JPH08113638A - Production of aromatic polycarbonate - Google Patents

Abstract

PURPOSE: To enable the production of an arom. polycarbonate which is reduced in the amt. of unreacted 6,6'-dihydroxy-3,3,3',3'-tetramethylspirobiindane. CONSTITUTION: In producing an arom. polycarbonate by the interfacial polymn. of 6,6'-dihydroxy-3,3,3',3'-tetramethylspirobiindane, a hydrate of this compd. is used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic polycarbonate. More specifically, it relates to a method for producing an aromatic polycarbonate by an interfacial polymerization method using 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane.

[0002]

Aromatic polycarbonates are widely used as engineering plastics in the fields of automobiles, electricity and optics. Generally, the well-known aromatic polycarbonate produced from 2,2-bis (4′-hydroxyphenyl) propane has transparency, heat resistance, impact resistance,
Excellent balance of physical properties such as dimensional stability. However, the heat resistance (glass transition temperature) of ordinary aromatic polycarbonate is still lower than that of engineering plastics such as aromatic polyether ketone, aromatic polyether ether ketone, aromatic polyimide, aromatic polyester, and aromatic polyamide. Not a satisfactory value. Therefore, a technique for producing an aromatic polycarbonate having excellent heat resistance by variously modifying the aromatic dihydroxy compound constituting the aromatic polycarbonate has been disclosed.

Among them, an aromatic polycarbonate having a relatively high glass transition temperature is an aromatic polycarbonate derived from 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane. Are known. 6,6 '
-Dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane has an extremely low solubility in aqueous alkaline solution as compared to 2,2-bis (4'-hydroxyphenyl) propane. Therefore, the following method is used when using in the interfacial polymerization method. That is, after the derivative of 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane such as bischloroformate into a compound soluble in an organic solvent such as dichloromethane, an interfacial polymerization method is performed. By the method [Journal of Polymer Scienc
e: part A Vol.3,3209 (1965)], 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane in a suspended state for interfacial polymerization.

The method of 6,6'-dihydroxy-3,3,3 ',
After producing bischloroformate of 3'-tetramethylspirobiindane, in order to produce an aromatic polycarbonate, a step of producing bischloroformate is required, and the operation may be complicated. Not preferred when producing aromatic polycarbonate. As a method for producing an aromatic polycarbonate by an interfacial polymerization method using 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane in a suspension state of There is a manufacturing method described in JP-A-60-127327 and a manufacturing method described in JP-A-63-314235. However, in the production methods described in these publications, from the relationship between the weight and the number of moles of 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane described in Examples. As is clear, 6,6'-dihydroxy
An anhydride of -3,3,3 ', 3'-tetramethylspirobiindane is used.

The inventors of the present invention conducted additional tests on these production methods, and found that unreacted solid state 6,6 ′ after the reaction was completed.
It was confirmed that -dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane remained. Further, in the aromatic polycarbonate obtained from the reaction mixture in the state where unreacted 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane in the solid state thus remains, Reaction 6,
It was confirmed that a large amount of 6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane was contained. Incorporation of the unreacted aromatic dihydroxy compound into the aromatic polycarbonate is not preferable because it lowers the thermal stability (weight reduction temperature) of the aromatic polycarbonate. Thus, at present, when producing an aromatic polycarbonate by an interfacial polymerization method using 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane in a suspension state, After completion of the reaction, unreacted solid state 6,6'-dihydroxy-3,3,3 ',
A method for producing an aromatic polycarbonate in which 3'-tetramethylspirobiindane does not remain is desired.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to overcome the above-mentioned problems of the prior art and to provide 6,6'-dihydroxy-3,
Using 3,3 ', 3'-tetramethylspirobiindane,
In producing an aromatic polycarbonate in a suspension state, a method for producing an aromatic polycarbonate that suppresses the residual unreacted 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane is provided. It is a thing.

[0007]

[Means for Solving the Problems] The inventors of the present invention have made extensive studies in order to solve the above problems, and arrived at the present invention. That is, the present invention uses 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane in producing an aromatic polycarbonate by an interfacial polymerization method, 6,6'-
The present invention relates to a method for producing an aromatic polycarbonate using a hydrate of dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane.

The present invention will be described in detail below. In the method for producing an aromatic polycarbonate of the present invention, as the aromatic dihydroxy compound, 6,6′-dihydroxy-3,3,
Hydrate of 3 ', 3'-tetramethylspirobiindane, and, if desired, aromatic dihydroxy compound other than 6,6'-dihydroxy-3,3,3', 3'-tetramethylspirobiindane, carbonate Precursor, organic solvent, alkaline aqueous solution,
If desired, a polymerization catalyst, a molecular weight regulator, a branching agent and the like are used. 6,6'-dihydroxy-3,3, used in the present invention
3 ', 3'-tetramethylspirobiindane (hereinafter referred to as SBI
Is a hydrate and exhibits a strong peak characteristic at a diffraction angle (2θ) of 11.5 ° and a relatively strong peak at 18.0 ° in a powder X-ray diffraction method using Cu-Kα ray. An X-ray diffraction diagram (FIG. 1) is given (hereinafter this crystal is called a-type crystal). On the other hand, the SBI used in the prior art has diffraction angles (2θ) of 16.3 °, 17.6 ° and 19.20 in the powder X-ray diffraction method using Cu—Kα rays.
An X-ray diffraction diagram (FIG. 2) showing a strong peak characteristic at 7 ° is given (hereinafter, this crystal is referred to as a b-type crystal). An error of about ± 0.2 ° is allowed in the display of the diffraction angle.

As is clear from the X-ray diffraction diagrams of FIGS. 1 and 2, the a-type crystal of the present invention is different from the b-type crystal used in the prior art. Further, the a-type crystal of the present invention contains about 5.5% by weight of water of crystallization when the amount of water in the crystal is measured by a Karl Fischer moisture meter, and it is confirmed to be a monohydrate. . On the other hand, the SBI used in the prior art has only a water content of about 1.0% by weight or less observed by the Karl Fischer water content meter. Such SBI hydrates according to the invention are
After the BI is produced, it is obtained by recrystallization in a system containing water (for example, alcohol-water system), and then 100 ° C.
It can be obtained by drying at atmospheric pressure or under pressure at the following temperature, preferably 40 to 90 ° C, more preferably 45 to 80 ° C. The crystals of the hydrate become SBI substantially free of water of crystallization by drying under reduced pressure (for example, about 0.1 to 5 mmHg) at a temperature of 100 ° C. or higher.

