RU2358967C2 - Method of producing aromatic carbonate - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to improvement of the method of producing aromatic carbonate, which involves reaction of initial substance, chosen from a group consisting of dialkylcarbonate with formula (1), alkylarylcarbonate with formula (2), and their mixture, with a reagent, chosen from a group consisting of an aromatic monohydroxy compound, with formula (3), alkylarylcarbonate with formula (4), and their mixture, in the presence of metal-containing catalyst, with distillation of by-product of alcohols and/or by-product of dialkylcarbonates from the reaction system, thereby obtaining aromatic carbonate, with formula (5) and/or formula (6), corresponding to the initial substance and reagent. The obtained aromatic carbonate is subsequently purified using two distillation columns, where the distillate from the first distillation column is fed into the second distillation column, and aromatic carbonate is obtained in form of a bottom product. The metal-containing catalyst is an organic polytitanoxane composition with molecular weight of 480 or more, which contains at least, two titanium atoms and is dissolved in a liquid phase in the reaction system or is present in form of a liquid during the reaction,

Ar¹OH (3)

where R¹, R², and R³ in formulae (1)-(4) independently represent an alkyl group, with 1 to 10 carbon atoms, alicyclic group, with 3 to 10 carbon atoms, or aralkyl group, with 6 to 10 carbon atoms, and Ar¹, Ar² and Ar³ independently represent an aromatic group, with 5 to 30 carbon atoms

and where each of R and Ar in formulae (5) and (6) are chosen from R¹, R², R³, Ar¹, Ar² and Ar³ of the corresponding initial substance and reagent.

EFFECT: method allows for obtaining highly pure aromatic carbonate in stable conditions for a long period of time.

13 cl, 4 dwg, 18 ex

Description

FIELD OF THE INVENTION

The present invention relates to a method for producing aromatic carbonate. More specifically, the present invention relates to a method capable of stably producing high-purity aromatic carbonate in a stable mode for a long time, which includes reacting a starting material selected from the group consisting of dialkyl carbonate, alkyl aryl carbonate and a mixture thereof, and a reagent selected from the group consisting of an aromatic monohydroxy compound, an alkyl aryl carbonate and a mixture thereof, in the presence of a metal-containing catalyst that has a molecular weight of 450 or higher and which finds I in a liquid or dissolved in a liquid phase reaction system, while distilling off by-product alcohol and / or dialkyl carbonate by-product from the reaction system.

State of the art

Aromatic carbonate is used as a raw material for the production of aromatic polycarbonate, which has recently become more and more important as a structural plastic without the use of toxic phosgene, or as a raw material for the production of isocyanate without the use of toxic phosgene. As for the method for producing aromatic carbonate, a method is known which includes transesterification of a dialkyl carbonate, an alkyl aryl carbonate or a mixture thereof, which is a starting material, and an aromatic monohydroxy compound, an alkyl aryl carbonate or a mixture thereof, which are a reagent, to obtain the corresponding aromatic carbonate or a mixture of aromatic carbonates.

However, any such transesterification is an equilibrium reaction, and due to the shift of the equilibrium towards the reagent and due to the slow reaction rate, the industrial production of aromatic carbonate in this way was very difficult. Several approaches have been proposed to improve this method, most of them are associated with catalysts to increase the reaction rate, and a number of metal-containing catalysts are known. In the method for producing an alkyl aryl carbonate, diaryl carbonate or a mixture thereof by reaction between a dialkyl carbonate and an aromatic hydroxy compound, the following catalysts are provided as catalysts: a Lewis acid such as a transition metal halide or a compound that produces a Lewis acid (Patent Document 1, Patent Document 2, patent document 3 (which corresponds to patent documents 4-6)), tin compounds such as organotin alkoxide and organotin oxide (patent document 7 (which corresponds Patent Document 8)), Patent Document 9, Patent Document 10 (which corresponds to Patent Document 11), Patent Document 12 (which corresponds to Patent Document 13), Patent Document 14 and Patent Document 15), alkali metal or alkaline earth metal salts and alkoxides (patent document 16), lead compounds (patent document 16), metal complexes such as copper, iron or zirconium (patent document 17), titanates (patent document 18, which corresponds to patent document 19), a mixture of Lewis acid and roton acid (Patent Document 20 which is corresponding to Patent Document 21), a compound of Sc, Mo, Mn, Bi, Te (Patent Document 22) and iron acetate (III) (Patent Document 23).

In addition, in the method for producing diaryl carbonate by disproportionation of diaryl carbonate and diaryl carbonate by transesterification between alkylaryl carbonate molecules of the same type, the following catalysts were proposed as such catalysts: a Lewis acid and a transition metal compound that can produce a Lewis acid (patent document 24, which corresponds to patent documents 24 25 and 26), a polymer compound of tin (patent document 27, which corresponds to patent document 28), the compound represented e the formula RX (= O) OH, in which X is selected from Sn and Ti and R is selected from monovalent hydrocarbon groups (patent document 29, which corresponds to patent document 30), a mixture of Lewis acid and protic acid (patent document 31, which corresponds to patent 32), a lead catalyst (patent document 33), a titanium or zirconium compound (patent document 34), a tin compound (patent document 35), and a compound Sc, Mo, Mn, Bi, Te (patent document 36).

On the other hand, there have also been attempts to develop a suitable reaction system to increase the yield of aromatic carbonate, shifting the equilibrium as much as possible towards the product. For example, a method has been proposed in which a methanol by-product is distilled off with an azeotropic agent by azeotropic distillation in the reaction between dimethyl carbonate and phenol (patent document 37 and corresponding patent documents 38 and 39, patent document 40), and a method in which the methanol by-product is removed adsorption using molecular sieves (patent document 41, which corresponds to patent document 42).

Further, there is also known a method in which the alcohol obtained in the above reaction is distilled off from the reaction mixture using an apparatus comprising a distillation column at the top of the reactor (examples in patent document 43, which corresponds to patent document 44, examples in patent document 45, examples in patent document 46, corresponding to patent document 47, examples in patent document 48, which corresponds to patent document 49, examples in patent document 50, which corresponds to patent document entu 51, examples in patent documents 52, 53 and 54).

More preferred methods include a process in which a dialkyl carbonate and an aromatic hydroxy compound are continuously fed to a multi-stage distillation column and continuously reacted in the column while continuously removing the resulting low boiling components, including alcohol, by distilling and recovering the formed products containing alkyl aryl carbonate from the bottom of the column (patent document 55), and a method in which an alkyl aryl carbonate is continuously fed into a multi-stage distillation column and continuously eagiruet in the column with the simultaneous removal by distillation of the obtained low-boiling components, including dialkyl, and removing the products formed containing the diaryl carbonate from the bottom of the column (Patent Document 56). These methods are the first descriptions of the efficient and continuous production of aromatic carbonate. After that, similar continuous production methods were patented, such as a method in which substances are brought into contact in a column type reactor for transesterification (patent documents 57, 58 and 59), a method in which several reaction devices are connected in a cascade (patent documents 60 and 61), a method in which a bubble column reactor is used (patent document 62), and a method in which a vertical reaction apparatus is used (patent document 63).

Regarding the industrial production of aromatic carbonate by these methods, methods have also been proposed for stable and continuous operation. Patent Document 64 discloses a method in which an aliphatic alcohol is removed from a distillation column connected to a reactor, so that the concentration of aliphatic alcohol in the reactor after obtaining aromatic carbonate from dialkyl carbonate and aromatic hydroxy compound is 2 wt.% Or less, and it is written that stable continuous operation achieved. The method in this publication aims to avoid the problems of catalyst deposition in a distillation column. Further, Patent Document 65 describes a method that enables long-term stable operation by suppressing catalyst deposition by controlling the weight ratio of the aromatic polyhydroxy compound and / or its residue to the metal component of the catalyst in the liquid substance in the catalyst containing system at a level of 2 or less .

On the other hand, the catalyst used in this reaction system is usually dissolved in the reaction mixture under reaction conditions and has a higher boiling point than aromatic carbonate. Therefore, in order to obtain a high-purity aromatic carbonate from the reaction mixture, low-boiling components are first removed from the mixture, and then the diaryl carbonate in the high-boiling components is separated from the catalyst to purify the diaryl carbonate. It is known that in this case, the catalyst can be recovered as a high boiling component and reused, and deactivated components can be removed. Examples of such a catalyst separation process are described in Patent Document 66.

Titanium compounds are known to be excellent catalysts (e.g., patent documents 67 and 68). However, when titanium-based catalysts are used, for example, titanium phenoxide, Ti (OPh) ₄ , or titanium alkoxide, Ti (OR) ₄ , there is a problem that the end-product diaryl carbonate has a dark red color, as described in the patent 69. This is because the commonly used titanium butoxide, Ti (OBu) ₄ , has a boiling point of 206 ° C at 1.3 KPa, and the commonly used titanium phenoxide has a boiling point of about 250 ° C at about 27 Pa (non-patent document 1), they also drive off in a proportion corresponding to yes the appearance of their vapors after separation of the diaryl carbonate by distillation and, therefore, are not sufficiently separated from the product. Further, as described in Patent Document 70, decomposition of the catalyst and degradation of the properties of diaryl carbonate due to the high temperature during the separation of titanium phenoxide were reported. Also, Patent Document 71 describes a problem that when Ti (OPh) _{4 is used} and a mixture of starting materials and catalyst is fed into a continuous multi-stage distillation column to continue the reaction, the distillation column may become clogged. Thus, well-known titanium-based catalysts have problems in that it is difficult to separate the resulting diaryl carbonate due to the high pressure of their vapors under the reaction conditions, and this fraction at high temperature for a long time will cause decomposition of the catalyst, clogging of the distillation column and deterioration of properties diaryl carbonate.

[patent document 1] JP-A-51-105032

[patent document 2] JP-A-56-123948

[patent document 3] JP-A-56-123949

[patent document 4] DE 2528412

[patent document 5] Patent GB 1499530

[patent document 6] Patent US 4182726

[patent document 7] JP-A-54-48733

[patent document 8] DE 2736062

[patent document 9] JP-A-54-63023

[patent document 10] JP-A-60-169444

[patent document 11] Patent US 4554110

[patent document 12] JP-A-60-169445

[Patent Document 13] US Pat. No. 4,552,704

[patent document 14] JP-A-62-277345

[patent document 15] JP-A-1-265063

[patent document 16] JP-A-57-176932

[patent document 17] JP-A-57-183745

[patent document 18] JP-A-58-185536

[patent document 19] Patent US 4410464

[patent document 20] JP-A-60-173016

[Patent Document 21] Patent US 4,609,501

[patent document 22] JP-A-1-265064

[patent document 23] JP-A-61-172852

[patent document 24] JP-A-51-75044

[patent document 25] DE 2552907

[Patent Document 26] Patent US 4045464

[patent document 27] JP-A-60-169444

[patent document 28] Patent US 4554110

[patent document 29] JP-A-60-169445

[Patent Document 30] Patent US 4,552,704

[patent document 31] JP-A-60-173016

[patent document 32] Patent US 4609501

[patent document 33] JP-A-1-93560

[patent document 34] Japanese patent 2540590

[patent document 35] JP-A-1-265063

[patent document 36] JP-A-1-265064

[patent document 37] JP-A-54-48732

[patent document 38] DE 736063

[patent document 39] Patent US 4252737

[patent document 40] JP-A-61-291545

[patent document 41] JP-A-58-185536

[Patent Document 42] Patent US 410464

[patent document 43] JP-A-56-123948

[Patent Document 44] Patent US 4182726

[patent document 45] JP-A-56-25138

[patent document 46] JP-A-60-169444

[patent document 47] Patent US 4554110

[patent document 48] JP-A-60-169445

[Patent Document 49] US Pat. No. 4,552,704

[patent document 50] JP-A-60-173016

[Patent Document 51] Patent US 4,609,501

[Patent Document 52] Examples JP-A-61-172852

[Patent Document 53] Examples JP-A-61-291545

[patent document 54] JP-A-62-277345

[patent document 55] JP-A-3-291257

[Patent Document 56] JP-A-4-9358

[patent document 57] JP-A-6-41022

[patent document 58] JP-A-6-157424

[patent document 59] JP-A-6-184058

[patent document 60] JP-A-6-234707

[patent document 61] JP-A-6-263694

[patent document 62] JP-A-6-298700

[patent document 63] JP-A-6-345697

[patent document 64] JP-A-6-157410

[Patent Document 65] National Publication of International Patent Application 9-11049

[patent document 66] JP-A-9-169704

[patent document 67] Patent DE 2528412

[Patent Document 68] Patent DE 2552907

[patent document 69] Patent EP 879

[patent document 70] JP-A-9-169704

[patent document 71] JP-A-2004-307400

[Non-Patent Document 1] J. Inorg. Nucl. Chem. Vol. 28, 2410 (1966).

Description of the invention

Problems to be Solved by the Invention

The aim of the present invention is to provide a method for producing high-purity diaryl carbonate, in which the catalyst can be easily separated without the above problems in producing aromatic carbonate by reacting a starting material selected from the group consisting of dialkyl carbonate, alkyl aryl carbonate and a mixture thereof, and a reagent selected from the group consisting of an aromatic monohydroxy compound, an alkyl aryl carbonate, and mixtures thereof, in the presence of a metal-containing catalyst, with distillation of the by-product and alcohol and / or a dialkyl carbonate by-product from the reaction system.

Problem Solving Tools

As a result of the intense research conducted by the authors of the present invention to solve the above problems, the authors found that the goal can be achieved by using a special metal-containing catalyst as a catalyst in the preparation of aromatic carbonate by reacting a starting material selected from the group consisting of dialkyl carbonate, an alkylaryl carbonate and mixtures thereof, with a reagent selected from the group consisting of an aromatic monohydroxy compound, an alkyl aryl carbonate and mixtures thereof, in the presence of a metal-containing catalyst, with distillation of the alcohol by-product and / or dialkyl carbonate by-product from the reaction system, and thereby the present invention has been completed. It was unexpectedly found that the present invention can solve the problem of the traditional method, in which clogging and blocking of the distillation column is often encountered when the reactants and the catalyst are fed to the middle plate of the distillation column; the present invention also facilitates the separation of the resulting diaryl carbonate from other components and, thus, can give a high-purity diaryl carbonate, in which the impurity amount of the metal compound originating from the catalyst is extremely small.

Accordingly, the present invention is as follows.

[1] A method for producing an aromatic carbonate, which comprises introducing into the reaction a starting material selected from the group consisting of a dialkyl carbonate represented by the formula (1), an alkyl aryl carbonate represented by the formula (2), and a mixture thereof, with a reagent selected from the group consisting of from an aromatic monohydroxy compound represented by the formula (3), an alkyl aryl carbonate represented by the formula (4) and a mixture thereof, in the presence of a metal-containing catalyst, with distillation of the alcohol by-product and / or dialkyl by-product bonates from the reaction system, thereby obtaining an aromatic carbonate represented by the formula (5) and / or the formula (6) corresponding to the starting material and the reagent, the metal-containing catalyst being an organic polytitanoxane composition with a molecular weight of 480 or higher, which contains at least two a titanium atom and is dissolved in the liquid phase in the reaction system or is present as a liquid during the reaction,

where R ¹ , R ² and R ³ in formulas (1) to (4) independently mean an alkyl group having from 1 to 10 carbon atoms, an alicyclic group having from 3 to 10 carbon atoms, or an aralkyl group having from 6 to 10 carbon atoms, and

Ar ¹ , Ar ² and Ar ³ independently mean an aromatic group having from 5 to 30 carbon atoms, and

where each of R and Ar in formulas (5) and (6) is selected from R ¹ , R ² , R ³ , Ar ¹ , Ar ² and Ar ^{3 of the} corresponding starting material and reagent.

[2] The method according to [1], wherein the organic polytitanoxane composition comprises at least one alkoxy group and / or an aryloxy group as an organic group.

[3] The method according to [1], wherein the organic polytitanoxane composition is obtained by the polycondensation reaction of at least one feedstock selected from the group consisting of tetraalkoxytitanium, tetragalotitan (TiX ₄ , wherein X is selected from Cl and Br) and titanium hydroxide.

[4] the method according to [3], wherein the organic polytitanoxane composition is obtained by sequentially or simultaneously carrying out two stages:

1) obtaining a partially hydrolyzed product by partial hydrolysis of tetraalkoxy titanium and

2) distillation of the formed low-boiling component, including alcohol, from the partially hydrolyzed product and exposure of the polycondensation product.

[5] The method according to [3], wherein the organic polytitanoxane composition is obtained by subjecting tetraalkoxy titanium to heat, deesterification and polycondensation.

[6] The method according to [3], wherein the organic polytitanoxane composition is obtained by sequentially or simultaneously carrying out three stages:

1) obtaining a partially hydrolyzed product by partial hydrolysis of tetragalotitan,

2) distillation of the low boiling component from the partially hydrolyzed product and exposure of the product to polycondensation and

3) the interaction obtained with alcohol, the removal of HX from it and its alkoxylation.

[7] The method according to any one of [1] to [6], wherein the polytitanoxane composition is used as is or after exchanging alkoxy groups by reacting the composition with a composition containing at least one member selected from alcohol, an aromatic hydroxy compound, and carboxylic acid ester.

[8] The method according to any one of [1] to [7], wherein the titanium-containing compound contains at least two Ti atoms in one molecule.

[9] The method according to [8], wherein the titanium-containing compound contains from 2 to 6 Ti atoms in one molecule.

[10] The method according to [8], wherein the titanium-containing compound contains at least one Ti-O-Ti bond in the molecule.

[11] The method according to [1], wherein the metal-containing catalyst has a vapor pressure at 230 ° C. of 10 Pa or less.

[12] The method according to any one of [1] to [11], wherein the metal-containing catalyst is used in a proportion of from 0.0001 to 30 wt.% Based on the total weight of the starting material and reagent.

[13] The method according to any one of [1] to [12], wherein the aromatic hydroxy compound is phenol.

[14] Diphenyl carbonate obtained by the method according to [13], containing 1 ppm or less of a metal component derived from a metal-containing catalyst.

[15] A polycarbonate containing diphenyl carbonate obtained by the method according to [13] containing 1 ppm or less of a metal component derived from a metal-containing catalyst.

Although titanium-based catalysts, as described above, have excellent catalytic effects, including good reaction rate and selectivity, it was difficult to separate such a titanium catalyst or titanium-containing compound derived from a titanium catalyst from the resulting diaryl carbonate in the reaction mixture after the reaction and obtain diaryl carbonate in which the titanium content is small. The new data obtained that the use of a special titanium catalyst facilitates separation, for the first time made it possible to easily obtain diaryl carbonate, the content of titanium in which is small.

According to the present invention, a diaryl carbonate, in which the titanium content is low, can be easily obtained without problems such as staining due to the presence of titanium.

