JPH07165901A - Production of aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To efficiently produce an aromatic polycarbonate having a small take-in of nitrogen component by using a tertiary amine without using a specific reactor. CONSTITUTION:An aromatic polycarbonate is produced by preparing an aromatic polycarbonate oligomer from an aromatic dihydroxy compound, an alkali metal or an alkaline earth metal base and a halogenated carbonyl compound under an interfacial condition of two phases of water and a water-insoluble organic solvent in the absence of a tertiary amine, and subjecting the aromatic carbonate oligomer to polycondensation in the presence of a tertiary amine. The tertiary amine is added under the condition where the amount of the haloformate group of the aromatic polycarbonate oligomer is 15-0.1mol% based on a structural unit of the aromatic polycarbonate oligomer and the equivalent ratio of the haloformate group and the alkali metal or the alkaline earth metal base of 1:1.5-1:5.5.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic polycarbonate.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an aromatic polycarbonate, a carbonyl halide compound such as phosgene is reacted with an alkali metal or alkaline earth metal base aqueous solution of an aromatic dihydroxy compound in the presence of an organic solvent to give a chloro compound. A method for producing a high molecular weight aromatic polycarbonate by preparing a low molecular weight aromatic polycarbonate oligomer containing a formate group and then polycondensing the oligomer is disclosed.
science Publishing, "Encyclopedia of PolymerScienc
e and Technology ", vol.10, Polycarbonate, p.710-76
4, (1969), H. Schnell, "Chemistry and Physics of Po.
lycarbonate ", Interscience Pub-lishing, p.9-76, (19
64)].

As a method of polycondensing a low-molecular weight aromatic polycarbonate oligomer, for example, a two-phase mixture containing the oligomer is emulsified and the emulsion state is maintained to efficiently produce a high-molecular weight aromatic polycarbonate. (Japanese Patent Publication No. 37-2198) and a method of using a catalyst in polycondensation (US Pat. No. 3,275,601).
No.) etc. are disclosed. However, Japanese Patent Publication No. 37-219
In order to form a highly emulsified state, the method disclosed in Japanese Patent No. 8
For example, since stirring at a rotation speed of about 10,000 rpm is required, a special stirring device must be used, which is not a generally useful method. On the other hand, US Pat. No. 3,275,560 in which a tertiary amine is added as a catalyst during polycondensation.
The method described in No. 1 makes it possible to easily obtain a high molecular weight aromatic polycarbonate by ordinary stirring. But,
In this method, the ammonium salt produced by the reaction between the haloformate group and the tertiary amine undergoes a decomposition reaction, and as a result, a carbamate bond is formed at the terminal and the nitrogen component of the aromatic polycarbonate is taken in. Therefore, the aromatic polycarbonate obtained by this method has a problem that coloring occurs during melt molding.

The following methods have been disclosed in order to solve these problems. For example, an alkaline aqueous solution of an aromatic dihydroxy compound and phosgene are reacted in the presence of an organic solvent to form a low molecular weight oligomer, which is then maintained in an emulsified state and polymerized to produce a high molecular weight oligomer. In the method for producing an aromatic polycarbonate, when the molecular weight of the aromatic polycarbonate in an emulsified state reaches 70% or more of a desired value, a tertiary amine is added to form a high molecular weight aromatic polycarbonate. A method for producing an aromatic polycarbonate (JP-A-2-133425), a method for producing an aromatic polycarbonate by polymerizing an aromatic polycarbonate oligomer in a water-in-oil emulsion state in the presence of an alkali, wherein The average droplet size of the dispersed aqueous phase in the water-in-oil emulsion state is 10 microns or less. After a state, a method of manufacturing an aromatic polycarbonate, which comprises adding a tertiary amine (JP-A-3-199231
Japanese patent publication). According to these methods, 3
It is possible to considerably suppress the uptake of the nitrogen component of the aromatic polycarbonate accompanying the decomposition of the primary amine. But,
In all of these methods, it is necessary to carry out the reaction in an emulsified state, and a special stirring device must be used as in the case of JP-B-37-2198, so that it is not a generally useful method. I can't say.

Further, when an aromatic polycarbonate is produced under the two-phase interface condition, the hydrolysis reaction of the haloformate group is suppressed by controlling the concentration of the alkali metal or alkaline earth metal base in the aqueous phase, and washing is performed. Method for producing aromatic polycarbonate having improved properties
No. 278528) is also disclosed. In this method, the aromatic polycarbonate oligomer has a molecular weight of 3,000 to
After increasing to 15,000, an alkali metal or alkaline earth metal base is added to adjust the concentration of the alkali metal or alkaline earth metal base to a desired value, and then the aromatic polycarbonate is produced. However, there is no description in the specification of the method regarding incorporation of a nitrogen component into the aromatic polycarbonate, and in the examples, since the molecular weight of the aromatic polycarbonate oligomer is increased to 3000 to 15000, a low content is obtained. A tertiary amine is added to a molecular weight aromatic polycarbonate oligomer. Therefore, it is difficult for this method to suppress the incorporation of the nitrogen component into the aromatic polycarbonate due to the decomposition of the tertiary amine.

Further, as a method for producing a branched aromatic polycarbonate by an interfacial polymerization method, JP-A-3-1825 is known.
In the specification of Japanese Patent No. 24, a branching agent and a tertiary amine are added during the reaction of an aromatic dihydroxy compound and an aromatic polycarbonate oligomer, and after the viscosity of the aromatic polycarbonate increases, the mixed state is changed from turbulent flow to laminar flow. The amount of the alkali metal added at this time is 1.40 <(M + N) / the number of moles of the chloroformate group of the oligomer <1.60 (M is an aqueous solution in which the aromatic dihydroxy compound is dissolved). Of the alkali metal base, and N represents the number of moles of the alkali metal base added at the time of switching from the turbulent flow to the laminar flow). However, also in this method, the number of moles of the haloformate group of the aromatic polycarbonate oligomer when the tertiary amine is added, and the equivalent ratio of the haloformate group and the alkali metal or alkaline earth metal base when the tertiary amine is added. There is no description about etc. In addition, since the tertiary amine is added to the low molecular weight aromatic polycarbonate oligomer,
It is difficult to suppress the incorporation of the nitrogen component into the aromatic polycarbonate due to the decomposition of the tertiary amine. Thus, when producing an aromatic polycarbonate using a tertiary amine, a method for suppressing the decomposition reaction of the tertiary amine and efficiently producing an aromatic polycarbonate using a general reaction apparatus is desired. It is rare.

[0007]

SUMMARY OF THE INVENTION The present invention provides a method for solving the above-mentioned problems of the prior art.
More specifically, the present invention provides a method for suppressing the decomposition reaction of a tertiary amine when an aromatic polycarbonate is produced using a tertiary amine, and efficiently producing the aromatic polycarbonate using a general reaction apparatus. It is a thing.

[0008]

[Means for Solving the Problems] The inventors of the present invention have made diligent studies to solve the above problems, and in order to suppress the decomposition reaction of the tertiary amine when producing an aromatic polycarbonate using the tertiary amine. The factor of was found and the present invention was completed. That is, the present invention relates to an aromatic dihydroxy compound, an alkali metal or alkaline earth metal base and a carbonyl halide under the two-phase interface condition of water and a substantially water-insoluble organic solvent in the absence of a tertiary amine. A method for producing an aromatic polycarbonate by producing an aromatic polycarbonate oligomer from a compound and polycondensing the oligomer in the presence of a tertiary amine,
The haloformate group of the aromatic polycarbonate oligomer in the two-phase mixture is 15 to 0.1 mol% per structural unit of the aromatic polycarbonate oligomer, and the equivalent ratio of the haloformate group to the alkali metal or alkaline earth metal base is 1 : 1.5 to 1: 5.5 under the condition that a tertiary amine is added.

The present invention relates to a method for producing an aromatic polycarbonate in a general reaction apparatus without using a special stirring device. Examples of the special stirring device include a high-speed stirrer such as a homogenizer and a homomixer. The present invention is directed to the production of an aromatic polycarbonate oligomer in the absence of a tertiary amine, and the addition of the tertiary amine to the oligomer to carry out polycondensation. By suppressing the decomposition reaction of the tertiary amine by defining the molar ratio of the haloformate group and the equivalent ratio of the alkali metal or alkaline earth metal base (hereinafter abbreviated as base) to the haloformate group to a predetermined amount. is there.

