JP2009057574A - Polycarbonate and optical material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To give an useful polycarbonate as an optical material and a blow molding material with little content of impurities such as residual monomer and oligomer, and exhibiting excellent physical properties such as impact strength. <P>SOLUTION: The polycarbonate is obtained by preparation of a polycarbonate prepolymer by a preliminary polymerization followed by an ester exchange polymerization reaction under solid, swelled solid or melted thin film conditions, with 3.5 or 3.0 wt.% or less of an acetone soluble content, less than 2 or 15 mol% of hydroxy group terminal molar fraction and 0.45 wt.% of a cyclic oligomer content. The optical materials and blow molding materials use them. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polycarbonate, and more particularly to a polycarbonate, an optical material, and a blow molding material having a low content of impurities such as residual monomers and oligomers and excellent physical properties such as impact strength.

  Polycarbonate is widely used in various fields as an excellent engineering plastic, but as its production method, a method of directly reacting an aromatic dihydroxy compound such as bisphenol A and phosgene (interface method), or an aromatic such as bisphenol A is used. There is known a method in which a dihydroxy compound and a carbonic acid diester such as diphenyl carbonate are transesterified (melting method / solid phase method) in a molten state or a solid phase.

In the interface method, toxic phosgene must be used, equipment is corroded by by-product hydrogen chloride and chlorine-containing compounds such as sodium chloride, and the methylene chloride mixed in the resin is very difficult to remove. There are problems such as being easy to contain chlorine. On the other hand, the melting method has solved these problems in the interfacial method, but it contains many residual monomers and low molecular weight components in the produced polymer, which causes a decrease in impact strength and adhesion to the mold. was there.
In order to solve these problems, a method of adding a low-boiling compound to an extruder in a melting method (Japanese Patent Laid-Open No. 09-5936) has been proposed, but it is still not sufficient. In the solid-phase method, no proposals or reports have been made about these.

JP 09-5936 A

  An object of the present invention is to solve the problems of the polycarbonate produced by such a conventional transesterification reaction, and to provide a polycarbonate, an optical material and a blow molding material excellent in quality such as impact resistance.

  As a result of intensive studies to achieve the above object, the present inventors have made it possible to remarkably reduce residual monomers and low molecular weight components by appropriately selecting the reaction method or reaction conditions in the transesterification method. It has been found that a polycarbonate having quality is obtained. The present invention has been completed based on such findings.

That is, the present invention provides the following polycarbonates.
[1] A polycarbonate obtained by a transesterification reaction between a dihydroxy compound and a carbonic acid diester, wherein the content of acetone-soluble component in the resulting polycarbonate is 2.0% by weight or less.
[2] A polycarbonate obtained by preparing a polycarbonate prepolymer by prepolymerization and then polymerizing the prepolymer by a transesterification reaction in a thin film melt state, wherein the content of acetone-soluble component in the resulting polycarbonate is 3.0. Polycarbonate that is less than wt%.
[3] A polycarbonate obtained by preparing a polycarbonate prepolymer by prepolymerization and then polymerizing the prepolymer by a transesterification reaction in a solid phase state or a swollen solid phase state. Polycarbonate having a content of 3.5% by weight or less.
[4] A polycarbonate obtained by preparing a polycarbonate prepolymer by prepolymerization and then polymerizing the prepolymer by a transesterification reaction in a solid phase state or a swollen solid phase state. Polycarbonate having a rate of less than 2 mol%.
[5] A polycarbonate obtained by preparing a polycarbonate prepolymer by prepolymerization and then polymerizing the prepolymer by a transesterification reaction in a thin film melt state, wherein the hydroxyl group terminal fraction in the resulting polycarbonate is 15 mol%. Polycarbonate that is less than.
[6] A polycarbonate obtained by preparing a polycarbonate prepolymer by prepolymerization and then polymerizing the prepolymer by a transesterification reaction in a solid phase state, a swollen solid phase state or a thin film molten state, Polycarbonate having a cyclic oligomer content of 0.45% by weight or less.
[7] The polycarbonate prepolymer is prepared by heating and prepolymerizing (A) an aromatic dihydroxy compound, (B) a carbonic acid diester, and (C) a monovalent hydroxy compound, as described in [3] or [6] above Polycarbonate.
[8] After preparing a polycarbonate prepolymer by heating (A) an aromatic dihydroxy compound, (B) a carbonic acid diester, and (C) a monovalent hydroxy compound and then prepolymerizing it, the prepolymer is in a solid state or swollen A polycarbonate obtained by polymerizing by a transesterification reaction in a solid phase, wherein the terminal fraction derived from a monovalent hydroxy compound in the resulting polycarbonate is 50 mol% or more.
[9] After preparing a polycarbonate prepolymer by heating (A) an aromatic dihydroxy compound, (B) a carbonic acid diester, and (C) a monovalent hydroxy compound, the prepolymer is then in a solid state or swollen. A polycarbonate obtained by polymerizing by a transesterification reaction in a solid phase, wherein the hydroxyl group terminal fraction in the produced polycarbonate is less than 15 mol%.
[10] An optical material comprising the polycarbonate described in any one of [1] to [9].
[11] The above-mentioned [3], wherein (A) an aromatic dihydroxy compound, (B) a carbonic acid diester, and (C) a polyfunctional organic compound having three or more functional groups are heated and prepolymerized. Or the polycarbonate as described in [6].
[12] After preparing a polycarbonate prepolymer by heating and prepolymerizing (A) an aromatic dihydroxy compound, (B) a carbonic acid diester and (C) a polyfunctional organic compound having three or more functional groups, A polycarbonate obtained by polymerizing the prepolymer by a transesterification reaction in a solid phase state or a swollen solid phase state, wherein the polycarbonate has a hydroxyl group terminal fraction of less than 15 mol%.
[13] A blow molding material comprising the polycarbonate described in [11] or [12].

  According to the present invention, a polycarbonate having a low content of impurities such as residual monomers and oligomers and excellent physical properties such as impact strength can be provided.

  The polycarbonate according to the present invention comprises a raw material (A) component dihydroxy compound and component (B) carbonic acid diester, and optionally component (C) a terminal terminator or branching agent in a molten or solid phase. Obtained by transesterification in the state, in particular, (A) component dihydroxy compound and (B) component carbonic acid diester or phosgene, and (C) component end terminator or branching agent as required A polycarbonate prepolymer prepared by prepolymerization using a polymer, and then polymerized by subjecting the prepolymer to a transesterification reaction in a solid phase state, a swollen solid phase state or a thin film molten state. A catalyst is used during the preparation of the polycarbonate prepolymer and in the polymerization reaction.

1. Features of the polycarbonate according to the present invention (1) A polycarbonate obtained by prepolymerizing a polycarbonate prepolymer and then polymerizing the prepolymer by a transesterification reaction in a solid state, a swollen solid phase state or a thin film melt state. The total of the dihydroxy compound content, the carbonic acid diester content and the monohydroxy compound content in the resulting polycarbonate is less than 100 ppm. The measurement of the dihydroxy compound content, the carbonic acid diester content and the monohydroxy compound content in the produced polymer is based on the following high performance liquid chromatography measurement. That is, 2 grams of polycarbonate is dissolved in 50 ml of dichloromethane, and 250 ml of acetone is added little by little to precipitate the polymer. After suction filtration, 50 ml of acetonitrile is added to the filtrate and concentrated to about 10 ml. The concentrate is placed in a 50 ml volumetric flask and the volume is adjusted to acetonitrile / water = 1/1. This is filtered using a chromatodisc 13P and measured by high performance liquid chromatography. The measurement conditions are as follows. That is, using a column (TSKgel ODS-80Ts manufactured by Tosoh Corporation), as a mobile phase, acetonitrile aqueous solution (A solution) (acetonitrile: water = 3: 7 (volume) and acetonitrile aqueous solution (B solution), A solution and B solution. The ratio was changed from 100: 0 (volume) to 0: 100 over 35 minutes, the flow rate was 1.0 ml / min, the injection amount was 20 microliters, and detection was performed using a wavelength of 217 nm.

(2) A polycarbonate obtained by a transesterification reaction between a dihydroxy compound and a carbonic acid diester, and in particular after preparing a polycarbonate prepolymer by prepolymerization, the prepolymer is in a solid state, a swollen solid state or a thin film melted state. In the polycarbonate obtained by polymerizing by transesterification in step 1, the acetone-soluble content in the resulting polycarbonate is 3.5% by weight or less in the previous two solid phase reactions, and 3.0% by weight in the subsequent liquid phase reactions. Hereinafter, it is preferably 2.0% by weight or less. Here, the acetone soluble content is measured by the following method. That is, 3 g of a sample of polycarbonate flakes that passed through a 100-mesh wire mesh was subjected to cylindrical filter paper No. 84 (28 mm × 100 mm) was collected and extracted by refluxing with 100 ml of acetone at a reflux rate of once every 3 to 4 minutes (20 ml / times) for 8 hours. Thereafter, 100 ml of acetone was evaporated and the residue after vacuum drying at 110 ° C. overnight was weighed to obtain an acetone-soluble component.

(3) A polycarbonate obtained by pre-polymerizing a polycarbonate prepolymer and then polymerizing the prepolymer by a transesterification reaction in a solid phase state, a swollen solid phase state or a thin film molten state, The polycarbonate has a cyclic oligomer content of 0.45% by weight or less. Here, about the measurement of cyclic oligomer content in a production | generation polycarbonate, it is based on the following method. That is, 2 g of a polycarbonate sample is dissolved in 50 ml of dichloromethane, and 250 ml of acetone is added little by little to precipitate the polymer. This is suction filtered and dried. This is dissolved in 50 ml of diethyl ether, filtered at atmospheric pressure, and dried. This is made up to 20 ml with chloroform. This is filtered using a chromatodisc 13P and measured by a high performance liquid chromatograph.

