CN108395374A - The preparation method of diaryl carbonate - Google Patents
The preparation method of diaryl carbonate Download PDFInfo
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- CN108395374A CN108395374A CN201710760626.6A CN201710760626A CN108395374A CN 108395374 A CN108395374 A CN 108395374A CN 201710760626 A CN201710760626 A CN 201710760626A CN 108395374 A CN108395374 A CN 108395374A
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- carbonate
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- diaryl carbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
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Abstract
The present invention provides the preparation method of diaryl carbonate, and this method can remove the existing water for causing catalyst degradation in diaryl carbonate manufacturing process without using special device.The manufacturing method of the diaryl carbonate of the present invention is the method for the dialkyl carbonate manufacture diaryl carbonate of the compound represented by aromatic monohydroxy compound and comprising following formula (1) in the presence of a catalyst, wherein, for above-mentioned dialkyl carbonate, the compound represented by the formula (1) containing 0.01 mass of mass ppm~1000 ppm in the dialkyl carbonate as raw material is (in formula (1), R1, R2, R4 each independently represents the aliphatic group that carbon atom number is 1~20, R3 indicates the aliphatic group that hydrogen atom or carbon atom number are 1~20).
Description
Technical field
The present invention relates to the industrially preparing process of diaryl carbonate.More particularly it relates to remove effectively
The method of existing water in diaryl carbonate manufacturing process.
Background technology
Known diaryl carbonate is by dialkyl carbonate or phosgene are with reacting for aromatic monohydroxy compound
Manufacture.
In method of the manufacture as the dialkyl carbonate of raw material, there are various methods.Representative dialkyl carbonate
For dimethyl carbonate, as the preparation method of the dimethyl carbonate, such as there are following methods：By carbon dioxide, ethylene oxide and methanol
Manufacture the method (hereinafter referred to as " EO methods ") of dimethyl carbonate；Dimethyl carbonate is manufactured by carbon dioxide, propylene oxide and methanol
Method (hereinafter referred to as " PO methods ")；And the method for dimethyl carbonate is manufactured (hereinafter referred to as by carbon monoxide, oxygen and methanol
" CO methods ") etc..
In addition, further developed following methods in recent years：Methyl nitrite is manufactured by nitric oxide, oxygen and methanol, makes to lead to
Crossing makes the methyl nitrite with reaction of carbon monoxide to manufacture the method (hereinafter referred to as " MN methods ") of dimethyl carbonate；By urea and first
Alcohol manufactures the method (hereinafter referred to as " direct urea method ", hereinafter referred to as " indirect urea method ") of dimethyl carbonate.
The method for making dialkyl carbonate react with aromatic monohydroxy compound to manufacture diaryl carbonate is carbonic acid
The representative manufacture method of diaryl ester.But if there are water in diaryl carbonate manufacturing process, having can cause to urge
The problem of agent deteriorates.There are the reason of water it is due in aromatic monohydroxy compound in diaryl carbonate manufacturing process
Reaction of formation is secondary on the way to generate water, and the water which generates is included in as in the aromatic monohydroxy compound of raw material, direct quilt
In supply to diaryl carbonate manufacturing process.
Existing water can cause to use in diaryl carbonate manufacturing process in known diaryl carbonate manufacturing process
Catalyst degradation, thus the reduction of reaction efficiency can be incurred namely incur the production quantity reduction of finished product diaryl carbonate.Cause
This, studies the method for removing existing water in diaryl carbonate manufacturing process.For example, in patent document 1
The method that water is distilled off in the leading portion in reactor is described, is described in patent document 2 using the vapour for enclosing steam stripping agent
Put forward the method that column removes water.
Existing technical literature
Patent document 1：Japanese Unexamined Patent Publication 2002-322130 bulletins
Patent document 2：Japanese Unexamined Patent Application Publication 2002-525346 bulletins
Invention content
Problems to be solved by the invention
But using the method for patent document 1 or patent document 2 although can remove in diaryl carbonate manufacturing process
Existing water, but special device is required in both methods.
Present invention is made in view of the above circumstances, project be to provide without using leading portion be distilled off or vapour
The method that existing water in diaryl carbonate manufacturing process is easily removed in the case of carrying the special devices such as column.
The means to solve the problem
The present inventor has made intensive studies in order to solve the above problems, as a result, it has been found that, pass through the carbonic acid for making to be used as raw material
There are the compounds represented by the following general formula (1) of 0.01 mass ppm~1,000 mass ppm in dialkyl ester, without using spy
The water in diaryl carbonate manufacturing process can be removed effectively in the case of different device, so as to complete the present invention.
That is, the present invention is as described below.
[1]
A kind of manufacturing method of diaryl carbonate, be in the presence of a catalyst by aromatic monohydroxy compound and
Including the method that the dialkyl carbonate of the compound represented by following formula (1) manufactures diaryl carbonate, wherein
For above-mentioned dialkyl carbonate, 0.01 mass ppm~1000 are contained in the dialkyl carbonate as raw material
Compound represented by the above-mentioned formula (1) of quality ppm.
【Change 1】
(in formula (1), R1, R2, R4 each independently represent the aliphatic group that carbon atom number is 1~20, and R3 indicates that hydrogen is former
The aliphatic group that son or carbon atom number are 1~20.)
[2]
The manufacturing method of diaryl carbonate as described in [1], wherein the compound represented by above-mentioned formula (1) is two
Alkoxy alkane.
[3] manufacturing method of the diaryl carbonate as described in [2], wherein above-mentioned dialkoxyalkane is dimethoxy
Base propane.
[4]
The manufacturing method of diaryl carbonate as described in any one of [1]~[3], wherein above-mentioned dialkyl carbonate
For dimethyl carbonate.
The effect of invention
The present invention can remove effectively the water for causing catalyst degradation in diaryl carbonate manufacturing process, can prevent
The production quantity of diaryl carbonate caused by catalyst degradation reduces.
Description of the drawings
Fig. 1 be the diaryl carbonate for showing present embodiment manufacturing method in the stream of an example of manufacturing device that uses
Cheng Tu.
Symbol description
1：Supply pipeline of the dialkyl carbonate into the 1st continuous multi-stage destilling tower 101
2：The bottom of tower ingredient of 1st continuous multi-stage destilling tower 101 extracts pipeline out
3：The bottom of tower ingredient of 2nd continuous multi-stage destilling tower 102 extracts pipeline out
4：The tower top ingredient of 2nd continuous multi-stage destilling tower 102 extracts pipeline out
5：The tower top ingredient of 1st continuous multi-stage destilling tower 101 extracts pipeline out
6：The bottom of tower ingredient of 3rd continuous multi-stage destilling tower 103 extracts pipeline out
7：The tower top ingredient of 3rd continuous multi-stage destilling tower 103 extracts pipeline out
8：Supply pipeline of the aromatic monohydroxy compound into the 2nd continuous multi-stage destilling tower 102
9：Liquid supply tube line into the 2nd continuous multi-stage destilling tower 102
101：1st continuous multi-stage destilling tower
102：2nd continuous multi-stage destilling tower
103：3rd continuous multi-stage destilling tower
Specific implementation mode
The mode (hereinafter referred to as " present embodiment ") for implementing the present application is further carried out specifically below
It is bright, but the present invention is not limited to this, can carry out various modifications within a range that does not deviate from its main point.
Present embodiment provides a kind of manufacturing method of diaryl carbonate, is in the presence of a catalyst by aromatic series
Monohydroxy compound and comprising the compound represented by formula (1) dialkyl carbonate manufacture diaryl carbonate method,
In,
For above-mentioned dialkyl carbonate, 0.01 mass ppm~1000 are contained in the dialkyl carbonate as raw material
Compound represented by the above-mentioned formula (1) of quality ppm.
【Change 2】
(in formula (1), R1, R2, R4 each independently represent carbon atom number be 1~20 aliphatic group, R3 indicate hydrogen or
The aliphatic group that carbon atom number is 1~20.)
The aliphatic group for being 1~20 as carbon atom number, for example, alkyl, alkenyl, alkynyl, aryl etc..
As alkyl, for example, methyl, ethyl, propyl (including Isomers), butyl (including Isomers),
Amyl (include Isomers), hexyl (including Isomers), heptyl (including Isomers), octyl (including Isomers),
The chain-like alkyls such as nonyl (including Isomers), decyl (including Isomers), cyclohexyl methyl；Cyclopropyl, cyclobutyl, ring penta
The cyclic alkyls such as base, cyclohexyl, suberyl；Etc..
As alkenyl, for example, vinyl, acrylic (including Isomers), cyclobutenyl (include each isomery
Body), pentenyl (include Isomers), hexenyl (including Isomers) etc..