The manufacturing method of the present invention comprises the following steps.
That is, step [1]: under a two-phase interface condition consisting of water and a substantially water-insoluble organic solvent, in the absence of a tertiary amine, a low molecular weight compound of aromatic dihydroxy compound, base and carbonyl halide compound A step of producing an aromatic polycarbonate oligomer, step [2]: a step of polycondensing until the haloformate group of the aromatic polycarbonate oligomer reaches 15 to 0.1 mol% per structural unit of the aromatic polycarbonate, step [3]: In the reaction mixture obtained in the step [2], the equivalence ratio of the haloformate group to the base in the two-phase mixture was 1: 1.
A step of adding a tertiary amine under the conditions of 5-1: 5.5, step [4]: further polycondensing the aromatic polycarbonate oligomer obtained in step [2] in the presence of a tertiary amine. 4 steps of producing an aromatic polycarbonate.

In the production method of the present invention, the step [1]
And in step [2], an aromatic polycarbonate oligomer having a haloformate group of 15 to 0.1 mol% per structural unit of the aromatic polycarbonate oligomer is produced.
The step [1] and the step [2] can be performed simultaneously. That is, the reaction of the aromatic dihydroxy compound with the base and the carbonyl halide compound and the polycondensation reaction of the aromatic polycarbonate oligomer until the haloformate group becomes 15 to 0.1 mol% per structural unit of the aromatic polycarbonate oligomer are simultaneously performed. Is the way. In the production method of the present invention, in the step [1], an aromatic dihydroxy compound, a base, a carbonyl halide compound, water and an organic solvent are used. If desired, a molecular weight regulator and a branching agent are used. The molecular weight modifier is a compound that functions to control the molecular weight at the time of producing the aromatic polycarbonate, and is preferably used at the time of producing the aromatic polycarbonate. The addition of the molecular weight modifier is not particularly limited to either step, but it is preferably performed in step [1], step [2] or step [3], and step [1] or step [2] It is more preferable to carry out in step [2], and it is particularly preferable to carry out in step [2].

In step [2], the reaction mixture containing the aromatic polycarbonate oligomer produced in step [1] is used. If desired, a molecular weight modifier and a branching agent are used. The reaction mixture containing the aromatic polycarbonate oligomer produced in the step [1] may be a two-phase mixture of an aqueous phase and an organic phase, or an organic solvent solution containing the aromatic polycarbonate oligomer obtained by separating the two-phase mixture. Good. In the case of an organic solvent solution obtained by separating a reaction mixture containing an aromatic polycarbonate oligomer, a desired amount of additional base and additional aromatic dihydroxy compound are used.

In step [3], the reaction mixture containing the aromatic polycarbonate oligomer obtained in step [2] and the tertiary amine are used. If desired, a molecular weight modifier and a branching agent are used. The reaction mixture containing the aromatic polycarbonate oligomer produced in the step [2] may be a two-phase mixture of an aqueous phase and an organic phase, or an organic solvent solution containing the aromatic polycarbonate oligomer obtained by separating the two-phase mixture. Good. In the case of an organic solvent solution obtained by separating a reaction mixture containing an aromatic polycarbonate oligomer, a desired amount of additional base and additional aromatic dihydroxy compound are used. At this time, the amount of the base is 1: 1.5 to the haloformate group in an equivalent ratio.
Adjust it to be in the range of 1: 5.5.

In the step [4], the reaction mixture containing the aromatic polycarbonate oligomer produced in the step [3] and, if desired, the molecular weight modifier and the branching agent are used. The haloformate group in the aromatic polycarbonate oligomer at the start of the step [3] of the present invention is
15 to 0. per structural unit of aromatic polycarbonate.
It is preferably 1 mol%, more preferably 13 to 0.7 mol%, further preferably 12 to 1.0 mol%, particularly preferably 12 to 1.5 mol%. .. The term “per structural unit of the aromatic polycarbonate oligomer” means that the aromatic dihydroxy compound constituting the aromatic polycarbonate oligomer is 2
It is a value based on the molecular weight obtained by removing one hydrogen atom and adding a carbonyl group based on a carbonate bond thereto. For example, in an aromatic polycarbonate derived from bisphenol A, the value of the structural unit is 254, which is obtained by subtracting 2 of two hydrogen atoms from the molecular weight 228 of bisphenol A and adding 28 of the carbonyl group.

In step [3], the equivalent ratio of the haloformate group to the base of the aromatic polycarbonate oligomer is preferably 1: 1.5 to 1: 5.5, more preferably 1: 1.8 to 1. 1: 4.5, more preferably 1: 2.0 to 1: 3.5, and 1: 2.5 to 1:
It is particularly preferably 3.0.

In step [3], the concentration of the base in the aqueous phase is preferably in the range of 0.05 to 0.2 mol / liter, more preferably 0.06 to 0.18, and further preferably. 0.07 to 0.15 and 0.08 to
It is particularly preferably 0.13 mol / liter. In the step [3], the concentration of the haloformate group in the organic phase is preferably 0.0006 to 0.2 mol / liter, more preferably 0.001 to 0.1.
9, more preferably 0.003 to 0.18,
It is particularly preferably 0.008 to 0.16 mol / liter.

In the step [1] of the present invention, a method well known in the art is known as a method for obtaining a low molecular weight aromatic polycarbonate oligomer from a aromatic dihydroxy compound, a base and a carbonyl halide compound by a haloformate reaction. Can be adopted. For example, a base aqueous solution of an aromatic dihydroxy compound and an organic solvent are introduced into a tubular reactor to form a multiphase flow, and a carbonyl halide compound is cocurrently reacted with this, and heat of reaction generated at that time is temporarily transferred to an organic solvent. Of the aromatic polycarbonate oligomer by removing it by heat of vaporization (Japanese Patent Publication No. 46-214).
No. 60), a method of producing an aromatic polycarbonate oligomer by reacting a base aqueous solution of an aromatic dihydroxy compound with a carbonyl halide compound in the presence of an organic solvent, wherein 1 to 10 mol% of the carbonyl compound is used. Process for producing aromatic polycarbonate oligomer characterized by coexistence of inert gas (Japanese Patent Laid-Open No. 51-
No. 136690), an aqueous base solution of an aromatic dihydroxy compound and a carbonyl halide compound are reacted in the presence of an organic solvent,
In the method for producing an aromatic polycarbonate oligomer, an aqueous base solution of an aromatic dihydroxy compound, a carbonyl halide compound and an organic solvent are premixed to carry out an initial reaction, and the obtained initial reaction mixture is kept in a large amount at a constant temperature. A method for producing an aromatic polycarbonate oligomer, which is characterized in that it is brought into contact with a reaction product (Japanese Patent Application Laid-Open No. Sho 5).
2-150496),

In a method for producing an aromatic polycarbonate oligomer by reacting a base solution of an aromatic dihydroxy compound with a carbonyl halide compound in the presence of an organic solvent, the reaction is maintained in a temperature range of 2 to 20 ° C. A method for continuously producing an aromatic polycarbonate oligomer, which is characterized in that it is carried out in a tubular reactor (JP-A-58-58).
No. 108225), a base aqueous solution of an aromatic dihydroxy compound and a carbonyl halide are reacted in a tubular reactor in the presence of an organic solvent to produce an aromatic polycarbonate oligomer. Continuous method for producing an aromatic polycarbonate oligomer, characterized by introducing a carbonyl halide compound into the reaction system from the position The organic solvent and the cooled reaction product mixture of the second reactor are introduced into the first reactor in an amount such that the concentration of the aromatic dihydroxy compound is 55 to 150 g / liter, and the amount is 0.5 to 10 at 25 ° C. Let react for 20 seconds,
Then, a method for producing an aromatic polycarbonate oligomer is characterized by reacting in a second reactor at 10 to 30 ° C. for 1 to 20 minutes (JP-A-62-167321),

In the reaction tube in which a part of the reaction product mixture passes outside the reaction tube and the rest of the reaction product mixture passes in a turbulent state from one port to the other port. An aromatic polycarbonate comprising reacting a base aqueous solution of an aromatic dihydroxy compound with a carbonyl halide compound in the presence of an organic solvent, combining the obtained reaction mixture with the above-mentioned partial reaction mixture, and then reacting the mixture. Oligomer production method (JP-A-62-235322), a base aqueous solution of an aromatic dihydroxy compound, a carbonyl halide compound, and an organic solvent having a volume of 0.3 to 1.0 times the base aqueous solution from one end of the reaction column. And the cooled reaction mixture is continuously fed at a rate of 55 to 150 g / liter of aromatic dihydroxy compound in the total aqueous base solution, It is possible to obtain an aromatic polycarbonate oligomer having a low molecular weight by a method such as a continuous production method of an aromatic polycarbonate oligomer characterized by reacting at 25 ° C. (JP-A-62-267324).

