 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 of the carboxylic acid phenyl ester containing the amount more than 0.076 weight %, below 10 weight %, can pass through profit With the phenostal distilation obtained by the ester exchange reaction of dialkyl oxalate and phenol, so that carboxylic acid phenyl ester becomes Above range, thus obtain.

Herein, above-mentioned carboxylic acid phenyl ester is generally high than phenostal boiling point.Therefore, can be by from using oxalic acid dialkyl group Phenostal obtained by the ester exchange reaction of ester and phenol mainly only removes the low-boiling material than phenostal and obtains Arrive.

Additionally, when the phenostal obtained by by the ester exchange reaction by dialkyl oxalate and phenol purifies, If the high composition of imprudence continued proportion phenostal boiling point also removes, there is the amount of the carboxylic acid phenyl ester contained by phenostal The situation fewer than above-mentioned lower limit can be become.

[de- carbonylic catalyst]

Catalyst (below, sometimes referred to as " decarbonylation base according to the present invention used in the manufacture method of the carbonic diester of the present invention Catalyst ", " de- carbonylic catalyst " or " catalyst "), the quantivalence that can enumerate phosphorus atoms is trivalent or organic phosphatization of 5 valencys Compound etc..The quantivalence of phosphorus atoms is the organic phosphorus compound of trivalent or 5 valencys, preferably has having of at least one carbon-phosphorus (C-P) key Machine phosphorus compound, more preferably has the organic phosphorus compound of carbon-phosphorus (C-P) key of more than 3.

As such organic phosphorus compound, can illustrate as salt system organic phosphorus compound (hereinafter also referred to as salt), phosphine It is organic phosphorus compound, dihalide phosphine system's organic phosphorus compound and phosphine oxide system organic phosphorus compound etc..Wherein, as this The bright de- carbonylic catalyst being related to, preferably salt system organic phosphorus compound.

The salt that the preferably following formula (A) of salt system organic phosphorus compound represents.

[changing 8]

In formula, R¹、R²、R³And R⁴Represent fragrant ring group, aralkyl or the alkyl can with substituent group, X independently of one another Expression can the atom of ion balance of forming salt or atomic group.

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

As described aralkyl, the carbon of the had unsaturated bond of benzyl, phenethyl, cinnamyl, menaphthyl etc. can be enumerated Aralkyl of atomic number 7～15 etc..

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

The R of described formula (A)¹～R⁴Including various isomers, can have the substituent group of more than 1.

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

Additionally, the R of described formula (A)¹～R⁴For have substituent group phenyl when, there are various isomers.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 of carbon number 1～12 of 2,4,6- trimethylphenyl, 4- trifluoromethyl, 3,5- bis trifluoromethyl phenyl etc. or halogen Change alkyl and combine the alkyl phenyl on phenyl；The carbon number 1～12 of 3- methoxyphenyl, 2,4,6- trimethoxyphenyl etc. Alkoxyl combine alkoxyl phenyl on phenyl；The halogen atom of 3- (or 4-) chlorphenyl, 3- fluorophenyl etc. combines in phenyl On halogenophenyl etc..

The R of described formula (A)¹～R⁴During for fragrant ring group, they can take outside described substituent group on its ring in conduct Dai Ji has the alkyl (preferably carbon number 1～12) of more than 1, and this alkyl (preferably carbon number 1～12) can have ring knot Structure (containing heterocycle) or unsaturated bond.Additionally, R¹～R⁴During for aromatic heterocycle, they, can be miscellaneous at it outside described substituent group The aromatic ring alkyl (preferably carbon number 6～16) of more than 1 is had as substituent group on ring.

The R of described formula (A)¹～R⁴Mutually can identical it is also possible to different.Additionally, between 2 groups, can be in Key or crosslinking.But, based on dissolubility aspect, R¹～R⁴Any 1 group preferably and any one of other 3 groups All different groups.Herein, different groups refers to, including the different situation of the presence or absence of substituent group, species, the position of substitution, phase Mutually arbitrarily different group.Additionally, 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 referred to as " asymmetric ".

Ion balance X as described formula (A)^-, the halogen ion of chloride ion, bromide ion, iodide ion etc. can be enumerated, and two Halogenation hydride ion of chlorination hydrion, dibrominated hydrion, diiodinating hydrion, chlorine bromination hydrion etc. etc..Wherein, this In the bright de-carbonyl reaction being related to, due to easily working as highly active catalyst, the preferred halogen ion of X, more preferably chlorine from Son.

As preferred salt system organic phosphorus compound, specifically, the compound being exemplified below.That is, as described logical The R of formula (A)¹～R⁴It is all the organic chloride phosphine of unsubstituted aromatic hydrocarbyl, tetraphenylphosphonium chloride can be enumerated, to xenyl three Tetraphenylphosphonium chloride phosphine, 1- naphthyl triphenyl phosphine dichloride, 2- naphthyl triphenyl phosphine dichloride etc..

R as described formula (A)¹～R⁴For unsubstituted aromatic hydrocarbyl or the aromatic hydrocarbyl with substituent group Organic chloride phosphine, can enumerate o-methyl-phenyl-triphenyl phosphine dichloride, an 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 of the aromatic hydrocarbyl having 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, the aromatic hydrocarbyl having containing alkoxyl to ethoxyl phenenyl triphenyl phosphine dichloride etc. Compound；The compound of the aromatic hydrocarbyl having containing amino of p-aminophenyl triphenyl phosphine dichloride etc.；Between cyano-phenyl Triphenyl phosphine dichloride, the compound to the aromatic hydrocarbyl with cyano-containing of cyano-phenyl triphenyl phosphine dichloride etc. and to nitre Compound of aromatic hydrocarbyl having containing nitro of base phenyl-three-p-methylphenyl phosphonium chloride etc. etc..

R as described formula (A)¹～R⁴All the organic chloride phosphine of aralkyl, can enumerate benzyl triphenyl phosphonium chloride phosphine with And phenethyl triphenyl phosphine dichloride etc..R as described formula (A)¹～R⁴It is all the organic chloride phosphine of alkyl, tetrem can be enumerated Base phosphonium chloride, tetrabutylphosphonium chloride, cetyltributylphosphonium phosphonium chloride etc..

R as described formula (A)¹～R⁴For the organic chloride phosphine of aromatic hydrocarbyl or alkyl, methyl triphenyl can be enumerated Phosphonium chloride, ethyltriphenyl phosphonium chloride phosphine, propyl group triphenyl phosphine dichloride, butyltriphenylphosphonium chloride phosphine, hexyltriphenylphosphonium phosphonium chloride, heptan Base triphenyl phosphine dichloride, myristyl triphenyl phosphine dichloride, dimethyl diphenyl phosphonium chloride, pi-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.； Compound of alkyl having containing unsaturated bond of 1,3- butadienyl triphenyl phosphine dichloride etc. etc..Additionally, as described formula (A) R¹～R⁴For the organic chloride phosphine of aromatic hydrocarbyl or the alkyl with substituent group, can enumerate (1,3- dioxolane- 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 alkyl having containing heterocyclic radical compound；Bromomethyl triphenyl phosphine dichloride etc. There is the compound of the alkyl of halogen atom；4- carboxybutyl triphenyl phosphine dichloride, 2- carboxyallyl triphenyl phosphine dichloride etc. The compound with carboxylic alkyl；The having containing alkoxy carbonyl of 4- ethoxycarbonylbutyl triphenyl phosphine dichloride etc. The compound of alkyl；The compound of the alkyl having containing alkyl-substituted amino of 2- dimethylaminomethyl triphenyl phosphine dichloride etc. And the compound of alkyl having containing acyl group of phenacyl triphenyl phosphine dichloride etc. etc..

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

As de- carbonylic catalyst according to the present invention, in these salt system organic phosphorus compounds, particularly preferably described The R of formula (A)¹～R⁴It is all fragrant ring group, more preferably R¹～R⁴It is all aromatic hydrocarbyl.And it is particularly preferred to asymmetric four virtues Base halogenation phosphine, most preferably 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride.

Additionally, sometimes by the R of this described formula (A)¹～R⁴It is all that the salt system organic phosphorus compound of fragrant ring group is referred to as " four aryl halogenation phosphines according to the present invention " or it is only called " four aryl halogenation phosphines ".

Additionally, in this four aryl halogenation phosphine according to the present invention, sometimes by particularly preferred R¹～R⁴For asymmetrical four virtues Base halogenation phosphine is referred to as " asymmetric four aryl halogenation phosphines according to the present invention " or is only called " asymmetric four aryl halogenation phosphines ".

It is following leading to as de- carbonylic catalyst according to the present invention four aryl halogenation phosphines preferably according to the present invention The compound that formula (10) represents.

[changing 9]

In formula, Ar¹、Ar²、Ar³And Ar⁴Represent the fragrant ring group can with substituent group independently of one another, X represents that halogen is former Son.

As Ar¹～Ar⁴Fragrant ring group, the aromatic series of the carbon number 6～14 of phenyl, xenyl, naphthyl etc. can be enumerated The virtue of the carbon number 4～16 containing sulphur atom, oxygen atom or nitrogen-atoms of alkyl and thienyl, furyl, pyridine radicals etc. Fragrant race heterocyclic radical etc..Wherein, due to catalyst, optimization aromatic alkyl, more preferably phenyl can be manufactured inexpensively.

Ar¹～Ar⁴Comprise various isomers, each fragrance ring group can have the substituent group of more than 1.As described substituent group, Can illustrate as alkyl (preferably carbon number 1～12), alkoxyl (preferably carbon number 1～12), (preferably carbon is former for thio alkoxy Subnumber 1～12), aralkoxy (preferably carbon number 7～13), aryloxy group (preferably carbon number 6～16), thio-aryloxy (preferably carbon number 6～16), acyl group (preferably carbon number 1～12), alkoxy carbonyl (preferably carbon number 2～16), carboxylic Base, amino, the amino (preferably carbon number 2～16) of alkyl replacement, nitro, cyano group, hydroxyl, halogen atom (fluorine, chlorine, bromine etc.) Deng.Additionally, these substituent groups can have substituent group further, as its substituent group, fragrant ring group and halogen atom etc. can be enumerated.

Wherein, due to hot stable, thus preferred alkyl, the more preferably alkyl of carbon number 1～12, further preferably The alkyl of the branch of carbon number 3～8.Further, since catalyst is thermally-stabilised, this substituent group is anti-as the decarbonylation base of the present invention Applications catalyst is difficult to decompose when using, thus this substituent group does not preferably have benzylic protons.That is, the particularly preferred carbon of this substituent group The alkyl without benzylic protons of atomic number 3～8, the most preferably tert-butyl group.

Additionally, Ar¹～Ar⁴For have substituent group fragrant ring group when, there are various isomers, but Ar¹～Ar⁴Can be Wherein any number of.As these isomers, such as Ar¹～Ar⁴For have substituent group phenyl when, 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 of carbon number 1～12 of phenyl, 3,5- bis trifluoromethyl phenyl etc. or halogenated alkyl combine the alkylbenzene on phenyl Base；The alkoxyl of the carbon number 1～12 of 3- methoxyphenyl, 2,4,6- trimethoxyphenyl etc. combines the alcoxyl on phenyl Base phenyl；2- (or 3-, 4-) nitrobenzophenone；The halogen atom of 3- (or 4-) chlorphenyl, 3- fluorophenyl etc. combines the halogen on phenyl For phenyl etc..

Ar¹～Ar⁴Can be mutual bonding or crosslinking between 2 groups.

In four aryl halogenation phosphines according to the present invention, Ar¹～Ar⁴At least any 1 group preferably and other 3 At least any one different group of group.That is, asymmetric four aryl halogenation phosphines according to the present invention are above-mentioned formulas (10) The compound representing, is Ar¹、Ar²、Ar³And Ar⁴For asymmetrical compound.

When four aryl halogenation phosphines according to the present invention are asymmetric, due to Ar¹～Ar⁴At least any 1 group be and it At least any one different group of his 3 groups, excellent by this dissolubility.

When four aryl halogenation phosphines according to the present invention are asymmetric, Ar¹～Ar⁴Remaining 3 groups mutually can be identical, Can also be different.As asymmetric four aryl halogenation phosphines according to the present invention, due to hot upper easily stabilize, thus preferably Ar¹～Ar⁴It is all fragrant ring group, more preferably Ar¹～Ar⁴Any 1 be that there is the fragrant ring group of substituent group, and be left 3 bases Group is unsubstituted fragrant ring group, particularly preferred Ar¹～Ar⁴At least any 1 be that there is the aryl of substituent group, and remaining Group is unsubstituted aryl, most preferably Ar¹～Ar⁴Any 1 be that there is substituent group phenyl, and remaining 3 groups are no to take The phenyl in generation.

The halogen atom X of formula (10) is the halogen atom of chlorine atom, bromine atoms, atomic iodine etc..Wherein, according to the present invention de- In carbonyl reaction, due to easily working as highly active catalyst, thus preferred chlorine atom.That is, according to the present invention four Aryl halogenation phosphine preferably (can have substituent group) tetraphenylphosphonium chloride.Additionally, four aryl halogenation phosphines according to the present invention are preferred There are no benzylic protons.That is, particularly preferably there are no the asymmetric four aryl phosphonium chlorides of benzylic protons.

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

As Ar¹～Ar⁴For the organic chloride phosphine of unsubstituted aromatic hydrocarbyl or the aromatic hydrocarbyl with substituent group, There are no benzylic protons and having of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, m-benzotrifluoride base triphenyl phosphine dichloride etc. can be enumerated The compound of the 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 of the aromatic hydrocarbyl having containing alkoxyl of phosphine etc.；The having containing amino of p-aminophenyl triphenyl phosphine dichloride etc. Aromatic hydrocarbyl compound；Between cyano-phenyl triphenyl phosphine dichloride, having of cyano-phenyl triphenyl phosphine dichloride etc. is contained The fragrance having containing nitro of the compound of the aromatic hydrocarbyl of cyano group and p-nitrophenyl-three-p-methylphenyl phosphonium chloride etc. Compound of race's alkyl etc..

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

Additionally, catalyst used in the manufacture method of the carbonic diester of the present invention, particularly preferably above-mentioned asymmetric four virtues Base halogenation phosphine and hydrogen halides adduct (below, sometimes referred to as " asymmetric adduct according to the present invention " or be only called " non-right Claim adduct ").Additionally, be sometimes referred to as this hydrogen halides be " hydrogen halides according to the present invention ", this adduct be called " the present invention relates to Adduct " or be only called " adduct ".

As hydrogen halides according to the present invention, fluohydric acid gas, hydrogen chloride, hydrogen bromide, hydrogen iodide can be enumerated.According to the present invention The halogen of hydrogen halides, due to when for de-carbonyl reaction catalyst etc., if the species increase of halogen, the species of by-product Increase, reaction system easily complicates, the therefore halogen identical preferably with above-mentioned four aryl halogenation phosphines according to the present invention Halogen.

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

Additionally, adduct is normally used as meaning that the term of addition product crystallization uses.Adduct according to the present invention, leads to On Chang Si aryl halogenation phosphine, addition has the material after the solid of hydrogen halides or its melting or the material after dissolving etc. also to be comprised In adduct according to the present invention.Generally, with respect to 1 mole of four aryl halogenation phosphine, adduction in adduct according to the present invention There are 0.01～1.0 mole of hydrogen halides.That is, in adduct according to the present invention, generally with molar ratio computing, with respect to 100 4 virtues Base halogenation phosphine, addition has 1～100% hydrogen halides.

Additionally, with regard to as de- carbonylic catalyst according to the present invention asymmetric adduct most preferably according to the present invention Preparation method, particle diameter and hygroscopicity etc., will be aftermentioned.

The species of de- carbonylic catalyst, can be by elemental microanalysis method, mass analysis, nuclear magnetic resonance spectrometry and liquid phase The known method analysis of chromatography etc..Specifically, for example during the situation of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, by using unit Plain analytic process, mass analysis and NMR (Nuclear Magnetic Resonance) spectrum are analyzed, and can confirm that it is 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride.

Additionally, by the liquid chromatogram measuring the material being identified as this 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, profit With liquid chromatography, can more easily confirm.With regard to the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, first, Carry out as described above, confirm to contain 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, then, dense by the chlorine contained by mensure adduct Degree, can calculate is adduct and its adduction rate with hydrogen chloride.

De- carbonylic catalyst according to the present invention, is preferably soluble in carbonic diester.Its reason is because, the carbon of the present invention The precipitation of catalyst in the manufacture method of acid diesters, by using dissolving in the catalyst of carbonic diester, can not be caused, turned with high Rate stably carries out de-carbonyl reaction, reduces remaining oxalate diester amount, can suppress the furan of the by-product when making carbonic diester evaporate Mutter the generation of based compound.

Additionally, by the state supply that catalyst is dissolved in carbonic diester, reacted unreacted oxalate diester is relatively Less, contain the recycling of the catalyst liquid of carbonic diester with high concentration, reset by the Fu Laisi (Fries) of this oxalate diester and generate The by-product of the phenol that thing brings etc. is difficult to occur, and can get highly purified carbonic diester.

In the present invention, dissolve in carbonic diester and refer to, at 150 DEG C, for carbonic diester 100g, catalyst generally dissolves More than 10g, preferably dissolves more than 50g.Additionally, dissolubility is more high more preferred, but generally it is limited to 1000g thereon.Dissolve in carbonic acid The catalyst of diester, simply can be selected by measuring its dissolubility for carbonic diester to above-mentioned de- carbonylic catalyst.

Additionally, generally, there are four aryl salt of more than 1 alkyl, because the dissolubility for carbonic diester is higher, because This is preferred.There is the quantity preferably more than 1, less than 3 of the alkyl that four aryl salt of more than 1 alkyl have.Herein, There are four aryl salt of more than 2 alkyl, can have 1 fragrance that the alkyl of more than 2 is contained as substituent group Ring group, it is possible to have 2 fragrant ring groups that the alkyl of more than 1 is contained as substituent group, due to synthesis easily, preferably The latter.

Additionally, asymmetric four aryl halogenation phosphines according to the present invention, due to returning of the catalyst by the present invention described later Receiving method, easily by highly purified catalyst high efficiente callback, therefore preferably for polar organic solvent and water dissolubility relatively Low.

On the other hand, asymmetric adduct according to the present invention, due to the recovery method by the catalyst of the present invention, holds Easily by highly purified catalyst high efficiente callback, the therefore dissolubility preferably for polar organic solvent is higher, for the dissolving of water Degree is relatively low.

Therefore, specifically, for the meltage of the polar organic solvent 100g described later according to the present invention at 40 DEG C, Asymmetric adduct more than 0.5g more than asymmetric four aryl halogenation phosphines according to the present invention preferably according to the present invention, more preferably Many more than 1.0g, particularly preferably many more than 1.5g.

That is, asymmetric four aryl halogenation phosphines according to the present invention, at 40 DEG C, for polarity according to the present invention described later Organic solvent 100g, preferably will not dissolve more than 2.0g, more preferably will not dissolve more than 1.5g.

On the other hand, asymmetric adduct according to the present invention, at 40 DEG C, for polarity according to the present invention described later Organic solvent 100g, preferably dissolves more than 2.5g, more preferably dissolves more than 3.0g.

Additionally, asymmetric four aryl halogenation phosphines according to the present invention and asymmetric adduct according to the present invention, 40 At DEG C, for pure water 100g, preferably will not dissolve more than 2.5g, more preferably will not dissolve more than 2.0g.

Relation between reclaiming with regard to these dissolubilities and catalyst, in the preferred manufacture method of carbonic diester described later In the 3rd operation in describe in detail.

In addition thus it is speculated that asymmetric adduct according to the present invention, in the manufacture method of the carbonic diester of the present invention, dissolve In the reactant liquor of de-carbonyl reaction, hydrogen halides dissociate simultaneously, and asymmetric four aryl halogenation phosphines work as catalyst.Cause This, in the recovery method of the catalyst of the present invention described later, can similarly reclaim asymmetric four aryl phosphonium chlorides and its and chlorination The adduct of hydrogen.

The amount of de- carbonylic catalyst used in the manufacture method of the carbonic diester of the present invention, based on production efficiency aspect, Response speed easily quickening aspect, preferably more, but based on manufacturing cost and in the purification process of carbonic diester catalyst It is difficult to precipitation aspect, preferably less.

Therefore, and specifically, it is preferable to be more than 1.0 weight %, more than more preferably 2.0 weight %, particularly preferably 3.0 weights Amount more than %, additionally, on the other hand, below preferably 15.0 weight %, below more preferably 10.0 weight %, more preferably Below 8.0 weight %.

Additionally, with respect to 1 mole of oxalate diester, de- carbonylic catalyst preferably uses more than 0.001 mole, more preferably uses More than 0.01 mole, additionally, on the other hand, preferably using less than 1 mole, more preferably using less than 0.5 mole.

De- carbonylic catalyst with respect to 100 moles of total mole of the oxalate diester in reactor and carbonic diester Amount is preferably more than 0.001 mole, more preferably more than 0.1 mole, additionally, on the other hand, preferably less than 50 moles, more excellent Elect less than 20 moles as.

Additionally, catalyst can be used alone a kind it is also possible to by multiple with arbitrary ratio and being applied in combination, using many When planting, the above-mentioned amount of preferably using represents its total amount.Additionally, when using adduct, referring to that adduct and this adduct divide The total amount of the four aryl halogenation phosphines solving and producing.

Additionally, in the manufacture method of the carbonic diester of the present invention, supplying the phenostal to reactor and four aryl halides 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 above-mentioned Preferably scope, therefore with respect to 100 moles of phenostal, preferably set the total amount of four aryl halogenation phosphines as 0.1 mole with On, more preferably it is set to more than 1 mole, additionally, on the other hand, being preferably set to less than 50 moles, being more preferably set to less than 20 moles.

[halogen compounds]

In the manufacture method of the carbonic diester of the present invention, due to easily de-carbonyl reaction being maintained with high selectivity, therefore preferably with De- carbonylic catalyst halogen compounds (hereinafter sometimes referred to " halogen compounds according to the present invention ") used along.

When using phosphine or phosphine oxide particularly as organic phosphorus compound, or use beyond halogenide and dihalide hydrogen Salt when, or during using the halogenation phosphine of low concentration or dihalide hydrogen phosphine, so that halogen compounds is existed.

As halogen compounds according to the present invention, following inorganic halogen compounds and/or organic halogen can be enumerated Compound etc..In these halogen compounds, preferably chlorine compound or bromine compoundss, wherein, particularly preferred chlorine compound.

Halogen compounds can use in such a way：With respect to de- carbonylic catalyst, mol ratio (halogen compounds/de- Carbonylic catalyst) it is usually more than 0.0001, preferably more than 0.001, more preferably more than 0.01, particularly preferred more than 0.1, this Outward, on the other hand, usually less than 300, preferably less than 100, more preferably less than 3.00, particularly preferred less than 1.00.Additionally, halogen Plain compound can be used alone a kind it is also possible to by multiple with arbitrary ratio and being applied in combination, using multiple when, above-mentioned The amount of preferably using represents its total amount.

