KR20000023134A - Carbonic acid diester, aromatic polycarbonate and facilities, and preparation thereof - Google Patents

Abstract

PURPOSE: Title compounds are prepared which has a good color and thermal stability by using nitrogen-containing basic compound as an ester exchange catalyst. CONSTITUTION: A powdered aromatic dihydroxy compound(formula 1; W is -O-, -S-, -SO or SO2-; R2 and R3 are same or not, halogen atom, C1- C12 hydrocarbon; n= 0- 4) and a carbonic ester(formula2; R7, R8, R9 and R10 are same or not, H, C1- C4 alkyl, phenyl or halogen) such as diphenyl carbonate, are melted in a melting tank, followed by melt-polymerization at 0-0.05 MPa. Thus, 1 mole of 2,2-bis(4-hydroxyphenyl)propane and 1.01 mole of diphenyl carbonate are melted, followed by polymerization adding 10 minus six square equivalent weight of bisphenol A disodium salt and 1x10 minus four square equivalent weight of tetramethyl ammonium hydride, removing produced phenol to give the polycarbonate.

Description

Diester Carbonate, Aromatic Polycarbonate, Manufacturing Equipment and Manufacturing Method {CARBONIC ACID DIESTER, AROMATIC POLYCARBONATE AND FACILITIES, AND PREPARATION THEREOF}

One of the present invention relates to a method for producing an aromatic polycarbonate resin, and more particularly, to a method for stably and economically producing an aromatic polycarbonate having good quality by melt polymerization.

In addition, one of the present invention relates to a method for producing an aromatic polycarbonate having excellent thermal stability and color.

Moreover, one of this invention relates to the manufacturing method of the aromatic polycarbonate which recycles the monohydroxy compound byproduced by this melt condensation polymerization reaction, and uses it as a catalyst solvent when obtaining an aromatic polycarbonate by melt condensation polymerization reaction. .

In addition, one of the present invention relates to the production of diester carbonate, which is a raw material for producing an aromatic polycarbonate, and an aromatic polycarbonate therefrom, and more particularly, a diester carbonate having good storage stability, and a quality produced from the carbonate ester, It relates to an aromatic polycarbonate with improved color tone.

In addition, one of the present invention relates to a method for producing an aromatic polycarbonate, and more particularly, in producing an aromatic polycarbonate by transesterification of a dihydroxy compound and a diester carbonate compound, a certain amount of a specific metal is contained. By using the reaction apparatus which consists of stainless alloys, it is related with the manufacturing method of the aromatic polycarbonate in which foreign material generation was suppressed.

In addition, one of the present invention relates to an apparatus for producing an aromatic polycarbonate, and more particularly, to an apparatus having a specific oxide film. The apparatus disclosed in the present invention is suitable for producing an aromatic polycarbonate by a melt transesterification method, and is suitable for producing an aromatic polycarbonate in which foreign matters represented by micro foreign matters in a polymer are reduced.

In addition, in the description of the present specification and claims, the "aromatic dihydroxy compound" may be referred to as an aromatic diol compound, the "catalyst deactivator" may be referred to as a "catalyst deactivator", and the term "end sealant". May be referred to as a "terminal blocker".

In addition to the "gel" derived from the crosslinked molecular structure, "foreign material" is composed of black foreign material represented by polymer deterioration, microcrystals of aromatic polycarbonate, garbage from outside, dust, sand, and the like. In particular, the gel-like foreign material is also called "gel", "gel foreign material". In addition, in the case of a "fine foreign material", it means a thing smaller than a foreign material, specifically 10 micrometers or less.

Aromatic polycarbonate resins are widely used as molding materials because they are excellent in mechanical properties such as impact resistance and also excellent in heat resistance and transparency. As a method for producing such an aromatic polycarbonate resin, a method of directly reacting an aromatic dihydroxy compound such as bisphenol and phosgene (interfacial method), or an aromatic dihydroxy compound such as bisphenol and diester carbonate such as diphenyl carbonate The method of transesterification (melting method) is known.

Among these production methods, an aromatic polycarbonate is produced by transesterification of an aromatic dihydroxy compound and a diester carbonate, which is an environmentally friendly method because no harmful phosgene or methylene chloride is used. It is drawing attention as the possibility of surpassing the law is pointed out.

However, the quality of the aromatic polycarbonate obtained by the melting method is difficult to obtain a good quality, such as deterioration of color due to the strict reaction conditions, especially used for various optical information recording media substrates, including DVD, CD, MO, etc. Aromatic polycarbonates can be further added to the aromatic polycarbonates because coloration due to lack of thermal stability and gelation due to thermal modification directly affect optical properties such as block error rate of the final product and mechanical properties such as tensile, warpage and toughness. The improvement of the color tone and the heat stability improvement are calculated | required.

In addition, diphenyl carbonate is preferably used as the diester of carbonate used as a raw material of the aromatic polycarbonate, and diphenyl carbonate is conventionally used in the presence of an acid scavenger, preferably using a basic catalyst, It is produced by reacting phenyl.

Diphenyl carbonate prepared by this method usually contains a chlorine compound derived from the raw material phosgene or intermediate chloroformate, and this chlorine compound reduces the chlorine compound by paying attention to this chlorine compound because it adversely affects the color tone of the polymer. Various purification methods have been proposed.

Japanese Patent Application Laid-Open No. 38-18686; Method for producing diphenyl carbonate using a basic catalyst such as amine, Japanese Patent Application Laid-open No. 41-10812; Removal of chloroformate by surfactants, plastic material lecture (17) Polycarbonate, pages 4 to 47, and various purification methods have been proposed. However, diphenyl carbonate prepared or purified by this method usually contains nitrogen-containing compounds used as catalysts as impurities.

Also, as a method of not using phosgene, a method of producing diphenyl carbonate directly from phenol and carbon monoxide in the presence of a Group 8 precious metal catalyst has recently attracted attention.

Also in this method, for example, Japanese Patent Application Laid-open No. Hei 7-188, 116 (Bayer) describes quaternary ammonium as an essential component of the catalyst system, and the diphenyl carbonate prepared by such a method is a nitrogen used as a catalyst. There is a problem that the containing compound is usually contained as an impurity.

As for the device material, there are the following problems.

That is, in recent years, aromatic polycarbonates used in optical discs and the like have been required to have a material having a lower error rate as the recording density is improved, and aromatic polycarbonates satisfying these requirements have micro foreign matters, which is one of the causes of the error rate. The polymer which reduced the foreign material represented by is calculated | required.

On the other hand, as a manufacturing method of the aromatic polycarbonate by the transesterification method, various examination is conventionally made. For example, Japanese Patent Application Laid-Open No. 9-241370 discloses a method for producing aromatic polycarbonate having good color tone and high molecular weight by using a material that is substantially free of FeOOH, CrOOH, and NiOOH components present on the surface of the liquid contact part. It is starting.

Japanese Patent Laid-Open No. 8-277327 discloses a method of producing aromatic polycarbonates having good color tone and high molecular weight by heat-treating the stainless steel of the liquid contact portion. In addition, Japanese Patent Application Laid-open No. Hei 8-5957 discloses an aromatic polycarbonate having a good color by carrying out a reaction apparatus made of a metal or an alloy having a copper or / or nickel content of 85% by weight or more for the material in contact with the reaction mixture. A method of preparing is disclosed.

Japanese Unexamined Patent Publication No. 6-345860 discloses that the material in contact with the reaction mixture is 20% or less of iron in the first polymerization step, and 20% or more of iron in the second polymerization step. A method for producing a high molecular weight aromatic polycarbonate excellent in degradability, color, and impact resistance is disclosed.

In addition, in order to reduce the cost, it is preferable to use a stainless steel alloy which is easily available as a polymer manufacturing apparatus. As for the method for producing aromatic polycarbonate using this stainless alloy, improving the quality of the polymer by pretreatment of the apparatus has already been studied and disclosed in some publications.

For example, Japanese Laid-Open Patent Publication No. Hei 4-7328 discloses a method for producing an aromatic polycarbonate, wherein a method of producing an aromatic polycarbonate by transesterification is performed by buffing the inner wall of the reactor. . Japanese Laid-Open Patent Publication No. Hei 4-7329 discloses a method characterized by using a pickle of a stainless steel reactor. Japanese Unexamined Patent Application Publication No. Hei 6-200008 discloses a method of washing the reaction apparatus after the completion of the reaction using a phenol compound. JP-A-6-56984 discloses a method of washing a stainless steel reactor with a liquid containing an aromatic hydroxy compound and then polymerizing it.

However, the use of optical discs of aromatic polycarbonates requires glazes having reduced foreign matters such as mixed matters such as dust and dirt, micromaterials caused by microcrystals of aromatic polycarbonates, and black foreign matters in which polymers are deteriorated. The method of producing a polymer that meets the requirements has not been solved.

However, none of these publications considers that the foreign material represented by the micro foreign matter referred to in the present invention is reduced.

In addition, as another method for obtaining an aromatic polycarbonate in which this foreign material is reduced, for example, JP-A-5-239334, an aromatic hydroxy compound and a diester carbonate are melt-condensed in the presence of a catalyst, and then an additive is added. And kneading, and filtering by a polymer filter after kneading to produce an optically aromatic polycarbonate with little foreign matter is described. Japanese Patent Laid-Open No. 6-234845 describes a method of installing at least one filter at each of the front and the outlet from the final reactor.

However, these methods can remove foreign matter of a certain size according to the degree of filtration of the filter, but it is insufficient to reduce the generation of foreign matter itself, and it is not a fundamental solution. In addition, in order to prevent the loading of the filter and to suppress the increase in the process cost due to the filter replacement, development of an aromatic polycarbonate manufacturing process capable of suppressing the generation of foreign substances including the above-described micromaterials is required.

Japanese Unexamined Patent Publication No. 10-226723 discloses that when the polymer during or after the polymerization is transferred through a pipe to produce an aromatic polycarbonate, the linear velocity is 0.05 m / sec or more when the number average molecular weight of the molten polymer is less than 2500. And a number average molecular weight of the molten polymer of 2500 or more, a method for obtaining an aromatic polycarbonate with less coloring and less foreign matters is characterized by being 0.005 m / sec or more. However, all are still insufficient for the fundamental solution of the problem.

In addition, these coloring and foreign matter problems are required as a common characteristic such as all block error rates in the case of optical use, and therefore, voices requiring comprehensive measures from aromatic polycarbonates, which are raw materials for optical products, are increasing.

Therefore, various studies have been attempted to solve such a problem.

Disclosure of the Invention

In the above process, it was evident that one effective method is to strictly control the molar balance between the aromatic dihydroxy compound and the diester carbonate, which are two kinds of raw materials used in the melting method. In practice, however, it is difficult to manage the equilibrium strictly, and much effort is needed to realize this.

Speaking of the molar balance of the aromatic dihydroxy compound and the diester carbonate, the reason for obtaining the aromatic polycarbonate of good quality by strictly controlling the molar balance of the raw materials in the melting method is that the esters in which the end groups of the two raw materials are involved. Since the polymerization proceeds by the exchange reaction, it is considered that the polymerization speed is increased when the concentrations of both are matched, and as a result, the time (thermal history) subject to the strict polymerization conditions is shortened.

Since the end group concentration decreases at the same time as the polymerization proceeds, and the polymerization conditions are generally more stringent at the same time as the polymerization proceeds, it is important to maintain a proper molar balance of the terminal at the reduced end group, and thus to maintain a strict molar balance. Management is required.

In particular, in recent years, aromatic polycarbonates have been used in optical products requiring high density and high precision such as DVD, MO, CDR, and the like. In this case, coloring, branching, and gelation of aromatic polycarbonates have optical characteristics such as block error rate of the final product directly. And since it has a big influence on mechanical properties, such as tension, bending, toughness, etc., the importance of raw material molar balance management is increasing in order to avoid this problem.

On the other hand, since the aromatic dihydroxy compound used as a raw material has a high melting point and often lacks stability in the molten state, handling by powder is preferably used, but the conveyance and metering of the powder is difficult compared with liquid.

One of the present inventions has been made in order to solve this problem. That is, an object of the present invention is to provide a manufacturing method for efficiently obtaining aromatic polycarbonate having excellent quality by improving the problems of the prior art. According to this invention, accurate raw material molar ratio adjustment is made, therefore, there is little coloring and the target degree of polymerization can be obtained, and therefore a very good result is obtained for product quality.

In addition, the present inventors made diligent studies to find a method for producing a transesterified aromatic polycarbonate having excellent color tone and thermal stability. As a result, the present inventors have prepared the nitrogen-containing basic compound concentration used as a transesterification catalyst in the reaction mixture in a specific range. The aromatic polycarbonate polymer was found to have excellent color tone and thermal stability, and the present invention was completed.

In the present invention, in preparing an aromatic polycarbonate, an aromatic polycarbonate having a specific range of viscosity average molecular weights using a specific amount of an alkali metal compound and / or an alkaline earth metal compound as a catalyst and a nitrogen-containing basic compound as a catalyst The nitrogen-containing basic compound contained in the reaction mixture in the production is in a specific range, and the transesterification reaction proceeds, whereby an aromatic polycarbonate having little heat denaturation and color deterioration and excellent color tone can be obtained.

Regarding the solvent for the catalyst, there are the following problems. That is, when producing an aromatic polycarbonate by melt condensation polymerization reaction, superposition | polymerization is performed in presence of a catalyst, Usually, amines, such as an alkali metal salt, alkaline earth metal salt, a quaternary ammonium salt, etc. are used as the catalyst. As the addition method, a solution in which a catalyst is dissolved in the same monohydroxy compound as the polymerization effluent or a slurry supernatant in which the catalyst is dispersed is used, and is added at the start of polymerization and during the polymerization.

In that case, after obtaining an aromatic polycarbonate by melt polymerization reaction as a solvent from the viewpoint of a manufacturing cost normally, a by-product monohydroxy compound is recycled and used, but in a monohydroxy compound recycled, in a normal monohydroxy compound Impurities derived from additives such as catalysts and stabilizers added during polymerization that are not contained are contained.

In addition, when the by-produced monohydroxy compound is used as a catalyst addition solvent in melt polycondensation of aromatic polycarbonate, purification is carried out by distillation under reduced pressure to remove impurities, and the impurities in the monohydroxy compound are highly removed. It is considered that it is possible to repeat the purification several times or to use a large-scale facility, but it is disadvantageous in terms of cost and productivity, and since the impurities are likely to remain in the monohydroxy compound even after purification, the aromatic polycarbonate using this as a catalyst addition solvent In the manufacture of the cause of the coloring.

As a result of intensive studies on the above problems, in the production of aromatic polycarbonates by melt condensation polymerization reaction using diester carbonate as a raw material, by-product monohydroxy compounds are recycled and used as a catalyst addition solvent, This catalyst addition solvent was found to contain a specific amount of anisole and / or a specific amount of trimethylamine to be effective in the production of aromatic polycarbonates with excellent color, thus completing one of the present inventions.

In the method for producing an aromatic polycarbonate by melt condensation polymerization reaction using diester carbonate as a raw material, the monohydroxy compound by-produced by this melt condensation polymerization reaction is recycled and used as a catalyst addition solvent, Moreover, this catalyst addition solvent can provide the manufacturing method of the aromatic polycarbonate excellent in color by containing a specific amount of anisole and a specific amount of trimethylamine.

In addition, the present inventors have diligently studied to produce aromatic polycarbonate having excellent color tone by transesterification, and found that it is effective to use diester carbonate in which the content of specific impurities is reduced to a specific value or less, thus completing one of the present inventions. It came to the following.

The present invention can provide a diester carbonate having excellent storage stability suitable for producing an aromatic polycarbonate by transesterification with an aromatic dihydroxy compound. In addition, the aromatic polycarbonate having good quality and color can be obtained by this diester carbonate.

In addition, as for the material of the apparatus, a study was made in order to find a production method capable of producing an aromatic polycarbonate in which foreign matter generation was suppressed by the transesterification method on an industrial scale. As a result, a stainless steel alloy containing a certain amount of a specific metal as a reaction apparatus was surprisingly found. It has been found that foreign matter generation is suppressed by using a reaction apparatus consisting of.

That is, one of the present invention is to provide a method for producing an aromatic polycarbonate in which foreign matter generation is suppressed, which is produced using a reaction apparatus made of a stainless alloy containing a certain amount of a specific metal.

According to the above invention, an aromatic polycarbonate in which foreign matter generation is suppressed can be obtained by using a reactor in which the material is a stainless alloy and the total content of niobium and / or vanadium contained in the stainless alloy is 10 ppm to 1000 ppm. This makes it possible to produce aromatic polycarbonates which are particularly useful for applications in which foreign matters such as optical disks need to be reduced.

One object of the present invention is to provide a polymerization apparatus useful for producing a high quality aromatic polycarbonate with reduced foreign matters represented by micro foreign matters. More specifically, even in general materials such as stainless steel, by forming a specific oxide film on the inner wall surface of part or all of the reaction apparatus, foreign matters represented by micro foreign matters are reduced, and there is no problem such as loading of a polymer filter. It is an object to provide a reactor useful for producing high quality aromatic polycarbonates which are preferably used.

In addition, another object of the present invention is to provide a method for producing a high-quality aromatic polycarbonate by transesterification, which reduces foreign matters, especially gel foreign matters represented by micro foreign matters, and which is useful for optical purposes. The purpose.

Further, according to the present invention, the production of an aromatic polycarbonate using a device having a specific surface oxide layer, in particular, when producing the aromatic polycarbonate by a transesterification method, by using the device to produce an aromatic polycarbonate in which foreign matters represented by micro foreign matters are reduced. can do.

By the apparatus and method of the said invention, it became clear that a microgel foreign material can be reduced more effectively among the foreign materials represented by a micro foreign material.

Aromatic polycarbonates produced using the apparatus disclosed in the above invention are particularly useful for optical materials, particularly for optical disks, and for recording materials with less error rate.

That is, the present invention is as follows.

1. A method for producing a polycarbonate by supplying an aromatic dihydroxy compound and a diester carbonate to a raw material dissolution tank, mixing and melting the same, and then melt-polymerizing in the presence / nonexistence of a catalyst. Method for producing an aromatic polycarbonate, characterized in that to maintain at 0 MPa to 0.05 MPa gauge pressure.

2. The process according to 1 above, wherein at least 90% by volume of the atmosphere gas in the transport pipe immediately before the raw material melting tank for supplying the aromatic dihydroxy compound of the powder to the raw material melting tank is a non-oxidizing gas, and its linear velocity is 0.5 cm / min or more. Manufacturing method characterized in that.

3. The method according to 1 or 2 above, wherein the vent pipe of the raw material dissolution tank is connected to the scrubber.