As alkynyl, for example, acetenyl, propinyl (including Isomers), butynyl (include each isomery
Body), pentynyl (include Isomers), hexin base (including Isomers) etc..
As aryl, for example, phenyl, naphthalene etc..
Compound represented by formula (1) may be used singly or in combination of two or more.
In the aliphatic group that carbon atom number is 1~20, chain-like alkyl, alkenyl and alkynes that preferably carbon atom number is 1~6
Base, the chain-like alkyl that further preferred carbon atom number is 1~3.
As the compound represented by above-mentioned formula (1), such as it is entirely carbon atom that can suitably enumerate R1, R2, R3, R4
The 2,2- dimethoxy propanes for the aliphatic group that number is 1；R1, R4 be carbon atom number be 1 aliphatic group, R2 be carbon atom
Several aliphatic groups for being 2, R3 are the dialkoxyalkanes of 1,1- dimethoxy propanes of hydrogen etc..It is excellent in dialkoxyalkane
Select dimethoxy propane.
【Change 3】
2,2- dimethoxy propanes
【Change 4】
1,1- dimethoxy propanes
In dialkyl carbonate in present embodiment, 2,2-dimethoxypropane and 1,1- dimethoxy propanes are in conduct
0.01 mass of mass ppm~1000 ppm is preferably comprised in the dialkyl carbonate of raw material.To 2,2- dimethoxy propanes and 1,1-
The mass ratio of dimethoxy propane is not particularly limited, and preferably 20：1~1：20,10 are more preferably：5~10：1.
It is believed that the compound represented by above-mentioned formula (1) removes existing water in diaryl carbonate manufacturing process
Mechanism is as follows.It should be noted that hereinafter to be said for 1,1- dimethoxy propanes and 2,2-dimethoxypropane
It is bright, but present embodiment is not limited to these dialkoxyalkanes.
1,1- dimethylpropane is reacted according to following reaction equations with water, generates hemiacetal.
【Change 5】
2,2- dimethylpropanes generate hemiacetal according to following reaction equation and reaction of moisture.
【Change 6】
In addition, the hemiacetal generated forms aldehydes and ketone according to following reaction equation separating methanols.
【Change 7】
The aldehydes and ketone generated by above-mentioned reaction is used to refine from what is be arranged in diaryl carbonate manufacturing process
It is removed in destilling tower of diaryl carbonate etc. etc..Therefore, R1, R2, R3, R4 in the compound represented by above-mentioned formula (1)
Carbon atom number is fewer, and water is lower with the boiling point of the reaction product of the compound represented by above-mentioned formula (1), thus is easy to utilize steaming
Evaporate the separation such as tower.
Compound represented by above-mentioned formula (1) can add the dialkyl carbonate in the raw material as diaryl carbonate
In, it can also will be represented by for example following secondary above-mentioned formulas (1) generated of reaction in the process of manufacture dialkyl carbonate
Compound remains in oxide spinel dimethyl ester, reduces distillation separative efficiency, load.
【Change 8】
A concentration of 0.01 mass ppm~1000 of the compound represented by above-mentioned formula (1) contained by dialkyl carbonate
Quality ppm, preferably 1 mass of mass ppm~200 ppm.Above-mentioned formula (1) if represented by compound concentration be less than 0.01 weight
Ppm is measured, then remains water in diaryl carbonate manufacturing process, has the effect of fully obtaining the possibility of the present invention
Property.Above-mentioned formula (1) if represented by the concentration of compound be higher than 1000 mass ppm, the compound represented by above-mentioned formula (1) with
Side reaction occurs for aromatic monohydroxy compound etc., and reaction product is mixed into as impurity in diaryl carbonate, makes carbon
The purity of sour diaryl ester reduces, additionally may be for the aromatic copolycarbonate that is produced as raw material using diaryl carbonate
Tone etc. bring harmful effect.
Dialkyl carbonate as raw material can be manufactured by the either method in following methods：By carbon dioxide, epoxy
The method (EO methods) of ethane and methanol manufacture dimethyl carbonate；Dimethyl carbonate is manufactured by carbon dioxide, propylene oxide and methanol
Method (PO methods)；The method (CO methods) of dimethyl carbonate is manufactured by carbon monoxide, oxygen and methanol；By nitric oxide, oxygen and first
Alcohol manufactures methyl nitrite, and the method (MN of dimethyl carbonate is manufactured by making the methyl nitrite with reaction of carbon monoxide
Method)；The method (direct urea method, indirect urea method) of dimethyl carbonate is manufactured by urea and methanol, the dialkyl carbonate is by formula (2) institute
It indicates.
RaOCOORa (2)
Herein, RaIndicate the alcyl that alkyl, carbon atom number that carbon atom number is 1~10 are 3~10, carbon atom number 6
~10 aralkyl.As such Ra, for example, methyl, ethyl, propyl (including Isomers), allyl, fourth
Base (include Isomers), cyclobutenyl (including Isomers), amyl (including Isomers), hexyl (including Isomers),
Heptyl (include Isomers), octyl (including Isomers), nonyl (including Isomers), decyl (including Isomers),
The alkyl such as cyclohexyl methyl；The alcyls such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl；Benzyl, phenethyl (include
Isomers), phenylpropyl (include Isomers), benzene butyl (including Isomers), methylbenzyl (including Isomers) etc.
Aralkyl.It should be noted that these alkyl, alcyl, aralkyl can replace have other substituent groups, such as low alkyl group,
Lower alkoxy, cyano, halogen etc., it is possible to have unsaturated bond.
As with such RaDialkyl carbonate, for example, dimethyl carbonate, diethyl carbonate, carbonic acid
Dipropyl (including Isomers), diallyl carbonate, carbonic acid dibutene ester (including Isomers), dibutyl carbonate (include
Isomers), diamyl carbonate (include Isomers), carbonic acid dihexyl (including Isomers), two heptyl ester of carbonic acid is (comprising each
Isomers), carbonic acid dioctyl ester (include Isomers), two nonyl ester of carbonic acid (including Isomers), carbonic acid didecyl is (comprising different
Structure body), two ring pentyl ester of carbonic acid, dicyclohexyl carbonate, two cycloheptyl ester of carbonic acid, dimethyl benzyl, dipheryl carbonate ethyl ester is (comprising different
Structure body), carbonic acid two (phenylpropyl) ester (include Isomers), carbonic acid two (benzene butyl) ester (including Isomers), two (chlorine of carbonic acid
Benzyl) ester (include Isomers), carbonic acid two (methoxy-benzyl) ester (including Isomers), carbonic acid two (methoxy)
Ester, carbonic acid two (methoxy ethyl) ester (including Isomers), carbonic acid two (chloroethyl) ester (including Isomers), carbonic acid two
(cyano ethyl) ester (including Isomers) etc..
Among them, preferred R in the present embodimentaCarbon atom number to be halogen-free is formed by 4 alkyl below
Dialkyl carbonate, more preferably dimethyl carbonate.In addition, further preferred dialkyl carbonate is substantially to be free of
The dialkyl carbonate produced in the state of halogen, for example, by be substantially free of halogen alkylene carbonates and substantially not
The dialkyl carbonate that halogen-containing alcohol produces.
In addition, the impurity such as ethers, esters, alcohols, carbonates, alkanes can be contained in dialkyl carbonate.Make
It is not particularly limited for the impurity in above-mentioned dialkyl carbonate, for example, impurity below.
0.01 mass of mass ppm~50 ppm of dimethyl ether
0.01 mass of mass ppm~50 ppm of 2- methoxyl groups propylene
0.01 mass of mass ppm~50 ppm of 1,1- dimethoxy-ethanes
0.01 mass of mass ppm~50,000 ppm of methanol
0.01 mass of mass ppm~50 ppm of methylpropionate
0.01 mass of mass ppm~50 ppm of 3,3- dimethoxy -1- propylene
0.01 mass of mass ppm~50 ppm of 1,4- dioxane
0.01 mass of mass ppm~500 ppm of methyl ethyl carbonate
Bis- 0.01 mass of mass ppm~500 ppm of (2- methoxy ethyls) ester of carbonic acid
0.01 mass of mass ppm~50 ppm of toluene
0.01 mass of mass ppm~50 ppm of 3- methyl butyrates
0.01 mass of mass ppm~50 ppm of 2- ethyl -4- methyl-1,3-dioxy heterocyclic pentenes
0.01 mass of mass ppm~50 ppm of cycloheptatriene
0.01 mass of mass ppm~50 ppm of 1- methoxy-2-propanols
0.01 mass of mass ppm~50 ppm of diethylene glycol diethyl ether
0.01 mass of mass ppm~50 ppm of dodecane
0.01 mass of mass ppm~50 ppm of the tetradecane
0.01 mass of mass ppm~50 ppm of hexadecane
0.01 mass of mass ppm~50 ppm of octadecane
0.01 mass of mass ppm~50 ppm of icosane
As long as in present embodiment as the aromatic monohydroxy compound hydroxyl Direct Bonding of raw material on aromatic radical
Compound be just not particularly limited, such as can suitably enumerate the compound represented by following formula (3).