As a specific method for producing the SBI hydrate according to the present invention, for example, 2,2-bis (4'-hydroxyphenyl) propane is heated in the presence of an acid catalyst to remove phenol. A method of recrystallizing in an alcohol-water system, an alcohol-water-recrystallization solvent (excluding alcohol) system, or an aromatic hydrocarbon solvent-water system can be mentioned later. The hydrate of SBI thus obtained is 10
In order to remove water of crystallization by drying under reduced pressure at 0 ° C. or higher, it is usually preferable to dry by a method such as ventilation drying at a temperature lower than 100 ° C. SBI according to the present invention
Is preferably a crystal recrystallized from an alcohol-water system. Although the alcohol is not particularly limited, an alcohol having 1 to 5 carbon atoms is usually preferable, and methanol or ethanol is more preferable. still,
When recrystallizing SBI from an alcohol-water system, a recrystallization solvent (excluding alcohol) may be further present, if desired. Examples of the recrystallization solvent that is optionally present include aromatic hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbon solvents such as dichloromethane and chloroform, and the like. The SBI monohydrate used in the present invention has a melting point of 215 to 217 ° C.

In the production method of the present invention, the hydrate of SBI is used, but the advantage of using the hydrate of SBI is that its reactivity in the interfacial polymerization method in which the reaction is started from a suspension state is used. Is to raise. We have
As a result of diligent studies, it was found that the reactivity is increased in the case of using a hydrate of SBI under the interfacial polymerization condition as compared with the case of using SBI containing substantially no water of crystallization. Furthermore, the anhydrous SBI used in the prior art
Found that they were not easily converted into hydrates by contact with water under interfacial polymerization conditions. As a result, in carrying out the interfacial polymerization reaction in a suspended state, it became possible to improve the reactivity by using a hydrate of SBI.

In the method for producing an aromatic polycarbonate of the present invention, an aromatic dihydroxy compound other than SBI can be used in combination. When SBI and an aromatic polycarbonate other than SBI are used, the resulting aromatic polycarbonate is a copolycarbonate. The copolymerized polycarbonate may be a random copolymer, an alternating copolymer, or a block copolymer. When SBI and another aromatic dihydroxy compound are used in combination as the aromatic dihydroxy compound to produce a copolycarbonate, the composition ratio of the two is not particularly limited, and usually, SBI is 3 to 99 mol%. Yes,
It is preferably 5 to 95 mol%. SBI is 3 mol%
When it is below, the effect of improving the heat resistance (glass transition temperature) by introducing SBI into the aromatic polycarbonate may not be clearly exhibited.

The aromatic dihydroxy compound other than SBI used in the production method of the present invention is preferably an aromatic dihydroxy compound represented by the general formula (1) or (2). ^{HO-Ar 1 -X-Ar 2} -OH (1) HO-Ar 3 -OH (2) ( wherein, Ar ^1, Ar ² and Ar ³ are aromatic groups, X is Ar ¹
And represents a linking group that links Ar ² ) In the general formulas (1) and (2), Ar ¹ , Ar ² and Ar ³ represent an aromatic group. It is preferably a phenylene group, and the phenylene group may have a substituent. Examples of the substituent include a halogen atom, a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group and an alkoxy group. Preferably, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group,
An alkoxy group, more preferably a halogen atom selected from chlorine or bromine, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12
And an alkoxy group having 1 to 5 carbon atoms. A
r ¹ and Ar ² are 1,4-phenylene group, 1,3-phenylene group, 1,
A 2-phenylene group is preferable, a 1,4-phenylene group and a 1,3-phenylene group are more preferable, and a 1,4-phenylene group is more preferable. Ar ³ is a 1,4-phenylene group,
It is a 1,3-phenylene group or a 1,2-phenylene group, and preferably a 1,4-phenylene group or a 1,3-phenylene group.

In the aromatic dihydroxy compound represented by the general formula (1) or (2) according to the present invention, X is Ar ¹
And represents a linking group that connects Ar ² and Ar ² . Preferably a single bond,
Divalent hydrocarbon group or -O-, -S-, -SO-,-
Examples thereof include SO ₂ — and —CO— groups. Examples of the divalent hydrocarbon group include saturated hydrocarbon groups, for example, alkylidene groups such as methylene group, ethylene group, 2,2-propylidene group, cyclohexylidene group, etc. An alkylidene group is also included, and it may be a divalent hydrocarbon group containing an aromatic group or other unsaturated hydrocarbon group. More preferably, the carbon number is 1 to
The alkylidene group having 9 carbon atoms and the cycloalkylidene group having 4 to 10 carbon atoms are more preferable, and the alkylidene group having 2 to 8 carbon atoms and the cycloalkylidene group having 5 to 8 carbon atoms are more preferable.

Specific examples of the aromatic dihydroxy compound represented by the general formula (1) or (2) include bis (4-hydroxyphenyl) methane, 1,1-bis (4'-hydroxyphenyl) ethane and 1 , 2-bis (4'-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,1-bis (4'-hydroxyphenyl) -1-phenylethane, 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"], 2- (4'-hydroxyphenyl) -2- (3'-hydroxy Phenyl) propane, 2,2-bis (4'-hydroxyphenyl) butane, 1,1-bis (4'-
Hydroxyphenyl) butane, 1,1-bis (4′-hydroxyphenyl) -2-methylpropane, 2,2-bis (4′-hydroxyphenyl) -3-methylbutane, 2,2-bis (4′-hydroxy) Phenyl) pentane, 3,3-bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxyphenyl) heptane, 2,2-bis (4'-hydroxyphenyl)
Octane, 2,2-bis (3'-methyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-ethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-n -Propyl-
4'-hydroxyphenyl) propane, 2,2-bis (3'-isopropyl-4'-hydroxyphenyl) propane, 2,2-
Bis (3'-sec-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-tert-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-cyclohexyl-4) '
-Hydroxyphenyl) propane, 2,2-bis (3'-allyl-4'-hydroxyphenyl) propane, 2,2-bis (3 '
-Methoxy-4'-hydroxyphenyl) propane, 2,2-
Bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane, 2,2-bis (2', 3 ', 5', 6'-tetramethyl-4'-hydroxyphenyl) propane, 2,2 -Bis (3'-chloro-4 '
-Hydroxyphenyl) propane, 2,2-bis (3 ', 5'-dichloro-4'-hydroxyphenyl) propane, 2,2-bis (3'-bromo-4'-hydroxyphenyl) propane, 2,
2-bis (3 ', 5'-dibromo-4'-hydroxyphenyl) propane, 2,2-bis (2', 6'-dibromo-3 ', 5'-dimethyl-
4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl) cyanomethane, 1-cyano-3,3-bis (4 '
-Hydroxyphenyl) butane, bis (hydroxyaryl) alkanes such as 2,2-bis (4'-hydroxyphenyl) hexafluoropropane,