(4) A polycarbonate obtained by pre-polymerizing a polycarbonate prepolymer and then polymerizing the prepolymer by a transesterification reaction in a solid phase state, a swollen solid phase state or a thin film molten state, The hydroxyl group terminal fraction is less than 2 mol% in the first two solid phase reactions and less than 15 mol% in the latter liquid phase reaction. Here, about the measurement of the hydroxyl-terminal fraction in a production | generation polycarbonate, it is based on the following method. That is, ¹ H-NMR (400 MHz, number of integration 128 times) was measured using CD ₂ Cl ₂ as a solvent, and Ha and He were obtained from the obtained chart and calculated by the following formula.
OH terminal fraction = (Ha / 2) / (Ha / 2 + He / 2)
(In the formula, Ha represents the cumulative ratio of peaks derived from two hydrogens in the ortho position relative to the OH group of the benzene ring in the terminal phenyl group, and He represents the meta position relative to the COO of the benzene ring in the terminal phenyl carbonate group. (The integration ratio of the peaks derived from the two hydrogen atoms in FIG.

(5) A polycarbonate prepolymer is prepared by heating and prepolymerizing (A) an aromatic dihydroxy compound, (B) a carbonic acid diester and (C) a monovalent hydroxy compound, and then the prepolymer is solid-phased or swollen. A polycarbonate obtained by polymerizing by a transesterification reaction in a solid phase, wherein the terminal fraction derived from a monovalent hydroxy compound in the resulting polycarbonate is 50 mol% or more. Here, for the analysis of the terminal structure of the produced polycarbonate, CD ₂ Cl ₂ was used as a solvent, and ¹³ C-NMR (125.65 MHZ, 24 times of integration) was measured and calculated.

(6) After preparing a polycarbonate prepolymer by heating (A) an aromatic dihydroxy compound, (B) a carbonic acid diester and (C) a monovalent hydroxy compound, and then prepolymerizing the polycarbonate prepolymer, the prepolymer is solid phase or swollen. It is a polycarbonate obtained by polymerizing by a transesterification reaction in a solid phase, wherein the hydroxyl group terminal fraction in the produced polycarbonate is less than 15 mol%. Here, the measurement of the hydroxyl terminal fraction in the produced polycarbonate is the same as (4) above.

(7) After preparing a polycarbonate prepolymer by heating and prepolymerizing (A) an aromatic dihydroxy compound, (B) a carbonic acid diester, and (C) a polyfunctional organic compound having three or more functional groups, A polycarbonate obtained by polymerizing the prepolymer by a transesterification reaction in a solid phase state or a swollen solid phase state, wherein the hydroxyl group terminal fraction in the produced polycarbonate is less than 15 mol%. Here, the measurement of the hydroxyl terminal fraction in the produced polycarbonate is the same as (4) above.

2. Production method of polycarbonate according to the present invention (1) Raw material

(A) Dihydroxy compound For example, an aromatic dihydroxy compound and an aliphatic dihydroxy compound are mentioned, and it is at least one compound selected from these.
The aromatic dihydroxy compound used as one of the components (A) has the general formula (I)

で表される化合物を挙げることができる。
上記一般式（Ｉ）において、Ｒ³ 及びＲ⁴ は、それぞれフッ素、塩素、臭素、ヨウ素のハロゲン原子又は炭素数１〜８のアルキル基、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、ヘブチル基、オクチル基などを示す。Ｒ³ 及びＲ⁴ はたがいに同一であっても異なっていてもよい。また、Ｒ³ が複数ある場合は複数のＲ³ は同一でも異なっていてもよく、Ｒ⁴ が複数ある場合は複数のＲ⁴ は同一でも異なっていてもよい。ｍ及びｎは、それぞれ０〜４の整数である。そして、Ｚは単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基、又は−Ｓ−、−ＳＯ−、−ＳＯ₂−、−Ｏ−、−ＣＯ−結合若しくは式（II)、（II')

The compound represented by these can be mentioned.
In the general formula (I), R ³ and R ⁴ are each a halogen atom of fluorine, chlorine, bromine, iodine or an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group. N-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, hebutyl group, octyl group and the like. R ³ and R ⁴ may be the same or different. Also, it may be a plurality of R ³ when there are a plurality of R ³ are identical or different, a plurality of R ⁴ if R ⁴ there are a plurality may be the same or different. m and n are each an integer of 0 to 4. Z is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or -S-, —SO—, —SO ₂ —, —O—, —CO— bond or formula (II), (II ′)

で示される結合を示す。炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基としては、例えばメチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、エチリデン基、イソプロピリデン基などが挙げられ、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基としては、例えばシクロペンチレン基、シクロヘキシレン基、シクロペンチリデン基、シクロヘキシリデン基などが挙げられる。

The bond shown by is shown. Examples of the alkylene group having 1 to 8 carbon atoms and the alkylidene group having 2 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an ethylidene group, and an isopropylidene group. Examples of the cycloalkylene group having 5 to 15 carbon atoms and the cycloalkylidene group having 5 to 15 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, and a cyclohexylidene group.

  Examples of the aromatic dihydroxy compound represented by the general formula (I) include bis (4-hydroxyphenyl) methane; bis (3-methyl-4-hydroxyphenyl) methane; bis (3-chloro-4-hydroxyphenyl). ) Methane; bis (3,5-dibromo-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (2-tert-butyl-4-hydroxy-3-methyl) Phenyl) ethane; 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane; 1-phenyl-1,1-bis (3-fluoro-4-hydroxy-3-methylphenyl) 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A); 2,2-bis (3-methyl-4-hydroxyphenyl) pro 2,2-bis (2-methyl-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (2-t-butyl- 4-hydroxy-5-methylphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2,2-bis (3-bromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) Nyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-1-methylphenyl) propane; 1,1-bis (4-hydroxy-t-butylphenyl) 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 2,2-bis (4-hydroxy-3-) 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane; 2,2-bis (3-bromo) -4-hydroxy-5-chlorophenyl) propane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (4-hydro) 2,2-bis (3-methyl-4-hydroxyphenyl) butane; 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane; 1,1-bis (2- t-butyl-4-hydroxy-5-methylphenyl) butane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) isobutane; 1,1-bis (2-t-amyl- 4-hydroxy-5-methylphenyl) butane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane; 4 1,2-bis (4-hydroxyphenyl) heptane; 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane; 2,2-bis (4-hydroxyphenyl) Bis (hydroxyaryl) alkanes such as 1,1- (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane; bis (4-hydroxyphenyl) ether; bis (4-hydroxy-3-methyl); Bis (hydroxyaryl) ether such as phenyl) ether Bis (4-hydroxyphenyl) sulfide; bis (hydroxyaryl) sulfides such as bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide; bis (3-methyl-4-hydroxy); Bis (3-phenyl-4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) sulfone; bis (3-methyl-4-hydroxyphenyl) sulfone; bis (3 Bis (hydroxyaryl) sulfones such as -phenyl-4-hydroxyphenyl) sulfone, 4,4'-dihydroxybiphenyl; 4,4'-dihydroxy-2,2'-dimethylbiphenyl; 4,4'-dihydroxy-3 3'-dimethyl bifu 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl; dihydroxybiphenyls such as 3,3'-difluoro-4,4'-dihydroxybiphenyl and the like.

  Examples of aromatic dihydroxy compounds other than the above general formula (I) include dihydroxybenzenes, halogen and alkyl-substituted dihydroxybenzenes. For example, resorcin, 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin; 2,3,4,6- Tetrafluororesorcin; 2,3,4,6-tetrabromoresorcin; catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenyl Hydroquinone, 3-cumylhydroquinone; 2,5-dichlorohydroquinone; 2,3,5,6-tetramethylhydroquinone; 2,3,4,6-tetra-t-butylhydroquinone; 2,3,5,6- Tetrafluorohydroquinone; 2, 3, 5, - such as tetrabromo hydroquinone.

  In addition, there are various types of aliphatic dihydroxy compounds used as one of the components (A). For example, butane-1,4-diol; 2,2-dimethylpropane-1,3-diol; hexane-1,6-diol; diethylene glycol; triethylene glycol; tetraethylene glycol; octaethylene glycol; dipropylene glycol N, N-methyldiethanolamine; cyclohexane-1,3-diol; cyclohexane-1,4-diol; 1,4-dimethylolcyclohexane; p-xylylene glycol; 2,2-bis- (4-hydroxycyclohexyl); Propane and dihydric alcohol or phenol ethoxylation or propoxylation products such as bis-oxyethyl-bisphenol A; bis-oxyethyl-tetrachlorobisphenol A or bis-oxyethyl-tetrachlorohydroquinone It is.

  In the preferred production method of the present invention, as the dihydroxy compound of component (A), one or more of the above compounds are appropriately selected and used. Among them, bisphenol A which is an aromatic dihydroxy compound is used. Is preferred. Furthermore, diesters of dihydroxy compounds, dicarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and the like can also be used.

That is, examples of diesters of dihydroxy compounds include bisphenol A diacetate, bisphenol A dipropionate, bisphenol A dibutyrate, and bisphenol A dibenzoate. Examples of dihydroxy compounds of dihydroxy compounds include bismethyl carbonate of bisphenol A, bisethyl carbonate of bisphenol A, and bisphenyl carbonate of bisphenol A.
Examples of the monohydroxy esters of dihydroxy compounds include bisphenol A monomethyl carbonate, bisphenol A monoethyl carbonate, bisphenol A monopropyl carbonate, and bisphenol A monophenyl carbonate.