Ar3OH(3)
(in formula (3), Ar3Indicate that carbon atom number is 5~30 aromatic radical.)
(include as the compound represented by formula (3), such as using phenol, cresols (including Isomers), dimethlbenzene
Isomers), pseudocuminol (include Isomers), tetramethyl phenol (including Isomers), ethyl -phenol is (comprising different
Structure body), propylphenol (include Isomers), butylphenol (including Isomers), diethyl phenol (including Isomers),
Methylethyl phenol (including Isomers), methyl-propyl phenol (including Isomers), dipropyl phenol (include each isomery
Body), methyl butyl phenol (include Isomers), amyl phenol (including Isomers), hexylphenol (including Isomers),
The various alkylbenzene phenols such as cyclohexylphenol (including Isomers)；Metoxyphenol (including Isomers), thanatol
Various alkoxy benzene phenols such as (including Isomers)；The aralkylphenols classes such as phenylpropyl phenol (including Isomers)；Naphthols
(including Isomers) and various substituted naphthol classes；Pyridone (including Isomers), Hydroxycoumarin (include each isomery
Body), the heteroaromatic monohydroxy compound class such as oxyquinoline (include Isomers) etc..
These aromatic monohydroxy compounds can use a kind or be used in the form of the mixture more than it.At these
In aromatic monohydroxy compound, preferred Ar in the present embodiment3It is that the aromatic radical that carbon atom number is 6 to 10 is formed by virtue
Fragrant race's monohydroxy compound, more preferably phenol.In addition, in these aromatic monohydroxy compounds, it is excellent in the present embodiment
Choosing is substantially free of the aromatic monohydroxy compound of halogen.
In addition, water is usually contained with the range of 0 mass of mass ppm~500 ppm in aromatic monohydroxy compound, but
The effect of the present invention will not be interfered.
It is usually the compound represented by following formula (4) using the diaryl carbonate that present embodiment produces.
Ar4-OCOO-Ar5(4)
(in formula, Ar4、Ar5Each independently represent 1 valence aromatic radical.)
Ar4And Ar5In 1 valence fragrance basis representation, 1 valence carbon-ring type or hetero ring type aromatic radical, in the Ar4、Ar5In, 1 with
On hydrogen atom the reaction in the method for the manufacture diaryl carbonate of present embodiment will not can be affected its
He is replaced substituent group, other substituent groups be, for example, halogen atom, carbon atom number be 1~10 alkyl, carbon atom number be 1~10
Alkoxy, phenyl, phenoxy group, vinyl, cyano, ester group, amide groups, nitro etc..Ar4、Ar5Can it is identical, can not also
Together.As 1 valence aromatic radical Ar4And Ar5Typical example, phenyl, naphthalene, xenyl, pyridyl group can be enumerated.They can be upper
1 kind or more of the substituent group stated is replaced.As preferred Ar4And Ar5, such as the base represented by following formula (5) can be enumerated respectively
Group.
【Change 9】
It is the substituted or non-substituted diphenyl carbonate represented by following formula (6) as preferred diaryl carbonate.
【Change 10】
(in formula, R9And R10Each independently represent hydrogen atom, the alkyl that carbon atom number is 1~10, carbon atom number be 1~
10 alkoxy, the naphthenic base that ring carbons number is 5~10 or phenyl, the integer that p and q are 1~5, when p is 2 or more, each R9
Respectively can be different, when q is 2 or more, each R10It respectively can be different.)
In the diaryl carbonate, preferably non-substituted diphenyl carbonate or dimethyl benzyl, dimethyl dicarbonate butyl phenyl ester
Etc the symmetric forms diaryl carbonate such as low alkyl group substituted diphenylamine base carbonic ester, more preferably non-substituted diphenyl carbonate.
These diaryl carbonates esters may be used alone, or two or more kinds may be used in combination.
Amount ratio of the dialkyl carbonate that raw material as present embodiment uses relative to aromatic monohydroxy compound
It is preferably 0.1~10 with molar ratio computing.It is outside if the range, then residual relative to the regulation output of target diaryl carbonate
The unreacted raw material stayed increases, inefficent, and needs mass energy to recycle these unreacted raw materials.From this side
Face considers that dialkyl carbonate is more preferably 0.5~5, further preferably relative to the molar ratio of aromatic monohydroxy compound
For 0.8~3, be still more preferably 1~2.
The manufacturing method of diaryl carbonate as present embodiment, in particular, it is preferred that it includes following processes to be
The manufacturing method of diaryl carbonate：(i) into the 1st continuous multi-stage destilling tower, supply includes 0.01~1000 mass ppm formulas (1)
The dialkyl carbonate of represented compound is carried out continuously distillation, will pass through compound represented by above-mentioned formula (1) and water
Reaction generated aldehydes and/or ketone are extracted out from tower top, will include the chemical combination represented by above-mentioned dialkyl carbonate and formula (1)
The process of the mixture extraction of object；It (ii) will be continuous by mixture and aromatic monohydroxy compound that above-mentioned operation (i) obtains
The low process being supplied in the 2nd continuous multi-stage destilling tower there are catalyst；(iii) make above-mentioned dialkyl carbonate with it is above-mentioned
Aromatic monohydroxy compound reacts in above-mentioned 2nd continuous multi-stage destilling tower to generate alcohols and alkyl aryl carbonate class
Process；(iv) by the 2nd low-boiling reaction mixture comprising alcohols generated from above-mentioned 2nd continuous multi-stage destilling tower top
Continuously extract out, at the same by the 2nd tower high boiling reaction mixture comprising alkyl aryl carbonate class generated with liquid from
The process that above-mentioned 2nd continuous multi-stage destilling tower lower part is continuously extracted out；(v) above-mentioned 2nd tower high boiling reaction mixture is continuous
Ground, which is supplied to the presence being connect with above-mentioned 2nd continuous multi-stage destilling tower, to be had in the 3rd continuous multi-stage destilling tower of catalyst, while
Process of the reaction to generate dialkyl carbonates and diaryl carbonates esters in above-mentioned 3rd continuous multi-stage destilling tower；And
(vi) the 3rd tower low-boiling reaction mixture comprising dialkyl carbonates generated is distilled from above-mentioned 3rd continuous multi-stage
Tower top is continuously extracted out, while by the 3rd tower high boiling reaction mixture comprising diaryl carbonates esters generated with liquid
The process that state is continuously extracted out from above-mentioned 3rd continuous multi-stage destilling tower lower part.
In the manufacturing method of above-mentioned diaryl carbonate, preferably in the 1st continuous multi-stage destilling tower, the 2nd continuous multi-stage
Generated aldehydes will be reacted in destilling tower and the 3rd continuous multi-stage destilling tower by compound represented by formula (1) and water
And/or ketone is extracted out with gaseous state from tower top.
In the preferred supply to the 1st continuous multi-stage destilling tower of 2nd low-boiling reaction mixture, the reaction mixing of the 3rd tower low boiling point
In the preferred supply to the 2nd continuous multi-stage destilling tower of object.In the 2nd low-boiling reaction mixture and the 3rd tower low-boiling reaction mixture
In can include for example selected from the compound represented by alcohols, dialkyl carbonate, aromatic monohydroxy compound, formula (1)
And one or more of group of compositions such as water.
As catalyst used in present embodiment, for example, selected from by lead compound below, copper race gold
The compound of category, the complex compound of alkali metal, the complex compound of zinc, the complex compound of cadmium, the compound of iron group metal, zirconium complex, road
One or more of groups of compositions such as Lewis acid class compound, organo-tin compound.