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (4'-hydroxyphenyl) cycloheptane, 1,1 -Bis (3'-methyl-4'-hydroxyphenyl) cyclohexane, 1,1-bis (3 ', 5'-dimethyl-
4'-hydroxyphenyl) cyclohexane, 1,1-bis (3 ', 5'-dichloro-4'-hydroxyphenyl) cyclohexane, 1,1-bis (4'-hydroxyphenyl) -4-methylcyclohexane, 1, 1-bis (4'-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4'-
Hydroxyphenyl) cyclooctane, 1,1-bis (4'-
Hydroxyphenyl) cyclononane, 1,1-bis (4′-hydroxyphenyl) cyclododecane, 2,2-bis (4′-hydroxyphenyl) norbornane, 8,8-bis (4′-hydroxyphenyl) tricyclo [5, 2,1,0 ^2,6 ] decane, 2,
Bis (hydroxyaryl) cycloalkanes such as 2-bis (4′-hydroxyphenyl) adamantane,

4,4'-dihydroxydiphenyl ether,
Bis (hydroxyaryl) ethers such as 3,3′-dimethyl-4,4′-dihydroxydiphenyl ether and ethylene glycol bis (4-hydroxyphenyl) ether, 4,4′-dihydroxydiphenyl sulfide, 3,3′-
Dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,
3'-dicyclohexyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl Bis (hydroxyaryl) sulfides such as sulfides, 4,4'-dihydroxydiphenyl sulfoxide, bis (hydroxyaryl) sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'- Bis (hydroxyaryl) sulfones such as dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, bis (4-hydroxyphenyl) ketone, bis (3-methyl-4-hydroxyphenyl) ketone Bis (hydroxyaryl) ketones such as

Furthermore, trans-2,3-bis (4'-hydroxyphenyl) -2-butene, 9,9-bis (4'-hydroxyphenyl) fluorene, 3,3-bis (4'-hydroxyphenyl) ) -2-Butanone, 1,6-bis (4'-hydroxyphenyl) -1,6-hexanedione, 1,1-dichloro-2,2-bis (4'-hydroxyphenyl) ethylene, 1,1- Dibromo-
2,2-bis (4'-hydroxyphenyl) ethylene, 1,1-
Dichloro-2,2-bis (5'-phenoxy-4'-hydroxyphenyl) ethylene, α, α, α ', α'-tetramethyl-α, α'-bis (4-hydroxyphenyl) -p-xylene , Α, α, α ', α'-tetramethyl-α, α'
-Bis (4-hydroxyphenyl) -m-xylene, 3,3-
Bis (4'-hydroxyphenyl) phthalide, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-
Examples thereof include dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin and the like. Furthermore, for example, aromatic dihydroxy containing an ester bond, which can be produced by reacting 2 mol of 2,2-bis (4′-hydroxyphenyl) propane with 1 mol of isophthaloyl chloride or terephthaloyl chloride. Compounds are also useful. These aromatic dihydroxy compounds other than SBI may be used alone or in combination.

In the production method of the present invention, SBI is used in the reaction in a solid state or in a state of being suspended in an organic solvent and / or an alkaline aqueous solution. As a method for adding SBI to the reaction system, it may be added as an aqueous suspension or as an organic solvent suspension. When an aromatic dihydroxy compound other than SBI is used, if desired, it may be used as an aqueous alkaline solution,
It may be used as an organic solvent suspension or an aqueous suspension. When the aromatic dihydroxy compound is used as an aqueous alkaline solution, a reducing agent such as sodium sulfite, sodium hydrosulfite, or sodium borohydride can be added as an antioxidant during the preparation of the aqueous solution. Examples of the carbonate precursor used in the production method of the present invention include a carbonyl halide compound, a haloformate derivative of an aromatic dihydroxy compound, and a haloformate derivative of an aliphatic dihydroxy compound. Specific examples thereof include carbonyl chloride (phosgene), carbonyl bromide, carbonyl iodide and mixtures thereof, trichloromethyl chloroformate which is a dimer of carbonyl chloride, and 3 of carbonyl chloride.
Carbonyl halide compounds such as bis (trichloromethyl) carbonate which is a monomer, 2,2-bis (4'-chlorocarbonyloxyphenyl) propane, 1,4-bis (chlorocarbonyloxy) benzene, 1,3-bis Haloformate derivatives of aromatic dihydroxy compounds such as (chlorocarbonyloxy) benzene, 6,6'-bis (chlorocarbonyloxy) -3,3,3 ', 3'-tetramethylspirobiindane, 1,2-bis ( Examples thereof include haloformate derivatives of aliphatic dihydroxy compounds such as chlorocarbonyloxy) ethane and 1,4-bis (chlorocarbonyloxy) butane. Furthermore, in the production method of the present invention, an acid halide derivative of an aliphatic dicarboxylic acid and / or an aromatic dicarboxylic acid can be used in combination with the carbonate precursor, if desired. When using an acid halide derivative, the resulting aromatic polycarbonate is
The aromatic polyester carbonate has both ester bond and carbonate bond. Preferably, 50 mol% or less of the acid halide derivative is used with respect to the carbonate precursor, and more preferably 30 mol% or less of the acid halide derivative is used.