As inorganic halogen compounds, can illustrate as aluminum chloride, aluminium bromide etc. aluminum halogenide；Platinum chloride, chloroplatinic acid, The halogenide of the platinum group metal of ruthenic chloride, Palladous chloride. etc.；Phosphorous chloride., phosphorus pentachloride, phosphorus oxychloride, phosphorus tribromide, pentabromo- Change the halogenide of the phosphorus of phosphorus, phosphorus oxybromide etc.；The hydrogen halides of hydrogen chloride, hydrogen bromide etc.；Thionyl chloride, sulfonic acid chloride, dichloride The halogenide of the sulfur of sulfur, disulphur dichloride etc.；Halogen monomer of chlorine, bromine etc. etc..

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

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

[changing 10]

In formula, Hal represents the halogen atom of chlorine atom, bromine atoms etc., n¹Integer for 1～4, n²Represent 1～3 integer.

As organohalogen compound, can concrete example compound as follows.

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

As having as formula (b) represents, structure organic halogen that halogen atom is combined with carbonyl carbon Compound, can enumerate chloroacetic chloride, ethanedioly chloride, propionyl chloride, stearyl chloride, Benzenecarbonyl chloride., 2- naphthalene-carboxylic acid acyl chlorides, 2-Thiophene Carboxylic Acid acyl 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 1 as formula (c) represents, the having of structure being combined with halogen atom on the silicon atoms Machine halogen compounds, can enumerate halogenated silane of diphenyl dichlorosilane, tri-phenyl chloride etc. etc..

As having as formula (d) the represents, organic halogen of halogen atom is combined with sulphur atom structure Compound, can enumerate sulfonyl halide of paratoluensulfonyl chloride, 2- naphthalene sulfonyl chloride etc. etc..

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

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

Additionally, based on the by-product aspect that can suppress from halogen compounds, preferably inorganic halogen compounds, more preferably halogen Change hydrogen, particularly preferred hydrogen chloride.Further, since when the species of the halogen existing in reaction system increases, the species of by-product increases Plus, reaction system easily complicates, and the halogen of halogen compounds therefore preferably according to the present invention is and halogen according to the present invention Change the halogen of hydrogen and the halogen identical halogen of adduct according to the present invention.

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

[de-carbonyl reaction]

De-carbonyl reaction (below, sometimes referred to as " decarbonylation base according to the present invention in the manufacture method of the carbonic diester of the present invention React " or it is only called " de-carbonyl reaction ") preferably carried out by liquid phase reactor.Additionally, using the catalysis dissolving in carbonic diester During agent, preferably be dissolved in carbonic diester state supply catalyst, more preferably with the state being dissolved in carbonic diester supply to Catalyst contained by reacted reactant liquor is particularly preferably directly carried out profit again with the state being dissolved in carbonic diester by reactor With.

The reaction temperature of de-carbonyl reaction, is preferably high temperature based on response speed aspect, but the purity based on carbonic diester Aspect is preferably low temperature.Therefore, during normal pressure, preferable reaction temperature is usually more than 100 DEG C, particularly more than 160 DEG C, especially More than 180 DEG C.Additionally, on the other hand, usually less than 450 DEG C, preferably less than 400 DEG C, more preferably less than 350 DEG C, further Preferably below the boiling point of oxalate diester, and specifically, it is preferable to less than 340 DEG C, particularly preferred less than 320 DEG C, most preferably 300 DEG C with Under.

Pressure during reaction, is determined by the important document in operation.But, it is difficult to occur based on the by-product of impurity, hold Be easy to get highly purified carbonic diester, therefore preferably carries out under specific pressurized conditions.That is, preferably make de-carbonyl reaction than React under normal pressure (absolute pressure 0.109MPa) condition of high voltage.

And specifically, it is preferable to absolute pressure is more than 0.105MPa, below 10MPa.Additionally, more preferably 0.110MPa with On, more preferably more than 0.130MPa, particularly preferably more than 0.150MPa, on the other hand additionally, preferably 8MPa with Under, particularly preferably below 5MPa.Additionally, under decompression when carrying out de-carbonyl reaction, it is typically due to maintain decompression state Using vacuum pump, therefore absolute pressure is usually below 0.990MPa.

The control of pressure during reaction, preferably by the adjustment of the output of the carbon monoxide of by-product in de-carbonyl reaction Carry out.That is, so that at least a portion of the carbon monoxide of by-product in de-carbonyl reaction is discharged from reactor, one aoxidized by this The output of carbon, the control of absolute pressure during adjustment de-carbonyl reaction.

Specifically, for example pass through pressure-control valve etc. to control, so that the discharge pressure of carbon monoxide is with respect to above-mentioned decarbonylation Pressure during base reaction is 0.9 times～1.1 times about.Additionally, the carbon monoxide being discharged is preferably from reactant liquor gas-liquid naturally Separate.

Additionally, the carbon monoxide being discharged, former during oxalate diester preferably as being manufactured by nitrites and carbon monoxide Material utilizes.(for example, referring to the method for the records such as Japanese Laid-Open flat 10-152457 publication).

That is, preferably by least a portion of the carbon monoxide of by-product in de-carbonyl reaction, as by nitrites and an oxygen Change carbon manufacture oxalate diester when raw material use, more preferably set using the carbon monoxide of this by-product as raw material manufactured by oxalic acid two Ester is as the manufacture raw material of carbonic diester.

Preferably while from the bottom of reactor with superficial linear velocity 0.00001m s^-1Above 0.01m s^-1Following to de- Carbonyl reaction supply non-active gas are (below, sometimes referred to as " non-active gas according to the present invention " or be only called that " present invention relates to And gas "), carry out de-carbonyl reaction.

Non-active gas can be using the noble gases of argon etc., nitrogen, carbon monoxide etc..During using carbon monoxide, preferably make Carbon monoxide with by-product in de-carbonyl reaction according to the present invention.Additionally, it is anti-to carry out decarbonylation base with multi-groove type flow reactor At once, the carbon monoxide producing in the reactor of leading portion and reactant liquor together can be supplied to the reactor of back segment.

Herein, when by phenol, carbon dioxide, hydrogen halides will be contained in carbon monoxide obtained from reactant liquor gas-liquid separation Deng impurity when, preferably use absorption tower or scrubber etc. purification after use.Furthermore it is preferred that non-active gas use aerator etc. Recycle, more efficiently.

Because de-carbonyl reaction according to the present invention is the endothermic reaction, therefore preferably stir, so that fast in reactor Speed and equably heat, reacted.Therefore, in de-carbonyl reaction according to the present invention, by by non-active gas from The bottom supply of reactor, elongated by the time of contact between this gas and reactant liquor, while effectively stirring, can make to take off During carbonyl reaction, the phenol of by-product gasifies and removes.

That is, can there is no agitator or with less by by non-active gas from the supply of the bottom of reactor, stirring In agitator stirred reactor.Additionally it is believed that：By removing the phenol of by-product, can improve the response speed of de-carbonyl reaction with And conversion ratio.

Additionally, reactor lower part, typically refer to compare central part in the short transverse of the reactant liquor in reactor more under Side.Further, the position supply from the supply of the gas of reactor lower part, preferably near the central part of reactor lower part.

The supply of reaction raw materials is it is also preferred that the position near the central part of reactor lower part supplies.Because can be by pair The carbon monoxide producing stirs the raw material oxalate diester locally uprising near the supply mouth of reaction raw materials effectively.Additionally, in court To in the supply mouth of the gas of reactor lower part, it is preferably provided with check-valves etc. so that liquid is difficult to spill.The amount of the gas of supply, Based on while stirring reaction liquid, the easily together gasification aspect of the phenol in reactant liquor, preferably more.

Additionally, the present inventors finds, in de-carbonyl reaction according to the present invention, hydrogen halides can be from formula (10) sometimes Volatilize in the four aryl halogenation phosphines representing；If carrying out de-carbonyl reaction under reduced pressure, this volatile quantity increases；And if halogen Amount is less, then the conversion ratio of the phenostal in de-carbonyl reaction reduces.

When therefore, based on the higher halogen compounds of the volatility using hydrogen chloride etc., it is difficult to together by the aspect that gasifies, The amount of the preferably gas of supply is less.Therefore, during supply gas, preferably with superficial linear velocity 0.00001m s^-1More than 0.01m·s^-1Hereinafter supply.Quantity delivered is more preferably 0.0001m s^-1More than, particularly preferably 0.005m s^-1Below.

Additionally, gas circulating load (3～30 times of appearances of the carbon monoxide of generation in flat No. 11-246487 of Japanese Laid-Open 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 about, it is estimated as 0.018m s^-1Left and right.

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

But, in de-carbonyl reaction according to the present invention, if by non-active gas and reaction raw materials together from reactor Portion supplies, then more efficiently.Additionally, the gas of supply and the carbonic diester manufacturing, preferably take out from reactor top.

Based on high-efficiency stirring with the gasification aspect that easily carries out phenol, the bubble footpath of gas is preferably less, and specifically, it is preferable to For below 50mm, more preferably below 10mm.The control in bubble footpath, can be carried out using gas sparger or blender etc.. Aperture now, preferably below 10mm, more preferably below 5mm.

De-carbonyl reaction, can be batch reactions or successive reaction, industrial, preferably successive reaction, due to holding Easily make high conversion, more preferably carried out with continuous multi-stage reaction, particularly preferably non-active gas supplied as described above, While carrying out its at least one reaction.With regard to the conventional method of successive reaction, Japanese Laid-Open flat 10-109962 public affairs can be used Methods of record such as report, Japanese Laid-Open flat 10-109963 publication and Japanese Laid-Open 2006-89416 publication etc..

For reaction material fusing point more than temperature reacted when, de-carbonyl reaction not using solvent must Will but it is also possible to suitably using the aprotic polar solvent of sulfolane, N-Methyl pyrrolidone, methylimidazole alkanone etc., Hydrocarbon solvent, aromatic hydrocarbon solvents etc..

The material of reactor, as long as can make carbonic diester just generate not especially by de-carbonyl reaction according to the present invention Limit.Due in side reaction, generating the aromatic monohydroxy compound of phenol etc., the gold of therefore preferred acid resistance material sometimes Belong to container or enamel container.The form of reactor, as long as carbonic acid two can be made by de-carbonyl reaction according to the present invention Ester generates, and any type of reactor can use.As such reactor, for example can be complete using 1 groove or multi-groove type Full hybrid reactor (agitator tank), tower reactor etc..

In de-carbonyl reaction according to the present invention, based on being difficult to generate the impurity being led to by the side reaction of oxalate diester, anti- Answer the excellent aspect of efficiency, the conversion ratio of oxalate diester is preferably higher.Specifically, the conversion ratio of oxalate diester is preferably set to 96 weights Amount more than %, is more preferably set to more than 97 weight %, is further preferably set to more than 98 weight %, be particularly preferably set to 99 weights Amount more than %.Additionally, the upper limit of the conversion ratio of oxalate diester, according to catalyst etc. for carbonic diester dissolubility, not Can cause in the scope of the obturation being led to by the precipitation of catalyst etc. and can suitably select, but most preferably 100 weight %.

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

First, if the conversion ratio of oxalate diester be x [%], the amount of reacted reactant liquor be y [g], oxalate diester and carbonic acid two Total charge of ester and catalyst is sum [g].

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

Additionally, amount y [g] of reacted reactant liquor is, " sum [g] "-" growing amount [g] of carbon monoxide ".

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

Additionally, the amount [g] of reacted oxalate diester is, " y [g] " × " concentration [weight %] of reacted oxalate diester/ 100 "=" charge [g] of oxalate diester " × (100-x [%])/100.

If merging two calculating formulas, for as described below.

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

If both sides are multiplied by 100, for as described below.

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

If launching this formula, for as described below.

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

Herein, if solving with regard to x [%], for as described below.

" sum [g] " × " concentration [weight %] of reacted oxalate diester "-" charge [g] of oxalate diester " × 100= " charge [mole] of oxalate diester " × " x [%]/100 " × " molecular weight of carbon monoxide " × " reacted oxalate diester Concentration [weight %] "-" charge [g] of oxalate diester " × " x [%] "

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

[taking-up of carbonic diester]

By above-mentioned de-carbonyl reaction, the carbonic diester corresponding with raw material oxalate diester can be made to generate.The carbonic acid two of the present invention Ester, 2 R in the carbonic diester preferably generating in above-mentioned reaction equation (1) are the compound of fragrant ring group, more preferably 2 R It is the compound of aromatic ring alkyl, particularly preferred 2 R are the diphenyl carbonate of phenyl.

In the manufacture method of the carbonic diester of the present invention, preferably steamed by making the carbonic diester contained by reacted reactant liquor Send out (below, sometimes referred to as " evaporation according to the present invention " or be only called " evaporation ") and take out.If making carbonic diester evaporate, When containing high boiling substance in de- carbonylic catalyst and reacted reactant liquor, it also can remain in reactant liquor together.Cause This, taken out by making carbonic diester evaporate from reacted reactant liquor, can make carbonic diester and de- carbonylic catalyst and height Boilers separate.

Based on improving the response rate of carbonic diester, obtaining the catalyst liquid aspect of high concentration, the enrichment factor of carbonic diester (steams The rate of sending out) preferably higher.Herein, as catalyst according to the present invention, using dissolve in carbonic diester catalyst when, even if making Substantial amounts of carbonic diester evaporation is also difficult to separate out.It is therefore preferable that by 50 weight % making contained carbonic diester in reactant liquor Evaporate above and take out.

The separated of diphenyl carbonate, can carry out it is also possible to by reactant liquor in the reactor carrying out de-carbonyl reaction Move to vaporising device to carry out.With regard to vaporising device (method of evaporating), as long as above-mentioned purpose can be reached, just it is not particularly limited.

As vaporising device, due to easily separating at short notice, thus preferably for example using downward film evaporator, thin film Formula vaporizer etc. is carried out.Additionally, when evaporating in reactor, bumping is preferably difficult to stir while bumping occurs and slowly subtracts Pressure, is allowed to evaporate.

Time required for separating also is affected by the shape of heat transfer efficiency and separation container, but is based on and is difficult to cause impurity By-product aspect, preferably carry out at short notice, preferably less than 20 hours, more preferably less than 15 hours, particularly preferred 10 hours Below.

Based on being difficult to the by-product aspect of impurity, preferably carry out under low-temp low-pressure.Pressure preferably evaporates under reduced pressure, Specifically, preferred more than the 0.1kPaA of pressure, more preferably more than 0.2kPaA, on the other hand, preferably below 50kPaA, more preferably Below 20kPaA.

Further, temperature is preferably carried out below the reaction temperature in de-carbonyl reaction.Specifically it is usually preferred to 100 More than DEG C, particularly preferred more than 160 DEG C, particularly preferred more than 180 DEG C, in addition it is usually preferred to less than 450 DEG C, particularly preferred 400 Below DEG C, particularly preferred less than 350 DEG C.

[purification of carbonic diester]

Carbonic diester, de- carbonylic catalyst and unreacted oxalate diester is contained in reactant liquor after de-carbonyl reaction.Additionally, Beyond it, exist also to contain by oxalate diester, carbonic diester, the rearrangement taking off carbonylic catalyst etc., decomposition, reaction etc. and produce The probability of raw by-product etc..

As by-product, can illustrate as the aromatic monohydroxy compound of phenol etc., 4- chlorobenzoic acid phenyl ester, pass through oxalic acid The Fu Laisi (Fries) of diphenyl ester resets the carboxylic acid phenyl ester generating and the decarbonylated reaction by following reaction equation (11) Furan based compound of the benzofuran -2,3- diketone generating etc. etc..

Additionally, the aromatic monohydroxy compound of phenol etc., 4- chlorobenzoic acid phenyl ester etc. also can be enumerated.Using above-mentioned halogen During plain compound, there is also the probability containing this halogen compounds or its by-product.As the carboxylic acid phenyl ester of by-product, can lift Go out phenyl (to phenyloxycarbonyl phenyl) carbonic ester (PCPC) that above-mentioned formula (8) represents etc..

[changing 11]

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

Additionally, in de-carbonyl reaction by-product carbon monoxide, preferably from reactant liquor gas-liquid separation, discharge naturally.Additionally, Carbon monoxide is also used as being recycled by the raw material that nitrites and carbon monoxide manufacture during oxalate diester.(for example, join Method according to records such as Japanese Laid-Open flat 10-152457 publications).

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

In de-carbonyl reaction according to the present invention, using adduct according to the present invention as catalyst use when it is believed that anti- Answer the amount of contained phenol in liquid less.Think that its reason is, be because adduct hygroscopicity is relatively low as described later, therefore by water The by-product of the phenol that solution leads to is difficult to occur.

Further, since phenol becomes the Obstacle Factors of de-carbonyl reaction according to the present invention, thus the carbonic acid in the present invention In the manufacture method of diester, using adduct according to the present invention as catalyst use when, can use easy method, efficiently To highly purified carbonic diester.

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

Therefore, in the manufacture method of the carbonic diester of the present invention, with regard to using the phenostal containing carboxylic acid phenyl ester It is also possible to the method for simplicity when being reacted, it is efficiently obtained by the less highly purified carbonic diester of the content of phenol.

Further, with regard to carrying out during de-carbonyl reaction according to the present invention it is believed that carboxylic acid phenyl ester under an increased pressure By-product be difficult to occur, can get the less highly purified carbonic diester of the content of carboxylic acid phenyl ester.

Its reason is considered due to by carrying out de-carbonyl reaction under an increased pressure, decomposing during by this de-carbonyl reaction The Fu Laisi (Fries) of the oxalate diester that catalyst is led to resets and is difficult to occur.Specifically, it is believed that：For example by formula (10) When the four aryl halogenation phosphines representing use as catalyst, it is broken down into four benzene by the four aryl halogenation phosphines that formula (10) represents Base phosphine phenolate and halogen compounds, this 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：With the halogen compounds of this tetraphenyl phosphine phenolate together by-product, with by-product in de-carbonyl reaction Carbon monoxide together distillates from reactant liquor, thereby promotes the decomposition reaction of this catalyst.

However, it is believed that：If carrying out de-carbonyl reaction under an increased pressure, due to four aryl halides being represented by formula (10) The halogen compounds produced by decomposition changing phosphine become to be difficult to distillate from reactant liquor, so inhibiting phenyl (to phenyloxycarbonyl Phenyl) carbonic ester (PCPC) generation.That is, in the manufacture method of the carbonic diester of the present invention, can be by entering under an increased pressure The such easy method of row de-carbonyl reaction, efficiently and stably obtains highly purified carbonic diester.

Even if with regard to while supplying non-active gas from the bottom of de-carbonyl reaction device to de-carbonyl reaction, being taken off The situation of carbonyl reaction, is also considered as phenol etc. and is together gasified in the lump with non-active gas, thus contained phenol in reactant liquor Amount less.

Especially, when catalyst is four aryl halogenation phosphine of formula (10), led to due to the reaction with the phenol of by-product The obstruction to de-carbonyl reaction that generation of tetraphenyl phosphine phenolate etc. leads to is difficult to occur, thus the carbonic diester of the present invention In manufacture method, available easy method efficiently obtains carbonic diester.

If remaining substantial amounts of oxalate diester in reactant liquor, having by heating during evaporation and generating furan system chemical combination The probability of thing.Such as diphenyl oxalate esters presence is reset by the Fu Laisi (Fries) of following reaction equation (12) and is generated Benzofuran -2,3- diones and the probability of phenols.

Especially, due to benzofuran -2,3- diketone is in orange compound, becomes the coloring of carbonic diester sometimes Benzofuran -2 in reason, therefore preferred carbonic acid diester, the amount of 3- diketone is less.

But, in the manufacture method of the carbonic diester of the present invention, using the catalyst dissolving in carbonic diester, with conversion ratio More than 96% when carrying out de-carbonyl reaction, and remaining oxalate diester is less, can suppress the furan system that heating when evaporating is led to The by-product of compound.

Specifically, the amount of contained furan based compound in the carbonic diester of evaporation is although also can be subject to de-carbonyl reaction In the conversion ratio of oxalate diester impact, but generally can be set to below 1ppm, be preferably set to below 0.1ppm.

[changing 12]

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

Additionally, in the above-mentioned manufacture method of the carbonic diester of the preferred present invention, when so that carbonic diester is evaporated, evaporation Usually contain in fraction more than 70 weight %, more than preferably 80 weight %, more than more preferably 90 weight %, further preferred 97 weights Carbonic diesters more than amount more than %, particularly preferred 98 weight %.Additionally, its upper limit, usually 100 weight %.

When containing oxalate diester in this fraction, usually more than 0.001 weight %, more than preferably 0.01 weight %, more excellent Select more than 0.1 weight %, additionally, on the other hand, usually below 3 weight %, below preferably 2 weight %, more preferably 1 weight % Hereinafter, below more preferably 0.5 weight %.But most preferably 0 weight %.

Additionally, containing content during composition outside them, with respect to total amount 100 weight of carbonic diester and oxalate diester Amount part, usually below 1 weight portion, below preferably 0.5 weight portion, below more preferably 0.1 weight portion.Containing ionic chlorine etc. When content, usually below 0.0001 weight %, below preferably 0.00001 weight %, more preferably 0.000001 weight % with Under.

With regard to contained phenyl (to phenyloxycarbonyl phenyl) carbonic ester (PCPC) in this fraction, usually 0.35 weight % Hereinafter, below preferably 0.30 weight %, below more preferably 0.10 weight %, below more preferably 0.08 weight %, particularly preferably Below 0.05 weight %.

As the composition outside them, sometimes with the aromatic monohydroxy compound etc. of phenol etc., but content now It is usually below 1 weight %, below preferably 0.5 weight %, below more preferably 0.3 weight %.

Additionally, contained benzofuran -2 in this fraction, content usually 10 weights of the furan based compound of 3- diketone etc. Amount more than ppb, more than preferably 100 weight ppb, more than more preferably 1000 weight ppb, additionally, on the other hand, usually 2 weight Amount below %, below preferably 1 weight %, below more preferably 0.5 weight %.

The carbonic diester of evaporation is used directly for the purposes that Merlon manufactures etc., but can purity as needed etc. enter One step is purified.Further, it is also possible to carry out the evaporation of above-mentioned carbonic diester by distillation, by boiling than carbonic diester respectively The high composition of point from bottom of towe side, by carbonic diester from stage casing, low-boiling composition will go out from tower top side draw than carbonic diester, thus Obtain highly purified carbonic diester.

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

In the manufacture method of the carbonic diester of the present invention, using the catalyst dissolving in carbonic diester, with conversion ratio 96% More than carry out during de-carbonyl reaction it is suppressed that the by-product of furan based compound, thus remove furan from the carbonic diester of evaporation The operation of based compound can not as desired purity design even.That is, compared to the rear work removing furan based compound Sequence is necessary conventional method, can obtain highly purified carbonic diester simple and effectively.