Further, the present invention is described in detail. The dialkyl carbonate used in the present invention is represented by the formula (1):

where R ¹ means an alkyl group having from 1 to 10 carbon atoms, an alicyclic group having from 3 to 10 carbon atoms, or an aralkyl group having from 6 to 10 carbon atoms.

Examples of dialkyl carbonates containing such R ¹ include dimethyl carbonate, diethyl carbonate, dipropyl carbonate (and its isomers), dibutenyl carbonate (and its isomers), dibutyl carbonate (and its isomers), dipentyl carbonate (and its isomers), dihexyl carbonate (its) and its isomers), dioctyl carbonate (and its isomers), dinonyl carbonate (and its isomers), didecyl carbonate (and its isomers), dicyclopentyl carbonate, dicyclohexyl carbonate, dicycloheptyl carbonate, dibenzyl carbonate, diphenethyl carbonate and its measures), diphenylbutyl carbonate (and its isomers), dichlorobenzyl carbonate (and its isomers), dimethoxybenzyl carbonate (and its isomers), dimethoxymethyl carbonate, dimethoxyethyl carbonate (and its isomers), dichloroethyl carbonate (and its isomers) and dimethyl ethyl carbonate. Of these dialkyl carbonates, those in which R ¹ contains an alkyl group having from 1 to 6 carbon atoms are preferably used in the present invention. More preferably, R ¹ is an n-butyl group, an isobutyl group and an alkyl group having 5 or 6 carbon atoms, and a dialkyl carbonate containing a linear or branched alkyl group in which the carbon atom in the b-position to the oxygen is secondary carbon (-CH ₂ -). Dibutyl carbonate and bis (2-ethylbutyl) carbonate are particularly preferred.

Alkyl aryl carbonate used in the present invention as a starting material is represented by the formula (2):

where R ² may be the same or different from R ¹ and means an alkyl group having from 1 to 10 carbon atoms, an alicyclic group having from 3 to 10 carbon atoms, or an aralkyl group having from 6 to 10 carbon atoms, and

Ar ² means an aromatic group having from 5 to 30 carbon atoms.

Examples of such R ² are the groups listed above for R ¹ . Examples of Ar ² include phenyl, tolyl (and its isomers), xylyl (and its isomers), alkyl phenyl groups such as trimethyl phenyl (and its isomers), tetramethyl phenyl (and its isomers), ethyl phenyl (and its isomers), propyl phenyl (and its isomers), butylphenyl (and its isomers), diethylphenyl (and its isomers), methylethylphenyl (and its isomers), pentylphenyl (and its isomers), hexylphenyl (and its isomers) and cyclohexylphenyl (and its isomers); alkoxyphenyl groups such as methoxyphenyl (and its isomers), ethoxyphenyl (and its isomers) and butoxyphenyl (and its isomers); halogenated phenyl groups such as fluorophenyl (and its isomers), chlorophenyl (and its isomers), bromophenyl (and its isomers), chloromethylphenyl (and its isomers) and dichlorophenyl (and its isomers); substituted phenyl groups represented by formula (7):

where A is a bond, a divalent group, such as —O—, —S—, —CO— or —SO ₂ -, an alkylene group or a substituted alkylene group represented by the formula (8), or a cycloalkylene group represented by the formula (9), and the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, an ester group, a hydroxy group, a nitro group, a halogen or a cyano group,

where R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently means a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, which may optionally be substituted by a halogen atom or an alkoxy group, and

where k is an integer from 3 to 11, and the hydrogen atom may be substituted by a lower alkyl group, an aryl group or a halogen atom;

naphthyl (and its isomers), substituted naphthyl groups such as methylnaphthyl (and its isomers), dimethylnaphthyl (and its isomers), chloronaphthyl (and its isomers), methoxynaphthyl (and its isomers) and cyanonaphthyl (and its isomers); and

substituted or unsubstituted heteroaromatic groups such as pyridine (and its isomers), coumaril (and its isomers), quinolyl (and its isomers), methylpyridyl (and its isomers), chloropyridyl (and its isomers), methylcoumaril (and its isomers) and methylquinolyl (and its isomers).

Examples of alkyl aryl carbonates containing such R ² and Ar ² include methyl phenyl carbonate, ethyl phenyl carbonate, propyl phenyl carbonate (and its isomers), allyl phenyl carbonate, butyl phenyl carbonate (and its isomers), pentyl phenyl carbonate (and its isomers), hexyl phenyl carbonate and its ( isomers), octyltolyl carbonate (and its isomers), nonylethyl phenyl carbonate (and its isomers), decylbutyl phenyl carbonate (and its isomers), methyltolyl carbonate (and its isomers), ethyltolyl carbonate (and its isomers), propyltolyl isolyl carbonate nat (and its isomers), allyltolyl carbonate (and its isomers), methylxyl carbonate (and its isomers), methyl trimethyl phenyl carbonate (and its isomers), methyl chlorophenyl carbonate (and its isomers), methyl nitrophenyl carbonate (and its isomers), methyl methoxy isomethyl carbonate (methyl) (and its isomers), methyl naphthyl carbonate (and its isomers), methyl pyridyl carbonate (and its isomers), ethyl cumyl carbonate (and its isomers), methyl benzoyl phenyl carbonate (and its isomers), ethyl xilyl carbonate (and its isomers) and benzyl xyl carbonate.

Of these alkylaryl carbonates, those in which

R ² is an alkyl group having from 1 to 6 carbon atoms, and more preferably R ¹ is an n-butyl, isobutyl or alkyl group having 5 or 6 carbon atoms, and Ar ² is an aromatic group having from 6 to 10 carbon atoms . Butyl phenyl carbonate and (2-ethyl butyl) phenyl carbonate are particularly preferred. The starting material used in the present invention is selected from the group consisting of dialkyl carbonate represented by the above formula (1), an alkyl aryl carbonate represented by the formula (2), and mixtures thereof.

The aromatic monohydroxy compound used as a reagent in the present invention is represented by formula (3) and any compound can be used if the hydroxyl group is directly linked to the aromatic group.

In this formula, Ar ¹ may be the same or different from Ar ² and means an aromatic group having from 5 to 30 carbon atoms. Examples of such Ar ¹ are the examples listed above as Ar ² .

Examples of aromatic monohydroxy compounds containing such Ar ¹ include phenol, alkyl phenols such as cresol (and its isomers), xylene (and its isomers), trimethyl phenol (and its isomers), tetramethyl phenol (and its isomers), ethyl phenol (and its isomers), propylphenol (and its isomers), butylphenol (and its isomers), diethylphenol (and its isomers), methylethylphenol (and its isomers), methylpropylphenol (and its isomers), dipropylphenol (and its isomers), methylbutylphenol (and its ), pentylphenol (and its isomers), hexylphenol (and its isomers) and cyclohexylphenol (and its isomers); alkoxyphenols such as methoxyphenol (and its isomers) and ethoxyphenol (and its isomers); substituted phenols represented by formula (10):

where A is a group as defined above;

naphthol (and its isomers) and substituted naphthols; and heteroaromatic monohydroxy compounds such as hydroxypyridine (and its isomers), hydroxycoumarin (and its isomers) and hydroxyquinoline (and its isomers). Of these aromatic monohydroxy compounds, in the present invention, aromatic monohydroxy compounds are preferred in which Ar ¹ is an aromatic group having from 6 to 10 carbon atoms, phenol is particularly preferred.

The alkyl aryl carbonate used as a reagent in the present invention is represented by the formula (4)

In this formula, R ³ may be the same or different from R ¹ and R ² and means an alkyl group having from 1 to 10 carbon atoms, an alicyclic group having from 3 to 10 carbon atoms, or an aralkyl group having from 6 to 10 carbon atoms, and Ar ³ may be the same or different from Ar ¹ and Ar ² and means an aromatic group having from 5 to 30 carbon atoms. Examples of such R ³ are the groups listed above as R ¹ , and examples of Ar ³ are the groups listed above as Ar ² .

Examples of alkylaryl carbonates containing such R ³ and Ar ³ are the examples listed above in formula (2). Of these alkyl aryl carbonates, those are preferably used in which R ³ contains an alkyl group having from 1 to 6 carbon atoms, and Ar ³ is an aromatic group having from 6 to 10 carbon atoms. More preferably, R ³ is an n-butyl group, an isobutyl group or a linear or branched alkyl group having 5 or 6 carbon atoms, in which the carbon atom in the b-position to the oxygen is secondary carbon (—CH ₂ -). Butyl phenyl carbonate and (2-ethyl butyl) phenyl carbonate are particularly preferred.

The reagent of the present invention is selected from the group consisting of an aromatic monohydroxy compound represented by formula (3), an alkyl aryl carbonate represented by formula (4), and mixtures thereof. The method of the present invention for producing an aromatic carbonate or a mixture of aromatic carbonates, which comprises reacting a starting material and a reagent in the presence of a metal-containing catalyst, typically involves the reactions of equations (E1), (E2), (E3) and (E4).

In these formulas, R ¹ , R ² , R ³ , Ar ¹ , Ar ² and Ar ³ are as defined above; in the reaction of equation (E4), Ar independently means Ar ² or Ar ³ and R independently means R ² or R ³ ; when in the reaction according to equation (E4) R ² = R ³ and Ar ² = Ar ³ , the reaction is a transesterification between molecules of the same species, which in general can also be called the disproportionation reaction.

When carrying out the reactions according to equations (E1), (E2), (E3) and (E4) in accordance with the method of the present invention, one or at least two dialkyl carbonates and an alkyl aryl carbonate can be used as starting material. Further, one or at least two aromatic monohydroxy compounds and alkylaryl carbonates can be used as reagents.

The case in which in the transesterification represented by the reaction according to equation (E4), R ² = R ³ = R and Ar ² = Ar ³ = Ar, is preferable, since diaryl carbonate and dialkyl carbonate are obtained by transesterification of molecules of the same type of one alkyl aryl carbonate. Further, when in the reaction according to equations (E1) and (E4), R ¹ = R ² = R ³ = R and Ar ^{1 =} Ar ² = Ar ³ = Ar, the diaryl carbonate is obtained from the dialkyl carbonate and aromatic monohydroxy compound via an alkyl aryl carbonate as described in the following reaction equations (E5) and (E6), by combining the reaction represented by reaction equation (E1) and the reaction represented by reaction equation (E4), and this is a particularly preferred embodiment of the present invention

When the dialkyl carbonate obtained as a by-product of the reaction represented by the reaction equation (E6) is reused as a raw material in the reaction represented by the reaction equation (E5), 1 mol of the diaryl carbonate and 2 moles of the aliphatic are obtained from 1 mol of the dialkyl carbonate and 2 moles of the aromatic monohydroxy compound alcohol. In the above reaction equation (E5), when R is selected from n-butyl, isobutyl and an alkyl group having 5 or 6 carbon atoms and Ar = C ₆ H ₅ , the by-product alcohol has the lowest boiling point in the reaction system and does not form an azeotrope with dialkyl carbonate, which is a reagent. This case is especially advantageous, since the reaction proceeds efficiently and easily produces diphenyl carbonate, which is an important raw material for polycarbonate and isocyanate.

The metal-containing catalyst used in the present invention means a special metal-containing catalyst that facilitates the above reactions according to reaction equations (E1) to (E4), has a molecular weight of 450 or higher, more preferably a molecular weight of 480 or higher, and under the above reaction conditions is in the form liquid or dissolved in the liquid phase of the reaction system. The metal-containing catalyst is preferably a titanium-containing compound containing titanium. Examples of preferred titanium-containing compounds that are in liquid form under the above reaction conditions or dissolved in the liquid phase of the reaction system include an organic polytitanoxane composition such as polyorthotitanate and condensed orthotitanate. Preferably, the organic polytitanoxane has at least one alkoxy group and / or an aryloxy group as an organic group.

When the metal-containing catalyst is a metal-containing catalyst containing titanium and / or a metal-containing catalyst having a vapor pressure of 10 Pa or less and containing titanium at 230 ° C., the catalyst preferably contains at least two Ti atoms in one molecule, more preferably from 2 to 6 Ti atoms in one molecule. When the metal-containing catalyst contains 2 or more Ti atoms in one molecule, the compound contains at least one Ti — O — Ti bond per molecule. When the metal-containing catalyst contains Sn, it contains at least 3 Sn atoms.

Examples of such compounds include metal-containing catalysts represented by formulas (11), (12) and (13), titanate oligomers containing at least one titanoxane structure (Ti-O-Ti bond) in one molecule (for example, titanium compounds represented by the formula (14)), and tin compounds represented by the formula (15). Since the metal-containing catalysts described above are readily associated, they can be in monomeric form, in an associated form, or in an adduct form, or in an associated form with an alcohol or aromatic hydroxy compound. These catalyst components may be a reaction product with an organic compound present in the reaction system, for example, aliphatic alcohols, aromatic monohydroxy compounds, alkyl aryl carbonates, diaryl carbonates or dialkyl carbonates, or may be heated as a raw material or product before the reaction. The titanium compound represented by the formula (11) and / or the formula (14) (for example, when R ⁴⁴ -R ⁶¹ in the formula (14) are aromatic groups, for example a phenyl group), tend to form an adduct, in particular with aromatic hydroxy- connection. The structure of the adduct is not determined by modern analytical methods, but this structure represented by the formula has a molecular weight of 450 or higher, more preferably a molecular weight of 480 or higher, minus the molecular weight of the molecules involved in the formation of the adduct. Such molecules involved in adduct formation can be identified by a method such as NMR, or an aromatic hydroxy compound involved in adduct formation can be removed in a known manner (e.g., recrystallization using a solvent described in J. Indian. Chem. Soc ., Vol. 38, No. 3, 147-152 (1961)).

In the formula (11), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ ,

R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ independently mean a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, X ₁ and X ₂ mean an alkyl group, an aralkyl group or an aryl group; R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are not simultaneously a hydrogen atom, and at least four of them are an alkyl group, an aralkyl group or an aryl group; R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ can be covalently linked within such a range that the molecular weight is 450 or higher, more preferably 480 or higher.

In the formula (12), R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ independently mean a hydrogen atom, an alkyl group, an aralkyl group or an aryl group; X ₁ and X ₂ mean an alkyl group, an aralkyl group and an aryl group; at least two of R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , X ₁ and X ₂ are an aralkyl group or an aryl group.

In the formula (13), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ independently mean a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, at least two of them are aralkyl a group or an aryl group, and these R ³⁶ -R ⁴³ may be bonded to each other.

In the formula (14), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ and R ⁶¹ independently mean a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or an acyl group, a, b, c, d, e and f independently represent an integer from 0 to 4, and each of R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ and R ⁶¹ in formula (14) may be covalently linked.

In the formula (15), R ⁶² is an alkyl group, an aralkyl group or an aryl group having 4 or more carbon atoms, R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl a group or an acyl group, g is an integer of 1 or more, and each of R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ in the formula (15) can be covalently linked.

Examples of alkyl groups represented by R ⁸ -R ⁶¹ include linear or cyclic alkyl groups having from 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group (and its isomers), a butyl group (and its isomers), pentyl group (and its isomers), hexyl group (and its isomers), heptyl group (and its isomers), octyl group (and its isomers), nonyl group (and its isomers), decile group (and its isomers), cyclobutyl group , cyclopentyl group (and its isomers) and cyclohexyl group (and its isomers). Groups containing an ether bond are also applicable, examples thereof include a methoxyethyl group (and its isomers), an ethoxyethyl group (and its isomers), a methoxypropyl group (and its isomers), an ethoxypropyl group (and its isomers), a methoxybutyl group (and its isomers) and ethoxybutyl group (and its isomers).

Examples of the aralkyl groups represented by R ⁸ -R ⁶¹ include aralkyl groups having from 7 to 12 carbon atoms which may have substituents such as a benzyl group and a phenylethyl group.

Examples of the aryl groups represented by R ⁸ -R ⁶¹ include phenyl or alkylphenyl groups such as phenyl, tolyl (and its isomers), xylyl (and its isomers), trimethylphenyl (and its isomers), tetramethylphenyl (and its isomers), ethylphenyl (and its isomers), propylphenyl (and its isomers), butylphenyl (and its isomers), diethylphenyl (and its isomers), methylethylphenyl (and its isomers), pentylphenyl (and its isomers), hexylphenyl (and its isomers) and cyclohexylphenyl ( and its isomers); alkoxyphenyl groups such as methoxyphenyl (and its isomers), ethoxyphenyl (and its isomers) and butoxyphenyl (and its isomers); halogenated phenyl groups such as fluorophenyl (and its isomers), chlorophenyl (and its isomers), bromophenyl (and its isomers), chloromethylphenyl (and its isomers) and dichlorophenyl (and its isomers); substituted phenyl groups represented by formula (16):

where B is a bond, a divalent group such as —O—, —S—, —CO— and —SO ₂ -, an alkylene group or a substituted alkylene group represented by the formula (17), or a cycloalkylene group represented by the formula (18), and the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, an ester group, a hydroxy group, a nitro group, a halogen or a cyano group,

where R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently means a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, which may optionally be substituted by a halogen atom or an alkoxy group, and

where m is an integer from 3 to 11 and the hydrogen atom may be substituted by a lower alkyl group, an aryl group or a halogen atom;

naphthyl (and its isomers), substituted naphthyl groups such as methylnaphthyl (and its isomers), dimethylnaphthyl (and its isomers), chloronaphthyl (and its isomers), methoxynaphthyl (and its isomers) and cyanonaphthyl (and its isomers); and substituted or unsubstituted heteroaromatic groups such as pyridine (and its isomers), coumaril (and its isomers), quinolyl (and its isomers), methylpyridyl (and its isomers), chloropyridyl (and its isomers), methyl coumaril (and its isomers) and methylquinolyl (and its isomers).

The aryl group represented by R ⁸ -R ⁶¹ may also be a hydroxy-substituted aryl group which is represented by the formula (19):

where Ar ⁴ means an aromatic group having a valency n, wherein n is an integer of 2 or more, and each —OH group can be attached at any position of Ar ⁴ .

The remainder of the aromatic polyhydroxy compound is represented by formula (20) and is chemically bonded to at least one member selected from the group consisting of a metal-containing metal catalyst, an alkoxycarbonyl group derived from a dialkyl carbonate or alkyl aryl carbonate, an aryloxy carbonyl group derived from an alkyl aryl carbonate or diaryl carbonate, and carbon a group derived from dialkyl carbonate, alkyl aryl carbonate or diaryl carbonate,

where Ar ⁴ and n are as described above, p is an integer from 1 to m and the —OH group and —O group can be attached at any position of the aromatic ring of Ar ⁴ .