(B) component
I) Various carbonic acid diesters are used. For example, it is at least one compound selected from a diaryl carbonate compound, a dialkyl carbonate compound or an alkylaryl carbonate compound.
The diaryl carbonate compound used as one of the components (B) is represented by the general formula (III)

（式中、Ａｒ¹ 及びＡｒ² はそれぞれアリール基を示し、それらはたがいに同一でも異なっていてもよい。）で表される化合物、又は一般式（IV）

(Wherein Ar ¹ and Ar ² each represents an aryl group, and they may be the same or different from each other), or a compound represented by the general formula (IV)

（式中、Ａｒ³ 及びＡｒ⁴ はそれぞれアリール基を示し、それらはたがいに同一でも異なっていてもよく、Ｄ¹ は前記芳香族ジヒドロキシ化合物から水酸基２個を除いた残基を示す。）で表される化合物である。また、炭酸ジアルキル化合物は、一般式（Ｖ）

(Wherein Ar ³ and Ar ⁴ each represents an aryl group, which may be the same or different, and D ¹ represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound). It is a compound represented. The dialkyl carbonate compound is represented by the general formula (V)

（式中、Ｒ⁵ 及びＲ⁶ はそれぞれ炭素数１〜６のアルキル基又は炭素数４〜７シクロアルキル基を示し、それらはたがいに同一でも異なっていてもよい。）で表される化合物、又は一般式（VI)

(Wherein R ⁵ and R ⁶ each represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, which may be the same or different from each other), Or general formula (VI)

（式中、Ｒ⁷ 及びＲ⁸ はそれぞれ炭素数１〜６のアルキル基又は炭素数４〜７のシクロアルキル基を示し、それらはたがいに同一でも異なっていてもよく、Ｄ² は前記芳香族ジヒドロキシ化合物から水酸基２個を除いた残基を示す。）で表される化合物である。そして、炭酸アルキルアリール化合物は、一般式（VII)

(In the formula, R ⁷ and R ⁸ each represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, which may be the same or different, and D ² represents the aromatic group. It shows a residue obtained by removing two hydroxyl groups from a dihydroxy compound. The alkyl aryl carbonate compound is represented by the general formula (VII)

（式中、Ａｒ⁵ はアリール基、Ｒ⁹ は炭素数１〜６のアルキル基又は炭素数４７のシクロアルキル基を示す。）で表される化合物、又は一般式（VIII)

(Wherein Ar ⁵ represents an aryl group, R ⁹ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 47 carbon atoms), or a compound represented by the general formula (VIII)

（式中、Ａｒ⁶ はアリール基，Ｒ¹⁰ は炭素数１〜６のアルキル基又は炭素数４〜７のシクロアルキル基、Ｄ³ は前記芳香族ジヒドロキシ化合物から水酸基２個を除いた残基を示す。）で表される化合物である。ここで、炭酸ジアリール化合物としては、例えば、ジフェニルカーボネート，ジトリルカーボネート、ビス（クロロフェニル）カーボネート、ｍ−クレジルカーボネート、ジナフチルカーボネート、ビス（ジフェニル）カーボネート、ビスフェノールＡビスフェニルカーボネートなどが挙げられる。

(In the formula, Ar ⁶ is an aryl group, R ¹⁰ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, and D ³ is a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound. It is a compound represented by. Here, examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, bisphenol A bisphenyl carbonate, and the like.

  Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate, and the like. Examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate, and the like.

  In the present invention, as the carbonic acid diester of the component (B), one or more of the above compounds are appropriately selected and used. Among these, diphenyl carbonate is preferably used. As the carbonic acid diester of the component (B), one or more of the above compounds are appropriately selected and used. Among these, diphenyl carbonate is preferably used.

II) Phosgene In preparing a polycarbonate prepolymer by prepolymerization, phosgene can also be used as the component (B).

Component (C) As a raw material for the polycarbonate of the present invention, a terminal terminator, a branching agent, and an antioxidant may be added to the reaction system as necessary.
I) End terminator Examples of the terminator include: on-butylphenol; mn-butylphenol; pn-butylphenol; o-isobutylphenol; m-isobutylphenol; p-isobutylphenol; Butylphenol; mt-butylphenol; pt-butylphenol; on-pentylphenol; mn-pentylphenol; pn-pentylphenol; on-hexylphenol; mn-hexylphenol; -N-hexylphenol; o-cyclohexylphenol; m-cyclohexylphenol; p-cyclohexylphenol; o-phenylphenol; m-phenylphenol; p-phenylphenol; on-nonylphenol; mn-nonylphenol; n-no N-phenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,6-di-t-butylphenol, 2,5- 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; p-tert-butylphenol; Examples thereof include monohydric phenols such as cumylphenol; p-phenylphenol; o, m, pt-octylphenol; o, m, pn-octylphenol. These can be used alone or in combination of two or more. Of these, 2,6-di-t-butylphenol; 2,5-di-t-butylphenol; 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-Dicumylphenol; 3,5-Dicumylphenol; p-tert-butylphenol; p-cumylphenol; pt-octylphenol;

II) Branching agent As the branching agent, a polyfunctional organic compound having three or more functional groups is used. Specifically, a compound having three or more functional groups such as a hydroxyl group, a carboxyl group, an amino group, an imino group, a formyl group, an acid halide group, and a haloformate group, such as phloroglucin; merit acid; trimellitic acid Trimellitic chloride; trimellitic anhydride; gallic acid; n-propyl gallate; protocatechuic acid; pyromellitic acid; pyromellitic dianhydride; α-resorcinic acid; β-resorcinic acid; resorcinaldehyde; Trichlorotrichloride; 4-chloroformylphthalic anhydride; benzophenone tetracarboxylic acid; 2,4,4'-trihydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; 2,4,4 '-Trihydroxyphenyl ether; 2,2', 4,4'-tetrahydroxy 2,4,4′-trihydroxydiphenyl-2-propane; 2,2′-bis (2,4-dihydroxy) propane; 2,2 ′, 4,4′-tetrahydroxydiphenylmethane; 4,4′-trihydroxydiphenylmethane; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,6-bis (2′-hydroxy-5′-methylbenzyl) -4-methylphenol 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -heptene-2; 4,6-dimethyl-2,4,6-dimethyl-tris (4-hydroxyphenyl) -heptane- 2; 1 3,5-tris (4-hydroxyphenyl) -benzene; 1,1,1-tris (4′-hydroxyphenyl) -ethane; 2,2-bis [4,4-bis (4′-hydroxyphenyl) cyclohexyl ] -Propane; 2,6-bis (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol; bis [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl) -5 Methylphenyl] methane; bis [2-hydroxy-3- (2′-hydroxy-5′-isopropylbenzyl) -5-methylphenyl] methane; tetrakis (4-hydroxyphenyl) methane; tris (4-hydroxyphenyl) phenyl Methane; 2 ′, 4,7-trihydroxyflavan; 2,4,4-trimethyl-2 ′, 4′-dihydroxyphenylisopropyl ) Benzene; tris (4′-hydroxyaryl) -amyl-s-triazine; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -3- [α ′, α′-bis (4 ′) '-Hydroxyphenyl) ethyl] benzene; isatin bis (o-cresol); α, α, α', α'-tetrakis (4-hydroxyphenyl) -p-xylene; α, α, α ', α'-tetrakis ( 3-methyl-4-hydroxyphenyl) -p-xylene; α, α, α ′, α′-tetrakis (2-methyl-4-hydroxyphenyl) -p-xylene; α, α, α ′, α′- Tetrakis (2,5-dimethyl-4-hydroxyphenyl) -p-xylene; α, α, α ′, α′-tetrakis (2,6-dimethyl-4-hydroxyphenyl) -p-xylene; α, α ′ -Dimethyl-α, α, α ', α'-tetrakis (4-H And droxyphenyl) -p-xylene. These branching agents may be used alone or in combination of two or more.

  Among these, 1,1,1-tris (4-hydroxyphenyl) ethane; 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane; 1,1,1-tris (4-hydroxy-) 1,1,1-tris (3-chloro-4-hydroxyphenyl) ethane; 1,1,1-tris (3,5-dichloro-4-hydroxyphenyl) ethane; 1,1,1-tris (3-bromo-4-hydroxyphenyl) ethane; 1,1,1-tris (3,5-dibromo-4-hydroxyphenyl) ethane; tris (4-hydroxyphenyl) methane; 4-hydroxy-3-methylphenyl) methane; tris (4-hydroxyphenyl-3,5-dimethylphenyl) methane; tris (3-chloro-4-hydroxyphenyl) Nyl) methane; Tris (3,5-dichloro-4-hydroxyphenyl) methane; Tris (3-bromo-4-hydroxyphenyl) methane; Tris (3,5-dibromo-4-hydroxyphenyl) methane; α, α '-Dimethyl-α, α, α', α'-tetrakis (4-hydroxyphenyl) -p-xylene and the like are preferable.

III) Antioxidants Phosphoric antioxidants are preferred as antioxidants, such as trialkyl phosphites, tricycloalkyl phosphites, triaryl phosphites, monoalkyl diaryl phosphites, trialkyl phosphates, tricycloalkyl phosphates. And triaryl phosphate.

(2) Preparation of prepolymer by prepolymerization In the prepolymerization, the dihydroxy compound of component (A) and the carbonic acid diester or phosgene of component (B) which are raw materials, and the end-stopper or branching of component (C) as necessary A prepolymer is prepared using an agent or the like. In this case, at least one selected from nitrogen-containing organic basic compounds or phosphorus-containing basic compounds is preferably used as the polymerization catalyst.