In the production method of the present invention, the haloformate group of the aromatic polycarbonate oligomer is 15 to 0.
After reaching 1 mol%, a tertiary amine is added. The weight average molecular weight of the aromatic polycarbonate oligomer at this time varies depending on the amount of the molecular weight modifier used, the amount of the carbonyl halide compound used, the reaction conditions and the like. When used in an amount of about mol%, the weight average molecular weight is about 130.
It is preferably from 0 to about 48,000, and about 1400.
More preferably from 0 to 42000, about 1500
More preferably from 0 to about 36000, about 16
It is particularly preferable that it is 000 to about 33000.

The aromatic dihydroxy compound, base, carbonyl halide compound, tertiary amine, water, organic solvent, molecular weight modifier and branching agent used in the present invention will be described in detail below. The aromatic dihydroxy compound used in the production method of the present invention is a compound represented by the general formula (1) or (2). HO-Ar ¹ -X-Ar ² -OH (1) HO-Ar ³ -OH (2) (In the formula, Ar ¹ , Ar ² and Ar ³ are each a divalent aromatic group, and X is Ar ^1- . linking a group) formula that links Ar ² in (1) or (2), Ar ^1, Ar ² and Ar ³ each represent a divalent aromatic group, preferably a phenylene group. The phenylene group may have a substituent, and 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. Ar ¹ and Ar ² are both p-phenylene groups and m-
It is preferable that a phenylene group or an o-phenylene group, or one of them is a p-phenylene group and the other is an m-phenylene group or an o-phenylene group, especially Ar ¹ and A.
It is preferred that both r ² are p-phenylene groups. Ar ³
Is a p-phenylene group, m-phenylene group or o-phenylene group, and preferably a p-phenylene group or m-phenylene group. X is a linking group that connects Ar ¹ and Ar ² , and is a single bond or a divalent hydrocarbon group,
Furthermore -O -, - S -, - SO -, - SO 2 -, - CO
It may be a group containing an atom other than carbon and hydrogen, such as-.
The divalent hydrocarbon group means, for example, an alkylidene group such as a methylene group, an ethylene group, a 2,2-propylidene group, a cyclohexylidene group, an alkylidene group substituted with an aryl group, an aromatic group or other It is a hydrocarbon group containing a saturated hydrocarbon group.

Specific examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4'-hydroxyphenyl) ethane, 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'-hydroxyphenyl) 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'-hydroxyphenyl) 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, 2, 2-bis (4'-hydroxyphenyl) hexafluoropropane and other bis (hydroxyaryl) alkanes,

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (4'-hydroxyphenyl) cycloheptane, 1,1 -Bis (4'-hydroxyphenyl) cyclooctane, 1,1-bis (4'-hydroxyphenyl) cyclononane, 1,1-bis (4'-hydroxyphenyl) cyclododecane, 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, 2,2-bis (4'-
Hydroxyphenyl) norbornane, 8,8-bis (4'-hydroxyphenyl) tricyclo [5.2.1.0 ^2.6] decane,
Bis (hydroxyaryl) cycloalkanes such as 2,2-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

Further, 6,6'-dihydroxy-3,3,3 ', 3'-
Tetramethyl spiro (bis) indan ["spirobiindane bisphenol"], 7,7'-dihydroxy-3,3 ', 4,
4'-tetrahydro-4,4,4 ', 4'-tetramethyl-2,2'-spirobi (2H-1-benzopyran), 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,
Examples thereof include 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone and resorcin. Further, for example, an aromatic dihydroxy compound containing an ester bond, which can be produced by reacting 2 mol of bisphenol A with 1 mol of isophthaloyl chloride or terephthaloyl chloride, is also useful. These may be used alone or in combination of two or more. In the production method of the present invention, it is preferable to use bisphenol A from the viewpoint of easy availability and various physical properties of the produced aromatic polycarbonate.

The base used in the production method of the present invention reacts with the hydroxy group of the aromatic dihydroxy compound to form a phenolate ion, and further receives hydrogen halide produced by the reaction between the haloformate compound and the hydroxy group. It has a function. The base used in the production method of the present invention is a hydroxide of an alkali metal or an alkaline earth metal such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and sodium hydroxide and potassium hydroxide which are easily available. Is preferred,
Sodium hydroxide is particularly preferable. Further, in the present specification,
"Base" does not include alkali metal or alkaline earth metal carbonates and hydrogen carbonates.

The carbonyl halide compound used in the production method of the present invention is a compound which forms a haloformate group and a carbonate bond by the reaction with the hydroxy group of the aromatic dihydroxy compound. Specific examples include phosgene (carbonyl chloride), carbonyl bromide, carbonyl iodide, carbonyl fluoride and the like. Further, these carbonyl halide compounds can be used together. Furthermore, trichloromethyl chloroformate, which is a dimer of phosgene, and bis (trichloromethyl) carbonate, which is a trimer of phosgene, can also be used. Usually, it is preferable to use phosgene. Carbonyl halide compounds are gases, liquids,
It may be used in any state of the organic solvent solution. When the carbonyl halide compound is phosgene, it is preferably used in a gas state, but it may be used in a state of being dissolved in an organic solvent such as dichloromethane or the like in an organic solvent solution.

The relationship among the amounts of the aromatic dihydroxy compound, the base and the carbonyl halide compound used in producing the aromatic polycarbonate by the production method of the present invention is as follows:
When the number of moles of the aromatic dihydroxy compound is α and the number of moles of the carbonyl halide compound is β, 1 ≦ β /
α, preferably 1 ≦ β / α ≦ 2, more preferably 1
≦ β / α ≦ 1.5, more preferably 1 ≦ β / α ≦
1.4, particularly preferably 1 ≦ β / α ≦ 1.3.
When the equivalent of the base is γ, 4β-2α ≦ γ,
Preferably, 4β-2α ≦ γ ≦ 4β-2α + 0.5α,
More preferably, 4β-2α ≦ γ ≦ 4β-2α + 0.4
α, more preferably 4β-2α ≦ γ ≦ 4β-2α +
0.3α, particularly preferably 4β-2α ≦ γ ≦ 4β-2
It is α + 0.2α. 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 hydroxy 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. When γ is 4β-2α + 0.5α or more, no particular advantage is found.

The base and the aromatic dihydroxy compound may be used in the whole amount in the step [1] of the present invention, or may be appropriately added in other steps without using the whole amount in the step [1]. For example, the following method can be used. A. In the step [1], the whole amount of the aromatic dihydroxy compound and the base is used to react with the carbonyl halide compound, and in the step [2], the haloformate group is 15 mol to 0.1 mol per structural unit of the aromatic polycarbonate oligomer. % Of the haloformate groups and the amount of the base in the two-phase mixture is 1: 1.5 to 1: 1.
A method in which a tertiary amine is added after reaching 5.5 (step [3]), and then step [4] is performed. B. In the step [1], about 2 times the amount of the carbonyl halide compound and about 2 times the equivalent number of bases of the aromatic dihydroxy compound and the aromatic dihydroxy compound relative to the number of moles of the aromatic dihydroxy compound, An aromatic polycarbonate oligomer is produced. Next, in step [2], an additional aromatic dihydroxy compound and an additional base are added to the reaction mixture obtained in step [1] so that the haloformate group is 15 to 0.1 per structural unit of the aromatic polycarbonate oligomer. A method in which polycondensation is carried out until it reaches a mol%, a predetermined base amount is appropriately obtained by using an additional base in the step [3], a tertiary amine is added, and further polycondensation is carried out in the step [4]. C. In the step [1], the reaction with the carbonyl halide compound is carried out using the total amount of the aromatic dihydroxy compound and a base in an amount of about 2 times the amount of the aromatic dihydroxy compound, and the reaction is carried out in the step [1] in the step [1]. An additional base is added to the reaction mixture obtained in step 1, so that the haloformate group is 15 to 0.1 per structural unit of the aromatic polycarbonate oligomer.
A method in which polycondensation is carried out until it reaches a mol%, a predetermined base amount is appropriately obtained by using an additional base in the step [3], a tertiary amine is added, and further polycondensation is carried out in the step [4].

The tertiary amine used in the production method of the present invention is preferably a trialkylamine, more preferably a trialkylamine having an alkyl group of C _{1 to} C ₈ . Specific examples include, for example, triethylamine, tri-n-propylamine, diethyl-n-propylamine, tri-n-butylamine, dimethylcyclohexylamine, diethylcyclohexylamine. Further, a tertiary amine may be used in combination with a known polymerization catalyst. Examples of the known polymerization catalyst include quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, nitrogen-containing heterocyclic compounds and salts thereof, imino ethers and The salt, the compound which has an amide group, etc. are mentioned. The amount of the tertiary amine used is preferably 0.0005 to 1.5 mol%, more preferably 0.0008 to 1.0 mol%, based on the number of moles of the aromatic dihydroxy compound. It is more preferably 0.0010 to 0.8 mol%, and particularly preferably 0.0015 to 0.6 mol%. Extremely less than 0.0005 mol% 3
With the amount of the primary amine, the effect for efficiently forming the aromatic polycarbonate does not appear so much, and a long reaction time may be required. Further, when the amount of the tertiary amine is excessively larger than 1.5 mol% with respect to the number of moles of the aromatic dihydroxy compound, no special effect is confirmed. When the tertiary amine is added in the step [3], the concentration of the tertiary amine in the organic phase in the two-phase mixture is 0.65 to 260.
0 ppm, preferably 1.0 to 2000 ppm, more preferably 1.5 to 1500 ppm. In the production method of the present invention, the tertiary amine is added to the reaction mixture containing the aromatic polycarbonate oligomer, and the addition method can be a liquid state, a solid state, an aqueous solution or an organic solvent solution state. Further, it may be added together with the aqueous base solution, or may be added together with the aqueous solution of the molecular weight modifier or the organic solvent solution.