Examples of Ar ⁴ in formulas (19) and (20) include aromatic groups represented by the following formulas (21), (22), (23), (24) and (25):

where Q ¹ is a single bond, a divalent alkylene group having from 1 to 30 carbon atoms, or a divalent group selected from —O—, —CO—, —S—, —SO ₂ -, —SO—, and —COO—;

where Q ¹ is as defined above, and all Q ¹ may be the same or different; and

where Q ² means a trivalent group, such as a trivalent alkanetriyl group having from 1 to 30 carbon atoms, or a trivalent aromatic group; moreover, at least one hydrogen atom on the aromatic ring may be substituted by another substituent, such as a halogen atom, an alkoxy group having from 1 to 30 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or nitro group.

Examples of such hydroxy-substituted aryl groups include hydroxyphenyl (and its isomers), dihydroxyphenyl (and its isomers), trihydroxyphenyl (and its isomers), hydroxytolyl (and its isomers), hydroxyxylyl (and its isomers), [1- (hydroxyphenyl) - 1-methylethyl] phenyl (and its isomers), [4- (hydroxybenzyl)] phenyl (and its isomers), (hydroxyphenoxy) phenyl (and its isomers), hydroxybenzoylphenyl (and its isomers), hydroxybiphenyl (and its isomers), 2 - (hydroxyphenyl) -hydroxypropylphenyl, tri- (hydroxyphenyl) phenyl (and its isomers), hydroxynaphthyl (and its isomers) and trihydroxy-naphthyl ( and its isomers).

Examples of acyl groups include acyl groups represented by formula (26):

where Ar ⁵ means an aromatic group.

Examples of the aromatic group represented by Ar ⁵ include phenyl or alkylphenyl groups such as phenyl, tolyl (and its isomers), xylyl (and its isomers), trimethylphenyl (and its isomers), tetramethylphenyl (and its isomers), ethylphenyl (and its isomers), propylphenyl (and its isomers), butylphenyl (and its isomers), diethylphenyl (and its isomers), methylethylphenyl (and its isomers), pentylphenyl (and its isomers), hexylphenyl (and its isomers) and cyclohexylphenyl (and its isomers) ); alkoxyphenyl groups such as methoxyphenyl (and its isomers), ethoxyphenyl (and its isomers) and butoxyphenyl (and its isomers); halogenated phenyl groups such as fluorophenyl (and its isomers), chlorophenyl (and its isomers), bromophenyl (and its isomers), chloromethylphenyl (and its isomers) and dichlorophenyl (and its isomers), and substituted phenyl groups represented by the above formulas ( 16), (19) and (20).

Examples of such acyl groups include a benzoyl group, a phthaloyl group, a terephthaloyl group and a salicylic group.

The same types of groups as those selected from R ¹ , R ² , R ³ , Ar ¹ , Ar ² and Ar ^{3 of the} starting material and / or reagent are preferred as R ⁴⁴ -R ⁶¹ groups, since the number of types of products can be reduced. In the case of the compound represented by formula (11), these are groups

R ⁸ -R ²⁷ when the molecular weight of the compound is 450 or higher, more preferably 480 or higher. In the case of the compound represented by formula (14), R ⁴⁴ -R ⁶¹ groups are selected so that the molecular weight of the compound is 450 or higher, more preferably 480 or higher.

Examples of alkyl groups represented by R ⁶² in formula (15) include a linear or cyclic alkyl group having from 4 to 10 carbon atoms, such as a butyl group (and its isomers), a pentyl group (and its isomers), a hexyl group (and its isomers), heptyl group (and its isomers), octyl group (and its isomers), nonyl group (and its isomers), decyl group (and its isomers), cyclobutyl group, cyclopentyl group (and its isomers) and cyclohexyl group ( and its isomers). Groups containing an ether bond are also applicable, examples thereof include a methoxyethyl group (and its isomers), an ethoxyethyl group (and its isomers), a methoxypropyl group (and its isomers), an ethoxypropyl group (and its isomers), a methoxybutyl group (and its isomers) and ethoxybutyl group (and its isomers).

Examples of the aralkyl groups represented by R ⁶² include aralkyl groups having from 7 to 12 carbon atoms which may have substituents such as a benzyl group and a phenylethyl group.

Examples of the aryl groups represented by R ⁶² include phenyl or alkylphenyl groups such as phenyl, tolyl (and its isomers), xylyl (and its isomers), trimethylphenyl (and its isomers), tetramethylphenyl (and its isomers), ethylphenyl (and its isomers), propylphenyl (and its isomers), butylphenyl (and its isomers), diethylphenyl (and its isomers), methylethylphenyl (and its isomers), pentylphenyl (and its isomers), hexylphenyl (and its isomers) and cyclohexylphenyl (and its isomers) ); alkoxyphenyl groups such as methoxyphenyl (and its isomers), ethoxyphenyl (and its isomers) and butoxyphenyl (and its isomers); halogenated phenyl groups such as fluorophenyl (and its isomers), chlorophenyl (and its isomers), bromophenyl (and its isomers), chloromethylphenyl (and its isomers) and dichlorophenyl (and its isomers).

Examples of R ⁶³ -R ⁶⁷ in the formula (15) include alkyl groups, aralkyl groups and aryl groups listed above as examples for R ⁸ -R ⁶¹ .

The same types of groups are preferred as those selected from R ¹ , R ² , R ³ , Ar ¹ , Ar ² and Ar ^{3 of the} starting material and / or reagent, since the number of types of products can be reduced.

Examples of compounds represented by formula (11) include titanium methyl phenoxide, Ti (OPhMe) ₄ , and titanium dimethyl phenoxide, Ti (OPh (Me) ₂ ) ₄ .

In the compound represented by formula (12), Ti has a valency of 4, and the compound may contain alcohol or aromatic alcohol in the form of an alcoholate or phenolate as a ligand. Examples of compounds of formula (12) include compounds of formula (27):

Examples of the compounds represented by formula (13) include titanedisalicylate, titanium bis (2-methyl salicylate) and titanium bis (3-methyl salicylate).

Of the titanium-containing compounds, an organic polytitanoxane composition obtained in a known manner can be used. Such known methods include a process in which titanium alkoxide is partially hydrolyzed and polycondensed while removing alcohol (for example, Journal of Polymer Science, vol. VII, No. 6, 591-602). Examples of such polytitanoxane compositions also include polytitanoxane obtained by the method described in JP-Al-129031, and cyclic titanoxane obtained by the method described in JP-A-1-31793, JP-A-1-52786 and JP-A-64- 52,786.

Further, a copolymer with another metal alkoxide obtained by the method described in JP-B-5-31900 can also be used. Polytitanoxane or copolytitanoxane having 2 or more, preferably from 2 to 6, more preferably from 4 to 6 Ti atoms in the molecule, is preferably used. These polytitanoxane and copolytitanoxane may contain at least one Ti — O — Ti bond per molecule. Although the analysis of Ti-O-Ti bonds is very complex, researchers in the art currently believe that the Ti-O-Ti bond is formed when the titanium alkoxide described above is partially hydrolyzed and polycondensed to remove alcohol, and the present invention also according with this argument. In particular, as shown in formula (28), one Ti-O-Ti bond is formed by partial hydrolysis of titanium tetraalkoxide by adding one water molecule to two titanium tetraalkoxide molecules followed by removal of two alcohol molecules.

Further, in the case of an oligomerization reaction, a polytitanoxane having several Ti-O-Ti bonds in a molecule can be obtained by adding water in an amount suitable for the degree of oligomerization and removing the resulting alcohol. To obtain a titanium compound containing from 2 to 6 Ti atoms in the molecule, tetraalkoxy titanium is partially hydrolyzed with water, in a molar ratio of not more than 0.1-2 per mol of Ti atoms, preferably water in a molar ratio of not more than 0.3-1, 5, more preferably water in a molar ratio of not more than 0.5-1.2, in order to avoid the formation of solid components caused by excessive partial hydrolysis; and then it can be obtained by polycondensation, in which low-boiling components are removed. The amount of water used for the partial hydrolysis described above is calculated on the total amount of tetraalkoxy titanium used to produce the organic polytitanoxane composition. All the water needed for partial hydrolysis can be used to partially hydrolyze the portion of tetraalkoxy titanium used to produce, and then the rest of tetraalkoxy titanium is added to this to carry out the reaction. In this case, it is possible to obtain an organic polytitanoxane composition containing many branched structures. Solid components formed during partial hydrolysis can be removed by filtration. Regarding partial hydrolysis, tetraalkoxy titanium is dissolved in an alcohol solvent and the solution is cooled to 80 ° C or lower, preferably 5 ° C or lower, then alcohol containing the desired amount of water is added dropwise with stirring over 1-5 hours, solution temperature is set between 30 and 150 ° C, and low boiling components are removed by distillation. The reaction may be terminated when alcohol is no longer released. A known reactor can be used, a mixing apparatus is preferred in which cooling and heating can be carried out. Thus, in the method for producing the organic polytitanoxane of the present invention, the organic polytitanoxane can be obtained by sequentially or simultaneously carrying out two steps: 1) obtaining a partially hydrolyzed product by partial hydrolysis of tetraalkoxytitanium and 2) removing the formed low boiling component, including alcohol, from the partially hydrolyzed product and subjecting the product polycondensation.

Alternatively, the organic polytitanoxane composition can be prepared by partial hydrolysis of tetragalotitan (TiX ₄ : X = Cl, Br), removing -HX from it and subjecting the resulting polycondensation reaction or removing -HX from titanium hydroxide and tetragalotitan and subjecting the resulting polycondensation reaction. An organic polytitanoxane composition obtained by sequentially or simultaneously carrying out three stages is also preferable: 1) obtaining a partially hydrolyzed product by partial hydrolysis of tetragalotitan, 2) removing a low-boiling component from a partially hydrolyzed product and subjecting the polycondensation product to it, and 3) reacting the resulting alcohol with HX-HX and its alkoxylation.

You can also remove the alcohol from titanium hydroxide and tetraalkoxytitanium and subject the resulting polycondensation.

Another well-known process for the preparation of an organic titanoxane composition involves subjecting tetraalkoxy titanium to heat, deesterification and polycondensation. Preferably used is an organic polytitanoxane composition obtained after removal of from 0.1 to 2 moles, preferably from 0.3 to 1.5 moles, more preferably from 0.5 to 1.2 moles of ether, based on a mole of titanium atoms, contained in tetraalkoxytitanium, at a temperature of deesterification from 100 to 300 ° C, preferably from 150 to 250 ° C for 1-300 hours.

These known organic polytitanoxanes obtained by the polycondensation reaction of at least one feedstock selected from tetraalkoxy titanium, tetragalotitan (TiX ₄ , wherein X is selected from Cl and Br) and titanium hydroxide can be used in the present invention.

The above-described organic polytitanoxane and metal-containing catalyst can be used as is or after exchanging organic groups before use. For example, they can be used after exchanging alkoxy groups by reaction with a composition containing at least one component selected from alcohol, an aromatic hydroxy compound, and a carboxylic acid ester. In other words, they can be used in the present invention after mixing or reaction with the starting material, reagent or by-product of the transesterification or disproportionation reaction.

When traditional organic titanate is used, more specifically when dimethyl carbonate is used as the starting material, phenol is used as a reagent, and phenyl titanate [Ph (OPh) ₄ ] (phenol adduct is also suitable) is used as organic titanate to produce aromatic carbonate, specifically methyl phenyl carbonate methyl titanate [Ti (OMe) ₄ ] can be formed in a distillation column in an equilibrium reaction due to the exchange of alkoxy groups. Since methyl titanate is poorly soluble in the reaction mixture and sublimates, it can adhere to the wall of the distillation column, which can cause clogging. However, it was unexpectedly found that the organic polytitanoxane composition (titanate oligomer, etc.) used in the present invention is unlikely to have such poor solubility or cause adhesion to the walls due to sublimation.

Whether the Ti-O-Ti bond is present or not, it can simply be determined by elemental analysis of the catalyst and NMR. When the structure of the organic group bound or coordinated to Ti is known, the amount of bridging oxygen corresponding to Ti-O-Ti can be determined by subtracting from the value obtained by elemental analysis, the number of oxygen atoms corresponding to the organic group. The number of bridged oxygen atoms involved in Ti-O-Ti bonds and the number of bonds can be determined from the ratio of the number of Ti atoms to the number of bridged oxygen atoms. In addition, the valency of Ti and the number of oxygen atoms involved in Ti-O-Ti can be determined by known crystallographic analysis using x-rays (for example, JP-A-2004-256719), assuming that the Ti-O bond is present, when the atomic distance between Ti and O is less than the sum (2.87 E) of the ionic radii of the Ti atom and the oxygen atom.

In addition, such a polytitanoxane or copolytitanoxane obtained in a known manner can be alkoxy substituted by reaction with an alcohol or aromatic hydroxy compound by a known method (e.g., J. Inorg. Nucl. Chem., Vol. 28, 2410 (1966), J. Indian Chem. Soc., Vol. 38, No. 3, p. 147-152 (1961)). These catalyst components can be a reaction product with an organic compound present in the reaction system, for example, aliphatic alcohols, aromatic monohydroxy compounds, alkylaryl carbonates, diaryl carbonates or dialkyl carbonates, or they can be heated before the reaction as a raw material or product, or after heating, they can be low boiling components removed. The catalyst may be an adduct or an associated form with an alcohol or aromatic hydroxy compound present in the reaction system.

The structure of the polytitanoxane obtained by the above method is shown in the above formula (14).

Examples of such titanium compounds include

1) linear polytitanate represented by formula (29), and cyclic polytitanate represented by formula (30).

In the formula (29), R ⁷² means an alkyl group having from 1 to 10 carbon atoms, an aralkyl, aryl or acyl group, R ⁷² may be the same or different from each other or may be linked to each other and h is an integer from 1 up to 5.

In the formula (30), R ⁷³ means an alkyl group having from 1 to 10 carbon atoms, an aralkyl, aryl or acyl group, R ⁷³ may be the same or different from each other or may be linked to each other and i is an integer from 1 to 4, j is an integer from 0 to 4 and i + j = 4.

When R ⁷² in the formula (29) and R ⁷³ in the formula (30) have a small number of carbon atoms, the catalyst itself may not be in the form of a liquid or it may not be a liquid in the reaction system, since it has extremely low solubility in the liquid phase of the reaction system. Thus, preferred examples of R ⁷² and R ⁷³ are an alkyl group having from 3 to 10 carbon atoms, such as a propyl group (and its isomers), a butyl group (and its isomers), a pentyl group (and its isomers), a hexyl group (and its isomers), heptyl group (and its isomers), octyl group (and its isomers), nonyl group (and its isomers), decyl group (and its isomers), cyclobutyl group, cyclopentyl group (and its isomers) and cyclohexyl group (and its isomers). Groups containing an ether bond are also suitable, examples thereof include alkyl groups such as a methoxyethyl group (and its isomers), an ethoxyethyl group (and its isomers), a methoxypropyl group (and its isomers), an ethoxypropyl group (and its isomers), and methoxybutyl group (and its isomers) and ethoxybutyl group (and its isomers). Preferred examples thereof also include aralkyl groups having from 7 to 12 carbon atoms, which may have substituents, such as a benzyl group and a phenylethyl group. Preferred examples thereof also include aryl groups, for example phenyl or alkylphenyl groups such as phenyl, tolyl (and its isomers), xylyl (and its isomers), trimethylphenyl (and its isomers), tetramethylphenyl (and its isomers), ethylphenyl (and its isomers), propylphenyl (and its isomers), butylphenyl (and its isomers), diethylphenyl (and its isomers), methylethylphenyl (and its isomers), pentylphenyl (and its isomers), hexylphenyl (and its isomers) and cyclohexylphenyl (and its isomers); alkoxyphenyl groups such as methoxyphenyl (and its isomers), ethoxyphenyl (and its isomers) and butoxyphenyl (and its isomers); halogenated phenyl groups such as fluorophenyl (and its isomers), chlorophenyl (and its isomers), bromophenyl (and its isomers), chloromethylphenyl (and its isomers) and dichlorophenyl (and its isomers).

Examples of such compounds include compounds whose structural formula is as described below, for example, butoxy titanate dimer, phenoxy titanate oligomers such as phenoxy titanate dimer, phenoxy titanate trimer and phenoxy titanate tetramer (and its isomers), phenoxy sialicyl titanate oligomers, such as a titanate dimer (obtained from phenol and bisphenol A); and a titanate dimer (obtained from phenol and bisphenol A). Compounds containing 2 to 6 Ti atoms in a molecule are preferred because of their solubility. Titanate oligomers have a molecular weight distribution, and they may contain a component that does not satisfy the molecular weight of 450 or higher defined in the present invention, or contain a component whose vapor pressure at 230 ° C. is 10 Pa or higher. Such titanate oligomers can be used as is, but they can be used after removal of the low boiling components or low molecular weight components by distillation.

These catalyst components can be a reaction product with an organic compound present in the reaction system, for example, an aliphatic alcohol, an aromatic monohydroxy compound, an alkyl aryl carbonate, a diaryl carbonate or a dialkyl carbonate, or they can be heated prior to the reaction as a raw material or a product, or after heating, they can be low boiling components removed.

Examples of compounds represented by formula (15) include monoalkyltin (IV) alkoxide oxide. Among scientists engaged in research in this field, it is well known that the Sn = O double bond is usually present and the monoalkyltin (IV) alkoxide is usually in the form of an oligomer of bound molecules. Examples of such compounds include butyl tin butoxide (IV), (2-ethyl butyl oxide) butyl tin (IV) oxide, (3-methoxypropyl oxide) butyl tin (IV) oxide, (2-methoxy ethoxide) butyl tin (IV) oxide, (2-ethoxy ethoxide) oxide butyltin (IV), butyltin (IV) oxide, butyl oxide octyltin (IV) oxide, (2-ethylbutyl oxide) octyltin oxide (IV), (3-methoxypropyl oxide) octyltin (IV) oxide, (2-methoxyethoxide) octyltin oxide (IV ), (2-ethoxyethoxide) octyltin (IV) oxide and octyltin (IV) oxide.

The type of reaction apparatus in the present invention is not particularly limited, and conventional reaction apparatuses, such as a mixing apparatus, a multi-stage mixing apparatus, a multi-stage distillation column, or a combination thereof, can be used. These reaction apparatuses can be used both for a batch reaction and for a continuous reaction. In order to effectively shift the reaction equilibrium towards the product system, a process using a multi-stage distillation column is preferable, a continuous process using a multi-stage distillation column is more preferable. Multistage distillation columns have two or more theoretical distillation steps, and any type can be used if they can be distilled continuously.