The procedure and conditions of the preferred production method are specifically shown.
I) Prepolymerization method (a) A prepolymer is prepared while removing an aromatic monohydroxy compound by treating a dihydroxy compound and a carbonic acid diester and, if necessary, a terminal terminator or a branching agent under heating. be able to. The polymerization average molecular weight of the prepolymer produced in this preliminary polymerization step is preferably selected in the range of 2000 to 20000. This prepolymerization reaction is preferably carried out in a molten state. In this case, for example, aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene and methylnaphthalene, gases such as carbon dioxide, dinitrogen monoxide and nitrogen, chlorofluorohydrocarbons, ethane and propane Inert solvents such as alkanes, cycloalkanes such as alkane, cyclohexane, tricyclo (5,2,10) decane, cyclooctane and cyclodecane, alkenes such as ethene and propene may be used. Also good. The use ratio (feed ratio) of the dihydroxy compound and the carbonic acid diester varies depending on the reaction conditions such as the type used, the reaction temperature, the reaction pressure, etc., but the carbonic acid diester is usually at 0. It is used in a proportion of 9 to 2.5 mol, preferably 0.95 to 2.0 mol, more preferably 0.98 to 1.5 mol. In the case of using a terminal stopper that is a monovalent hydroxy compound or a branching agent that is a polyfunctional organic compound having three or more functional groups, the former is usually 0 per 1 mol of the dihydroxy compound. 0.001 to 20 moles, preferably 0.0025 to 15 moles, more preferably 0.005 to 10 moles, and the latter is usually 0.001 to 20 moles per mole of the dihydroxy compound. , Preferably 0.0025 to 15 mol, more preferably 0.005 to 10 mol.
The reaction temperature, reaction pressure, and reaction time vary depending on the type and amount of raw materials and catalyst used, the required polymerization amount of the resulting prepolymer, other reaction conditions, etc., but preferably 50 to 350 ° C., more preferably 100 to 320. At a temperature of 150 ° C., further 150 to 280 ° C., preferably 0.1 Torr to 5 kg / cm ² G, preferably 1 minute to 100 hours, more preferably 2 minutes to 10 hours.

  In order not to color the prepolymer, it is desirable to carry out the prepolymerization reaction at the lowest possible temperature and in a short time. Any reactor used in such a prepolymer production process may be used as long as it is a conventionally known polymerization reactor. The reaction step may be a single step or may be produced by dividing it into further steps. Moreover, the reactor can also be used by connecting one or more reactors in series or in parallel. For this production, any of a batch method, a continuous method, or a method using these in combination may be used.

  The terminal ratio of the prepolymer produced by this step is preferably phenyl carbonate terminal: hydroxyl terminal = 1: 1 to 1: 0.1, more preferably in the range of 1: 0.6 to 1: 0.25. It is. If the terminal ratio is outside the above range, the final molecular weight reached is limited, and it becomes difficult to achieve a high molecular weight. In this prepolymerization reaction, as the reaction proceeds, an aromatic monohydroxy compound, which is a compound in which a hydroxyl group is bonded to an aryl group based on diaryl carbonate, is produced, but this must be removed from the reaction system. Therefore, effective mixing is performed, and at the same time, an inert gas such as nitrogen, argon, helium, carbon dioxide, or a lower hydrocarbon gas is introduced to generate the aromatic mono- gen. A method of removing a hydroxy compound accompanied with these gases, a method of performing a reaction under reduced pressure, a method of using these in combination, or the like is preferably used.

(B) A prepolymer can also be prepared by reacting an aromatic dihydroxy compound and phosgene by a known method.

II) Catalyst in prepolymerization It is preferable to use a nitrogen-containing organic basic compound as a catalyst. The nitrogen-containing organic basic compound is not particularly limited, and examples thereof include aliphatic tertiary amine compounds, aromatic tertiary amine compounds, and nitrogen-containing heterocyclic compounds. Furthermore, the general formula (IX)
(NR ¹¹ ₄ ) ⁺ (X ¹ ) -... (IX)
The quaternary ammonium salt represented by these can be mentioned.
In the general formula (IX), R ¹¹ represents an organic group such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a cyclohexyl group, a cycloalkyl group, a phenyl group, An aryl group such as a tolyl group, a naphthyl group or a biphenyl group, an arylalkyl group such as a benzyl group, and the like are shown. The four R ^{1 s} may be the same or different, and two R ¹¹ may be bonded to form a ring structure. X ¹ represents a halogen atom, a hydroxyl group or BR ₄ .
Here, R represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group, and the four Rs may be the same or different.

  Examples of such quaternary ammonium salts include ammonium hydroxides having an alkyl group, aryl group, araryl group, and the like such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. And basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetramethylammonium tetraphenylborate.

Among these nitrogen-containing organic basic compounds, a quaternary ammonium salt represented by the above general formula (I), which has high catalytic activity, is easy to be thermally decomposed and hardly remains in the polymer, Specifically, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium borohydride, and tetrabutylammonium borohydride are preferable, and tetramethylammonium hydroxide is particularly preferable.
Such nitrogen-containing organic basic compounds may be used singly or in combination of two or more. The nitrogen-containing organic basic compound is preferably used in an amount of 10 ⁻² to 10 ⁻⁸ mol, more preferably 10 ⁻³ to 10 ⁻⁷ mol. When the amount of the nitrogen-containing organic basic compound used is less than 10 ⁻⁸ mol, the catalytic activity at the initial ^stage of the reaction becomes insufficient, and when it exceeds 10 ⁻² mol, the cost increases, which is not preferable.

III) Crystallization of prepolymer The method for crystallizing the prepolymer is not particularly limited, but a solvent treatment method and a heat crystallization method are preferably used. The former solvent treatment method is a method in which a prepolymer is crystallized using an appropriate solvent such as chloromethane, methylene chloride, or chloroform. The amount of the solvent to be used varies depending on various conditions, but is preferably selected in the range of 0.05 to 100 times, preferably 0.1 to 50 times, based on the weight of the prepolymer.
On the other hand, the heat crystallization method is a method in which the prepolymer is crystallized by heating at a temperature not lower than the glass transition temperature of the target aromatic polycarbonate and less than the temperature at which the prepolymer starts to melt. is there. The temperature Tc (° C.) for performing the heat crystallization is not particularly limited as long as it is not lower than the glass transition temperature of the target aromatic polycarbonate and lower than the melting temperature Tm (° C.) of the prepolymer.

(3) Production of polycarbonate by polymerization In producing a polycarbonate according to the present invention, after preparing a polycarbonate prepolymer, a quaternary phosphonium salt is used as a polymerization catalyst, and the prepolymer is in a solid phase state and a swollen solid phase state. Alternatively, the polymerization is preferably performed in a thin film molten state.
I) Quaternary phosphonium salt There are no particular limitations on the quaternary phosphonium salt, and there are various types. For example, general formula (IX) or (X)
_{^{(PR 12 4) + (X}} 2) - ··· (X)
(PR ¹² ₄ ) ₂ ⁺ (Y ¹ ) ² -... (XI)
Is preferably used.
In the general formula (X) or (XI), R ¹² represents an organic group. Examples of the organic group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a cyclohexyl group. And alkyl groups such as cycloalkyl groups, aryl groups such as phenyl groups, tolyl groups, naphthyl groups, and biphenyl groups, and arylalkyl groups such as benzyl groups. Four R ¹² may be the same or different, and two R ¹² may be bonded to form a ring structure. X ² can form a monovalent anion such as a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, R′COO, HCO ₃ , (R′O) ₂ P (═O) O or BR ″ ₄ Indicates a group. Here, R ′ represents a hydrocarbon group such as an alkyl group or an aryl group, and two R′O may be the same or different. R ″ represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group, and the four R ″ may be the same or different. Y ¹ represents a group capable of forming a divalent anion such as CO ₃ .

  Examples of such quaternary phosphonium salts include tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide. Tetra (aryl or alkyl) phosphonium hydroxides such as tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate , Methyltriphenylphosphonium tetraphenyl volley , Benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra (pt-butylphenyl) phosphonium diphenylphosphate, triphenylbutylphosphonium phenolate, And triphenylbutylphosphonium tetraphenylborate.