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

In the manufacture method of the carbonic ester of the present invention, obtained by preferably passing through to make by the decarbonylated reaction of oxalate diester Carbonic diester is contacted with alkali compoundss, thus decomposes contained furan based compound in this carbonic diester, by so easy Method, efficient stable and be continuously manufactured by the less highly purified carbonic diester of content of furan based compound.

[alkali compoundss]

As the alkali compoundss for removing furan based compound, for example, as alkali metal compound, hydroxide can be enumerated The alkali-metal hydroxide of lithium, sodium hydroxide, potassium hydroxide, Cesium hydrate. etc.；Lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, The bicarbonate alkali metal salt of caesium bicarbonate etc.；The alkali-metal carbonate of lithium carbonate, sodium carbonate, potassium carbonate etc.；Lithium acetate, acetic acid The alkali-metal acetate of sodium, potassium acetate, cesium acetate etc.；Lithium stearate, sodium stearate, potassium stearate, stearic acid caesium etc. hard The alkali metal salt of fat acid；The alkali metal salt of the boron hydride of lithium borohydride, sodium borohydride, potassium borohydride, hydroboration caesium etc.；Benzoinum The alkali-metal benzoate of sour lithium, sodium benzoate, benzoic acid potassium, benzoic acid caesium etc.；Lithium dihydrogen phosphate, di(2-ethylhexyl)phosphate The alkali-metal dihydric phosphate of hydrogen sodium, potassium dihydrogen phosphate, cesium dihydrogen phosphate etc.；Phosphenylic acid two lithium, disodium phenylphosphate, benzene The alkali-metal phenyl microcosmic salt of base dikalium phosphate, phosphenylic acid two caesium etc.；Lithium, sodium, potassium, the alkoxide of caesium；Lithium, sodium, potassium, the phenol of caesium Salt；The dilithium salt of bisphenol-A, disodium salt, di-potassium, two cesium salts etc..

As alkali earth metallic compound, the alkali of calcium hydroxide, barium hydroxide, magnesium hydroxide, Strontium hydrate. 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 alkali-metal carbonate of Calcium Carbonate, brium 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 bis(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 organoboron compound, can enumerate triethyl phosphine, three-n-pro-pyl phosphine, tri isopropyl phosphine, three-normal-butyl phosphine, three Phenylphosphine, tributylphosphine or quaternary salt etc..

As organic ammonium salt, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, 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, PA, N, N- dimethyl -4-aminopyridine, 4- bis- can be enumerated Ethylamino pyridine, 2 hydroxy pyrimidine, 2- methoxypyridine, 4-methoxypyridine etc..As imidazolium compoundss, 2- bis- can be enumerated Methylamino imidazoles, 2- methoxyl group imidazoles, imidazoles, 2- mercaptoimidazole, 2-methylimidazole etc..Additionally, quinolin-2-ylamine also can be enumerated Deng.

Wherein, because volatility is relatively low, preferred as alkali compound and alkali earth metallic compound, more preferably alkali metal Compound.

Alkali compoundss, as long as can contact with the impurity of contained furan based compound in carbonic diester etc., in the present invention The manufacture method of carbonic diester in can arbitrarily supply.By being easy to the decarbonylated reaction institute by oxalate diester to storage The groove tank of the carbonic diester obtaining or its purifying column etc. supply, thus preferred alkali compoundss.

As the groove tank of storage carbonic diester, specifically, storage can be enumerated from by the decarbonylated reaction of oxalate diester Obtained reactant liquor removes the groove tank of the composition of catalyst liquid.Additionally, as the purifying column of carbonic diester, can enumerate as Japan The ground distillation column being distilled etc. described in state's JP 2002-322130 Publication.

Alkali compoundss can only alkali compoundss state supply it is also possible to be dissolved in solvent etc. state supply.? When supplying alkali compoundss with the state being dissolved in solvent, preferably phenol is such higher for the dissolubility of diphenyl carbonate Solvent.

Aspect is susceptible to based on the decomposition of furan based compound, preferred to the amount of the alkali compoundss of carbonic diester supply More, but generation aspect is difficult to based on the decomposition of carbonic diester, preferably less.Accordingly, with respect to carbonic diester 100 weight portion, It is usually more than 0.0000001 weight portion, more than preferably 0.000001 weight portion, more than more preferably 0.00001 weight portion, this Outward, on the other hand, usually below 1 weight portion, below preferably 0.1 weight portion, below more preferably 0.01 weight portion.

The decomposition of furan based compound, high temperature be more susceptible to, but generation side is difficult to based on the decomposition of carbonic diester Face, is preferably carried out at low temperature.Therefore, generally more than 100 DEG C, carry out in preferably more than 130 DEG C, more preferably more than 150 DEG C. Additionally, on the other hand, generally below 300 DEG C, carry out in preferably less than 280 DEG C, more preferably less than 250 DEG C.

The removing of furan based compound, generally to containing the carbonic acid obtained by the decarbonylated reaction by oxalate diester The composition removing the carbonic diester after catalyst liquid in diester is carried out.

[recovery of de- carbonylic catalyst]

In the manufacture method of the carbonic diester of the present invention, carrying out de-carbonyl reaction using the catalyst dissolving in carbonic diester When, even if being reacted with high conversion, in the reactant liquor after making carbonic diester evaporate, the catalyst of remaining is generally also dissolved in Remain in the carbonic diester of reactant liquor.

It is therefore preferable that taking out at least a portion of this catalyst from residual liquid, supplying and recycling to de-carbonyl reaction. That is, preferably by using at least a portion of contained catalyst in this residual liquid as catalyst, by catalyst to dissolve State in carbonic diester supplies to reactor.

The viewpoint of the accumulation based on the higher-boiling compound preventing in reaction system, the recycling of catalyst preferably will be from making Remove the liquid after the compound higher than carbonic diester boiling point in reactant liquor after carbonic diester evaporation to supply to reactor.

As the composition being removed by this operation, 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 (under 1 air pressure, boiling point is higher than phenostal) etc..Can pass through The known method such as distillation, extraction, crystallize removes higher-boiling compound.

Specifically, method that for example can be recorded with Japanese Laid-Open 2002-45704 publication etc. separates.Additionally, phenyl (to phenyloxycarbonyl phenyl) carbonic ester (PCPC) boiling point under 1 air pressure is 340 DEG C, thus is contained in high boiling point chemical combination Thing.

And, when recycling the residual liquid containing catalyst, in this residual liquid contained carbonic diester and carbonic diester it The total amount of the by-product of outer de-carbonyl reaction, with respect to the total amount of the composition beyond catalyst, preferably 85～100 weights Amount %.

When recycling catalyst, can only not made it is also possible to mix in the catalyst reclaiming using the catalyst reclaiming Catalyst etc. and use.Further, it is also possible to supply the molten of carbonic diester in this residual liquid further to reactor supply Liquid.Additionally, with removing this higher-boiling compound, the part of the analyte that catalyst and catalyst are decomposed and produce also by Remove etc., may not be reused by the catalyst of this whole amount.It is therefore preferable that adjustment catalytic amount, so that de- Carbonyl Catalysis The amount of agent becomes above-mentioned preferred scope.

The adjustment of catalytic amount, preferably passes through by and the catalyst being together removed and catalyst divides with higher-boiling compound Solution thing the mole of total mole same degree catalyst, with remove higher-boiling compound after liquid together supply to Carry out in the reactor of de-carbonyl reaction.Herein, when using adduct according to the present invention as catalyst, this catalyst The analyte being decomposed and producing refers to the analyte of adduct.

Also, it is preferred that with remove higher-boiling compound after liquid together, using with four aryl as adduct analyte The adduct of the mole of total mole same degree of halogenation phosphine supplies to the reactor of de-carbonyl reaction.Same degree Mole, is decomposed with respect to the catalyst of be together removed with higher-boiling compound, catalyst and four aryl halogenation phosphines etc. 1 mole of the total amount of thing, preferably more than 0.7 mole, more preferably more than 0.8 mole, particularly preferably more than 0.9 mole, Additionally, on the other hand, preferably less than 2 moles, more preferably less than 1.4 moles, particularly preferably less than 1.1 moles.

When de- carbonylic catalyst in residual liquid is supplied to de-carbonyl reaction, preferably by above-mentioned halogen compounds and remaining Liquid together supplies to de-carbonyl reaction.The amount of the halogen compounds preferably being supplied is, with respect to de- in the presence of reactor The total amount of carbonylic catalyst (particularly salt catalyst), the halogen compounds in the presence of reactor are rubbed for 0.01～100 You are % (equimolar).

During by catalyst recycle, sometimes become in catalyst liquid the also carboxylic acid phenyl ester containing by-product in de-carbonyl reaction Deng high boiling substance state.Additionally, when using the phenostal containing carboxylic acid phenyl ester, sometimes becoming in catalyst liquid State containing it.

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

[preparation method of preferred carbonic diester]

As the manufacture method of the carbonic diester of the present invention, the method particularly preferably containing the 1st～3 following operation successively.

1st operation：Manufacture the operation of carbonic diester by above-mentioned de-carbonyl reaction according to the present invention,

2nd operation：The carbonic diester that will manufacture in 1st operation, the decomposition with the generation that is decomposed containing catalyst and/or catalyst The detached operation of catalyst liquid of thing,

3rd operation：The work of the reactor to the 1st operation will be supplied by least a portion of detached catalyst liquid in 2nd operation Sequence.

1st operation, preferably obtains the fraction containing non-active gas from reactor, it is supplied at least partially to anti- Answer the operation of device.The acquirement of the fraction containing this non-active gas, for example can be by from simplicity such as reactor top gas bleedings Ground is carried out.

Herein, the together gasification of the phenol being led to based on non-active gas is susceptible to aspect, the oxalic acid two in reactant liquor The concentration of phenyl ester is preferably relatively low.Therefore, specifically, the concentration of the phenostal in reactant liquor is preferably below 30 weight %, Below more preferably 10 weight %, below particularly preferably 5 weight %.

Further, since being difficult to occur to the obstruction of de-carbonyl reaction, the concentration of the phenol in reactant liquor is preferably relatively low, specifically Ground, with respect to catalyst mol ratio (phenol/catalyst) be preferably less than 2, more preferably less than 1, particularly preferably 0.5 with Under.

In 1st operation, if at least a portion of the fraction containing non-active gas is supplied to reactor, recycling Non-active gas, the carbon monoxide that effectively utilizes generate in de-carbonyl reaction simultaneously.Herein, evaporating containing non-active gas Point, reactor can be directly fed to, but preferably supply one part to reactor.By the fraction containing non-active gas When a part supplies to reactor, preferably by beyond the non-active gas of contained phenol in the fraction containing non-active gas etc. Composition by distillation etc. remove after resupply.

In 2nd operation, by the carbonic diester manufacturing in the 1st operation and urging containing catalyst and/or catalyst analyte Agent liquid separates.Separation in 2nd operation can use the known method of distillation, extraction, crystallize etc. to carry out.According to the present invention four Aryl halogenation phosphine and adduct according to the present invention are usually high boiling point, thus using these compounds as catalyst use when, Separation in 2nd operation, by distillation carbonic diester, detached method is easier, is preferred.

That is, in the manufacture method of the carbonic diester of the present invention, contained in the reactant liquor preferably after make de-carbonyl reaction Carbonic diester evaporation and take out, thus obtain decomposing the catalyst liquid of the analyte producing containing catalyst and/or catalyst.

Additionally, the Fu Laisi containing oxalate diester and carbonic diester (Fries) weight in reactant liquor after de-carbonyl reaction During the high boiling substance of row's compound etc., these materials also become to be contained in decompose containing catalyst and/or catalyst and produce State in the catalyst liquid of analyte.

Additionally, as described above, it is preferred to making to be contacted with alkali compoundss by detached carbonic diester in the 2nd operation.Additionally, can Purity as needed etc., before being contacted with alkali compoundss and/or after contact, is distilled further to diphenyl carbonate or is inhaled Attached etc..

In 3rd operation, at least a portion of the catalyst liquid obtaining in the 2nd operation is supplied to the reactor of the 1st operation. So, recycling de- carbonylic catalyst.The catalyst of the separated of carbonic diester of the 2nd operation and the 3rd operation is again Using preferably being carried out by said method and condition.

In the manufacture method of the carbonic diester of the present invention, even if as described above, the catalyst being used for de-carbonyl reaction is returned Receive and recycle it is also difficult to generate by-product, available easy method is efficiently obtained by highly purified diphenyl carbonate.

[recovery method of catalyst]

As de- carbonylic catalyst, use (can have substituent group) four aryl halogenation phosphine and/or (can have substituent group) four During the adduct of aryl halogenation phosphine and hydrogen chloride, can be by following method (below, sometimes referred to as " catalyst of the present invention Recovery method "), reclaim highly purified catalyst from reactant liquor simple and effectively.Additionally, by recycling this catalyst, can Steady and continuous ground manufactures highly purified carbonic diester.

The recovery method of the catalyst of the present invention, will be used for the catalyst of above-mentioned de-carbonyl reaction, from by de-carbonyl reaction Obtain the residual liquid (below, sometimes referred to as " catalyst liquid ") after the composition containing carbonic diester in reactant liquor afterwards to reclaim.Specifically, The recovery method of the catalyst of the present invention, has and makes polar organic solvent and hydrogen halides contact the operation of this residual liquid.

The recovery method of the catalyst of the presumption present invention is carried out as follows, reclaims contained de- Carbonyl Catalysis in catalyst liquid Agent.

In de-carbonyl reaction, using four aryl halogenation phosphines as catalyst agent use when, in catalyst liquid contain should Four aryl halogenation phosphines.Additionally, in de-carbonyl reaction it is believed that with regard to using the adduct of four aryl halogenation phosphines and hydrogen chloride as catalysis When agent uses, in catalyst liquid, also contain the four aryl halogenation phosphines separating out hydrogen halides from this adduct middle reaches.

Further, in catalyst liquid contain symmetrical four aryl halogenation phosphine when, this symmetrical four aryl halogenation phosphine by with halogen Change the contact of hydrogen, become the adduct of this symmetrical four aryl halogenation phosphine and hydrogen halides.This symmetrical four aryl halogenation phosphine and hydrogen halides Adduct, the dissolubility generally for polar organic solvent is relatively low.

Therefore, if making this catalyst liquid contact with polar organic solvent, the carbonic diester of residual generally in catalyst liquid It is dissolved in polar organic solvent with impurity etc., but symmetrical four aryl halogenation phosphines according to the present invention can separate out.Then, can be by taking Obtain this precipitate, reclaim de- carbonylic catalyst.

On the other hand, in catalyst liquid contain asymmetric four aryl halogenation phosphine when, this symmetrical four aryl halogenation phosphine by with The contact of hydrogen halides, becomes the adduct of this asymmetric four aryl halogenation phosphine and hydrogen halides.Herein, asymmetric four aryl halogenations Phosphine, the dissolubility generally for polar organic solvent is relatively low.

Additionally, its adduct with hydrogen halides, the dissolubility generally for polar organic solvent is higher, but molten for water Xie Du is relatively low.Therefore, if making this catalyst liquid contact with polar organic solvent, the carbonic diester of residual generally in catalyst liquid It is dissolved in polar organic solvent with impurity etc., and asymmetric four aryl halogenation phosphines according to the present invention are due to organic molten for polarity The dissolubility of agent is relatively low, thus separates out, and this catalyst liquid is slurry.

Additionally, when contained asymmetric four aryl halogenation phosphines in this catalyst liquid are contacted with hydrogen halides, becoming and hydrogen halides Adduct, due to for polar organic solvent dissolubility improve, thus dissolving.Further, due to asymmetric four aryl The adduct of halogenation phosphine is relatively low for the dissolubility of water, is therefore separated out by the contact with water, and generally this catalyst liquid is again Become slurry.

Therefore, de- carbonylic catalyst can be reclaimed by obtaining this precipitate.That is, de- carbonylic catalyst is asymmetric four virtues During the adduct of base halogenation phosphine and/or asymmetric four aryl halogenation phosphines and hydrogen halides, contained catalyst in this residual liquid, by connecing After tactile polar organic solvent and hydrogen halides, contact water, thus can reclaim as precipitate.

The recovery method of the catalyst of the present invention, by asymmetric four aryl halogenation phosphines and/or asymmetric four aryl halogenation phosphines With the adduct of hydrogen halides, as catalyst in the manufacture of the diphenyl carbonate that the de-carbonyl reaction by phenostal is carried out During use, so implement, easy method can be passed through from reactant liquor and efficiently reclaim highly purified catalyst.

In the recovery method of the catalyst of the present invention, polar organic solvent contact to this residual liquid with hydrogen chloride, can be simultaneously Carry out it is also possible to make the opposing party contact after so that either party is first contacted again.That is, polar organic solvent and hydrogen halides connect to residual liquid Touch, residual liquid can be made to contact with hydrogen halides after contacting with polar organic solvent dissolving again.Additionally, polar organic solvent and hydrogen halides pair The contact of residual liquid, so as to contact residual liquid after can making polar organic solvent contact with hydrogen halides.

But, based on easily efficiently reclaiming highly purified catalyst aspect, preferably by using absorbing hydrogen halides Polar organic solvent etc., is thus allowed to contact simultaneously, or contacts with hydrogen halides after contacting with polar organic solvent again, more preferably and Contact with hydrogen halides again after polar organic solvent contact.

Reason be it is believed that：If hydrogen halides first contact this residual liquid, dividing by contained carbonic diester in this residual liquid Solution, generates phenol, has the probability of the reaction causing four aryl halogenation phosphines to be changed into tetraphenyl phosphine phenolate, thus passes through and polarity Organic solvent contacts simultaneously, or first contacts polar organic solvent, can make to cause this reaction to become difficult.

And, the manufacture method of the carbonic diester of the present invention, the precipitate preferably reclaiming this is as de-carbonyl reaction Catalyst is recycled, and the precipitate more preferably reclaiming this uses as the catalyst of de-carbonyl reaction, and is allowed to carry out Successive reaction.

For the polar organic solvent of the recovery method of the catalyst of the present invention, preferably for contained lacking in catalyst liquid The intermiscibility of the carbonic diester of amount and by-product high boiling substance and water is higher, easily make four aryl halogenation phosphines and hydrogen halides plus Compound dissolves, easily makes the solvent of four aryl halogenation phosphines precipitations.As the preference of polar organic solvent, ketone, ether can be enumerated Class, halogenated hydrocarbon, and esters etc..

As ketone, can illustrate as dimethyl ketone, metacetone, methyl ethyl ketone, methyl n-pro-pyl ketone, isopropyl methyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl isoamyl ketone, ethyl n-pro-pyl ketone, ethylisopropyl The low alkyl group ketone of carbon number 1～15 of base ketone, ethyl normal-butyl ketone, ethyl isobutylo ketone etc. and Ketohexamethylene, ring penta Ring-type ketone of carbon number 3～10 of ketone etc. etc..

As ethers, can illustrate 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 number 2～10 of base ether, ethyl n-butyl ether, ethyl isobutyl ether, dimethoxy-ethane, diethoxyethane etc. low Level alkyl ether；Diaryl ethers of the ring-type ethers of oxolane etc. and diphenyl ether etc. etc..

As halogenated hydrocarbon, can illustrate as monochloro methane, dichloromethane, chloroform, 1- ethyl chloride, 1,2- bis- chloroethene Alkane, 1,1- dichloroethanes, 1,1,2- trichloroethane, n-propyl chloride, 2 cbloropropane isopropyl chloride, 1,2- dichloropropane, 1,1- dichloropropane, 2, Halogenated hydrocarbon of carbon number 1～6 of 2- dichloropropane etc. etc..

As esters, can illustrate as alkyl fatty race carboxylate, alkylcarbonic acid diester, alkyl oxalate diester and ethylene glycol Fatty acid 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 The low alkyl group acetate of ester, n-butyl acetate, isobutyl acetate etc. and methyl propionate, ethyl propionate, n propyl propionate, third 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., ethyl oxalate etc. etc. can be enumerated.Make For glycol acetate, ethyl acetate, propyl acetate, butyl acetate etc. can be enumerated.

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

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

Therefore, in particular it is preferred to alkyl ketone, more preferably total carbon number is 3～10 alkyl ketone, 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 contacting with catalyst liquid, based on being difficult to cause carbonic diester and by-product height boiling The point precipitation of material and the solidification aspect of residual liquid, preferably more, additionally, another aspect, the response rate based on catalyst and pole Property organic solvent separation and recovery required for the less aspect of energy, preferably less.

Therefore, specifically, with respect to catalyst liquid, preferably more than 0.5 times, more preferably more than 1 times, additionally, another Aspect, preferably less than 10 times, more preferably less than 5 times, particularly preferably less than 3 times.

The amount of the water in polar organic solvent, if more, the dissolubility of the hydrogen chloride adduct of four aryl halogenation phosphines becomes Little, and the phenol with contained diphenyl carbonate reaction in catalyst liquid and by-product, with four aryl halogenation phosphine reactions, easily become Become tetraphenyl phosphine phenolate, thus the weight with respect to polar organic solvent, usually below 2.0 weight %, preferably 1.0 weights Amount below %, below more preferably 0.5 weight %, below particularly preferred 0.2 weight %.

When de- carbonylic catalyst is adduct, the hydrogen halides contacting with catalyst liquid are preferably the hydrogen halides phase with adduction Same hydrogen halides.Additionally, when de- carbonylic catalyst is four aryl halogenation phosphine, preferably former with the halogen contained by this four aryl halogenation phosphine The hydride of sub- identical halogen atom.

Further, due to de- carbonylic catalyst according to 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 being reclaimed The preferred hydrogen chloride of hydrogen halides.

The hydrogen halides contacting with catalyst liquid, when in catalyst liquid, contained catalyst is symmetrical four aryl halogenation phosphine, By the contact with polar organic solvent, adduct separates out, and this point is not changed in, thus can be gas, liquid it is also possible to 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 easy Operation, more preferably hydrogen chloride gas or hydrochloric acid.

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

Hydrogen halides are to add contained four aryl halogenation phosphines in catalyst liquid as the hydrogen halides of four aryl halogenation phosphines Compound and use.Therefore, the amount of the hydrogen halides contacting with catalyst liquid, with respect to contained four aryl halogenations in catalyst liquid 1 mole of phosphine, preferably more than 1 mole, more preferably more than 1.1 moles, additionally, on the other hand, preferably less than 5 moles, more It is preferably less than 2 moles.

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

Additionally, the organic efficiency easily raising aspect based on catalyst, the temperature of the hydrogen halide of contact and with contain The temperature of the polar organic solvent containing hydrogen halides when the polar organic solvent having hydrogen chloride contacts, preferably relatively low.Specifically, It is preferably less than 50 DEG C, more preferably less than 40 DEG C, particularly preferably less than 30 DEG C.Reason is, if carbonic diester and by-product High boiling substance is contacted with hydrogen chloride, then have by the hydrolysis such as contained water in polar organic solvent and generate the probability of phenol.