The water used in the production method of the present invention is
Distilled water, deionized water, etc., but the washing water or reaction water produced during the production of the aromatic polycarbonate oligomer and / or aromatic polycarbonate may be used after purification by a purification means such as distillation, if desired, You may use it, mixing with distilled water, deionized water, etc. The amount of water is 0.5 with respect to the number of moles of the aromatic dihydroxy compound.
~ 2.5 liters / mole, preferably 0.6
It is more preferable that the amount is ~ 2.2 liter / mol,
It is more preferably 0.7 to 2.0 liters / mole, and particularly preferably 0.8 to 1.8 liters / mole. In the production method of the present invention, it is not necessary to use the entire amount of water at once in the step [1], and for example, the aromatic dihydroxy compound used in the reaction of an aromatic dihydroxy compound with a base and a carbonyl halide compound. The amount of water necessary for dissolving the base is used in step [1], and water is appropriately added in step [2] or step [3] to adjust the base concentration in step [3] to a predetermined value. can do. Further, using an amount of water necessary for dissolving the aromatic dihydroxy compound in the step [1], the aqueous phase is separated from the reaction mixture containing the aromatic polycarbonate oligomer produced in the step [1], In the step [2] or the step [3], a base and water are appropriately added to the step [3]
It is also possible to adjust the base concentration in step 1 to a predetermined value.

The organic solvent used in the production method of the present invention is substantially insoluble in water, inert to the reaction, and capable of dissolving the aromatic polycarbonate oligomer and / or the aromatic polycarbonate. It can be used as desired. As the organic solvent, dichloromethane, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane, aliphatic chlorinated hydrocarbons such as dichloropropane, chlorobenzene, aromatic chlorinated hydrocarbons such as dichlorobenzene, Or it is possible to use mixtures thereof. Further, it is also possible to use an organic solvent in which an aromatic hydrocarbon such as toluene, xylene, or ethylbenzene, an aliphatic hydrocarbon such as hexane, heptane, or cyclohexane is mixed with these chlorinated hydrocarbons or a mixture thereof. is there. Dichloromethane is preferred because of its excellent ability to dissolve an aromatic polycarbonate. In addition, the recovered organic solvent produced when the aromatic polycarbonate oligomer and / or the aromatic polycarbonate is produced by the method of the present invention may be purified by a purification means such as distillation, if desired, and used, and mixed with a new organic solvent. You may use it.

The amount of the organic solvent is usually preferably such that the concentration of the aromatic polycarbonate in the organic solvent solution of the aromatic polycarbonate at the end of the polycondensation reaction is about 5 to 35% by weight, and about 10 to 20% by weight. Is more preferable.
When the concentration of the aromatic polycarbonate in the organic solvent solution of the aromatic polycarbonate is extremely low, a large amount of the organic solvent is required, resulting in poor production efficiency. Further, when the concentration of the aromatic polycarbonate in the organic solvent solution of the aromatic polycarbonate is a concentration close to the saturated state, the viscosity of the organic solvent solution of the aromatic polycarbonate becomes very high, and thus the efficiency of the interfacial polymerization reaction decreases. Problems such as deterioration of handleability after polymerization occur. It is not necessary to use the entire amount of the organic solvent at once in the step [1], and if desired,
An organic solvent may be added after the viscosity of the aromatic polycarbonate has increased in step [2], [3] or step [4] of the present invention. At this time, it is preferable to add the organic solvent so that the concentration of the haloformate group in the organic solvent phase in the step [3] becomes a predetermined concentration. Further, the volume ratio of the organic phase and the aqueous phase in the case of producing the aromatic polycarbonate is about 0.
Preferably, it will be from 5: 1 to about 1.5: 1.

The molecular weight regulator used in the production method of the present invention is a compound having a function of controlling the molecular weight at the time of producing an aromatic polycarbonate, and generally, a monovalent hydroxyaromatic compound is used. To 1
Alkali metal or alkaline earth metal salt of monovalent hydroxyaromatic compound, haloformate derivative of monovalent hydroxyaromatic compound, monovalent carboxylic acid, alkali metal or alkaline earth metal salt of monovalent carboxylic acid, monovalent The acid halide derivative of carboxylic acid can also be used. Examples of monovalent hydroxyaromatic compounds include phenol and p-te.
rt-Butylphenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, p-cumylphenol, p-phenylphenol, p-cyclohexylphenol, pn-
Octylphenol, p-nonylphenol, p-methoxyphenol, pn-hexyloxyphenol,
p-isopropenylphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o
-Bromophenol, m-bromophenol, p-bromophenol, pentabromophenol, pentachlorophenol, β-naphthol, α-naphthol, 2-
(4′-methoxyphenyl) -2- (4 ″ -hydroxyphenyl) propane, etc. Examples of the alkali metal or alkaline earth metal salt of a monovalent hydroxyaromatic compound include the above-mentioned monovalent hydroxyaromatics. Examples thereof include alkali metal or alkaline earth metal salts such as sodium salt, potassium salt and calcium salt of the compound. Examples of the monovalent hydroxy aromatic compound haloformate derivative include the above-mentioned monovalent hydroxy aromatic compound haloformate derivative and the like. Is mentioned.

As the monovalent carboxylic acid, acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid, 3-methylbutyric acid, 3,3-dimethylbutyric acid, 4-methylvaleric acid, 3,3-dimethylvaleric acid , 4-methylcaproic acid, 2,4-dimethylvaleric acid,
Aliphatic monovalent carboxylic acids such as 3,5-dimethylcaproic acid and phenoxyacetic acid, benzoic acid, p-methylbenzoic acid,
p-tert-butylbenzoic acid, pn-propoxybenzoic acid, pn-butoxybenzoic acid, pn-pentyloxybenzoic acid, pn-hexyloxybenzoic acid, p
Examples of the aromatic monovalent carboxylic acids such as -n-octyloxybenzoic acid include alkali metal or alkaline earth metal salts of monovalent carboxylic acid, and sodium salts and potassium salts of the above monovalent carboxylic acids. Alkali metal or alkaline earth metal salts such as salts and calcium salts are mentioned.
Examples of the acid halide derivative of a divalent carboxylic acid include the above-mentioned 1
Examples thereof include acid halide derivatives of divalent carboxylic acids. These may be used alone or in combination of two or more. Phenol, p-cumylphenol or p-tert-butylphenol is preferable from the viewpoint of easy availability.

The amount of the molecular weight modifier used is adjusted according to the desired average molecular weight of the finally obtained aromatic polycarbonate. The aromatic polycarbonate produced by the production method of the present invention can have an arbitrary average molecular weight by adjusting the amount of the molecular weight regulator used, but it has various molding processability, thermal decomposition resistance, impact resistance, and other properties. Considering physical properties, the weight average molecular weight is preferably about 10,000 to about 100,000, and more preferably about 20,000 to about 80,000. The amount of the molecular weight modifier necessary for producing the aromatic polycarbonate having the weight average molecular weight in the above range is about 0.5 to about 9. based on the number of moles of the aromatic dihydroxy compound used.
It is preferably 6 mol%, more preferably about 1.5 to about 8.7 mol%. The molecular weight modifier can be added as an aqueous solution or an organic solvent solution, or can be added as an aqueous solution together with an aqueous solution of an aromatic dihydroxy compound or a base.