Among these quaternary phosphonium salts, phosphonium salts having an alkyl group, specifically, tetramethylphosphonium methyltriphenyl are preferred because they have high catalytic activity, are easily thermally decomposed, and do not easily remain in the polymer. Borate, tetraethylphosphonium ethyltriphenylborate, tetrapropylphosphoniumpropyltriphenylborate, tetrabutylphosphoniumbutyltriphenylborate, tetrabutylphosphoniumtetraphenylborate, tetraethylphosphoniumtetraphenylborate, trimethylethylphosphoniumtrimethylphenylborate, trimethylbenzylphosphoniumbenzyltri Phenyl borate and the like are preferred.
In addition, tetraalkylphosphonium salts such as tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, and tetrabutylphosphonium hydroxide have a relatively low decomposition temperature, so that they are easily decomposed and are less likely to remain as impurities in the product polycarbonate. In addition, since the number of carbon atoms is small, the basic unit in the production of polycarbonate can be reduced, which is advantageous in terms of cost.
In addition to the compound represented by the general formula (X) or (XI), for example, a bis-tetraphenylphosphonium salt of 2,2-bis (4-hydroxyphenyl) propane, ethylenebis (triphenylphosphonium) dibromide, There may also be mentioned trimethylene bis (triphenylphosphonium) -bis (tetraphenylborate).
Furthermore, a quaternary phosphonium salt having an aryl group and / or a branched alkyl group can also be used. For example,
General formula (XI)
^{_{(R 13 n PR 14 4-}} n) + (X 2) - ···· (XII)
Or general formula (XII)
^{_{(R 13 n PR 14 4-}} n) + 2 (Y 1) 2- ··· (XIII)
The compound represented by these is used.
In the general formula (XII) or (XIII), n is an integer of 1 to 4.
R ¹³ represents at least one selected from an aryl group or a branched alkyl group. The branched alkyl group has a structure of “R ₃ C—”, where R is selected from hydrogen, an alkyl group, an alkyl group having a substituent, an aryl group, and an aryl group having a substituent. At least one, and at least two of the three Rs may be bonded to form a ring structure. However, it excludes when two are hydrogen simultaneously. Examples thereof include branched alkyl groups such as a cycloalkyl group, isopropyl group, and tert-butyl group, and arylalkyl groups such as a benzyl group. When n is 2 or more, R may be the same or different.
R ¹⁴ is an alkyl group, an alkyl group having a substituent, an aryl group, or an aryl group having a substituent.
X ² : Monovalent anion such as halogen atom, hydroxyl group, alkyloxy group, aryloxy group, R′COO, HCO ₃ , (R′O) ₂ P (═O) O or BR ″ ₄ can be formed. Indicates a group. Here, R ′ represents a hydrocarbon group such as an alkyl group or an aryl group, and two R′O may be the same or different. R ″ represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group, and the four R ″ may be the same or different.
Y ¹ represents a group capable of forming a divalent anion such as CO ₃ .

  Examples of such quaternary phosphonium salts include tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide, tetratolylphosphonium hydroxide, tetrahexylphosphonium hydroxide. Tetra (aryl or alkyl) phosphonium hydroxides, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, propyltriphenylphosphonium hydroxide, butyltriphenylphosphonium hydroxide, octyltriphenylphosphonium hydroxide, tetradecyl Triphenylphosphonium hydroxide, benzyltriphenylphosphonium Droxide, ethoxybenzyltriphenylphosphonium hydroxide, methoxymethyltriphenylphosphonium hydroxide, acetoxymethyltriphenylphosphonium hydroxide, phenacyltriphenylphosphonium hydroxide, chloromethyltriphenylphosphonium hydroxide, bromomethyltriphenylphosphonium hydroxide, Biphenyltriphenylphosphonium hydroxide, naphthyltriphenylphosphonium hydroxide, chlorophenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, acetoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphos Mono (aryl) such as mono (aryl or alkyl) triphenylphosphonium hydroxide, phenyltrimethylphosphonium hydroxide, biphenyltrimethylphosphonium hydroxide, phenyltrihexylphosphonium hydroxide, biphenyltrihexylphosphonium hydroxide such as nium hydroxide Diaryl dialkylphosphonium hydroxides such as trialkylphosphonium hydroxide, dimethyldiphenylphosphonium hydroxide, diethyldiphenylphosphonium hydroxide, di (biphenyl) diphenylphosphonium hydroxide, tetraphenylphosphonium tetraphenylborate, tetranaphthylphosphonium tetraphenyl Borate, tetra (chlorophenyl) phospho Tetraarylphosphonium tetraphenylborates such as nium tetraphenylborate, tetra (biphenyl) phosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, ethyltriphenylphosphonium tetraphenylborate, propyltriphenylphosphonium Tetraphenylborate, butyltriphenylphosphonium tetraphenylborate, octyltriphenylphosphonium tetraphenylborate, tetradecyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, ethoxybenzyltriphenylphosphonium tetraphenylborate, methoxymethyltrife Ruphosphonium tetraphenylborate, acetoxymethyltriphenylphosphonium tetraphenylborate, phenacyltriphenylphosphonium tetraphenylborate, chloromethyltriphenylphosphonium tetraphenylborate, bromomethyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, Mono (a) such as naphthyltriphenylphosphonium tetraphenylborate, chlorophenyltriphenylphosphonium tetraphenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate, acetoxyphenyltriphenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate Or aryl) triphenylphosphonium tetraphenylborate, phenyltrimethylphosphonium tetraphenylborate, biphenyltrimethylphosphonium tetraphenylborate, phenyltrihexylphosphonium tetraphenylborate, biphenyltrihexylphosphonium tetraphenylborate, monoaryltrialkylphosphonium tetra Examples thereof include diaryldialkylphosphonium tetraphenyl borates such as phenyl borates, dimethyldiphenylphosphonium tetraphenylborate, diethyldiphenylphosphonium tetraphenylborate, and di (biphenyl) diphenylphosphonium tetraphenylborate.

Furthermore, as a counter anion, instead of the above hydroxide and tetraphenylborate, an aryloxy group such as phenoxide, an alkyloxy group such as methoxide and ethoxide, an alkylcarbonyloxy group such as acetate, and an arylcarbonyloxy group such as benzonate And the above-mentioned quaternary phosphonium salts using halogen atoms such as chloride and bromide.
In addition to the compound represented by the general formula (XII), those having a divalent counter anion represented by the general formula (XIII), such as bis (tetraphenylphosphonium) carbonate, bis (biphenyltriphenyl) Quaternary phosphonium salts such as phosphonium) carbonate, and further, for example, bis-tetraphenylphosphonium salt of 2,2-bis (4-hydroxyphenyl) propane, ethylenebis (triphenylphosphonium) dibromide, trimethylenebis (triphenylphosphonium) ) -Bis (tetraphenylborate) and the like.

Furthermore, a compound represented by the general formula (XIV) or (XV) is also used.
((R ¹⁵ -Ph) _n -PPh _(4-n) ) ⁺ (X ³ ) ^- (XIV)
_{^{((R 15 -Ph) n -PPh}} (4-n)) 2 + (Y 2) 2- ··· (XV)
[Wherein, R ¹⁵ represents an organic group, and may be the same or different, and X ³ represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ Or BR ₄ (R represents a hydrogen atom or a hydrocarbon group, and four Rs may be the same or different from each other), Ph represents a phenyl group,
Y ² represents CO ₃ , and n represents an integer of 1 to 4. ]
Specific examples of such quaternary phosphonium compounds include, for example, tetraphenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, and naphthylphenyltriphenylphosphonium hydroxide. , Tetraphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, methoxyphenyltriphenylphosphonium tetraphenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium phenoxide, biphenyltrif Nylphosphonium phenoxide, methoxyphenyltriphenylphosphonium phenoxide, phenoxyphenyltriphenylphosphonium phenoxide, naphthylphenyltriphenylphosphonium phenoxide, tetraphenylphosphonium chloride, biphenyltriphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride or Examples thereof include naphthylphenyltriphenylphosphonium chloride. Of these quaternary phosphonium salts, tetraphenylphosphonium tetraphenylborate is preferably used in view of the balance between the catalytic effect and the quality of the obtained polycarbonate.

  Specific examples of the quaternary phosphonium salt containing a branched alkyl group include isopropyltrimethylphosphonium; isopropyltriethylphosphonium; isopropyltributylphosphonium; isopropyltriphenylphosphonium; tetraisopropylphosphonium; cyclohexyltriethylphosphonium; cyclohexyltributylphosphonium; cyclohexyltributylphosphonium; cyclohexyl. Tetraphenylphosphonium; 1,1,1-triphenylmethyltrimethylphosphonium; 1,1,1-triphenylmethyltriethylphosphonium; 1,1,1-triphenylmethyltributylphosphonium; 1,1,1- And triphenylmethyltriphenylphosphonium.

Specific examples of X ³ related to the counter anion include hydroxide; borohydride; tetraphenylborate; acetate; propionate; fluoride; chloride; Specific examples of Y ² include carbonate. Specific examples of the salt composed of a quaternary phosphonium (cation) containing a branched alkyl group and X or Y (anion) can include various salts from combinations of the above-mentioned various examples. Isopropyltrimethylphosphonium hydroxide Cyclohexyl triphenylphosphonium chloride; 1,1,1-triphenylmethyltriethylphosphonium acetate; bis (isopropyltriethylphosphonium) carbonate and the like.

  Among these quaternary phosphonium salts containing a branched alkyl group, cyclohexyl triphenylphosphonium tetraphenylborate or cyclopentyltriphenylphosphonium tetraphenylborate is particularly preferably used because of its excellent balance between the catalytic effect and the quality of the polycarbonate obtained. . Furthermore, tetramethylphosphonium acetate, tetraethylphosphonium acetate, tetrapropylphosphonium acetate, tetrabutylphosphonium acetate, tetrapentylphosphonium acetate, tetrahexylphosphonium acetate, tetraheptylphosphonium acetate, tetraoctylphosphonium acetate, tetradecylphosphonium acetate, tetradodecylphosphonium Acetate, tetratolylphosphonium acetate, tetraphenylphosphonium acetate, tetramethylphosphonium benzoate, tetraethylphosphonium benzoate, tetrapropylphosphonium benzoate, tetraphenylphosphonium benzoate, tetramethylphosphonium formate, tetraethylphospho Um formate, tetrapropylphosphonium formate, tetraphenylphosphonium formate, tetramethylphosphonium propionate, tetraethylphosphonium propionate, tetrapropylphosphonium propionate, tetramethylphosphonium butyrate, tetraethylphosphonium butyrate, tetrapropylphosphonium butyrate Carboxylic acid salts such as

These quaternary phosphonium salts are preferably those having as little metal impurity content as possible, and those having an alkali metal and alkaline earth metal compound content of 50 ppm or less are particularly preferred. The quaternary phosphonium salt is preferably used in an amount of 10.sup.- ² to 10.sup.- ⁸ mol with respect to 1 mol of the dihydroxy compound (A) as a raw material. When the amount of the quaternary phosphonium salt used is less than 10 ⁻⁸ mol, the catalytic activity in the latter stage of the reaction becomes insufficient, and when it exceeds 10 ⁻² mol, the cost increases, which is not preferable.