The organic solvent used in the production method of the present invention includes aliphatic halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, trichloroethane and tetrachloroethane, aromatic halogenated hydrocarbon solvents such as chlorobenzene and dichlorobenzene. Halogenated hydrocarbon solvent, n-pentane, n-hexane, n
-Heptane, n-octane, n-nonane, n-decane,
2-methylpentane, 3-methylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,2
3-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3,4-tetramethylpentane, 2,
2,3,3-tetramethylpentane, 2-methylhexane, 3-methylhexane, 2,2-dimethylhexane,
2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 2,2,3-trimethylhexane, 2,2,4-trimethylhexane, 2,
2,5-trimethylhexane, 2,3,4-trimethylhexane, 2,3,5-trimethylhexane, 2,3
Aliphatic hydrocarbon solvents such as 3-trimethylhexane, 2,4,4-trimethylhexane, 2,4,5-trimethylhexane, benzene, methylbenzene (toluene),
1,2-dimethylbenzene (o-xylene), 1,3-
Dimethylbenzene (m-xylene), 1,4-dimethylbenzene (p-xylene), ethylbenzene, 1,2-
Diethylbenzene, 1,3-Diethylbenzene, 1,4
-Diethylbenzene, 1-methyl-2-ethylbenzene, 1-methyl-3-ethylbenzene, 1-methyl-4
-Ethylbenzene, methoxybenzene (anisole),
1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, 1-methyl-2-
Hydrocarbon solvents such as aromatic hydrocarbon solvents such as methoxybenzene, 1-methyl-3-methoxybenzene, 1-methyl-4-methoxybenzene and the like can be mentioned. These organic solvents may be used alone or in combination. Halogenated hydrocarbons are preferable, and dichloromethane is more preferable.

The amount of the organic solvent used is preferably such that the concentration of the aromatic polycarbonate in the organic solvent at the end of the polymerization is about 5 to 50% by weight, more preferably about 10 to 40% by weight, and more preferably about 10 to 40% by weight. An amount of 15 to 35% by weight is more preferable. If the concentration of aromatic polycarbonate in the organic solvent is too low, a large amount of organic solvent may be required. Further, when the concentration of the aromatic polycarbonate in the organic solvent is close to the saturated concentration, the aromatic polycarbonate may gel during the polymerization process. It is also possible to reduce the amount of organic solvent at the start of the reaction, add an organic solvent at any time during the polymerization reaction, or add an organic solvent after the molecular weight increases due to the polymerization reaction and the viscosity increases. You can also

The aqueous alkali solution used in the present invention means an aqueous solution of an alkali metal or alkaline earth metal base. Examples of the alkali metal or alkaline earth metal base include hydroxides and carbonates, hydrogen carbonates and the like of alkali metals or alkaline earth metals such as lithium, sodium, potassium and calcium. Also,
The water used when preparing the alkaline aqueous solution is not particularly limited, but distilled water, deionized water, or the like is preferably used. Further, when the alkaline aqueous solution of the aromatic dihydroxy compound is prepared, the amount of water used is not particularly limited, but is preferably such an amount that the aromatic dihydroxy compound can be dissolved.

The molecular weight of the aromatic polycarbonate produced by the production method of the present invention is not particularly limited, and is usually the weight as a standard polystyrene-equivalent molecular weight measured by GPC (gel permeation chromatography). Average molecular weight is 5,000 to 100,000
The degree is preferably about 10,000 to 90,000, and more preferably about 15,000 to 80,000. Also, the molecular weight distribution represented by the polydispersity index (Mw / Mn) is not particularly limited,
Usually, it is about 1.5 to 4.0, preferably 2.0.
It is about 3.5.

The relationship between the amounts of at least two kinds of aromatic dihydroxy compounds, alkali metal or alkaline earth metal bases (hereinafter abbreviated as bases) and carbonate precursors in the production method of the present invention is at least two kinds. When the sum of the number of moles of the aromatic dihydroxy compound is α and the number of moles of the carbonate precursor is β, 1 ≦ β / α, preferably 1 ≦ β / α ≦ 2, more preferably 1 ≦ β / α ≦
1.5, and more preferably 1 ≦ β / α ≦ 1.3. When the equivalent of the base is γ, 4β-2α ≦
γ, preferably 4β-2α ≦ γ ≦ 4β-1.5α, more preferably 4β-2α ≦ γ ≦ 4β-1.6α, and still more preferably 4β-2α ≦ γ ≦ 4β-1.8α. . Here, when β / α is 1 or less, a hydroxy-terminated aromatic polycarbonate is obtained because the amount of the carbonyl halide compound is insufficient with respect to the aromatic dihydroxy compound. When β / α is 2 or more, a carbonyl halide compound that does not participate in the reaction is produced. When γ is 4β-2α or less, a haloformate-terminated aromatic polycarbonate is obtained. γ is 4β
No special advantages are found above -1.5α.

In the production method of the present invention, a polymerization catalyst optionally used is a tertiary amine, a quaternary ammonium salt,
Examples thereof include a tertiary phosphine, a quaternary phosphonium salt, or a nitrogen-containing heterocyclic compound and a salt thereof, an imino ether and a salt thereof, and a compound having an amide group. A tertiary amine or a quaternary ammonium salt is preferable, a tertiary amine is more preferable, and a still more preferable.
It is a trialkylamine. The trialkylamine has no branch on the carbon atoms at the 1-position and 2-position,
A trialkylamine in which the alkyl group has 1 to 4 carbon atoms is preferable, and specific examples thereof include triethylamine, tri-n-propylamine, diethyl-n-propylamine, and tri-n-butylamine. Triethylamine is particularly preferable because it is easily available and has a catalytic effect. The amount of the polymerization catalyst used is about 0.0 based on the total number of moles of the aromatic dihydroxy compound used.
It may be 05 mol% or more, preferably 0.01 to
It is 1.5 mol%.

In the production method of the present invention, the molecular weight regulator optionally used is a monovalent hydroxyaromatic compound, an alkali metal or alkaline earth metal salt of a monovalent hydroxyaromatic compound, or a monovalent hydroxyaromatic compound. Examples thereof include haloformate compounds of group compounds, monovalent carboxylic acids, alkali metal or alkaline earth metal salts of monovalent carboxylic acids, and acid halides of monovalent carboxylic acids. Specific examples of the molecular weight modifier include the following compounds. That is, as monovalent hydroxy aromatic compounds, phenol, 4-tert-butylphenol, 2-methylphenol, 3-methylphenol, 4
-Methylphenol, 2-ethylphenol, 4-ethylphenol, 4-cumylphenol, 4-phenylphenol, 4-cyclohexylphenol, 4-n-octylphenol, 4-isooctylphenol, 4-
Nonylphenol, 4-methoxyphenol, 4-n-
Hexyloxyphenol, 4-isopropenylphenol, 2-chlorophenol, 3-chlorophenol,
4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dichlorophenol, 2,4-dibromophenol, pentachlorophenol, pentabromophenol, β-naphthol, α-naphthol, 2- (4′-methoxyphenyl) -2- (4 ″ -hydroxyphenyl) propane and the like can be mentioned.