It is also within the scope of the present invention to produce a branched aromatic polycarbonate by adding a branching agent if desired. The branching agent is a compound having three or more (which may be the same or different) reactive groups selected from an aromatic hydroxy group, a haloformate group, a carboxyl group, a carbonyl halide group and an active halogen atom,
For example, 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, 1,1,4,4-tetrakis (4 ' -Hydroxyphenyl)
Cyclohexane, 1,4-bis (4 ', 4''-dihydroxytriphenylmethyl) benzene, trimesic acid trichloride, cyanuric acid chloride, 3,5-dihydroxybenzoic acid, 5-hydroxyisophthalic acid, 3,5-bis (Chlorocarbonyloxy) benzoic acid, 5-chlorocarbonyloxyisophthalic acid, 4-chlorocarbonyloxyphthalic acid, 3,3-
Examples include bis (4'-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 3,3-bis (4'-hydroxy-3'-methylphenyl) -2-oxo-2,3-dihydroindole. To be

The amount of the branching agent is adjusted according to the degree of branching of the desired branched aromatic polycarbonate, but usually it is based on the number of moles of the aromatic dihydroxy compound.
It is preferably about 0.05 to 2.0 mol%. The branching agent can be used as an aqueous solution or an organic solvent solution, and can also be used as an aqueous solution together with an aromatic dihydroxy compound and a base. In the present invention, when a branching agent is used, the branching agent is the step [1], the step [2],
It is added in any step of the step [3], but the step [1]
It may be added before the reaction of the aromatic dihydroxy compound with the base and the carbonyl halide compound, or at the time when the reaction of the aromatic dihydroxy compound with the carbonyl halide compound in step [1] is completed. May be. The production method of the present invention is usually carried out at a temperature of about 10 ° C. to the boiling point of the organic solvent used in the reaction. The temperature is preferably about 10 to about 50 ° C., more preferably about 10 to about 50 ° C.
The temperature is 40 ° C, more preferably about 10 to 35 ° C. Further, it is usually carried out under atmospheric pressure, and if desired, it can be carried out under atmospheric pressure or under atmospheric pressure.

The production method of the present invention is usually carried out while stirring the reaction mixture. The stirring may be performed to such an extent as to prevent the separation of the organic solvent phase and the aqueous phase, and is usually performed to such an extent that the organic solvent phase and the aqueous phase are uniformly mixed. Excessively vigorous stirring will accelerate the hydrolysis of the carbonyl halide compound and / or the haloformate compound. Further, in order to perform excessively vigorous stirring, a special stirring device is required, which is not preferable. Further, if the stirring is excessively inefficient, the reaction will not proceed efficiently under the interfacial conditions. Since the stirring conditions are influenced by the shape of the tank reactor and the shape of the stirring blade, it is not possible to show the preferable stirring conditions only by the rotation speed of stirring, but a simple experiment shows that the preferable stirring conditions suitable for the reactor Can be asked. In addition, stirring does not always have to be a constant condition during the process of producing an aromatic polycarbonate, and for example, after producing a low molecular weight aromatic polycarbonate oligomer, the stirring condition is increased to efficiently perform the polycondensation reaction. You can also

The method of the present invention may be carried out batchwise or continuously. The reactor used in the production method of the present invention is a known reactor such as a tank reactor, a tubular reactor, a packed tower, a static mixer, or a reactor in which those reactors are arbitrarily combined. is there. The production method of the present invention can be carried out batchwise. For example, using a tank type reactor, an aromatic dihydroxy compound, a base, water, an organic solvent, and optionally a molecular weight modifier and a branching agent are charged therein, and the two-phase mixture is
The carbonyl halide compound is supplied under stirring to carry out the haloformate reaction. Furthermore, after the haloformate group of the aromatic polycarbonate oligomer obtained by the haloformate reaction becomes 15 to 0.1 mol%,
The equivalent ratio of haloformate groups to base in the two-phase mixture is 1:
It can be 1.5 to 1: 5.5, a tertiary amine can be added, and an aromatic polycarbonate oligomer can be further polycondensed. It is also possible to combine the tank reactor and other reactors and carry out in a semi-batch mode.

The production method of the present invention can also be carried out continuously by using a continuous stirred tank reactor (CSTR) in which several tank reactors are continuously connected. For example, an aromatic dihydroxy compound, a base, water, an organic solvent, a carbonyl halide compound, and, if desired, a molecular weight modifier and a branching agent are continuously supplied to a first tank reactor of a continuous stirred tank reactor. Then, the reaction mixture is stirred and mixed in the first tank reactor for a predetermined residence time. Then, the reaction mixture produced in the first tank reactor was supplied to the second tank reactor, and the mixture was stirred and mixed for a predetermined residence time in the same manner, so that the aromatic polycarbonate oligomer had a haloformate group of 15 to 15%. The equivalence ratio of the haloformate group to the base in the two-phase mixture of the tank type reactor which becomes 0.1 mol% is 1 :.
It can be 1.5 to 1: 5.5 equivalents, and a tertiary amine can be added to this tank reactor to further polycondense the aromatic polycarbonate oligomer. Further, the production method of the present invention can be carried out continuously by using a tubular reactor.

The production method of the present invention can be carried out continuously by using a reaction device in which any combination of reaction devices such as a tank-type reaction device, a tube-type reaction device, a packed tower and a static mixer is used. it can. For example, at the initial stage of the reaction, a device such as a tubular reactor, a packed column or a static mixer for performing initial contact between an aromatic dihydroxy compound and a carbonyl halide compound is provided to continuously produce a low molecular weight aromatic polycarbonate oligomer. . Next, a tank reactor, a tubular reactor, a static mixer or the like is used to further react to carry out polycondensation of the aromatic polycarbonate oligomer. Then, after the haloformate group of the aromatic polycarbonate oligomer reaches 15 to 0.1 mol%, the equivalent ratio of the haloformate group to the base in the two-phase mixture is 1: 1.5 to.
The amount can be 1: 5.5 equivalent, a tertiary amine can be added, and an aromatic polycarbonate oligomer can be further polycondensed.

When a continuous stirred tank reactor is used, the residence time means the average residence time, and the residence time for each reactor is preferably about 1 to 60 minutes.
It is more preferably ˜50 minutes, even more preferably 4 to 40 minutes. The average residence time is per unit time of the internal volume of the tank reactor and the aromatic dihydroxy compound, water, carbonyl halide compound, organic solvent, base and optionally a molecular weight regulator and branching agent supplied to the tank reactor. It can be calculated from the sum of the capacities supplied to. For example, when a total of 0.5 liter of feed is supplied per minute to a tank reactor having an internal volume of 5 liters, the residence time is 10 minutes. When the continuous stirred tank reactor is used, the number of tank reactors is preferably 2 or more, more preferably 2 to 10, and further preferably 3 to 8. . In addition, the tank-type reactor has a stirring blade such as a Faudler blade, turbine blade, paddle blade, Maxblend blade (manufactured by Sumitomo Heavy Industries, Ltd.), full zone blade (manufactured by Shinzuna Pantech Co., Ltd.).
A reactor equipped with, etc. can be used. Usually, it is preferable to use a continuous stirred tank reactor in order to stably produce an aromatic polycarbonate.

The reaction mixture containing the aromatic polycarbonate produced according to the present invention is then subjected to post-treatment by continuous operation or batch operation, preferably continuous operation, to recover the aromatic polycarbonate. Work-up of the reaction mixture is
The organic solvent phase containing the aromatic polycarbonate and the aqueous phase are separated, and then the organic solvent phase containing the aromatic polycarbonate is washed with water or a dilute aqueous alkaline solution as necessary, and further neutralized with a dilute aqueous acid solution. To do. Examples of the acid used here include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid. After that, washing with water is further repeated until the electrolyte is substantially absent. Then, the organic solvent is removed from the washed organic solvent solution of the aromatic polycarbonate by a known method to recover the aromatic polycarbonate.

As a method of removing the organic solvent from the organic solvent solution of the aromatic polycarbonate and recovering the aromatic polycarbonate, a method of removing the organic solvent by distillation or steam distillation, or an organic solvent that does not dissolve the aromatic polycarbonate ( (Poor solvent) is added to the organic solvent solution of the aromatic polycarbonate to make the aromatic polycarbonate in a solid state, and the organic solvent is separated from the obtained aromatic polycarbonate organic solvent slurry by a method such as filtration. it can. As a more specific method, a predetermined amount of the organic solvent is distilled off from the organic solvent solution of the aromatic polycarbonate, and the organic solvent solution of the aromatic polycarbonate is saturated to crystallize the aromatic polycarbonate. A method of removing the organic solvent contained by pulverizing and drying, a method of immediately pelletizing the aromatic polycarbonate in a molten state by heating while removing the organic solvent directly from the organic solvent solution of the aromatic polycarbonate, aromatic polycarbonate The method of pulverizing the gel-like substance produced while removing the organic solvent by supplying the organic solvent solution of the above to the organic solvent solution, adding the poor solvent or non-solvent for the aromatic polycarbonate to the organic solvent solution of the aromatic polycarbonate, and water. , By heating and concentrating, the solid state aromatic polycarbonate is A method of obtaining a slurry, a method of obtaining an aromatic polycarbonate in a solid state as an aqueous slurry by adding an organic solvent solution of an aromatic polycarbonate to warm water containing powder of the aromatic polycarbonate and evaporating and distilling off the organic solvent, A method for obtaining an aromatic polycarbonate in a solid state as an aqueous slurry by evaporating and distilling off the organic solvent while supplying an organic solvent solution of the aromatic polycarbonate into warm water containing a poor solvent for the powder of the aromatic polycarbonate and the aromatic polycarbonate. Etc. can be mentioned.