4. The production method according to any one of 1 to 3, wherein the vent pipe of the raw material melting tank is connected to a capacitor maintained at a temperature of 70 ° C or higher.

5. The process according to 1 to 4, wherein the diester carbonate is diphenyl carbonate.

6. A mixture containing an aromatic dihydroxy compound and a carbonic acid diester as a main compound is reacted by a transesterification reaction using an alkali metal compound and / or an alkaline earth metal compound and a nitrogen-containing basic compound as a catalyst, and the aromatic polycarbonate is reacted. In the preparation, the concentration of the nitrogen-containing basic compound in the reaction mixture is maintained at 0.1 ppm or more and 10 ppm or less between 500 and 3000 for the viscosity average molecular weight of the reaction mixture, and the viscosity average molecular weight of the reaction mixture is 3000 to 10000. The method for producing an aromatic polycarbonate, which is maintained at 0.01 ppm or more and 1 ppm or less.

7. The process according to 6 above, wherein ^10-3 to ^10-8 equivalents of alkali metal compound and / or alkaline earth metal compound are used as the metal per mole of aromatic dihydroxy compound.

8. The method according to the above 6, wherein an alkali metal compound and / or an alkaline earth metal compound of 5 × 10 ⁻⁶ to 1 × 10 ⁻⁸ equivalent is used as the metal per mole of the aromatic dihydroxy compound.

9. The nitrogen-containing basic compound according to any one of 6 to 8, wherein R ₁ is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. Manufacturing method.

(R ₁ ) ₄ NOH

10. Production of an aromatic polycarbonate according to any one of 6 to 9, wherein the aromatic dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane and the diester carbonate is diphenyl carbonate. Way.

11. A method for producing an aromatic polycarbonate by melt condensation polymerization using diester carbonate as a raw material, wherein the monohydroxy compound produced by the melt condensation polymerization is recycled and used as a catalyst addition solvent. The process for producing an aromatic polycarbonate, wherein the catalyst addition solvent contains 1 ppm or more and 1000 ppm or less of anisole.

12. A method for producing an aromatic polycarbonate by melt condensation polymerization using diester carbonate as a raw material, wherein the monohydroxy compound produced by the melt condensation polymerization is recycled and used as a catalyst addition solvent. The catalyst addition solvent contains trimethylamine of 1 ppm or more and 100 ppm or less, The manufacturing method of the aromatic polycarbonate characterized by the above-mentioned.

13. A method for producing an aromatic polycarbonate by melt condensation polymerization using diester carbonate as a raw material, wherein the monohydroxy compound produced by the melt condensation polymerization is recycled and used as a catalyst addition solvent. The catalyst addition solvent contains 1 ppm or more and 1000 ppm or less of anisole, and 1 ppm or more and 100 ppm or less of trimethylamine.

14. The process for producing an aromatic polycarbonate according to any one of 11 to 13, wherein the monohydroxy compound is phenol.

15. The catalyst according to any one of 11 to 14, wherein the catalyst used in the melt condensation polymerization method is quaternary ammonium salt or quaternary phosphonium salt and / or alkali metal salt, quaternary ammonium salt or quaternary phosphonium salt and / Or a process for producing an aromatic polycarbonate which is an alkaline earth metal salt.

In addition, the present invention provides a nitrogen-containing compound suitable for preparing an aromatic polycarbonate by heating and melting and transesterifying an aromatic dihydroxy compound and a diester carbonate in the presence of an alkali metal compound and / or a catalyst containing an alkaline earth metal compound as a nitrogen atom. The present invention relates to a diester carbonate having excellent storage stability, containing no more than 5 ppm, 0.5 ppm of metal elements, and 10 ppm of organic impurities.

In the present invention, an aromatic dihydroxy compound and a diester carbonate are heated and melted in the presence of a catalyst to produce an aromatic polycarbonate by a transesterification reaction, wherein the content of a specific impurity is suppressed to a specific value or less. It also relates to a method for producing an aromatic polycarbonate having good quality and color by using.

That is, one of the present invention is as follows.

16. Nitrogen-containing compounds suitable for the production of aromatic polycarbonates by heating and melting and transesterifying aromatic dihydroxy compounds and diester carbonates in the presence of a catalyst containing an alkali metal compound and / or an alkaline earth metal compound are nitrogen atoms. A diester carbonate having excellent storage safety, characterized in that 5 ppm or less, 0.5 ppm or less of metal elements to be contained, and 10 ppm or less of salicylic acid derivatives to be contained.

17. The diester carbonate according to the above 16, wherein the total amount of iron, tin, chromium, titanium, and copper is 0.5 ppm or less with respect to this metal element.

18. The diester carbonate according to any one of 16 to 17, wherein the total amount of all metals is 0.5 ppm or less with respect to this metal element.

19. A method of heating and melting an aromatic dihydroxy compound and a diester carbonate in the presence of a catalyst containing an alkali metal compound and / or an alkaline earth metal compound, transesterifying the same, and producing an aromatic polycarbonate. 5.0 * ^10-8 to 5.0 * ^10-6 equivalents of an alkali metal compound and / or an alkaline earth metal compound per mole of aromatic dihydroxy compound, using the diester carbonate according to any one of 16 to 18 as the catalyst, and A nitrogen-containing basic compound, 1.0 * ^10-5 to 5.0 * ^10-4 equivalents, for producing an aromatic polycarbonate.

In addition, one of the present invention is as follows.

20. A method for producing an aromatic polycarbonate by transesterification of an aromatic dihydroxy compound and a diester carbonate compound, wherein the material of the reaction apparatus is a stainless alloy and the sum of niobium and / or vanadium contained in the stainless alloy. A method for producing an aromatic polycarbonate in which foreign matter generation is suppressed, wherein the content is 10 ppm to 1000 ppm.

21. The catalyst used in the transesterification reaction according to the above 20 contains an alkali metal compound and / or a nitrogen-containing basic compound, and the amount of the alkali metal compound used is from 1 × 10 ⁻⁸ mol to 1 mol of the aromatic dihydroxy compound. It is 5 * 10 <^-6> moles, The manufacturing method of the aromatic polycarbonate.

22. An apparatus for producing an aromatic polycarbonate, wherein at least 20 nm or more of an oxide layer containing iron oxide as a main component is formed on the inner wall of part or all of the reaction apparatus used to produce the aromatic polycarbonate.

23. The apparatus for producing an aromatic polycarbonate according to the above 22, wherein an oxide layer containing iron oxide as a main component is formed on an inner wall surface of a material made of a stainless alloy.

24. The apparatus for producing an aromatic polycarbonate according to any one of 22 and 23, wherein an oxide layer containing iron oxide and chromium oxide as a main component is formed on at least part of the inner wall of the reaction apparatus at least 20 nm.

25. The apparatus for producing an aromatic polycarbonate according to any one of 22 to 24, wherein the aromatic polycarbonate is produced by transesterification of an aromatic dihydroxy compound and a diester carbonate compound in the presence of a catalyst.

26. A method for producing an aromatic polycarbonate in which an aromatic dihydroxy compound and a diester carbonate compound are produced by a transesterification method in the presence of a catalyst, using the reactor according to any one of 22 to 25 above. Method for producing an aromatic polycarbonate, characterized in that.

27. A method for producing an aromatic polycarbonate, comprising the combination of 19 and 6, 8 or 9 above.

28. A method for producing an aromatic polycarbonate, comprising the combination of 27 and 26 and / or 20.

29. A method for producing an aromatic polycarbonate, comprising the combination of any one of 27 and 1 or 4 above.

30. A method for producing an aromatic polycarbonate, comprising the combination of 27 and 14 above.

31. A method for producing an aromatic polycarbonate, comprising the combination of 28 and 14 above.

32. A method for producing an aromatic polycarbonate, comprising the combination of 31 and 1 or 4 above.

33. A process for producing an aromatic polycarbonate comprising two or more of 19, 6, 26, 20, 11, and 1, wherein the combination of 19 and 6 and the combination of 19 and 6 and 26 are used. Except for the method for producing an aromatic polycarbonate comprising the combination of 19, 6, and 20 and the combination of 19, 6, and 1.

In addition, "the viscosity average molecular weight of the reaction mixture is between 500 and 3000" or "the viscosity average molecular weight of the reaction mixture is between 3000 and 10,000" means that the viscosity average molecular weight of the reaction mixture is substantially between 500 and 3000 or between 3000 and 10000. In the case of using a complete mixing tank to obtain a reaction mixture in a continuous reactor, the state in the complete mixing tank when the viscosity average molecular weight of the reaction mixture at the outlet of the complete mixing tank is within the range of this value This condition is satisfied.

Hereinafter, the present invention will be described in more detail.

Fig. 1 shows the results of Auger Electron Spectroscopy analysis of analytical test pieces (10 mm in diameter and 1 mm in thickness) treated in the same manner.

Although the aromatic polycarbonate which concerns on this invention is various, Especially the mixture containing the aromatic dihydroxy compound represented by following formula (1a), and the mixture containing diester carbonate represented by following formula (1b) as a main compound, and a nitrogen-containing basic compound, Aromatic polycarbonates melt-polymerized in the presence of an transesterification catalyst made of an alkali metal compound are preferable.

(W is the following two formulas, -O-, -S-, -SO- or SO _2- )

In Formula 1a, n represents 0 to 4, R ₂ , and R ₃ , which are the same or different from each other, or a hydrocarbon group having 1 to 12 carbon atoms. R ₄ and R ₅ represent the same or different halogen atoms, hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group or an aromatic hydrocarbon group having 6 to 12 carbon atoms such as a phenyl group. Examples of the halogen atom include chlorine, bromine and iodine. R ₆ is an alkylene group having 3 to 8 carbon atoms. A pentylene group etc. are mentioned as an alkylene group.

Aromatic dihydroxy compounds related to the present invention include, for example, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl ) Propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3, 5-dibromophenyl) propane, bis (4-hydroxyphenyl) oxide, bis (3,5-dichloro-4-hydroxyphenyl) oxide, p, p'-dihydroxydiphenyl, 3,3 ' -Dichloro-4,4'-dihydroxyphenyl, bis (hydroxyphenyl) sulfone, resorcinol, hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydrate Hydroxy-3-methylbenzene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide and the like can be given, but in particular 2,2-bis (4-hydroxyphenyl) propane is preferred. Do.

In Formula 1b, R ₇ , R ₈ , R ₉ , and R ₁₀ are the same or different hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, phenyl groups or halogen groups.

Examples of the diester carbonate according to the present invention include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclo Although hexyl carbonate is mentioned, Diphenyl carbonate and a tolyl carbonate are especially preferable.

In preparing the aromatic polycarbonate in the present invention, the diester carbonate is used in an amount of 1.00 to 1.20 mol, preferably 1.005 to 1.10 mol, more preferably 1.01 to 1.05 per mol of the aromatic dihydroxy compound.

As the aliphatic dihydroxy compound (diol), for example, ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,10-decanediol, etc. As the leric acids, for example, succinic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, cyclohexanecarboxylic acid, terephthalic acid and the like; As the oxyacids, for example, lactic acid, P-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and the like can be contained.

Alkali metal compounds, alkaline earth metal compounds and nitrogen-containing basic compounds may be used as the catalyst.

As a transesterification catalyst of the melt condensation polymerization method when the by-product monohydroxy compound is recycled and used as a catalyst solvent, quaternary ammonium salts or quaternary phosphonium salts and / or alkali metal salts, quaternary ammonium salts or quaternary Preference is given to using quaternary phosphonium salts and / or alkaline earth metal salts.

In the present invention, alkali metal compounds used as catalysts include, for example, hydroxides, carbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, boron hydrides and benzoates of alkali metals. And hydrogen phosphates, bisphenols, and salts of phenols.

Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium nitrate, potassium nitrate, lithium nitrate Sodium nitrite, potassium nitrite, lithium nitrite, sodium sulfite, potassium sulfite, lithium sulfite, sodium cyanate, potassium cyanate, lithium cyanate, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, sodium stearate, stearic acid Potassium, lithium stearate, sodium borohydride, potassium borohydride, lithium borohydride, sodium phenyl borate, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dihydrogen phosphate, bisphenol A Sodium salts, dipotassium salts, dilithium salts, sodium salts of phenols, potassium salts, lithium salts, and the like. Cerium salts such as disodium salts of bisphenol A or sodium salts of aromatic monohydroxy compounds such as sodium salts of phenol can be preferably used.

As the transesterification catalyst, an alkali metal compound and / or an alkaline earth metal compound catalyst are the most preferable in terms of performance. However, when used alone, for example, when the transesterification rate of diester carbonate and BPA is less than 50%, That is, since it is slow in the initial stage of polymerization, it becomes a problem when it is industrially performed. Accordingly, it is preferable to use a nitrogen-containing basic compound and / or basic phosphorus compound described later together with the alkali (earth) metal compound catalyst.

Alkali metal compounds and / or alkaline earth metal compounds as catalysts according to the present invention are those in which the alkali metal elements and / or alkaline earth metal compounds in the catalyst are metals per mole of aromatic dihydroxy compound as 1 × 10 ⁻³ to 1 × 10 ^It is used in an amount of ^-8 equivalents. Preferably it is used in the range of ^5x10-6 to ^1x10-8 equivalents, and more preferably ^5x10-6 to ^1x10-7 equivalents.

It is not preferable to deviate from the above use range because it adversely affects the physical properties of the aromatic polycarbonate obtained, or there is a problem that the transesterification reaction does not proceed sufficiently and a high molecular weight aromatic polycarbonate cannot be obtained. In particular, when the alkali metal compound and / or the alkaline earth metal compound catalyst are used in a large amount, when the polymerization temperature is increased in the later stage of the reaction, the aromatic polycarbonate bond is transferred, so that decomposition and branching components are easily generated. That is, since the amount of such decomposition and branching components is large, the melt polymerization aromatic polycarbonate by transesterification is poor in fluidity and color tone compared to the interfacial polymerization aromatic polycarbonate.

In order to make the fluidity | liquidity and color tone of melt polymerization aromatic polycarbonate the level similar to an interfacial polymerization aromatic polycarbonate, it is necessary to make the said decomposition | disassembly and branching component amount into 0.2 mol% or less per repeating unit. For this purpose, it is preferable to suppress the catalyst amount of the alkali metal compound and / or the alkaline earth metal compound to less than 5.0 * 10 ⁻⁶ equivalents per mole of aromatic dihydroxy compound.

That is, the preferable ratio of the usage-amount of an alkali metal compound and / or alkaline-earth metal compound is a ratio which becomes 5 * 10 <^-8> -5 * 10 <^-6> equivalent per mole of aromatic dihydroxy compound. It is not preferable to deviate from the above use range because it adversely affects the physical properties of the obtained aromatic polycarbonate, or there is a problem that the transesterification reaction does not proceed sufficiently and a high molecular weight aromatic polycarbonate cannot be obtained. Occurs.

When the amount of the nitrogen-containing basic compound contained in the reaction mixture according to the present invention will be described later, when the molecular weight of the reaction mixture is within a specific range, a specific value can be used to obtain an aromatic polycarbonate having excellent color tone and thermal stability. Within the range of the catalyst used, more excellent color tone and thermal stability can be obtained, and a higher molecular weight aromatic polycarbonate can be easily obtained, and the properties of the aromatic polycarbonate are also excellent.

In Formula 1, R ₁ is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms, but in addition to these preferred compounds, tertiary amines such as triethylamine or borate may also be used.

As the nitrogen-containing basic compound as such a catalyst, for example, tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), benzyltrimethylammonium Ammonium hydroxides having alkyl, aryl, alkylaryl groups, such as hydroxide (Φ-CH ₂ (Me) ₃ NOH), hexadecyltrimethylammonium hydroxy, triethylamine, tributylamine, dimethylbenzylamine, Tertiary amines such as hexadecyldimethylamine, or tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ And basic salts such as tetrabutylammoniumtetraphenylborate (Bu ₄ NBPh ₄ ), and tetramethylammonium hydroxide (Me ₄ NOH) is most preferably used.

Examples of quaternary phosphonium salts are, for example, tetramethylphosphonium hydroxide (Me ₄ POH), benzyltrimethylphosphonium hydroxide (Φ-CH ₂ (Me) ₃ POH), hexadecyltrimethylphosphonium hydroxy Phosphonium hydroxides having alkyl, aryl, alkylaryl groups such as these, or basic groups such as tetramethylphosphonium bolohydride (Me ₄ PBH ₄ ) and tetramethylphosphonium tetraphenylborate (Me ₄ PBPh ₄ ) Can be mentioned.

The nitrogen-containing basic compound is preferably used in a ratio such that the basic nitrogen atom in the nitrogen-containing basic compound is 1 × 10 ⁻⁵ to 5 × 10 ⁻⁴ equivalents per mole of aromatic diol compound. A more preferable ratio is a ratio which becomes 2x10 <^{-5> -5} * 10 <^-4> equivalent with respect to the same reference | standard. Especially preferable ratio is the ratio used as 5 * 10 <^{-5> -5} * 10 <^-4> equivalent with respect to the same reference | standard.

In addition, according to the studies by the present inventors, in order to produce an aromatic polycarbonate having excellent quality by a transesterification method, the amount (ie, the amount of addition) of the nitrogen-containing basic compound to the aromatic dihydroxy compound, which is conventionally important, is not very important. On the contrary, when the viscosity average molecular weight of the reaction mixture is between 500 and 3000, the concentration of the nitrogen-containing basic compound in the reaction mixture is maintained at 0.1 ppm or more and 10 ppm or less, and when the viscosity average molecular weight is between 3000 and 10000 in the reaction mixture It was found that it is very important to proceed with the transesterification reaction while maintaining the concentration of the nitrogen-containing basic compound at 0.01 ppm or more and 1 ppm or less. Here, the "reaction mixture" means a mixture containing mainly the aromatic hydroxy compound represented by the general formula (1a) and the diester carbonate represented by the general formula (1b), a nitrogen-containing basic compound, an alkali metal compound and / or an alkaline earth metal compound. In the process of melt-condensation-polymerization reaction in the presence of a transesterification catalyst etc. which consists of the above-mentioned, the polycondensation reaction is started or advanced in the process of obtaining an aromatic polycarbonate. The furnace is in the state of "prepolymer", and what is further advanced is in the state of "polymer" in general chemical terminology.

In the present invention, an alkali metal salt of an art complex of an element of Group 14 of the Periodic Table or an alkali metal salt of Oxo acid of an element of Group 14 of the Periodic Table can be used as the alkali metal compound that is a catalyst as desired. Here, the elements of group 14 of the periodic table refer to silicon, germanium and tin.

By using this alkali metal compound as a polycondensation reaction catalyst, it has the advantage that a polycondensation reaction can be advanced quickly and fully. It is also possible to suppress undesirable side reactions, such as branching reactions generated during polycondensation reactions, at low levels.