In the manufacture method of the carbonic diester of the present invention, anti-by recycling above-mentioned recovery catalyst to carry out decarbonylation base Should, thus can manufacture highly purified carbonic diester in steady and continuous ground.Obtained by successive reaction by using recovery catalyst The purity of carbonic diester, usually more than 99 weight %, more than preferably 99.3 weight %, more preferably 99.5 weight % with On.During containing impurity, sometimes with ionic chlorine etc., but content now is usually below 1 weight ppm, preferably 0.1 weight Amount below ppm, below more preferably 0.01 weight ppm.

Additionally, de- carbonylic catalyst be asymmetric four aryl halogenation phosphines or asymmetric four aryl halogenation phosphines with hydrogen halides plus During compound, in order that the amount of water that the adduct of this asymmetric four aryl halogenation phosphine and hydrogen halides separates out and contacts, based on non-right The hydrogen halides adduct claiming four aryl halogenation phosphines easily separates out, and response rate raising aspect is preferably more, additionally, on the other hand, base It is difficult to separate out in carbonic diester and by-product high boiling substance, easily reclaim highly purified catalyst aspect, preferably less.

Therefore, specifically, the amount of water is with respect to the amount (weight ratio) of polar organic solvent, preferably more than 0.001 times, more It is preferably more than 0.01 times, particularly preferably more than 0.02 times, additionally, on the other hand, preferably less than 0.5 times, more preferably Less than 0.2 times, particularly preferably less than 0.1 times.

The temperature of the water of contact, preferably less than 50 DEG C, more preferably less than 40 DEG C, particularly preferably less than 30 DEG C.Base It is easily to become high-purity aspect in the catalyst reclaiming, the contact with water is preferably slowly time-consumingly carried out.That is, with make whole water one Secondary contact is compared, and preferably by water separately, or contacts on a small quantity every time.

That is, de- carbonylic catalyst is asymmetric four aryl halogenation phosphines or the adduction of asymmetric four aryl halogenation phosphines and hydrogen halides During thing, the 3rd operation in the above-mentioned manufacture method of the carbonic diester of the present invention, preferably have successively following 3A operations and The manufacture method of the carbonic diester of the present invention is more preferably carried out by 3B operation as successive reaction.

3A operation：By make in the 2nd operation at least a portion of detached catalyst liquid and polar organic solvent and After hydrogen halides contact, contact water, obtain the operation of precipitate,

3B operation：Using at least a portion of the precipitate obtaining in the 3rd operation as the catalyst of de-carbonyl reaction supply to The operation of the 1st operation.

In 3A operation, by make in the 2nd operation at least a portion of detached catalyst liquid and polar organic solvent with And after hydrogen halides contact, contact water, thus obtain precipitate.In 3A operation, by making this catalyst liquid organic with polarity molten After agent contacts with hydrogen halides, contact water, thus obtain precipitate, estimating this is to be led to by producing phenomenon as described above 's.

In 3B operation, using at least a portion urging as de-carbonyl reaction of the precipitate obtaining in above-mentioned 3A operation Agent supplies to above-mentioned 1st operation.The serosity obtaining in 3A operation, makes to be dried by the solid obtaining its solid-liquid separation, And supply to the reactor of de-carbonyl reaction, accordingly can be used as catalyst recycle.But, based on the storage preventing high boiling substance Long-pending viewpoint, the serosity obtaining in 3A operation supplies to the 1st operation after preferably removing the composition higher than carbonic diester boiling point.

As the composition being removed herein, can illustrate as to Para Hydroxy Benzoic Acid phenyl ester or phenyl (adjacent phenyloxycarbonyl benzene Base) carbonic ester (PCPC) etc. by-product high boiling substance.Solid-liquid separation can be passed through pressure filtration etc. and carry out.Additionally, drying is logical Cross the solid making to obtain under about 80～220 DEG C, 0.1～50kPa, be dried about 1～10 hour, thus can be organic molten except depolarization Agent and water.

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

But, in above-mentioned 3A operation, even if the catalyst liquid of the whole amount obtaining from the 2nd operation carries out catalyst returning Receipts are processed, and are sometimes associated with the process of the removing of by-product high boiling substance etc., a part for catalyst also can be removed.Therefore, When carrying out successive reaction, as described above, it is preferred to by reclaim catalyst while supply asymmetric four aryl halogenation phosphines and/or Asymmetric four aryl halogenation phosphines and the adduct of hydrogen halides, adjust catalytic amount, so that asymmetric four aryl halogenations in reactor The total amount of phosphine becomes above-mentioned preferred scope.

[recovery of polar organic solvent]

The recovery method of the catalyst of the present invention, preferably has and reclaims the polar organic solvent reclaiming for catalyst, and profit again Operation for catalyst recovery process.That is, de- carbonylic catalyst is four aryl halogenation phosphines and/or four aryl halogenation phosphines and halogenation During the adduct of hydrogen, can will obtain contained catalyst in the residual liquid after the composition containing carbonic diester from reactant liquor, use Polar organic solvent reclaims, and meanwhile, also reclaims the polar organic solvent reclaiming for this catalyst, is reused in catalyst Reclaim.

Specifically, make polarity organic molten when the 3rd operation in the manufacture method of the carbonic diester of the above-mentioned present invention has The operation that agent is contacted with least a portion of the catalyst liquid obtaining in the 2nd operation with hydrogen halides, and make institute in this catalyst liquid When the catalyst containing separates out, preferably reclaim the polar organic solvent for the recovery of this catalyst and recycled.

Estimate catalyst in the 3rd operation to separate out by phenomenon as described above.Additionally, with regard to contacting with catalyst liquid The species of polar organic solvent and amount (weight), the amount of hydrogen chloride, the temperature of hydrogen chloride contacting or the pole containing hydrogen chloride Property organic solvent temperature, make water contact when amount and temperature, also as described in the recovery method with regard to catalyst.

But, when de- carbonylic catalyst is four aryl halogenation phosphines and/or adduct, the pole of the recovery of this catalyst will be used for Property organic solvent recycle when, the hydrogen chloride being contacted with residual liquid can be supplied as hydrochloric acid.

The recovery method of the catalyst of the present invention, preferably passes through sequentially to enter following (A) operation and (B) operation with this OK, thus reclaim the polar organic solvent reclaiming for catalyst, be reused in catalyst recovery process.

(A) operation：By using the polar organic solvent evaporation reclaimed in described catalyst, in the Liquid liquid Separation loading water Distillate in device, make described Liquid liquid Separation device polar organic solvent be mutually back to described residual liquid side, remove institute in described residual liquid At least one of operation of the hydrogen chloride containing,

(B) operation：Operation by the liquid obtaining in (A) operation distillation.

(A), in operation, make to reclaim the residual liquid evaporation after catalyst as precipitate as described above, in Liquid liquid Separation device Distillate.Herein, due in Liquid liquid Separation device equipped with water, thus the phase (upper strata) of polar organic solvent and water in Liquid liquid Separation device Phase (lower floor) separated, but contained hydrogen chloride in polar organic solvent, compared with polar organic solvent, in aqueous phase side It is easier to dissolve.Therefore, mutually it is back to residual liquid side by make polar organic solvent, can remove contained in polar organic solvent Hydrogen chloride.

(A) distilling apparatus (method of evaporating) used in operation, as long as can reach above-mentioned purpose be just not particularly limited. As vaporising device, such as downward film evaporator, thin-film evaporator etc. are because easily separating at short notice, thus are preferred 's.Additionally, when evaporating in reactor, being preferably difficult to stir while bumping occurs and slowly reduce pressure, while being allowed to evaporate.

Remove the contained time required for hydrogen chloride in polar organic solvent, by the shape of heat transfer efficiency and separation container Impact, but based on being difficult to the by-product aspect of impurity, preferably carry out at short notice, preferably less than 20 hours, more preferably 15 Below hour, particularly preferred less than 10 hours.

Based on being difficult to occur the by-product aspect of 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, preferred more than the 1kPaA of pressure, more preferably more than 2kPaA.On the other hand additionally, preferably 100kPaA with Under, more preferably below 80kPaA.And, temperature is usually more than 50 DEG C, preferably more than 60 DEG C, particularly preferred more than 70 DEG C, this Outward, on the other hand, usually less than 200 DEG C, preferably less than 190 DEG C, particularly preferred less than 180 DEG C.

The amount of water loading in Liquid liquid Separation device and temperature, as long as the polar organic solvent distillating and hydrogen chloride are divided by liquid liquid From being just not particularly limited.The amount of water present in Liquid liquid Separation device, is preferably set to catalyst as after precipitate recovery More than 1 weight % of residual liquid, more than more preferably 2 weight %, on the other hand, below preferably 50 weight %, more preferably 30 Below weight %.

Due to easy Liquid liquid Separation, the temperature of Liquid liquid Separation device is preferably set to less than 60 DEG C, is more preferably set to less than 50 DEG C, Additionally, on the other hand, therefore it is preferably set to more than 0 DEG C because aqueous phase is difficult to solidification, more preferably more than 5 DEG C.

Such preferably under the conditions of carry out (A) operation when, in the phase of the polar organic solvent being back to residual liquid side, lead to Often contain more than polar organic solvent 70 weight %, more than preferably 80 weight %, more than more preferably 90 weight %.Additionally, thereon Limit is usually 100 weight %.Additionally, being back to contained hydrogen chloride in the phase of the polar organic solvent of residual liquid side, usually 1 weight Amount below %, below preferably 0.5 weight %, below more preferably 0.3 weight %.

(B), in operation, the liquid obtaining in (A) operation is distilled.By distillation, can remove from polar organic solvent Water.(A) distilling apparatus (method of evaporating) used in operation, can be implemented in the same manner as (A) operation.Additionally, distillation condition, as long as Energy separating polar organic solvent and water are just not particularly limited.But, with regard to vapo(u)rizing temperature, organic molten based on can be easily separated polarity 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 machine solvent, preferably low temperature.

The recovery method of the catalyst of the present invention, can so pass through easy method high efficiente callback and recycle high-purity Catalyst meanwhile, high efficiente callback be used for catalyst reclaim polar organic solvent, by highly purified polar organic solvent Recycled.And, recycled by the catalyst reclaiming the recovery method of the catalyst by the present invention, can be stablized Ground manufactures highly purified diphenyl carbonate.

[manufacture method of Merlon]

One of purposes of carbonic diester manufacturing in the present invention, i.e. Merlon, can be by making the carbon being manufactured by above-mentioned method Acid diesters, particularly diaryl carbonate, and the aromatic series with bisphenol-A as representative or aliphatic dihydroxy compounds, in alkali gold Carry out ester exchange reaction in the presence of belonging to compound and/or alkali earth metallic compound and manufacture.

Above-mentioned ester exchange reaction can suitably select known method to carry out.Herein, carry out the two of ester exchange with carbonic diester Hydroxy compounds, can be aromatic dihydroxy compound or aliphatic dihydroxy compounds, but optimization aromatic two Hydroxy compounds.Hereinafter, with diphenyl carbonate and bisphenol-A as raw material is described.

In the manufacture method of above-mentioned Merlon, preferably diphenyl carbonate is using the amount superfluous with respect to bisphenol-A.Relatively The amount of the diphenyl carbonate using in bisphenol-A, the heat stability of polymer less based on terminal hydroxyl on the Merlon manufacturing Excellent aspect, preferably more, additionally, the Merlon side of easy to manufacture desired molecular weight fast based on ester exchange reaction speed Face, preferably less.And specifically, it is preferable to using for example with respect to 1 mole of bisphenol-A, usually more than 1.001 moles, preferably 1.02 More than mole, usually less than 1.3 moles, preferably less than 1.2 moles.

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

When Merlon is manufactured with the ester exchange reaction of diphenyl carbonate and bisphenol-A, catalyst is usually used.Above-mentioned is poly- This point of minute of carbonic ester, as this ester exchange catalyst, preferably uses alkali metal compound and/or alkaline-earth metal chemical combination Thing.They can be using a kind it is also possible in any combination and ratio uses by two or more.In practicality, preferred as alkali Compound.

With respect to 1 moles of bisphenol A or diphenyl carbonate, generally more than 0.05 micromole, preferably 0.08 micro- rubs catalyst More than you, more than more preferably 0.10 micromole, additionally, on the other hand, usually below 5 micromoles, below preferably 4 micromoles, Scope below more preferably 2 micromoles uses.

By the usage amount of catalyst within the above range, it is readily available and manufacture needed for the Merlon of desired molecular weight The polymerization activity wanted, and, polymer form and aspect are excellent, and the branch of excessive polymer will not be carried out, it is readily obtained molding When the excellent Merlon of mobility.

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

Merlon is manufactured by said method, preferably two kinds of above-mentioned raw materials continuously to be supplied to raw material mixing channel Give, the mixture obtaining and ester exchange catalyst are continuously supplied to polymerization tank.

In the manufacture of the Merlon being carried out by ester-interchange method, generally, exist to two kinds of raw materials of raw material mixing channel supply After homogeneous stirring, it is supplied to the polymerization tank adding catalyst, produce polymer.

[Merlon]

As noted previously, as it is very high, by making by this by the carbonic diester purity obtained by the manufacture method of the present invention Carbonic diester obtained by bright manufacture method and aliphatic dihydroxy compounds or aromatic dihydroxy compound are in ester exchange Polycondensation in the presence of catalyst, can get highly purified Merlon.

Especially, by the manufacture method of the carbonic diester of the present invention, can get the less highly purified carbon of by-product phenol Acid diesters, thus the Merlon of high-quality can be obtained with it.Additionally, in the manufacture method of the carbonic diester of the present invention, when Using the catalyst dissolving in carbonic diester, when de-carbonyl reaction is carried out with conversion ratio more than 96%, furan system chemical combination can be suppressed The by-product of thing, thus can obtain colouring the Merlon of less high-quality.

In the manufacture method of the carbonic diester of the present invention, even if with regard to making absolute pressure during de-carbonyl reaction be More than 0.105MPa, below 10MPa and when reacting, also can get less highly purified of by-product of aromatic monohydroxy compound Diphenyl carbonate, thus can use it to obtain the polycarbonate resin of high-quality.Even if additionally, with regard to make generation carbonic diester and During alkali compoundss contact, also can get the less highly purified diphenyl carbonate of furan based compound, thus can use it to obtain The Merlon of high-quality.

[adducts of asymmetric four aryl halogenation phosphines and hydrogen halides]

Described in as flat in Japanese Laid-Open No. 9-328492, four aryl halogenation phosphines can be by making triaryl phosphine and aryl halide in metal React in the presence of halogen compounds catalyst and water soluble high boiling point solvent and obtain.

And, described in Japanese Laid-Open 2013-82695, by containing aryl halide, metal halogen compound catalysis The liquid of agent and water soluble high boiling point solvent separately or continuously adds triaryl phosphine, thus can high yield, in high selectivity Manufacture asymmetric four aryl halogenation phosphines.Additionally, described in Japanese Laid-Open 2013-82695, by so obtained asymmetric four Aryl bromide phosphine is transformed to chloride.

The present inventor is with regard to the de-carbonyl reaction using so obtained asymmetric four aryl halogenation phosphines as catalyst Study in detail.As a result, distinguished using the above-mentioned asymmetric tetraphenyl halogenation phosphine obtaining as with hydrogen halides When adduct (asymmetric adduct according to the present invention) carries out de-carbonyl reaction for catalyst, by-product phenol can be reduced Amount.

As described later, its reason be considered due to adduct hygroscopicity relatively low, thus the by-product of the phenol being led to by hydrolysis It is difficult to occur.That is, because asymmetric four aryl halogenation phosphines are the relatively low structures of symmetry, therefore crystallinity is relatively low, easily becomes Micropowder disperses.If additionally it is believed that asymmetric four aryl halogenation phosphines higher for hygroscopicity are used as catalyst, due to urge Agent together supplies to the moisture of reaction system, and carbonic diester and oxalate diester hydrolyze, and can generate phenol.On the other hand, recognize It is because adduct particle diameter ratio according to the present invention is larger, so hygroscopicity is relatively low it is difficult to generation is by carbonic diester and oxalic acid two The by-product of the phenol that ester hydrolysis lead to.

Asymmetric adduct according to the present invention, because particle diameter is larger, hygroscopicity relatively low it is difficult to disperse, it is easy easily to become The solid of operation.Therefore, when the catalyst as de-carbonyl reaction uses, can by catalyst at short notice, before moisture absorption Load reactor, the by-product of phenol tails off, and can be readily derived highly purified carbon by oxalate diester with high conversion, high selectivity Diphenyl phthalate.

The particle diameter of asymmetric adduct according to the present invention, specifically preferably more than 50 μm, more preferably more than 60 μm, more excellent Select more than 80 μm, particularly preferred more than 100 μm.Additionally, the upper limit of the particle diameter of asymmetric adduct according to the present invention is usually 1mm.

Additionally, the particle diameter of asymmetric adduct according to the present invention, can make as with methyl iso-butyl ketone (MIBK) as disperse medium Measured with Nikkiso Company Limited マイ Network ロトラッ Network (Microtrac) particle size distribution device " MT3300EXII " Meso-position radius (D50) and obtain.

Additionally, the hygroscopicity of asymmetric adduct according to the present invention, can be by comparing in 15～20 DEG C of temperature, humidity 40 Evaluate from the moisture content moisture absorption specifying to the time required for the moisture content of regulation under～45% air.

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

The dissolubility of asymmetric adduct according to the present invention, is usually soluble in carbonic diester.Due to according to the present invention Asymmetric adduct dissolves in carbonic diester, therefore in the manufacture method of the carbonic diester of the present invention, can not cause catalyst Precipitation, stably de-carbonyl reaction is carried out with high conversion, reduces the amount of the oxalate diester of remaining, can suppress to make carbonic diester The generation of the furan based compound of by-product during evaporation.

Further, since asymmetric adduct according to the present invention dissolves in carbonic diester, therefore make high turn of phenostal After reacting for carbonic diester to rate, even if making carbonic diester concentrate in high concentration, in residual liquid, also will not separate out catalyst, thus Easily recycle contained catalyst in residual liquid.

Further, because asymmetric adduct according to the present invention dissolves in carbonic diester, therefore can by catalyst with Be dissolved in the state supply of carbonic diester, by reacted unreacted oxalate diester less, carbonic diester contained with high concentration The recycling it is difficult to occur to reset the phenol that leads to of product etc. by the Fu Laisi (Fries) of oxalate diester of catalyst liquid By-product, can get highly purified carbonic diester.

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

Additionally, by the liquid chromatogram measuring the material being confirmed to be this 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, utilizing Liquid chromatography, can more easily confirm.

With regard to the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, first, implemented as above, confirm to contain There is 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, then, by measuring the cl concn contained by adduct, can calculate is to add with hydrogen chloride Compound and its adduction rate.

The composition analysis being carried out using liquid chromatography, can be carried out according to following order and condition.

Device：Shimadzu Seisakusho Ltd. LC-2010, Imtakt Cadenza 3mm CD-C18 250mm × 4.6mmID.Low pressure ladder Degree method.30 DEG C of analysis temperature.Chromatographic column uses Shimadzu Seisakusho Ltd.'s system " ODS3VID ".Eluent forms：A liquid acetonitrile:Water=7.2: 1.0 weight %/weight %, B liquid 0.5 weight % biphosphate sodium water solution.0 minute～12 minutes analysis time.A liquid:B liquid= 65:35 (volume ratios, following identical).In 12～35 minutes analysis times, make eluent composition slowly varying for A liquid:B liquid= 92:8, in 35～40 minutes analysis times, maintain A liquid:B liquid=92:8, flow velocity 1 ml/min.

Additionally, with regard to milli-Q water and be extracted in the toluene that cl concn is less than 1 weight ppb, make mensure as Liquid be dissolved as uniform solution after, add ultra-pure water, the aqueous phase obtained by being sufficiently stirred for, by the chromatography of ions with following Order and condition measure cl concn.

Device：DIONEX company system ION CROMATOGRAPH, IonPac AS12A.Eluent uses and adds in ultra-pure water Plus sodium bicarbonate is to 0.3 mM of dm^-3, make sodium carbonate be 2.7 mMs of dm^-3Liquid.

[manufacture method of adduct according to the present invention]

Adduct according to the present invention, can be by the asymmetric four aryl halogenation phosphines that will be manufactured with known method as described above With hydrogen halides together crystallize and obtain.Specifically, polarity can be dissolved in and have by making asymmetric four aryl halogenation phosphines and hydrogen halides Crystallize after machine solvent, taking-up and obtain.(below, sometimes the method obtaining this adduct is referred to as " adduct according to the present invention Manufacture method ").And, adduct according to the present invention, preferably use the manufacture method by adduct according to the present invention Obtained adduct.

In the manufacture method of adduct according to the present invention, by using organic solvent, asymmetric four aryl halogenations can be made Phosphine dissolves, additionally, by using polar solvent, hydrogen halides can be made to dissolve.

Further, in the manufacture method of adduct according to the present invention, can be utilized asymmetric four aryl halogenation phosphines with non- Poor solubility between the hydrogen halides adduct of symmetrical four aryl halogenation phosphines, makes adduct crystallize obtain.Then, so in fact Apply, because particle diameter is larger, hygroscopicity is relatively low, thus can obtain being difficult to dispersing, maneuverable solid.

Used in the manufacture method of adduct according to the present invention, this polarity (below, is had by polar organic solvent sometimes Machine solvent is referred to as " polar organic solvent that the manufacture method of the adduct of the present invention is related to " or " manufacture for adduct Polar organic solvent ") the asymmetric four aryl halogenation phosphines of preferred pair and hydrogen halides have while sufficient dissolubility to adduction Thing shows insoluble organic solvent.

Herein, hydrogen halides used in the manufacture method of adduct according to the present invention, usually as the water of hydrogen halides Solution uses.That is, will have sufficient dissolubility to aqueous solution of hydrogen halide and referred to as there is polarity.

There is sufficient dissolubility to hydrogen halides refer to, generally at 25 DEG C, in organic solvent 100g, hydrogen halides dissolve More than 1g.Used in the manufacture method of adduct according to the present invention polar organic solvent preferably with aqueous solution of hydrogen halide in height The lower organic solvent in uniform state of temperature.High temperature refers to, usually more than 50 DEG C, preferably more than 60 DEG C, more preferably more than 70 DEG C.

Crystallize can carry out it is also possible to be carried out by contacting with poor solvent by cooling down adduct, but by cooling The method separating out is easy, is preferred.

As the preference of the polar organic solvent of the manufacture for adduct, alcohols, ketone, ethers, halo can be enumerated Hydro carbons, esters etc..

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

As ketone, can illustrate as dimethyl ketone, metacetone, methyl ethyl ketone, methyl n-pro-pyl ketone, isopropyl methyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl isoamyl ketone, ethyl n-pro-pyl ketone, ethylisopropyl The low alkyl group ketone of carbon number 1～10 of base ketone, ethyl normal-butyl ketone, ethyl isobutylo ketone etc. and Ketohexamethylene, ring penta Ring-type ketone of carbon number 3～10 of ketone etc. etc..