As such a multi-stage distillation column, any commonly used multi-stage distillation column can be used, examples thereof include plate-type columns using plates such as a cap plate, a strainer plate, a valve plate or a counterflow plate, and packed columns equipped with any of various nozzles such as Raschig rings, Lessing rings, Poll rings, Burl saddle, Interlox saddle nozzle, Dixon nozzle, McMagh saddle mesh nozzle she, Helipak, Sulzer nozzle and Mellapack. Further, preferably packed column-type columns may also be used, having both a column column section and a packed column section with nozzles. When a continuous process using a multi-stage distillation column is used to produce aromatic carbonates, the starting materials and reagents are fed to a continuous multi-stage distillation column, and these substances are reacted with each other in the presence of a metal-containing catalyst in the liquid phase or in the gas-liquid phase in the distillation column with simultaneously extracting from the bottom of the column the resulting high boiling point reaction mixture containing aromatic carbonate, or a mixture Panchromatic carbonates in liquid form, and continuously removing by distillation from the top of distillation column resulting low boiling point reaction mixture containing a by-product in a gaseous form.

The catalyst in the present invention is usually used in a concentration of from 0.0001 to 30 wt.%, Preferably from 0.001 to 10 wt.%, More preferably from 0.01 to 5 wt.%, Based on the total weight of the feed, although the concentration depends on the type of catalyst used; the type and amount of feed; and reaction conditions, such as reaction temperature and reaction pressure. The duration of the reaction (residence time in a continuous process) in the present invention is not particularly limited and is usually from 0.001 to 50 hours, preferably from 0.01 to 10 hours, more preferably from 0.05 to 5 hours.

The reaction is carried out at a reaction temperature usually from 50 to 350 ° C, preferably from 100 to 280 ° C, depending on the type of starting compounds. The reaction is carried out under reduced pressure, atmospheric pressure or increased pressure, usually from 0.1 to 2.0 · 10 ⁷ Pa, depending on the type of starting compounds used and the reaction temperature. In the present invention, it is not always necessary to use a solvent in the reaction, but a suitable inert solvent such as an ether, an aliphatic hydrocarbon, an aromatic hydrocarbon or a halogenated aromatic hydrocarbon can be used as a solvent in the reaction to facilitate the reaction.

The present invention has the difference that the high-boiling substances containing the liquid and the metal-containing catalyst are removed from the reaction system, and the resulting aromatic carbonate is transferred in the form of gas, and the liquid-containing metal-containing catalyst is returned to the system.

In this process, a portion of the liquid containing the metal-containing catalyst may be withdrawn and fresh catalyst may be added to the liquid. The liquid can also react with the active substance to obtain a reaction mixture of a substance formed from a high boiling substance and a substance formed from a metal-containing catalyst, and the mixture is separated into a component consisting mainly of a substance formed from a high boiling substance and into a component consisting mainly of from a substance formed from a metal-containing catalyst, and a substance formed from a metal-containing catalyst can be returned to the system.

The term "reaction system" refers to the space inside the reactor, pipe and equipment surrounding the reactor, equipment and pipe for the catalyst extraction system. A “liquid containing a high boiling point material and a metal-containing catalyst” in the present invention refers to a liquid containing a catalyst and a high boiling point fed to the reactor, to a reaction mixture containing a catalyst and a high boiling point present in the reactor, to a reaction mixture containing a catalyst and a high boiling point discharged from the reactor and a concentrated liquid having an increased concentration of catalyst and a high boiling point obtained by evaporation of part of the reaction mixture. The catalyst can be completely dissolved in a liquid or in suspension. In the case of suspension, undissolved parts in suspension are also included in the concept of “liquid containing a high boiling point and a metal-containing catalyst”.

A "high boiling point" in the present invention is an organic substance whose boiling point is the same or higher than that of the aromatic carbonate obtained in the present invention. Examples thereof include aromatic polyhydroxy compounds and their residues, aromatic carboxyl compounds and their residues and xanthones. Another example of such a high boiling point substance is a high molecular weight by-product obtained by the additional reaction of the above aromatic polyhydroxy compounds and their residues, aromatic carboxy compounds and their residues and xanthones.

The aromatic polyhydroxy compound is represented by the formula (31):

where Ar ⁶ is an aromatic group having a valency q, q is an integer of 2 or more, and each —OH group can be attached at any position of the Ar ⁶ group.

The remainder of the aromatic polyhydroxy compound is represented by formula (32) and is chemically bonded to at least one member selected from the group consisting of a metal-containing metal catalyst, an alkoxycarbonyl group derived from a dialkyl carbonate or alkyl aryl carbonate, an aryloxy carbonyl group derived from an alkyl aryl carbonate or diaryl carbonate, and carbon a group derived from dialkyl carbonate, alkyl aryl carbonate or diaryl carbonate

where Ar ⁶ and q are as defined above, v is an integer from 1 to m, and the —OH group and —O group can be attached at any position on the aromatic ring of the Ar ⁶ group.

Examples of Ar ⁶ in formulas (23) and (24) include aromatic groups represented by the following formulas (33), (34), (35), (36) and (37):

where Y ¹ is a single bond, a divalent alkylene group having from 1 to 30 carbon atoms, or a divalent group selected from —O—, —CO—, —S—, —SO ₂ -, —SO—, and —COO—;

where Y ¹ is as defined above, and all Y ¹ may be the same or different; and

where Z is a trivalent group, such as a trivalent alkanetriyl group having from 1 to 30 carbon atoms, and a trivalent aromatic group; at least one hydrogen atom on the aromatic ring may be substituted with another substituent, such as a halogen atom, an alkoxy group having from 1 to 30 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or nitro group.

Particular examples of the aromatic polyhydroxy compounds described above include hydroquinone, resorcinol, catechin, trihydroxybenzene (and its isomers), bis (hydroxyphenyl) propane (and its isomers), bis (hydroxyphenyl) methane (and its isomers), simple bis - (hydroxyphenyl) ether (and its isomers), bis- (hydroxyphenyl) ketone (and its isomers), bis- (hydroxyphenyl) sulfone (and its isomers), bis- (hydroxyphenyl) sulfide (and its isomers), dihydroxydiphenyl (and its isomers), bis- (dihydroxyphenyl) methane (and its isomers), 2- (hydroxyphenyl) hydroxypropylphenol, dihydroxy- (hydroxyphenyldi enyl) (and isomers thereof), tri- (hydroxyphenyl) ethane (and isomers thereof), tri- (hydroxyphenyl) benzene (and its isomers), dihydroxynaphthalene (and isomers thereof) and trigidroksinaftalin (and isomers thereof).

Of these aromatic polyhydroxy compounds and their residues, the compounds that are often found in the process for producing the aromatic carbonate of the present invention require great attention. Examples of aromatic polyhydroxy compounds often found in the manufacturing process include the following: (A), (B) and (C):

(A) an oxidation product of an aromatic monohydroxy compound that is a reactant;

(B) the product obtained by the Fris rearrangement of the diaryl carbonate obtained by the present reaction and the product of its oxidation;

(C) an aromatic dihydroxy compound obtained from phenol, which is a reagent, represented by formula (38), and its oxidation product:

where Y ¹ is as defined above.

Examples of oxidation products of (A) aromatic monohydroxy compounds include compounds represented by the following formulas (39) and (40):

Examples of products (B) obtained by the Fris rearrangement of diaryl carbonate include compounds represented by the following formulas (41), (42) and (43).

Examples of the oxidation products of the compound represented by formula (41) include compounds represented by formulas (44) and (45). Examples of the oxidation products of the compounds represented by formulas (42) and (43) include compounds represented by formulas (46) and (47).

Examples of aromatic dihydroxy compounds (C) represented by the formula (38) include compounds represented by the formula (48).

Examples of the oxidation products of the compound represented by formula (48) include compounds represented by formulas (49) and (50).

where Y is as defined above.

An aromatic polyhydroxy compound of type (A) is present in the production process, since it is obtained by oxidizing an aromatic monohydroxy compound due to the formation of a trace amount of oxygen in the system upon receipt of aromatic carbonate or because it is introduced into the reaction system as an impurity contained in the feed aromatic monohydroxy compound. Typical examples of the aromatic polyhydroxy compound (A) include dihydroxybenzene (and its isomers) and dihydroxydiphenyl (and its isomers).

The product obtained by the Fris rearrangement of type (B) diaryl carbonate is usually obtained as a result of a side reaction after receiving the diaryl carbonate. Examples of the polyhydroxy compounds (B) include 2,2'-dihydroxybenzophenone, 2,4'-dihydroxybenzophenone and 4,4'-dihydroxybenzophenone.

An aromatic dihydroxy compound of type (C) is a compound commonly used as a monomer to produce aromatic polycarbonate. Aromatic polycarbonate can be obtained by transesterification of such an aromatic dihydroxy compound and diaryl carbonate, and in the transesterification an aromatic monohydroxy compound is obtained as a by-product. An aromatic dihydroxy compound of type (C) is easily formed in the production process when the by-product aromatic monohydroxy compound is to be used as a reagent in the present invention. Typical examples of such polyhydroxy compounds include 2,2-bis- (4-hydroxyphenyl) propane.

Aromatic polyhydroxy compounds in the present invention also include an aromatic polyhydroxy compound described below, which usually coexists with 2,2-bis- (4-hydroxyphenyl) propane:

The aromatic carboxyl compound relating to the high boiling point substance in the present invention is represented by the formula (51):

where Ar ⁷ is an aromatic group having a valency r, wherein r is an integer from 1 or more, s is an integer from 0 to r-1, and each —OH group and - (COOH) group can be attached at any position of the Ar group ⁷ .

The remainder of the aromatic carboxyl compound is represented by formula (52) and is chemically bonded to at least one member selected from the group consisting of a metal-containing metal catalyst, an alkoxycarbonyl group derived from a dialkyl carbonate or alkyl aryl carbonate, an aryloxy carbonyl group derived from an alkyl aryl carbonate or diaryl carbonate, and a carbonyl group obtained from dialkyl carbonate, alkyl aryl carbonate or diaryl carbonate.

where Ar ⁷ , r and s are as defined above, t is an integer from 0 to s, u is an integer from 0 to rs and -OH group, - (COOH) group, -O- group and - (COO) - the group can be attached at any position of Ar ⁷ .

A particular example of such aromatic carboxylic compounds and its residues includes: aromatic carboxylic acids such as benzoic acid, terephthalic acid, isophthalic acid, phthalic acid or the like; aromatic carbonates such as methyl benzoate, phenyl benzoate, dimethyl terephthalate or the like; hydroxyl aromatic carboxylic acids, such as salicylic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, dihydroxybenzoic acid (its isomers), carboxydiphenol (its isomers), 2- (4-hydroxyphenyl) -2- (3'-carboxy-4 '-hydroxyphenyl) propane or the like; aryloxycarbonyl- (hydroxyl) arenes, such as phenyl salicylate, phenyl p-hydroxybenzoate, tolyl salicylate, tolyl p-hydroxybenzoate, phenyl dihydroxybenzoate (its isomers), tolyldihydroxybenzoate (its isomers), phenoxycarbonyl-2-phenylene ) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane or the like; alkoxycarbonyl- (hydroxyl) arenes such as methyl salicylate, methyl p-hydroxybenzoate, ethyl salicylate, ethyl p-hydroxybenzoate, methyldihydroxybenzoate (its isomers), methoxycarbonyl diphenol (its isomers), 2- (4-hydroxyphenyl) -2- -methoxycarbonyl-4'-hydroxyphenyl) propane or the like; aryloxycarbonyl- (alkoxy) arenes, such as phenylmethoxybenzoate (its isomers), tolylmethoxybenzoate (its isomers), phenylethoxybenzoate (its isomers), tolylethoxybenzoate (its isomers), phenylhydroxylmethoxybenzoate (its isomers), phenylmethoxybenzoic (phenomeric) phenylmethyl 2- (4-methoxyphenyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-methoxyphenyl) propane or the like; aryloxycarbonyl- (aryloxy) arenes such as phenylphenoxybenzoate (its isomers), tolylphenoxybenzoate (its isomers), tolyltolyloxybenzoate (its isomers), phenylhydroxylphenoxybenzoate (its isomers), hydroxyphenoxy (phenoxyphenyl-2-phenylcarbonyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-phenoxyphenyl) propane or the like; alkoxycarbonyl- (alkoxy) arenes such as methyl methoxybenzoate (its isomers), ethyl methoxybenzoate (its isomers), methylethoxybenzoate (its isomers), ethyl ethoxybenzoate (its isomers), methylhydroxylmethoxybenzoate (its isomers), hydroxyphenylmethoxy (2-methyl) methoxymethoxybenzoate - (4-methoxyphenyl) -2- (3'-methoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3'-methoxycarbonyl-4'-methoxyphenyl) propane or the like; alkoxycarbonyl- (aryloxy) arenes, such as methylphenoxybenzoate (its isomers), ethylphenoxybenzoate (its isomers), methyltolyloxybenzoate (its isomers), ethyltolyloxybenzoate (its isomers), phenylhydroxylmethoxybenzoate (its, isomers) 2- (4-methoxyphenyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-phenoxycarbonyl-4'-methoxyphenyl) propane or the like; aryloxycarbonyl- (aryloxycarbonyloxy) arenes, such as phenylphenoxycarbonyloxybenzoate (its isomers), tolylphenoxycarbonyloxybenzoate (its isomers), tolyltolyloxycarbonyloxybenzoate (its isomers), phenylhydroxyl-phenoxycarbonyloxy (benzoyloxy) -benzo (benzoyloxy) -benzo (benzoyloxy) -benzo (benzoyloxy) -benzo 2- [4- (phenoxycarbonyloxy) phenyl-2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- [3'-phenoxycarbonyl-4 '- (phenoxycarbonyloxy) phenyl] propane or the like; aryloxycarbonyl (alkoxycarbonyloxy) arenas, such as fenilmetoksikarboniloksibenzoat (its isomers), tolilmetoksikarboniloksibenzoat (its isomers), feniletoksikarboniloksibenzoat (its isomers), toliletoksikarboniloksibenzoat (its isomers), phenylhydroxy-methoxycarbonyloxy-benzoate (isomers thereof), hydroxyl-methoxycarbonyloxy (phenoxycarbonyl) diphenyl (its isomers), 2- [4- (methoxycarbonyloxy) phenyl] -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- [3'-phenoxycarbonyl-4 ' - (methoxycarbonyloxy) phenyl] propane or the like; alkoxycarbonyl- (aryloxycarbonyloxy) arenas, such as metilfenoksikarboniloksibenzoat (its isomers), etilfenoksikarboniloksibenzoat (its isomers), metiltoliloksikarboniloksibenzoat (its isomers), etiltoliloksikarboniloksibenzoat (its isomers), methyl hydroxy-fenoksikarboniloksibenzoat (isomers thereof), hydroxyl-fenoksikarboniloksi- (methoxycarbonyl) biphenyl ( its isomers), 2- [4- (phenoxycarbonyloxy) phenyl] -2- (3'-methoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- [3'-methoxycarbonyl-4 '(phenoxycarbonyloxy ) phenyl] propane or the like; alkoxycarbonyl- (alkoxycarbonyloxy) arenes, such as methylmethoxycarbonyloxybenzoate (its isomers), ethylmethoxycarbonyloxybenzoate (its isomers), methylethoxycarbonyloxybenzoate (its isomers), ethylethoxycarbonyloxybenzoic (methoxycarbonyloxymethoxy) -methyloxybenzo diphenyl (its isomers), 2- [4- (methoxycarbonyloxy) phenyl] -2- (3'-methoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- [3'-methoxycarbonyl-4 ' - (methoxycarbonyloxy) phenyl] propane or the like.

Of these aromatic carboxyl compounds and their residues, particular attention should be paid to those that are likely to be present in the process of producing aromatic carbonates of the present invention. Aromatic carboxyl compounds that are likely to be present may include (D) and (E) described below.

(D) includes Fris rearrangement products of aromatic carbonates that are obtained by transesterification of the present invention, and their hydrolysis products. (E) includes Fries rearrangement products of transesterification products of aromatic polyvalent hydroxyl compounds and their hydrolysis products.

As described above, in the process for producing aromatic carbonates of the present invention, the reactions of producing butyl phenyl carbonate and diphenyl carbonate from dibutyl carbonate and phenol are especially important, and therefore the aromatic carboxyl compounds and their residues (D) and (E) described above are shown below as examples.

Example (D) may include: salicylic acid, p-hydroxybenzoic acid, phenyl salicylate, phenyl p-hydroxybenzoate, butyl salicylate, butyl p-hydroxybenzoate, phenylbutoxybenzoate (its isomers), phenylphenoxybenzoate (its isomers) (its isomers), butylbutoxycarbonyloxybenzoate (its isomers) or the like.

Example (E) may include: dihydroxybenzoic acid (its isomers); phenyl dihydroxybenzoate (its isomers); phenoxycarbonyl diphenol (its isomers); 2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane or the like.

Xanthones which are included in the high boiling substances of the present invention include xanthon, wherein the xanthon has at least one substituent on the aromatic ring selected from the following group of different substituents, consisting of: alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group; hydroxyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group and butoxy group; aryloxy groups such as a phenoxy group, a tolyloxy group; alkoxycarbonyloxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, propoxycarbonyloxy group and butoxycarbonyloxy group; aryloxycarbonyloxy groups such as a phenoxycarbonyloxy group, a tolyloxycarbonyloxy group; carboxyl group; alkoxycarbonyl groups such as a methoxycarbonyl group and an ethoxycarbonyl group; aryloxycarbonyl groups such as a phenoxycarbonyl group and a tolyloxycarbonyl group; and arylcarbonyloxy groups such as a benzoyloxy group and a tolylcarbonyloxy group.

The active substance in the present invention is a substance that reacts with a high boiling substance and / or a metal-containing catalyst, and any substance can be used as long as the reaction results in a separable reaction mixture. For example, the active substance includes an oxidizing agent, a reducing agent, a precipitant, an adsorbent, a reactive solvent, or the like. In particular, an oxidizing agent, a precipitating agent, a reactive solvent or the like are preferably used. These active substances can be used singly or in combination of two or more types and, in addition, simultaneously or sequentially.

The product obtained from the high boiling point material in the present invention is the reaction product and / or unreacted high boiling point substances, which are obtained from the reaction between the high boiling point substance and the active substance.

Also, the product obtained from the metal-containing catalyst is a reaction product, which is formed as a result of the reaction between the metal-containing catalyst and the active substance, and / or unreacted metal-containing catalyst.

Separation of the reaction mixture containing the product obtained from the high boiling substance and the product obtained from the metal-containing catalyst can be carried out by any separation method, if only this method is able to separate this reaction mixture into two components: one that mainly contains the product obtained from high boiling substances, and another, which mainly contains a product obtained from a metal-containing catalyst. For example, gas / condensed phase separation methods such as gas-liquid separation, gas / solid separation, gas / solid / liquid separation, or the like, may be used; solid / liquid separation methods such as sedimentation, centrifugation, filtration or the like; rectification method; extraction method; adsorption method or the like, separation methods such as sedimentation, rectification and adsorption are preferably used. Further, these separation methods can be used individually or in combination of two or more methods simultaneously or sequentially.