<Lead compound>
As lead compound, for example,：
PbO、PbO2、Pb3O4Equal lead oxide class；
PbS、Pb2The vulcanized lead class such as S；
Pb(OH)2、Pb2O2(OH)2Equal lead hydroxides class；
Na2PbO2、K2PbO2、NaHPbO2、KHPbO2Equal plumbous acid salt；
Na2PbO3、Na2H2PbO4、K2PbO3、K2[Pb(OH)6]、K4PbO4、Ca2PbO4、CaPbO3Equal plumbic acids salt；
PbCO3、2PbCO3·Pb(OH)2The carbonate and its alkaline salt of equal lead；
Pb(OCOCH3)2、Pb(OCOCH3)4、Pb(OCOCH3)2·PbO·3H2The lead salt and its carbonate of the organic acids such as O
Or alkaline salt；
Bu4Pb、Ph4Pb、Bu3PbCl、Ph3PbBr、Ph3Pb (or Ph6Pb2)、Bu3PbOH、Ph3The organo-lead compounds such as PbO
Class (Bu indicates that butyl, Ph indicate phenyl)；
Pb(OCH3)2、(CH3O)Pb(OPh)、Pb(OPh)2Equal alkoxies lead class, aryloxy group lead class；
The metals class such as Pb-Na, Pb-Ca, Pb-Ba, Pb-Sn, Pb-Sb；
The hydrate of the lead ores such as galena, zincblende species and their lead compound；Etc..
<The compound of copper race metal>
As the compound of copper race metal, for example,：
CuCl、CuCl2、CuBr、CuBr2、CuI、CuI2、Cu(OAc)2、Cu(acac)2, copper oleate, Bu2Cu、(CH3O)2Cu、AgNO3, AgBr, silver picrate, AgC6H6ClO4、[AuC≡C-C(CH3)3]n、[Cu(C7H8)Cl]4The salt of Deng Tong races metal
With complex compound (acac indicates acetylacetone,2,4-pentanedione cheland)；Etc..
<The complex compound of alkali metal>
As the complex compound of alkali metal, for example,：
Li(acac)、LiN(C4H9)2The complex compound of equal alkali metal；Etc..
<The complex compound of zinc>
As the complex compound of zinc, for example,：
Zn(acac)2The complex compound of equal zinc；Etc..
<The complex compound of cadmium>
As the complex compound of cadmium, for example,：
Cd(acac)2The complex compound of equal cadmiums；Etc..
<The compound of iron group metal>
As the compound of iron group metal, for example,：
Fe(C10H8)(CO)5、Fe(CO)5、Fe(C4H6)(CO)3, Co (trimethylbenzene)2(PEt2Ph)2、CoC5F5(CO)7、Ni-
π-C5H5The complex compound of the iron group metals such as NO, ferrocene；Etc..
<Zirconium complex>
As zirconium complex, for example,：
Zr(acac)4, the zirconiums such as zirconocene complex compound；Etc..
<Louis's acid compounds>
As Louis's acid compounds, for example,：
AlX3、TiX3,TiX4、VOX3、VX5、ZnX2、FeX3、SnX4(X is halogen, acetoxyl group, alkoxy, fragrant oxygen herein
Base) etc. lewis acids and generate lewis acidic transistion metal compound；Etc..
<Organo-tin compound>
As organo-tin compound, for example,：
(CH3)3SnOCOCH3、(C2H5)3SnOCOC6H5、Bu3SnOCOCH3、Ph3SnOCOCH3、Bu2Sn(OCOCH3)2、
Bu2Sn(OCOC11H23)2、Ph3SnOCH3、(C2H5)3SnOPh、Bu2Sn(OCH3)2、Bu2Sn(OC2H5)2、Bu2Sn(OPh)2、
Ph2Sn(OCH3)2、(C2H5)3SnOH、Ph3SnOH、Bu2SnO、(C8H17)2SnO、Bu2SnCl2, the organotins chemical combination such as BuSnO (OH)
Object；Etc..
Above-mentioned metal-containing compound is used as catalyst.These catalyst can be to be fixed in multistage distillation tower
Solid catalyst, or dissolve soluble catalyst in the reaction system.
In addition, these catalyst components can be with organic compound present in reaction system, such as aliphatic alcohols, virtue
Fragrant race's monohydroxy compound class, alkyl aryl carbonate class, diaryl carbonates esters, dialkyl carbonates etc. react,
It can also be heated before reactions using raw material or product.
In the case where implementing diaryl carbonate manufacturing process using the soluble catalyst of dissolving in the reaction system,
In these catalyst, the high catalyst of solubility preferably at reaction conditions in reaction solution.It is molten from reaction solution
It sets out in terms of solution property, as preferred catalyst, for example, PbO, Pb (OH)2、Pb(OPh)2；TiCl4、Ti
(OMe)4、(MeO)Ti(OPh)3、(MeO)2Ti(OPh)2、(MeO)3Ti(OPh)、Ti(OPh)4；SnCl4、Sn(OPh)4、
Bu2SnO、Bu2Sn(OPh)2；FeCl3、Fe(OH)3、Fe(OPh)3Deng or by these catalyst using phenol or reaction solution etc.
The processed material etc. handled.
The catalyst used in the 2nd continuous multi-stage destilling tower and the catalyst used in the 3rd continuous multi-stage destilling tower
Can be identical type or variety classes, the preferably catalyst of identical type.Above-mentioned catalyst is more preferably identical
Type, the catalyst that can be dissolved in two kinds of reaction solutions.It is identical type, two kinds can be dissolved in instead in above-mentioned catalyst
When answering in liquid, state and alkyl of the usual catalyst to be dissolved in the high boiling reaction mixture of the 2nd continuous multi-stage destilling tower
Aryl carbonates etc. are extracted out from the lower part of above-mentioned 2nd destilling tower together, are supplied directly onto above-mentioned 3rd continuous multi-stage destilling tower
In, thus be preferred embodiment.It should be noted that as needed, it can also be in above-mentioned 3rd continuous multi-stage destilling tower
Again catalyst is added.
1st continuous multi-stage destilling tower, the 2nd continuous multi-stage destilling tower and the 3rd continuous multi-stage destilling tower preferably have column plate
And/or destilling tower of the filler as internals.So-called internals refer to that the part of gas-liquid contact is actually carried out in destilling tower.Make
For column plate, such as preferred bubble-cap type column plate, porous plate column plate, valve plate, adverse current column plate, superfractionation column plate (superfrac
Tray), maximum rectifiying plate (maxfrac tray) etc..As filler, such as preferred Raschig ring, Lessing ring, Pall ring, arc
The irregular filling such as saddle filling, Intalox saddle packing, Dixon ring, MacMahon packing, Heli-Pack packing
Object；Perforated plate corrugated filler (MellaPak), GemPak, Techno-Pak, Flexi-Pak, Su Caier (Sulzer) filler,
The regular fillers such as Goodroll fillers, Glitchgrid.As the 1st continuous multi-stage destilling tower, the 2nd continuous multi-stage destilling tower and
3rd continuous multi-stage destilling tower can also use multistage distillation tower of the combination with column plate portion and the part filled with filler.
It should be noted that referring to the number of plates in column plate, in filler about " series of internals " hereinafter
It refer to theoretical stage.Thus, it is interior in the case of the multistage distillation tower of part of the combination with column plate portion and filled with filler
The series of part is the total of the number of plates and theoretical stage.
The reaction time of the ester exchange reaction carried out in diaryl carbonate manufacturing process is believed that and the 2nd continuous multi-stage
It is suitable with the mean residence time of each reaction solution in the 3rd continuous multi-stage destilling tower in destilling tower, according to above-mentioned each destilling tower
The difference of the shape or series of internals, raw material supply amount, the type of catalyst or amount, reaction condition etc. and it is different, the 2nd is continuous more
The respective reaction time is usually 0.01 hour~10 hours, is preferably in grade destilling tower and in the 3rd continuous multi-stage destilling tower
0.05 hour~5 hours, more preferably 0.1 hour~3 hours.
The reaction temperature of 2nd continuous multi-stage destilling tower can by the type of used raw material, the type of catalyst or
Amount is adjusted, usually 100 DEG C~350 DEG C of range.From the aspect of improving reaction speed, reaction temperature is preferably improved
Degree, but when reaction temperature is high also easily cause the by-products such as side reaction, such as alkyl aryl ether and can increase, it is thus not preferred.From
From the aspect of improving reaction speed while also inhibiting side reaction, the reaction temperature in the 2nd continuous multi-stage destilling tower is preferably 130
DEG C~280 DEG C, more preferably 150 DEG C~260 DEG C, further preferably 180 DEG C~250 DEG C of range.