Examples of the alkali metal or alkaline earth metal salt of the monovalent hydroxyaromatic compound include sodium salt and potassium salt of the above monovalent hydroxyaromatic compound.
Examples thereof include calcium salts, and examples of the monovalent hydroxyaromatic compound haloformate derivative include the above monovalent hydroxyaromatic compound chloroformates and bromoformates. Examples of monovalent carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid, and 3
-Methylbutyric acid, 3,3-dimethylbutyric acid, 4-methylvaleric acid, 3,3-dimethylvaleric acid, 4-methylcaproic acid,
Aliphatic carboxylic acids such as 2,4-dimethylvaleric acid, 3,5-dimethylcaproic acid and phenoxyacetic acid, benzoic acid, 4-propoxybenzoic acid, 4-butoxybenzoic acid,
Benzoic acids such as 4-pentyloxybenzoic acid, 4-hexyloxybenzoic acid and 4-octyloxybenzoic acid can be mentioned. Examples of the alkali metal or alkaline earth metal salt of monovalent carboxylic acid include sodium salt, potassium salt, calcium salt of the above monovalent carboxylic acid,
Examples of the monovalent carboxylic acid halide derivative include the above monovalent carboxylic acid chlorides and bromides. The amount of the molecular weight regulator used is usually 1 to the total number of moles of the aromatic dihydroxy compound used.
It is 10 mol%, preferably 1.5 to 8 mol%, and more preferably 2 to 5 mol%.

In the production method of the present invention, the branching agent optionally used is a compound having three or more phenolic hydroxyl groups, haloformate groups, carboxyl groups, carbonyl halide groups and active halogen atoms. , Phloroglucinol, 4,6-dimethyl-2,4,6
-Tris (4'-hydroxyphenyl) -2-heptene, 4,
6-Dimethyl-2,4,6-tris (4'-hydroxyphenyl)
Heptane, 1,3,5-tris (4'-hydroxyphenyl) benzene, 1,1,1-tris (4'-hydroxyphenyl) ethane, 1,3,5-tris (4'-hydroxyphenylisopropyl) benzene , Α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
Tris (4'-hydroxyphenyl) phenylmethane, 2,
2-bis [4 ', 4'-bis (4 "-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (hydroxyphenylisopropyl) phenol, 2,6-bis (2'-hydroxy-
5'-methylbenzyl) -4-methylphenol, 2- (4'-
Hydroxyphenyl) -2- (2 ", 4" -dihydroxyphenyl) propane, 1,4-bis (4 ', 4 "-dihydroxytriphenylmethyl) benzene, 3,5-dihydroxybenzoic acid,
3,5-bis (chlorocarbonyloxy) benzoic acid, 4-hydroxyisophthalic acid, 4-chlorocarbonyloxyisophthalic acid, 5-hydroxyphthalic acid, 5-chlorocarbonyloxyphthalic acid, trimesic acid trichloride, cyanuric acid chloride, 3,3-bis (4'-hydroxyphenyl)-
2-oxo-2,3-dihydroindole, 3,3-bis (4'-hydroxy-3'-methylphenyl) -2-oxo-2,3-dihydroindole and the like. The amount of the branching agent used is not particularly limited, but is usually preferably 0.05 to 2.0 mol% with respect to the total number of moles of the aromatic dihydroxy compound used.

When an aromatic polycarbonate is produced by using the hydrate of SBI according to the production method of the present invention, the solid state existing in the reaction mixture at the end of the polymerization is obtained under any production conditions. The amount of unreacted SBI is virtually undetectable. Furthermore, the amount of unreacted SBI (aromatic dihydroxy compound) in the obtained aromatic polycarbonate is reduced, and the thermal stability of the aromatic polycarbonate is increased. In carrying out the present invention, the reaction temperature is not particularly limited, but it can usually be carried out at about 10 ° C to the boiling temperature of the organic solvent used in the reaction.
When the reaction temperature is excessively low, the reaction efficiency of the polymerization reaction may decrease. If the reaction temperature is excessively high, side reactions such as decomposition of the polymerization catalyst during the polymerization reaction may occur. The preferred reaction temperature is about 10-100 ° C.
And more preferably about 10 to 70 ° C. The pressure during the reaction is also not particularly limited, but it is usually carried out under atmospheric pressure, and if desired, it can be carried out under atmospheric pressure or under atmospheric pressure.

The method for producing an aromatic polycarbonate of the present invention can be carried out in a batch system, a semi-batch system or a continuous system, and is not particularly limited. The reaction apparatus used in the production method of the present invention is not particularly limited, and is a tank-type reaction apparatus, a reaction apparatus such as a tube-type reaction apparatus or a packed tower, or any combination thereof. It is possible to use a reactor or the like. These reactors may optionally be equipped with various stirrers. Specific examples of the stirring device include paddle blades, propeller blades, turbine blades, stirring blades such as lattice blades or chi-type blades, high-speed stirrers such as homogenizers, mixers, homomixers, static mixers, and orifice mixers. You can When the method for producing an aromatic polycarbonate of the present invention is carried out batchwise, a tank-type reactor is usually used to prepare a suspension of SBI consisting of an organic solvent and an alkaline aqueous solution.
The reaction is carried out by supplying a carbonate precursor.

When the method for producing an aromatic polycarbonate of the present invention is carried out in a semi-batch manner, a suspension composed of SBI and an aqueous alkali solution, an organic solvent and a carbonate precursor are simultaneously packed in a column, a static mixer, an orifice mixer. It is possible to employ a method in which the reaction mixture is supplied to a reactor such as the above and brought into contact therewith to cause the reaction, and the reaction mixture flowing out from the reactor is supplied to the tank reactor and stirred and mixed in the tank reactor. When the aromatic polycarbonate of the present invention is continuously produced, it can be carried out by using a tank-type continuous reaction apparatus in which several tank-type reaction apparatuses are continuously connected. For example, a suspension of SBI and an aqueous alkali solution and a carbonate precursor, an organic solvent, or an organic solvent solution of a carbonate precursor is continuously supplied to the first tank. After a certain residence time in the first tank, the reaction mixture is continuously discharged into the second tank. Similarly, after a certain residence time, the reaction mixture can be continuously discharged to the next reactor to produce an aromatic polycarbonate. Furthermore, the production method of the present invention can be carried out continuously by using a tubular reactor. In this case, the production method of the present invention can be carried out by the same operation as in the case of using the tank type continuous reaction device.