(a) As an alkali metal salt of the art complex of group 14 element of a periodic table, what is described in Unexamined-Japanese-Patent No. 7-268091, Specifically, it is a germanium (Ge) compound; NaGe (OMe) ₅ , NaGe (OEt) ₃ , NaGe (OPr) ₅ , NaGe (OBu) ₅ , NaGe (OPh) ₅ , LiGe (OMe) ₅ , LiGe (OBu) ₅ , LiGe (OPh) ₅ have.

Tin (Sn) compounds include NaSn (OMe) ₃ , NaSn (OMe) ₂ (OEt), NaSn (OPr) ₃ , NaSn (OnC ₆ H ₁₃ ) ₃ , NaSn (OMe) ₅ , NaSn (OEt) ₅ , NaSn (OBu) ₅ , NaSn (OnC ₁₂ H ₂₅ ) ₅ , NaSn (OEt) ₅ , NaSn (OPh) ₅ , NaSnBu ₂ (OMe) ₃ .

(B) Alkali metal salts of oxo acids of periodic table 14 elements include, for example, alkali metal salts of silicic acid, alkali metal salts of stanic acid, and alkalis of germanium (II) acid (germanous acid). Preferable examples thereof include metal salts and alkali metal salts of germanium (IV) acid.

Alkali metal salts of silicic acid are, for example, acidic or neutral alkali metal salts of monosilicic acid or its condensates, examples of which are monosodium monosilicate, disodium sodium silicate, trisodium silicate and tetrasodium silicate. Can be.

Alkali metal salts of tartaric acid are, for example, acidic or neutral alkali metal salts of monostanic acid or a condensate thereof, for example monodiacid disodium salt (Na ₂ SnO ₃ xH ₂ O, x = 0 to 5). And monotartrate tetrasodium salt (Na ₄ SnO ₄ ).

Alkali metal salts of germanium (II) acid (germanous acid) are, for example, acidic or neutral alkali metal salts of monogermanic acid or its condensates, for example, germanium acid monosodium salt (NaHGeO ₂ ).

Alkali metal salts of germanium (IV) acid are, for example, acidic or neutral alkali metal salts of monogermanic (IV) acid or condensates thereof, for example oltgerate monolithic acid (LiH ₃ GeO ₄ ) olt Germanium disodium salt, oltgermanic acid tetrasodium salt, digermanic acid disodium salt (Na ₂ Ge ₂ O ₅ ), tetragermanic acid disodium salt (Na ₂ Ge ₄ O ₉ ), pentagermanic acid disodium salt ( Na ₂ Ge ₅ O ₁₁ ).

The above polycondensation reaction catalyst is preferably used when the alkali metal element in the catalyst is 1 × 10 ^-8 to 5 × 10 ^-5 equivalents per mole of aromatic diol compound. A more preferable ratio is a ratio which becomes 5x10 <^{-7> -5} * 10 <^-5> equivalent with respect to the same reference | standard.

In the polycondensation reaction of the present invention, at least one cocatalyst selected from the group consisting of an oxo acid and an oxide of the copper element of the Periodic Table 14 element can coexist with the catalyst as necessary.

By using these cocatalysts in a specific ratio, it is possible to produce foreign substances in the apparatus during branching or molding processing, which are likely to be produced during the polycondensation reaction, without inhibiting the terminal blocking reaction and the polycondensation reaction rate. It is possible to more effectively suppress undesirable side reactions.

Examples of the oxo acid of the Group 14 element of the periodic table include silicic acid, tartaric acid and germanium acid.

Examples of the oxide of the Group 14 element of the periodic table include silicon monoxide, silicon dioxide, tin monoxide, tin dioxide, germanium monoxide, germanium dioxide and these condensates.

The cocatalyst is preferably present at a rate such that 1 mole (atomic) of the alkali metal element in the polycondensation reaction catalyst is 50 mole (atomic) or less of the metal element of Group 14 of the periodic table in the cocatalyst. The use of a promoter in a proportion of more than 50 moles (atoms) of the same metal element is undesired because the polycondensation reaction rate is delayed.

The cocatalyst is preferably present at a rate such that 0.1 to 30 moles (atoms) of the metal elements of Group 14 of the periodic table of the cocatalyst are present per mole of alkali metal elements (atoms) of the polycondensation reaction catalyst.

These catalyst systems have the advantage of being able to proceed the polycondensation reaction and the end encapsulation reaction quickly and sufficiently by using in the polycondensation reaction. In addition, undesirable side reactions such as branching reactions generated in the polycondensation reaction system can be suppressed to a low level.

In preparing an aromatic polycarbonate by reacting a mixture mainly containing an aromatic hydroxy compound and a diester carbonate under heating melting, when the transesterification reaction is carried out, the mixture mainly contains an aromatic dihydroxy compound and a diester carbonate under an inert gas atmosphere. It is common to add the aforementioned catalyst to the melt mixture (reaction mixture) generated by heating and stirring the mixture to initiate the transesterification reaction.

In the present invention, the temperature and pressure for transesterifying the aromatic hydroxide compound and the diester carbonate are not particularly limited, and the temperature and pressure at which the reaction is initiated and the monohydroxy compound produced by the reaction is rapidly removed out of the reaction system. Although any conditions may be sufficient as this, generally, reaction temperature is 120-350 degreeC normally, and it is generally performed to raise reaction temperature with progress of superposition | polymerization. In addition, the pressure of the reaction system may be normal pressure or pressurization, but the pressure of the reaction system is often reduced, and the phenol generated by combining a large amount of a small amount of inert gas with these conditions again is used. It is generally practiced to facilitate the extraction and to advance the reaction.

Specifically, after initiating the reaction at a temperature of 150 ° C. to 200 ° C. and a pressure of 300 Torr to 100 Torr, as the molecular weight of the aromatic polycarbonate accompanying the progress of the reaction increases, the reaction temperature is increased to lower the reaction pressure, Finally, reaction is often performed at the temperature of 270-350 degreeC and the pressure of 1 Torr or less.

The type of apparatus used to carry out the present invention is not particularly limited, but a generally known male stirring vessel or a horizontal stirring vessel or a luder may be used.

More specifically, in the case of carrying out the reaction in a batch, two groups of aqueous stirring tanks are used, and the aromatic hydroxy compound and the diester carbonate are injected into the first stirring tank in which the rectification column is installed at the molar ratio to substitute an inert gas. After heating and melting, the predetermined amount of the polymerization catalyst is added thereto, and then the system is heated while vacuuming. After the initial polymerization, the reaction liquid is transferred to a second stirring tank having no rectifying tower, thereby further increasing the system into a higher vacuum. In addition, it is common to continue the polymerization until the temperature is also increased to a predetermined degree of polymerization. At this time, in order to maintain the concentration in the reaction system of the nitrogen-containing basic compound in the range of the present invention, an appropriate amount of the nitrogen-containing basic compound may be further reacted, for example, during the reaction in the first stirring tank or during the transfer to the second stirring tank. have.

In the case of carrying out the reaction continuously, a plurality of stirring tanks are used, and among these, an initial polymerization tank having a low viscosity of the reactants is used an aqueous stirring tank having a rectifying column, and the aromatic monohydride is produced by increasing the viscosity of the reactants. Later polymerization tanks, where it is difficult to remove oxy compounds, are installed in series using a horizontal stirring tank or a two-axis looper, and the molten raw material and the catalyst are continuously sent to the first polymerization tank and continuously prescribed in the final polymerization tank. It is generally practiced to derive an aromatic polycarbonate of degree of polymerization. In this case, in order to maintain the concentration in the reaction system of the nitrogen-containing basic compound in the range of the present invention, an appropriate amount of the nitrogen-containing basic compound may be added and reacted to each polymerization tank including the first stirring tank.

In addition, in order to maintain the concentration in the reaction system of the nitrogen-containing basic compound within the scope of the present invention, it is necessary to strictly control the concentration of impurities containing nitrogen present in a raw material called a diester carbonate or a dihydroxy compound used in the reaction. The concentration of the nitrogen-containing compound in the raw material is preferably 5 ppm or less, more preferably 4 ppm or less. By using a raw material containing few such nitrogen-containing compounds, it is possible to accurately grasp and manage the concentration in the reaction system of the nitrogen-containing basic compound used as a catalyst.

In such a facility, it is very important to manage the mixing molar ratio of diester carbonate and aromatic dihydroxy compound as raw materials within a certain range.

In this invention, it is preferable that the ratio of the aromatic dihydroxy compound and diester carbonate used is a little excessive use of diester carbonate. Since the boiling point of diester carbonate is less likely to be lower than the boiling point of aromatic dihydroxy compound, even when the initial polymerization is carried out using a reactor having a rectifying column, the ratio of diester carbonate flowing out of the system is aromatic dihydrate. This is because more than the oxy compound. That is, in the present invention, the molar ratio of diester carbonate to the aromatic dihydroxy compound is generally 1.005 to 1.2: 1, more preferably 1.005 to 1.05. : 1 is used.

In the present invention, the balance of the raw material moles is set within the above molar ratio depending on the amount of terminal OH groups of the aromatic polycarbonate to be obtained, but the management precision is within 5% of the set value, preferably within 1%, more preferably. It is important to keep it within 0.5%. By doing in this way, the aromatic polycarbonate which has the quantity of the terminal group of interest can be obtained stably with good quality.

The inventors have found that to achieve these goals it is not enough to use a high precision weighing system that is commonly used.

The diester carbonate with excellent thermal stability of the melt is usually measured in the liquid phase. For example, the use of a high-precision flow meter is used to control the amount of the aromatic dihydroxy compound having poor thermal stability. It is often carried out in. For example, it is carried out by putting a dihydroxy compound, which is powder, in a weighing tank insulated from the surroundings by weight, taking this out using a screw feeder, etc. and weighing the weight with a load cell or the like.

These weighing systems are known per se to have sufficient weighing accuracy within 0.5% of error.

However, even when such a high-precision measuring equipment is used, it has been found that much effort is required, such as additionally adding one of the raw materials, in order to realize the strict molar balance.

As a result of earnestly examining in order to solve this problem, the present inventors have found that it is important to maintain the pressure of the gaseous phase portion of the raw material melting tank at preferably 0 MPa to 0.5 MPa, more preferably 0 MPa to 0.01 MPa. It was found that the management accuracy of the balance was greatly improved. In addition, in this specification, the pressure at the time of expressing the pressure of the gaseous-phase part of a raw material melting tank by MPa is what is called a gauge pressure, and makes normal atmospheric pressure into 0 MPa.

Although the cause is not certain, the evaporated matter, the branch system tank, and the like generated in the raw material melting tank are reduced in that the raw material is smoothly sent from the powder system tank to the raw material melting tank, and the adhesion and closing of powder in the piping is undesirable. Or it is inferred because entry into the piping that sends raw materials from the split system tank to the raw material melting tank is suppressed.

In the present invention, it has been found that at least 90% by volume of the atmosphere gas in the transport piping immediately before the raw material dissolution tank supplied to the raw material dissolution tank is a non-oxidizing gas, and the linear velocity of 0.5 cm / min or more is effective for increasing the measurement accuracy. . Here, "non-oxidizing gas" means a gas which does not cause coloring by oxidizing an aromatic dihydroxy compound or diester carbonate as a raw material. Specifically, for example, an inert gas such as nitrogen, argon of group 18 of the periodic table, etc. And carbon dioxide gas.

In addition, the use of a screw bar and / or a condenser in the middle of the vent piping system of the raw material melting tank causes the pressure of the gas phase part of the raw material melting tank to be within a certain range due to the fact that it appears to be due to reduced adhesion in the piping. I found it effective to increase As a result, it is possible to easily and stably and precisely manage the balance of the moles of the raw materials, and to successfully improve and stabilize the quality of the aromatic polycarbonate obtained by the melt polymerization method.

It is an unexpected fact that has never been known in the prior art that such subtle technical factors in transport piping or vents greatly affect the quality of aromatic carbonate production.

In the present invention, the raw material dissolution tank is a device for completely melting the aromatic dihydroxy compound and the diester carbonate stored at a constant mixing molar ratio at 120 to 150 占 폚, and includes a stirring device and a pump.

The stirring device has a function for completely melting and uniformizing the raw material, and is started when a certain amount of raw material exists in the raw material melting tank. In addition, the pump is connected to a pipe connected to the bottom of the raw material melting tank, has a self-circulating line if necessary, and is connected to the raw material storage tank or direct melt polymerization tank.

In the present invention, the scrubber is a general collection system for circulating the scrabbin liquid and absorbing the generated steam. For example, a vent pipe extending from the ceiling of the raw material melting tank is connected to the center in the longitudinal direction in the vertical tank. The upper part of the tank is provided with an exhaust pipe for discharging the gas after absorbing the steam. This exhaust pipe may be directly open to the atmosphere or may be connected to the main vent pipe in which the vent pipes of other facilities are collected.

Although it is not specifically limited as a scrabbin liquid, A low volatility solvent which can melt | dissolve or decompose | dissolve and absorb an aromatic dihydroxy compound or diester carbonate, or a low temperature liquid which can freeze and solidify steam at temperature is used, for example For example, water, aqueous sodium hydroxide solution, triethylene glycol, or the like can be used.

By supplying such a scrub liquid into the scrubber, the gas containing the vapor induced by the vent pipe of the raw material dissolution tank is sufficiently brought into contact with the scrabbin liquid to collect the aromatic dihydroxy compound or the diester carbonate in the gas.

In addition, when the concentration of the aromatic dihydroxy compound or diester carbonate in the solvent becomes a certain level or more, the scrabbin solution can be continuously operated by removing all or part thereof and adding a new scrabbin solution.

In the present invention, the vent pipe is a pipe for quickly removing the pressure of the gas phase part in the raw material melting tank generated when the raw material is sent from the split system tank to the raw material melting tank.

The pipe is preferably heated to a temperature of 120 ° C. or higher in order to prevent condensation and crystallization of the aromatic dihydroxy compound or diester carbonate between the raw material melting tank and the scrubber and / or condenser of the present invention.

In the present invention, the condenser generally used is preferably used as the condenser, and examples thereof include a double tube and a multi-tube condenser. Also in this case, it is preferable that the vent pipe connecting the raw material dissolution tank and the condenser is heated to 120 ° C. or higher to prevent precipitation of the aromatic dihydroxy compound or diester carbonate. Moreover, a scrubber can also be attached behind a condenser.

The outlet of the condenser may be directly open to the atmosphere, or may be connected to the main vent pipe in which the vent pipes of other equipment are collected.

70 degreeC or more is preferable and, as for the temperature inside a capacitor | condenser, More preferably, it is 70 degreeC-100 degreeC. Here, the gas from the dissolution tank is cooled inside the condenser, and the aromatic dihydroxy compound or diester carbonate in the gas is condensed and returned to the raw material dissolution tank again.

In addition, a cooling plate may be provided inside the condenser in order to increase the heat exchange efficiency.

As for the nitrogen-containing basic compound, it is known in a general sense that the amount (addition amount) of the nitrogen-containing basic compound is important in the course of the transesterification reaction.

However, it is possible to reproducibly produce an aromatic polycarbonate having excellent quality only by maintaining the amount of the nitrogen-containing basic compound initially known, in other words, the amount of the nitrogen-containing basic compound to the aromatic dihydroxy compound in a specific range. It turned out that there was no case.

As a result of examining this cause in detail, the inventors found that the following facts occur.

That is, the nitrogen-containing basic compound activates the transesterification reaction, but has low heat resistance in its own reaction system, and is easily pyrolyzed or reacts with the monohydroxy compound produced in the transesterification reaction, and trialkylamine or triaryl The effective concentration in the reaction mixture is rapidly reduced by decomposition with amine and alkylphenyl ether or arylphenyl ether and water. Furthermore, like trialkylamines, the effective concentration in the reaction mixture may be rapidly reduced because of the high volatility of the nitrogen-containing basic compound itself. It was found that the rate of reduction was greatly influenced by the type of diester carbonate used in the reaction, the reaction temperature and the reaction pressure.

In these facts, the concentration of nitrogen-containing basic compound which effectively contributes to the transesterification reaction varies in various ways depending on the reaction conditions, and this is an aromatic polycarbonate of good quality in the conventional method which defines the initial amount of the nitrogen-containing basic compound. It is inferred to be the cause that cannot be obtained reproducibly.

Therefore, as a result of various studies, the transesterification reaction is carried out by maintaining the concentration of the basic compound containing nitrogen at 0.1 ppm to 10 ppm at a viscosity average molecular weight of 500 to 3000, more preferably from 0.5 ppm to The transesterification reaction is maintained at 5 ppm, and the viscosity average molecular weight of the reaction mixture is maintained at a concentration of 0.01 ppm to 1 ppm, more preferably 0.05 ppm to 1 ppm, between 3000 and 10,000. It has been found that maintaining this is very important in order to impart excellent color tone and thermal stability to the resulting aromatic polycarbonate.

When the concentration of the nitrogen-containing basic compound in the reaction mixture of which the viscosity average molecular weight of the reaction mixture is between 500 and 3000 exceeds 10 ppm, excellent color tone and thermal stability cannot be imparted to the resulting aromatic polycarbonate, and the viscosity average of the reaction mixture is If the concentration of the nitrogen-containing basic compound in the reaction mixture between 500 and 3000 is less than 0.1 ppm, the transesterification reaction becomes difficult to proceed and problems such as deterioration of color tone due to the increase of the thermal history due to the increase of the residence time occur. Not desirable

In addition, when the viscosity average molecular weight of the reaction mixture is between 3000 and 10000, when the concentration of the nitrogen-containing basic compound in the reaction mixture exceeds 1 ppm, the aromatic carbonate during the transesterification reaction with the viscosity average molecular weight of 10000 or more is carried out. It is not preferable because deterioration of remarkably and adversely affects color tone deterioration. If the concentration of nitrogen-containing basic compound in the reaction mixture is less than 0.01 ppm, the transesterification reaction is less likely to proceed and the heat history is increased by the increase of residence time. This is not preferable because problems such as color tone deterioration occur.

In order to make the amount of nitrogen-containing basic compounds contained in the specific viscosity average molecular weight within a specific range, the increase and decrease of the nitrogen-containing basic compounds added to the mixture mainly containing aromatic dihydroxy compounds and diester carbonate are carried out. It can be achieved by increasing or decreasing the required amount of heat, increasing or decreasing the degree of vacuum in the system to facilitate the outflow of the by-product phenolic compound, increasing or decreasing the residence time, and can be achieved by combining one or two or more of them. In addition, the concentration in the reaction system of the nitrogen-containing basic compound in the reaction system can be maintained by supplying the nitrogen-containing basic compound in several portions as the polymerization proceeds.