As esters, can illustrate as the lower aliphatic carboxylic acid of alkyl formate, alkyl acetates, alkyl propionate etc. 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 Acetate of the fatty acid ester of ester and ethylene glycol etc. etc..

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

Additionally, in the manufacture method of adduct according to the present invention, becoming the adduct with asymmetric four aryl halogenation phosphines Hydrogen halides, usually as hydrogen halides aqueous solution use.That is, adduct according to the present invention, by making the water with hydrogen halides Solution contact the asymmetric four aryl halogenation phosphine crystallizes of liquid condition, taking-up and obtain.

Specifically, for example can use hydrochloric acid (hydrochloride aqueous solution) when obtaining the adduct with hydrogen chloride, obtain Hydrobromic acid (aqueous solution of hydrogen bromide) can be used during with the adduct of hydrogen bromide, can make when obtaining the adduct with hydrogen iodide Obtained with hydroiodic acid (aqueous solution of hydrogen iodide).As the aqueous solution of hydrogen halides, wherein, particularly preferred hydrochloric acid.

Next, the order of the manufacture method with regard to implementing adduct according to the present invention, lift a preferred explanation.

First, asymmetric four aryl halogenation phosphines are made to contact with polar organic solvent and halogen acids.

Herein, based on asymmetric four aryl halogenation phosphine easily dissolving aspects when heating up, the amount of polar organic solvent is preferably relatively Many, but based on adduct easily sucking-off aspect during cooling, preferably less.

Therefore, the amount of polar organic solvent, with respect to asymmetric four aryl halogenation phosphines, with weight ratio meter, preferably uses More than 0.15 times, more preferably using more than 0.2 times, additionally, on the other hand, preferably use less than 2 times, more preferably using 1 times with Under.

Additionally, the production rate easily raising aspect based on adduct, the amount of the hydrogen halides contained by halogen acids is preferably more, but Based on the water contained by halogen acids less, cooling when asymmetric four aryl halogenation phosphine easily precipitation aspects, preferably less.

Therefore, the amount of the hydrogen halides contained by halogen acids, with respect to asymmetric four aryl halogenation phosphines, with weight ratio meter, preferably Using more than 0.5 times, additionally, on the other hand, preferably using less than 2.0 times, more preferably using less than 1.5 times.

With respect to the relative quantity of the water of polar organic solvent, due to when heating up asymmetric four aryl halogenation phosphines easily dissolve, During cooling, adduct easily separates out, thus preferably more than 2 times, additionally, on the other hand, preferably less than 20 times, more preferably 15 times with Under.

Next, by this liquid heats up, making asymmetric four halogenation phosphine dissolvings.During till dissolving, preferably stir liquid Body.Liquid temperature after intensification, forms according to liquid, and preferred temperature is different, but is based on and easily so that asymmetric four halogenation phosphines is existed Dissolving aspect in short time, preferably high temperature, but be based on and be difficult to boiling aspect, preferably low temperature.Especially, different using methyl During the polar organic solvent of the easy like that azeotrope with water of butyl ketone, it is preferably set to relatively low.It is therefore preferable that more than 50 DEG C, more excellent Select more than 60 DEG C, additionally, on the other hand, preferably less than 95 DEG C, more preferably less than 90 DEG C.

Then, asymmetric four aryl halides can thus be made by cooling down the solution being dissolved with asymmetric four aryl halogenation phosphines Change phosphine and the adduct of hydrogen halides separates out.

Based on being difficult to the solidification aspect of solution itself, make the preferred high temperature of temperature during adduct precipitation, but be based on and add The yield aspects of compound, preferably low temperature.Therefore it is usually preferred to more than 5 DEG C, more preferably more than 10 DEG C, particularly preferred more than 20 DEG C, Additionally, on the other hand, preferably less than 70 DEG C, more preferably less than 60 DEG C.

The cooling rate separating out to adduct from the state heating up, based on skinny device precipitation aspect at short notice, excellent Choosing is very fast, but based on hygroscopicity is relatively low, be difficult to the easy-operating big crystallization aspect of easy precipitation of dispersing, preferably slower.Therefore, lower the temperature 0.1～2 DEG C preferably per minute of speed.

Adduct with regard to organic chloride phosphine and hydrogen chloride is it is also possible to pass through flat No. 9-328491 record of Japanese Laid-Open Method obtains.But, the document is with regard to being manufactured the document that the method for organic chloride phosphine is recorded, this article by organic bromide phosphine In offering, organic dichloride hydrogen phosphine is only to record merely as obtaining single intermediate of organic chloride phosphine, wherein, should Organic chloride phosphine as various reactions catalyst (alternate moving catalyst, polymerization catalyst, halogenide halogen exchange reaction urge Agent etc.) useful.

Additionally, the method described in the document, by the hydrochloric acid cooling after organic bromide phosphine dissolving will be made, make organic dichloro Change after hydrogen phosphine separates out, heating, remove hydrogen halides, accordingly synthesis tetraphenyl dichloride hydrogen phosphine (symmetrical four aryl phosphines and hydrogen chloride Adduct.Embodiment 1), or the mixture of benzyltriphenyl phosphonium dichloride hydrogen phosphine and benzyl triphenyl phosphonium chloride phosphine is (containing asymmetric The compound of the adduct of organic phosphine and hydrogen chloride.Embodiment 9) etc..

Herein, asymmetric four aryl halogenation phosphines according to the present invention, preferably 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride etc. are like that The relatively low material of hydrophilic, due to insoluble in hydrochloric acid, thus cannot obtain adduct in this way.Additionally, comparison as be described hereinafter Shown in example 1, the method recorded by the document is it is impossible to obtain adduct according to the present invention.

Embodiment

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

[raw material and reagent]

Phenostal is using the material after purifying the 1 grade of reagent simple distillation of Tokyo chemical conversion industry company system.This distillation The purity of obtained phenostal is more than 99 weight %, water 50 weight ppm, phenol 200 weight ppm, oxalic acid methylbenzene Base ester 10 weight ppm, phenol (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) is for Monitoring lower-cut (1 weight ppm) below.

4- 2-methyl-2-phenylpropane base triphenylphosphinebromide passes through the method synthesis that Japanese Laid-Open 2013-82695 publication is recorded.

4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride passes through the method synthesis that Japanese Laid-Open flat 11-217393 publication is recorded. This 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, oxolane, pyridine, toluene, fragrant to hydroxybenzoate Acid phenenyl ester, sodium bicarbonate, anhydrous magnesium sulfate, sodium chloride, sodium hydroxide, sodium nitrite, sulphuric acid, activated carbon, ethyl acetate, heptane And phosphorus pentoxide uses the product of Wako Pure Chemical Industries, Ltd..

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

Tetraphenylphosphonium chloride uses the product of Tokyo chemical conversion industry company.Diphenyl carbonate and phenol use Mitsubishi Chemical The product of Co., Ltd..Additionally, 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 use the product of Sumitomo Seika Co., Ltd.

4- aminomethyl phenyl triphenyl phosphine dichloride passes through the method synthesis that Japanese Laid-Open flat 8-333307 publication is recorded.

[analysis]

Composition analysis are by high performance liquid chromatography, are carried out with following order and condition.

Device：Shimadzu Seisakusho Ltd. LC-2010A, Imtakt Cadenza 3mm CD-C18 250mm × 4.6mmID.Low pressure ladder Degree method.30 DEG C of analysis temperature.Chromatographic column uses Shimadzu Seisakusho Ltd.'s system " ODS3VID ".Eluent forms：A liquid acetonitrile:Water=7.2: 1.0 weight %/weight %, B liquid 0.5 weight % biphosphate sodium water solution.0 minute～12 minutes analysis time.A liquid:B liquid= 65:35 (volume ratios, following identical).In 12～35 minutes analysis times, make eluent composition slowly varying for A liquid:B liquid= 92:8, in 35～40 minutes analysis times, maintain A liquid:B liquid=92:8, flow velocity 1 ml/min, analyze accordingly.

Benzofuran -2, the quantitation of 3- diketone is by high performance liquid chromatography, is carried out with following order and condition.

Device：18,3 μm of C, 250mm × 4.6mmID between Shimadzu Seisakusho Ltd. LC-2010A, Scherzo S.Low pressure gradient method. 40 DEG C of analysis temperature.Eluent forms：A liquid acetic acid:Acetonitrile:Water=0.1 volume %:10 volumes %:90 volumes %, B liquid 0.2 weight Amount % ammonium acetate aqueous solution:Acetonitrile=90 volume %:10 volumes %.In 0～20 minute analysis time, with A liquid:B liquid=60:40 Fixing (volume ratio, identical below).In 20～25 minutes analysis times, make eluent composition slowly varying for A liquid:B liquid=85: 5, in 25～35 minutes analysis times, maintain A liquid:B liquid=60:40, flow velocity 0.85 ml/min, analyze accordingly.

The quantitation of methyl iso-butyl ketone (MIBK) is by gas chromatography, is carried out with following order and condition.Device uses island Tianjin manufacturing company system " GC-2014 ".Chromatographic column uses Agilent Technologies' system " DB-17 " (internal diameter 0.53mm, column length Degree 60m, 1 μm of thickness).Carrier gas is helium, and its flow is set to 7.34cm per minute³, linear velocity is set to 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 keeping 3 minutes at 75 DEG C, with 10 DEG C per minute are warming up to 220 DEG C, keep 10 minutes, then, be warming up to 250 DEG C with 40 DEG C per minute at 220 DEG C, keep 10 Minute, it is analyzed.

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

The mensure of moisture content, by the state to be placed on disk for the four aryl halogenation phosphines, using moisture meter (capital of a country electronics work Industry society system " MKS-500 ") measure.The test that difficulty is dried is by loading sample in 100 milliliters of eggplant type flask, by it It is arranged in the rotary evaporator possessing oil bath, by heating oil bath heating to 100 DEG C, under pressure 10Torr, compare Carry out from the moisture content drying specifying to the time required for the moisture content of regulation.Additionally, hygroscopic test is to pass through Under 15～20 DEG C of temperature, the air of humidity 40～45%, compare from the moisture content moisture absorption specifying to needed for the moisture content of regulation Time of wanting and carry out.

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

The quantitation of bromide ion is to be measured using DIONEX company system ion chromatography device " ION CHROMATOGRAPH " 's.Chromatographic column uses DIONEX company system separation chromatography post " IonPac AS12A ".Prepare eluent in ultra-pure water, so that carbon Sour sodium is 2.7 mMs of dm^-3And sodium bicarbonate is 0.3 mM of dm^-3.

With regard to milli-Q water and be extracted in the toluene that cl concn is less than 1 weight ppb, making the liquid of mensure elephant After being dissolved as uniform solution, add ultra-pure water, be sufficiently stirred for obtained by aqueous phase, by the chromatography of ions use following order with Condition carries out the mensure of cl concn.

Device：DIONEX company system ION CROMATOGRAPH, IonPac AS12A.Eluent is using the interpolation carbon in ultra-pure water Sour sodium is to becoming 2.7 mMs of dm^-3, and add sodium bicarbonate to becoming 0.3 mM of dm^-3Liquid.

[synthesis example 1]

To in the detachable flask of 500 milliliters of a complete set of tubular type possessing thermometer and blender, load tetraphenylphosphonium chloride 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, this serosity is filtered by glass filter, by the solid obtaining Move to eggplant type flask.By being placed on eggplant type flask in the rotary evaporator possessing oil bath, by oil bath heating to 100 DEG C, in pressure It is dried 2 hours under power 10Torr, obtain 42g solid.By the cl concn of this solid potential difference of capital of a country Electronics Industry Company The result that titration appratuss " AT-610 " are analyzed is 17 weight %.

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

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

[embodiment 1]

To in the detachable flask of 500 milliliters of a complete set of tubular type possessing thermometer and blender, load 4- 2-methyl-2-phenylpropane base triphen Base phosphonium chloride 70g (0.162 mole), methyl iso-butyl ketone (MIBK) 18g and 28 weight % hydrochloric acid 263g, are heated under nitrogen atmosphere 90 DEG C, make in uniform solution.Then, obtain serosity by detachable flask is cooled to room temperature.

This serosity is filtered by glass filter, the solid obtaining is moved to eggplant type flask.By by this eggplant type flask It is arranged in the rotary evaporator possessing oil bath, by oil bath heating to 100 DEG C, be dried 2 hours under pressure 10Torr, obtain 75g solid.The knot that the potential difference titration appratuss " AT-610 " of the cl concn capital of a country Electronics Industry Company of this solid are analyzed Fruit is 14.6 weight %.

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

In possessing the there-necked flask of thermometer and stirrer, load phenostal 300g (1.238 moles), by making This there-necked flask is immersed in 230 DEG C of oil bath and heats, and so that phenostal is dissolved.By uncle 4- obtained as described above Adduct (the adduction rate 91%) 20g (0.043 mole) of butylbenzene base triphenyl phosphine dichloride and hydrogen chloride, is 4mm with bottom bore Funnel supply to this there-necked flask.After the supply of adduct terminates 30 minutes, take out one of the liquid in there-necked flask Part, carries out composition analysis by high performance liquid chromatography.

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

With regard to its adduct obtained by tetraphenylphosphonium chloride, synthesis example 1,4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and reality Apply its adduct obtained by example 1, by its character, volume density, particle diameter, difficulty is dried (moisture content is reduced from 2 weight % Drying time to required for 0.5 weight %) and hygroscopicity (moisture content brings up to required for 0.5 weight % from 0.2 weight % Time) collect in Table 1.

As table 1 is expressed, specify that by 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is made 4- 2-methyl-2-phenylpropane base triphenyl chlorine Change the adduct of phosphine and hydrogen chloride, can become easily to operate, easily be dried, so that hygroscopicity is reduced.

[table 1]

The character of each catalyst, volume density, particle diameter, difficulty is dried (moisture content is reduced to 0.5 weight % from 2 weight % Required drying time) and hygroscopicity (moisture content brings up to the time required for 0.5 weight % from 0.2 weight %)

※ for DPC dissolubility ... at 150 DEG C, be dissolved in the amount in diphenyl carbonate 100g.

※ TPPC ... tetraphenylphosphonichloride chloride phosphorus.

※ TPPC HCl ... tetraphenylphosphonichloride chloride phosphorus and the adduct of hydrogen chloride.

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

※ tBu-TPPC HCl ... 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and the adduct of hydrogen chloride.

[comparative example 1]

To in the detachable flask of 500 milliliters of a complete set of tubular type possessing thermometer and blender, load 4- 2-methyl-2-phenylpropane base triphen Base phosphonium chloride 50g (0.116 mole), 28 weight % hydrochloric acid 200g, are heated to 90 DEG C in a nitrogen atmosphere, but are not in homogeneous shape State, and it is in slurry condition.Then, detachable flask is cooled to room temperature, this serosity is filtered by glass filter, will To solid move to eggplant type flask.

By being placed on eggplant type flask in the rotary evaporator possessing oil bath, by oil bath heating to 100 DEG C, in pressure It is dried 2 hours under 10Torr, obtain 45g micropowder.The potential difference of the cl concn capital of a country Electronics Industry Company of this micropowder is dripped Determining the result that device " AT-610 " analyzes is 8.0 weight %.

Lower than theoretical value 8.2 weight % of the cl concn of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, thus confirm obtain micro- Powder becomes the adduct with hydrogen chloride.Additionally, this micropowder is white particle, its volume density is 0.23g cm³, particle diameter is 31μm.

Next, use micropowder as catalyst, implement the de-carbonyl reaction of phenostal.Specifically, except In the de-carbonyl reaction of embodiment 1, as catalyst, this micropowder is used in addition as catalyst, real similarly to Example 1 Apply, carry out de-carbonyl reaction.After the supply of adduct terminates 30 minutes, by the part taking-up of the liquid in there-necked flask, Composition analysis are carried out by high performance liquid chromatography.

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

[embodiment 2]

To in the detachable flask of 500 milliliters of a complete set of tubular type possessing thermometer and blender, load 4- 2-methyl-2-phenylpropane base triphen Base bromide phosphine 50g (0.105 mole), methyl iso-butyl ketone (MIBK) 13g and 28 weight % hydrochloric acid 188g, in addition, with embodiment 1 Similarly implement, obtain serosity.This serosity is filtered by glass filter, obtains solid.

Detachable by together moving to the solid obtaining and methyl iso-butyl ketone (MIBK) 13g and 28 weight % hydrochloric acid 188g Flask, is heated to 90 DEG C under nitrogen atmosphere, after uniform solution, detachable flask is cooled to room temperature, becomes serosity, leads to Cross and this serosity glass filter is filtered, obtain solid.

This solid is together heated with methyl iso-butyl ketone (MIBK) and hydrochloric acid, after uniform solution, by the serosity obtained by cooling The operation filtered and obtain solid repeats 3 times and (4- 2-methyl-2-phenylpropane base triphenylphosphinebromide is transformed to 4- 2-methyl-2-phenylpropane base triphenyl Phosphonium chloride).

By the solid obtaining is moved to eggplant type flask, eggplant type flask is arranged in the rotary evaporator possessing oil bath, By oil bath heating to 120 DEG C, it is dried 2 hours under pressure 10Torr, obtains 35g solid.

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

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

By contained bromide ion in this solid, with DIONEX company system ion chromatography device " ION The result that CHROMATOGRAPH " measures, is 0.5 mole of below %.

[embodiment 3]

In embodiment 1, replace methyl iso-butyl ketone (MIBK) 18g, use 35 weight % hydrochloric acid 263g to replace 28 weights using n-butyl alcohol 18g Amount % hydrochloric acid 263g, in addition, implements similarly to Example 1, obtains serosity.This serosity is passed through glass filter mistake Filter, the solid obtaining is moved to eggplant type flask.By being arranged on this eggplant type flask in the rotary evaporator possessing oil bath, by oil Bath is heated to 130 DEG C, is dried 2 hours, obtains 72g solid under pressure 10Torr.

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

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

[embodiment 4]

By obtained (0.011 mole) loading eggplant type flask of adduct 5g in embodiment 3, it is placed on the rotary evaporation possessing oil bath On device, by oil bath heating to 180 DEG C, it is dried 2 hours under pressure 10Torr.

Used that the potential difference titration appratuss " AT-610 " of capital of a country Electronics Industry Company are analyzed as a result, adduct Adduction rate is reduced to 2%.With regard to embodiment 1～3 and above-mentioned adduct, (moisture content is from 0.2 will to measure adduction rate and hygroscopicity Weight % rises to the time required for 0.5 weight %) result be summarized in table 2.

As 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 adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride and the relation 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 possess thermometer, blender, distillate pipe and accepter 500 milliliters of a complete set of tubular type detachable flask In, load embodiment 1 obtained by 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride adduct (adduction rate 91%) 11g (0.024 mole) and diphenyl carbonate 96g (0.0448 mole), will be heated to 150 DEG C, makes adduct in detachable flask Dissolving.

By 185 DEG C will be heated in detachable flask, if pressure is 2kPa, it is dried 3 hours, thus makes water and carbonic acid Diphenyl ester is total to distillate 20g, makes to be dried in detachable flask.Add phenostal 160g in this detachable flask (0.661 mole), by being heated to 150 DEG C, makes phenostal dissolve.

Further, it is blown into 0.012 mole of hydrogen chloride gas in this detachable flask, be warming up to 225 DEG C.Additionally, When reaching 225 DEG C, the part taking-up of the liquid in detachable flask carries out composition analysis by high performance liquid chromatography When, it is phenol 0.2 weight %, phenostal 55.1 weight %, diphenyl carbonate 40.0 weight %.

After reaching 225 DEG C in detachable flask, the carbon monoxide producing in reaction is removed with nitrogen at ambient pressure Go to outside reaction system, react 80 minutes in the state of keeping 225 DEG C.A part by the liquid after reacting 80 minutes Take out, when composition analysis are carried out by high performance liquid chromatography, be phenol 0.2 weight %, phenostal 8.5 weight %, carbon Diphenyl phthalate 84.4 weight %.Herein, the conversion ratio of phenostal is 88%.

[comparative example 2]

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

Reach being tied by the composition analysis that high performance liquid chromatography is drawn of the liquid in detachable flask when 225 DEG C It is really, phenol 0.4 weight %, phenostal 54.8 weight %, diphenyl carbonate 40.1 weight %.

Additionally, by the composition analysis being drawn by high performance liquid chromatography of the liquid after reaction 80 minutes as a result, benzene Phenol 0.4 weight %, phenostal 22.2 weight %, diphenyl carbonate 72.4 weight %.Herein, the conversion ratio of phenostal For 68%.

The result of embodiment 5 and comparative example 2 is summarized in table 3.Confirmed by table 3, due to 4- 2-methyl-2-phenylpropane base triphenyl Phosphonium chloride hygroscopicity is higher, and the by-product quantitative change of the phenol therefore being led to by phenostal and dipheryl carbonate ester hydrolysis is many, its As a result, the conversion ratio of phenostal is relatively low, and reactivity reduces.

[table 3]

The liquid composition of embodiment 5 and comparative example 2

[embodiment 6]

Possess thermometer, blender, distillate pipe and accepter 500 milliliters of a complete set of tubular type detachable flask in, fill After entering phenostal 300g (1.238 moles), by being heated to 150 DEG C, it is allowed to dissolve.In this detachable flask, add Plus adduct (the adduction rate 91%) 15g (0.032 of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride that obtains in embodiment 1 and hydrogen chloride Mole) dissolving after, be warming up to 230 DEG C.

Additionally, reaching by the part taking-up of the liquid in detachable flask when 230 DEG C, by high performance liquid chromatography When carrying out composition analysis, it is phenol 0.2 weight %, phenostal 75.5 weight %, diphenyl carbonate 18.0 weight %.

After reaching 230 DEG C in detachable flask, the carbon monoxide producing in reaction is removed with nitrogen at ambient pressure Go to outside reaction system, react 6 hours in the state of keeping 230 DEG C.A part for liquid after reacting 6 hours is taken Go out, when composition analysis are carried out by high performance liquid chromatography, be diphenyl carbonate 92.7 weight %, phenol 0.2 weight %, oxalic acid Diphenyl ester 484.6 weight ppm, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 5.0 weight %.Herein, the conversion ratio of phenostal is 99.9%.

Additionally, reacted reactant liquor (before taking out the sample of composition analysis) is 279g, 4- 2-methyl-2-phenylpropane base triphenyl chlorine The molecular weight changing phosphine is 431.Therefore, calculating contained 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride in reacted reactant liquor is 279g × 0.05 431=0.032 mole of ÷.

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, slowly reduce pressure to 10Torr, so that thick diphenyl carbonate 230g is distillated.Additionally, making thick diphenyl carbonate Residual liquid 47g in detachable flask after distillating, visually dissolves at 200 DEG C.

Therefore, enrichment factor (evaporation rate) is 230g/ (230g+47g)=83%.Additionally, passing through high performance liquid chromatography, survey Benzofuran -2 in fixed thick diphenyl carbonate, during the concentration of 3- diketone, are 11 weight ppm.