The reaction temperature of 3rd continuous multi-stage destilling tower can by the type of used raw material, the type of catalyst or
Amount is adjusted, usually 100 DEG C~350 DEG C of range.From the aspect of improving reaction speed, reaction temperature is preferably improved
Degree, but when reaction temperature is high also easily cause side reaction, such as alkyl aryl ether, as the alkylaryl carbon of raw material or product
The by-products such as Fries rearrangement reaction products of acid esters or diaryl carbonate or derivatives thereof can increase, thus not preferred.From
From the aspect of improving reaction speed while also inhibiting side reaction, the reaction temperature in the 3rd continuous multi-stage destilling tower is preferably 130
DEG C~280 DEG C, more preferably 150 DEG C~260 DEG C, further preferably 180 DEG C~250 DEG C of range.
The pressure of 1st continuous multi-stage destilling tower can be warm by the type or composition of used raw material compound, reaction
Degree etc. is adjusted, and can be decompression, normal pressure, any one of pressurization, usual tower top pressure be preferably 0.1Pa~2 ×
107Pa, more preferably 105Pa~107Pa, further preferably 2 × 105Pa~5 × 106The range of Pa.
As long as the temperature of the 1st continuous multi-stage destilling tower is the compound and water that can be distilled off by represented by formula (1)
The temperature of aldehydes and/or ketone that is generated of reaction be just not particularly limited.
The reaction pressure of 2nd continuous multi-stage destilling tower can be by the type or composition of used raw material compound, anti-
Answer temperature etc. to be adjusted, can be decompression, normal pressure, any one of pressurization, usual tower top pressure be preferably 0.1Pa~2 ×
107Pa, more preferably 105Pa~107Pa, further preferably 2 × 105Pa~5 × 106The range of Pa.
The reaction pressure of 3rd continuous multi-stage destilling tower can be by the type or composition of used raw material compound, anti-
Answer temperature etc. to be adjusted, can be decompression, normal pressure, any one of pressurization, usual tower top pressure be preferably 0.1Pa~2 ×
107Pa, more preferably 103Pa~106Pa, further preferably 5 × 103Pa~105The range of Pa.
It should be noted that as the 2nd continuous multi-stage destilling tower in diaryl carbonate manufacturing process, can also use
2 or more destilling towers.In this case, 2 or more destilling towers can be connected in series with, can be connected in parallel and then may be used also
It is connected with parallel combination with series connection.
Constitute the 1st continuous multi-stage destilling tower, the 2nd continuous multi-stage destilling tower used in diaryl carbonate manufacturing process
Material with the 3rd continuous multi-stage destilling tower is mainly carbon steel, stainless steel and other metal materials, from manufactured diaryl carbonate
From the aspect of quality, preferred stainless steel.
Can also using aromatic dihydroxy compound and by present embodiment manufacture diaryl carbonate as raw material
Manufacture aromatic copolycarbonate.For example, following methods：Keep aromatic dihydroxy compound anti-with diaryl carbonate
Should come manufacture aromatic copolycarbonate molten condition prepolymer (hereinafter also referred to " molten prepolymer "), make to melt using one side
Melt the rotation that prepolymer flows down the guider contact downward flow type polymerizer, agitating paddle that are polymerize on one side along the surface of guider
Axis manufactures aromatic copolycarbonate for horizontal polymerizers such as the horizontal polymerization tank of horizontal direction etc..
It will make aromatic dihydroxy compound and diaryl carbonates below for guider contact downward flow type polymerizer is used
Ester reacts and the method that polymerize to manufacture aromatic copolycarbonate of the molten prepolymer that produces is specifically described, but
Embodiment is not limited to method described below.
The aromatic dihydroxy compound used in the manufacture of aromatic copolycarbonate is the compound represented by formula (7).
HO-Ar-OH (7)
(in formula, Ar indicates the aromatic radical of divalent.)
The aromatic radical Ar of divalent is preferably, for example, the group represented by formula (8).
-Ar1-Y-Ar2- (8)
(in formula, Ar1And Ar2Each independently represent the carbon-ring type or hetero ring type fragrance of the divalent that carbon atom number is 5~70
Base, Y indicate that carbon atom number is the alkyl of 1~30 divalent.)
The aromatic radical Ar of divalent1、Ar2In, 1 or more hydrogen atom can will not be replaced to reacting other that affect
Alkoxy that alkyl that base, such as halogen atom, carbon atom number are 1~10, carbon atom number are 1~10, phenyl, phenoxy group, ethylene
Base, cyano, ester group, amide groups, nitro etc. are replaced.As the preferred concrete example of hetero ring type aromatic radical, can enumerate with 1
It is a or 2 or more ring member nitrogen atoms, oxygen atom or sulphur atom aromatic radical.The aromatic radical Ar of divalent1、Ar2Such as indicate substitution
Or the groups such as non-substituted phenylene, substituted or non-substituted biphenylene, substituted or non-substituted sub-pyridyl group.Taking herein
It is as described above for base.
The alkyl Y of divalent is, for example, the organic group represented by following formula.
【Change 11】
(in formula, R1、R2、R3、R4Each independently represent hydrogen, the alkyl that carbon atom number is 1~10, carbon atom number be 1~
Homocyclic aromatic groups that naphthenic base that 10 alkoxy, ring carbons number are 5~10, ring carbons number are 5~10, carbon atom
The carbocyclic ring aralkyl that number is 6~10.K indicates 3~11 integer, R5And R6It is selected respectively for each X, indicates hydrogen independently of each other
Or the alkyl that carbon atom number is 1~6, X indicate carbon.In addition, in R1、R2、R3、R4、R5、R6In, 1 or more hydrogen atom can be
It is former by other substituent groups, such as alkyl that halogen atom, carbon atom number are 1~10, carbon in the range of will not being had an impact to reaction
Subnumber is replaced by 1~10 alkoxy, phenyl, phenoxy group, vinyl, cyano, ester group, amide groups, nitro etc..)
As the aromatic radical Ar of such divalent, for example, the group represented by following formula.
【Change 12】
(in formula, R7、R8Each independently represent hydrogen atom, halogen atom, the alkyl that carbon atom number is 1~10, carbon atom number
For 1~10 alkoxy, ring carbons number be 5~10 naphthenic base or phenyl, the integer that m and n are 1~4, when m is 2~4,
Each R7It can be the same or different respectively, when n is 2~4, R8It can be the same or different respectively.)
In addition, the aromatic radical Ar of divalent can be the group represented by following formula.
-Ar1-Z-Ar2-
(in formula, Ar1And Ar2As described above, Z indicates singly-bound or-O- ,-CO- ,-S- ,-SO2-、-SO-、-COO-、-CON
(R1The group of)-wait divalents.R1As described above.)
As the aromatic radical Ar of such divalent, for example, the group represented by following formula.
【Change 13】
(in formula, R7、R8, m and n it is as described above.)
In addition, the concrete example of the aromatic radical Ar as divalent, can enumerate substituted or non-substituted phenylene, substitution or non-
Substituted naphthylene, substituted or non-substituted sub-pyridyl group etc..
Aromatic dihydroxy compound can be individually a kind of, or two or more.As aromatic series dihydroxy
The typical example for closing object, can enumerate bis- (3- methyl -4- hydroxy phenyls) propane of bisphenol-A, 2,2- etc..In addition, as aromatic series two
Hydroxy compounds can also share the aromatic series trihydric compounds of the trivalent for introducing branched structure.
In the manufacturing process of aromatic copolycarbonate, the use ratio of aromatic dihydroxy compound and diaryl carbonate
(ingredient proportion) can be poly- according to the type of used aromatic dihydroxy compound and diaryl carbonate, polymerization temperature etc.
Conjunction condition is adjusted, and relative to 1 mole of aromatic dihydroxy compound, diaryl carbonate is to be usually 0.9 mole~2.5
Mole, preferably 0.95 mole~2.0 moles, more preferably 0.98 mole~1.5 moles of ratio used.
Molten prepolymer in aromatic copolycarbonate manufacturing process refer to with targeted degree of polymerization fragrant adoption carbon
The fusant of the acid esters polymerization low compared to the degree of polymerization on the way, can be oligomer.It should be noted that aromatic series dihydroxy
Closing object can only be reacted by heating melting with the mixture of diaryl carbonate, therefore their mixture is substantially
Molten prepolymer.About the number-average molecular weight of the molten prepolymer used in aromatic copolycarbonate manufacturing process, as long as
It melts under polymerization temperature and is just not particularly limited, and the number-average molecular weight is different also according to its chemical constitution.Melt pre-polymerization
The number-average molecular weight of object is preferably 500~100,000, more preferably 500~10,000, further preferably 1,000~8,
000。
In addition, the material of the polymerizer and other reactors for aromatic copolycarbonate manufacturing process does not limit especially
System, the material for constituting at least internal face of polymerizer or reactor can be the material selected in never becoming rusty steel, nickel, glass etc..