The monohydroxy compound produced in the reaction of obtaining an aromatic polycarbonate by melt polymerization reaction using diester carbonate as a raw material is not contained in the usual monohydroxy compound, such as a catalyst or stabilizer added during polymerization. Impurities derived from additives are contained. The impurities include trimethylamine, anisole, olcrecresol, paracresol, 2-methylbenzofuran, hydroxyacetone, acetophenyl, organic compounds such as various metal salts, and the like. There are many parts that are not.

Among them, by-product monohydroxy compound is recycled and used as a catalyst addition solvent, and when the anisole contained in the monohydroxy compound is 1 ppm or more and 1000 ppm or less or trimethylamine is 1 ppm or more and 100 ppm or less, aromatic color is excellent. It has been found that it is effective for the production of polycarbonates.

The by-product monohydroxy compound is recycled and used as a catalyst addition solvent, and the anisole contained in this monohydroxy compound is 1 ppm or more and 1000 ppm or less, and trimethylamine is 1 ppm or more and 100 ppm or less, and is excellent in color It was found to be more preferred for the production of polycarbonates.

Although the mechanism is not known, deterioration tends to occur in the monohydroxy compound by adding anisole and / or trimethylamine in the monohydroxy compound used as the catalyst addition solvent, with the catalyst added to the monohydroxy compound. Is suppressed, the monohydroxy compound is stabilized, and the color of the aromatic polycarbonate obtained is estimated to be improved.

Moreover, when the anisole contained in the recycled monohydroxy compound used as a catalyst addition solvent exceeds 1000 ppm or trimethylamine exceeds 100 ppm, the color of the aromatic polycarbonate obtained falls and is unpreferable. The mechanism is not clear, but if anisole exceeding 1000 pm or trimethylamine exceeding 100 ppm is present in the catalyst addition solvent, polymerization inhibition or side reactions occur during the polymerization reaction and cause coloring of the aromatic polycarbonate. It is estimated to generate impurities. Alternatively, when the content in the recycled monohydroxy compound used as the catalyst addition solvent of anisole and trimethylamine was not more than 1 ppm of anisole and 1 ppm or less of trimethylamine, the effect was hardly confirmed.

In order to obtain a monohydroxy compound having anisole of 1 ppm or more and 1000 ppm or less and / or trimethylamine of 1 ppm or more and 1000 ppm or less, after recovering the monohydroxy compound produced by production of aromatic polycarbonate by melt condensation polymerization It may or may not be purified.

As a method for purifying a monohydroxy compound by-produced when producing an aromatic polycarboate by melt condensation polymerization, a commonly used method may be used, and a vacuum distillation method is preferable.

Specific examples of the monohydroxy compound include phenol, cresol, xylenone, chlorophenol, naphthyl alcohol and biphenyl alcohol, and phenol is preferably used.

In the monohydroxy compound to be used as the catalyst addition solvent, it is preferable that the impurities mentioned above other than anisole and trimethylamine are substantially contained substantially, and the concentration of oxygen causing oxidative deterioration is also preferably 100 ppm or less.

Nitrogen-containing compounds based on these various sources included in carbonic acid diesters are not single compounds with definite chemical structures. If the nitrogen-containing compound in an amount exceeding 5 ppm as a nitrogen atom is contained in the carbonic acid diester, the carbonic acid diester is gradually colored during storage or storage even if it has a good color tone (measured by molten hazen) immediately after manufacture. And a part is unsuitable as an aromatic polycarbonate raw material.

In other words, weather resistance of a plurality of carbonic acid diester samples (Hazen value: the sample is blocked in direct sunlight in the air indoors, stored in a cool dark place for a long time, based on the color number test method shown in JIS K-4101, flat pyrex color tube After holding in the molten state, the measurement is compared with the Hazen standard colorimetric liquid), and the sample has an extremely high Hazen value, such as a sample having a defective Hazen value of more than 20. . When the carbonic acid diester in which the sample with the hazen value exceeded 20 was used, the hue and transparency of the aromatic polycarbonate obtained become bad. In other words, the color tone of the aromatic polycarbonate produced using the raw material carbonic acid diester having a nitrogen content of more than 5 ppm is inferior to that of the aromatic polycarbonate obtained by the interfacial polymerization method.

That is, in order to obtain a color which is not inferior to the aromatic polycarbonate prepared by the melt polymerization method using the carbonic acid diester at least compared to the aromatic polycarbonate prepared by the interfacial polymerization method, the nitrogen content is suppressed to 5 ppm or less. Needs to be. Furthermore, it is preferable to keep nitrogen content to 4 ppm.

If a nitrogen-containing compound of more than 5 ppm is present in the carbonic acid diester, the compound itself may cause coloration of the carbonic acid diester, and may also interact with other impurities contained in the carbonic acid diester to cause the carbonic acid diester and When manufacturing a polymer, coloring of aromatic polycarbonate may occur.

In addition, when the aromatic polycarbonate is produced by melt polymerization using a carbonic acid diester having a large amount of metal elements, it is well known to those skilled in the art that coloring occurs in the aromatic polycarbonate.

There are many causes of such metal element incorporation. For example, when the material of the reaction apparatus which manufactured the carbonic acid diester melt | dissolved and mixed, or the catalyst at the time of manufacturing a carbonic acid diester, etc. are mentioned.

The present inventors have found that the coloring of the diester carbonate and the aromatic polycarbonate and the deterioration in transparency are particularly severe when the metal element component and the nitrogen-containing compound coexist in the carbonate diester. Examples of the metal element causing such deterioration include iron, tin, chromium, titanium, and copper, which are particularly adversely affected.

When these metal elements and impurity nitrogen-containing compounds of 5 ppm or more are present, the interaction between the metal elements and nitrogen-containing compounds occurs and the degree of coloration and in particular the magnitude of the color deviation is remarkable. When the metal element is present in excess of 1 ppm, it becomes difficult to become a commodity in the aromatic polycarbonate obtained by causing the coloring and in particular the deviation of the coloring to be more remarkable.

Each of these metal elements needs to be suppressed to 0.5 ppm or less, more preferably 0.3 ppm or less, still more preferably 0.1 ppm or less.

Furthermore, it is preferable to suppress the total amount of iron, tin, chromium, titanium and copper to 0.5 ppm or less, more preferably 0.3 ppm or less, even more preferably 0.1 ppm or less with respect to the metal element.

It is also preferable to suppress the total amount of all metals to 0.5 ppm or less, more preferably 0.3 ppm or less, even more preferably 0.1 ppm or less with respect to the metal element.

In addition to these metal elements, salicylic acid derivatives in carbonic acid diesters also cause coloration and color deviation. Salicylic acid derivatives cause coloration and coloration deviations, and are particularly badly affected when coexisting with nitrogen compounds and metal element components. Specific examples of these salicylic acid derivatives include salicylic acid, methyl salicylate and phenyl salicylate.

Although the salicylic acid derivative is rarely detected in a significant amount (for example, 1 ppm) in ordinary carbonic acid diesters, for example, even when a trace amount is present, when the nitrogen compound coexists, and when the metal elements coexist, the quality of the carbonic acid diester It is more adverse.

In order to suppress such an adverse effect, it is necessary to suppress content of the salicylic acid derivative to 10 ppm or less. More preferably, it is 5 ppm or less.

The raw material carbonic acid diester may be a carbonic acid diester obtained by a conventionally known method, and is not particularly limited by the production method.

The purification for obtaining the carbonic acid diester which suppressed the impurity content of this invention below a specific value is difficult to implement | achieve the said quality only by combining conventionally well-known purification methods.

As a preferred method for the purification of carbonic acid diesters, for example, the raw material carbonic acid diester is dissolved in a nonpolar solvent, 1) hydrotalcite treatment to separate the carbonic acid diester crystals, and then the solvent is changed to a polar solvent. A) strong base ion exchange resin treatment, 3) strong acid ion exchange resin treatment, 4) activated carbon treatment, and 5) distillation under reduced pressure and / or recrystallization. The carbonic acid diester which suppressed impurity content below a specific value by this purification method can be obtained.

The points of this purification method are to treat hydrotalcite in a nonpolar solvent, to treat with two kinds of ion exchange resins in a polar solvent, and to perform activated carbon treatment.

Hydrotalcite is a mineral name including natural and synthetic, and is a mineral represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. The crystal structure has a structure in which a part of Mg of Mg (OH) ₂ is substituted by Al, and as an intermediate layer, a layer charged negatively to neutralize its positive charge and to maintain electrical neutrality (CO ₃ · 4H _2). It is a layered compound which has O).

Natural hydrotalcite is a slightly different hydrotalcite-type compound released by Kyogawa Chemical Co., Ltd. under the name of DHT-4A (Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ ㆍ 3H ₂ O). Since it has the same function, a natural hydrotalcite and the synthesized hydrotalcite-type compound are collectively called hydrotalcite below.

Treatment of the carbonic acid diester raw material by hydrotalcite also includes a batch method, a continuous method, or a combination thereof, so that the conventionally known solid-liquid contact reaction type can be preferably used. Moreover, the contact treatment of the carbonate diester by the following ion exchange resin can also be preferably performed by the same method.

Examples of nonpolar solvents include hydrocarbons such as aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methylnaphthalene, tetralin and chlorbenzene, and aliphatic hydrocarbons such as heptane, octane and cyclohexane. Especially, the low boiling point aromatic hydrocarbon of below 200 degreeC, such as benzene, toluene, and xylene, is preferable.

As a polar solvent, Alcohol; Monohydric alcohols such as methyl alcohol, ethyl alcohol, i-propyl alcohol, n-butyl alcohol, polyhydric alcohols such as ethylene glycol, 1,4-butanediol and glycerin, or ketones and ethers; For example, other esters, such as acetone, methyl ethyl ketone, acetophenone, dibutyl ether, diphenyl acetate, etc .; For example, acetonitrile, nitromethane, etc., such as ethyl acetate and butyl acetate, are also mentioned as a preferable thing.

In this invention, it is preferable to use what consists of stainless alloys containing a specific amount of niobium and / or vanadium as an apparatus used for polymer manufacture. More specifically, the content of these niobium and / or vanadium in the stainless steel is preferably 10 to 1000 ppm, more preferably 20 to 500 ppm. More specifically, the total content of niobium and / or vanadium contained in stainless steel within 1 mm from the surface is preferably 10 ppm to 1000 ppm, more preferably 20 to 500 ppm. If the content of niobium and / or vanadium is more than 1000 ppm, the color of the polymer is adversely affected, and if it is less than 10 ppm, the effect of suppressing the generation of foreign matters is difficult to be obtained.

The part using these specific materials in the reaction apparatus is not particularly limited as long as it is a part constituting the reaction apparatus. Preferably, it is effective to use in the reaction vessel, and is produced by polycondensation from the monomer to the polymer or by the transesterification. It is preferred to use those of these specific materials in areas where the byproducts, such as phenol, directly touch. In a distillation column, it is preferable to use the thing of these specific materials for the lower part and the piping part through which a polymer (oligomer) flows.

The amount of niobium and / or vanadium present in the stainless alloy can be measured by surface evaluation methods such as elemental analysis of metals, fluorescence X-ray analysis, and the like.

The stainless steel alloy containing these niobium and / or vanadium is not particularly limited as long as it is a stainless steel containing niobium and / or vanadium in an alloy steel containing iron as a main component and nickel or chromium contained therein. Austenitic stainless steels, also called 8 stainless steels, are preferred. As this specific example, SUS302, SUS304, SUS304L, SUS309S, SUS310S, SUS316, SUS316L, SUS317, SUS321, SUS347 etc. are mentioned, for example. Among them, SUS304 or SUS316 is preferable. When niobium and vanadium are included in these, a predetermined metal can be added to molten steel, or it can be added by methods, such as ion etching and vapor deposition.

Although the foreign substance herein is not accurate about the cause of the occurrence or the formation process, the black foreign substance carbonized with the polycondensate from the monomer to the polymer, the by-product produced by the reaction, or the gel foreign material highly crosslinked with the polymer is used. Say. The size is about 10 micrometers or more in diameter, and can be observed by an enlarger, such as a microscope. In the case of black foreign matter, the main element constituting it is often carbon, and is often generated at the top of the transesterification vessel. It is assumed that this is a byproduct such as phenol produced by the reaction, a scattered polymer, an oligomer, and a monomer that is thermally decomposed into foreign matter. In addition, in the case of a gel foreign material, it does not melt | dissolve in dichloromethane, and it means what appears to emit light white-yellow-brown depending on a state under irradiation of an ultraviolet lamp. These foreign substances can be investigated by dissolving the obtained polymer in an organic solvent such as a dichloromethane solvent and then filtering the same with a filtration membrane such as a Millipore filter.

As described above, it was found that by using stainless steel containing niobium and / or vanadium in the reaction vessel for producing aromatic polycarbonate, it was effective for reducing foreign matters in the produced aromatic polycarbonate. This is considered to be because the activity of the transesterification catalyst is stabilized.

As for the problems related to the material of the device, the inventors have made intensive efforts to solve the above problems, and as a result, by forming a specific oxide film on the inner surface of some or all of the reaction apparatus used to manufacture, The discovery of the ability to produce aromatic polycarbonates has led to the completion of the present invention. The content is demonstrated below.

The apparatus used for producing an aromatic polycarbonate in the present invention refers to all of reactors used for the entire process of producing aromatic polycarbonate, piping connected thereto, and the like, and the shape, size, and type thereof are not particularly limited.

Inner or outer wall of part or all of the reaction apparatus used for producing aromatic polycarbonate, preferably raw materials, intermediates for polymerization, polymer after completion of polymerization, by-products produced by the reaction, catalysts or stabilizers added during the process, and the like. The part in contact with the additive has a specific oxide film formed later.

As a specific example of the preferable part in which a specific oxide film is formed, the polymerization container at the time of superposition | polymerization by a transesterification method, the piping conveying a molten polymer, a twin screw extruder, a polymer filter, its jacket, etc. are mentioned.

There is no restriction | limiting in particular in the metal material used for these apparatus, Although what kind of material may be used, it is preferable to use the low cost and excellent workability, such as stainless steel. Stainless steel here is an alloy containing iron, nickel, and chromium as a main component, and among these, an austenitic stainless steel also called 18-8 stainless steel is preferably used.

As this specific example, SUS302, SUS304, SUS304L, SUS309, SUS309S, SUS310, SUS310S, SUS316, SUS316L, SUS317, SUS321, SUS347, etc. are mentioned. Among them, SUS304 and SUS316 are preferably used in view of being easy to obtain and excellent in workability. Moreover, even if it uses hard stainless steel, such as Hastelloy, there is no restriction | limiting in particular in the scope of this invention.

The present invention is characterized in that a specific oxide film is formed on part or all of the inner surface of the apparatus formed of these materials. The specific oxide film as used herein means that the iron oxide as a main component has a thickness of at least 10 nm or more, preferably 20 nm or more.

In the present invention, by forming an oxide film containing iron oxide and chromium oxide as a main component at least 10 nm or more, preferably 20 nm or more, foreign matters represented by micro foreign matters can be reduced more effectively. These oxide films can be measured by Auger electron spectroscopy on the metal surface.

Iron oxide and chromium oxide as the main components of the oxide film means that 50% by weight or more of iron oxide and chromium oxide are present in the total oxide film, and the ratio is preferably 60% by weight or more. Examples of the component which may be included as components other than iron oxide and chromium oxide with respect to the oxide film include nickel, silicon and carbon, and the ratio thereof is not particularly limited but is preferably 30% by weight or less.

Any known method can be used as the method for forming the oxide film surface. Specific examples of the material mainly containing iron include a method of heat treatment and a method of contacting with various chemicals, but are not limited to these methods. When using stainless steel, the method of forming an oxide film by baking is preferable, As temperature, 300 degreeC or more is preferable, More preferably, 320 degreeC or more is good.

The firing time is not particularly limited as long as the oxide film of iron oxide described in the present invention is 10 nm or more, preferably 20 nm or more. The concentration of oxygen, nitrogen or water vapor during firing is not particularly limited as long as the desired oxide film can be obtained. Examples of the chemicals include various acids and liquids containing the same, such as chemicals containing an oxidizing agent such as aqueous nitric acid solution and hexavalent chromium.

In the present invention, it is preferable that the oxide film is formed on the entire inner surface of the apparatus, but in view of suppressing the cost of pretreatment of the apparatus and efficiently obtaining a high-quality aromatic polycarbonate, the reaction mixture or reaction mixture such as oligomers or polymers can be used. It is preferable to use the apparatus in which the said film was formed in the part which contacts with the by-product produced | generated by (eg phenol produced at the time of superposition | polymerization by transesterification). Furthermore, it is more preferable to use the apparatus in which the said film was formed in the part which contact | connects the polymer which became more polymerizable.

The foreign material represented by the micro foreign matter in the aromatic polycarbonate referred to herein refers to the foreign matter represented by the micro foreign matter which occurs during the polymer production, not the garbage or dust that invades from the outside, and is disclosed in the present invention. It is effective to reduce this by using a specific device. There are various kinds of foreign matters generated during these processes. In particular, the apparatus is effective in reducing microgel foreign matters.

The microgel foreign matter referred to herein is not dissolved in dichloromethane and remains on the filter when the solution of the aromatic polycarbonate is filtered by a filter, and when viewed with a magnifying glass or the like, it appears to be translucent to transparent and has a central spectrum at 340 nm. When it emits ultraviolet light, it means to emit light. More specifically, when the microgel foreign material is measured by a micro-infrared spectrometer or the like, a spectrum similar to that of an aromatic polycarbonate is obtained. When the aromatic polycarbonate is in a molten state, a branch structure is formed by any chemical structural change, and a gel is formed. I think that.

Although the size of the microgel foreign material seen in a polymer varies widely, the thing about 100-100 micrometers in diameter is seen a lot. It is difficult to determine whether anything smaller than this is a gel.

The branching structure is not completely elucidated, and it is thought that several reactions are entangled in pluralities. Specifically, it is known to form a structure similar to the branched structure described in, for example, the Journal of Applied Polymer Science, volume 52, 1549-1558, 1994 by Rufes.

And in the manufacturing method disclosed by this invention, you may seal the hydroxyl group terminal of a polymer, for example using the terminal blocker of Unexamined-Japanese-Patent No. 10-36497 by the applicant's application.

In the present invention, the hydroxyl group terminal of the aromatic polycarbonate before adding the end capping agent is 75 to 35 mol%, preferably 70 to 40 mol%, more preferably 60 to 40 mol% from the viewpoint of the reaction rate with respect to the entire terminal. It is preferable to control with. In this way, the terminal hydroxyl group can be finally controlled at a low ratio, thereby improving the polymer modification effect.