The combination of this active substance and the separation method is not particularly limited, but preferred embodiments of the present invention include the following:

(I) A gas / condensed phase separation method where the active substance is an oxidizing agent, the reaction is an oxidation reaction, the product obtained from the high boiling substance is low boiling oxidized products, and the product obtained from the metal-containing catalyst is metal oxide.

(II) A solid / liquid separation method wherein the active substance is a precipitant, the reaction is a precipitation reaction, and the product obtained from the metal-containing catalyst is a metal containing a solid that is present in the reaction mixture.

(III) A rectification separation method, where the active substance is a reactive solvent, the reaction is solvolysis, and the product obtained from the high boiling substance is one of the solvolysis products with a low boiling point.

When applying the above method (I), the oxidizing agent to be used is an oxidizing agent that oxidizes a high boiling point substance, producing low boiling point oxidation products as derivatives of a high boiling point substance, and which oxidizes a metal containing catalyst, producing a metal oxide as a product obtained from the metal containing catalyst. Examples of such oxidizing agents include: air, molecular oxygen, ozone, hydrogen peroxide, silver oxide; organic peroxides such as peracetic acid, perbenzoic acid, benzoyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide or the like; oxo acids such as nitrous acid, nitric acid, hypochlorous acid, hypochlorous acid and their salts or the like. Preferably, air, molecular oxygen, ozone, hydrogen peroxide, nitrous acid and nitric acid are used, more preferably air and molecular oxygen are used.

The reaction between the liquid and the oxidizing agent is carried out in a phase selected from the group consisting of the liquid phase, the mixed gas-liquid phase and the mixed gas / liquid / solid phase, although the reaction depends on the type of oxidizing agent and the reaction conditions. The reaction temperature, although it may vary depending on the type of oxidizing agent used, is usually -30-2000 ° C, preferably 0-1200 ° C, more preferably 0-900 ° C. The duration of the reaction, although it may vary depending on the type of oxidizing agent, is usually 0.001-100 hours, preferably 0.1-20 hours. The reaction is usually carried out at a pressure of 10-10 ⁷ Pa, preferably 10 ² -3 · 10 ⁶ PA. This reaction can be carried out as a periodic reaction or a continuous reaction.

In the above method (I), the separation of the reaction mixture is carried out by gas / condensed phase separation. Condensed phase means a liquid phase, a solid phase or a mixed phase of a solid and a liquid. If the reaction mixture in the above oxidation reaction is at the end of the oxidation reaction in the liquid phase, the mixed gas-liquid phase or the mixed gas / solid / liquid phase, then components of the condensed phase, consisting mainly of metal oxide, can be obtained by phase separation of the reaction mixture into gas-phase components, consisting mainly of low-boiling oxidation products, and a condensed phase containing metal oxides; and by distillation or evaporation of low-boiling oxidation products from the obtained components of the condensed phase.

If the metal-containing catalyst in the liquid is oxidized to metal oxide to form a solid phase during the above oxidation reaction, a liquid / solid mixture can be obtained during the reaction.

Further, the reaction mixture of the oxidation reaction can be converted into a solid phase only by evaporation, together with the volatile components of the liquid, of low-boiling oxidation products, which are obtained by oxidation of a high-boiling substance. This is a preferred method since, at the same time as the oxidation reaction, the solid phase, consisting mainly of metal oxide, is separated from the gas phase containing the low boiling oxidation product.

A low boiling point oxidation product is a compound that is obtained by oxidizing a high boiling point material with an oxidizing agent having a lower boiling point than a high boiling point substance. Examples of the low boiling point oxidation product include carbon dioxide, water, carbon monoxide, organic compounds containing oxygen, unsaturated organic compounds, low boiling point carbon compounds or the like, although they may vary depending on the type of oxidizing agent and high boiling point used.

The metal oxide is a metal oxide in a metal-containing catalyst and includes TiO, Ti ₂ O ₃ , TiO ₂ or the like. When a metal-containing catalyst containing several metals is used, a mixture of the corresponding metal oxides and / or mixed metal oxide is obtained.

If the above method (II) is used, this metal-containing substance can be any metal-containing substance, provided that it is in a solid state in this reaction mixture and contains this metal. For example, it includes: metal hydroxide; a metal chalcogenide such as a metal oxide, a metal sulfide or the like; an inorganic acid salt such as metal carbonate, metal sulfate or the like; a metal salt of an organic acid; metal complex; double metal salt or the like. Preferred are metal carbonates, metal hydroxides, metal oxides, metal sulfides and metal sulfates, since their solubility in this reaction mixture is low. A reactive substance, a starting material or the like may be coordinated with these metal-containing substances.

Any precipitant that reacts with the metal-containing catalyst can be used to give the metal-containing substance described above. For example, in order to precipitate these metal hydroxides, inorganic hydroxides such as alkali metal hydroxides, alkaline earth metal hydroxides or the like, and water are used. In order to precipitate these metal oxides, inorganic oxides such as alkali metal oxides, alkaline earth metal oxides or the like, and oxidizing agents such as hydrogen peroxide or the like are used. In order to precipitate these metal sulfides, inorganic sulfides such as alkali metal sulfide, alkaline earth metal sulfide or the like, and hydrogen sulfide are used. In order to precipitate these metal carbonates, inorganic carbonate salts such as alkali metal carbonates, alkaline earth metal carbonates or the like, and carboxylic acid, carbon dioxide and water are used. In order to precipitate this metal sulfate, inorganic sulfate salts such as alkali metal sulfate, alkaline earth metal salt or the like, sulfuric acid, sulfur trioxide and water are used.

The reaction between the metal-containing catalyst and the precipitant, although it may vary depending on the type of catalyst and precipitant used and the reaction conditions, is usually carried out under single-phase conditions selected from the group consisting of a liquid phase, a mixed gas-liquid phase, a mixed gas / liquid / solid phase and mixed phase solid / liquid. The reaction temperature, although it may vary depending on the type of precipitant used, is usually -70-600 ° C, preferably -30-400 ° C, more preferably -10-250 ° C.

The duration of the reaction, although it may vary depending on the type of precipitant and the reaction temperature, is usually 0.001-100 hours, preferably 0.1-20 hours. The reaction is usually carried out at a pressure of 10-10 ⁷ Pa. This reaction can be carried out as a periodic or continuous reaction.

In a precipitation reaction, a preferred method is to add a substance that forms crystallization centers. Further, although the metal-containing substance is in a solid state upon separation of the reaction mixture, it does not have to be solid during the precipitation reaction, and it can be cured by operations such as cooling or the like after this reaction. In the case of the above method (II), the separation of the reaction mixture is solid-liquid separation, and the mixture is separated into a solid phase consisting mainly of a metal-containing substance and a liquid phase consisting mainly of a product obtained from a high boiling substance. For this solid-liquid separation, precipitation, centrifugation, filtration, or a similar separation method is usually used.

Further, when implementing method (II), a high boiling point substance contained in a liquid may or may not react in a precipitation reaction.

In the case of the application of the above method (III), the reactive solvent used may be any reactive solvent, provided that it reacts with a high boiling substance and gives compounds with a boiling point lower than that of a high boiling substance. For example, water may be used; lower alcohols such as methanol, ethanol, propanol (its isomers), butanol (its isomers) or the like; lower carboxylic acids such as formic acid, acetic acid, propionic acid or the like; carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate or the like. Water, methanol, ethanol, acetic acid, methyl acetate, ethyl acetate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or the like are preferably used, and water is more preferably used.

Solvolysis in the present invention means a reaction between a reactive solvent and a high boiling point substance, and solvolysis products may undergo further reactions, such as a decarboxylation reaction, which is different from a solvolysis reaction. This low-boiling solvolysis product may be a product with a lower boiling point than that of the high-boiling substance, and its variant or structure may vary depending on the reactive solvent and the type of high-boiling substance. The solvolysis products with a low boiling point are specifically disclosed in the following paragraphs (i) to (iii), where the high boiling point substance is phenyl salicylate, which is one of the aromatic carboxyl compounds.

(i) In the case where the reactive solvent is water: phenol and salicylic acid are obtained by hydrolysis and this salicylic acid is further subjected to decarboxylation to obtain phenol and carbon dioxide.

(ii) In the case where the reactive solvent is an alcohol: alkyl salicylate and phenol are obtained by alcoholysis.

(iii) In the case where the reactive solvent is a carboxylic acid: salicylic acid and phenyl carboxylate are obtained by transesterification and this salicylic acid is further subjected to decarboxylation to phenol and carbon dioxide.

The above explanations are based on the example of phenyl salicylate, which is an aromatic carboxyl compound with a relatively simple structure, but similar reactions involving more complex aromatic carboxyl compounds can also form the corresponding solvolysis products, such as aromatic monohydroxy compound, lower carboxylic acid ester and aromatic monohydroxy compounds, an ester of an aromatic carboxyl compound and a lower alcohol, carbon dioxide or the like e. In particular, aromatic monohydroxy compounds are preferred as solvolysis products since they are reactive substances in the present invention and can be reused.

Since the liquid contains a metal-containing catalyst, which usually acts as a catalyst for the solvolysis reaction, it is not necessary to use a separate catalyst for the solvolysis reaction. However, in order to increase the reaction rate or the like, a catalyst may be used.

The reaction between the high boiling agent and the reactive solvent, although it may vary depending on the reaction conditions, is usually carried out under single-phase conditions of a liquid phase or a mixed solid / liquid phase.

The reaction temperature, although it may vary depending on the type of reactive solvent used, is usually from -30 to 400 ° C, preferably from -10 to 300 ° C, more preferably from 0 to 250 ° C.

The duration of the reaction, although it may vary depending on the type of reactive solvent and the reaction temperature, is usually 0.001-100 hours, preferably 0.1-20 hours. The reaction is usually carried out at a pressure of 10-10 ⁷ Pa. This reaction can be carried out as a periodic or continuous reaction.

The metal-containing catalyst may or may not catalyze the solvolysis reaction. In the case of the reaction of water or alcohols as reactive solvents with a liquid containing an aromatic carboxyl compound as a high boiling point, decarboxylation produces carbon dioxide as one of the derivatives of a high boiling point. Thus, this carbon dioxide acts as a precipitant and reacts with a metal-containing catalyst, and metal-containing substances, such as metal carbonate or the like, can be obtained in soluble and / or cured states.

In the above method (III), the reaction mixture is separated by distillation, and the low boiling point solvolysis products, which are products derived from the high boiling point substance, are obtained mainly as distillates. The metal-containing catalyst remains in the residual liquid in the still. This distillation separation is usually carried out at a temperature of 10-300 ° C, preferably 50-250 ° C, which is the temperature of the liquid in the still. The reaction is usually carried out at a pressure of 0.1-1.0 · 10 ⁶ Pa, preferably 1.0-1.0 · 10 ⁵ Pa. Distillation can be carried out in batch mode or continuously.

When products derived from a metal-containing catalyst that are obtained by separating a liquid from an active substance in a reaction mixture are to be returned to the system, a composition containing products derived from a metal-containing catalyst that are obtained by separating a reaction mixture from a liquid, solid or mixed phase solid, can be returned to the system as is, or, if this composition contains other components, in addition to products derived from a metal-containing catalyst, part or all of Components can be separated and then returned to the system. Further, a reaction solution or suspension that is obtained by reacting products derived from a metal-containing catalyst with a starting material or a reactive substance can be returned. This method is preferred when products derived from a metal-containing catalyst are in a solid phase or a mixed solid / liquid phase.

As for high boiling liquid substances that must be removed from the system, their concentrations, which can vary depending on the type of substances, should preferably not be kept extremely low, since the volume of liquid that is being removed becomes too large. Also, if the concentration of the high boiling substance is too high, handling becomes difficult due to the increase in boiling point and viscosity. Thus, the concentration in the liquid of the high boiling point material which is to be removed is usually 0.01-99% by weight, preferably 0.1-95% by weight, more preferably 1-90% by weight.

Further, when the high boiling point substance is an aromatic polyvalent hydroxyl compound, the weight ratio of the aromatic polyvalent hydroxyl compound to the metal of the catalyst in the liquid is usually kept at a level of 2 or lower to prevent deposition and adhesion of the catalyst in the reactor and lines.

When using the metal-containing catalyst of the present invention, factors that in the past made production unstable, such as clogging of a distillation column, deposition of catalyst components on the wall, were unexpectedly improved.

Further, a preferred example of the present invention includes the use of diaryl carbonate, purified by the method of the present invention, to produce aromatic polycarbonate by the transesterification method. The polycarbonate obtained by the transesterification method, depending on the polymerization method, tends to exhibit a red color due to the presence of metal in the diphenyl carbonate catalyst, which is used as a raw material, especially if the Ti content is more than 1 ppm. However, an aromatic carbonate, an especially important diphenyl carbonate obtained by the process of the present invention, contains Ti in an amount of 1 ppm or less. Polycarbonate is readily prepared with bisphenol A by transesterification with polymerization. Thus, the polycarbonate obtained in the present invention is of high quality since it contains less Ti, which causes the polycarbonate to stain.

Further, in the preparation of aromatic polycarbonate by transesterification, a high polymerization rate can be achieved using the diaryl carbonate obtained by the process of the present invention. In addition, the aromatic polycarbonate obtained by the transesterification method, which was obtained using the aromatic dihydroxy compound, and the diaryl carbonate obtained by the method of the present invention are of high quality and have no color.

The effect of the invention

According to the present invention, a high-purity diaryl carbonate is obtained, which is easily separated from the catalyst, and the starting material selected from the group consisting of dialkyl carbonate, alkyl aryl carbonate and a mixture thereof, and a reagent selected from the group consisting of aromatic monohydroxy compound, alkyl aryl carbonate and a mixture thereof in the presence of a metal-containing catalyst to produce aromatic carbonates, and by-products alcohols and / or dialkyl carbonates are distilled from the system.

Brief Description of the Drawings

Figure 1: block diagram of a process related to the production of aromatic carbonate in the present invention; and

figure 2: block diagram of the process related to the purification of diaryl carbonate in the present invention.

Figure 3: process flow diagram related to the structure of an aromatic carboxylic acid ester.

4: a flowchart of a process related to the structure of an aromatic carboxylic acid ester.

Description of symbols

1, 4, 7, 10, 13, 16, 19, 22, 25, 28, 31, 34, 37, 40, 43, 46, 54, 57, 58, 60: line

50, 56: input line

2, 14, 26, 38, 51: heater

3, 15, 27, 39, 49: continuous multi-stage distillation column

5, 17, 29, 41: refrigerator

55: capacitor

6, 18, 30, 42: gas-liquid separator

11, 23, 35, 47, 59: reboiler

8, 12, 20, 24, 33, 36, 44, 48: storage tank

9, 21, 32, 45: pressure valve

52: top of the column

53: bottom of the column

The best way to implement the invention

Further, the present invention will be explained with particular examples, but the present invention is not limited to these examples. Further, measurements of the concentration in the aromatic carbonate of the catalyst and the concentration of the metal obtained from the metal-containing catalyst were carried out using ICP / AES methods (Inductively coupled plasma / Atomic emission spectroscopy: detection limit of 0.1 ppm). The concentration of organic components in the liquid was measured by gas chromatography.

(1) Conditions for gas chromatographic analysis.

Column: DB-1 (J&W Scientific)

Liquid phase: 100% dimethylpolysiloxane

Length: 30 m

Inner Diameter: 0.25mm

Film thickness: 1 μm

Column temperature: 50 ° C (rise 10 ° C / min) 300 ° C

Sample Inlet Temperature: 300 ° C

Detector Temperature: 300 ° C

Detection Method: Flame Ionization Detector

(2) Quantitative analysis

Solutions of samples for analysis were analyzed quantitatively based on standard curves obtained by analyzing calibration samples of each standard substance.

(3) Ti-O-Ti link confirmation.

The presence of the Ti-O-Ti bond is established by identifying the Ti substituent (or ligand) according to the results of ¹ H-NMR and subtracting the oxygen number related to this substituent (or ligand) from the result of elemental analysis (C, H, O, Ti), counting this is the oxygen number corresponding to bridging oxygen atoms corresponding to Ti-O-Ti.

(4) Conditions for NMR analysis

Device: JNM-A400, Fourier transform NMR system, manufactured by JEOL Ltd.

Obtaining samples for ^one H-NMR ¹³ C-NMR analysis

To obtain samples for NMR analysis, the metal-containing catalyst was weighed in the range of 0.1-1 g and uniformly mixed with deuterated chloroform (Aldrich Co. 99.8%) or carbon tetrachloride, which was weighed in the range of 0.05-0.7 g TMS (tetramethylsilane) was used as an internal standard.

Examples

The present invention will be described based on examples.

Example 1

[Preparation of aromatic carboxylic acid ester]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a rate of about 109 g / h, through heater 2 and line 1, of a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, an adduct of a phenyl titanate dimer with 2PhOH [(PhO) ₃ -Ti-O-Ti - (OPh) ₃ · 2PhOH] (result of elemental analysis: C = 67.2, H = 4.93, O = 16.77, Ti = 11.1; result of ¹ H-NMR analysis: PhOH and PhO groups are present in ratio 2: 6. In one molecule there are two Ti atoms and one oxygen atom, which cannot be obtained from the PhOH and PhO groups, that is, there is one Ti-O-Ti bond, molecular weight without adduct PhOH: 670, vapor pressure: 1 or lower (at 230 ° C) (a mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at about 65/35 and the Ti level of atoms was set at about 10,000 ppm of the total liquid) to the middle stage of a multi-stage distillation continuous column 3, which consisted of a condensation section having an inner diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section which had an internal diameter of 2 inches, 1 m in length of the column and was loaded nozzle Dixon (w 6 mm). The condensation section was located in the lower part of the stage, where the mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. The catalyst was dissolved in the reaction liquid.

After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9).

The liquid withdrawn into storage tank 12 contained about 23 wt.% Phenol, about 56 wt.% Dibutyl carbonate, about 12 wt.% Butyl phenyl carbonate, about 0.2 wt.% Diphenyl carbonate, about 0.3 wt.% 1-butanol and catalyst. The liquid withdrawn into storage tank 8 contained about 99% by weight of 1-butanol, about 0.5% by weight of phenol and about 0.2% by weight of dibutyl carbonate.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multistage distillation column 15 of continuous operation, as in the case of the multistage distillation column 3 of continuous operation, consisted of a condensation section, which has an inner diameter of 2 inches, 0.5 m in length and was filled with 10 steps of sieve plates, and an extraction section, which has an internal diameter of 2 inches, 1 m in the length of the column and was loaded with a Dixon nozzle (w 6 mm), the condensation section was located at the bottom of the stage, where continuous distillation column 15 from the storage tank 12 clearly fed reaction liquid containing the catalyst and recovery section was located at the top.