II) Polymerization in Solid State The above-described solid prepolymer in a crystallized state is further subjected to a polymerization reaction using a quaternary phosphonium salt as a catalyst. In this case, the reaction is promoted by extracting the aromatic monohydroxy compound, diaryl carbonate or both produced as a by-product from the reaction. For that purpose, by introducing inert gas such as nitrogen, argon, helium, carbon dioxide, hydrocarbon gas or poor solvent vapor, etc., a method of removing these gases accompanying them, a method of performing a reaction under reduced pressure Or a method using these in combination is preferably used. In addition, when introducing the accompanying gas, it is desirable to heat these gases to a temperature close to the reaction temperature.

  As the poor solvent, the solubility of polycarbonate in the solvent under the following reaction conditions is 0.1% by weight or less, and the saturated carbonization having 4 to 18 carbon atoms having a linear or branched chain that is less likely to participate in the reaction. A hydrogen compound or an unsaturated hydrocarbon compound having 4 to 18 carbon atoms and a low degree is preferred. If the boiling point exceeds 250 ° C., it is difficult to remove the residual solvent, and the quality may be deteriorated. There are no particular restrictions on the shape of the crystallization prepolymer when this solid phase polymerization reaction is carried out, but a shape such as a pellet shape or a bead shape is preferred.

As the reaction catalyst in this solid-phase polymerization, preferably a quaternary phosphonium salt and other catalysts are used as required, but it is added in the prepolymer production process, and the remaining catalyst can be used as it is. Alternatively, the catalyst may be added again in a powder, liquid or gas state. Regarding the reaction temperature Tp (° C.) and the reaction time when this solid-state polymerization reaction is carried out, the type (chemical structure, molecular weight, etc.) and shape of the crystallization prepolymer, the presence / absence of the catalyst in the crystallization prepolymer, the type or Amount, type or amount of catalyst added as necessary, difference in crystallization prepolymer crystallization degree or melting temperature Tm ′ (° C.), desired degree of polymerization of aromatic polycarbonate, or other Although it depends on the reaction conditions, etc., it is preferably a temperature within the range of the glass transition temperature of the target aromatic polycarbonate and in a range where the crystallization prepolymer during solid phase polymerization does not melt and remains in a solid state, more preferably the formula Tm “−50 ≦ Tp <Tm” (XVI)
Is heated for about 1 minute to 100 hours, more preferably about 0.1 to 50 hours, to carry out the solid phase polymerization reaction.

  As such a temperature range, when manufacturing the polycarbonate of bisphenol A, for example, about 150-260 degreeC is preferable, and about 180-245 degreeC is especially preferable. In addition, in the polymerization step, stirring is performed, the reactor itself is rotated, or it is fluidized by a heated gas in order to give heat to the polymer during polymerization as uniformly as possible, or to advantageously extract by-products. A method or the like is preferably used.

  Generally, the industrially useful aromatic polycarbonate has a weight average molecular weight of about 6000 to 200,000. By carrying out the solid phase polymerization step, a polycarbonate having such a polymerization degree can be easily obtained. Since the crystallinity of the aromatic polycarbonate obtained by solid-phase polymerization of the crystallized prepolymer is usually higher than the crystallinity of the original prepolymer, the method of the present invention usually employs a crystalline aroma. Group polycarbonate powder is obtained. The crystalline aromatic polycarbonate powder can be directly introduced into an extruder and pelletized without cooling, or can be directly introduced into a molding machine and molded without cooling. The ratio between the prepolymerization contributing to the polymerization and the solid phase polymerization may be varied within a wide range.

III) Polymerization in a swollen solid phase state This is a method in which the prepolymer obtained in the prepolymerization step is crystallized and then further polymerized by solid phase polymerization in a swollen state with a swelling gas described later. This production method is a method for producing a polycarbonate by transesterification, and in the case where a low-molecular compound such as phenol produced as a by-product is delustered or extracted and removed, from a polymer (prepolymer) in a swollen state by a swelling gas, It is applied to the fact that the desorption or extraction removal of low molecular weight compounds has a higher mass transfer rate and can react with higher efficiency than the desorption or extraction removal from high viscosity molten polymer or crystallized solid. .

  The above method is divided into a flaking step of the prepolymer obtained as described above, and a high molecular weight increasing step (swelling solid phase polymerization step) in which the high molecular weight is increased by a solid phase polymerization method under the flow of a swelling solvent. The molecular weight of the prepolymer suitable for the flaking process is 1500-30000 in terms of viscosity average molecular weight (Mv). If the molecular weight is lower than this range, the melting point is lowered, the solid phase polymerization temperature needs to be lowered, and the reaction rate is lowered, which is not preferable.

  In the flaking process, conventionally known methods such as rolling granulation method, extrusion granulation method, compression granulation method, melt granulation method, spray drying granulation method, fluidized bed granulation method, crushing granulation A method, a stirring granulation method, a liquid phase granulation method, a vacuum freeze granulation method, or the like can be used according to circumstances. The shape of the flakes is not particularly limited, but pellets, beads and the like are preferable from the viewpoint of operability. Also effective is a stirring granulation method in which a prepolymer is once dissolved in a swelling solvent used in the next step, and then mixed with a poor solvent for polycarbonate to form flakes. In the polymerization, it is not particularly necessary to dry the flakes.

  The swelling solvent used here is a single swelling solvent that can swell polycarbonate under the reaction conditions shown below, a mixture of these single swelling solvents, or a single swelling solvent or a mixture thereof. It shows what was mixed as one or several kinds of mixtures. The swollen state in this step refers to a state in which the prepolymer flakes which are reaction raw materials are increased in volume or weight above the thermal swelling value within the range of reaction conditions shown below, and the swelling solvent is the following reaction A single compound or a mixture thereof having a boiling point that completely evaporates within a range of conditions, or a vapor pressure of usually 50 mmHg or more, and capable of forming the above swelling state at the same time.

Such a swelling solvent is not particularly limited as long as it satisfies the above swelling conditions. For example, an aromatic compound or an oxygen-containing compound usually having a solubility parameter in the range of 4 to 20 (cal / cm ³ ) ^1/2 , preferably in the range of 7 to 14 (cal / cm ³ ) ^1/2 is applicable. Specific swelling solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, and dipropylbenzene; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone. Is mentioned. Among these, a single compound of aromatic hydrocarbon having 6 to 20 carbon atoms or a mixture thereof is preferable.

  Moreover, as a condition of the poor solvent mixed with the swelling solvent, the solubility of polycarbonate in the solvent is 0.1% by weight or less under the following reaction conditions, and it has a linear or branched chain that is less likely to participate in the reaction. A saturated hydrocarbon compound having 4 to 18 carbon atoms or an unsaturated hydrocarbon compound having 4 to 18 carbon atoms and a low degree is preferable. If the boiling point of both the swelling solvent and the poor solvent exceeds 250 ° C., it is difficult to remove the residual solvent, and the quality may be deteriorated.

When such a poor solvent and a swelling solvent are mixed and used, the mixed solvent may contain 1% by weight or more of the swelling solvent, and preferably 5% by weight or more of the swelling solvent is contained in the mixed solvent. To exist. In this swelling solid phase polymerization step, the reaction temperature is preferably 100 to 240 ° C., and the pressure during the reaction is preferably 10 Torr to 5 kg / cm ² G, particularly preferably atmospheric pressure. If the reaction temperature is lower than the above range, the transesterification reaction does not proceed, and under high temperature conditions where the reaction temperature exceeds the melting point of the prepolymer, the solid phase state cannot be maintained, causing phenomena such as fusion between particles, resulting in operation operation. Remarkably deteriorates. Therefore, the reaction temperature needs to be lower than the melting point.

As a reaction catalyst in this swelling solid phase polymerization step, a quaternary phosphonium salt and other catalysts are also used as necessary. Alternatively, the catalyst may be added again in a powder, liquid or gas state. The swelling solvent gas may be supplied to the reactor in a liquid state and vaporized in the reactor, or may be vaporized in advance by a heat exchanger or the like and then supplied to the reactor. Velocity of the swelling solvent gas may be any 1 × 10 ^-3 cm / s or more, preferably at least 1 × 10 ^-3 cm / s. Further, as the gas supply amount, it is preferable to supply 0.5 liter (standard state) / hr or more of gas per 1 g of the prepolymer to the reactor. The flow rate of the swelling solvent gas is closely related to the reaction rate and acts as a heat medium at the same time as the phenol removal effect, so that the reaction rate improves as the gas flow rate increases. There is no particular limitation on the reactor used for such swelling solid phase polymerization.

  Conventional methods can be used for drying and pelletizing the high molecular weight polycarbonate, and there is no particular limitation. When mixing the additive, it is preferable to apply the additive powder directly to the flakes before or after drying, or to spray the liquid and absorb the gas, but it can also be mixed with an extruder at the time of pelletization . The mixing ratio of the inert gas and the swelling solvent may be such that the mixed solvent gas contains 1% by volume or more of the swelling solvent, but preferably 5% by volume or more of the swelling solvent is mixed in the mixed solvent. What you let me do is good.