[embodiment 7]

In the state that the residual liquid in the detachable flask obtaining in embodiment 6 is maintained 150 DEG C, take out wherein 40g.This Place, the molecular weight of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is the adduct of 431,4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride Molecular weight be 467, thus in this residual liquid 40g, the 4- 2-methyl-2-phenylpropane base triphenyl that contained with the state being dissolved in diphenyl carbonate Phosphonium chloride is 15g × (431 ÷ 467) × (40 ÷ 47)=11.8g.

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

Additionally, when reaching 230 DEG C, by the part taking-up of the liquid in detachable flask, by high performance liquid chromatography When method carries out composition analysis, it is phenostal 59.6 weight %, diphenyl carbonate 33.67 weight %, phenol 0.2 weight %.

After reaching 230 DEG C in detachable flask, the carbon monoxide producing in reaction is removed with nitrogen at ambient pressure Go to outside reaction system, react 6 hours in the state of keeping 230 DEG C.A part for liquid after reacting 6 hours is taken Go out, when composition analysis are carried out by high performance liquid chromatography, be diphenyl carbonate 92.7 weight %, phenol 0.3 weight %, oxalic acid Diphenyl ester 548.1 weight ppm.Herein, the conversion ratio of phenostal is 99.9%.

Then, slowly reduce pressure to 10Torr, so that thick diphenyl carbonate 200g is distillated.After so that thick diphenyl carbonate is distillated Detachable flask in residual liquid 36g, visually dissolve at 200 DEG C.

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

[comparative example 3]

In embodiment 6, the charge weight of phenostal is reduced to 95g (0.392 mole) by 300g, obtains using in synthesis example 1 The tetraphenylphosphonium chloride arriving and the adduct 5g replacement 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of hydrogen chloride and the adduct of hydrogen chloride 15g, the response time at 230 DEG C shortened to from 6 hours 1.3 hours, in addition, manufactured carbonic acid similarly to Example 6 Diphenyl ester.

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

Additionally, making thick diphenyl carbonate distillate 38g.The residual liquid in detachable flask after slightly diphenyl carbonate distillates 45g, is in visually slurry at 200 DEG C.Therefore, enrichment factor (evaporation rate) is 38g/ (38g+45g) × 100=46%.Additionally, By benzofuran -2 in the thick diphenyl carbonate of high effective liquid chromatography for measuring, during the concentration of 3- diketone, it is 150 weight ppm.

[comparative example 4]

In embodiment 6, the charge weight of phenostal is reduced to 95g (0.392 mole) by 300g, using tetraphenylphosphonium chloride 5g Replace the adduct 15g of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, make tetraphenylphosphonium chloride add hydrogen chloride after dissolving 300cm³, the response time at 230 DEG C was shortened to 1.3 hours from 6 hours, in addition, manufactures similarly to Example 6 Diphenyl carbonate.

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

Additionally, making thick diphenyl carbonate distillate 66g.The residual liquid in detachable flask after slightly diphenyl carbonate distillates 22g is in visually slurry at 200 DEG C.Therefore, enrichment factor (evaporation rate) is 66g/ (66g+22g) × 100=75%.Additionally, By benzofuran -2 in the thick diphenyl carbonate of high effective liquid chromatography for measuring, during the concentration of 3- diketone, it is 120 weight ppm.

The result of embodiment 6, comparative example 3 and comparative example 4 is summarized in table 4.Confirmed by table 4,4- 2-methyl-2-phenylpropane base triphen Base phosphonium chloride, compared with the adduct of tetraphenylphosphonium chloride and tetraphenylphosphonium chloride and hydrogen chloride, can get benzofuran -2, Less, the highly purified diphenyl carbonate of 3- diketone.

In addition 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 dissolubility of diphenyl carbonate, even if making the phenostal with high conversion reaction be After diphenyl carbonate, so that diphenyl carbonate is concentrated in high concentration, in residual liquid, catalyst also will not separate out, thus easily recycle residual Contained catalyst in liquid.

[table 4]

The species of catalyst and reaction achievement

※ TPPC ... tetraphenylphosphonichloride chloride phosphorus.

※ DPO ... phenostal.

※ DPC ... diphenyl carbonate.

※ YF ... benzofuran -2,3- diketone.

[embodiment 8]

To in the detachable flask of 500 milliliters of a complete set of tubular type possessing thermometer and blender, load 4- 2-methyl-2-phenylpropane base triphen Base phosphonium chloride 20g (0.05 mole), n-butyl alcohol 5g and 28 weight % hydrochloric acid 75g, are heated to 90 DEG C, under nitrogen atmosphere in equal One solution.Then, obtain serosity by detachable flask is cooled to 10 DEG C.

This serosity is filtered by glass filter, the solid obtaining is moved to eggplant type flask.By by this eggplant type flask It is arranged in the rotary evaporator possessing oil bath, by oil bath heating to 100 DEG C, be dried 2 hours under pressure 10Torr, obtain 15g solid.

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

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

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

[embodiment 9]

In embodiment 6, using the adduct 15g of the 4- tolyl triphenyl phosphine dichloride obtaining in embodiment 8 and hydrogen chloride (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 Response time was foreshortened to 3 hours by 6 hours, and in addition, and embodiment 6 similarly manufactures diphenyl carbonate.

Reach liquid when 230 DEG C to consist of, phenostal 66.2 weight %, diphenyl carbonate 26.6 weight %, 4- Tolyl triphenyl phosphine dichloride 5.1 weight %, phenol 1.5 weight %.

Additionally, the consisting of of liquid after reaction 3 hours, diphenyl carbonate 49.5 weight %, phenostal 39.5 weight Amount %, 4- tolyl triphenyl phosphine dichloride 3.6 weight %, phenol 2.3 weight %.Herein, the conversion ratio of phenostal is 61%.

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

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

Therefore, confirm that there are no the asymmetric four aryl halogenation phosphines of benzylic protons from the comparison of embodiment 6 and embodiment 9, The i.e. adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, the stability in de-carbonyl reaction is higher, is especially excellent Choosing.

[embodiment 10]

In possessing the test tube of stirrer and thermometer, load the thick diphenyl carbonate obtaining in embodiment 6 (containing 11 weight ppm Benzofuran -2,3- diketone) after 100g, with oil bath heating, make the interior temperature of this test tube be 100 DEG C.

Heat further, make the interior temperature of this test tube be 230 DEG C, add 1 mole of dm^-3Sodium hydrate aqueous solution 1cm³ (as 1 mM of sodium hydroxide), maintain 230 DEG C as former state, after 120 minutes, by its benzo of high effective liquid chromatography for measuring The concentration of furan -2,3- diketone.As a result, being 100 weight ppb.

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

[synthesis example 2]

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

By with the method identical method described in No. 5892091 description of U.S. Patent No., synthesize chloro oxalic acid phenyl ester (PCO).

That is, in 1 liter of conical flask possessing magnetic stirring apparatuss, load phenostal 27.3g (0.11 mole) and third Ketone 600cm³.By in 50cm³Beaker in load water 25cm³, it is slowly added to acetic acid 6.8g (0.11 mole) and carbonic acid thereto Potassium 7.8g (0.06 mole) simultaneously mixes, and thus obtains acetic acid aqueous solutions of potassium.

This acetic acid aqueous solutions of potassium is loaded Dropping funnel, stirs in the acetone soln of the previous phenostal prepared Mix, 4 hours used times instilled.After instillation terminates, stir 2 hours further, obtain serosity.To be reduced pressure by this serosity and obtain The solid constituent arriving is suspended with acetone and cleans, and obtains the solid of white.By making this white solid constituent drying under reduced pressure, obtain Oxalic acid phenyl ester potassium salt 20.1g (0.10 mole).

This oxalic acid phenyl ester potassium salt is loaded 100cm³Eggplant type flask in, be incubated at 20 DEG C using water-bath.To dropping liquid leakage Bucket adds thionyl chloride 17.5g (0.15 mole), and 30 minutes used times instilled in the oxalic acid phenyl ester potassium salt in eggplant type flask.

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

By this chloro oxalic acid phenyl ester and oxolane 100cm³Together load 500cm³Eggplant type flask in.By the used time 10 Minute instills pyridine 6.6g (0.08 mole) thereto, obtains serosity.

By phenyl salicylate 18.0g (0.08 mole) and oxolane 100cm³Load 200cm³Beaker in, add previously Serosity after, react 2 hours.After reaction terminates, add toluene 100cm³, add water 100cm further³, hydrolysis.

This 2 separated liquid hydrolyzing is moved to separatory funnel, separation water.By adding saturated carbon in the organic faciess obtaining Sour hydrogen sodium water solution 100cm³It is sufficiently mixed, neutralization, after obtaining 2 separated liquid, separate aqueous phase.

By adding saturated sodium-chloride water solution 100cm further in the organic faciess obtaining³, after dehydration, separate aqueous phase. The organic faciess obtaining are moved to 500cm³Conical flask, add magnesium sulfate 30g, be dehydrated further.

By filtering this organic facies, after filtering magnesium sulfate, organic faciess are moved to 500cm³Eggplant type flask, use under reduced pressure Vaporizer makes oxolane distillate.It is slowly added hexane in liquid to after make this oxolane distillate, when crystallization separates out, stop The interpolation of hexane, lets cool.

By the serosity obtaining filtration under diminished pressure, obtain the solid constituent of white.By making this white solid constituent decompression dry Dry, obtain phenyl (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) 10.2g (0.03 mole).

[embodiment 11]

Possess thermometer, blender, distillate pipe and accepter a complete set of tubular type 500cm³Detachable flask in, load Phenostal 89g (0.367 mole), aftermentioned real apply the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride manufacturing in example 25 and hydrogen chloride Adduct 10g (0.021 mole) and phenyl (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) 1g) after (0.003 mole), To heat up in detachable flask.

After reaching 230 DEG C in detachable flask, the carbon monoxide that reaction is produced removes to outside reaction system, While carrying out the de-carbonyl reaction of 60 minutes in the state of keeping 230 DEG C.A part for liquid after reacting 60 minutes is taken Go out, when composition analysis are carried out by high performance liquid chromatography, be phenol 1.33 weight %, phenostal 20.36 weight %, carbon Diphenyl phthalate 64.92 weight %.

[embodiment 12]

In embodiment 11, phenostal is changed to 85g (0.351 mole), phenyl (adjacent phenyloxycarbonyl phenyl) grass from 89g Acid esters (OCPO) is changed to 5g (0.014 mole) from 1g, in addition, implements similarly to Example 11, carries out de-carbonyl reaction, Analyze its liquid after reacting 60 minutes.As a result, phenol 1.19 weight %, phenostal 12.89 weight %, carbonic acid two Phenyl ester 68.47 weight %.

[embodiment 13]

In embodiment 11, phenostal is increased to 90g (0.372 mole) from 89g, not using phenyl (adjacent phenyloxycarbonyl Phenyl) oxalate (OCPO), in addition, implement similarly to Example 1, carry out de-carbonyl reaction, analyze its 60 points of reaction Liquid after clock.As a result, phenol 1.40 weight %, phenostal 21.98 weight %, diphenyl carbonate 64.40 weight Amount %.

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

[table 5]

The result of embodiment 11～13

※ Monitoring lower-cut is below 1 weight ppm

Confirmed by table 5, by using the grass of the phenyl containing specified quantitative (adjacent phenyloxycarbonyl phenyl) oxalate (OCPO) Diphenyl phthalate, thus efficiently and stably manufactures the amount minimizing of phenol, highly purified diphenyl carbonate.

[embodiment 14]

In the tube sealing teat glass of wall thickness 5mm, load the 4- 2-methyl-2-phenylpropane base triphenyl chlorine manufacturing in embodiment 25 described later Change the adduct 0.03g (0.06 mM) and phenostal 0.57g (2.35 mMs) of phosphine and hydrogen chloride.Using vacuum pump Closing, so that being 10kPa in tube sealing teat glass, tube sealing volume becomes 30cm³.Impregnated in 230 DEG C making this tube sealing React 1 hour in the state of in oil bath.

Reacted reactant liquor is taken out from tube sealing, composition analysis are carried out by high performance liquid chromatography.As a result, benzene Phenol 0.66 weight %, phenostal 34.13 weight %, diphenyl carbonate 58.81 weight %, phenyl is (to phenyloxycarbonyl benzene Base) carbonic ester (PCPC) 0.27 weight %.Additionally, 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 ideal gases Equation of state, the absolute pressure in reacted tube sealing is：Yield × gas constant × temperature ÷ the tube sealing of carbon monoxide Volume=(0.00235 mole × 0.67) × 8.314Pa m³·K^-1× mole^-1×(230+273)K÷(0.000030m³)= 0.2MPa.

[embodiment 15]

In the tube sealing teat glass of wall thickness 5mm, load the 4- 2-methyl-2-phenylpropane base triphenyl chlorine manufacturing in embodiment 25 described later Change the adduct 0.10g (0.21 mM) and phenostal 1.90g (7.84 mMs) of phosphine and hydrogen chloride, with embodiment 14 Similarly implement, react 1 hour.

Reacted reactant liquor is taken out from tube sealing, composition analysis are carried out by high performance liquid chromatography.As a result, benzene Phenol 0.65 weight %, phenostal 34.85 weight %, diphenyl carbonate 57.88 weight %, phenyl is (to phenyloxycarbonyl benzene Base) carbonic ester (PCPC) 0.27 weight %.Additionally, the conversion ratio of phenostal is 66%.

Herein, in de-carbonyl reaction, with generation carbon monoxide correspondingly, the pressure in tube sealing rises, according to ideal gases Equation of state, the absolute pressure in reacted tube sealing is：Yield × the gas constant of carbon monoxide × temperature ÷ envelope Pipe volume=(0.00784 mole × 0.66) × 8.314Pa m³·K^-1× mole^-1×(230+273)K÷(0.000030m³) =0.7MPa.

[embodiment 16]

In the tube sealing teat glass of wall thickness 5mm, similarly to Example 14 load 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and The adduct of hydrogen chloride and phenostal, after making to be 10kPa in tube sealing teat glass, are back to normal pressure (absolute pressure 0.10MPa), react 1 hour under the dress state in the oil bath that former state impregnated in 230 DEG C.

Reacted reactant liquor is taken out from tube sealing, composition analysis are carried out by high performance liquid chromatography.As a result, benzene Phenol 0.63 weight %, phenostal 34.61 weight %, diphenyl carbonate 58.33 weight %, phenyl is (to phenyloxycarbonyl benzene Base) carbonic ester (PCPC) 0.41 weight %.

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 %

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

[embodiment 17]

Possess thermometer, blender, distillate pipe, accepter and diameter 2mm glass tubing a complete set of tubular type 500cm³Can In separate type flask, load the 4- manufacturing in phenostal 185.8g, diphenyl carbonate 74.0g and embodiment described later 25 After the adduct 13.9g of 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, start the stirring being carried out with agitator.By dividing It is warming up to 150 DEG C in formula flask, make the adduct dissolving of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.

By this liquid a part taking-up, calculate chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride mol ratio when, be 1.225 (0.03660 mole/0.02988 moles).Additionally, the amount of chlorine atom, pass through potential difference titration appratuss (capital with silver nitrate The potential difference titration appratuss " AT-610 " of all Electronics Industry Companies) measure.Additionally, the amount of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride By high effective liquid chromatography for measuring.

Adjustment glass tubing front end position, make glass tubing front end position in the bottom of detachable flask (from liquid Body upper table faces down 60mm, from flask bottom 20mm upwards) become the center side of flask bottom surface, and then heat up, when detachable burning If reach 230 DEG C in bottle, by this glass tubing with 0.08cm per minute³It is blown into nitrogen, start to bubble.Herein, with respect to can The superficial linear velocity of the nitrogen of separate type flask is 0.00046m s^-1, the bubble footpath of nitrogen is about 7mm.

While remove the gas of the nitrogen being blown into from the bottom of detachable flask etc. from reactor top, protecting Continue reaction in the state of holding 230 DEG C.By the part taking-up of the reaction liquid of 1 hour, carried out by high performance liquid chromatography During composition analysis, obtain the diphenyl carbonate containing phenol 0.33 weight %, phenostal 13.57 weight %.Additionally, this is anti- The mol ratio answering the chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride in the liquid after 1 hour is 1.051.

Under keeping this state, so that reaction is proceeded further, after reaction starts 3 hours, take out reactant liquor again 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 %.Additionally, chlorine atom/4- 2-methyl-2-phenylpropane base the triphenyl phosphine dichloride in liquid after this reaction 3 hours Mol ratio be reduced to 1.034.Additionally, the conversion ratio of the phenostal between after reaction beginning 1～3 hour is 94.4%.

In the case of keeping this state, so that reaction is proceeded further, after reaction starts 5 hours, take out reactant liquor A part, when carrying out composition analysis by high performance liquid chromatography, the concentration of phenostal is 1.53 weight %, phenol concentration It is reduced to 0.29 weight % further.Additionally, chlorine atom/4- 2-methyl-2-phenylpropane base triphenyl the chlorine in liquid after this reaction 3 hours The mol ratio fall changing phosphine is reduced to 1.028.

Additionally, the conversion ratio of the phenostal between after reaction beginning 3～5 hours is 98.0%, than reaction beginning 1～ Improve after 3 hours.Additionally, 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 to 0.3cm³(the void tower linear speed with respect to the nitrogen of detachable flask Spend for 0.00170m s^-1, the bubble footpath of nitrogen is about 7mm), in addition, carry out diphenyl carbonate similarly to Example 17 Manufacture, carry out the composition analysis of its reacted liquid.

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

The amount of contained phenostal in reacted diphenyl carbonate, is 16.54 weight % after reacting 1 hour, Reaction was 1.05 weight % after 3 hours, and reaction was 0.001 weight % after 5 hours.The conversion ratio of phenostal, opens in reaction Be 93.7% between after beginning 1～3 hour, after reaction beginning 3～5 hours between be 98.0%, when less than reaction beginning 1～3 after Improve.Additionally, 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, carry out the manufacture of diphenyl carbonate similarly to Example 17, enter The composition analysis of its reacted liquid of row.

In reacted diphenyl carbonate, the amount of contained phenol does not reduce substantially, is 0.39 weight % after reacting 1 hour, It is 0.36 weight % after 3 hours of reaction, after reacting 5 hours, phenol is 0.37 weight %.

Additionally, the mol ratio of the chlorine atom of reacted liquid/4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride slowly reduces, 5 It is 1.250 after hour reaction.The amount of contained phenostal in reacted diphenyl carbonate, after reacting 1 hour be 17.04 weight %, reaction was 0.71 weight % after 3 hours, and reaction was 0.042 weight % after 5 hours.

The conversion ratio of phenostal, after reaction beginning 1～3 hour between be 95.9%, reaction beginning 3～5 hours Be 94.1% between afterwards, when less than reaction beginning 1～3 after reduce.Additionally, 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 mol ratio of butylbenzene base triphenyl phosphine dichloride is summarized in table 7.

[table 7]

The superficial linear velocity of the nitrogen in embodiment 17～19, phenol concentration, reaction conversion ratio and chlorine atom/4- 2-methyl-2-phenylpropane base The mol ratio of triphenyl phosphine dichloride

Confirmed by table 7, by nitrogen is supplied specified quantitative from reactor lower part, the phenol amount in reactant liquor reduces, can be more Efficiently, more stably manufacture diphenyl carbonate.In addition it was demonstrated that：The quantity delivered of nitrogen is more, and in catalyst, contained chlorine is easier Volatilization.

[reference example 1]

Possessing the 200cm of stirrer³Eggplant type flask in, load phenostal 100g (413 mMs), 4- 2-methyl-2-phenylpropane base Triphenyl phosphine dichloride (molecular weight 431) 20g, impregnated in 150 DEG C of oil bath.Make hydrogen chloride gas (molecular weight 36) 560 wherein After (23 mMs) of milliliter bubbles, the temperature of oil bath is warming up to 230 DEG C, reacts 2 hours.

After reaction, this eggplant type flask is installed and distillates pipe, make diphenyl carbonate and phenol under full vacuum with membrane pump Mixture 56g distillate.The stillage residue obtaining is cooled to after 100 DEG C, when adding methyl iso-butyl ketone (MIBK) 100g, white slurry Liquid.

This serosity is cooled to room temperature (about 30 DEG C), when so that (60 mMs) of 1450 milliliters of hydrogen chloride gas is bubbled, absorb (with respect to 1 mole of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, supplying hydrogen chloride 1.3 moles=0.060 ÷ (20 ÷ 431)), obtains It is in visually homogeneous liquid.

In this liquid, when 30 minutes used times added water 5g, white slurry again.By this serosity was reduced pressure After filter, suspended with methyl iso-butyl ketone (MIBK) 20g and clean, obtain 26g solid.Additionally, the filterability in the filtration under diminished pressure of this solid is good Good.

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

[embodiment 20]

Possessing the 200cm of stirrer³Eggplant type flask in, load phenostal 102g (421 mMs), enforcement described later The 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride manufacturing in example 25 and adduct (molecular weight 467) 20g of hydrogen chloride, impregnated in 230 DEG C Oil bath in, reaction 2 hours (conversion ratio of phenostal be 99.99%).

After reaction, this eggplant type flask is installed and distillates pipe, make diphenyl carbonate and phenol under full vacuum with membrane pump Mixture 56g distillate (amount of liquid before distillating be 110g, thus the enrichment factor (evaporation rate) of diphenyl carbonate be 56g/110g =51%).The stillage residue obtaining is cooled to after 100 DEG C, when adding methyl iso-butyl ketone (MIBK) 100g, white slurry.

This serosity is cooled to room temperature (about 30 DEG C), when so that (56 mMs) of 1330 milliliters of hydrogen chloride gas is bubbled, absorb (with respect to 1 mole of the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, supply hydrogen chloride 1.3 moles=0.056 ÷ (20 ÷ 467)), obtain being in visually homogeneous liquid.

In this liquid, when 30 minutes used times added water 5g, white slurry again.By this serosity was reduced pressure After filter, suspended with methyl iso-butyl ketone (MIBK) 21g and clean, obtain 25g solid.Additionally, the filterability in the filtration under diminished pressure of this solid is good Good.

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

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 response rate of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (25g × 0.730 ÷ 431) ÷ (20 ÷ 467) × 100=99%.

[reference example 2]

In reference example 1, using adding water to the methyl-isobutyl making water content be 3500 weight ppm in this methyl iso-butyl ketone (MIBK) Ketone substitutes methyl iso-butyl ketone (MIBK) (water containing 500 weight ppm), in addition, in 4- 2-methyl-2-phenylpropane base triphen in the same manner as reference example 1 After carrying out the de-carbonyl reaction of phenostal in the presence of base phosphonium chloride and hydrogen chloride gas, make diphenyl carbonate and phenol Mixture distillates, and obtains the solid of 26g 2-methyl-2-phenylpropane containing 4- base triphenyl phosphine dichloride from the stillage residue obtaining.But, if should Filterability in the filtration under diminished pressure of solid is compared with the filterability of the solid of reference example 1, then the filterability of the solid of reference example 1 is more For good.