Here, the number-of-moles of terminal hydroxyl groups in a fixed amount of a polymer can be determined, for example by 1H-NMR. Moreover, the ratio of the hydroxyl group terminal of a polymer can also be controlled by the feed ratio of the aromatic diol and diester carbonate which are raw materials.

As described above, when producing an aromatic polycarbonate using bisphenol A (also referred to herein as "BPA") as an aromatic diol compound and diphenyl carbonate (also referred to as "DPC" herein) as a carbonic acid diester. The reaction scheme for producing an aromatic polycarbonate is;

PhOH (phenol), which is represented by the formula above, is removed out of the system by an operation such as reduced pressure,

An aromatic polycarbonate represented by is produced, but one end of the aromatic polycarbonate molecule represented by the above formula has an aromatic hydroxyl group. It is known that it is not preferable about the short-term and long-term stability of the aromatic polycarbonate which an aromatic hydroxyl terminal produces | generates. For example, JP-A-61-87724 and JP-A-61-87725 (GE) include polymer stability, that is, aging test; It is reported that the fall value of the intrinsic viscosity after 15 hrs at 250 degreeC temperature can be reduced. However, the aromatic hydroxyl group present at one end of the molecule is an essential active point in the preparation of the melt polymerization aromatic polycarbonate, as shown in the above formula.

The inventors of the present invention have developed a method of maintaining the required number of hydroxyl groups necessary for producing an aromatic polycarbonate, and reducing the terminal hydroxyl group of the aromatic polycarbonate to a desired value after the polymerization degree (intrinsic viscosity) of the aromatic polycarbonate reaches a desired value. .

That is, for example, after the intrinsic viscosity of the aromatic polycarbonate reaches at least 0.3 dl / g,

(Wherein R ¹ is a chlorine atom, a methoxycarbonyl group or an ethoxycarbonyl group, and R ² is an alkyl group of 1 to 30 carbon atoms, an alkoxy group of 1 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms or 6 to 30 carbon atoms). Aryloxy group)

The terminal blocked aromatic polycarbonate can be obtained by adding the compound shown by these.

The compound represented by Chemical Formula 2 used in the present invention includes carbonate and carboxylic acid ester by the definition of R ² .

In formula (2), R ¹ is a chlorine atom, a methoxycarbonyl group (CH ₃ OCO-) or an ethoxycarbonyl group (C ₂ H ₅ OCO-), of which a chlorine atom and a methoxycarbonyl group are preferable, and a methoxycarbonyl group is particularly desirable.

Moreover, R <^2> is a C1-C30 alkyl group, a C1-C30 alkoxy group, a C6-C30 aryl group, or a C6-C30 aryloxy group, Even if a C1-C30 alkyl group is linear, it is branched. It may be also cyclic and may have an unsaturated group. As such an alkyl group, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-dodecanyl group, n- Linear alkyl groups such as lauryl group, n-palmityl group and stearyl group; Branched alkyl groups such as isopropyl group, t-butyl group and 4-butylnonyl group; Alkyl group which has unsaturated groups, such as an aryl group, butenyl group, pentenyl group, hexenyl group, dodecenyl group, and oleyl group, ie, alkenyl group; Cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Among these, in view of improving the releasability of the polymer, a long-chain alkyl group, specifically, a lauryl group, a stearyl group, and a dodecenyl group is particularly preferable.

In addition, the alkoxyl group having 1 to 30 carbon atoms may be linear, branched or cyclic, or may have an unsaturated group. As such an alkoxyl group, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-octo group, n-nonyloxy group, n-deca Linear alkoxyl groups such as a silyloxy group, n-lauryloxy group, n-palmityloxy group and stearyloxy group; branched alkoxyl groups such as iso-propyl group, t-butyloxy group, and 4-butylnonyloxy group; An alkoxy group having an unsaturated group such as an allyloxy group, butenyloxy group, pentenyloxy group, hexenyloxy group, dodecenyloxy group and oleyloxy group; Cycloalkyloxy groups, such as a cyclopentyloxy group and a heclohexyloxy group, etc. are mentioned. Among these, in view of improving the releasability of the polymer, a long-chain alkyl group such as a lauryloxy group, a stearyloxy group, and a dodecenyloxy group is particularly preferable.

As mentioned above, a C1-C30 alkyl group and a C1-C30 alkoxyl group are methoxycarbonyl, ethoxycarbonyl, (O-methoxycarbonylphenyl) oxycarbonyl

Or (O-ethoxycarbonylphenyl) oxycarbonyl

May be substituted.

As a C6-C30 aryl group, phenyl, naphthyl, biphenyl, anthranyl, etc. are mentioned, for example.

Moreover, as a C6-C30 aryloxy group, phenoxy, naphthoxy, biphenyloxy, anthranyloxy etc. are mentioned, for example.

These aryl groups having 6 to 30 carbon atoms and aryloxy groups having 6 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl, (O-methoxycarbonylphenyl) oxycarbonyl, and (O-ethoxycarbonylphenyl) It may be substituted by oxycarbonyl, C1-C30 alkyl, or C1-C30 alkoxyl. Examples of alkyl having 1 to 30 carbon atoms and alkoxyl having 1 to 30 carbon atoms include the same groups as those exemplified above.

Compound represented by the formula (2), based on the definition of R ² , for the convenience, formula (2a)

(Wherein R ¹ is a chlorine atom, a methoxycarbonyl group or an ethoxycarbonyl group, and R ²¹ is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and an alkyl group having 1 to 30 carbon atoms is methoxycarbonyl , Ethoxycarbonyl, (O-methoxycarbonylphenyl) oxycarbonyl or (O-ethoxycarbonylphenyl) oxycarbonyl may be substituted, and the aryl group having 6 to 30 carbon atoms is methoxycarbonyl, Ethoxycarbonyl, (O-methoxycarbonylphenyl) oxycarbonyl, (O-ethoxycarbonylphenyl) oxycarbonyl, alkyl having 1 to 30 carbon atoms, alkoxyl having 1 to 30 carbon atoms may be substituted)

A carbonate compound represented by the formula and the formula

(Wherein R ¹ is a chlorine atom, a methoxycarbonyl group or an ethoxycarbonyl group, and R ²² is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms and 1 to 30 carbon atoms). The alkoxyl group may be substituted with methoxycarbonyl, ethoxycarbonyl, (O-methoxycarbonylphenyl) oxycarbonyl or (O-ethoxycarbonylphenyl) oxycarbonyl, and further having 6 to 30 carbon atoms. The aryl group and the aryloxy group having 6 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl, (O-methoxycarbonylphenyl) oxycarbonyl, (O-ethoxycarbonylphenyl) oxycarbonyl and 1 carbon atom. It may be substituted by alkyl of -30 and an alkoxyl group having 1 to 30 carbon atoms.)

It can be classified into carboxylic acid aryl ester represented by.

Especially as a compound represented by the said Formula (2), 2-methoxycarbonylphenyl benzoate, 4-cumylbenzoic acid- (2'-methoxycarbonylphenyl) ester, 2-ethoxycarbonylphenyl benzoate, 4- (O -Methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester is preferred.

In the method of the present invention, the compound represented by Formula 2 is added to an aromatic polycarbonate,

The aromatic polycarbonate terminal is blocked by reacting with the terminal OH (˜OH) of the aromatic polycarbonate so as to appear. In order to carry out end block | block quickly and in high yield, it is preferable to carry out distilling off the produced | generated 2-substituted phenol.

The compound represented by the formula (2) is melt-condensed with an aromatic diol and diphenyl carbonate, and is added after the intrinsic viscosity of the aromatic polycarbonate reaches at least 0.3 dl / g. After addition, since the terminal blockade of an aromatic polycarbonate advances rapidly, the change of the intrinsic viscosity of an aromatic polycarbonate exists in the range of 0.1 dl / g, and a terminal hydroxyl group concentration can be suppressed to low level as 0-30 mol%. .

The compound represented by the said Formula (2) is used in the ratio of 1 equivalent of terminal hydroxyl groups of aromatic polycarbonate, Preferably it is 0.5-2 mol, More preferably, it is 0.7-1.5 mol, Especially preferably, it is 0.8-1.2 mol.

It is preferable that the terminal hydroxyl group concentration in the polymer is measured and checked each time prior to addition. When performing polycondensation continuously under the same polycondensation conditions, the hydroxyl concentration obtained at the time of preceding polycondensation may be used as it is for convenience.

In order to perform the end-sealing reaction, a catalyst is required, and the catalyst used for the polycondensation reaction can be preferably used as it is.

In particular, when the aromatic polycarbonate polycondensation is completed, it is preferable to carry out the end-sealing reaction when the polymer is still in the molten state. Therefore, the end-sealing reaction should not occur before the addition of the sulfonic acid compound than the end of the polycondensation. If the above-mentioned time point, the end-sealing reaction can be preferably carried out.

After the aromatic polycarbonate polycondensation, even after the sulfone compound is added, it is possible to end-seal in the same manner if a catalyst used in the end-sealing reaction is newly added to the aromatic polycarbonate.

In the present invention, the amount of free chlorine which is not covalently bound to the polymer contained in the aromatic polycarbonate (prepolymer) before blocking the terminal is low, preferably 50 ppm or less, more preferably 5 ppm or less. It is advantageous to.

If the amount of free chlorine is greater than this, the catalytic activity associated with the terminal blocking reaction tends to be lowered and the terminal blocking is difficult to be achieved quickly and sufficiently, which is not preferable.

In addition, a large amount of chlorine is not preferable because it adversely affects the color and stability of the obtained polymer. Reducing the amount of chlorine contained in the polymer to a low level can be achieved by suppressing the amount of chlorine contained in the raw material to a low level.

Moreover, in this invention, it is advantageous to suppress the quantity of iron contained in the aromatic polycarbonate before blocking the terminal to 1 ppm or less, more preferably 0.7 ppm or less.

If the amount of iron is larger than 1 ppm, the activity of the catalyst involved in the end-reforming reaction tends to be lowered, and end blocking is difficult to be achieved quickly and sufficiently, which is not preferable. In addition, a large amount of iron is not preferable because it adversely affects the color and stability of the obtained polymer.

Inhibiting the amount of iron contained in the prepolymer at a low level can be achieved by suppressing the amount of iron contained in the raw material at a low level and preventing the incorporation of iron throughout the manufacturing process.

After addition of an end blocking agent, pressure reduction conditions are preferable at least in order to remove the phenols produced | generated by reaction. Specifically, it is 50 Torr or less, More preferably, it is 10 Torr or less. Usually, it is preferable to carry out in the range of 0.01-100 Torr.

The reaction temperature after the terminal blocker is added is usually in the range of 250 to 360 ° C, preferably 260 to 340 ° C. The polymer is not melted at a temperature lower than this range, and the polymer is decomposed and colored at a temperature higher than this range. Not desirable The reaction time is usually 1 to 30 minutes, preferably 1 to 20 minutes, and may be 1 to 15 minutes if desired.

In the present invention, residual phenols contained in the polymer after the end blocking can be suppressed to a low level.

The concentration of the remaining phenols in the polymer after the terminal blocking reaction is 300 ppm or less, more preferably 200 ppm or less. If there are more residual phenols than this concentration, the fall of molecular weight and coloring will occur easily, and are unpreferable.

As long as the endblocking agent has reached the intrinsic viscosity of 0.3, the amount may be added in a predetermined amount or divided into several times. In other words, the terminal blocker is preferably added after the intrinsic viscosity of the polymer reaches at least 0.3 dl / g.

Furthermore, according to the research of the present inventors, certain compounds containing a specific compound in the compound represented by the above formula (2) can advantageously end-block two molecules of the aromatic polycarbonate with one molecule, and as a result, the aromatic polycarbonate It became clear that the action of remarkably improving the degree of polymerization of the polymer, i.e., the polymerization promotion action, was obtained.

Therefore, according to the present invention, secondly, in the method for producing an aromatic polycarbonate by melt condensation polymerization of an aromatic diol compound and diphenyl carbonate, after the intrinsic viscosity of the aromatic polycarbonate reaches at least 0.3 dl / g, Formula 7

Wherein R ¹ , R ' ¹ is a chlorine atom, methoxycarbonyl or ethoxycarbonyl, and X is an oxygen atom or

-R "-COO-

[Where R "is an alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 30 carbon atoms]

Is represented by)

The method for producing an aromatic polycarbonate exhibiting a high intrinsic viscosity is provided in the same way, by adding a compound represented by to generate an aromatic polycarbonate exhibiting an intrinsic viscosity of more than 0.1 higher than the intrinsic viscosity at the time of addition.

The polymerization promoter represented by the formula (7) is added to an aromatic polycarbonate having an intrinsic viscosity of at least 0.3 dl / g, and is an aromatic poly with an intrinsic viscosity greater than 0.1 dl / g than the intrinsic viscosity of the aromatic polycarbonate at the time of addition. Give carbonate.

The polymerization accelerator represented by the formula (7) is preferably about 0.3 to about 0.7 moles, more preferably about 0.4 to about 0.6 moles, particularly preferably about 0.45 to about 0.55 moles per one equivalent of the terminal hydroxyl group at the time of addition. Is added in proportion.

The polymerization promoter is added to the aromatic polycarbonate, and the following reaction formula

As indicated by, the two molecules of the aromatic polycarbonate are coupled by reacting with the terminal OH (-OH) of the aromatic polycarbonate.

Since the reaction produces two molecules of 2-substituted phenols as shown in the above reaction scheme, it is preferable to carry out distillation of the produced 2-substituted phenols in order to carry out the coupling quickly and in high yield.

At the end of the coupling, an aromatic polycarbonate is produced that preferably has an intrinsic viscosity of more than 0.4 and less than 1.0 dl / g, more preferably of 0.41 to 0.8 dl / g.

A catalyst deactivator may be added to the aromatic polycarbonate obtained in the present invention.

As the catalyst deactivator used in the present invention, a known catalyst deactivator is effectively used. Among these, sulfonic acid compounds such as salts of eutectic acid such as ammonium salt of sulfonic acid, eutectic acid ester, euphonic acid anhydride, and euphonic acid betaine; And phosphonium salts are preferable, and more specifically, the following Chemical Formulas 3 to 6

A ^1- (Y ¹ -SO ₃ X ¹ ) m

[Wherein A ¹ is an m-valent hydrocarbon group which may have a substituent, Y ¹ is a single bond or an oxygen atom, X ¹ is a secondary or tertiary monovalent hydrocarbon group, one equivalent of a metal cation or an ammonium cation Or a sulfonium cation, m is an integer of 1-4. Provided that when Y ¹ is a single bond, the total of m X ¹ 's is not one equivalent of metal cation].

⁺ X ² -A ² -Y ¹ -SO ₃

[Herein, A ² is a divalent hydrocarbon group, ⁺ X ² is a 2-4 quaternary ammonium cation or a 2-4 quaternary phosphonium cation, and the definition of Y ¹ is the same as that of Chemical Formula 3].

^{A 3 - (+ X 3)} n · (RY 1 -SO 3 -) n

[Wherein A ³ is an n-valent hydrocarbon group, ⁺ X ³ is a 2-4 quaternary ammonium cation or a 2-4 quaternary sulfonium cation, R is a monovalent hydrocarbon group and n is an integer of 2-4 And the definition of Y ¹ is the same as that of Chemical Formula 3].

A ⁵ -Ad ¹ -A ^4- (Ad ² -A ⁵ ) _k

[Wherein A ⁵ is a monovalent or divalent hydrocarbon group, A ⁴ is a divalent hydrocarbon group, and Ad ¹ and Ad ² are the same or differently —SO ₂ —O—SO ₂ —, —SO ₂ —O— Is an acid anhydride group selected from CO- or -CO-O-SO _2- , and k is 0 or 1; However, when k is 0,-(Ad ² -A ⁵ ) _k represents a hydrogen atom or a bonding method for bonding A ⁴ and A ⁵ (in this case, A ⁵ is a divalent hydrocarbon group or a single bond to be).]

What is represented by at least 1 sort (s) of sulfonic acid phosphonium compound chosen from the group which consists of a compound represented by these is used preferably. More preferably, the salts of dodecylbenzenesulfonic acid such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt and the above salts of paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluene sulfonic acid are preferable. As esters of sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, benzene sulfonate, benzene sulfonate octyl, benzene sulfonate methyl, paratoluene sulfonate methyl, paratoluene sulfonate butyl, paratoluene sulfonate octyl, paratoluene sulfonate phenyl, etc. In particular, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

When these catalyst deactivators are added to the polymer, the catalyst can be quickly deactivated and the desired stabilized polymer can be obtained. These catalyst deactivators are used alone or by using a phosphite ester compound or a phenolic antioxidant in combination to obtain an aromatic polycarbonate having a more stable value. Among the catalyst deactivators of the above formulas (3) to (6), the phosphonium salt or ammonium salt type catalyst deactivator is stable and preferable even at 200 ° C or higher.

In the present invention, at least one catalyst deactivator selected from the group consisting of the compounds represented by the above formulas (3) to (6) is produced after the end polycloning after the end of the aromatic polycarbonate melt condensation polymerization or after the reaction described below. It is preferably used in a ratio of 1 * 10 ^-6 to 0.1 parts by weight, preferably 1 * 10 ^-6 to 0.05 parts by weight, more preferably 1 * 10 ^-6 to 0.03 parts by weight, based on 100 parts by weight of the aromatic polycarbonate. . Moreover, it is preferable to use such a catalyst deactivator in the ratio of 0.5-50 mol per mol of transesterification catalysts in the ratio with respect to an alkali metal transesterification catalyst.

The organophosphonium salt and organoammonium salt of sulfonic acid described in JP-A-8-59975 are also preferably used.

The amount of these catalyst deactivators is 0.5-50 moles per mole of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds, preferably 0.5-10 moles, more preferably 0.8-5. It can be used in the ratio of moles.

These catalyst deactivators are dissolved or dispersed directly or in a suitable solvent and added and kneaded to the aromatic polycarbonate in a molten state. Although there is no restriction | limiting in particular in the equipment used for performing such an operation, For example, a biaxial luther etc. are preferable, and when a catalyst deactivator is melt | dissolved or disperse | distributed in a solvent, the biaxial luther with a vent is especially preferable. Used.

The aromatic polycarbonate may be once pelletized and then remelted and added. This makes it possible to stabilize the produced aromatic polycarbonate using a transesterification catalyst, thereby effectively preventing the dirt of the mold during injection molding.

Moreover, in this invention, various additives can be added to aromatic polycarbonate in the range which does not impair the objective of this invention. This additive is preferably added to the aromatic polycarbonate in the molten state in the same manner as the catalyst deactivator. Examples of such additives include processing stabilizers, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, metal inactivators, and metals. Soaps, nucleating agents, antistatic agents, lubricants, flame retardants, mold release agents, mold inhibitors, colorants, antifogging agents, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers, epoxy compounds, colorants, slip agents, antiblocking agents, etc. Can be mentioned.