As the poor solvent or non-solvent for the aromatic polycarbonate used here, for example, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, octane, cyclohexane and methylcyclohexane, Examples include alcohols such as methanol, ethanol, propanol, butanol, pentanol, and hexanol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone, and esters such as ethyl acetate, butyl acetate, and amyl acetate. it can. The aromatic polycarbonate obtained by the production method of the present invention can be mixed with another polymer and used as a molding material. 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 polycarbonate, and further, during or after the production of the aromatic polycarbonate, by a known method by a known method. Known additives such as agents, antioxidants, ultraviolet absorbers, release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, barium sulfate and TiO ₂ may be added. . The aromatic polycarbonate produced by the production method of the present invention, alone or in a state of being mixed with another polymer, is added with the above-mentioned additive, if desired, as a molding material, such as a chassis or a housing material of an electric device or an electronic component. , Automobile parts, substrates for information recording media such as compact discs, optical materials such as lenses for cameras and spectacles, building materials instead of glass, etc., injection molding, extrusion molding, blow molding in the molten state ,
It can be impregnated with a filler or the like, and can be easily molded by a known molding method.

[0048]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. The physical properties of each example and comparative example were measured by the following methods. Table 1 (Table 1) summarizes the reaction conditions at the time of adding the tertiary amines of Examples 1 to 11 and Comparative Examples 1 to 4, and the physical property values of the aromatic polycarbonates produced in Examples and Comparative Examples. -Molecular weight: 0.2 wt% chloroform solution of aromatic polycarbonate oligomer and aromatic polycarbonate was measured by GPC [gel permeation chromatography, Showa Denko KK System-11], and the weight average molecular weight (Mw ) Was asked. The measured values are standard polystyrene equivalent values. -Number of moles of haloformate group of aromatic polycarbonate oligomer: 0.01% by weight dichloromethane solution of 4- (4'-nitrobenzyl) pyridine (Wako Pure Chemical Industries, special grade reagent) was added to dichloromethane solution of phenylchloroformate to develop color. , Spectrophotometer [Shimadzu Corporation, U
V-2200] was used to measure the extinction coefficient (ε ₄₄₀ = 2.58 × 10 ⁴ liter / mol · cm) at a wavelength of 440 nm. About 30 mg of solid-state aromatic polycarbonate oligomer was precisely weighed based on this extinction coefficient, dissolved in 50 ml of dichloromethane, and 0.01% by weight solution of 4- (4′-nitrobenzyl) pyridine in dichloromethane 2
Color was added by adding ml, and the number of moles of haloformate groups per structural unit of the aromatic polycarbonate oligomer in the sample was determined. -Measurement of amount of nitrogen component taken in aromatic polycarbonate: The aromatic polycarbonate was measured by a total nitrogen analyzer [TN-10 type manufactured by Mitsubishi Kasei Co., Ltd.]. -Haloformate group hydrolysis amount: The amount of sodium carbonate in the aqueous phase when the tertiary amine was added and the amount of sodium carbonate in the aqueous phase when the polycondensation was completed were each determined by potentiometric titration using 1/2 normal hydrochloric acid. The amount of hydrolysis of the haloformate group after addition of the tertiary amine was calculated from the measured value. Base concentration in aqueous phase when tertiary amine was added: The base concentration in the aqueous phase was calculated by potentiometric titration using 1/2 normal hydrochloric acid.

Example 1 A baffled flask having an internal capacity of 10 liters was equipped with a stirrer having a Maxblend blade, a reflux condenser, and a dipping tube for blowing phosgene. 912g in this flask
(4.0 mol) bisphenol A, 20.64 g
(0.1376 mol, 3.4 with respect to bisphenol A
(4 mol%) p-tert-butylphenol, 4 liters of dichloromethane and 4 liters of deionized water were added to form a suspension, and a nitrogen purge was performed to remove oxygen in the flask. Next, to the above suspension, 448 g (11.2
2.2 liters of an aqueous sodium hydroxide solution in which 1.2 g of sodium hydroxide and 1.2 g of sodium hydrosulfite were dissolved were supplied to dissolve bisphenol A. Next, 466.9 g (4.7%) was added to this two-phase mixed solution.
(2 mol) phosgene was bubbled in at a feed rate of 7.78 g / min. After the supply of phosgene was completed, stirring and mixing were performed for 60 minutes, and then 0.64 g of triethylamine was added, and the reaction solution was further stirred and mixed to carry out a polycondensation reaction of the aromatic polycarbonate oligomer. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate The weight average molecular weights of the oligomers are summarized in Table 1. Then, the reaction solution was allowed to stand still, the organic phase was separated, neutralized with hydrochloric acid, and washed with deionized water until the electric field disappeared. To the thus obtained dichloromethane solution of the aromatic polycarbonate, 2 liters of toluene and 5 liters of water were added, and the mixture was heated to 98 ° C. to distill off dichloromethane and toluene to obtain a polycarbonate powder. Table 1 shows the weight average molecular weight of the obtained aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 2 An aromatic polycarbonate was produced in the same manner as in Example 1 except that stirring was carried out for 30 minutes after the completion of blowing phosgene. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate Table 1 shows the weight average molecular weight of the oligomer, the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 3 A baffled flask having an internal capacity of 10 liters was equipped with a stirring base having a Maxblend blade, a reflux cooling tube, and a dipping tube for blowing phosgene. 912g in this flask
(4.0 mol) bisphenol A and 20.64
g (0.1376 mol, 3.
(44 mol%) p-tert-butylphenol, 4 liters of dichloromethane, 4 liters of deionized water were charged to prepare a suspension. The suspension was nitrogen purged to remove oxygen from the reaction system. In this suspension,
424 g (10.6 mol) sodium hydroxide, 1.2
2.0 liter of sodium hydroxide aqueous solution containing g of sodium hydrosulfite was supplied to dissolve bisphenol A. Next, to this two-phase mixed solution, 455.
0 g (4.6 mol) of phosgene was bubbled in at a feed rate of 7.58 g / min. After the completion of blowing phosgene, the reaction mixture was mixed with stirring for 15 minutes, 0.2 liter of sodium hydroxide aqueous solution containing 24 g of sodium hydroxide was further added, and 0.64 g of triethylamine was added,
The polycondensation reaction of the aromatic polycarbonate oligomer was performed by mixing with stirring. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate The weight average molecular weights of the oligomers are summarized in Table 1. Further, the aromatic polycarbonate after the polycondensation reaction was washed with water and isolated in the same manner as in Example 1 to obtain a powder. Table 1 shows the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 4 A flask equipped with a baffle having an internal volume of 10 liters was equipped with a stirrer having a Maxblend blade, a reflux condenser, and a dip tube for blowing phosgene. 912g in this flask
(4.0 mol) bisphenol A, dichloromethane 4
1 liter and 2 liters of deionized water were added to make a suspension, and a nitrogen purge was performed to remove oxygen in the flask. Next, to the above suspension, 2.2 liters of an aqueous sodium hydroxide solution in which 320 g (8.0 mol) of sodium hydroxide and 1.2 g of sodium hydrosulfite were dissolved was supplied to dissolve bisphenol A. . next,
To this two-phase mixed solution, 443.2 g (4.48 mol) of phosgene was fed at a feed rate of 7.38 g / min. After the supply of phosgene was completed, 0.2 liter of an aqueous sodium hydroxide solution containing 104 g of sodium hydroxide, 2
0.64 g (0.1376 mol, 3.44 mol% with respect to bisphenol A) of p-tert-butylphenol was dissolved in 0.2 liter of dichloromethane and added.
Then, the mixture is stirred and mixed for 30 minutes, 0.2 liter of sodium hydroxide aqueous solution containing 24 g of sodium hydroxide and 0.64 g of triethylamine are added, and the reaction liquid is further stirred and mixed to obtain an aromatic polycarbonate oligomer. A polycondensation reaction was performed. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, ratio of mole number of haloformate group to amount of base, concentration of base in aqueous phase The weight average molecular weights of the aromatic polycarbonate oligomers are summarized in Table 1. afterwards,
The reaction solution is allowed to stand, the organic phase is separated, neutralized with hydrochloric acid,
It was washed with deionized water until the electrolyte was gone. To the dichloromethane solution of the aromatic polycarbonate thus obtained, 2 liters of toluene and 5 liters of water were added.
Dichloromethane and toluene were distilled off by heating to 8 ° C to obtain a polycarbonate powder. Table 1 shows the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 5 A flask equipped with a baffle having an internal capacity of 10 liters was equipped with a stirrer having a Maxblend blade, a reflux condenser, and a dip tube for blowing phosgene. 912g in this flask
(4.0 mol) bisphenol A, dichloromethane 4
1 liter and 4 liters of deionized water were added to make a suspension, and a nitrogen purge was performed to remove oxygen in the flask. Next, to the above suspension, 448 g (11.2 mol)
2.2 liters of an aqueous sodium hydroxide solution containing 1.2 g of sodium hydroxide and 1.2 g of sodium hydrosulfite were supplied to dissolve bisphenol A. Next, 466.9 g (4.72 mol) of phosgene was fed to the two-phase mixed solution at a feeding rate of 7.78 g / min. After the supply of phosgene is completed, 20.64 g
(0.1376 mol, 3.4 with respect to bisphenol A
4 mol% of p-tert-butylphenol dissolved in 0.2 liter of dichloromethane and added. Then 3
After stirring and mixing for 0 minutes, 0.64 g of triethylamine was added, and the reaction liquid was further stirred and mixed to carry out a polycondensation reaction of the aromatic polycarbonate oligomer.
Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate The weight average molecular weights of the oligomers are summarized in Table 1. Then, the reaction solution is allowed to stand still, the organic phase is separated,
It was neutralized with hydrochloric acid and washed with deionized water until the electrolyte was gone. To the dichloromethane solution of the aromatic polycarbonate thus obtained, 2 liters of toluene and 5 liters of water were added, and the mixture was heated to 98 ° C. to distill off dichloromethane and toluene to obtain a polycarbonate powder. Table 1 shows the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 6 8406 g (36.87 mol) of bisphenol A, 1
Dissolve 74.756 g (1.165 mol) p-tert-butylphenol, 4277 g (106.93 mol) sodium hydroxide and 16.794 g sodium hydrosulfite in 57.06 kg deionized water, total weight A 69.96 kg homogeneous base aqueous solution of bisphenol A was prepared. This aqueous solution, phosgene and dichloromethane were respectively 129.56 g / min, 7.970
g (0.08057 mol) / min, and a supply rate of 127.3 g / min were supplied to a tank reactor having an overflow tube with an internal volume of 5 liters. The reaction mixture is discharged from the overflow outlet at a rate of 264.57 g / min. The residence time was 20 minutes. The continuously discharged reaction mixture was continuously supplied to the second tank reactor by using a pipe. In a second tank reactor, polycondensation was performed by stirring and mixing for a residence time of 30 minutes. Further, the reaction mixture was supplied to the third tank reactor. Simultaneously with the supply of the reaction mixture, triethylamine was supplied to the third tank reactor at a supply rate of 0.0111 g (0.16 mol% based on bisphenol A) / min. In the third tank reactor, the reaction mixture was stirred and mixed for a residence time of 30 minutes to carry out a polycondensation reaction of the aromatic polycarbonate oligomer. Further, the reaction mixture discharged from the third tank reactor was supplied to the fourth tank reactor, and mixed by stirring for a residence time of 40 minutes to terminate the polycondensation reaction. Fourth
The dichloromethane solution of the aromatic polycarbonate discharged from the tank reactor of Example 1 was washed with water according to the method of Example 1,
Isolation was performed. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate Table 1 shows the weight average molecular weight of the oligomer, the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate.