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

[comparative example 5]

Possessing the 200cm of stirrer³Eggplant type flask in, load phenostal 102g (421 mMs), enforcement described later 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 22g (51 mMs) manufacturing in example 25, impregnated in 150 DEG C of oil bath.Make wherein After (26 mMs) of 574 milliliters of hydrogen chloride gas bubble, the temperature of oil bath is warming up to 230 DEG C, reacts 2 hours.

After reaction, this eggplant type flask is installed and distillates pipe, make diphenyl carbonate and phenol under full vacuum with membrane pump Mixture 57g distillate.The stillage residue obtaining is cooled to after 100 DEG C, when adding methyl iso-butyl ketone (MIBK) 110g, white slurry Liquid.

When this serosity is cooled to room temperature (about 30 DEG C), mobility disappears, in the state that cannot filter.Therefore, by rising Temperature, to 80 DEG C, improves mobility and filters, thus obtain 45g solid.Additionally, the filtration under diminished pressure of this solid is time-consuming.

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

[comparative example 6]

Carry out phenostal in the same manner as reference example 1 in the presence of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride gas De-carbonyl reaction after, distillated by making the mixture of diphenyl carbonate and phenol, by the stillage residue obtaining cool down, add methyl Isobutyl ketone, thus obtains white serosity.

This serosity is cooled to room temperature (about 30 DEG C), when adding 28 weight % hydrochloric acid 2580mg and stirring, precipitate coagulation. The precipitate scraper of this coagulation is scraped broken, after filtration under diminished pressure, cleaned by being suspended with methyl iso-butyl ketone (MIBK) 20g, thus obtain 21g solid.Additionally, the filtration under diminished pressure of this solid is time-consuming.

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

[embodiment 21]

Possessing the 500cm of stirrer³Eggplant type flask in, load phenostal 250g (1032 mMs), reality described later Apply adduct (molecular weight 467) 66g of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride manufacturing in example 25 and hydrogen chloride, impregnated in 230 DEG C oil bath in, reaction 2 hours (conversion ratio of phenostal be 99.99%).

After reaction, this eggplant type flask is installed and distillates pipe, make diphenyl carbonate and phenol under full vacuum with membrane pump Mixture 117g distillate (amount of liquid before distillating be 287g, thus the enrichment factor (evaporation rate) of diphenyl carbonate be 117g/ 287g=40.8%).By the stillage residue obtaining is cooled to 100 DEG C, obtain catalyst liquid 170g.The composition of this 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) for this liquid is moved to other 500cm³Eggplant type flask in, add methyl iso-butyl ketone (MIBK) 166g When, white slurry.This serosity is cooled to room temperature (about 30 DEG C), so that (83 mMs) of 2000 milliliters of hydrogen chloride gas is risen (with respect to 1 mole of the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, 1.3 moles of hydrogen chloride is supplied when bubble, absorption =0.083 ÷ { (66 ÷ 467) × (78 ÷ 170) }), obtain being in visually homogeneous liquid.

In this liquid, when 30 minutes used times added water 3g, white slurry again.By this serosity was reduced pressure After filter, suspended with methyl iso-butyl ketone (MIBK) 46g and clean, obtain 36g solid.Additionally, the filterability in the filtration under diminished pressure of this solid is good Good.

When moisture concentration in this solid is analyzed with moisture meter (capital of a country Electronics Industry Company system " MKS-500 "), it is 6.7 Weight %.Additionally, potential difference titration appratuss (capital of a country Electronics Industry Company system " the AT-610 ") analysis by using silver nitrate should During hydrogen cloride concentration in solid, it is 7.2 weight %.

Further, when the composition of this solid being passed through high-efficient liquid phase chromatogram technique analysis, it is 4- 2-methyl-2-phenylpropane base triphenyl chlorine Change phosphine 75.0 weight %, methyl iso-butyl ketone (MIBK) 8.9 weight %, diphenyl carbonate 0.2 weight %, and other compositions 2.0 weight Amount % (except water 6.7 weight % and hydrogen chloride 7.2 weight %).The response rate 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, load methyl iso-butyl ketone (MIBK) 220g.Wherein, hydrogen chloride gas are made with every Minute 300cm³Bubble, supply 30 minutes.By the hydrogen cloride concentration in the methyl iso-butyl ketone (MIBK) after bubbling by using nitre During potential difference titration appratuss (capital of a country Electronics Industry Company system " the AT-610 ") analysis of acid silver, it is 6.6 weight %.

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

[embodiment 22]

A part (90g) for the catalyst liquid obtaining in embodiment 21 is moved to the 100cm of a complete set of tubular type³Dropping funnel in, It is heated to 160 DEG C.In other 500cm³Eggplant type flask in, load formulation example 1 in configuration containing hydrogen chloride 2.0 weight % first (with respect to 1 mole of the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride, hydrogen chloride is supplied after base isobutyl ketone 180g 1.3 moles=(180 × 0.020 ÷ 36) ÷ { (66 ÷ 467) × (90 ÷ 170) }), this eggplant type flask be impregnated in 30 DEG C of water In bath.Add catalyst liquid 90g from 1 hour Dropping funnel used time, so that the interior temperature of this eggplant type flask maintains 30 DEG C, obtain mesh Depending in homogeneous liquid.

In this liquid, when 20 minutes used times instilled 4g water, white slurry.By by this serosity filtration under diminished pressure Afterwards, suspended with methyl iso-butyl ketone (MIBK) 20g and clean, thus obtain 22g solid.Additionally, the filterability in the filtration under diminished pressure of this solid Well.

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

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

With regard to the character of the catalyst of recovery and recovery 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 by the recovery method of the catalyst of the present invention, can be simple and effectively with height Purity reclaims the catalyst of the manufacture for the diphenyl carbonate being carried out by the de-carbonyl reaction of phenostal.

[table 8]

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

	Cohesion	Filterability	The response rate
				Reference example 1	No	Well	95%
Embodiment 20	No	Well	99%
				Reference example 2	No	May filter that	90%
Embodiment 21	No	Well	94%
				Embodiment 22	No	Well	95%
Comparative example 5	Have	Difference	53%
				Comparative example 6	No	Difference	75%

[embodiment 23]

15g in the solid that will obtain in embodiment 22 loads 100cm³Eggplant type flask in, be arranged on the rotation possessing oil bath On vaporizer.By oil bath heating to 100 DEG C, it is dried 1 hour under pressure 10Toor.Moisture concentration in the solid that will be dried is used During moisture meter (capital of a country Electronics Industry Company system " MKS-500 ") analysis, according to moisture meter (capital of a country Electronics Industry Company system " MKS- 500 ") it is 0.3 weight %.

The 5g in solid that be dried this and phenostal 100g (413 mMs), loads 500cm³Eggplant type flask In, impregnated in 230 DEG C of oil bath.By when from dipping, the composition after 1 hour passes through high-efficient liquid phase chromatogram technique analysis, containing carbon Diphenyl phthalate 65.0 weight %, phenostal 29.6 weight %, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 5.0 weight %, phenol 0.4 weight %.

[embodiment 24]

In embodiment 23, with the adduct 5g of the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of manufacture and hydrogen chloride in embodiment 25 (11 mMs) substitute and make the dried 5g of solid that obtains in embodiment 22, carry out 1 hour de- similarly to Example 23 Carbonyl reaction.By the reacted composition of high-efficient liquid phase chromatogram technique analysis.

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

Reacted liquid composition in embodiment 23 and reference example 3 is summarized in table 9.Confirmed by table 9, by using Reclaimed by the recovery method of the catalyst of the present invention, diphenyl carbonate for being carried out by the de-carbonyl reaction of phenostal Manufacture catalyst, can stably manufacture highly purified diphenyl carbonate.

[table 9]

Reacted liquid composition in embodiment 23 and 24

[embodiment 25]

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

First, the method recorded by Japanese Laid-Open 2013-82695 publication, synthesizes 4- 2-methyl-2-phenylpropane base triphen bromide Change phosphine.This bromide is passed through the method that Japanese Laid-Open flat 11-217393 publication is recorded, is transformed to 4- 2-methyl-2-phenylpropane base triphen Base phosphonium chloride (chloride).

Load this 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, butanol and hydrochloric acid in detachable flask, in nitrogen atmosphere Under be heated to 90 DEG C so as to be in uniform solution.Then, obtain serosity by detachable flask is cooled to room temperature.This is starched Liquid is filtered by glass filter, and the solid obtaining is moved to eggplant type flask.By eggplant type flask being placed on the rotation possessing oil bath Turn on vaporizer, by oil bath heating to 100 DEG C, be dried 2 hours under pressure 10Torr, obtain solid.

The result that the potential difference titration appratuss " AT-610 " of this solid capital of a country Electronics Industry Company are analyzed, is 14.2 Weight %, thus confirming is the adduct of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride and hydrogen chloride.Additionally, with moisture meter, (capital of a country is electric Sub- industrial group system " MKS-500 ") moisture content that measures is 0.4 weight %.

[embodiment 26]

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

After reaction, this eggplant type flask is installed and distillates pipe, make diphenyl carbonate and phenol under full vacuum with membrane pump Mixture 20g distillate (amount of liquid before distillating be 400g, thus the enrichment factor (evaporation rate) of diphenyl carbonate be 20g/400g =5%).The stillage residue obtaining is cooled to after 100 DEG C, when adding methyl iso-butyl ketone (MIBK) 800g, white slurry.

This serosity is cooled to room temperature (about 20 DEG C), makes hydrogen chloride gas (molecular weight 36) 0.01m³(with respect to reactant liquor In contained 1 mole of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, hydrogen chloride is 1.2 moles) when bubbling, absorbing, obtain being in visually all One liquid.During to 30 minutes this liquid used times interpolation water 40g, white slurry again.By reducing pressure to by this serosity The solid being filtrated to get, is suspended with methyl iso-butyl ketone (MIBK) 100g after cleaning, filtration under diminished pressure thus, obtains filtrate 1100g and solid 167g.

Herein, the concentration of contained methyl iso-butyl ketone (MIBK) in the filtrate obtaining is passed through the result of gas chromatogram standard measure, It is 74.0 weight %.Additionally, the result measuring the concentration of contained water in this filtrate by moisture meter, it is 3.5 weight %.Will In this filtrate, the concentration of contained hydrogen chloride passes through the quantitative result of potential difference titration appratuss, is 0.3 weight %.

Additionally, the filterability in the filtration under diminished pressure of the solid obtaining is good.Additionally, the composition of this solid is passed through efficient liquid During GC headspace analysis, the concentration of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride (molecular weight 431) is 73 weight %.Therefore, calculate work For solid reclaim 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride the response rate be (167g × 0.73 ÷ 431) ÷ (160g ÷ 467) × 100=83%.

By the bavin field science strain formula meeting by the tower diameter 32mm possessing a complete set of tubular type detachable flask, thermometer and blender Society's system " Oldershaw " (plate column) and the batch distillation column of Liquid liquid Separation groove composition, are arranged to make detachable flask When interior filtrate is evaporated, evaporation liquid is supplied to the bottom of Liquid liquid Separation groove by plate column, meanwhile, from Liquid liquid Separation groove Top overflow and return in plate column.Additionally, being arranged to the plugging of connecting plate type tower and Liquid liquid Separation groove to fore-running Groove tank or main flow groove tank, substitute Liquid liquid Separation groove.

The 300g in above-mentioned filtrate is loaded in detachable flask.Additionally, loading water 20cm in Liquid liquid Separation groove³ With methyl iso-butyl ketone (MIBK) 80cm³(64) g, makes Liquid liquid Separation groove be 15 DEG C.By 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, is distilled.

The evaporation liquid distillating from Liquid liquid Separation groove, is separated into lower phase with water as main constituent and with methyl tert-butyl by two-phase Base ketone is the upper phase of main constituent.Herein, in the lower groove in Liquid liquid Separation be detained, but upper mutually spilling and be back in plate column.Companion Evaporated together with methyl iso-butyl ketone (MIBK) with water, the interface of lower phase and upper phase slowly rises, the tower top temperature of plate column rises, But in the near future, the ratio of the methyl iso-butyl ketone (MIBK) along with evaporation and water reaches the full of the water with respect to isobutyl ketone when 15 DEG C And dissolubility, the temperature of the tower top temperature of plate column rises and becomes slow near 57.7 DEG C, meanwhile, 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 groove is switched to fore-running groove tank from Liquid liquid Separation groove, along with flashing to In point, contained water concentration reduces, and entirely distillates tower top temperature to plate column 58.2 DEG C near, and it is slow that temperature rises change, obtains Head fraction 57g.Herein, by the concentration of the methyl iso-butyl ketone (MIBK) contained by head fraction pass through gas chromatography as a result, 98.0 weight %.

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

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

[embodiment 27]

In embodiment 26, add filtrate 300g in detachable flask, reinstall the head fraction 57g obtaining in embodiment 26, It is maintained at embodiment 26 and will evaporate the state that liquid accumulates in Liquid liquid Separation groove, in addition, make the bottom of detachable flask Temperature heats up, and continues to distillate to 67.3 DEG C, till obtaining the operation of main distillate fraction, is distilled similarly to Example 26.

Specifically, detachable flask loads the head fraction 57g obtaining in above-mentioned filtrate 300g and embodiment 26. Additionally, making Liquid liquid Separation groove keep being incorporated with the state accumulating evaporation liquid in embodiment 26, Liquid liquid Separation groove is made to be 15 DEG C.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, Distilled.

The evaporation liquid distillating from Liquid liquid Separation groove, is separated into lower phase with water as main constituent and with methyl tert-butyl by two-phase Base ketone is the upper phase of main constituent.Herein, in the lower groove in Liquid liquid Separation be detained, but upper mutually overflow, be 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 is slow nearby to become, and meanwhile, the rising at the interface of lower phase and upper phase also stops.

The pipeline of connecting plate type tower and Liquid liquid Separation groove is switched to fore-running groove tank from Liquid liquid Separation groove, entirely distillates to adjoint Near 58.2 DEG C, temperature rises and becomes slow the tower top temperature contained water concentration reduction in evaporation composition, plate column, obtains Head fraction 60g.Herein, by the concentration of the methyl iso-butyl ketone (MIBK) contained by head fraction pass through gas chromatography analysis as a result, 98.0 weight %.

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

Therefore, the response rate calculating methyl iso-butyl ketone (MIBK) in main distillate fraction is, (202g × 0.999) ÷ (300g × 0.740+ 57g × 0.980) × 100=73%.Additionally, calculate the methyl iso-butyl ketone (MIBK) it supplied in head fraction reclaim component after The response rate of the 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, sets similarly to Example 26 Put batch distillation column.

Above-mentioned filtrate 300g is loaded in detachable flask.By making reflux ratio be 2, board-like tower pressure interior force is subtracted from normal pressure It is depressed into 133kPa, the bottom temp of detachable flask is warming up to 60.4 DEG C from room temperature, is distilled.

Entirely distillate and evaporated together along with methyl iso-butyl ketone (MIBK) to water, the tower top temperature of plate column rises, and evaporates composition In contained water concentration reduce, meanwhile, temperature rises and becomes slow near 58.2 DEG C, obtains head fraction 131g.Herein, will The concentration of the methyl iso-butyl ketone (MIBK) contained by head fraction pass through gas chromatography analysis as a result, 92.0 weight %.

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

Additionally, contained water in main distillate fraction, 0.1 weight % is calculated as according to moisture, contained hydrogen chloride in main distillate fraction, according to Potential difference titration appratuss, below detection boundary.Therefore, the response rate 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 to the ratio of main distillate fraction 79 with weight ratio meter head fraction 131, as full distillate.Entirely Contained water in distillate, is calculated as 5.0 weight % according to moisture, contained hydrogen chloride in full distillate, is titrated according to potential difference Device, is 0.1 weight %.

By the response rate 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 response rate 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 pass through the present invention Catalyst recovery method, can will be used for by phenostal de-carbonyl reaction manufacture diphenyl carbonate catalyst return Receive used polar organic solvent, reclaim simple and effectively.

[table 10]

The response rate of methyl iso-butyl ketone (MIBK) (MIBK) in the composition of the main distillate fraction in embodiment 26～28, main distillate fraction and entirely evaporating The response rate of the methyl iso-butyl ketone (MIBK) (MIBK) in part

	The water concentration of main distillate fraction	The hydrogen cloride concentration of main distillate fraction	The response rate of the MIBK in main distillate fraction
				Embodiment 26	0.1 weight %	Below detection boundary	53 weight %
Embodiment 27	0.1 weight %	Below detection boundary	73 weight %
				Embodiment 28	0.1 weight %	Below detection boundary	36 weight %

[embodiment 29]

Using the main distillate fraction obtaining in embodiment 27, carry out catalyst recovery.

Specifically, in the eggplant type flask possessing stirrer, make in loading phenostal 27g (0.11 mole), embodiment 25 The 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride made and adduct (molecular weight 467) 16g of hydrogen chloride, impregnated in 240 DEG C of 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, this eggplant type flask is installed and distillates pipe, make diphenyl carbonate and phenol under full vacuum with membrane pump Mixture 2g distillate (amount of liquid before distillating be 40g, thus the enrichment factor (evaporation rate) of diphenyl carbonate be 2g/40g= 5%).The stillage residue obtaining is cooled to after 100 DEG C, when adding the main distillate fraction 80g obtaining in embodiment 26, white serosity Shape.

This serosity is cooled to room temperature (about 20 DEG C), makes hydrogen chloride gas (molecular weight 36) 0.001m³(with respect to reactant liquor In contained 1 mole of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, hydrogen chloride is 0.04 mole) when bubbling, absorbing, obtain being in visually all One liquid.To in this liquid, when 30 minutes used times added water 4g, white slurry again.By subtracting to by this serosity The solid that press filtration obtains, is suspended after cleaning with methyl iso-butyl ketone (MIBK) 10g, and filtration under diminished pressure thus obtains solid 18g.

Filterability in the filtration under diminished pressure of the solid obtaining is good.Additionally, the composition of this solid is passed through high-efficient liquid phase color During chromatography, the concentration of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is 76 weight %.

Therefore, calculating the response rate as 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride (molecular weight 431) of solid recovery is (18g × 0.76 ÷ 431) ÷ (16g ÷ 467) × 100=93%.Additionally, by high-efficient liquid phase chromatogram technique analysis, but phenol is in inspection Survey below boundary.

[embodiment 30]

In embodiment 29, with the main distillate fraction 80g obtaining in the full distillate 80g alternate embodiment 27 that obtains in embodiment 28, In addition, catalyst reclaims similarly to Example 29.But, the white serosity adding whole distillates is cooled to room temperature (about 20 DEG C), make 1 liter of hydrogen chloride gas bubble, absorb, but are not in visually homogeneous liquid.

[reference example 3]

Add water to the methyl iso-butyl ketone (MIBK) with light pure medicine Co. Ltd. system, being configured to water solubility becomes 0.3 weight %.In embodiment In 29, the main distillate fraction that obtains in the methyl iso-butyl ketone (MIBK) alternate embodiment 27 with this moisture concentration 0.3 weight %, in addition, Catalyst reclaims similarly to Example 29.

But, the white serosity adding whole distillates is cooled to room temperature (about 20 DEG C), so that hydrogen chloride gas 1 is risen Bubble, absorption, but visually it is only the white serosity of the dissolved residue of visible solid.By adding water 4g to 30 minutes this liquid used times Afterwards, solid filtration under diminished pressure being obtained, is suspended after cleaning with methyl iso-butyl ketone (MIBK) 10g, and filtration under diminished pressure thus obtains solid 18g.

By the composition of the solid obtaining pass through high-efficient liquid phase chromatogram technique analysis when, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride dense Spend for 77 weight %.Therefore, the response rate of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride is (18g × 0.77 ÷ 431) ÷ (16g ÷ 467) × 100=94%.But, during by this solid high-efficient liquid phase chromatogram technique analysis, the phenol detecting is 3 weight %.

With regard to the water being used in embodiment 29,30 and reference example 3 in the methyl iso-butyl ketone (MIBK) (MIBK) that catalyst reclaims Concentration and the response rate of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride, are summarized in table 11.

Confirmed by table 11, the polar organic solvent reclaiming for catalyst, preferably water concentration is relatively low, particularly preferred water concentration Below 0.3 weight %.

[table 11]

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

	Water concentration in MIBK	The response rate of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride
			Embodiment 29	0.1 weight %	93 weight %
Embodiment 30	5.0 weight %	Cannot reclaim
			Reference example 3	0.3 weight %	94 weight %

[embodiment 31]

Using the recovery catalyst obtaining in embodiment 29, carry out de-carbonyl reaction.

First, the solid 10g obtaining in embodiment 29 is loaded 100cm³Eggplant type flask, be arranged on possess oil bath rotation steam Send out on device, 140 DEG C of oil bath temperature, it is dried 1 hour under full vacuum with membrane pump.

Possessing the 500cm of stirrer³Eggplant type flask in, load the solid 5g and phenostal 95g of this drying (0.4 mole), impregnated in 230 DEG C of oil bath, reacts 1 hour.

During by reacted liquid composition by high-efficient liquid phase chromatogram technique analysis, containing diphenyl carbonate 66.0 weight %, Phenostal 28.6 weight %, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 5.0 weight %, phenol 0.4 weight %.

[embodiment 32]

In embodiment 31, replaced with the 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride of manufacture in embodiment 25 and the adduct 5g of hydrogen chloride In generation, makes the dried material of solid obtaining in embodiment 29, carries out de-carbonyl reaction in the same manner as embodiment 31.

During by reacted liquid composition by high-efficient liquid phase chromatogram technique analysis, it is diphenyl carbonate 65.4 weight %, grass Diphenyl phthalate 29.2 weight %, 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 5.0 weight %, phenol 0.4 weight %.

By the reacted liquid composition in comparing embodiment 31 and 32 it was demonstrated that there being the polarity being used for catalyst recovery Machine solvent recycles, and carries out catalyst recovery it is also possible to efficiently and stably manufacture highly purified diphenyl carbonate.

As described above it was demonstrated that by the recovery method in the catalyst by the present invention, recycling and reclaim the same of catalyst When, recycle for catalyst recovered solvent, can efficiently and stably manufacture highly purified diphenyl carbonate.

[synthesis example 3]

Method according to described in Bull.Chem.Soc.Jpn.82 (2009) 475, synthesizes benzofuran -2,3- diketone.

Possessing the 500cm of magnetic stir bar³Beaker in, add isatin 1.5g and 1 mole of dm^-3Sodium hydrate aqueous solution 150cm³, dissolving, with water-bath cooling, while add sodium nitrite 0.7g.It is slowly added 2.5 moles of dm thereto^-3's Sulphuric acid 15cm³, stir 10 minutes.

Then, beaker is placed in water-bath, is warming up to 60 DEG C.Former state was maintained at 60 DEG C after 1 hour, cooling, added activity Charcoal 0.1g, is filtered afterwards.The filtrate obtaining is moved to separatory funnel, uses ethyl acetate 30cm³Extraction.