Molten prepolymer used in aromatic copolycarbonate manufacturing process can by well known any means come
It arrives.Such as it can manufacture as follows：Using 1 or the vertical stirring tank more than it, in about 120 DEG C~about 280 DEG C of temperature range,
The molten mixture formed by the aromatic dihydroxy compound and diaryl carbonate of specified amount one side in normal pressure and/or is subtracted
Pressure stirring removes the secondary aromatic monohydroxy compound generated in dereaction on one side, to manufacture the molten prepolymer.It is especially excellent
Select following methods：Using 2 or more vertical stirring tanks being connected in series with, the degree of polymerization is improved successively, is continuously manufactured by with institute
The molten prepolymer of the degree of polymerization needed.
In aromatic copolycarbonate manufacturing process, the molten prepolymer is preferably continuously fed to guider contact stream
In following formula polymerizer, it is continuously manufactured by the aromatic copolycarbonate with targeted degree of polymerization.The guider contacts downward flow type polymerization
Device is the polymerizer for making prepolymer be flowed down along the guider melting being made of vertical line and it being made to be polymerize, for example, international
Disclose No. 2005/121210, International Publication No. 2005/121211, International Publication No. 2012/056903, International Publication
Polymerizer disclosed in No. 2015/141501 etc..
In aromatic copolycarbonate manufacturing process, make to be obtained by aromatic dihydroxy compound and diaryl carbonate
Molten prepolymer is polymerize the temperature of the reaction to manufacture aromatic copolycarbonate using guider contact downward flow type polymerizer
Preferably 80 DEG C~350 DEG C, more preferably 100 DEG C~290 DEG C, further preferably 150 DEG C~270 DEG C.
In aromatic copolycarbonate manufacturing process, preferred reaction pressure can pass through manufactured aromatic series in polymerizer
The type or molecular weight of makrolon, polymerization temperature etc. are adjusted, for example, it is pre- to obtain melting by bisphenol-A and diphenyl carbonate
Polymers, by the molten prepolymer manufacture aromatic copolycarbonate when, number-average molecular weight 5, the reaction pressure of 000 range below
Preferably 400Pa~3,000Pa, reaction pressure when number-average molecular weight 5,000~10,000 is preferably 50Pa~500Pa.
When number-average molecular weight is 10,000 or more, reaction pressure is preferably 300Pa or less, more preferably 20Pa~250Pa.
In aromatic copolycarbonate manufacturing process, with the progress of polymerisation, aromatic monohydroxy compound is gradual
It generates, by the way that by the aromatic monohydroxy compound, in addition to going to reaction system, reaction speed is improved.It is therefore preferable that making
Use following methods：The inert gas that nitrogen, argon, helium, carbon dioxide, rudimentary appropriate hydrocarbon gas etc. will not have an impact reaction is imported into
In polymerizer, make the aromatic monohydroxy compound increasingly generated and these gas phases companion and the method for removing；Under reduced pressure into
The method of row reaction；Etc..Or the method for sharing them is further preferably used, even if need not be to polymerization if in the case of these
A large amount of inert gas is imported in device, can be the degree that inside is maintained to inert gas atmosphere.
It should be noted that following methods is also preferred method：Molten prepolymer is being supplied to guider contact
Before in downward flow type polymerizer, it is made to absorb above-mentioned inert gas, next makes the molten prepolymer of the absorption inert gas poly-
It closes.
When implementing aromatic copolycarbonate manufacturing process, contacts downward flow type polymerizer merely with 1 guider and also can
The aromatic copolycarbonate with targeted degree of polymerization is manufactured, it is also preferred that following modes：According to the polymerization of raw material molten prepolymer
The output etc. of degree, aromatic copolycarbonate, by 2 or more a plurality of guiders contact downward flow type polymerizer connections, successively
Improve the degree of polymerization.In this case, it in each polymerizer, can be respectively adopted and the prepolymer to be manufactured or fragrant adoption carbon
The adaptable guider of the degree of polymerization of acid esters, reaction condition, thus be preferred mode.
In aromatic copolycarbonate manufacturing process, fragrance is manufactured by aromatic dihydroxy compound and diaryl carbonate
The reaction of adoption carbonic ester can be implemented under conditions of not adding catalyst, can also be according to need in order to improve polymerization speed
It to be reacted in the presence of a catalyst.
The catalyst used in reaction as manufacture aromatic copolycarbonate, as long as urging used in the field
Agent is just not particularly limited, and can enumerate following catalyst：Lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide etc.
The hydroxide species of alkali and alkaline earth metal ions；The hydride of the boron such as lithium aluminium hydride reduction, sodium borohydride, tetramethyl ammonium borohydride or aluminium
Alkali metal salt, alkali salt, quaternary ammonium salt；The hydrogenation of the alkali and alkaline earth metal ions such as lithium hydride, sodium hydride, calcium hydride is closed
Species；The alkanol salt of the alkali and alkaline earth metal ions such as lithium methoxide, sodium ethoxide, calcium methoxide；Phenol lithium, sodium phenate, phenol magnesium,
LiO-Ar7-OLi、NaO-Ar7-ONa(Ar7For aryl) etc. alkali and alkaline earth metal ions phenol salt；Lithium acetate, calcium acetate,
The organic acid salt of the alkali and alkaline earth metal ions such as sodium benzoate；The zinc compounds classes such as zinc oxide, zinc acetate, phenol zinc；Oxidation
Boron, boric acid, Boratex, trimethylborate, butyl borate, triphenyl borate, (R1R2R3R4)NB(R1R2R3R4) or
(R1R2R3R4)PB(R1R2R3R4) represented by ammonium borate salt or Peng Suan phosphonium salt classes (R1、R2、R3、R4The boronations such as described above)
Close species；The silicon compounds classes such as silica, sodium metasilicate, tetraalkyl silicon, four aryl silicon, diphenyl-ethyl ethyoxyl silicon；Germanium oxide,
The germanium compounds classes such as germanium tetrachloride, ethyl alcohol germanium, phenol germanium；Tin oxide, dialkyltin, dialkyltincarboxylates, tin acetate, three
The tin compounds classes such as the tin compound, the organo-tin compounds that are combined with alkoxy or aryloxy group such as butanol ethyl tin；Lead oxide, second
The lead compounds such as lead plumbate, ceruse, basic carbonate, the alkoxide of lead and Organic leadP or fragrant and mellow salt；Quaternary ammonium salt, quaternary alkylphosphonium salts, season
The compounds such as arsenic；The antimonials class such as antimony oxide, antimony acetate；The manganese compounds class such as manganese acetate, manganese carbonate, manganese borate；
The titanium compounds classes such as titanium oxide, the alkoxide of titanium or fragrant and mellow salt；Zirconium acetate, zirconium oxide, the alkoxide of zirconium or fragrant and mellow salt, levulinic
The zirconium compounds class such as ketone zirconium；Etc..
Using catalyst, these catalyst can be used only a kind, two or more can also be applied in combination.Separately
Outside, the dosage of these catalyst relative to raw material aromatic dihydroxy compound preferably 10-10The mass of quality %~1 %, more
Preferably 10-9Quality %~10-1Quality %, further preferably 10-8Quality %~10-2The range of quality % is selected.
In the case of melt transesterification process, used polymerization catalyst remains in product aromatic copolycarbonate, these polymerizations are urged
The usual majority of agent can have an impact polymeric properties.It is therefore preferable that inhibiting the dosage of catalyst as far as possible.
In aromatic copolycarbonate manufacturing process, gather when manufacturing molten prepolymer and using guider contact downward flow type
When clutch etc. is polymerize, by reacting secondary raw a large amount of aromatic monohydroxy compound usually with gaseous state by continuously
Extraction, is preferably condensed into liquid and is recycled.It is preferred that carrying out aromatic monohydroxy compound recycles process, make fragrant adoption carbon
The secondary aromatic monohydroxy compound generated recycles in diaryl carbonate manufacturing process in acid esters manufacturing process.It is made in industry
It makes in method, the total amount of the aromatic monohydroxy compound of pair generation or loss is carried out recycling and carrying out it as few as possible
Cycle recycles, and this point is critically important.
In aromatic copolycarbonate manufacturing process in the secondary byproduct aromatic monohydroxy compound for generating and being recovered
It can include the diaryl carbonate of a part, due to its purity height, thus directly can also manufacture work in diaryl carbonate
Sequence carries out cycle and reuses.It should be noted that in the above-mentioned aromatic monohydroxy compound recycled mix have it is a small amount of
It in the case of aromatic dihydroxy compound, micro oligomer, is preferably further distilled, removes these high boiling products
Matter carries out cycle in diaryl carbonate manufacturing process and reuses later.