The reaction was carried out by continuously supplying through the line 13 the reaction liquid, which was discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12, with a flow rate of 100 g / h to the multistage distillation column 15 of continuous operation after heating by heater 14. The heat required for reaction and distillation, it was supplied by circulating liquid in the lower part of the column along line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was regulated ak to be about 220 ° C.

The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4).

The liquid withdrawn to storage tank 24 contained about 5% by weight of dibutyl carbonate, about 74% by weight of butyl phenyl carbonate, about 10% by weight of diphenyl carbonate, and a catalyst. The fluid diverted to storage tank 20 contained about 0.3 wt.% 1-butanol, about 18 wt.% Phenol and about 81 wt.% Dibutyl carbonate. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in FIG. 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 192 g / h, about 0.1 m above the average stage of a multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm), with an inner diameter of 2 inches and a length of 1 m.

The heat required for distillation separation was supplied by circulating the liquid in the bottom of the column through line 34 through a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 90 g / h. After removal from the top of the column through line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 102 g / h. The liquid withdrawn to storage tank 33 consisted of dibutyl carbonate: about 0.6% by weight, butyl phenyl carbonate: about 73% by weight, diphenyl carbonate: about 26% by weight.

Separation by distillation was carried out by a continuous supply of liquid, which was continuously discharged into the storage tank 33, through line 37 passing through heater 38, with a flow rate of about 101 g / h, to the middle stage of a multistage distillation column 39 of continuous operation, which was a column loaded with a nozzle Dixon (w 6 mm) with an internal diameter of 2 inches and a length of 2 m. The heat required for separation by distillation was supplied by circulating the liquid in the lower part of the column along line 46 through reboiler 47, and the temperature the bottom of the multi-stage distillation column was adjusted so as to be approximately 200 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a flow rate of about 19 g / h.

After removal from the top of the column through line 40, the distillate was liquidated in the refrigerator 41 and continuously discharged to the storage tank 44 at a rate of about 82 g / h. The liquid withdrawn to storage tank 44 consisted of dibutyl carbonate: about 0.7% by weight, butyl phenyl carbonate: about 90% by weight, diphenyl carbonate: about 9% by weight.

The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. Analysis of the liquid shows that the Ti content was below the detection limit. Inspection of the distillation column did not reveal any deposits or the like.

Comparative Example 1

[Production of aromatic carbonate]

Aromatic carbonate was obtained in the device shown in figure 1. The reaction was carried out by continuously feeding with a flow rate of about 109 g / h, through heater 2 and conveyor line 1, a mixed solution consisting of dibutyl carbonate, phenol and phenyl titanate [Ti (OPh) ₄ ] (this phenyl titanate: adduct with phenol; molecular weight without phenol adduct: 420; vapor pressure: about 15 Pa at 230 ° C) (a mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at about 65/35, and the level of Ti as atoms was set at about 10,000 ppm of the total liquid) multistage middle stage a continuous distillation column 3, which consisted of a condensation section having an inner diameter of 2 inches, 0.5 m long and filled with 10 steps of sieve plates, and an extraction section that had an internal diameter of 2 inches, 1 m long and loaded with a Dixon nozzle (w 6 mm). The condensation section was located in the lower part of the stage, where the mixture was continuously supplied, and the extraction section was located in the upper part.

The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h.

After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9). The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multi-stage distillation column 15 of continuous operation, like the multi-stage distillation column 3 of continuous operation, consists of a condensation section, which has an inner diameter of 2 inches, 0.5 m in length of the column and is filled with 10 steps of sieve plates, and an extraction section, which has an inner diameter 2 inches, 1 m in length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where in this distillation column 15 from the storage tank 12 continuously fed Zion liquid containing the catalyst and recovery section was located at the top.

The reaction was carried out by continuously supplying through line 13 a reaction liquid discharged from below of a continuous multi-stage distillation column 3 through line 10 to a storage tank 12 to a continuous multi-stage distillation column 15 with a flow rate of 100 g / h after heating by heater 14. The heat required for reaction and distillation, was supplied by circulating liquid in the lower part of the column along line 22 through reboiler 24, the temperature at the bottom of the multi-stage distillation column was regulated so that be approximately 220 ° C.

The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4).

The liquid discharged into storage tank 24 consisted of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight. The liquid discharged into storage tank 20 consisted of 1-butanol: 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid, which was removed to the storage tank 24, through line 25 passing through the heater 26, with a flow rate of about 100 g / h, about 0.1 m above the average stage of the multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm) with an inner diameter of 2 inches and a length of 1 m.

The heat required for distillation separation was supplied by circulating the liquid in the bottom of the column through line 34 through a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h.

The liquid discharged to storage tank 33 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%.

Separation by distillation was carried out by continuous supply of liquid, which was continuously discharged into storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a continuous multistage distillation column 39, which was a column loaded with a Dixon nozzle (w 6 mm), with an internal diameter of 2 inches and a length of 2 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 46 through reboiler 47, and the temperature the bottom of the multi-stage distillation column was adjusted so as to be approximately 230 ° C.

The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h.

The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 94 wt.%.

The fluid diverted to storage tank 48 was solid at ambient temperature but red in color. Liquid analysis showed that the Ti content was approximately 5 ppm.

Reference Example 2

[Production of aromatic carbonate]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a flow rate of about 100 g / h, through heater 2 and conveyor line 1, of a mixed solution of dibutyl carbonate, phenol and, as a catalyst, the adduct di (phenyl salicylate) titanate · diphenolate (molecular weight: 660, pressure vapor: 1 Pa or lower at 230 ° C) (a mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at about 65/35 and the Ti level of atoms was set at about 10,000 ppm of the total liquid) to the middle stage multistage p continuous rectification column 3, which consists of a condensation section having an inner diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section that has an internal diameter of 2 inches, 1 m in length of the column and loaded Dixon nozzle (w 6 mm).

The condensation section was located in the lower part of the stage, where the liquid mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C.

The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 95 g / h. The catalyst was dissolved in the reaction liquid.

After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 5 g / h, and the rest returned by reverse flow to the distillation column (reflux number 2).

The liquid withdrawn into storage tank 12 consisted of phenol: about 26 wt.%, Dibutyl carbonate: about 50 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.6 wt.%, And catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 90 wt.%, Phenol: about 7 wt.%, And dibutyl carbonate: about 3 wt.%.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multistage distillation column 15 of continuous operation, as in the case of the multistage distillation column 3 of continuous operation, consisted of a condensation section having an inner diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section that has an inner diameter 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed s reaction liquid containing the catalyst and recovery section was located at the top.

The reaction was carried out by continuously supplying through line 13 a reaction liquid discharged from the bottom of the multi-stage distillation column 3 of continuous operation via line 10 to the storage tank 12 to a multi-stage distillation column 15 of continuous operation with a flow rate of 95 g / h after heating by heater 14. The heat required for reaction and distillation was supplied by circulating liquid in the lower part of the column along line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was regulated so Oba be about 220 ° C.

The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a flow rate of about 19 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column via line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 76 g / h, and the rest was returned back flow to a distillation column (reflux number 4).

The liquid withdrawn into storage tank 24 consisted of dibutyl carbonate: about 0.3 wt.%, Butyl phenyl carbonate: about 38 wt.%, Diphenyl carbonate: about 14 wt.%, And also a catalyst. The liquid discharged into storage tank 20 consisted of 1-butanol: about 0.7% by weight, phenol: about 33% by weight, dibutyl carbonate: about 65% by weight, and butyl phenyl carbonate: about 1% by weight. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 192 g / h, about 0.1 m above the average stage of a multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm), with an inner diameter of 2 inches and a length of 1 m.

The heat required for distillation separation was supplied by circulating the liquid in the bottom of the column through line 34 through a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 90 g / h.

After removal from the top of the column through line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 102 g / h. The liquid withdrawn to storage tank 33 consisted of dibutyl carbonate: about 0.6% by weight, butyl phenyl carbonate: about 73% by weight, diphenyl carbonate: about 26% by weight.

Separation by distillation was carried out by continuously supplying liquid continuously discharged to storage tank 33, through line 37 passing through heater 38, with a flow rate of about 101 g / h to the middle stage of a continuous multistage distillation column 39, which was a column loaded with a Dixon nozzle ( w 6 mm), with an internal diameter of 2 inches and a length of 2 m. The heat required for separation by distillation was supplied by circulating the liquid in the lower part of the column along line 46 through reboiler 47, and the temperature below m The foot stage distillation column was adjusted to be approximately 200 ° C.

The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a flow rate of about 19 g / h. After removal from the top of the column through line 40, the distillate was liquidated in the refrigerator 41 and continuously discharged to the storage tank 44 at a rate of about 82 g / h.

The liquid withdrawn to storage tank 44 consisted of dibutyl carbonate: about 0.7% by weight, butyl phenyl carbonate: about 90% by weight, diphenyl carbonate: about 9% by weight. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was approximately 0.8 ppm. Inspection of the distillation column did not reveal any precipitation or the like.

Example 2

[Production of aromatic carbonate]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a flow rate of about 109 g / h, through heater 2 and line 1, of a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, the butyl titanate trimer [(BuO) _3- Ti-O-Ti- (OBu ) ₂ -O-Ti- (OBu) ₃ ] (the result of elemental analysis: C = 50.5, H = 9.5, O = 21.1, Ti = 18.9; since the oxygen number corresponding to BuO was 16.8, the number of bridging oxygen atoms was 2, i.e. there are two Ti-O-Ti bonds; molecular weight: 760; vapor pressure: 1 Pa or lower at 230 ° C) (mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at about 65/35, and the Ti level as atoms was set to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this mixture) to the middle stage of a continuous multistage distillation column 3, which consisted of a condensation section having an internal diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section, which had an internal diameter of 2 inches, 1 m in length of the column and was loaded with a Dixon nozzle (w 6 mm).

The condensation section was located in the lower part of the stage, where the liquid mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C.

The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. The catalyst was dissolved in the reaction liquid.

After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9). The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, As well as a catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multistage distillation column 15 of continuous operation, as in the case of the multistage distillation column 3 of continuous operation, consisted of a condensation section having an inner diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section that has an inner diameter 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed s reaction liquid containing the catalyst and recovery section was located at the top.

The reaction was carried out by continuously supplying through the line 13 of the reaction liquid discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12, to the multistage distillation column 15 of continuous operation with a flow rate of 100 g / h after heating by heater 14. The heat required for reaction and distillation was supplied by circulating liquid in the lower part of the column along line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was regulated so to be approximately 220 ° C.

The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned reverse flow to a distillation column (reflux number 4).

The liquid diverted to storage tank 24 consisted of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight, and also a catalyst. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 192 g / h, about 0.1 m higher than the average stage of a multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm) with an inner diameter of 2 inches and a length of 1 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 34 through reboiler 35, and the temperature the bottom of the multistage distillation column was controlled so as to be about 210 ° C.

The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 90 g / h. After removal from the top of the column through line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 102 g / h.

The liquid withdrawn into the storage tank 33 consisted of dibutyl carbonate: about 0.6% by weight, butyl phenyl carbonate: about 73% by weight, diphenyl carbonate: about 26% by weight.

Separation by distillation was carried out by continuous supply of liquid continuously discharged into the storage tank 33, through line 37 passing through heater 38, with a flow rate of about 101 g / h, to the middle stage of a multistage distillation column 39 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm), with an internal diameter of 2 inches and a length of 2 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 46 through reboiler 47, and the temperature below Multistage distillation column was controlled so as to be about 200 ° C.

The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a flow rate of about 19 g / h.

After removal from the top of the column through line 40, the distillate was liquidated in the refrigerator 41 and continuously discharged to the storage tank 44 at a rate of about 82 g / h. The liquid withdrawn to storage tank 44 consisted of dibutyl carbonate: about 0.7% by weight, butyl phenyl carbonate: about 90% by weight, diphenyl carbonate: about 9% by weight.

The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Example 3

[Production of aromatic carbonate]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a flow rate of about 109 g / h, through a heater 2 and a conveyor line 1, of a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, an organic polytitanoxane composition (Matsumoto Trading Co. Ltd. Orgatics TA-22) containing dimer of butyl titanate [(BuO) _3- Ti-O-Ti- (OBu) ₃ ] (molecular weight: 550; vapor pressure at 230 ° C: 1 Pa or lower) (mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at 65/35, and the level of Ti as atoms was set at about 10,000 h / million of the entire liquid, and this catalyst was dissolved in this mixture) to the middle stage of a continuous multistage distillation column 3, which consisted of a condensation section having an internal diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section, which had an internal diameter of 2 inches, 1 m in the length of the column and was loaded with a Dixon nozzle (w 6 mm).

The condensation section was located in the lower part of the stage, to which the liquid mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9).

The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, As well as a catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After a multistage distillation column 3 of continuous operation, the reaction was carried out using a multistage distillation column 15 of continuous operation. The multi-stage distillation column 15 of continuous operation, as in the case of the multi-stage distillation column 3 of continuous operation, consisted of a condensation section, which has an internal diameter of 2 inches, 0.5 m in length and filled with 10 steps of sieve plates, and an extraction section, which has the inner diameter is 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed The reaction liquid containing the catalyst was present, and the recovery section was located in the upper part. The reaction was carried out by continuously supplying through line 13 a reaction liquid discharged from the bottom of a continuous multi-stage distillation column 3 along line 10 to a storage tank 12, into a continuous multi-stage distillation column 15 with a flow rate of 100 g / h after heating by a heater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 220 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4). The liquid withdrawn into the storage tank 24 consisted of dibutyl carbonate: about 5 wt.%, Butyl phenyl carbonate: about 74 wt.%, Diphenyl carbonate: about 10 wt.%, As well as a catalyst. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 100 g / h, about 0.1 m higher than the average stage of a multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm) with an inner diameter of 2 inches and a length of 1 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 34 through reboiler 35, and the temperature the bottom of the multistage distillation column was controlled so as to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h. The liquid discharged into storage tank 33 consists of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%. Separation by distillation was carried out by continuously supplying liquid continuously discharged to storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a continuous multistage distillation column 39, which is a column loaded with a Dixon nozzle (w 6 mm), with an internal diameter of 2 inches and a length of 2 m.

The heat required for distillation separation was supplied by circulating liquid in the bottom of the column through line 46 through reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h. The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, And butyl phenyl carbonate: about 94 wt.%. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Reference Example 3

[Preparation of aromatic carboxylic acid ester]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a flow rate of about 109 g / h, through heater 2 and conveyor line 1, of a mixed solution of dibutyl carbonate, phenol and, as a catalyst, titanium methyl phenoxide (Azumax Co. Ltd. Ti-A KT881) (molecular weight: 476; vapor pressure: 1 Pa or lower at 230 ° C) (a mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at 65/35 and the Ti level of atoms was set at about 10,000 ppm of the total liquid ) to the middle stage of multistage distillation to continuous strings 3, which consisted of a condensation section having an inner diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section which had an inner diameter of 2 inches, 1 m in length of the column and was loaded Dixon nozzle (w 6 mm) (during feeding, the catalyst was dissolved in the solution).

The condensation section was located in the lower part of the stage, where the mixed solution was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9).

The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, And catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multistage distillation column 15 of continuous operation, as in the case of the multistage distillation column 3 of continuous operation, consisted of a condensation section having an inner diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section that has an inner diameter 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed s reaction liquid containing the catalyst and recovery section was located at the top. The reaction was carried out by continuously supplying through the line 13 a reaction liquid discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12 to a multistage distillation column 15 of continuous operation with a flow rate of 100 g / h after heating by heater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 220 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4). The liquid diverted to storage tank 24 consisted of dibutyl carbonate: about 5 wt.%, Butyl phenyl carbonate: about 74 wt.%, Diphenyl carbonate: about 10 wt.%, And a catalyst. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate ]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid, which was diverted to the storage tank 24, through line 25 passing through the heater 26, with a flow rate of about 100 g / h, about 0.1 m higher than the average stage of the multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm), with an inner diameter of 2 inches and a length of 1 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 34 through reboiler 35, and the rate The temperature at the bottom of the multi-stage distillation column was adjusted to be approximately 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h. The liquid discharged to storage tank 33 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%. Separation by distillation was carried out by a continuous supply of liquid continuously discharged into the storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a continuous multi-stage distillation column 39, which was a column loaded with a Dixon nozzle ( W 6 mm), with an internal diameter of 2 inches and a length of 2 m.

The heat required for distillation separation was supplied by circulating liquid in the lower part of the column along line 46 through reboiler 47, and the temperature at the bottom of the multi-stage distillation column was adjusted to be approximately 230 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h. The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 94 wt.%. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was 0.8 ppm. Upon inspection of the distillation column, no precipitation or the like was found.

Example 4

[Production of aromatic carbonate]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a flow rate of about 109 g / h, through a heater 2 and a conveyor line 1, of a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, an organic polytitanoxane composition (Nippon Soda Co. Ltd. B-4), containing tetramer butyl titanate (molecular weight: 970; vapor pressure: 1 Pa or lower at 230 ° C), (a mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at about 65/35, and the level of Ti as atoms was set to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this solution) to the middle stage of a continuous multistage distillation column 3, which consisted of a condensation section having an internal diameter of 2 inches, 0.5 m long column and filled with 10 steps of sieve plates, and an extraction section , which had an internal diameter of 2 inches, 1 m in the length of the column and was loaded with a Dixon nozzle (w 6 mm).

The condensation section was located in the lower part of the stage, where the mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11; the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. The catalyst was dissolved in the reaction liquid. After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9).

The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, And catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multi-stage distillation column 15 of continuous operation, as in the case of the multi-stage distillation column 3 of continuous operation, consisted of a condensation section, which has an internal diameter of 2 inches, 0.5 m in length and filled with 10 steps of sieve plates, and an extraction section, which has the inner diameter is 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed The reaction liquid containing the catalyst was present, and the recovery section was located in the upper part. The reaction was carried out by continuously supplying through the line 13 a reaction liquid discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12 to a multistage distillation column 15 of continuous operation with a flow rate of 100 g / h after heating by heater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 220 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4). The liquid diverted to storage tank 24 consisted of dibutyl carbonate: about 5 wt.%, Butyl phenyl carbonate: about 74 wt.%, Diphenyl carbonate: about 10 wt.%, And a catalyst. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 100 g / h, about 0.1 m higher than the average stage of a multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm) with an inner diameter of 2 inches and a length of 1 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 34 through reboiler 35, and the temperature the bottom of the multistage distillation column was controlled so as to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h. The liquid discharged to storage tank 33 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%. Separation by distillation was carried out by a continuous supply of liquid continuously discharged into the storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a continuous multi-stage distillation column 39, which was a column loaded with a Dixon nozzle ( W 6 mm), with an internal diameter of 2 inches and a length of 2 m.