Among these, heat stabilizers, ultraviolet absorbers, mold release agents, colorants and the like are particularly generally used, and these may be used in combination of two or more kinds.

As a heat resistant stabilizer used for this invention, a phosphorus compound, a phenol type stabilizer, an organic thioether type stabilizer, a hindered amine type stabilizer, etc. are mentioned, for example.

As a preferable phosphorus compound, phosphate ester and / or phosphite ester derivative are used.

Specific examples of these stabilizers include bis (2,4-di-t-butylphenyl) pentaerythryldiphosphite, bis (2,6-t-butyl-4-methylphenyl) pentaerythryldiphosphite and bis (nonylphenyl Arylalkyl phosphites such as pentaerythritol diphosphite, diphenyldecyl phosphite, diphenylisooctyl phosphite, phenyl diisooctyl phosphite and 2-ethylhexyl diphenyl phosphite, trimethyl phosphite and triethyl phosphate Trialkyl phosphites, such as tributyl phosphite, triphenyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, and distearyl pentaerythyl di phosphite, triphenyl phosphite, tri Triaryl phosphates such as credil phosphite, tris (ethylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite Yates, and bis (2,4-di-t-butylphenyl) pentaerythritol phosphate, pentaerythryl (2,4-di-t-butylphenyl) phosphate (2,4-di-t-butylphenyl) Aryl such as phosphite, bis (nonylphenyl) pentaerythryldiphosphate, pentaerythrityl (nonylphenyl) phosphate, diphenyldecylphosphate, diphenylisooctylphosphate, phenyldiisooctylphosphate and 2-ethylhexyldiphenylphosphate Alkyl phosphates, distearyl pentaerythyl diphosphate, pentaerythyl stearyl phosphate stearyl phosphite, bis (tridecyl) pentaerythrityl diphosphate, pentaerythrityl tridecyl phosphate tridecyl phosphate, tris (2 Trialkyl phosphates such as -chloroethyl) phosphate and tris (2,3-dichloropropyl) phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate and trimethoctyl phosphate Trialkyl phosphates such as trinonyl phosphate, tridecyl phosphate and trioctadecyl phosphate, triphenyl phosphate, tricredil phosphate, tris (ethylphenyl) phosphate and tris (2,4-di-t-butylphenyl) phosphate Although triaryl phosphates, such as a tris (nonylphenyl) phosphate and a tris (hydroxyphenyl) phosphate, can be illustrated, It is not limited to these.

These stabilizers may be used alone or in combination, or may be added to any step of the polymerization to pelletize process.

Moreover, as a ultraviolet absorber, a general ultraviolet absorber is used, For example, a salicylic acid type ultraviolet absorber, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, etc. are mentioned.

As the mold release agent, generally known mold release agents can be used, and for example, hydrocarbon type release agents such as paraffins, fatty acid type release agents such as stearic acid, fatty acid amide release agents such as stearic acid amide, alcohols such as stearyl alcohol and pentaerythritol Fatty acid ester type release agents, such as a type | system | group release agent and glycerin monostearate, and silicone type release agents, such as silicone oil, etc. are mentioned.

As the colorant, organic or inorganic pigments and dyes can be used.

Although there is no restriction | limiting in particular in the addition method of these additives, For example, you may add directly to aromatic polycarbonate, and you may prepare and add a master pellet.

As the processing stabilizer, for example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy- 3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate etc. are mentioned.

Moreover, as phosphorus antioxidant and sulfur type antioxidant, For example, tris (nonylphenyl) phosphite, tris (2, 4-di-t- butylphenyl) phosphite, bis (2, 4- di-t-butyl) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphite, 2,2'-ethylidenebis (4 , 6-di-t-butylphenyl) fluorophosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) octylphosphite, dilauryl-3,3'-thiodipropio Nate, distearyl-3, 3'- thiodipropionate, tetrakis (3-laurylthio propionyloxymethyl) methane, etc. are mentioned.

As a light stabilizer, it is 2- (3-t- butyl- 2-hydroxy-5-methylphenyl) -5-chloro phenzotriazole, 2- (3, 5- di-t- butyl- 2-hydroxy, for example. Phenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, 2- (3,5-di- Pentyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidemethyl) phenyl] benzotriazole, 2- [2-hydroxy Benzotriazole compounds such as oxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazole,

Benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone and 2-hydroxy-4-methoxybenzophenone, 2,4-di-t-butylphenyl, 3,5-di-t-butyl UV absorbers, such as hydroxy benzophenone type compounds, such as the 4-hydroxy benzoate, and cyanoacrylate type compounds, such as ethyl-2-cyano-3,3- diphenyl acrylate, and nickel dibutyl dithio cover And nickel-based quenchers such as mate and [2,2'-thiobis (4-t-octylphenolite)]-2-ethylhexylamine nickel.

As the metal inactivating agent, for example, N, N '-[3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, and the like, and as metal soaps, for example, calcium stearate And nickel stearate.

As the nucleating agent, for example, sorbitols such as sodium di (4-t-butylphenyl) phosphonate, dibenzylidene sorbitol, methylenebis (2,4-di-t-butylphenol) acid phosphate sodium salt, Phosphate compounds and the like.

As an antistatic agent, quaternary ammonium salt type | system | group compounds, such as ((beta)-lauramidpropyl) trimethylammonium methyl sulphate, and alkyl phosphate type compounds are mentioned, for example.

Examples of the lubricant include elcasanamide, stearic acid monoglyceride, and the like, and a flame retardant includes, for example, halogen-containing phosphate esters such as tris (2-chloroethyl) phosphate, hexabromocyclododecane, and decabromophenyl oxide. And metal inorganic compounds such as halides such as halides, antimony trioxide, antimony pentoxide, and aluminum hydroxide, and mixtures thereof.

There is no restriction | limiting in particular about the specific method of the kind, quantity, addition time, addition method, etc. of these agents, It is preferable to use the material of the apparatus which performs these operations also what is disclosed by this invention.

Example

Below, the Example of this invention is shown. In addition, this embodiment is for illustrating the present invention, the present invention is not limited by this embodiment. The physical property of the polycarbonate obtained by the following example is measured by the following method.

Examples 1 to 3 relate to the invention, wherein the pressure of the gas phase portion of the raw material dissolution tank is maintained at OMPa to 0.05 MPa. Compared with Comparative Example 1, Examples 4 to 10 are nitrogen-containing basics in the reaction mixture. It relates to an invention characterized by maintaining the concentration of the compound in a certain range, compared to Comparative Examples 2 to 6, Examples 11 to 13 relates to an invention characterized by using a specific by-product monohydroxy compound Compared with Comparative Examples 7,8, Examples 14-19 relate to inventions characterized in that they are specific diester carbonates, and are compared with Comparative Examples 9-11, and Examples 22, 23 are used for reactants of specific materials. It is related with the invention characterized by using, Comparing with the comparative example 12, Examples 24-26 are characterized by using the reaction apparatus which has an oxide layer which has iron oxide as a main component. To be compared with comparative examples 13 and 14 according to Examples 27 and 28 are compared with Comparative Example 15, Examples 29, 30 is compared with Comparative Example 16, Example 31 is compared with Comparative Example 17.

In addition, in all the cases of Examples 4 to 10 and Comparative Examples 2 and 6 described below, the reaction mixture obtained from the outlet of the stirring stirring tank is obtained because the stirring mixture for obtaining the reaction mixture (1) is substantially a complete mixing vessel. The viscosity average molecular weight of (1) and the amount of tetramethylammonium hydroxide (referred to herein as TMAH) coincide with the viscosity average molecular weight and TMAH amount of the reaction mixture collected in the shoulder agitator. In addition, since the agitation agitation for obtaining the reaction mixture (2) is substantially a complete agitation, the viscosity average molecular weight and the amount of TMAH of the reaction mixture (2) collected at the agitation exit of the agitation are collected in the agitation agitation. The viscosity average molecular weight and TMAH content of one reaction mixture correspond.

Intrinsic viscosity and viscosity average molecular weight measurement

Intrinsic viscosity is measured for a 0.7 g / dl methylene chloride solution using a Uberode viscometer, and the viscosity average molecular weight is calculated | required by following Formula.

[η] = 1.23 × 10 ^-4 M ^0.83

Hue (L / a / b value) measurement

L, a, b values which were polycarbonate pellets (short diameter x long diameter x length (mm) = 2.5x3.3x3.0) were measured by the reflection method using Nippon Denshoku Kogyo ND-1001DP. The higher the L value, the higher the brightness, and the smaller the b value, the smaller the yellow coloration, indicating that it is preferred.

Determination of basic nitrogen-containing compounds in the polymerization reaction

0.2 g of the reaction mixture is dissolved in 10 ml of cyclohexanone, 1 ml of an eluent (2.8 mmol of NaHCO ₃ /2.25 mmol of Na ₂ CO ₃ ) is added, followed by addition of 1 ml of pure water, followed by stirring. Centrifugation is carried out for 15 minutes at 3000 revolutions, the aqueous layer is filtered with a filter of 0.45 mu m, and quantified as basic nitrogen-containing basic ions by ion chromatography under the following conditions.

Dionex Corporation 4000I

Column IonpacCG14 / CS14

Eluent 10 mmol methanesulfonic acid

Regeneration solution pure

Detector conductivity

Flow rate of eluent 1 ml / min

Suppressor Auto (External Mode)

Terminal hydroxyl concentration measurement

0.02 g of the sample was dissolved in 0.4 ml of heavy chloroform, and the terminal hydroxyl group and the terminal phenyl group were measured using 1H-NMR (EX-270 manufactured by Nippon Denshisha) at 20 ° C., and the terminal hydroxyl group concentration was determined by the following formula. Measure

Terminal hydroxyl concentration (%) = (terminal hydroxyl number / end terminal number) × 100

Transparency Measurement

A flat plate of 50 × 50 × 5 mm was molded by a Sumitomo Juki Co., Ltd. neomat N150 / 75 injection molding machine with a cylinder temperature of 280 ° C. in a molding cycle of 3.5 seconds, and the total light transmittance of the flat plate was manufactured by Nippen Densho Co., Ltd. NDH - Measured by 80. The higher the total light transmittance, the better the transparency.

Determination of Nitrogen Aqueous Impurities in DPC

According to a conventional method, it is quantified by DN-1000 Deman microchemical emission spectrometer manufactured by Deman.

Analysis of Metal Elements

A sample is dissolved in an IPA for electronics industry by SPQ 9000ICP mass spectrometer manufactured by Seiko Instruments Co., Ltd., and quantified by a one-point weighing method.

Salicylic Acid Derivative Analysis

5 mg of a sample was dissolved in 5 ml of acetonitrile and subjected to high performance liquid chromatography; It is analyzed by Tosoh Co., Ltd. LC8020 and ODS-7 by column Nomura Kagaku Co., Ltd.

Measurement of metal components

The metal component measures the fragment by fluorescent X-rays. Device; Shimadzu Corporation XRF-1700, X-ray source; Rh.

Measurement of foreign matter

10 g of the polymer obtained after polymerization is dissolved in 500 ml of dichloromethane. This is filtered through a 10 pore size pre-pore filter. After filtration, the remaining dichloromethane soluble component is washed, and the foreign matter and soluble component are separated on the filter. The number of black foreign matters is visually counted, and the number of gels is dried under the irradiation of black light (ultraviolet wavelength 365nm, made by SPECTROLINE) after drying the filter. In order to ignore the influence of foreign matter incorporation from the external environment by this operation, the same operation is performed on the polymer which does not contain foreign matter (filter filtration treatment), and the result obtained is subtracted as a blank value.

Measurement of the amount of gel foreign matter

Dichloromethane is added to the polymer after polymerization so as to be about 7% by weight to obtain a polymer solution. This is filtered with a 10 pore size pre-pore filter. After filtration, the remaining dichloromethane solubles are washed, and the gel and the solubles are separated on the filter. The quantity of gel measures the dry weight of the filter after filtration, and makes the quantity of a gel foreign substance which subtracted the weight of the filter when the polymerization reaction was not performed by the same operation as a blank. Confirmation that the foreign material is a gel confirms that the filter emits light under irradiation with black light (ultraviolet wavelength 365 nm, manufactured by SPECTROLINE).

Auger Electrospectral Analysis of Stainless Steel Surfaces

The measuring device uses a PHI610 Auger electron spectrometer manufactured by Perkin-Elmer. Measured under the conditions of an electron beam acceleration voltage of 3 kV, a sample current of 100 nA, and a tilt angle of 30 degrees. The sputtering etching conditions were E = 2 KeV under an argon stream, etching rate-3.5 nm / min (indium oxide conversion). The film pressure of the oxide film is expected as an average interface that the proportion of oxygen in the power supply self-forming is less than 40 mol%.

In Example, the physical property evaluation of diphenyl carbonate (DPC) is based on the following method.

Weather resistance measurement

100 g of sample DPC flakes are placed in a clear glass container, and stored in a cool dark place for 6 months, blocking direct sunlight from inside the air. Based on the color number test method indicated in JIS K-4101, the DPC Hazen change was 140 mm in an liquid core using a flat bottom Pyrex color tube having a diameter of 23 mm and a thickness of 1.5 mm, and then maintained at 250 ° C. and 5 Hr in a molten state. Measured in comparison with Hazen standard colorimetric liquid. The melting apparatus uses an aluminum ingot hot bus represented by JIS K-4101, and also uses it for maintaining the molten state.

In the present specification, the ratio of the alkali metal compound, alkaline earth metal compound, and nitrogen-containing basic compound to the added aromatic dihydroxy compound is defined as "W (value) as a metal or basic nitrogen with respect to 1 mol of aromatic dihydroxy compound. Equivalents of Z (compound name), "which is, for example, Z having one sodium atom, such as sodium phenoxide and 2,2-bis (4-hydroxyphenyl) propanemono sodium salt, or triethylamine Likewise, if there is one basic nitrogen, it means that the amount of Z is equivalent to W mole, and if it is two like 2,2-bis (4-hydroxyphenyl) propanedisodium salt, it is equivalent to W / 2 mole. Means positive.

Example 1

99.5% by volume of the atmosphere gas in the transport piping immediately before the raw material melting tank for supplying the powdered aromatic dihydroxy compound to the raw material melting tank is nitrogen gas, and its linear velocity is 5 cm / min. In a facility in which a condenser maintained at a temperature of 110 ° C. is formed and the pressure of the gas phase portion of the raw material dissolution tank is managed at 0 MPa to 0.05 MPa, per 1 mol of powder 2,2-bis (4-hydroxyphenyl) propane, The injection setting was carried out at a ratio of 1.01 mol of molten diphenyl carbonate, and the mixture was injected into a melting tank equipped with a stirrer, and after complete melting, the molten mixture was transferred to a raw material tank maintained at 150 ° C.

Subsequently, the molten mixture was continuously supplied at a rate of 60 kg / hour to a vertical stirring tank equipped with a rectifying tower and kept at an internal temperature of 240 ° C. and an internal pressure of 1333 Pa (10 mmHg), and at the same time, 2,2-bis ( To 1 mole of 4-hydroxyphenyl) propane, 1 x 10 ^-6 equivalents of bisphenol A disodium salt and 1 x 10 ^-4 equivalents of tetramethylammonium hydroxide are added successively, and the resulting phenol is added to the rectifying column. The reaction was carried out by removing from. The resulting reaction was discharged continuously using a gear pump.

Subsequently, the said prepolymer was continuously supplied to the horizontal reactor which kept internal temperature 270 degreeC and internal pressure 133 Pa (1 mmHg). The resulting phenol was further polymerized while being removed out of the system, producing continuously.

As a result of measuring the quality of the polycarbonate after 2 days, [eta] was 0.35 and b value was 0.28.

Example 2

The polymerization reaction was carried out in the same manner as in Example 1, except that the condenser maintained at an internal temperature of 90 ° C. was used to maintain the pressure in the gas phase portion of the raw material dissolution tank at O MPa to 0.01 MPa.

As a result, when the quality of the polycarbonate after 2 days was measured, [η] was 0.35 and the b value was 0.01.

Example 3

A scrubber was provided in place of the condenser, and polymerization was carried out in the same manner as in Example 1 except that the pressure in the gas phase portion of the raw material melting tank was maintained at 0 MPa to 0.01 MPa.

As a result, when the quality of the polycarbonate after 2 days was measured, [(eta)] was 0.35 and b value was -0.05.

Comparative Example 1

The polymerization reaction was carried out in the same manner as in Example 1 except that neither the scrubber nor the condenser was provided in the vent of the raw material melting tank, and the pressure in the gas phase portion of the raw material melting tank was not adjusted.

As a result, when the quality of the polycarbonate after 2 days was measured, [η] was 0.35 and the b value was 2.32. After 10 days of operation, a part of the vent hole piping of the raw material melting tank was squeezed, and the pressure of the gas phase part of the raw material melting tank reached 0.1 MPa or more when the raw material was sent from the powder raw material tank to the raw material melting tank.

Example 4

To 1 mole of 2,2-bis (4-hydroxyphenyl) propane (BPA), diphenyl carbonate was injected into a melting tank equipped with a stirrer at a rate of 1.02 moles, dissolved at 150 ° C after nitrogen substitution, and the melted. The liquid mixture was transferred to the raw material tank maintained at 150 degreeC.

Subsequently, the molten mixture was continuously supplied to a vertical stirring tank equipped with a rectifying column and kept at an internal temperature of 220 ° C. and an internal pressure of 13333 Pa (100 mmHg), and 2,2-bis (4-hydroxyphenyl) propane To 1 mole, 5 x 10 ^-7 equivalents of sodium phenoxide (hereinafter referred to as NPO) as a metal and 1 x 10 ^-4 equivalents of TMAH as a nitrogen-containing basic compound are successively added, and the resulting phenol is added to the rectifying column. The reaction was carried out by removal from the reaction mixture, and the obtained reactant was continuously discharged using a gear pump.

The degree of polymerization of the obtained reactants was determined by measuring the intrinsic viscosity. Intrinsic viscosity [] was measured according to the above method. As a result, a reaction mixture (1) having a viscosity average molecular weight of 1500 and containing 2.7 ppm of TMAH was obtained.

Subsequently, the reaction mixture (1) was continuously supplied to a vertical stirring tank having an internal temperature of 250 ° C. and an internal pressure of 1333 Pa (10 mmHg), and the resulting phenol was removed from the rectification column to carry out the reaction. The reaction mixture was discharged continuously using a gear pump.