The method for producing an aromatic polycarbonate of the present invention is an interfacial polymerization method from a suspended state, and a solid state unreacted SB is contained in the reaction mixture at the end of the reaction.
This is a manufacturing method in which I does not substantially remain. Here, “substantially does not remain” means a state in which unreacted SBI in the solid state in the reaction mixture is not visually confirmed. Further, the content of unreacted SBI in the obtained aromatic polycarbonate is extremely low, and according to the production method of the present invention, an aromatic polycarbonate having an unreacted SBI content of 50 ppm or less, preferably 30 ppm or less is produced. Will be possible. The aromatic polycarbonate having a low unreacted SBI content obtained in this manner has high thermal stability (weight reduction temperature). For example, the 5% weight reduction temperature measured in air is 410 to 420 ° C ( The temperature is about the same (no stabilizer added).

The aromatic polycarbonate obtained by the production method of the present invention further comprises 2,2-bis (4 ′), if desired.
It is also possible to use it as a molding material by blending it with an aromatic polycarbonate derived from -hydroxyphenyl) propane. In addition, it can be used as a molding material in combination with another polymer.
Other polymers include polyethylene, polypropylene, polystyrene, ABS resin, polymethylmethacrylate, polytrifluoroethylene, polytetrafluoroethylene, polyacetal, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polyamide, polyimide, polyamideimide, poly. Examples thereof include ether imide, polysulfone, polyether sulfone, paraoxybenzoyl-based polyester, polyarylate, and polysulfide.

The aromatic polycarbonate obtained by the production method of the present invention may be used alone or in a mixture with another polymer, and further, at the time of or after the production of the aromatic polycarbonate by a known method, a pigment, a dye, Add known additives such as heat stabilizers, antioxidants, UV absorbers, mold release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, barium sulfate, TiO _{2 and the} like. Good. Aromatic polycarbonate obtained by the production method of the present invention, alone or in a state of being mixed with other polymers, if desired, the above additives are added as a molding material, such as chassis and housing materials for electric devices, It can be molded into electronic parts, automobile parts, substrates of information recording media such as compact discs, optical materials such as lenses of cameras and eyeglasses, building materials replacing glass, and the like. The aromatic polycarbonate of the present invention is thermoplastic, and in a molten state, injection molding, extrusion molding, blow molding,
It can be impregnated with a filler or the like, and can be easily molded by a known molding method.

[0035]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In addition, each physical property value was measured by the following methods. -Molecular weight: 0.2% by weight of aromatic polycarbonate in chloroform was added to GPC (gel permeation chromatography) [Showa Denko KK, System]
-11] to determine the weight average molecular weight and polydispersity index (Mw / Mn). The measured values are standard polystyrene equivalent values.・ X-ray crystal diffraction: X-ray diffractometer [Rigaku Denki KK, RI
NT-1500 system] was used to measure powder X-ray diffraction with Cu-Kα radiation. -Unreacted SBI content in aromatic polycarbonate: 0.2% by weight chloroform solution of aromatic polycarbonate in GPC [Showa Denko KK, System-11]
Unreacted SB in aromatic polycarbonate
The content of I was determined. -Measurement of water content in crystals: SBI by Karl Fischer water meter (KKA Electronics Co., Ltd., MKA-3 type)
The water content in (about 100 mg) was measured. -Thermal stability (5% weight loss temperature): Measured up to 750 ° C at a temperature rising rate of 10 ° C / min in an air atmosphere with a thermogravimetric measuring device (TGA-50 type manufactured by Shimadzu Corporation), and then 5 %
The weight loss temperature (TG, ° C) was determined and used as a measure of thermal stability. It should be noted that additives such as a heat stabilizer were not added to the polycarbonate produced in each of the examples and comparative examples.

Production Example 1 (Production of SBI Hydrate) 2.0 kg of 2,2-bis (4'-hydroxyphenyl) propane and 2.0 g of trifluoromethanesulfonic acid were added to 6 parts.
It heated at 140-150 degreeC for time, and was made to react in a molten state. Immediately after completion of the reaction, the by-product phenol was distilled off under reduced pressure, then cooled, and 1.2 liter of isopropanol was charged to dissolve the reaction mixture. Next, 4.08 kg of 9 wt% sodium hydroxide aqueous solution was charged to crystallize SBI sodium salt crystals. This is filtered, and further added with 2.4 liters of a 25 wt% isopropanol aqueous solution to obtain 8
It was treated at a temperature of 0 to 83 ° C., cooled and then filtered. Furthermore, the sodium salt of SBI was neutralized with aqueous ammonia in a 15% by weight isopropanol aqueous solution, and the precipitated SB
I was filtered. Further, the obtained SBI was dissolved in a mixed solvent of 400 ml of chloroform and 2 liters of methanol, and 2.4 liters of water was added to this solution to obtain SBI crystals. The obtained crystals were dried for 24 hours in a ventilation dryer at 60 ° C. to give colorless needle crystals of SBI.
I got The yield was 676 g, and the yield was 71%. The melting point was 216.0-211.6C. The water content in the crystal was 5.4% by weight, and it was confirmed that the crystal was a monohydrate. From the powder X-ray diffraction results of this crystal,
This crystal was an a-type crystal giving the X-ray diffraction pattern shown in (FIG. 1).

Production Example 2 The SBI hydrate obtained in Production Example 1 was further dried in a vacuum dryer under the conditions of 120 ° C. and about 0.1 mmHg for 7 hours. The obtained SBI was a colorless rough crystal and had a melting point of 215.0 to 216.2 ° C.
The water content in the crystals was 0.5% by weight. This crystal was a b-type crystal giving the X-ray diffraction pattern shown in (FIG. 2).

Example 1 A baffled flask having an internal capacity of 20 liters was equipped with a grid impeller, a reflux condenser, and a dipping tube for blowing carbonyl chloride. Into this flask was added 1630 g (5.0 mol as a monohydrate) of SBI prepared in Preparation Example-1 and 25.8 g of 4-tert-butylphenol, 560.
A suspension was prepared by charging g of sodium hydroxide and adding 6 liters of deionized water to the mixture. Six liters of dichloromethane was added to this suspension to prepare a three-phase suspension containing solids. Then, while stirring this three-phase suspension at a stirring speed of 400 rpm,
94 g of carbonyl chloride was fed at a feed rate of 9.9 g / min. After the supply of carbonyl chloride was completed, 0.808 g of triethylamine was added, and the reaction mixture was further stirred and mixed. After stirring and mixing for 90 minutes, a viscous dichloromethane solution containing an aromatic polycarbonate was obtained. After separating the reaction mixture, the organic phase was neutralized with an aqueous solution of hydrochloric acid, and then washing with deionized water was repeated until substantially no electrolyte was detected in the aqueous washing liquid.
Dichloromethane was distilled off from the obtained dichloromethane solution of the aromatic polycarbonate to obtain a solid aromatic polycarbonate. The physical properties of the obtained aromatic polycarbonate are summarized in Table 1 (Table 1). While the carbonyl chloride was being supplied, the reaction mixture was kept in a suspended state, but as the carbonyl chloride supply was completed, the solid matter disappeared, and the reaction mixture was left in the reaction mixture at the end of the polymerization. No solid state unreacted SBI was identified.