The heat required for distillation separation was supplied by circulating liquid in the bottom of the column through line 46 through reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h. The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 94 wt.%. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Reference Example 4

[Preparation of aromatic carboxylic acid ester]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a flow rate of about 109 g / h, through a heater 2 and a conveyor line 1, of a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, butyl oxide of monobutyltin (molecular weight: 660 or higher; vapor pressure: 1 Pa or lower at 230 ° C) (a mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at about 65/35 and the tin level of atoms was set at about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this solution) to the middle stage of a continuous multi-stage distillation column 3, which consisted of a condensation section having an inner diameter of 2 inches, 0.5 m long column and filled with 10 steps of sieve plates, and an extraction section that had an inner diameter of 2 inches, 1 m in length of the column and was loaded with a Dixon nozzle (w 6 mm).

The condensation section was located in the lower part of the stage, where the mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. The catalyst was dissolved in the reaction liquid. After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9).

The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, And catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multi-stage distillation column 15 of continuous operation, as in the case of the multi-stage distillation column 3 of continuous operation, consisted of a condensation section, which has an internal diameter of 2 inches, 0.5 m in length and filled with 10 steps of sieve plates, and an extraction section, which has the inner diameter is 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed The reaction liquid containing the catalyst was present, and the recovery section was located in the upper part. The reaction was carried out by continuously supplying through the line 13 a reaction liquid discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12 to a multistage distillation column 15 of continuous operation with a flow rate of 100 g / h after heating by heater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 220 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4). The liquid discharged into storage tank 24 consisted of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid, which was discharged into the storage tank 24, through line 25 passing through the heater 26, with a flow rate of about 100 g / h, about 0.1 m higher than the average stage of the multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm), with an internal diameter of 2 inches and a length of 1 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 34 through reboiler 35, and a tamper round bottom multi-stage distillation column was controlled so as to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h. The liquid discharged to storage tank 33 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%. Separation by distillation was carried out by a continuous supply of liquid continuously discharged into the storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a continuous multi-stage distillation column 39, which was a column loaded with a Dixon nozzle ( W 6 mm), with an internal diameter of 2 inches and a length of 2 m.

The heat required for distillation separation was supplied by circulating liquid in the bottom of the column through line 46 through reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h. The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 94 wt.%. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Sn content was 0.9 ppm. Upon inspection of the distillation column, no precipitation or the like was found.

Example 5

[Preparation of aromatic carboxylic acid ester]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuous feeding at a rate of about 109 g / h, through heater 2 and line 1, of a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, a titanate containing hexamer butyl titanate [(BuO) _3- Ti-O- ( Ti- (OBu) ₂ · O) ₄ -Ti- (OBu) ₃ ] (result of elemental analysis: C = 48.3, H = 9.1, O = 21.9, Ti = 20.7; since oxygen, the corresponding BuO was 16.1, the number of bridging oxygen atoms is 5, that is, there are 5 Ti-O-Ti bonds; molecular weight: 1390; vapor pressure: 1 Pa or lower at 230 ° C) (mixed solution in which weight the attitude the ibutyl carbonate to phenol was set at about 65/35, and the Ti level as atoms was set at about 10,000 ppm of the total liquid, and this catalyst was dissolved in this solution) to the middle stage of a continuous multistage distillation column 3, which consisted of a section condensation having an internal diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section, which had an internal diameter of 2 inches, 1 m in length of the column and was loaded with a Dixon nozzle (w 6 mm).

The condensation section was located in the lower part of the stage, where the mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. The catalyst was dissolved in the reaction liquid. After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9).

The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, As well as a catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multi-stage distillation column 15 of continuous operation, as in the case of the multi-stage distillation column 3 of continuous operation, consisted of a condensation section, which has an internal diameter of 2 inches, 0.5 m in length and filled with 10 steps of sieve plates, and an extraction section, which has the inner diameter is 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed The reaction liquid containing the catalyst was present, and the recovery section was located in the upper part. The reaction was carried out by continuously supplying through the line 13 a reaction liquid discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12 to a multistage distillation column 15 of continuous operation with a flow rate of 100 g / h after heating by heater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 220 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After that, the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back to distillation column (reflux number 4). The liquid diverted to storage tank 24 consisted of dibutyl carbonate: about 5 wt.%, Butyl phenyl carbonate: about 74 wt.%, Diphenyl carbonate: about 10 wt.%, And a catalyst. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 100 g / h, about 0.1 m higher than the average stage of a multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm) with an inner diameter of 2 inches and a length of 1 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 34 through reboiler 35, and the temperature the bottom of the multistage distillation column was controlled so as to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h. The liquid discharged to storage tank 33 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%. Separation by distillation was carried out by a continuous supply of liquid continuously discharged into the storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a continuous multi-stage distillation column 39, which was a column loaded with a Dixon nozzle ( W 6 mm), with an internal diameter of 2 inches and a length of 2 m.

The heat required for distillation separation was supplied by circulating liquid in the bottom of the column through line 46 through reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h. The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 94 wt.%. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Example 6

[Preparation of aromatic carboxylic acid ester]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuous feeding with a flow rate of about 109 g / h, through heater 2 and line 1, of a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, a phenolic adduct of tetramer phenyl titanate [(PhO) ₃ -Ti-O- (Ti (OPh) ₂ -O) ₂ -Ti- (OPh) ₃ ] (result of elemental analysis: C = 65.2, H = 4.8, O = 17.6, Ti = 12.4. According to analysis ¹ H- NMR of the PhOH and PhO groups is present at a ratio of 4:10. In one molecule there are 4 Ti atoms and 3 oxygen atoms not belonging to the PhOH and PhO groups, that is, the number of bridging oxygen atoms is 3, and therefore there are 3 bonds and Ti-O-Ti; molecular weight without phenolic adduct: 1170; vapor pressure: 1 Pa or lower at 230 ° C) (mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at about 65/35, and the Ti level as atoms was installed at about 10,000 ppm of the entire liquid) on the middle stage of a continuous multistage distillation column 3, which consisted of a condensation section having an internal diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and a section extraction that had int The initial diameter was 2 inches, 1 m in the length of the column and was loaded with a Dixon nozzle (w 6 mm).

The condensation section was located in the lower part of the stage, where the mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9). The catalyst was dissolved in the liquid phase.

The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, And catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multi-stage distillation column 15 of continuous operation, as in the case of the multi-stage distillation column 3 of continuous operation, consisted of a condensation section, which has an internal diameter of 2 inches, 0.5 m in length and filled with 10 steps of sieve plates, and an extraction section, which has the inner diameter is 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed The reaction liquid containing the catalyst was present, and the recovery section was located in the upper part. The reaction was carried out by continuously supplying through the line 13 a reaction liquid discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12 to a multistage distillation column 15 of continuous operation with a flow rate of 100 g / h after heating by heater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 220 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4). The liquid diverted to storage tank 24 consisted of dibutyl carbonate: about 5 wt.%, Butyl phenyl carbonate: about 74 wt.%, Diphenyl carbonate: about 10 wt.%, And a catalyst. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 100 g / h, about 0.1 m higher than the average stage of a multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm) with an inner diameter of 2 inches and a length of 1 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 34 through reboiler 35, and the temperature the bottom of the multistage distillation column was controlled so as to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h. The liquid discharged to storage tank 33 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%. Separation by distillation was carried out by continuously supplying liquid continuously discharged to storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a continuous multistage distillation column 39, which was a column loaded with a Dixon nozzle ( w 6 mm), with an internal diameter of 2 inches and a length of 2 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 46 through reboiler 47, and the temperature below The foot stage distillation column was adjusted to be approximately 230 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h. The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 94 wt.%. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Example 7

(Preparation of catalyst)

To a flask equipped with a stirrer, thermometer, heating and cooling device, and a reflux condenser, 3400 g (10 mol) of tetra-n-butoxy titanium and 1700 g of n-butanol were added and the liquid was cooled to 0 ° C with vigorous stirring. While maintaining the temperature of the liquid at 0 ° C, a mixture of 90 g (5 mol) of water and 2000 g of n-butanol was slowly added over an hour. After the addition, the temperature was raised to 80 ° C and stirred for 5 hours. The flask was connected to a rotary evaporator equipped with a vacuum regulator, a vacuum pump and an oil bath to heat the liquid after cooling to room temperature (about 20 ° C). The low boiling components were distilled off by reducing the pressure to about 25 kPa, keeping the liquid temperature at 80 ° C. When there was almost no distillate left, the temperature was slowly raised to 230 ° C and then the pressure was reduced to 1 Pa, after confirmation of the absence of distillate, nitrogen was added to return to normal pressure and the temperature was returned to room temperature (approximately 20 ° C) to obtain approximately 2750 g pale yellow viscous liquid. This liquid is catalyst A. The result of elemental analysis showed that the composition is: C: 52.3%, H: 9.9%, O: 20.4%, Ti: 17.4%, and that there is one Ti-O bond -Ti, since the number of oxygen atoms excluding oxygen corresponding to BuO was 1 per 2 Ti atoms. Thus, it is assumed that the catalyst A described above is a mixture containing the dimer of butyl titanate [(BuO) ₃ -Ti-O-Ti (OBu) ₃ ] as the main component.

[Preparation of aromatic carboxylic acid ester]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a flow rate of about 109 g / h, through heater 2 and line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, catalyst A (mixed solution in which the weight ratio of dibutyl carbonate to phenol was set at about 65/35, and the level of Ti as atoms was set at about 10,000 ppm of the entire liquid, and this catalyst was dissolved in this solution) at the middle stage of a continuous multistage distillation column 3, which consisted of a condensation section having an internal diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section that had an internal diameter of 2 inches, 1 m in length of the column and was loaded with a Dixon nozzle (w 6 mm )

The condensation section was located in the lower part of the stage, where the mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. The catalyst was dissolved in the reaction liquid. After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9).

The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, As well as a catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multi-stage distillation column 15 of continuous operation, as in the case of the multi-stage distillation column 3 of continuous operation, consisted of a condensation section, which has an internal diameter of 2 inches, 0.5 m in length and filled with 10 steps of sieve plates, and an extraction section, which has the inner diameter is 2 inches, 1 m in the length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located in the lower part of the stage, where this distillation column 15 from the storage tank 12 was continuously fed The reaction liquid containing the catalyst was present, and the recovery section was located in the upper part. The reaction was carried out by continuously supplying through the line 13 a reaction liquid discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12 to a multistage distillation column 15 of continuous operation with a flow rate of 100 g / h after heating by heater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 220 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4). The liquid diverted to storage tank 24 consisted of dibutyl carbonate: about 5 wt.%, Butyl phenyl carbonate: about 74 wt.%, Diphenyl carbonate: about 10 wt.%, And a catalyst. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 100 g / h, about 0.1 m higher than the average stage of a continuous multi-stage distillation column 27, which was a column loaded with a Dixon nozzle (w 6 mm), with an internal diameter of 2 inches and a length of 1 m. The heat required for the reaction and rectification was supplied by circulating liquid in the lower part of the column along line 34 through line reboiler 35, and a tamper round bottom multi-stage distillation column was controlled so as to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h. The liquid discharged to storage tank 33 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%. Separation by distillation was carried out by a continuous supply of liquid continuously discharged into the storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a continuous multi-stage distillation column 39, which was a column loaded with a Dixon nozzle ( W 6 mm), with an internal diameter of 2 inches and a length of 2 m.

The heat required for distillation separation was supplied by circulating liquid in the bottom of the column through line 46 through reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The bottoms liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 along line 46 to the storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h. The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 94 wt.%. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Example 8

(Preparation of catalyst)

To a flask equipped with a stirrer, thermometer, heating and cooling device, and a reflux condenser, 3400 g (10 mol) of tetra-n-butoxy titanium and 1700 g of n-butanol were added and the liquid was cooled to 0 ° C with vigorous stirring. While maintaining the temperature of the liquid at 0 ° C, a mixture of 216 g (12 mol) of water and 2000 g of n-butanol was slowly added over 1 hour. After the addition, the temperature was raised to 80 ° C and stirred for 5 hours. The flask was connected to a rotary evaporator equipped with a vacuum regulator, a vacuum pump and an oil bath to heat the liquid after cooling to room temperature (about 20 ° C). The low boiling components were distilled off by reducing the pressure to about 25 kPa, keeping the liquid temperature at 80 ° C. When there was almost no distillate left, the temperature was slowly raised to 230 ° C and then the pressure was reduced to 1 Pa, after confirmation of the absence of distillate, nitrogen was added to return to normal pressure and the temperature was returned to room temperature (approximately 20 ° C) to obtain approximately 2320 g pale yellow viscous liquid. This liquid is catalyst B. The elemental analysis showed that the composition is: C: 48.3%, H: 9.1%, O: 21.9%, Ti: 20.7%, and the number of bridging oxygen atoms was 5 since the number of oxygen atoms corresponding to BuO was 16.1 and there were 5 Ti-O-Ti bonds. The molecular weight was 1390 and the vapor pressure was 1 Pa or less at 230 ° C. Thus, it is assumed that the catalyst B described above is a mixture containing the hexamer of butyl titanate [(BuO) ₃ -Ti-O- (Ti (OBu) ₂ -O) _4- Ti- (OBu) ₃ ] as a main component.

[Preparation of aromatic carboxylic acid ester]

Aromatic carbonate was obtained using the device shown in figure 1. The reaction was carried out by continuously feeding at a flow rate of about 109 g / h, through heater 2 and line 1, of a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, catalyst B (in which the weight ratio of dibutyl carbonate to phenol was set at about 65 / 35, and the Ti level as atoms was set to approximately 10,000 ppm of the entire liquid, and this catalyst was dissolved in this solution) to the middle stage of a continuous multistage distillation column 3, which consisted of a section a condensation device having an internal diameter of 2 inches, 0.5 m in length of the column and filled with 10 steps of sieve plates, and an extraction section, which had an internal diameter of 2 inches, 1 m in length of the column and was loaded with a Dixon nozzle (w 6 mm).

The condensation section was located in the lower part of the stage, where the mixture was continuously supplied, and the extraction section was located in the upper part. The heat required for the reaction and distillation was supplied by circulating a liquid in the lower part of the column through line 10 through a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 3 along line 10 to storage tank 12 at a flow rate of 90 g / h. The catalyst was dissolved in the reaction liquid. After the low-boiling liquid mixture containing 1-butanol as a by-product was removed from the top of the column through line 4 and then transferred to the liquid state in the refrigerator 5, part of it was continuously discharged into storage tank 8 with a flow rate of 19 g / h, and the rest returned by reverse flow to the distillation column (reflux number 1.9).

The liquid withdrawn into storage tank 12 consisted of phenol: about 23 wt.%, Dibutyl carbonate: about 56 wt.%, Butyl phenyl carbonate: about 12 wt.%, Diphenyl carbonate: about 0.2 wt.%, 1-butanol: about 0.3 wt.%, As well as a catalyst. The liquid discharged into storage tank 8 consisted of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction, in a multi-stage distillation column 3 of continuous operation, the reaction was carried out using a multi-stage distillation column 15 of continuous operation. The multistage distillation column 15 of continuous operation, as well as the multistage distillation column 3 of continuous operation, consisted of a condensation section, which has an inner diameter of 2 inches, 0.5 m in length of the column and is filled with 10 steps of sieve plates, and an extraction section, which has an inner diameter 2 inches, 1 m in length of the column and loaded with a Dixon nozzle (w 6 mm), the condensation section was located at the bottom of the stage, where in this distillation column 15 from the storage tank 12 was continuously fed ktsionnaya liquid containing the catalyst and recovery section was located at the top. The reaction was carried out by continuously supplying through the line 13 a reaction liquid discharged from the bottom of the multistage distillation column 3 of continuous operation via line 10 to the storage tank 12 to a multistage distillation column 15 of continuous operation with a flow rate of 100 g / h after heating by heater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through line 22 through reboiler 24, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 220 ° C. The reaction liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 15 along line 22 to storage tank 24 at a rate of 17 g / h. After the low-boiling liquid mixture containing dibutyl carbonate as a by-product was removed from the top of the column through line 16 and then transferred to the liquid state in the refrigerator 17, part of it was continuously discharged to storage tank 20 with a flow rate of 83 g / h, and the rest was returned back flow to a distillation column (reflux number 4). The liquid diverted to storage tank 24 consisted of dibutyl carbonate: about 5 wt.%, Butyl phenyl carbonate: about 74 wt.%, Diphenyl carbonate: about 10 wt.%, And a catalyst. The liquid discharged to storage tank 20 consisted of 1-butanol: about 0.3 wt.%, Phenol: about 18 wt.%, And dibutyl carbonate: about 81 wt.%. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of diaryl carbonate]

The purification of diaryl carbonate was carried out using the device shown in figure 2. Separation by distillation was carried out by a continuous supply of liquid discharged into the storage tank 24, through a line 25 passing through a heater 26, with a flow rate of about 100 g / h, about 0.1 m higher than the average stage of a multistage distillation column 27 of continuous operation, which was a column loaded with a Dixon nozzle (w 6 mm) with an inner diameter of 2 inches and a length of 1 m. The heat required for separation by distillation was supplied by circulating liquid in the lower part of the column along line 34 through reboiler 35, and the temperature the bottom of the multistage distillation column was controlled so as to be about 210 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 along line 34 to the storage tank 36 at a flow rate of about 20 g / h.