As a result, a reaction mixture (2) having a viscosity average molecular weight of 6500 and containing 0.09 ppm of TMAH was obtained.

Subsequently, the reaction mixture (2) was continuously supplied to a horizontal uniaxial reaction vessel having an internal temperature of 270 ° C. and an internal pressure of 133 Pa (1 mmHg), and further polymerized while removing the generated phenol out of the system. Polycarbonates having an average molecular weight of 15,300 were continuously obtained, and the polycarbonates in the molten state were discharged by a gear pump, extruded from a die and pelletized by a pelletizer. The results are shown in Table 1.

Example 5

For 1 mole of 2,2-bis (4-hydroxyphenyl) propane, except that 5 × 10 ⁻⁶ equivalents of NPO as a metal and 1 × 10 ⁻⁴ equivalents of TMAH as a nitrogen-containing basic compound are added continuously. Polycarbonate was obtained in the same manner as in Example 4. The results are shown in Table 1.

Example 6

For 1 mole of 2,2-bis (4-hydroxyphenyl) propane, except that 1 × 10 ⁻⁵ equivalents of NPO as a metal and 1 × 10 ⁻⁴ equivalents of TMAH as a nitrogen-containing basic compound are added continuously. Polycarbonate was obtained in the same manner as in Example 4. The results are shown in Table 1.

Example 7

To 1 mol of 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate was injected into a melting tank equipped with a stirrer at a ratio of 1.02 mol, dissolved at 150 ° C after nitrogen replacement, and the melted mixture was It transferred to the raw material tank maintained at 150 degreeC.

Subsequently, the molten mixture solution was continuously supplied to a vertical stirring vessel equipped with a rectifying column and kept at 230 ° C in internal temperature and at an internal pressure of 13333 Pa (100 mmHg), and 2,2-bis (4-hydroxyphenyl) propane To 1 mole, 5 × 10 ⁻⁶ equivalents of NPO as a metal and 5 × 10 ⁻⁴ equivalents of TMAH as a nitrogen-containing basic compound are successively added, and the resulting phenol is removed from the rectification column to carry out the reaction, thereby obtaining. The reaction mixture was discharged continuously using a gear pump to obtain a reaction mixture (1).

Subsequently, the reaction mixture (1) was maintained at 260 ° C., internal pressure at 1333 Pa (10 mmHg), continuously supplied to a vertical stirring tank, and the resulting phenol was removed from the rectification column to carry out the reaction. A polycarbonate was obtained in the same manner as in Example 4 except that the obtained reaction mixture (2) was continuously discharged using a gear pump. The results are shown in Table 1.

Example 8

To 1 mol of 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate was injected into a melting tank equipped with a stirrer at a ratio of 1.02 mol, dissolved at 150 ° C after nitrogen replacement, and the melted mixture was It transferred to the raw material tank maintained at 150 degreeC.

Subsequently, the molten mixture was continuously supplied to a vertical stirring tank equipped with a rectifying column and kept at an internal temperature of 200 ° C. and an internal pressure of 13333 Pa (100 mmHg), and 2,2-bis (4-hydroxyphenyl) propane To 1 mole, 5 × 10 ⁻⁶ equivalents of NPO as a metal and 5 × 10 ⁻⁵ equivalents of TMAH as a nitrogen-containing basic compound are successively added, and the resulting phenol is removed from the rectification column to carry out the reaction. The reactant was discharged continuously using a gear pump to obtain a reaction mixture (1).

Subsequently, the reaction mixture (1) was kept at an internal temperature of 245 DEG C and an internal pressure of 1333 Pa (10 mmHg), continuously supplied to a vertical stirring tank, and the resulting phenol was removed from the rectification column to carry out the reaction, thereby obtaining. The polycarbonate was obtained in the same manner as in Example 4 except that the prepared reactant was continuously discharged using a gear pump to obtain a reaction mixture (2). The results are shown in Table 1.

Example 9

To 1 mol of 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate was injected into a melting tank equipped with a stirrer at a ratio of 1.02 mol, dissolved at 150 ° C after nitrogen replacement, and the melted mixture was It transferred to the raw material tank maintained at 150 degreeC.

Subsequently, the molten mixture was continuously supplied to a vertical stirring tank equipped with a rectifying column and kept at an internal temperature of 220 ° C. and an internal pressure of 13333 Pa (100 mmHg), and 2,2-bis (4-hydroxyphenyl) propane To 1 mole, 5 x 10 ^-7 equivalents of NPO as a metal and 1 x 10 ^-4 equivalents of TMAH as a nitrogen-containing basic compound are successively added, and the resulting phenol is removed from the rectification column to give a reaction. The reactant was discharged continuously using a gear pump to obtain a reaction mixture (1).

Subsequently, 2,2-bis (4-hydroxyphenyl) propane 1 was continuously supplied to the reaction mixture (1) while continuously supplying the inner temperature to the vertical stirring tank maintained at 270 ° C and the internal pressure at 2000 Pa (15 mmHg). To moles, 1 × 10 ⁻⁴ equivalents of TMAH are continuously supplied as a nitrogen-containing basic compound, the resulting phenol is removed from the rectification column, the reaction is carried out, and the obtained reactant is continuously discharged using a gear pump. , Except that the reaction mixture (2) was obtained, a polycarbonate was obtained in the same manner as in Example 4. The results are shown in Table 1.

Comparative Example 2

For 1 mole of 2,2-bis (4-hydroxyphenyl) propane, except that 5 × 10 ⁻⁶ equivalents of NPO as a metal and 5 × 10 ⁻⁴ equivalents of TMAH as a nitrogen-containing basic compound are added continuously. Polycarbonate was obtained in the same manner as in Example 4. The results are shown in Table 1.

Comparative Example 3

For 1 mole of 2,2-bis (4-hydroxyphenyl) propane, except that 5 × 10 ⁻⁶ equivalents of NPO as a metal and 5 × 10 ⁻⁵ equivalents of TMAH as a nitrogen-containing basic compound are added continuously. Polycarbonate was obtained in the same manner as in Example 4. The results are shown in Table 1.

Comparative Example 4

To 1 mol of 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate was injected into a melting tank equipped with a stirrer at a ratio of 1.02 mol, dissolved at 150 ° C after nitrogen substitution, and the melted mixture was 150 It transferred to the raw material tank maintained at ° C.

Subsequently, the molten mixture was transferred to a vertical stirring vessel equipped with a rectifying column and kept at an internal temperature of 220 ° C. and an internal pressure of 16000 Pa (120 mmHg), in the same manner as in Example 4 except that the reaction mixture 1 was obtained. Polycarbonate was obtained. The results are shown in Table 1.

Comparative Example 5

To 1 mol of 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate was injected into a melting tank equipped with a stirrer at a ratio of 1.02 mol, dissolved at 150 ° C after nitrogen replacement, and the melted mixture was It transferred to the raw material tank maintained at 150 degreeC.

Subsequently, the molten mixture solution was provided with a rectifying column and kept at an internal temperature of 220 ° C. and an internal pressure of 13333 Pa (100 mmHg), and was continuously supplied to a vertical stirring tank, and 2,2-bis (4-hydroxyphenyl) propane To 1 mole, 5 x 10 ^-7 equivalents of NPO as a metal and 1 x 10 ^-4 equivalents of TMAH as a nitrogen-containing basic compound are successively added, and the resulting phenol is removed from the rectification column to give a reaction. The reactant was discharged continuously using a gear pump to obtain a reaction mixture (1).

Subsequently, the reaction mixture (1) was continuously supplied to a vertical stirring tank kept at an internal temperature of 270 ° C. and an internal pressure of 2000 Pa (15 mmHg), and the resulting phenol was removed from the rectification column to carry out the reaction. The polycarbonate was obtained in the same manner as in Example 4 except that the reactant was continuously discharged using a gear pump to obtain a reaction mixture (2). The results are shown in Table 1.

Example 10

To 1 mol of 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate was injected into a melting tank equipped with a stirrer at a ratio of 1.02 mol, and dissolved at 150 ° C after nitrogen replacement. 100 kg of the melt mixture was injected into the reactor in a vertical batch type equipped with a rectifying tower and a stirrer at a time, and 5 x 10 ^-7 as a metal with respect to 1 mol of 2,2-bis (4-hydroxyphenyl) propane. As an equivalent sodium phenoxide and a nitrogen-containing basic compound, 1 × 10 ⁻⁴ equivalents of tetramethylammonium hydroxide are added, and the pressure is reduced to 30 mmHg over 0.5 hour while heating to 200 ° C., and the state is 1 hour. Then most of the phenols were removed. In the meantime, the reaction mixture was sampled one by one.

Subsequently, while raising the temperature to 270 ° C, the pressure was reduced to 1 mmHg over 0.5 hour, and then the reaction was carried out for 1 hour to obtain a polycarbonate having a viscosity average molecular weight of 15,300. Extruded and pelletized with a pelletizer. The reaction mixture was sampled one after another during this reaction. Table 2 shows the analysis results of each sample.

Comparative Example 6

To 1 mol of 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate was injected into a melting tank equipped with a stirrer at a ratio of 1.02 mol, and dissolved at 150 ° C after nitrogen replacement. 100 kg of the melt mixture was injected into the reactor in a vertical batch type equipped with a rectifying tower and a stirrer at a time, and 5 x 10 ^-7 as a metal with respect to 1 mol of 2,2-bis (4-hydroxyphenyl) propane. As an equivalent sodium phenoxide and a nitrogen-containing basic compound, 1 × 10 ^-4 equivalents of tetramethylammonium hydroxide were added, and the pressure was reduced to 100 mmHg over 0.5 hours while heating to 200 ° C., and then 0.5 hours 30 mmHg was over, and the state was continued for 1 hour, and most phenol was removed. In the meantime, the reaction mixture was sampled one by one. Subsequently, while raising the temperature to 270 ° C, the decompression degree was set to 10 mmHg over 0.5 hour, and then to 1 mmHg over 0.5 hour, and thereafter, the reaction was carried out over 1 hour, and the viscosity average molecular weight was 15,300. Polycarbonate was obtained, and the polycarbonate in the molten state was extruded from a die and pelletized by a pelletizer. In the meantime, the reaction mixture was sampled one by one. Table 2 shows the analysis results of each sample.

Example 11

115 parts by weight of diphenyl carbonate and 123 parts by weight of bisphenol A, 1.5 × 10 ⁻⁴ parts by weight of a sodium salt of bisphenol A as a transesterification catalyst, and 4,9 × 10 ⁻² parts by weight of tetramethylammonium hydroxide, trimethylamine A catalyst liquid obtained by adding 2.0 parts by weight of phenol obtained by recycling in a melt condensation polymerization reaction containing 10 ppm and 50 ppm of anisole, and injected into a reactor equipped with a stirring device, a distillation column, a condenser, and a vacuum suction unit. And nitrogen-substituted, it melt | dissolved at 140 degreeC. After stirring for 30 minutes, internal temperature was heated up at 180 degreeC, it was made to react at 100 torr of internal pressure for 15 minutes, and the phenol produced | generated was removed.

Subsequently, the inner temperature was raised to 200 ° C., and the reaction was carried out while gradually reducing the pressure and removing phenol at 50 torr for 20 minutes. In addition, the temperature was raised to 220 ° C, 30 torr, 240 ° C and 10 torr, and 270 ° C and 10 torr and reduced. Finally, the reaction was carried out at 270 ° C and 1 torr for 2 hours.

As a result, intrinsic viscosity (? Sp / C) measured at 20 ° C. in methylene chloride was 0.49 dl / g using the obtained polymer. In addition, a 3 mm t injection molded plate was prepared as the color of the polymer, and the b value was determined to be yellow by the Colorand Color Defference Meter ND-1001 DP manufactured by Nippon Denshoku Kogyo Co., Ltd. Yellow was not felt in.

Example 12

A polymer was obtained in the same manner as in Example 11 except for using phenol obtained by recycling in the melt condensation polymerization reaction containing 20 ppm of trimethylamine.

As a result, the intrinsic viscosity (ηsp / C) of the obtained polymer was 0.50 dl / g, the b value was 2.6, and yellow was not felt in visual determination.

Example 13

A polymer was obtained in the same manner as in Example 11 except for using phenol obtained by recycling in the melt condensation polymerization reaction containing 15 ppm of anisole. As a result, the intrinsic viscosity (ηsp / C) of the obtained polymer was 0.49 dl / g, the b value was 2.7, and yellow was not felt in visual determination.

Comparative Example 7

A polymer was obtained in the same manner as in Example 11 except for using phenol obtained by recycling in the melt condensation polymerization reaction containing 150 ppm trimethylamine and 2000 ppm anisole. The intrinsic viscosity (ηsp / C) of the resultant polymer was 0.45 dl / g, the b value was 3.1, and yellowness was strongly felt in visual determination.

Comparative Example 8

A polymer was obtained in the same manner as in Example 11 except that phenol obtained by recycling in the melt condensation polymerization reaction containing 0.5 ppm of trimethylamine and 0.1 ppm of anisole was used. The inherent viscosity (ηsp / C) of the resultant polymer was 0.48 dl / g, the b value was 3.2, and yellowness was strongly felt in visual determination.

Example 14; Including comparative example

(Purification of DPC: DPC 1-11)

1 kg of DPC purchased from Bayer was dissolved in industrial xylene 51, and 20 g of hydrotalcite DHT-4A manufactured by Kyowa Chemical Co., Ltd. was added thereto, followed by stirring for 5 hours at 100 ° C under nitrogen stream. The solvent was removed by a vacuum evaporator, concentrated to about one third, and the ice-cold DPC was precipitated and separated and dried in vacuo. The DPC was dissolved in 5 L of acetone and passed through a column packed with 1 kg of an H-type strong acid cation exchange resin, followed by a column packed with 1 kg of an OH-type strongly basic anion exchange resin.

100 g of activated carbon was added to the obtained DPC solution, followed by boiling for 30 minutes under a nitrogen stream. After cooling the solvent was removed in a vacuum evaporator. The obtained DPC was removed by 100 mmHg under reduced pressure, and 10 volume% of the total oil content and the after oil content were removed by the 10-stage Aldershow type automatic precision distillation apparatus.留 分) was collected. Impurities in the raw material and the purified DPC are shown in Tables 3 and 4 below. In the sample of Table 4, the expression (ratio) means a comparative example.

Examples 15-19 and Comparative Examples 9-11

228 parts by weight of bisphenol A (BPA), 220 parts by weight of a predetermined DPC, and a predetermined amount of a transesterification catalyst were injected into a reactor equipped with a stirring device, a distillation column, and a depressurizing device, nitrogen-substituted, and dissolved at 140 ° C. After stirring for 30 minutes, internal temperature was heated up to 180 degreeC, reaction was performed for 100 mmHg internal pressure for 30 minutes, and the phenol produced | generated was removed.

Subsequently, the reaction mixture was reacted while gradually reducing the pressure while raising the internal temperature to 200 ° C. and removing phenol at 50 mmHg for 30 minutes. In addition, the temperature was gradually increased and reduced to 220 ° C and 30 mmHg, and the reaction was continued by increasing the temperature and depressurizing in the same manner to 240 ° C, 10 mmHg, 260 ° C, and 1 mmHg for 30 minutes under the same temperature and pressure. . Finally, a part of polymer was collected while continuing polycondensation of polycarbonate at the temperature of 270 degreeC, and molecular weight was measured. The polycondensation was continued until the molecular weight became 15,300 and 25,100.

After the end of the polymerization, the OH group concentration was measured, and O-methoxyphenyl and phenyl carbonate terminal-sealed with O-methoxycarboxyphenyl and phenyl carbonate were used in molar amounts with the terminal OH group. Then dodecylbenzenesulfonic acid tetrabutylphosphonium salt was added 1.75 * 10 <^-4> weight part (3 * 10 <^-6> equivalent / 1 mol-BPA), and catalyst was deactivated. When the amount of sodium catalyst was changed, the catalyst was deactivated by using 3 times molar amount.

Intrinsic viscosity, color, transparency, and fluidity at the end of the polycondensation are shown in Tables 5 and 6 below.

As shown in the above results, when the amount of impurities exceeds a predetermined range, the b value exceeds 7.0 and the yellow color becomes stronger and cannot be used. In addition, when the amount of impurities exceeds a predetermined range, the transparency decreases to about 80%.

Examples 22 and 23 and Comparative Example 12

1L separable flask made of SUS316 stainless steel based on 66.6% by weight of iron, 12.4% by weight of nickel, and 16.6% by weight of chromium, and containing niobium and vanadium in the amounts shown in Table 7 below. And 228.31 g (1.0 mole) of bisphenol A from which foreign substances were removed in advance, diphenyl carbonate 224.93 g (1.05 mole), and the disodium salt of bisphenol A (1.0 x 10 ^-7 mole) as a catalyst. And tetramethylammonium hydroxide (1 × 10 ⁻⁵ mole) were injected under inexhaustible conditions to initiate a transesterification reaction. After melting at 200 ° C., the mixture was reacted at 100 mmHg for 1 hour to remove phenol. After hold | maintaining for 30 minutes at 220 degreeC and 30 mmHg, it hold | maintained for 30 minutes at 240 degreeC and 30 mmHg, 30 minutes at 260 degreeC, and 10 mmHg, and produced | generated phenol was removed.

Further, the polycondensation of the polymer was carried out at 280 ° C and 1 mmHg or less, and finally, the reaction was terminated at a reaction time of about 0.35 intrinsic viscosity of the polycarbonate resin in 1 hour of reaction time, and the obtained polymer was discharged under dust-free conditions. It was.

The number of foreign substances of the obtained polymer was counted by the above method. The results obtained are shown in Table 7.

Example 24

The inner surface of the separable flask of SUS316 1L volume (# 300), based on 61.9% by weight of iron, 10.1% by weight of nickel, and 17.4% by weight of chromium, was buffed (# 300) and degreased in heptane. . It was heated in air at 330 ° C. for 62 hours. The result of Auger electron spectroscopy analysis of the test piece for analysis (10 mm in diameter and 1 mm in thickness) treated in the same manner is shown in FIG. 1. As a result of the measurement, 45 nm of an oxide film centered on iron oxide was formed.

Using a reaction furnace equipped with a 20 cm distillation column and a 50 cm air-cooled condenser using a stirring blade made of copper, which was treated in the same way as the polymerization kiln, bisphenol A 228.31 g (1.0 mol), 224.93 g (1.05 mol) of diphenyl carbonates were injected | poured, 1.0x10 <^-6> mol of sodium salts of a phenol, and 1.0 * 10 <^-4> mol of tetramethylammonium acetate were added as a catalyst, and superposition | polymerization was started. After melt | dissolution at 200 degreeC, reaction was performed for 1 hour, improving the pressure reduction degree to 100 mmHg, removing the aromatic hydroxy compound produced by reaction. Moreover, reaction was continued for 30 minutes at 220 degreeC, 30 mmHg, 30 minutes at 240 degreeC, 30 mmHg, and 30 minutes at 260 degreeC, 30 mmHg.