There is the repetition represented by following formula (9) by the aromatic copolycarbonate that aromatic copolycarbonate manufacturing process manufactures
Unit.
【Change 14】
(Ar is definition same as described above.)
As aromatic copolycarbonate, following formula (10) institute table of 85 moles of % or more is included preferably in whole repetitive units
The aromatic copolycarbonate of the repetitive unit shown.
【Change 15】
In addition, aryl carbonate base structure of the end group of aromatic copolycarbonate usually represented by hydroxyl or following formula (11)
At.
【Change 16】
(Ar6For with above-mentioned Ar3、Ar4Identical definition.)
The ratio of hydroxyl and aryl carbonate base is not particularly limited, usually 95：5~5：95 range, preferably 90：
10~10：90 range, more preferably 80：20~20：80 range.As aromatic copolycarbonate, further preferred end
The aromatic copolycarbonate that ratio in group shared by carbonic acid carbobenzoxy is 60 moles of % or more.
It, can by the xenogenesis key section such as ester bond, ehter bond relative to main chain in the aromatic copolycarbonate of above-mentioned manufacture
It is branched.The amount of above-mentioned xenogenesis key is usually 0.005 mole of %~2 mole %, preferably 0.01 mole of % relative to carbonic acid ester bond
~1 mole of %, more preferably 0.05 mole of %~0.5 mole %.Stream when melt molding can be improved in the xenogenesis key of such amount
Dynamic characteristic is suitable for precise forming without making other polymers physical property be deteriorated, and can be molded at relatively low temperature,
The molding haveing excellent performance can be produced.It can also shorten molding cycle, additionally it is possible to energy saving when helping to be molded.
Embodiment
The present invention is further specifically described by the following examples, but the present invention is not limited to embodiments below.
[embodiment 1]
Such 1st continuous multi-stage destilling tower 101,102 and of the 2nd continuous multi-stage destilling tower shown in flow chart using Fig. 1
The device that 3rd continuous multi-stage destilling tower 103 is formed by connecting carries out reaction distillation, manufactures diphenyl carbonate.
[the 1st continuous multi-stage destilling tower 101]
Using the continuous multi-stage destilling tower for including recoverer and concentrating part, recoverer length 17m, internal diameter 1.8m, inside
Portion has 16 grades of internals, concentrating part length 25m, internal diameter 1m, has 55 grades of internals in inside.Internals are in recoverer, concentrating part
The use of the sectional area in every 1 hole is about 1.3cm2, hole count be about 550/m2Porous plate column plate.
[the 2nd continuous multi-stage destilling tower 102]
Using length 33m, internal diameter 5m, in the internal continuous multi-stage destilling tower with 80 grades of internals.Internals use every 1 hole
Sectional area be about 1.5cm2, hole count be about 250/m2Porous plate column plate.
[the 3rd continuous multi-stage destilling tower 103]
Using length 31m, internal diameter 5m, in the internal continuous multi-stage destilling tower with 30 grades of internals.As internals, on top
It is provided as 2 pieces of the perforated plate corrugated filler (Mellapak) (total 11 grades of theoretical cam curve) of regularity filler, is set in lower part
The sectional area for setting every 1 hole is about 1.3cm2, hole count be about 250/m2Porous plate column plate.
In the 1,1- for being added with 12 mass ppm with 2.5 tons/hr inputs by pipeline 1 in the 1st continuous multi-stage destilling tower 101
The dimethyl carbonate (100 mass %) of the 2,2-dimethoxypropane of dimethoxy propane and 80 mass ppm, in the pressure of top of tower
Power is 10 × 105Pa, reflux ratio continuously carry out distillation operating under conditions of being 2.9.
Methanol (100 mass %) and 7 matter are included with 1.8 tons/hr extractions from the tower top 5 of the 1st continuous multi-stage destilling tower 101
Amount ppm's is low with the aldehydes and ketone that are generated by reacting for water by 1,1- dimethoxy propanes, 2,2- dimethoxy propanes
Boiling point reaction mixture.
Dimethyl carbonate (71 mass %), benzene are included with 35 tons/hr extractions by the bottom of tower 2 of the 1st continuous multi-stage destilling tower 101
The height of phenol (29 mass %), unreacted 1,1- dimethoxy propanes (2 mass ppm), 2,2- dimethoxy propanes (14 mass ppm)
Boiling point reaction mixture is put into the 2nd destilling tower 102.
Catalyst Ti (OPh) is imported in the 2nd continuous multi-stage destilling tower 1024, so that the 2nd continuous multi-stage destilling tower 102
Bottom of tower reaction solution in a concentration of about 150 mass ppm of Ti, the temperature in bottom of tower is 226 DEG C, the pressure of top of tower be 7 ×
105Pa, reflux ratio continuously carry out reaction distillation under conditions of being 0.
From the tower top 4 of the 2nd continuous multi-stage destilling tower 102 by 1,1- dimethoxy propanes, 2,2- dimethoxy propanes and water
The aldehydes that is generated of reaction and ketone be vented removing in gaseous form, will include methanol (5 mass %), dimethyl carbonate (65
Quality %), phenol (30 mass %), 1,1- dimethoxy propanes (2 mass ppm), 2,2- dimethoxy propanes (9 mass ppm),
And the low-boiling reaction mixture of water (1 mass ppm) is extracted out with the flow of 34 ton hours, puts into the distillation of the 1st continuous multi-stage
In tower 101.
To include dimethyl carbonate (29 mass %), phenol (59 matter from the bottom of tower 3 of the 2nd continuous multi-stage destilling tower 102
Measure %), methyl benzol carbonate (12 mass %), 1,1- dimethoxy propanes (1 mass ppm), 2,2- dimethoxy propanes (6
Quality ppm) high boiling reaction mixture extracted out with the flow of 66 tons/hr, put into the 3rd continuous multi-stage destilling tower 103.By
Pipeline 8 is with 5.2 tons/hr input raw material phenols (100 mass %).Include the water of 10 mass ppm in raw material phenol.
In the 3rd continuous multi-stage destilling tower 103, by catalyst Ti (OPh)4It imported into the 3rd destilling tower 103, so that
A concentration of about 1600 mass ppm of Ti in the reaction solution of the bottom of tower of 3rd continuous multi-stage destilling tower 103, the temperature in bottom of tower are 205
DEG C, the pressure of top of tower be 3 × 104Pa, reflux ratio continuously carry out reaction distillation under conditions of being 0.25.
It will pass through 1,1- dimethoxy propanes, 2,2- dimethoxy propanes from the tower top 7 of the 3rd continuous multi-stage destilling tower 103
It is vented removing in gaseous form with the generated aldehydes and ketone of reacting of water, will include dimethyl carbonate (33 mass %), benzene
Phenol (67 mass %), 1,1- dimethoxy propanes (1 mass ppm), 2,2- dimethoxy propanes (5 mass ppm) and water (1 matter
Measure ppm) low-boiling reaction mixture extracted out with the flow of 65 tons/hr, put into the 2nd continuous multi-stage destilling tower 102.Low boiling
Feed intake following progress of the point reaction mixture into the 2nd continuous multi-stage destilling tower 102：Low-boiling reaction mixture is passed through into tower top
7 pipeline 7 is extracted out, and the pipeline 8 for putting into raw material phenol and the pipeline 7 are collaborated, fed intake via pipeline 9.
It includes methyl benzol carbonate continuously to be extracted out with 6.6 tons/hr from the bottom of tower 6 of the 3rd continuous multi-stage destilling tower 103
The high boiling reaction mixture of (44 mass %), diphenyl carbonate (56 mass %).Methyl benzol carbonate is converted into carbonic acid
The output of the diphenyl carbonate of diphenyl ester is 5.7 tons/hr.5,000 hours continuous fortune has steadily been carried out under this condition
Turn.
[embodiment 2]
Change containing for the 1,1- dimethoxy propanes and 2,2- dimethoxy propanes in the dimethyl carbonate put by pipeline 1
Amount carries out the production of diphenyl carbonate by the identical condition of device, operating condition with embodiment 1 in addition to this.
The dimethyl carbonate put by pipeline 1 uses the dimethyl carbonate produced by PO methods.At this point, in above-mentioned PO methods
In, using 1,1- dimethoxy propanes and 2,2-dimethoxypropane generate more conditions carry out the conjunctions of dimethyl carbonates
At.It is common 2 times of concentration using the catalyst concn made in dimethyl carbonate synthesis reactor specifically, in PO methods
Condition carry out dimethyl carbonate synthetic reaction.As a result, 1,1- dimethoxy propanes, 2,2- dimethoxies as by-product
Base propane ratio generally produces more, and 1,1- dimethoxy propanes, 20 mass ppm, 2,2- dimethoxies are contained in dimethyl carbonate
90 mass ppm of base propane.