After removal from the top of the column via line 28, the distillate was transferred to a liquid state in the refrigerator 29 and continuously discharged to the storage tank 33 at a flow rate of about 80 g / h. The liquid discharged to storage tank 33 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 86 wt.%, Diphenyl carbonate: about 7.5 wt.%. Separation by distillation was carried out by a continuous supply of liquid continuously discharged into the storage tank 33, through line 37 passing through heater 38, with a flow rate of about 100 g / h to the middle stage of a multistage distillation column 3 of continuous operation, which was a column loaded with a Dixon nozzle ( w 6 mm) with an inner diameter of 2 inches and a length of 2 m. The heat required for separation by distillation was supplied by circulating the liquid in the lower part of the column along line 46 through reboiler 47, and the temperature below The coagulation distillation column was adjusted to be approximately 230 ° C. The bottoms liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 into storage tank 48 at a rate of about 8 g / h. After removal from the top of the column through line 40, the distillate was transferred to a liquid state in the refrigerator 41 and continuously discharged to the storage tank 44 with a flow rate of about 92 g / h. The liquid withdrawn into storage tank 44 consisted of dibutyl carbonate: about 6 wt.%, Butyl phenyl carbonate: about 94 wt.%. The white liquid that solidified at ambient temperature was continuously discharged into storage tank 48 and contained diphenyl carbonate: about 100 wt.%, Butyl phenyl carbonate was below the detection limit. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Example 9

(Preparation of catalyst)

To a flask equipped with a stirrer, thermometer, heating and cooling device, and a reflux condenser, 3400 g (10 mol) of tetra-n-butoxy titanium and 1700 g of n-butanol were added and the liquid was cooled to 0 ° C with vigorous stirring. While keeping the liquid temperature at 0 ° C, a mixture of 90 g (5 mol) of water and 2000 g of n-butanol was slowly added over 1 hour. After the addition, the temperature was raised to 80 ° C and stirred for 5 hours. The flask was connected to a rotary evaporator equipped with a vacuum regulator, a vacuum pump and an oil bath to heat the liquid after cooling to room temperature (about 20 ° C). Low-boiling components were distilled off by reducing the pressure to about 25 kPa, keeping the temperature of the liquid at 80 ° C. When there was almost no distillate left, the temperature was slowly raised to 230 ° C and then the pressure was reduced to 1 Pa and after confirmation of the absence of distillate, nitrogen was added to return to normal pressure and the temperature was returned to room temperature (approximately 20 ° C) to obtain approximately 2750 g pale yellow viscous liquid. This liquid is catalyst A. The elemental analysis showed that the composition is: C: 52.3%, H: 9.9%, O: 20.4%, Ti: 17.4%, and there is one Ti-O bond -Ti, since the number of oxygen atoms, with the exception of oxygen corresponding to BuO, was 1 per 2 Ti atoms. Thus, it is assumed that the catalyst A described above is a mixture containing the dimer of butyl titanate [(BuO) ₃ -Ti-O-Ti (OBu) ₃ ] as the main component.

An agitator, a thermometer, a heating and cooling device and a reflux condenser were reattached to this flask, and the liquid was heated to 80 ° C with stirring. While keeping the liquid temperature at 80 ° C, 4700 g (50 mol) of distilled and dehydrogenated phenol were slowly added. After addition, the liquid was heated to 180 ° C, and the low boiling components evaporated. When the distillate was almost gone, the temperature of the liquid was slowly raised to 230 ° C to further remove the distillate. The flask was connected to a vacuum regulator and a vacuum pump, the pressure was slowly reduced to 1 Pa and the distillates were removed. Then the flask was removed from the oil bath, cooled to room temperature (approximately 20 ° C) and the pressure inside the flask was returned to normal with nitrogen. Approximately 4300 g of solids with an orange-red color were obtained. It was catalyst C. The result of elemental analysis showed that the composition is: C: 64.5%, H: 4.5%, O: 16.7%, Ti: 14.3%. Catalyst C described above is believed to be a mixture containing the phenolic adduct of the phenyl titanate dimer [(PhO) ₃ -Ti-O-Ti (OPh) ₃ · 2PhOH] as the main component.

[Preparation of aromatic carboxylic acid ester]

A mixture consisting of dimethyl carbonate, phenol and, as a catalyst, catalyst C, was continuously supplied as liquid from an inlet line 50 through a heater 51 to a point 1 m from the top of the multi-stage distillation column 49, as shown in FIG. 3, which consisted of from a packed column 4 m high and an inner diameter of 3 m loaded with a Dixon nozzle (w 6 mm) made of stainless steel. The heat required for the reaction and rectification was supplied by heating the liquid at the bottom of the column in a reboiler (liquid supply from the inlet line 50: 3.4 kg / h; composition of the liquid supply: DMC: about 68.3 wt.%, PhOH: about 33, 7 wt.%, Catalyst C: 13.5 mmol / kg). The temperature at the bottom of the column was approximately 201 ° C, the pressure at the top of the column was approximately 800 KPa, the reflux ratio was approximately 1. As a result of the reaction, a liquid containing a catalyst component, methyl phenyl carbonate and diphenyl carbonate, which were reaction products, was obtained from the bottom of 53 columns along lines 58 and 60. The gas distillate from line 54, located at the top of the 52 columns, was condensed by a condenser 55. A part of the condensed liquid was returned by return flow to the distillation column 49 through the inlet line 56, and the rest was discharged through line 57. From this condensed liquid, a low-boiling product, methanol, was obtained. The amount of liquid withdrawn through line 60 (average liquid composition: methyl phenyl carbonate = 50 g / kg / h, diphenyl carbonate = 0.4 g / kg / h) was approximately 2.3 kg / h. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of aromatic carbonate]

Aromatic carbonate was purified using the device shown in FIG. 2. The device was a multi-stage distillation column of continuous operation, which consisted of a column with an internal diameter of 2 inches and a height of 1 m, loaded with a Dixon nozzle (w 6 mm). Separation by distillation was carried out by continuous supply of liquid discharged through the aforementioned line 60, with a flow rate of about 100 g / h, along line 25 and a heater 26, to a multistage distillation column 27 of continuous operation at a point spaced about 0.1 m above the middle section. The heat required for distillation separation was supplied by circulating the liquid in the bottom of the column through line 34 through a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 210 ° C. The bottom liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 through line 34 to the storage tank 36. After removing the top of the column from line 28, the distillate was liquid in the refrigerator 29 and continuously discharged to the storage tank 33. Separation by distillation was carried out by continuous supply liquid continuously discharged into storage tank 33, with a flow rate of about 100 g / h, through line 37 and heater 38, to the middle stage of a multi-stage distillation column 39 eryvnogo action, which consisted of an inner column diameter of 2 inches and a height of 2 m, is loaded with Dixon packing (6 mm br). The heat required for distillation separation was supplied by circulating liquid in the bottom of the column through line 46 through reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The bottom liquid was continuously discharged from below the continuous multi-stage distillation column 39 through line 46 to the storage tank 48. After the discharge from the top of the column through line 40, the distillate was liquid in the refrigerator 41 and continuously discharged to the storage tank 44. The liquid discharged into the storage tank was storage 44, contained methyl phenyl carbonate at a level of about 94% by weight. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Reference Example 5

The aromatic carbonate was purified as in Example 9, except that the catalyst was changed from catalyst C to phenoxy titanate [Ti (OPh) ₄ ] (molecular weight: 420, vapor pressure: about 15 Pa at 230 ° C). The amount of liquid (average composition: methyl phenyl carbonate = 50 g / kg / h, diphenyl carbonate = 0.4 g / kg / h) discharged along line 60 was approximately 2.3 kg / h. The liquid diverted to storage tank 44 contained methyl phenyl carbonate: about 94% by weight. A liquid analysis indicates that Ti was detected at 9 ppm. Inspection of the inside of the column revealed white deposits on the wall of the distillation column and packing.

Example 10

(Preparation of catalyst)

To a flask equipped with a stirrer, thermometer, heating and cooling device, and a reflux condenser, 3400 g (10 mol) of tetra-n-butoxy titanium and 1700 g of n-butanol were added, and the liquid was cooled to 0 ° C with vigorous stirring. While keeping the liquid temperature at 0 ° C, a mixture of 90 g (5 mol) of water and 2000 g of n-butanol was slowly added over 1 hour. After the addition, the temperature was raised to 80 ° C and stirred for 5 hours. The flask was connected to a rotary evaporator equipped with a vacuum regulator, a vacuum pump and an oil bath to heat the liquid after cooling to room temperature (about 20 ° C). Low-boiling components were distilled off by reducing the pressure to about 25 kPa, keeping the temperature of the liquid at 80 ° C. When there was almost no distillate left, the temperature was slowly raised to 230 ° C, and the pressure was further reduced to 1 Pa, and after confirmation of the absence of distillate, nitrogen was added to return to normal pressure and the temperature was returned to room temperature (approximately 20 ° C) to obtain approximately 2750 g of a pale yellow viscous liquid. This liquid is catalyst A. The elemental analysis showed that the composition is: C: 52.3%, H: 9.9%, O: 20.4%, Ti: 17.4%, and there is one Ti-O bond -Ti, since the number of oxygen atoms, with the exception of oxygen corresponding to BuO, was 1 per 2 Ti atoms. Thus, it is assumed that the above catalyst A above is a mixture containing a dimer of butyl titanate [(BuO) ₃ -Ti-O-Ti (OBu) ₃ ] as a main component.

An agitator, a thermometer, a heating and cooling device, and a reflux condenser and liquid were heated to 80 ° C with stirring again. Keeping the liquid temperature at 80 ° C, 4700 g (50 mol) of distilled and dehydrogenated phenol were slowly added. After addition, the liquid was heated to 180 ° C, and the low boiling components evaporated. When there was almost no distillate left, the temperature was slowly raised to 230 ° C to further remove the distillate. The flask was connected to a vacuum regulator and a vacuum pump, the pressure was slowly reduced to 1 Pa, and the distillates were removed. Then the flask was removed from the oil bath, cooled to room temperature (approximately 20 ° C) and the pressure inside the flask was returned to normal with nitrogen. About 4300 g of a solid with an orange-red color were obtained. It was catalyst C. The result of elemental analysis showed that the composition is: C: 64.5%, H: 4.5%, O: 16.7%, Ti: 14.3%. Catalyst C described above is believed to be a mixture containing the phenolic adduct of the phenyl titanate dimer [(PhO) ₃ -Ti-O-Ti (OPh) ₃ · 2PhOH] as the main component.

[Preparation of aromatic carboxylic acid ester]

A mixture consisting of methyl phenyl carbonate (MFC) and a catalyst was continuously supplied as a liquid through an inlet line 62 through a heater 63 to a point spaced 1 m from the head of the multi-stage distillation column 61, as shown in FIG. 4, which consisted of a pressure regulator 68 and a packed column with a height of 4 m and an inner diameter of 3 inches loaded with a Dixon nozzle (w 6 mm) made of stainless steel, and the reaction was carried out by heating in a reboiler (liquid feed through the inlet line 62: 4.2 kg / h; composition of the liquid feed: MPC: approximately 99 weight %, catalyst C: 12.5 mmol / kg). The temperature at the bottom of the column was approximately 195 ° C, the pressure at the top of the column was approximately 30 KPa, the reflux ratio was approximately 2.1. As a result of the reaction, a liquid containing diphenyl carbonate, which was the reaction product, was obtained from the bottom 65 of a continuous multi-stage distillation column through the bottom outlet 70 for the bottoms liquid of the column. The gas distillate from the gas outlet 66, located at the top of the 64 columns, was condensed by a condenser 67. A part of the condensed liquid was returned in a reverse flow, and the rest was discharged through a condensed liquid outlet 69. From this condensed liquid, a by-product dimethyl carbonate was obtained. From the liquid withdrawn through line 70, diphenyl carbonate was obtained at a flow rate of 705 g / kg / h. Upon inspection of the distillation column, no precipitation or the like was found.

[Purification of aromatic carbonate]

Aromatic carbonate was purified using the device shown in FIG. 2. The device was a multi-stage distillation column of continuous operation, which consisted of a column with an internal diameter of 2 inches and a height of 1 m, loaded with a Dixon nozzle (w 6 mm). Separation by distillation was carried out by continuous supply of liquid discharged through the aforementioned line 60, with a flow rate of about 100 g / h, along line 25 and a heater 26, to a multistage distillation column 27 of continuous operation at a point approximately 0.1 m above the middle stage. The heat required for distillation separation was supplied by circulating the liquid in the bottom of the column through line 34 through a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was adjusted to be about 210 ° C. The bottom liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 27 through line 34 to the storage tank 36. After removing the top of the column from line 28, the distillate was liquid in the refrigerator 29 and continuously discharged to the storage tank 33. Separation by distillation was carried out by continuous supply liquid continuously withdrawn from storage tank 33, with a flow rate of about 100 g / h, along line 37 and heater 38, to the middle stage of a multi-stage distillation column 39 n intermittent, which consisted of a column with 2 inch internal diameter and 2 m in height, is loaded with Dixon packing (6 mm br). The heat required for distillation separation was supplied by circulating liquid in the bottom of the column through line 46 through reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be approximately 230 ° C. The bottom liquid was continuously discharged from the bottom of the continuous multi-stage distillation column 39 along line 46 to the storage tank 48. After discharge from the top of the column through line 40, the distillate was liquid in the refrigerator 41 and continuously discharged to the storage tank 44. The storage tank 48 was continuously a white liquid was removed which solidified at ambient temperature, and it was diphenyl carbonate, about 100% by weight. A liquid analysis indicates that the Ti content was below the detection limit. Upon inspection of the distillation column, no precipitation or the like was found.

Reference Example 6

The aromatic carbonate was purified as in Example 10, except that the catalyst was changed from catalyst C to phenolic phenoxy titanate adduct [Ti (OPh) ₄ · 2PhOH] (molecular weight without phenolic adduct: 420, vapor pressure: about 15 Pa at 230 ° C) (liquid supplied through inlet line 62: 4.2 kg / h; composition of the liquid feed: MPC = about 99 wt.%, Catalyst C = 12.5

mmol / kg). The temperature at the bottom of the column was approximately 195 ° C, the pressure at the top of the column was approximately 30 KPa, and the reflux ratio was approximately 2.1. A white liquid was continuously discharged into storage tank 48, which solidified at ambient temperature, and it was diphenyl carbonate, about 100% by weight. A liquid analysis indicates that Ti is detected at 5 ppm. Inspection inside the column revealed white deposits on the wall of the distillation column and packing.

Example 11 (Polycarbonate was obtained from diphenyl carbonate obtained by the method of obtaining example 1)

The diphenyl carbonate obtained in Example 1 (23.5 g) and bisphenol A (22.8 g) were placed in a vacuum reactor equipped with a stirrer and polymerized at 8000 Pa for 30 minutes and at 4000 Pa for 90 minutes with a gaseous purge nitrogen. After that, the temperature was raised to 270 ° C, and the polymerization was continued at 70 Pa for 1 hour. The aromatic polycarbonate obtained in this way was transparent, without color and of good quality. The number average molecular weight was 10500.

Comparative example 7 (polycarbonate was obtained from diphenyl carbonate obtained by the method of obtaining comparative example 1)

The diphenyl carbonate obtained in Example 2 (23.5 g) and bisphenol A (22.8 g) were placed in a vacuum reactor equipped with a stirrer and polymerized at 8000 Pa for 30 minutes and at 4000 Pa for 90 minutes with a gaseous purge nitrogen. After that, the temperature was raised to 270 ° C and the polymerization was continued at 70 Pa for 1 hour. Aromatic polycarbonate obtained in this way had a red color, the number average molecular weight was 9800.

Industrial applicability

According to the present invention, high-purity diaryl carbonate can be obtained with easy removal of the catalyst by producing aromatic carbonate by transesterification of the starting material and reagent in the presence of a metal-containing catalyst with distillation of the alcohol by-product and / or dialkyl carbonate by-product from the reaction system. Aromatic polyester carbonate obtained by transesterification containing diaryl carbonate obtained by the method of the present invention is of high quality and has no color.

Claims (13)

1. A method of producing an aromatic carbonate, which comprises introducing into the reaction a starting material selected from the group consisting of dialkyl carbonate represented by the following formula (1), an alkyl aryl carbonate represented by the following formula (2), and mixtures thereof, with a reagent selected from the group consisting of an aromatic monohydroxy compound represented by the following formula (3), an alkyl aryl carbonate represented by the following formula (4), and a mixture thereof, in the presence of a metal-containing catalyst, with distillation of a by-product of irta and / or by-product of dialkyl carbonates from the reaction system, thereby obtaining an aromatic carbonate represented by the following formula (5) and / or the following formula (6), corresponding to the starting material and reagent, and subsequent purification of the obtained aromatic carbonate using two distillation columns, where the distillate from the first distillation column is sent to a second distillation column, and the aromatic carbonate is obtained as a bottoms product, the metal-containing catalyst being I am an organic polytitanoxane composition with a molecular weight of 480 or higher, which contains at least two titanium atoms and is dissolved in the liquid phase in the reaction system or is present as a liquid during the reaction,

where R ¹ , R ² and R ³ in formulas (1) to (4) independently mean an alkyl group having from 1 to 10 carbon atoms, an alicyclic group having from 3 to 10 carbon atoms, or an aralkyl group having from 6 to 10 carbon atoms, and
Ar ¹ , Ar ² and Ar ³ independently mean an aromatic group having from 5 to 30 carbon atoms, and

where each of R and Ar in formulas (5) and (6) is selected from R ¹ , R ² , R ³ , Ar ¹ , Ar ² and Ar ^{3 of the} corresponding starting material and reagent. 2. The method according to claim 1, wherein said organic polytitanoxane composition contains at least one alkoxy group and / or an aryloxy group as an organic group. 3. The method according to claim 1, wherein said organic polytitanoxane composition is obtained by polycondensation reaction of at least one starting material selected from the group consisting of tetraalkoxytitanium, tetragalotitan (TiX ₄ , wherein X is selected from Cl and Br) and titanium hydroxide. 4. The method according to claim 3, in which the specified organic polytitanoxane composition obtained by sequential or simultaneous conduct of two stages:
1) obtaining a partially hydrolyzed product by partial hydrolysis of tetraalkoxy titanium and
2) distillation of the formed low-boiling component, including alcohol, from a partially hydrolyzed product and exposure of the polycondensation product. 5. The method according to claim 3, in which the specified organic polytitanoxane composition is obtained by subjecting tetraalkoxytitanium to heat, deesterification and polycondensation. 6. The method according to claim 3, in which the specified organic polytitanoxane composition obtained by sequential or simultaneous conduct of three stages:
1) obtaining a partially hydrolyzed product by partial hydrolysis of tetragalotitan,
2) distilling off the low boiling component from the partially hydrolyzed product and subjecting the product to polycondensation and
3) the interaction of the resulting alcohol, the removal of HX from it and its alkoxylation. 7. The method according to any one of claims 1 to 6, in which the specified polytitanoxane composition is used as is or after an alkoxy group exchange as a result of the reaction of the composition with a composition containing at least one member selected from alcohol, aromatic hydroxy compound and carboxylic ester acids. 8. The method according to any one of claims 1 to 6, in which the specified titanium-containing compound contains at least two Ti atoms in one molecule. 9. The method of claim 8, wherein said titanium-containing compound contains from 2 to 6 Ti atoms in one molecule. 10. The method of claim 8, wherein said titanium-containing compound contains at least one Ti-O-Ti bond in one molecule. 11. The method according to claim 1, wherein said metal-containing catalyst has a vapor pressure of 10 Pa or less at 230 ° C. 12. The method according to any one of claims 1 to 6, in which the specified metal-containing catalyst is used in a concentration of from 0.0001 to 30 wt.% Based on the total weight of the specified starting material and the specified reagent. 13. The method according to any one of claims 1 to 6, in which the specified aromatic hydroxy compound is phenol.

Images