Example 2 In Example 1, instead of using the lattice blade-shaped stirrer, a paddle blade-shaped stirrer was used and the stirring speed was 400 rp.
An aromatic polycarbonate was produced in the same manner as in Example 1 except that stirring was carried out at m. While supplying the carbonyl chloride, the reaction system was kept in a suspended state,
The solid matter disappeared as the supply of carbonyl chloride was completed, and unreacted SBI in the solid state was not confirmed in the reaction mixture at the completion of the polymerization. The physical properties of the obtained aromatic polycarbonate are shown in Table 1.

Example 3 Instead of using 1630 g of SBI in Example 1, 815 g of SBI (2.5 mol as monohydrate)
An aromatic polycarbonate was produced in the same manner as in Example 1 except that and 570 g (2.5 mol) of 2,2-bis (4'-hydroxyphenyl) propane were used.
While the carbonyl chloride was being supplied, the reaction system remained in a suspended state, but the solid matter disappeared as the carbonyl chloride supply was completed, and the solid state remained in the reaction mixture at the end of the polymerization. No unreacted SBI was confirmed. The physical properties of the obtained aromatic polycarbonate are shown in Table 1.

Example 4 Noritake Static Mixer CSM-12-5 [manufactured by Noritake Campany Co., Ltd.] having an inner diameter of 12 mm and eight elements was connected in series (total number of elements: 24) to a reactor. Using this reactor as (a)
3595.8 g of SBI monohydrate prepared in Preparation Example 1
(11.03 mol), 56.9 g of 4-tert-butylphenol, 2470 g of 50 wt% aqueous sodium hydroxide solution, 12.5 liters of water; (b) a solution of 1255 g of carbonyl chloride in 4650 g of dichloromethane; c) 16416 g of dichloromethane,
(a) 344.7 g / min; (b) 109.3 g / min; (c) 3
The reactor was fed at a feed rate of 00 g / min. The reaction mixture flowing out of the reactor was supplied to a tank reactor with a baffle having an internal volume of 40 liters. Then, 1.78 g of triethylamine was added, and the mixture was further stirred for 60 minutes by a stirrer in the form of a lattice blade at a stirring speed of 400 rpm. Although unreacted SBI in the solid state was confirmed in the reaction mixture containing the oligomer of aromatic polycarbonate flowing out from the reactor, the solid state was found in the reaction mixture after stirring and mixing for 60 minutes in the tank reactor. No unreacted SBI was confirmed. The obtained reaction mixture was separated, the organic phase was washed once with deionized water, and then neutralized with an aqueous hydrochloric acid solution. Then, the organic phase was washed with deionized water until substantially no electrolyte was confirmed in the wash water, and dichloromethane was removed from the organic phase to obtain a solid-state aromatic polycarbonate. The physical properties of the obtained aromatic polycarbonate are shown in Table 1.

Example 5 A tank reactor having an overflow outlet having an internal volume of 5 liters and a stirrer in the shape of a lattice blade, and a tank reactor having two overflow outlets having an internal capacity of 10 liters and a stirrer in the shape of a lattice vane were used. Using the devices connected in series, 12.02 kg (3
6.87 mol) and 4-tert-butylphenol 174.
76 g (1.165 mol), sodium hydroxide 4277
g (106.93 mol), hydrosulfite 16.
794 g was dissolved in 57.06 kg of water to give a total weight of 7
3.55 kg of alkaline suspension was prepared. Add 1 part each of this suspension, carbonyl chloride, and dichloromethane.
36.20 g / min, 7.638 g (0.07715 mol) / min, 127.37 g / min feed rate, internal volume 5
L of the first tank reactor was fed. The stirring speed of the first tank reactor was 400 rpm. The reaction mixture is discharged from the first tank reactor at a rate of 264.57 g / min. The residence time was about 20 minutes. The reaction mixture continuously discharged is continuously discharged through a pipe to a second
It was supplied to the tank reactor. The second tank reactor stirs at a stirring speed of 400 rpm for a residence time of 40 minutes, and further, the reaction mixture is supplied to the subsequent third tank reactor, a residence time of 40 minutes, and a stirring speed of 400 rpm. I went. The reaction mixture continuously discharged from the third tank reactor was immediately separated and neutralized with an aqueous hydrochloric acid solution. The resulting organic phase was washed with deionized water until virtually no electrolyte was detected. An aromatic polycarbonate was obtained by evaporating and removing dichloromethane from a dichloromethane solution containing this aromatic polycarbonate. The physical properties of the obtained aromatic polycarbonate are shown in Table 1. In addition, solid state unreacted SBI was not confirmed in the reaction mixture continuously discharged from the third tank reactor.

Example 6 A baffled flask having an internal capacity of 20 liters was equipped with a grid impeller and a reflux condenser. In this flask, 7
Production Example 1 of 53.1 g (2.31 mol as a monohydrate)
Was charged with SBI and 25.8 g of 4-tert-butylphenol, 560 g of sodium hydroxide,
A suspension was prepared by adding 6 liters of deionized water to this mixture. To this suspension was added 6 liters of dichloromethane in which 949.6 g (2.69 moles) of bischloroformate of 2,2-bis (4'-hydroxyphenyl) propane was dissolved to form a three phase solid containing phase. A suspension was prepared.
Then, while stirring this three-phase suspension at a stirring speed of 400 rpm, 594 g of carbonyl chloride was added thereto.
The feed rate was 9 g / min. After the end of the carbonyl chloride supply, 0.808 g of triethylamine was added,
Further, the reaction mixture was stirred and mixed. After stirring and mixing for 90 minutes, a viscous dichloromethane solution containing an aromatic polycarbonate was obtained. After separating the reaction mixture, the organic phase was neutralized with an aqueous solution of hydrochloric acid, and then washing with deionized water was repeated until substantially no electrolyte was detected in the aqueous washing liquid. Dichloromethane was distilled off from the obtained dichloromethane solution of the aromatic polycarbonate to obtain a solid aromatic polycarbonate. The physical properties of the obtained aromatic polycarbonate are summarized in Table 1. While the carbonyl chloride was being supplied, the reaction system was kept in a suspended state, but as the carbonyl chloride supply was completed, the solid matter disappeared, and the reaction mixture remained in the reaction mixture at the end of the polymerization. No solid state unreacted SBI was identified.