The output of diphenyl carbonate and 1 indifference of embodiment are 5.7 ton hours.It steadily carries out under this condition
It 1,000 hours continuously runs.
[comparative example 1]
1,1- dimethoxys third are not added in the dimethyl carbonate put by the pipeline 1 of the 1st continuous multi-stage destilling tower 101
Alkane, 2,2-dimethoxypropane operated under the same conditions as example 1 in addition to this, as a result diphenyl carbonate
Output is reduced to 4.5 ton hours.It is thought that this is because, by the water not removed out of diaryl carbonate manufacturing process
Effect, catalyst activity reduce.The time steadily continuously run under this condition is 1,000 hours.
[comparative example 2]
Using device same as Example 1, the carbonic acid diformazan put into the pipeline 1 by the 1st continuous multi-stage destilling tower 101
1, the 1- dimethoxy propanes of 1 mass % and the 2,2-dimethoxypropane of 1 mass % are added in ester, in addition to this, with
Embodiment 1 is operated under the same conditions.The output of diphenyl carbonate is 5.7 ton hours, with 2 phases of embodiment 1 and implementation
Than not reducing, but it has been mixed into through 1,1- dimethoxy propanes, 2,2-dimethoxypropane and phenol in diphenyl carbonate
The 100 mass ppm of impurity such as the generated 9,9- dimethylxanthenes of reaction.
[reference example 1]
Molten prepolymer is manufactured using the diphenyl carbonate obtained in bisphenol-A and embodiment 1 as raw material, is connect using guider
It touches downward flow type polymerizer and manufactures aromatic copolycarbonate.The internal diameter of the shell of above-mentioned guider contact downward flow type polymerizer is
180 a diameter of 3mm, length 9m is arranged in 1.5m, length 10m, the inside that downward flow type polymerizer is contacted in above-mentioned guider
Vertical line.
By diphenyl carbonate (molar ratio relative to bisphenol-A is 1.08) manufacture by being obtained in bisphenol-A and embodiment 1
, the molten prepolymer that number-average molecular weight that be maintained at 265 DEG C is 5,000 is continuously fed to above-mentioned guider and contacts downward flow type
In polymerizer, it is polymerize under conditions of temperature is 265 DEG C, pressure is 50Pa.The molten prepolymer continuously supplied is along vertical
Under linear flow, accompanying this carries out polymerisation, the aromatic copolycarbonate that manufacture number-average molecular weight is 13,000.
Obtained aromatic copolycarbonate is injected under conditions of barrel temperature is 300 DEG C, mold temperature is 90 DEG C
It is shaped to the tablet of thickness 3.2mm, the CR-400 manufactured using Konica Minolta company is placed on white correcting plate using anti-
Method (measure diameter 8mm) is penetrated to be measured, by and the difference of b* values of white correcting plate (b* values of tablet=by tablet are placed in white
The measured value of measured value-white correcting plate on correcting plate) coloration (Δ b*) is found out, tone is judged (chromatic value is smaller,
Tone is the better).Coloration is 0.1.
[reference example 2]
Other than making diphenyl carbonate be the diphenyl carbonate obtained in embodiment 2, virtue is manufactured in the same manner as reference example 1
Fragrant adoption carbonic ester.
It is produced by bisphenol-A and the diphenyl carbonate obtained by embodiment 2 (molar ratio relative to bisphenol-A is 1.08)
The molten prepolymer is continuously fed to above-mentioned guider and contacts downward flow type by the molten prepolymer that number-average molecular weight is 5,000
In polymerizer, the aromatic copolycarbonate that number-average molecular weight is 13,000 is manufactured.
Find out the coloration of obtained aromatic copolycarbonate, result 0.1, the aromatic copolycarbonate with reference example 1
Tone it is identical.
[comparison reference example 3]
Other than making diphenyl carbonate be the diphenyl carbonate obtained in comparative example 2, virtue is manufactured in the same manner as reference example 1
Fragrant adoption carbonic ester.
The diphenyl carbonate (molar ratio relative to bisphenol-A is 1.08) obtained by bisphenol-A and by comparing example 2 produces
The molten prepolymer is continuously fed to above-mentioned guider and contacts downward flow type by the molten prepolymer that number-average molecular weight is 5,000
In polymerizer, the aromatic copolycarbonate that number-average molecular weight is 13,000 is produced.
Find out the coloration of obtained aromatic copolycarbonate, result 0.7, than the aromatic copolycarbonate of reference example 1
Hue difference.
Industrial applicibility
In accordance with the invention it is possible to easily remove diaryl carbonate manufacturing process without using special device
The interior existing water for causing catalyst degradation, thus it is industrially applicable when manufacturing diaryl carbonate.
Claims (4)
1. a kind of manufacturing method of diaryl carbonate is in the presence of a catalyst by aromatic monohydroxy compound and packet
The method of dialkyl carbonate manufacture diaryl carbonate containing the compound represented by following formula (1), wherein
For the dialkyl carbonate, 0.01 mass of mass ppm~1000 is contained in the dialkyl carbonate as raw material
Compound represented by the formula (1) of ppm,
【Change 1】
In formula (1), R1, R2, R4 each independently represent carbon atom number be 1~20 aliphatic group, R3 indicate hydrogen atom or
The aliphatic group that carbon atom number is 1~20.
2. the manufacturing method of diaryl carbonate as described in claim 1, wherein the compound represented by the formula (1) is
Dialkoxyalkane.
3. the manufacturing method of diaryl carbonate as claimed in claim 2, wherein the dialkoxyalkane is dimethoxy
Propane.
4. the manufacturing method of diaryl carbonate according to any one of claims 1 to 3, wherein the dialkyl carbonate
Ester is dimethyl carbonate.
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Citations (4)
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| CN1265641A (en) * | 1997-09-16 | 2000-09-06 | 旭化成工业株式会社 | Process for preparation of aromatic carbonates |
| CN101084181A (en) * | 2004-12-21 | 2007-12-05 | 旭化成化学株式会社 | Asahi chemical corp (jp) |
| JP2009242306A (en) * | 2008-03-31 | 2009-10-22 | National Institute Of Advanced Industrial & Technology | Process for producing carbonic ester |
| CN102498087A (en) * | 2009-07-31 | 2012-06-13 | 国际壳牌研究有限公司 | Process for producing diphenyl carbonate |
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| DE19619949A1 (en) * | 1996-05-17 | 1997-11-20 | Bayer Ag | Process for the preparation of diaryl carbonates |
| US5917078A (en) | 1998-09-25 | 1999-06-29 | General Electric Company | Process for the isolation and removal of unwanted water from a chemical reaction |
| JP2001064234A (en) * | 1999-08-27 | 2001-03-13 | Chiyoda Corp | Production of aromatic carbonate |
| JP2001064235A (en) * | 1999-08-27 | 2001-03-13 | Chiyoda Corp | Production of diaryl carbonate |
| JP2002167359A (en) * | 2000-11-30 | 2002-06-11 | Teijin Ltd | Method for producing aromatic carbonate |
| JP3970627B2 (en) | 2001-02-26 | 2007-09-05 | 三菱化学株式会社 | Method for producing diphenyl carbonate and method for producing aromatic polycarbonate |
| JP4022439B2 (en) * | 2002-06-27 | 2007-12-19 | 独立行政法人産業技術総合研究所 | Method for producing carbonate ester |
| EA010425B1 (en) * | 2004-10-14 | 2008-08-29 | Асахи Касеи Кемикалз Корпорейшн | Process for production of high-purity diaryl carbonates |
| JP4953048B2 (en) * | 2005-10-06 | 2012-06-13 | 独立行政法人産業技術総合研究所 | Method for producing carbonate ester |
| CN102448573A (en) * | 2009-04-23 | 2012-05-09 | 伟图控股有限公司 | Method of dehydrating an ionic liquid |
| JP5652965B2 (en) * | 2010-02-23 | 2015-01-14 | 旭化成ケミカルズ株式会社 | Method for producing diaryl carbonate |
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| JP6347859B1 (en) | 2018-06-27 |
| CN108395374B (en) | 2021-03-30 |
| CN108586254B (en) | 2021-06-18 |
| KR101978568B1 (en) | 2019-05-14 |
| KR20180091682A (en) | 2018-08-16 |
| JP2018127404A (en) | 2018-08-16 |
| CN108586254A (en) | 2018-09-28 |
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