Reaction was performed at 260 degreeC and 1.0 mmHg for 3 hours, and reaction was complete | finished in the stage whose polymer intrinsic viscosity [(eta)] is 0.45. All of the obtained polymers were dissolved in dichloromethane, and the amount of gel foreign matter contained in the solution was measured. As a result, the amount of gel foreign matter was 9 mg per kg of the polymer.

Example 25

The same SUS316 1 L volume separable flask (buffed and degreased) as in Example 24 was reacted with 3% nitric acid solution for 2 hours, washed with water, dried and then heated in air at 300 ° C for 24 hours. As a result of the Auger Electron Spectroscopy analysis of the analytical test piece treated in the same manner, 21 nm of the oxide film centered on iron oxide and chromium oxide was formed in the surface oxide film.

This was put into a polymerization kiln and the polymer was polymerized in the same manner as in Example 24, and the amount of gel was measured. As a result, the amount of foreign matter on the gel was 11 mg per kg of the polymer.

Example 26

The same SUS316 1 L volume separable flask (buffed and degreasing) as in Example 24 was heated in air at 500 ° C for 1 hour. Auger electron spectroscopy analysis of the test piece for analysis was performed in the same manner. In the oxide film, about 100 nm of an oxide film centered on iron oxide was formed.

It was put into a polymerization kiln and the polymer was polymerized in the same manner as in Example 24, and the amount of gel was measured. As a result, the amount of gel foreign matter was 8 mg per kg of the polymer.

Comparative Example 13

A separable flask (buffed and degreasing) of the same SUS316 first L volume as in Example 24 was used, and no treatment was performed.

The surface oxide film was 5 nm as a result of Auger electron spectroscopic analysis of the test piece for analysis similarly processed.

It was put into a polymerization kiln and the polymer was polymerized in the same manner as in Example 24, and the gel amount was measured. As a result, the amount of foreign matter on the gel was 83 mg per kg of the polymer.

Comparative Example 14

The SUS316 1 L volume separable flask (buffed and degreased) was heated in air at 300 ° C. for 1 hour. The surface oxide film was 15 nm as a result of Auger electron spectroscopy of the analytical test piece treated in the same manner.

It was put into a polymerization kiln and the polymer was polymerized in the same manner as in Example 24, and the gel amount was measured. As a result, the amount of gel foreign matter was 65 mg per kg of polymer.

Examples 27-1 to 3 and Comparative Examples 15-1 to 3

3 L, SUS316 dissolution tank, rectifier tower, 1 L of SUS316, vertical reactor with horizontal stirrer, horizontal reactor 1 with stirrer, connected to each other by gear pump When polycarbonate was prepared using a polymerization apparatus consisting of a axial reactor, diphenyl carbonate (DPC) purified in Example 14 was converted to 1.02 with respect to 1 mol of 2,2-bis (4-hydroxyphenyl) propane (BPA). At a molar ratio, it was maintained at 150 DEG C, poured into a dissolution tank in a nitrogen atmosphere, and dissolved, and the molten mixture was continuously supplied to a first vertical reactor maintained at an internal temperature of 220 DEG C and an internal pressure of 100 mmHg, and the BPA was 5 * 10 ^-7 equivalents of NaOH as a Na element and tetramethylammonium hydroxide (TMAH) as a nitrogen-containing basic compound are dissolved in high purity phenol at a ratio of 1 * 10 ^-4 equivalents per mole, and continuously as a solution. Phenolic Formed by Addition Carrying out the reaction by removing from the fractionating column and, with appropriate sampling and the obtained reaction product, subsequently sent to the second reaction vessel with a gear pump.

Degree of polymerization of the discharged sample; Viscosity average molecular weight and TMAH amount were measured in the same manner as in Example 4.

In the second vertical reactor in which the reactant was maintained at 250 ° C. and internal pressure 10 mmHg, the produced phenol was removed from the rectification column, and the reaction was carried out. Sent to.

Degree of polymerization of the discharged sample; Viscosity average molecular weight and TMAH amount were measured in the same manner as in Example 4.

Subsequently, the phenol generated in the horizontal monoaxial reactor maintained at an internal temperature of 270 ° C. and internal pressure of 1 mmHg was removed from the system, and polymerization was further performed to continuously obtain a polycarbonate having a viscosity average molecular weight of 15,300 and continuously melted. The polycarbonate was discharged with a gear pump, extruded from a die, and pelletized with a pelletizer.

The conditions and the results are shown in Table 8.

The results in Tables 8 to 10 are values on the seventh day after the start of operation except for the color shades indicated in parentheses for Examples 27 and 28, but after Example 27 and Comparative Example 15 other than that, after the start of operation 24 It is the stable sample value of the hr-th.

Example 28

3 L of phenol generated at the time of polymerization was distilled under atmospheric pressure in a distillation apparatus equipped with a 30 cm Wimer distillation column, and 0.5 L of supernatant was removed to obtain 2 L of main stream. A phenol of 50 ppm of anisole and 10 ppm of trimethylamine was obtained.

NaOH in the phenol; 2 * 10 ^-2 parts by weight and 9.1 parts by weight of TMAH were dissolved and ³ parts by weight of 1 * 10 were used as a catalyst solution. The reaction was carried out in the same manner as in Example 27-1 using the catalyst solution, and further analyzed. The results are shown in Table 8.

Comparative Example 16-1

The component of SUS316 of the reaction apparatus used in Example 27 is a component similar to the comparative example 12, and is basic composition; Fe, 66.6 wt%, Ni, 12.4 wt%, Cr, 16.6 wt%, and Nb, V content was 10 ppm or less. Using this reactor, the reaction of Example 27-1 was continued for 7 days, and the number of foreign substances per 10 g of polycarbonate was examined for the samples on the first, third and seventh days. In addition, the amount of gel foreign matters (foreign weight per 1 Kg of polycarbonates; mg) described in Example 24 was also measured.

The catalyst solution was prepared using an industrial anti-purity phenol (and anisole, trimethylamine content; GC, not detected by ion chromatography; 0.1 ppm or less). The results are shown in Table 9.

Example 29-1

Material Nb = 100 ppm, V = 600 ppm containing SUS316 The material used in Example 22 was reacted under the same conditions as in Comparative Example 16-1. The same analysis was performed on the obtained polycarbonate. The results are shown in Table 9.

Example 29-2

The reactor of the same material as that used in Example 29-1 was treated in the same manner as in Example 25, and an iron oxide and chromium oxide layer 21 nm was prepared. Using this reactor, reaction analysis under the same conditions as in Example 29-1 was conducted. The results obtained are shown in Table 9.

Comparative Example 16-2

In the same reactor as in Example 29-2, using DPC-6 shown in Example 14, the reaction was carried out under the same conditions as in Comparative Example 16-1, and the analysis was performed. The results obtained are shown in Table 9.

Example 30-1

Using the catalyst solution prepared in Example 28, the reaction was carried out in the same manner as in Example 29-1, and the analysis was performed. The results obtained are shown in Table 9.

Example 30-2

Using the catalyst solution prepared in Example 28, the reaction was carried out in the same manner as in Example 29-2, and the analysis was performed. The results obtained are shown in Table 9.

From the results of the above examples, foreign matter generation can be suppressed by material selection and surface oxide layer formation, foreign matter suppression effect, in particular, foreign matter suppression effect when the reaction is continued for a long time, suppresses the amount of impurities in the DPC, and selects reactor material and surface. It can be understood that the effect of the catalyst solution can be achieved by using it in combination with the oxide layer formation, but the effect can be obviously reduced in the gel unexpectedly.

Example 31-3

99.5% of the atmospheric gas in the transport piping immediately before the raw material dissolution tank for supplying the powdered aromatic dihydroxy compound to the raw material dissolution tank is nitrogen gas, its linear velocity is 5 cm / min, and is provided in the vent hole of the raw material dissolution tank. In the equipment which installed the condenser maintained at internal temperature of 110 degreeC, and managed the pressure of the gaseous-phase part of the said dissolution tank to 0-0.05 Mpa, with respect to 1 mol of 2, 2-bis (4-hydroxyphenyl) propanes of a powder, The molten diphenyl carbonate purified in Example 14 was injected at a ratio of 1.02 mol, and injected into a dissolution tank equipped with a stirrer, and after complete dissolution, the molten mixture was transferred to a raw material tank maintained at 150 ° C.

Hereinafter, it reacted similarly to Example 4 and analyzed. Table 10 shows the results of obtaining the viscosity average molecular weight, TMAH content, and the polymer properties of the used DPC species, the conditional reaction mixtures (1) and (2) of the first and second vertical stirring tanks.

The reactor was made of the same material as in Example 22 and contained SUS316 containing Nb-100 ppm and V-600 ppm, and the catalyst was added as a high purity phenol solution.

Comparative Example 17-1

In Example 31-1, the reaction was carried out under the conditions described in Table 10. The results obtained are shown in Table 10.

Comparative Example 17-2

The reaction was carried out in the same manner as in Example 31-1, except that the capacitor was not installed and the pressure in the gas phase was not adjusted. The results obtained are shown in Table 10.

Example 31-2

The catalyst solution using the phenol prepared in Table 28 was created, and reaction and analysis similar to Example 31-1 were performed. The results obtained are shown in Table 10.

Example 31-3

The reaction apparatus prepared in Example 31-2 was subjected to the same treatment as in Example 25 to prepare iron oxide and chromium oxide layers 21 nm, and the reaction analysis was performed. The results obtained are shown in Table 10.

According to the present invention, accurate raw material molar ratio adjustment is made, and therefore, there is little coloration and the desired degree of polymerization can be obtained, so that a very good result is obtained in product quality.

In addition, the present inventors made diligent studies to find a method for producing a transesterified aromatic polycarbonate having excellent color tone and thermal stability. As a result, the present inventors have prepared the nitrogen-containing basic compound concentration used as a transesterification catalyst in the reaction mixture in a specific range. The aromatic polycarbonate polymer was found to have excellent color tone and thermal stability, and the present invention was completed.

In the present invention, in preparing an aromatic polycarbonate, an aromatic polycarbonate having a specific range of viscosity average molecular weights using a specific amount of an alkali metal compound and / or an alkaline earth metal compound as a catalyst and a nitrogen-containing basic compound as a catalyst The nitrogen-containing basic compound contained in the reaction mixture in the production is in a specific range, and the transesterification reaction proceeds, whereby an aromatic polycarbonate having little heat denaturation and color deterioration and excellent color tone can be obtained.

Claims (33)

A method of producing a polycarbonate by supplying an aromatic dihydroxy compound and a diester carbonate of powder to a raw material melting tank and mixing and melting the same, followed by melt polymerization in the presence / absence of a solvent, wherein the pressure in the gas phase of the raw material melting tank is reduced to OMPa. The method for producing an aromatic polycarbonate, which is maintained at ˜0.05 MPa. The non-oxidizing gas according to claim 1, wherein at least 90% by volume of the atmospheric gas in the transport pipe immediately before the raw material dissolution tank for supplying the aromatic dihydroxy compound of the powder to the raw material dissolution tank is a non-oxidizing gas, and the linear velocity is 0.5 cm / min or more. Manufacturing method characterized in that. The vent pipe of a raw material melting tank is connected to the scrubber, The manufacturing method of Claim 1 or 2 characterized by the above-mentioned. The method according to any one of claims 1 to 3, wherein the vent pipe of the raw material dissolution tank is connected to a condenser held at a temperature of 70 占 폚 or higher. The production method according to any one of claims 1 to 4, wherein the diester carbonate is diphenyl carbonate. In the reaction of a mixture mainly containing an aromatic dihydroxy compound and a diester carbonate by a transesterification reaction using an alkali metal compound and / or an alkaline earth metal compound and a nitrogen-containing basic compound as a catalyst, in producing an aromatic polycarbonate, The concentration of the nitrogen-containing basic compound in the reaction mixture is kept between 0.1 ppm and 10 ppm between 500 and 3,000 in the viscosity average molecular weight of the reaction mixture, and 0.01 ppm in the viscosity average molecular weight between 3,000 and 10,000. The method for producing an aromatic polycarbonate, which is maintained at 1 pm or less. The production method according to claim 6, wherein an alkali metal compound and / or an alkaline earth metal compound of 10 ^-3 to 10 ^-8 equivalents is used as the metal with respect to 1 mol of the aromatic dihydroxy compound. The production method according to claim 6, wherein an alkali metal compound and / or an alkaline earth metal compound of 5x10 ^{-6 to} 1x10 ^-8 equivalents is used as the metal with respect to 1 mol of the aromatic dihydroxy compound. The method according to any one of claims 6 to 8, wherein the nitrogen-containing basic compound is represented by Chemical Formula 1 (wherein R ₁ is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms). . [Formula 1] (R ₁ ) ₄ NOH 10. The aromatic polycarbonate according to any one of claims 6 to 9, wherein the aromatic dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane and the diester carbonate is diphenyl carbonate. Manufacturing method. A method for producing an aromatic polycarbonate by melt condensation polymerization reaction using diester carbonate as a raw material, wherein the monohydroxy compound by-produced by the melt condensation polymerization reaction is recycled and used as a catalyst addition solvent, and catalyst addition A solvent is a method for producing an aromatic polycarbonate, characterized in that it contains anisole of 1 ppm or more and 1000 ppm or less. A method for producing an aromatic polycarbonate by melt condensation polymerization reaction using diester carbonate as a raw material, wherein the monohydroxy compound by-produced by the melt condensation polymerization reaction is recycled and used as a catalyst addition solvent. The addition solvent contains trimethylamine which is 1 ppm or more and 100 ppm or less, The manufacturing method of the aromatic polycarbonate characterized by the above-mentioned. A method for producing an aromatic polycarbonate by melt condensation polymerization reaction using diester carbonate as a raw material, wherein the monohydroxy compound by-produced by the melt condensation polymerization reaction is recycled and used as a catalyst addition solvent, and the catalyst The addition solvent contains 1 ppm or more and 1000 ppm or less of anisole, and 1 ppm or more and 100 ppm or less of trimethylamine. The manufacturing method of the aromatic polycarbonate characterized by the above-mentioned. The process for producing an aromatic polycarbonate according to any one of claims 11 to 13, wherein the monohydroxy compound is phenol. The catalyst used in the melt condensation polymerization method is quaternary ammonium salt or quaternary phosphonium salt and / or alkali metal salt, or quaternary ammonium salt or quaternary phosphor. Process for producing aromatic polycarbonates which are nium salts and / or alkaline earth metal salts. Nitrogen-containing compounds suitable for preparing aromatic polycarbonates by heat-melting and transesterifying aromatic dihydroxy compounds and diester carbonates in the presence of a catalyst containing an alkali metal compound or an alkaline earth metal compound are used as nitrogen atoms. A diester carbonate having excellent storage stability, characterized in that the ppm or less, the metal elements to be contained are 0.5 ppm or less, respectively, and the salicylic acid derivatives are 10 ppm or less. The diester carbonate according to claim 16, wherein the total amount of iron, tin, chromium, titanium, and copper is 0.5 ppm or less with respect to the metal element. The diester carbonate according to claim 16 or 17, wherein the total amount of all metals is 0.5 ppm or less with respect to the metal element. A method for producing an aromatic polycarbonate by heating and melting an aromatic dihydroxy compound and a diester carbonate in the presence of a catalyst containing an alkali metal compound or an alkaline earth metal compound to produce an aromatic polycarbonate. An alkali metal compound and / or an alkaline earth metal compound per mole of aromatic dihydroxy compound is used as a catalyst using the diester carbonate according to any one of claims 18 to 18. A method for producing an aromatic polycarbonate, characterized by using 10 ^{-8 to} 5.0 x 10 ^-6 equivalents of catalyst and 1.0 x 10 ^{-5 to} 5.0 x 10 ^-4 equivalents of a basic compound containing nitrogen. In the method for producing an aromatic polycarbonate by transesterification of an aromatic dihydroxy compound and a diester carbonate compound, the material of the reaction apparatus is a stainless alloy, the total content of niobium and / or vanadium contained in the stainless alloy. It is 10 ppm-1000 ppm, The manufacturing method of the aromatic polycarbonate in which foreign material generation was suppressed. The catalyst used in the transesterification reaction contains an alkali metal compound and / or a nitrogen-containing basic compound, and the amount of the alkali metal compound used is 1 × 10 ^-8 moles to 5 moles to 1 mole of the aromatic hydroxy compound. A method for producing an aromatic polycarbonate, characterized in that x 10 ^-6 mol. An apparatus for producing an aromatic polycarbonate, characterized in that at least 20 nm or more of an oxide layer containing iron oxide as a main component is formed on the inner wall of part or all of the reaction apparatus used for producing the aromatic polycarbonate. 23. The apparatus for producing an aromatic polycarbonate according to claim 22, wherein an oxide layer containing iron oxide as a main component is formed on an inner wall surface of a material made of a stainless alloy. The apparatus for producing an aromatic polycarbonate according to any one of claims 22 and 23, wherein an oxide layer containing iron oxide and chromium oxide as a main component is formed on at least part of the inner wall of the reaction apparatus at least 20 nm. The apparatus for producing an aromatic polycarbonate according to any one of claims 22 to 24, wherein the aromatic polycarbonate is produced by transesterification of an aromatic dihydroxy compound and a diester carbonate compound in the presence of a catalyst. 26. The method for producing an aromatic polycarbonate according to any one of claims 22 to 25, wherein the aromatic dihydroxy compound and the diester carbonate compound are produced by transesterification in the presence of a catalyst. Method for producing an aromatic polycarbonate, characterized in that. 20. A method for producing an aromatic polycarbonate, comprising the combination of any one of claims 19 and 6, 8 or 9. A method for producing an aromatic polycarbonate, comprising the combination of claims 27, 26 and / or 20. A method for producing an aromatic polycarbonate, comprising the combination of any one of claims 27 and 1 to 4. A method for producing an aromatic polycarbonate, comprising the combination of claims 27 and 14. A method for producing an aromatic polycarbonate, comprising the combination of claims 28 and 14. A method for producing an aromatic polycarbonate, comprising the combination of any one of claims 31 and 1 to 4. 20. A method for producing an aromatic polycarbonate, comprising combining at least two of claims 19, 6, 26, 20, 11, and 1. A combination of claims 19 and 6, and Except for the preparation of aromatic polycarbonates consisting of a combination of clauses 6 and 26, a combination of clauses 19 and 6 and 20, and a combination of clauses 19 and 6 and 1.