IV) Oxygen concentration and water concentration in the gas phase in the polymerization system In the present invention, the oxygen concentration in the gas phase in the reaction system in which the polymerization is performed needs to be 2 ppm or less. Preferably it is 1 ppm or less, and more preferably 0.5 ppm or less. The water concentration in the reaction system is also preferably 2 ppm or less, more preferably 1 ppm or less. If the oxygen concentration in the reaction system in which the polymerization is carried out exceeds 2 ppm, the resulting resin is likely to be colored, resulting in poor thermal stability. Also, if the water concentration in the reaction system exceeds 2 ppm, hydrolysis may occur during the reaction, which is not preferable in terms of adverse effects such as a decrease in catalyst activity.

  The method for reducing the oxygen concentration in the reaction system to 2 ppm or less, and further the water concentration to 2 ppm or less is not particularly limited. For example, an oxygen removal pipe incorporating an oxygen filter or the like before the polymerization vessel inlet, a moisture filter, or the like. What is necessary is just to provide the moisture removal pipe | tube which incorporated.

V) Polymerization in the state of thin film melting The above-mentioned polycarbonate prepolymer is put into a main polymerization apparatus having heating / depressurization / liquid film forming means, and is melted to form a thin liquid film while operating the depressurization means. The molecular weight can be increased. This method is called a thin film polymerization method. In order to further promote the transesterification reaction required for increasing the molecular weight, the film thickness of a prepolymer in a molten state is usually increased in the presence of a catalyst such as the quaternary phosphonium salt described above. A thin film state of 5 mm or less, preferably 3 mm or less, more preferably 1 mm or less, reaction temperature 50 to 320 ° C., preferably 100 to 320 ° C., more preferably 150 to 280 ° C., reaction pressure 0.1 Torr to 5 kg / The reaction can be performed under the conditions of cm ² G, reaction time of 1 minute to 100 hours, preferably 2 to 20 hours.

  The means for forming the thin liquid film is not particularly limited. For example, the liquid obtained by dissolving the prepolymer using the solvent described in the above-mentioned I) prepolymerization method is applied to the bottom surface of a reactor having a large area. The film can be spread and heated to evaporate to form a thin film. This thin film polymerization method belongs to a class of special methods among the already known melt transesterification methods, and its aim is to promote the reaction by promoting the degassing of phenol, as well as desorbed phenol. The present invention intends to achieve the impurity reduction of the present invention by preventing the polymer cleavage reaction due to.

In the polycarbonate according to the present invention, known additives such as plasticizers, pigments, lubricants, mold release agents, stabilizers, inorganic fillers and the like can be blended and used. The polycarbonate can be blended with a polymer such as polyolefin, polystyrene, polyester, polysulfonate, polyamide, polyphenylene ether or the like. In particular, it is effective when used in combination with polyphenylene ether, polyether nitrile, terminal-modified polysiloxane compound, modified polypropylene, modified polystyrene, etc. having an OH group, COOH group, NH ₂ group or the like at its terminal.

3. Optical material made of polycarbonate and the like Since the polycarbonate according to the present invention has a reduced residual monomer content, it is extremely useful as an optical material without causing burning during molding, a decrease in molecular weight, and a decrease in physical properties.
Also, in the present invention, if necessary, polycarbonate using cumylphenol or other terminal terminator was difficult to incorporate at the end of the polycarbonate molecule by the melting method, but solid phase polymerization or swelling solid phase polymerization of the present invention. Then, in addition to the above-mentioned improvements, the physical properties such as low-temperature impact resistance have been improved and it is useful for optical materials.
Furthermore, the polycarbonate using a branching agent as required in the present invention is useful for blow molding because of improved physical properties such as melt tension as already known, in addition to the above-mentioned improvements.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited by these examples.
[Example 1]
In an autoclave made of nickel steel with a stirrer having an internal volume of 1 liter, 228 g (1.0 mol) of bisphenol A (BPA), 246 g (1.15 mol) of diphenyl carbonate (DPC), tetramethylammonium hydroxide (TMAH) (0. 5 mmol) was added, and argon substitution was performed 5 times. Thereafter, the mixture was heated to 190 ° C. and reacted for 30 minutes under an argon atmosphere. Next, the temperature was gradually raised to 235 ° C., and at the same time, the degree of vacuum was raised to 60 mmHg and reacted for 60 minutes. The temperature was gradually raised to 270 ° C. and the degree of vacuum was raised to 10 mmHg and reacted for 120 minutes. . Next, with the temperature kept at 270 ° C., the degree of vacuum was raised to 1 mmHg and reacted for 30 minutes, and then the degree of vacuum was raised to 0.5 mmHg and reacted for another 30 minutes. After completion of the reaction, the inside of the reactor was returned to atmospheric pressure with argon, and the prepolymer as the contents was taken out and pulverized.
The prepolymer had a viscosity average molecular weight of 7,200 and a terminal fraction of hydroxyl terminal was 30%. ^10-5 mol of cyclohexyl triphenylphosphonium tetraphenylborate (HPTB) (HPTB) as a prepolymer and a catalyst thus obtained was dissolved in methylene chloride, and n-heptane was added to precipitate a powder. After concentration to dryness, A prepolymer powder was obtained by vacuum drying. 9 g of this powder is put into a SUS tube having a diameter of 10 mm and a length of 200 mm, nitrogen gas is allowed to flow at a rate of 100 ml / min, the temperature is raised from room temperature to 240 ° C., and solid phase polymerization is performed for 4 hours to obtain a polycarbonate. It was. The results are shown in Table 1.

[Example 2]
In Example 1, it carried out like Example 1 except having made heptane gas the gas seed | species flowed at the time of solid-phase polymerization. The results are shown in Table 1.

Example 3
8.04 g of the prepolymer synthesized in Example 1 was placed on a petri dish made of SUS having a diameter of 32 cm, 10 ml of methylene chloride was added, and tetraphenylphosphonium tetraphenylborate (TPTB) 10 ⁻⁵ was used as the prepolymer and catalyst on the petri dish. Mol was dissolved. Thereafter, methylene chloride was evaporated to prepare a thin film having a thickness of 0.1 cm. Next, it was melt polymerized at 270 ° C. and 0.1 mmHg for 4 hours in a vacuum oven equipped with a hot plate to obtain a polycarbonate. The results are shown in Table 1.

[Comparative Example 1]
By changing the amount of charged DPC to 236 g (1.1 mol), etc., the terminal fraction of the hydroxyl group terminal of the prepolymer is made 50%, and the catalyst at the time of solid phase polymerization is tetraphenylphosphonium tetraphenylborate (TPTB). to 10 ^-5 mol, the polymerization time was replaced with 0.5 hours was carried out in the same manner as in example 1. The results are shown in Table 1.

[Comparative Example 2]
The same procedure as in Example 1 was conducted except that the terminal fraction of the hydroxyl group terminal of the prepolymer was changed to 61% by changing the amount of charged DPC to 236 g (1.1 mol). The results are shown in Table 1.

[Comparative Example 3]
The same procedure as in Example 1 was performed except that the catalyst was not used during the solid phase polymerization and the polymerization time was 93 hours. The results are shown in Table 1.

[Comparative Example 4]
Solid phase polymerization was not performed, but tetramethylammonium hydroxide (0.5 mmol) and tetraphenylphosphonium tetraphenylborate (0.01 mmol) were added as catalysts, and the polymerization time at a vacuum of 1 mmHg was set to 3 hours. The same operation as in Example 1 was performed. The results are shown in Table 1.

Example 4
In a nickel autoclave with a stirrer with an internal volume of 1 liter, 228 g (1.0 mol) of bisphenol A (BPA), 1.23 g of 1,1,1-tris (4-hydroxyphenylethane) (THPE) (0.004 mol) ), 257 g (1.2 mol) of diphenyl carbonate (DPC) and tetramethylammonium hydroxide (0.5 mmol) were added, and argon substitution was performed 5 times. Thereafter, the mixture was heated to 190 ° C. and reacted for 30 minutes under an argon atmosphere. Next, the temperature was gradually raised to 235 ° C., and at the same time, the degree of vacuum was raised to 60 mmHg and reacted for 60 minutes. The temperature was gradually raised to 270 ° C. and the degree of vacuum was raised to 10 mmHg and reacted for 120 minutes. . Next, with the temperature kept at 270 ° C., the degree of vacuum was raised to 1 mmHg and reacted for 30 minutes, and then the degree of vacuum was raised to 0.5 mmHg and reacted for another 30 minutes. After completion of the reaction, the inside of the reactor was returned to atmospheric pressure with argon, and the prepolymer as the contents was taken out and pulverized. The prepolymer had a viscosity average molecular weight of 10,900 and a hydroxyl group terminal fraction of 30%. As a prepolymer and a solid phase polymerization catalyst thus obtained, 0.0066 g (1 × 10 ⁻⁵ mol / BPA unit) of cyclohexyl triphenylphosphonium tetraphenylborate (HPTB) was dissolved in methylene chloride. Heptane was added to precipitate a powder, which was concentrated to dryness and then vacuum dried to obtain a prepolymer powder. 20 g of this powder is put into a SUS tube having a diameter of 58 mm and a length of 170 mm, nitrogen gas is allowed to flow at a rate of 100 ml / min, the temperature is raised from room temperature to 240 ° C., and solid phase polymerization is carried out for 4 hours to obtain a polycarbonate. It was. The results are shown in Table 2.

Example 5
In Example 4, it carried out like Example 4 except having made heptane gas the gas seed | species flowed at the time of solid-phase polymerization. The results are shown in Table 1.