Example 7 Except that the residence time in the second tank reactor was 15 minutes,
An aromatic polycarbonate was produced in the same manner as in Example 6.
Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate Table 1 shows the weight average molecular weight of the oligomer, the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 8 8406 g (36.87 mol) of bisphenol A, 1
74.756 g (1.165 mol) p-tert-butylphenol, 3947 g (98.68 mol) sodium hydroxide and 16.794 g sodium hydrosulfite were dissolved in 47.93 kg deionized water, A uniform aqueous base solution of bisphenol A having a total weight of 60.18 kg was prepared. This aqueous solution, phosgene, and dichloromethane were 111.44 g / min and 7.767, respectively.
g (0.07852 mol) / min and a supply rate of 127.3 g / min were fed to a tank reactor having an overflow pipe with an internal volume of 5 liters. The reaction mixture is discharged from the overflow outlet at a rate of 264.57 g / min. The residence time was 20 minutes. The continuously discharged reaction mixture was continuously supplied to the second tank reactor by using a pipe. Polycondensation was carried out by stirring and mixing with a second tank reactor for a residence time of 30 minutes. The reaction mixture was then fed to the third tank reactor. Simultaneously with the supply of the reaction mixture, 0.013 g of triethylamine (0.1% relative to bisphenol A was added to the third tank reactor).
6 mol%) / minute, and a total weight of 560 g of an aqueous sodium hydroxide solution in which 280 g of sodium hydroxide was dissolved was supplied at a rate of 1.166 g / minute. The reaction mixture was stirred and mixed in the third tank reactor for a residence time of 40 minutes to carry out a polycondensation reaction of the aromatic polycarbonate oligomer. Further, the reaction mixture discharged from the third tank reactor was fed to the fourth tank reactor,
The polycondensation reaction was terminated by stirring and mixing for a residence time of minutes. The dichloromethane solution of aromatic polycarbonate discharged from the fourth tank reactor was washed with water and isolated according to the method of Example 1. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when adding triethylamine, concentration of haloformate group in organic phase, equivalent ratio of haloformate group to base,
Table 1 shows the base concentration in the aqueous phase, the weight average molecular weight of the aromatic polycarbonate oligomer, the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 9 580 g total weight dissolved 280 g sodium hydroxide
Instead of supplying the aqueous sodium hydroxide solution of 1.66 g / min to the third tank reactor,
Aromatic polycarbonate was produced in the same manner as in Example 8 except that the aromatic polycarbonate was supplied to the tank reactor. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate Table 1 shows the weight average molecular weight of the oligomer, the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 10 8406 g (36.87 mol) of bisphenol A, 3
687 g (91.18 mol) of sodium hydroxide and 16.794 g of sodium hydrosulfite,
Dissolved in 47.93 kg deionized water to give a total weight of 6
A uniform aqueous solution of 0.04 kg of bisphenol A in base was prepared. 111.18 g / min and 7.767 g of this aqueous solution, phosgene, and dichloromethane, respectively.
(0.07852 mol) / min and 127.3 g / min were supplied to a tank-type reactor having an overflow tube with an internal volume of 5 liters. The reaction mixture is discharged from the overflow outlet at a rate of 264.57 g / min. The residence time was 20 minutes. The continuously discharged reaction mixture was continuously supplied to the second tank reactor by using a pipe. In this second tank reactor, 3.61
560 g of sodium hydroxide and 1 at a feed rate of 4 g / min
74.756 g (1.165 mol) of p-tert-butylphenol and a total weight of 1735 g of sodium hydroxide aqueous solution were supplied, and the mixture was stirred and mixed for a residence time of 40 minutes to carry out polycondensation. Further, the reaction mixture was fed to the subsequent third tank reactor, and at the same time as the reaction mixture was fed to the third tank reactor, 0.0111 g (0.16 mol% based on bisphenol A) / Triethylamine was fed to the third tank reactor at a feed rate of minutes. The reaction mixture was stirred and mixed in the third tank reactor for a residence time of 40 minutes to carry out a polycondensation reaction of the aromatic polycarbonate oligomer. Further, the reaction mixture discharged from the third tank reactor was supplied to the fourth tank reactor, and the mixture was stirred and mixed for a residence time of 40 minutes to terminate the polycondensation reaction.
A dichloromethane solution of the aromatic polycarbonate discharged from the fourth tank reactor was prepared according to the method of Example 1.
It was washed with water and isolated. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate Table 1 shows the weight average molecular weight of the oligomer, the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Example 11 In Example 1, 20.64 g (0.1376 mol,
3.44 mol% of bisphenol A) p-te
Instead of using rt-butylphenol, 18.00
An aromatic polycarbonate was produced in the same manner as in Example 1 except that g (0.12 mol, 3.0 mol% based on bisphenol A) of p-tert-butylphenol was used. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate Table 1 shows the weight average molecular weight of the oligomer, the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Comparative Example 1 A baffled flask having an internal capacity of 10 liters was equipped with a stirrer having a Maxblend blade, a reflux cooling tube, and a dipping tube for blowing phosgene. 912g in this flask
(4.0 mol) bisphenol A and 20.64 g
(0.1376 mol, 3.4 with respect to bisphenol A
4 mol% of p-tert-butylphenol, 4 liters of dichloromethane, 4 liters of deionized water,
A suspension was prepared. The suspension was nitrogen purged to remove oxygen from the reaction system. To this suspension 448
2.0 l of an aqueous sodium hydroxide solution containing g (12 mol) of sodium hydroxide and 1.2 g of sodium hydrosulfite was supplied to dissolve bisphenol A. Next, 466.9 g (4.
72 mol) of phosgene was bubbled in at a feed rate of 15.6 g / min. 0.64 immediately after blowing phosgene
The polycondensation reaction of the aromatic polycarbonate oligomer was carried out by adding g of triethylamine and mixing with stirring. The number of moles of haloformate groups per structural unit of the aromatic polycarbonate oligomer when triethylamine was added, the concentration of haloformate groups in the organic phase,
Equivalent ratio of haloformate group and base, base concentration in the aqueous phase,
The weight average molecular weight of the aromatic polycarbonate oligomer is summarized in Table 1. Further, the aromatic polycarbonate after the polycondensation reaction was washed with water and isolated in the same manner as in Example 1 to obtain a powder. Table 1 shows the weight average molecular weight of the obtained aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Comparative Example 2 A baffled flask having an internal capacity of 10 liters was equipped with a stirrer having a Maxblend blade, a reflux condenser, and a dip tube for blowing phosgene. 912g in this flask
(4.0 mol) bisphenol A and 20.64 g
(0.1376 mol, 3.4 with respect to bisphenol A
4 mol%) p-tert-butylphenol, 4 liters dichloromethane, 2 liters deionized water,
A suspension was prepared. The suspension was nitrogen purged to remove oxygen from the reaction system. 384 in this suspension
2.0 liter of an aqueous sodium hydroxide solution containing g (9.6 mol) of sodium hydroxide and 1.2 g of sodium hydrosulfite was supplied to dissolve bisphenol A. Next, in this two-phase mixed solution, 499.5 g
Phosgene (5.0 mol) was bubbled in at a feed rate of 7.75 g / min. After completion of blowing phosgene, the aromatic polycarbonate oligomer was polycondensed by stirring for 30 minutes, and then 0.2 liter of sodium hydroxide aqueous solution containing 108 g of sodium hydroxide and 0.64 g of triethylamine were added and stirred. A polycondensation reaction of the aromatic polycarbonate oligomer was performed by mixing. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate The weight average molecular weights of the oligomers are summarized in Table 1. Furthermore, the aromatic polycarbonate after the polycondensation reaction is washed with water and isolated in the same manner as in Example 1,
It was a powder. Table 1 shows the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Comparative Example 3 A flask equipped with a baffle having an internal capacity of 10 liters was equipped with a stirrer having a Maxblend blade, a reflux condenser, and a dip tube for blowing phosgene. 912g in this flask
(4.0 mol) bisphenol A, 20.64 g
(0.1376 mol, 3.4 with respect to bisphenol A
(4 mol%) p-tert-butylphenol, 4 liters of dichloromethane and 4 liters of deionized water were added to form a suspension, and a nitrogen purge was performed to remove oxygen in the flask. Next, 2.2 liters of an aqueous sodium hydroxide solution in which 432 g (11.0 mol) of sodium hydroxide and 1.2 g of sodium hydrosulfite were dissolved was supplied to the above suspension to dissolve bisphenol A.
Next, 495 g (5.0 mol) of phosgene was blown into the two-phase mixed solution at a feed rate of 8.25 g / min. After the supply of phosgene was completed, 0.16 g of triethylamine was added, and the reaction mixture was stirred and mixed for 10 minutes. Then, 0.2 liter of an aqueous solution containing 16 g of sodium hydroxide and 0.48 g of triethylamine were reacted. It was added to the mixture, and the reaction mixture was further stirred and mixed to carry out a polycondensation reaction of the aromatic polycarbonate oligomer.
The number of moles of haloformate groups per structural unit of the aromatic polycarbonate oligomer when the first addition of triethylamine was performed, the concentration of haloformate groups in the organic phase,
Table 1 shows the ratio of the number of moles of haloformate group to the amount of base, the concentration of base in the aqueous phase, and the weight average molecular weight of the aromatic polycarbonate oligomer. The produced aromatic polycarbonate-containing dichloromethane solution was washed with water and isolated in the same manner as in Example 1 to obtain an aromatic polycarbonate powder. Table 1 shows the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate after the addition of triethylamine.