The organic faciess obtaining are moved to 500cm³Eggplant type flask in, acetic acid is distilled off under reduced pressure with rotary evaporator Ethyl ester.Add toluene 30cm to the residue obtaining³With heptane 20cm³, it is allowed to dissolve.It is added thereto to phosphorus pentoxide 1.5g, peace Dress Di Muluo cooling tube, flows back 30 minutes.

The serosity being filtrated to get, adds heptane, crystallize in the filtrate obtaining, obtains benzofuran -2,3- diketone 0.6g.

[reference example 4]

After the phenostal that Tokyo is melted into Co. Ltd. system is purified by simple distillation, recrystallized with toluene.To obtain herein Phenostal in contained benzofuran -2, the amount of 3- diketone, by high effective liquid chromatography for measuring, but in detection boundary Below 10 weight ppb.

In the 500cm possessing stirrer and thermometer³There-necked flask in, load diphenyl carbonate 200.0g and oxalic acid two After phenyl ester 0.2g, it is heated to 210 DEG C.In this there-necked flask, add benzofuran -2 of synthesis in micro synthesis example 3,3- Diketone, by high performance liquid chromatography, measures its benzofuran -2, during the concentration of 3- diketone, is 8000 weight ppb.

Add sodium phenate 0.2g further in this there-necked flask, maintain 210 DEG C after 30 minutes, by high performance liquid chromatography Method, measures its benzofuran -2, during the concentration of 3- diketone, is 100 weight ppb.

[comparative example 7]

In the 500cm possessing stirrer and thermometer³There-necked flask in, load diphenyl carbonate 200.1g and oxalic acid two After phenyl ester 0.2g, it is heated to 210 DEG C.In this there-necked flask, add benzofuran -2 of synthesis in micro synthesis example 3,3- Diketone, by high performance liquid chromatography, measures its benzofuran -2, during the concentration of 3- diketone, is 578 weight ppb.

This there-necked flask is maintained 210 DEG C after 120 minutes, by high performance liquid chromatography, measures its benzofuran -2, During the concentration of 3- diketone, it is 174 weight ppb.

[comparative example 8]

In the 500cm possessing stirrer and thermometer³There-necked flask in, load diphenyl carbonate 201.2g and oxalic acid two After phenyl ester 0.2g, it is heated to 210 DEG C.Add the hydrogen chloride being saved in the pulling bag of Taide with gastight syringe in this there-necked flask Gas 40cm³, during by its cl concn of high effective liquid chromatography for measuring, it is 227 weight ppm.

In this there-necked flask, add benzofuran -2 of synthesis in micro synthesis example 3,3- diketone further, pass through High performance liquid chromatography, measures its benzofuran -2, during the concentration of 3- diketone, is 458 weight ppb.This there-necked flask is maintained By its benzofuran -2 of high effective liquid chromatography for measuring, during the concentration of 3- diketone, it is 547 weight 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]

Reference example 4 and the result of comparative example 7,8

※ resolution ratio is by by " benzofuran -2,3- diketone concentration during loading "-" benzofuran -2,3- two after heating Ketone concentration " as " benzofuran -2 of decomposition, 3- diketone concentration ", by it divided by " benzofuran -2 during loading, 3- diketone is dense Degree " calculates.

Confirm in table 12, by benzofuran -2 containing high concentration, the reference example 4 of the liquid short time heating of 3- diketone Resolution ratio, by benzofuran -2 containing low concentration, the resolution ratio of the comparative example 7 of 3- diketone liquid long-time heating is high for ratio, Thus by the presence of alkaline matter, promote benzofuran -2, the decomposition that the heating of 3- diketone leads to.

Additionally, by the comparison of comparative example 7 and 8, making acidic materials exist to substitute alkaline matter, benzo if also having distinguished The amount of furan -2,3- diketone can increase on the contrary.

[reference example 5]

In possessing the test tube of stirrer and thermometer, after loading diphenyl carbonate 20.0g, it is 200 with oil bath heating to interior temperature ℃.Add the sodium hydroxide water of the benzofuran -2,3- diketone 4.1mg of synthesis and 9.2 weight % in synthesis example 3 in this test tube Solution 53.7mg (as sodium hydroxide, be 0.1 mM).

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

[reference example 6]

In possessing the test tube of stirrer and thermometer, after loading diphenyl carbonate 20.0g, it is 200 with oil bath heating to interior temperature ℃.Add the benzofuran -2,3- diketone 5.1mg of synthesis and sodium phenate 14.3mg (0.1 mmoles in synthesis example 3 in this test tube You).

This test tube was maintained 200 DEG C after 30 minutes, by its benzofuran -2 of high effective liquid chromatography for measuring, 3- diketone 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 the sodium hydroxide-phenol solution of 0.9 weight %.

In possessing the test tube of stirrer and thermometer, after loading diphenyl carbonate 20.0g, it is 200 with oil bath heating to interior temperature ℃.

In this test tube, add benzofuran -2 of synthesis in synthesis example 3, the hydrogen-oxygen of 3- diketone 5.5mg and 0.9 weight % Change sodium-phenol solution 0.6g (as sodium hydroxide, be 0.1 mM).This test tube was maintained 200 DEG C after 30 minutes, passes through Its benzofuran -2 of high effective liquid chromatography for measuring, during the concentration of 3- diketone, are 86 weight ppm.Resolution ratio is 68.7%.

[comparative example 9]

In possessing the test tube of stirrer and thermometer, after loading diphenyl carbonate 20.0g, it is 200 with oil bath heating to interior temperature ℃.Add the benzofuran -2,3- diketone 2.8mg of synthesis in synthesis example 3 in this test tube.

This test tube was maintained 200 DEG C after 30 minutes, by its benzofuran -2 of high effective liquid chromatography for measuring, 3- diketone 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]

Reference example 5～7 and the result of comparative example 9

Confirmed by table 13, by the presence of alkaline matter, promote benzofuran -2, the heating of 3- diketone lead to point Solution.Additionally, than the reference example 5 of the sodium hydrate aqueous solution using high concentration, using the sodium hydroxide-phenol solution of low concentration The resolution ratio of reference example 7 is higher, it is thus regarded that, during using solvent, preferably the such dissolubility to diphenyl carbonate of phenol is relatively High solvent.

Confirm in above-described embodiment, furan based compound contained in thick diphenyl carbonate, by with alkali compoundss Contact and reduce, thus the manufacture method by the diphenyl carbonate of the present invention, can efficiently and stably use easy method continuous Manufacture highly purified diphenyl carbonate.

[reference example 8]

By possess thermometer, blender, distillate pipe and accepter 500 milliliters of a complete set of tubular type detachable flask in, Load phenostal 250g (1 mole), 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 13g (30 mMs), by detachable flask Inside it is heated to 150 DEG C, make uniform solution (visual).

Next, being blown into 12 mMs of hydrogen chloride gas in this detachable flask, heat up.If in detachable flask If reaching 230 DEG C, the carbon monoxide producing in detachable flask is extruded at ambient pressure by nitrogen, while with It is maintained at 230 DEG C of state response 6 hours.

Slowly it is decompressed to 10Torr by making this 6 hours reacted reactant liquors, in the bottom temperature by detachable flask Degree maintains in the state of being reduced to 180 DEG C, obtains thick diphenyl carbonate 217g as fraction.Additionally, now, detachable flask Bottom liquid, visually be in uniform state.

By the composition of 6 hours reacted reactant liquors before and thick diphenyl carbonate, by high performance liquid chromatography Analysis.As a result, in 6 hours reacted reactant liquors, diphenyl carbonate is 94 weight %, phenostal is 400 weight ppm (conversion ratio of phenostal is 99.97%).

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

[reference example 9]

In the Dropping funnel of 200 milliliters of a complete set of tubular type possessing nitrogen ingress pipe, load 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 13g (30 mMs) and Mitsubishi Chemical diphenyl carbonate 10g (47 mMs), supplies nitrogen, while at 150 DEG C Make uniform solution.

In the detachable flask of 500 milliliters of a complete set of tubular type possessing this Dropping funnel, thermometer and blender, dress Enter phenostal 150g (619 mMs), 150 DEG C will be heated in detachable flask.

Next, in this detachable flask, supply the carbon of 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride from this Dropping funnel After diphenyl phthalate solution, it is blown into 12 mMs of hydrogen chloride gas, is warming up to 230 DEG C.While by by reacting the oxidation producing Carbon is removed to outside reaction system with nitrogen at ambient pressure, carries out reaction in 5 hours with the state being maintained at 230 DEG C.

By the part taking-up of reacted liquid, when composition analysis are carried out 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, load 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 200g (0.46 mole), n-butyl alcohol 100g and 28 weight % hydrochloric acid 700g, are heated to 90 DEG C, under nitrogen atmosphere in uniform solution.Then, by being cooled to eggplant type flask Room temperature and obtain serosity.This serosity is filtered by glass filter, obtains solid 190g.

30g in the crystallization obtaining is moved to 500cm³Eggplant type flask in.Possessed by being arranged on this eggplant type flask In the rotary evaporator of oil bath, by oil bath heating to 70 DEG C, it is dried 2 hours under pressure 10Torr, obtains 25g solid.

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

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

Additionally, the solid obtaining is white particle, its volume density is 0.48g cm³, particle diameter be 180 μm.

Next, use the adduct of this adduction rate 95% as catalyst, the decarbonylation base carrying out phenostal is anti- Should.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, implements similarly to Example 1, carries out de-carbonyl reaction.Terminate 30 minutes from the supply of adduct Afterwards, by the part taking-up of the liquid in there-necked flask, composition analysis are carried out by high performance liquid chromatography.

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

[embodiment 34]

30g (0.46 mole) in the adduct that will obtain in embodiment 33 moves to 500 milliliters of eggplant type flask, and this eggplant shape is burnt Bottle is arranged in the rotary evaporator possessing oil bath., it is dried 2 hours under pressure 10Torr to 130 DEG C by by oil bath heating, Obtain 25g solid.

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

Herein, if the amount of this chlorine is considered as the amount (ignoring the hydrogen timesharing contained by hydrogen chloride) of the hydrogen chloride contained by adduct, The amount of the 4- 2-methyl-2-phenylpropane base triphenylphosphine contained by this solid is 25g × (1-0.127)=21.8g (0.055 mole), adduct The amount of the chlorine contained by hydrogen chloride is 0.090 mole -0.055 mole=0.035 mole, thus confirms that this solid is adduction rate 64% The 4- 2-methyl-2-phenylpropane base triphenylphosphine of (0.035 mole of ÷ 0.055 mole × 100) and the adduct of hydrogen chloride.Additionally, obtain consolidates Body is white particle, and its volume density is 0.45g cm³, particle diameter be 142 μm.

Next, use the adduct of this adduction rate 64% as catalyst, the decarbonylation base implementing phenostal is anti- Should.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, implements similarly to Example 1, carries out de-carbonyl reaction.Terminate 30 minutes from the supply of adduct Afterwards, by the part taking-up of the liquid in there-necked flask, composition analysis are carried out by high performance liquid chromatography.

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

[embodiment 35]

30g (0.06 mole) in the adduct that will obtain in embodiment 33 moves to 500 milliliters of eggplant type flask, and this eggplant shape is burnt Bottle is arranged in the rotary evaporator possessing oil bath., it is dried 2 hours under pressure 10Torr to 150 DEG C by by oil bath heating, Obtain 25g solid.

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

Herein, if the amount of this chlorine is considered as the amount (ignoring the hydrogen timesharing contained by hydrogen chloride) of the hydrogen chloride contained by adduct, Then the amount of the 4- 2-methyl-2-phenylpropane base triphenylphosphine contained by this solid is 25g × (1-0.102)=22.5g (0.057 mole), adduct The chlorine contained by hydrogen chloride amount be 0.073 mole -0.057 mole=0.016 mole, thus confirm this solid be adduction rate The 4- 2-methyl-2-phenylpropane base triphenylphosphine of 28% (0.016 mole of ÷ 0.057 mole × 100) and the adduct of hydrogen chloride.Additionally, obtaining Solid be white particle, its volume density be 0.45g cm³, particle diameter be 134 μm.

Next, use the adduct of this adduction rate 28% as catalyst, the decarbonylation base implementing phenostal is anti- Should.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, implements similarly to Example 1, carries out de-carbonyl reaction.

After the supply of adduct terminates 30 minutes, by the part taking-up of the liquid in there-necked flask, by efficient liquid Phase chromatography carries out composition analysis.As a result, phenol 0.6 weight %, phenostal 30.2 weight %, diphenyl carbonate 55.2 Weight %.Herein, the conversion ratio of phenostal is 70%.

[embodiment 36]

30g (0.06 mole) in the adduct that will obtain in embodiment 33 moves to 500 milliliters of eggplant type flask, and this eggplant shape is burnt Bottle is arranged in the rotary evaporator possessing oil bath., it is dried 2 hours under pressure 10Torr to 200 DEG C by by oil bath heating, Obtain 25g solid.

The knot that the potential difference titration appratuss " AT-610 " of the cl concn capital of a country Electronics Industry Company of this solid are analyzed Fruit is 8.6 weight %.Therefore, the amount of contained chlorine in this solid is 25g × 0.086=2.2g (0.062 mole).Herein, if The amount of this chlorine is considered as the amount (ignoring the hydrogen timesharing contained by hydrogen chloride) of the hydrogen chloride contained by adduct, the then 4- contained by this solid The amount of 2-methyl-2-phenylpropane base triphenylphosphine is 25g × (1-0.086)=22.9g (0.058 mole), the chlorine contained by the hydrogen chloride of adduct Amount be 0.062 mole -0.058 mole=0.004 mole, thus confirm this solid be adduction rate 7% (0.004 mole of ÷ 0.058 mole × 100) 4- 2-methyl-2-phenylpropane base triphenylphosphine and the adduct of hydrogen chloride.Additionally, the solid obtaining is white Grain, its volume density is 0.41g cm³, particle diameter be 110 μm.

Next, use the adduct of this adduction rate 7% as catalyst, the decarbonylation base implementing phenostal is anti- Should.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, implements similarly to Example 1, carries out de-carbonyl reaction.Terminate 30 minutes from the supply of adduct Afterwards, by the part taking-up of the liquid in there-necked flask, composition analysis are carried out by high performance liquid chromatography.

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

[embodiment 37]

In 500 milliliters of heart-shaped flask, after loading 4- 2-methyl-2-phenylpropane base triphenyl phosphine dichloride 30g (0.070 mole), make hydrogen chloride Gas circulates 1 hour to this flask, is replaced into hydrogen chloride gas by flask.So that the state of hydrogen chloride gas circulation, should Flask impregnated in the Dewar flask being incorporated with liquid nitrogen.Hydrogen chloride gas in flask are liquefied, and the composition in flask is in 100 milliliters Nebulousurine slurry.

Keep this state, after so that the state that there is 100 milliliters of the serosity of nebulousurine is maintained 2 hours, stop hydrogen chloride gas Circulation, making nitrogen circulate, while being to slowly warm up to room temperature, when the hydrogen halides in flask are driven out of, obtaining 25g solid.

The knot that the potential difference titration appratuss " AT-610 " of the cl concn capital of a country Electronics Industry Company of this solid are analyzed Fruit is 14.5 weight %.Therefore, the amount of contained chlorine in this solid is 25g × 0.145=3.6g (0.101 mole).Herein, if The amount of this chlorine is considered as the amount (ignoring the hydrogen timesharing contained by hydrogen chloride) of the hydrogen chloride contained by adduct, the then 4- contained by this solid The amount of 2-methyl-2-phenylpropane base triphenylphosphine is 25g × (1-0.145)=21.4g (0.054 mole), the chlorine contained by the hydrogen chloride of adduct Amount be 0.101 mole -0.054 mole=0.047 mole, thus confirm this solid be adduction rate 87% (0.047 mole of ÷ 0.054 mole × 100) 4- 2-methyl-2-phenylpropane base triphenylphosphine and the adduct of hydrogen chloride.Additionally, the solid obtaining is white powder Body, its volume density is 0.41g cm³, particle diameter be 45 μm.

Next, use the adduct of this adduction rate 87% as catalyst, the decarbonylation base implementing phenostal is anti- Should.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, implements similarly to Example 1, carries out de-carbonyl reaction.

After the supply of adduct terminates 30 minutes, by the part taking-up of the liquid in there-necked flask, by efficient liquid Phase chromatography carries out composition analysis.As a result, phenol 1.3 weight %, phenostal 51.2 weight %, 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, particle diameter, volume density, carry out the conversion ratio of phenostal during de-carbonyl reaction, reaction Liquid composition afterwards

It is unequivocally established by table 14, by asymmetric four aryl halogenation phosphines being made the adduct with hydrogen chloride, by this particle diameter Larger, volume density is higher, easy operation, and, during as catalyst using carrying out de-carbonyl reaction, phenostal Conversion ratio higher, the by-product amount of phenol is less, and the amount of unreacted phenostal is less, the generation quantitative change of diphenyl carbonate Many.

Especially, also confirm that the larger catalyst of particle diameter shows excellent reaction achievement.Use the present invention additionally, also confirming that The asymmetric adduct that the manufacture method of the adduct being related to manufactures, particle diameter is larger, shows excellent reaction achievement.

The present invention is described in detail with specific mode, but can carry out various without departing from the intent and scope of the present invention The change of various kinds and deformation, this is very clear to those skilled in the art.Additionally, the application is based on 2014 5 Filed in the moon 23, Japanese patent application (Patent 2014-107284), Japanese patent application filed in 14 days July in 2014 are (special Be willing to 2014-144298), Japanese patent application (Patent 2014-144297), October 28 in 2014 filed in 14 days July in 2014 Japanese patent application (Patent 2014-219463), Japanese patent application (Patent filed in 28 days October in 2014 filed in day 2014-219464), by quoting, to quote it whole.

Claims

1. a kind of manufacture method of diphenyl carbonate, is to carry out decarbonylation under conditions of there is catalyst by making phenostal Base reaction manufactures the method for diphenyl carbonate it is characterised in that using described catalyst as asymmetric four aryl halogenation phosphines and halogen Change the adduct supply of hydrogen.

2. the manufacture method of diphenyl carbonate according to claim 1, the mean diameter of described adduct is more than 50 μm, Below 1mm.

3. the manufacture method of the diphenyl carbonate recorded according to claim 1 or 2, described adduct is by making asymmetric four virtues Base halogenation phosphine and hydrogen halides are dissolved in obtained from crystallize after polar organic solvent.

4. the manufacture method of the diphenyl carbonate of wantonly 1 record according to claims 1 to 3, described asymmetric four aryl halogenations Phosphine does not have benzylic protons.

5. the manufacture method of the diphenyl carbonate of wantonly 1 record according to Claims 1-4, described adduct is 4- 2-methyl-2-phenylpropane Base triphenyl phosphine dichloride and the adduct of hydrogen chloride.

6. the manufacture method of the diphenyl carbonate of wantonly 1 record according to claim 1 to 5, exhausted during described de-carbonyl reaction To pressure be more than 0.105MPa, below 10MPa.

7. the manufacture method of the diphenyl carbonate of wantonly 1 record according to claim 1 to 6, from de-carbonyl reaction device Bottom is with 0.00001m s^-1Above 0.01m s^-1Following superficial linear velocity supplies nonactive gas to described de-carbonyl reaction Body, carries out de-carbonyl reaction.

8. the manufacture method of the diphenyl carbonate of wantonly 1 record according to claim 1 to 7 is it is characterised in that described catalyst Dissolve in diphenyl carbonate, after described de-carbonyl reaction is carried out with conversion ratio more than 96%, contained in reactant liquor by making More than 50 weight % of diphenyl carbonate evaporate and after taking-up, remaining reactant liquor is supplied to described de-carbonyl reaction.

9. the manufacture method of the diphenyl carbonate of wantonly 1 record according to claim 1 to 8 is it is characterised in that by described catalysis Agent is supplied with the state being dissolved in described diphenyl carbonate.

10. the manufacture method of the diphenyl carbonate of wantonly 1 record according to claim 1 to 8 is it is characterised in that described oxalic acid Diphenyl ester contains the carboxylic acid phenyl ester represented by following formulas (5) of more than 0.076 weight %, amount below 10 weight %；

[changing 13]

In formula, n is 1 or 2.

The manufacture method of 11. diphenyl carbonates according to wantonly 1 record of claim 1 to 10 is it is characterised in that make by institute State the diphenyl carbonate that decarbonylated reaction obtains to contact with alkali compoundss.

A kind of 12. manufacture methods of diphenyl carbonate are it is characterised in that contain following 1st～3 operations successively；

1st operation：Diphenyl carbonate is manufactured by the manufacture method of the diphenyl carbonate of wantonly 1 record of claim 1 to 11 Operation,

A kind of 13. recovery methods of catalyst, are for carrying out diphenyl carbonate by the de-carbonyl reaction of phenostal The recovery method of the catalyst manufacturing is it is characterised in that described catalyst is asymmetric four aryl halogenation phosphines and/or asymmetric four The adduct of aryl halogenation phosphine and hydrogen halides, by making polar organic solvent and hydrogen halide, and from described de-carbonyl reaction Obtain the contact of the residual liquid after the composition containing diphenyl carbonate in reactant liquor afterwards, then contact with water, and obtain precipitate, will Catalyst reclaims as described precipitate.

A kind of 14. recovery methods of catalyst, are for carrying out diphenyl carbonate by the de-carbonyl reaction of phenostal The recovery method of the catalyst manufacturing it is characterised in that described catalyst be four aryl halogenation phosphines and/or four aryl halogenation phosphines with The adduct of hydrogen halides, makes the residual liquid after obtaining the composition containing diphenyl carbonate from the reactant liquor after described de-carbonyl reaction After contact polar organic solvent and hydrogen halides, contained catalyst in the described residual liquid of recovery, as catalyst recovery process, with When, reclaim described polar organic solvent, be reused in described catalyst recovery process.

A kind of 15. manufacture methods of diphenyl carbonate, are to manufacture diphenyl carbonate by the de-carbonyl reaction of phenostal Method it is characterised in that as catalyst, using the catalysis reclaimed by the recovery method that claim 13 or 14 is recorded Agent.

A kind of 18. manufacture methods of Merlon, are to be urged there is ester exchange by making diphenyl carbonate and dihydroxy compounds Under conditions of agent polycondensation manufacture Merlon method it is characterised in that by claim 1 to 12 and 15 appoint After the manufacture method of the diphenyl carbonate of 1 record manufactures described diphenyl carbonate, with described dihydroxy compounds polycondensation.

A kind of 19. diphenyl carbonates, are the manufactures of the diphenyl carbonate of wantonly 1 record by claim 1 to 12 and 15 Method obtains.

A kind of 20. Merlon, are to be existed by making aromatic dihydroxy compound and the diphenyl carbonate of claim 19 record Have what polycondensation under conditions of ester exchange catalyst obtained.