Example 7 A tank-type reactor having an internal capacity of 3 liters, which has an overflow discharge port and a lattice blade-shaped stirrer, and three tank-type reactors having an internal capacity of 7 liters, which have an overflow discharge port and a lattice blade-shaped stirrer, were prepared. Using the devices connected in series, 3192 g (14 mol) of 2,2-bis (4'-hydroxyphenyl) propane, 103.2 g (0.688 mol) of 4-tert-butylphenol, 2320 g of hydroxylated An aqueous phase consisting of sodium, 8.8 g of sodium hydrosulfite and 24 kg of water, carbonyl chloride and dichloromethane were respectively added to a first reactor having a volume of 3 liters in a tank type reactor at 109.72 g / min (aqueous phase), 8 ．
The feed rates were 79 g / min (carbonyl chloride) and 74.10 g / min (dichloromethane). The stirring speed was 400 rpm. At the same time as the reaction mixture flows from the first tank-type reactor through the overflow outlet into the second tank-type reactor having an internal volume of 7 liters, the second tank-type reactor receives 1812.6 g (monohydrate). 5.56 mol) as a product of SBI monohydrate prepared in Preparation Example-1 and 4
A suspension consisting of 630 g of dichloromethane was added to 25.3
The feed rate was 6 g / min. Furthermore, at the same time that the reaction mixture in the second tank reactor flowed into the third tank reactor, triethylamine was supplied to the third tank reactor at a supply rate of 0.02 g / min. The reaction mixture continuously discharged from the fourth tank reactor was separated from the organic phase, neutralized with an aqueous hydrochloric acid solution, and the organic phase was deionized water until no electrolyte was detected. Washed. Dichloromethane was distilled off from the obtained dichloromethane solution of the aromatic polycarbonate to obtain a solid aromatic polycarbonate. The physical properties of the obtained aromatic polycarbonate are shown in Table 1. In addition, solid state unreacted SBI was not confirmed in the reaction mixture discharged from the fourth tank reactor.

Comparative Example 1 In Example 1, the SBI produced in Production Example 1 was 163
Instead of using 0 g (5.0 mol as monohydrate)
1540 g (5.0 mol) of SBI obtained in Production Example 2
An aromatic polycarbonate was produced in the same manner as in Example 1 except that the aromatic polycarbonate was used. The initial stage of the reaction is Example 1
It was in a suspended state like the above, and the solid matter disappeared with the supply of carbonyl chloride, but a white solid remained in the reaction mixture at the end of the polymerization, and a white solid was obtained by analysis by HPLC. Was confirmed to be unreacted SBI. The physical properties of the obtained aromatic polycarbonate are shown in Table 1.

COMPARATIVE EXAMPLE 2 In Example 3, the SBI produced in Production Example 1 was 815
The procedure of Example 3 was repeated except that 770 g (2.5 mol) of SBI obtained in Production Example 2 was used instead of g (2.5 mol of monohydrate). It was manufactured. At the beginning of the reaction, it was in a suspended state as in Example 3, and the solid matter disappeared with the supply of carbonyl chloride, but a white solid remained in the reaction mixture at the end of the polymerization. , HPLC analysis confirmed that the white solid was unreacted SBI. The physical properties of the obtained aromatic polycarbonate are shown in Table 1.

Comparative Example 3 In Example 5, the SBI produced in Production Example 1 was replaced with 12.
Instead of using 02 kg (36.87 mol as a monohydrate), the SBI obtained in Preparative Example 2 was 11.3 (36.87 mol).
Aromatic polycarbonate was produced in the same manner as in Example 5 except that 87 mol) was used. At the beginning of the reaction, the suspension was in the same state as in Example 5, and the solid matter disappeared with the supply of carbonyl chloride, but a white solid remained in the reaction mixture at the end of the polymerization. , HPL
Analysis by C confirmed that the white solid was unreacted SBI. The physical properties of the obtained aromatic polycarbonate are shown in Table 1.

Comparative Example 4 In Example 6, the SBI produced in Production Example 1 was replaced with 75
Instead of using 3.1 g (2.31 mol as monohydrate), 711.5 g (2.
Aromatic polycarbonate was produced in the same manner as in Example 6 except that 31 mol) was used. At the beginning of the reaction, the suspension was in the same state as in Example 6, and the solid matter disappeared with the supply of carbonyl chloride, but a white solid remained in the reaction mixture at the end of the polymerization. , HPL
Analysis by C confirmed that the white solid was unreacted SBI. The physical properties of the obtained aromatic polycarbonate are shown in Table 1.

[0049]

[Table 1] As is clear from Table-1, the aromatic polycarbonate produced by the production method of the present invention has a low content of unreacted SBI, and therefore has high thermal stability (5% weight loss temperature) and stability. Are better.

[0050]

EFFECT OF THE INVENTION According to the production method of the present invention, it is possible to produce an aromatic polycarbonate having a low content of unreacted SBI in an interfacial polymerization method using SBI in a suspended state.

[Brief description of drawings]

FIG. 1 SBI monohydrate (a-type crystal) used in the present invention
X-ray diffraction diagram of.

FIG. 2 is an X-ray diffraction diagram of SBI (b-type crystal).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. When producing an aromatic polycarbonate by an interfacial polymerization method using 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane, 6,6'-dihydroxy A process for producing an aromatic polycarbonate using a hydrate of 3,3,3 ', 3'-tetramethylspirobiindane. 2. The method for producing an aromatic polycarbonate according to claim 1, wherein the hydrate of 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane is a monohydrate. . 3. A monohydrate of 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane has a diffraction angle (2θ) in a powder X-ray diffraction method using Cu-Kα radiation. ) 11.5
The method for producing an aromatic polycarbonate according to claim 2, which is a crystal characterized by an X-ray diffraction pattern showing a strong peak characteristic at ° and a relatively strong peak at 18.0 °. 4. A hydrate of 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane and 2,2-bis (4′-hydroxyphenyl) propane are used. 1. The method for producing an aromatic polycarbonate according to 1.