Comparative Example 4 8406 g (36.87 mol) of bisphenol A and 1
Dissolve 74.756 g (1.165 mol) p-tert-butylphenol, 3687 g (91.18 mol) sodium hydroxide, 16.794 g sodium hydrosulfite in 57.06 kg deionized water, A uniform base aqueous solution of bisphenol A having a weight of 69.34 kg was prepared. 128.42 g / min and 7.638 g of this aqueous solution, phosgene, and dichloromethane, respectively.
(0.07715 mol) / min and 127.3 g / min were supplied to a tank-type reactor having an internal capacity of 5 liters with an overflow pipe. The reaction mixture is discharged from the overflow outlet at a rate of 264.57 g / min. The residence time was 20 minutes. The continuously discharged reaction mixture was continuously supplied to the second tank reactor by using a pipe. At the same time as the reaction mixture was supplied to the second tank reactor, triethylamine was supplied at a rate of 0.0111 (0.16 mol% with respect to bisphenol A) / minute, 2.333 g / minute. A total weight of 1.12 kg of sodium hydroxide aqueous solution in which 560 g of sodium hydroxide was dissolved was supplied at a rate. Stirring and mixing were performed for a residence time of 40 minutes in the second tank reactor to carry out a polycondensation reaction of the aromatic polycarbonate oligomer. Further, the reaction mixture was supplied to the subsequent third tank reactor, and the reaction mixture was stirred and mixed in the third tank reactor for a residence time of 40 minutes to carry out a polycondensation reaction of the aromatic polycarbonate oligomer. Further, the reaction mixture discharged from the third tank reactor was supplied to the fourth tank reactor, and the mixture was stirred and mixed for a residence time of 40 minutes to terminate the polycondensation reaction. The dichloromethane solution of aromatic polycarbonate discharged from the fourth tank reactor was washed with water and isolated according to the method of Example 1. Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer when triethylamine was added, concentration of haloformate group in organic phase, equivalence ratio of haloformate group to base, base concentration in aqueous phase, aromatic polycarbonate Table 1 shows the weight average molecular weight of the oligomer, the weight average molecular weight of the produced aromatic polycarbonate, the amount of nitrogen component incorporated, and the amount of hydrolyzed haloformate groups after the addition of triethylamine.

[0064]

[Table 1] a: Number of moles of haloformate group per structural unit of aromatic polycarbonate oligomer (mol%) b: Concentration of haloformate group in organic phase (mol / liter) c: Equivalent ratio of haloformate group to base d: In aqueous phase Concentration (mol / liter) e: Weight average molecular weight of aromatic polycarbonate oligomer f: Weight average molecular weight of aromatic polycarbonate g: Amount of nitrogen component mixed (ppm) h: Hydrolysis amount of haloformate group after addition of amine As is clear from 1, when a haloformate group and a base concentration in an aqueous phase are set within the range specified in the present invention and an aromatic polycarbonate is produced by adding a tertiary amine, a nitrogen uptake amount is small, and It can be seen that the decomposition of the haloformate group is also small.

[0065]

INDUSTRIAL APPLICABILITY As described above, in the present invention, a tertiary amine is used without using a special stirring device, and the aromatic polycarbonate can be efficiently used while suppressing the incorporation of the nitrogen component into the aromatic polycarbonate. It can be manufactured.

(72) Inventor Masakatsu Nakatsuka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Akihiro Yamaguchi 1190, Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (3)

[Claims] 1. An aromatic dihydroxy compound, an alkali metal or alkaline earth metal base, in the absence of a tertiary amine under two-phase interfacial conditions consisting of water and a substantially water-insoluble organic solvent, and A process for producing an aromatic polycarbonate oligomer by producing an aromatic polycarbonate oligomer from a carbonyl halide compound and polycondensing the oligomer in the presence of a tertiary amine, comprising a haloformate of an aromatic polycarbonate oligomer in a two-phase mixture. The group is 15 to 0.1 mol% per structural unit of the aromatic polycarbonate oligomer, and the equivalent ratio of the haloformate group to the alkali metal or alkaline earth metal base is 1: 1.5 to 1: 5.5. A method for producing an aromatic polycarbonate in which a tertiary amine is added under the conditions of. 2. The method according to claim 1, wherein the tertiary amine is added under the condition that the concentration of the alkali metal or alkaline earth metal base in the aqueous phase is 0.05 to 0.2 mol / liter. 3. The concentration of haloformate groups in the organic phase is 0.
The method according to claim 1, wherein the tertiary amine is added under the condition of 0006 to 0.2 mol / liter.