[Comparative Example 5]
Without solid-phase polymerization, tetramethylammonium hydroxide (TMAH) (0.5 mmol) and tetraphenylphosphonium tetraphenylborate (TPTB) (0.01 mmol) were added as catalysts and polymerization was performed at a vacuum of 0.5 mmHg. The same operation as in Example 4 was performed except that the time was changed to 3 hours. The results are shown in Table 1.

Example 6
In a nickel autoclave with a stirrer having an internal volume of 1 liter, 228 g (1.0 mol) of bisphenol A (BPA), 10.6 g (0.05 mol) of p-cumylphenol, tetramethylammonium hydroxide (TMAH) (0 .5 mmol) was added, and argon substitution was performed 5 times. Thereafter, the mixture was heated to 190 ° C. and reacted for 30 minutes under an argon atmosphere. Next, the temperature is gradually raised to 235 ° C., and at the same time the vacuum is raised to 60 mmHg and reacted for 60 minutes, and the temperature is gradually raised to 270 ° C. and the vacuum is raised to 10 mmHg and reacted for 120 minutes. It was. Next, with the temperature kept at 270 ° C., the degree of vacuum was raised to 1 mmHg and reacted for 30 minutes, and then the degree of vacuum was raised to 0.5 mmHg and further reacted for 30 minutes. After completion of the reaction, the inside of the reactor was returned to atmospheric pressure with argon, and the prepolymer as the contents was taken out and pulverized. The viscosity average molecular weight of this prepolymer was 8600, and the terminal fraction of the hydroxyl terminal was 33%. 0.0066 g (1 × 10 ⁻⁵ mol / BPA unit) of cyclohexyl triphenylphosphonium tetraphenylborate (HPTB) as a prepolymer and a catalyst for solid phase polymerization thus obtained were dissolved in methylene chloride, and n-heptane was used. Was added to precipitate a powder, which was concentrated to dryness and then vacuum dried to obtain a prepolymer powder. 20 g of this powder is put into a SUS tube having a diameter of 58 mm and a length of 170 mm, nitrogen gas is allowed to flow at a rate of 100 ml / min, the temperature is raised from room temperature to 240 ° C., and solid phase polymerization is carried out for 4 hours to obtain a polycarbonate. It was. The results are shown in Table 3.

Example 7
In Example 6, it carried out like Example 6 except having made heptane gas the gas seed | species flowed at the time of solid-phase polymerization. The results are shown in Table 3.

Example 8
The same procedure as in Example 6 was performed except that p-cumylphenol was replaced with p-tertbutylphenol. The results are shown in Table 3.

Example 9
The same procedure as in Example 6 was performed except that p-cumylphenol was replaced with p-tert octylphenol. The results are shown in Table 3.

[Comparative Example 6]
Without solid-phase polymerization, tetramethylammonium hydroxide (TMAH) (0.5 mmol) and tetraphenylphosphonium tetraphenylborate (TPTB) (0.01 mmol) were added as catalysts and polymerization was performed at a vacuum of 0.5 mmHg. The same operation as in Example 6 was performed except that the time was changed to 3 hours. The results are shown in Table 3.

Example 10
In an autoclave made of nickel steel with a stirrer having an internal volume of 1 liter, 228 g (1.0 mol) of bisphenol A (BPA), 246 g (1.15 mol) of diphenyl carbonate (DPC), 0.5 mol of tetramethylammonium hydroxide (TMAH) Molar and tetraphenylphosphonium tetraphenylborate (TPTB) 1 × 10 ⁻⁵ mol were added, and argon substitution was performed 5 times. Thereafter, the mixture was heated to 190 ° C. and reacted for 30 minutes under an argon atmosphere. Next, the temperature was gradually raised to 235 ° C., and at the same time, the degree of vacuum was raised to 60 mmHg and reacted for 60 minutes. The temperature was gradually raised to 270 ° C. and the degree of vacuum was raised to 10 mmHg and reacted for 120 minutes. . Next, with the temperature kept at 270 ° C., the degree of vacuum was raised to 1 mmHg and reacted for 30 minutes, and then the degree of vacuum was raised to 0.5 mmHg and further reacted for 30 minutes. After completion of the reaction, the inside of the reactor was returned to atmospheric pressure with argon, and the prepolymer as the contents was taken out and pulverized. The prepolymer had a viscosity average molecular weight of 7,200 and a terminal fraction of hydroxyl terminal was 30%. 8.04 g of the obtained prepolymer was placed on a petri dish made of SUS having a diameter of 32 cm, and 10 ml of methylene chloride was added to dissolve the prepolymer on the petri dish. Thereafter, methylene chloride was evaporated to prepare a thin film having a thickness of 0.01 mm, and vacuum dried at 120 ° C. overnight. Next, it was melt-polymerized at 270 ° C. and 0.1 mmHg for 4 hours in a vacuum oven equipped with a hot plate to obtain a polycarbonate. The results are shown in Table 4.

Example 11
In Example 10, it carried out like Example 10 except having changed the time which melt-polymerizes with a thin film from 4 hours to 1 hour. The results are shown in Table 4.

[Comparative Example 7]
In an autoclave made of nickel steel with a stirrer having an internal volume of 1 liter, 228 g (1.0 mol) of bisphenol A (BPA), 246 g (1.15 mol) of diphenyl carbonate (DPC), 0.5 mol of tetramethylammonium hydroxide (TMAH) Molar and tetraphenylphosphonium tetraphenylborate (TPTB) 1 × 10 ⁻⁵ mol were added, and argon substitution was performed 5 times. Thereafter, the mixture was heated to 190 ° C. and reacted for 30 minutes under an argon atmosphere. Next, the temperature was gradually raised to 235 ° C., and at the same time, the degree of vacuum was raised to 60 mmHg and reacted for 60 minutes. The temperature was gradually raised to 270 ° C. and the degree of vacuum was raised to 10 mmHg and reacted for 120 minutes. . Next, with the temperature kept at 270 ° C., the degree of vacuum was raised to 1 mmHg and reacted for 30 minutes, and then the degree of vacuum was raised to 0.5 mmHg and further reacted for 3 hours. After completion of the reaction, the inside of the reactor was returned to atmospheric pressure with argon, and the content polycarbonate was taken out. The prepolymer had a viscosity average molecular weight of 7,200 and a terminal fraction of hydroxyl terminal was 30%. The results are shown in Table 4.

Claims (13)

  A polycarbonate obtained by a transesterification reaction between a dihydroxy compound and a carbonic acid diester, wherein the acetone-soluble content in the produced polycarbonate is 2.0% by weight or less.   A polycarbonate obtained by pre-polymerizing a polycarbonate prepolymer and then polymerizing the prepolymer by a transesterification reaction in a thin film melt state, wherein the content of acetone-soluble component in the resulting polycarbonate is 3.0% by weight or less Polycarbonate.   A polycarbonate obtained by pre-polymerizing a polycarbonate prepolymer and then polymerizing the prepolymer by a transesterification reaction in a solid phase state or a swollen solid phase state, wherein the content of acetone-soluble component in the resulting polycarbonate is 3 Polycarbonate that is 5% by weight or less.   A polycarbonate prepolymer prepared by prepolymerization, and then obtained by polymerizing the prepolymer in a solid phase state or a swollen solid phase state by a transesterification reaction, wherein the hydroxyl group terminal fraction in the resulting polycarbonate is 2 Polycarbonate that is less than mol%.   A polycarbonate obtained by preparing a polycarbonate prepolymer by prepolymerization and then polymerizing the prepolymer by a transesterification reaction in a thin film melt state, wherein the hydroxyl group terminal fraction in the resulting polycarbonate is less than 15 mol%. Polycarbonate.   A polycarbonate obtained by preparing a polycarbonate prepolymer by prepolymerization and then polymerizing the prepolymer by a transesterification reaction in a solid phase state, a swollen solid phase state or a thin film molten state, and a cyclic oligomer in the resulting polycarbonate Polycarbonate having a content of 0.45% by weight or less.   The polycarbonate according to claim 3 or 6, wherein a polycarbonate prepolymer is prepared by heating and prepolymerizing (A) an aromatic dihydroxy compound, (B) a carbonic acid diester, and (C) a monovalent hydroxy compound.   (A) A polycarbonate prepolymer is prepared by heating and prepolymerizing an aromatic dihydroxy compound, (B) carbonic acid diester, and (C) a monovalent hydroxy compound, and then the prepolymer is in a solid phase state or a swollen solid phase state. A polycarbonate obtained by polymerizing by a transesterification reaction in which the terminal fraction derived from the monovalent hydroxy compound in the resulting polycarbonate is 50 mol% or more.   (A) A polycarbonate prepolymer is prepared by heating and prepolymerizing an aromatic dihydroxy compound, (B) carbonic acid diester, and (C) a monovalent hydroxy compound, and then the prepolymer is in a solid phase state or a swollen solid phase state. A polycarbonate obtained by polymerizing by a transesterification reaction in which the hydroxyl group terminal fraction in the resulting polycarbonate is less than 15 mol%.   An optical material comprising the polycarbonate according to claim 1.   7. A polycarbonate prepolymer prepared by heating (A) an aromatic dihydroxy compound, (B) a carbonic acid diester, and (C) a polyfunctional organic compound having three or more functional groups to prepare a prepolymer. Polycarbonate.   After preparing a polycarbonate prepolymer by heating (A) an aromatic dihydroxy compound, (B) a carbonic acid diester, and (C) a polyfunctional organic compound having three or more functional groups, the prepolymer A polycarbonate obtained by polymerizing a polymer in a solid phase state or a swollen solid phase state by a transesterification reaction, wherein the hydroxyl group terminal fraction in the resulting polycarbonate is less than 15 mol%.   A blow molding material comprising the polycarbonate according to claim 11 or 12.