JPH07179596A - Production of aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To obtain an aromatic polycarbonate little in the contents of cyclic oligomers by forming an oligomer in a reaction system containing an aromatic dihydroxy compound and a carbonate precursor, emulsifying the oligomer under a specific condition, and subsequently polymerizing the emulsified oligomer. CONSTITUTION:A reaction system containing an aromatic dihydroxy compound, a carbonate precursor (e.g. phosgene), an alkali(ne earth) metal base, water and an organic solvent is subjected to an interfacial polymerization reaction to form an oligomer. The oligomer is emulsified in the presence of a polycarbonate-producing catalyst and subsequently subjected to an interfacial polymerization reaction, while maintaining the emulsified state thus, an aromatic polycarbonate little in the contents of cyclic oligomers is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic polycarbonate. Specifically, it relates to a method for producing an aromatic polycarbonate having a low content of cyclic oligomer.

[0002]

2. Description of the Related Art Conventionally, aromatic dihydroxy compounds,
Carbonate precursor, alkali metal or alkaline earth metal base, water, organic solvent, polycarbonate generation catalyst (also called polymerization catalyst, polycondensation catalyst, etc.) and end capping agent (molecular weight regulator, polymerization terminator, chain) A method for producing an aromatic polycarbonate using a terminating agent) is also known. US Patent No. 3275
No. 601, bisphenol A as an aromatic dihydroxy compound, phosgene as a carbonate precursor, sodium hydroxide as an alkali metal base, dichloromethane as an organic solvent, triethylamine as a polycarbonate production catalyst, and p-tert-butylphenol as an end capping agent. A method for producing the aromatic polycarbonate used is described. In this method, aromatic polycarbonate is produced under normal stirring conditions.

JP-B-37-2198 discloses that an aromatic dihydroxy compound and a carbonate precursor are reacted in a two-phase medium of an organic solvent and an aqueous base solution to form a low molecular weight oligomer, and then a high molecular weight oligomer. A method of making a polycarbonate comprising forming a polycarbonate is described. This method is a method for producing a high-molecular weight polycarbonate in a reaction medium maintained in an emulsified state without using a polycarbonate-forming catalyst.
In JP-A-2-133425, a base aqueous solution of an aromatic dihydroxy compound is reacted with phosgene in the presence of an organic solvent to form a low molecular weight polycarbonate oligomer, and then the oligomer is emulsified. A method for producing a high molecular weight aromatic polycarbonate by maintaining and polymerizing is described. This method
A method for producing an aromatic polycarbonate, which comprises adding a tertiary amine to form a high-molecular-weight aromatic polycarbonate when the molecular weight of the polycarbonate in the emulsified state reaches 70% or more of the target molecular weight. is there.

JP-A-3-199231 discloses that a basic aqueous solution of an aromatic dihydroxy compound is reacted with phosgene in the presence of an organic solvent to form a low molecular weight polycarbonate oligomer containing a chloroformate group. Then, a method for producing an aromatic polycarbonate by polymerizing the oligomer in a water-in-oil type emulsion state in the presence of a base is described. In this method, the droplet diameter of the dispersed aqueous phase in the water-in-oil type emulsified state is 10 μm on average.
The method for producing an aromatic polycarbonate is characterized in that a tertiary amine is added after the following. However, the aromatic polycarbonate obtained by any of the above methods has a large content of cyclic oligomers. At present, there is a demand for a method for producing an aromatic polycarbonate having a low cyclic oligomer content.

[0005]

An object of the present invention is to provide a method for producing an aromatic polycarbonate having a low content of cyclic oligomer.

[0006]

Means for Solving the Problems The present inventors have completed the present invention as a result of extensive studies on a method for producing an aromatic polycarbonate in order to meet the above-mentioned demand. That is, the present invention, at least one aromatic dihydroxy compound, a carbonate precursor, a reaction system containing an alkali metal or alkaline earth metal base, water and an organic solvent, to perform an interfacial polymerization reaction, to form an oligomer, then, In the method for producing an aromatic polycarbonate by subjecting the oligomer to an emulsified state and performing an interfacial polymerization reaction while maintaining the emulsified state, the oligomer is emulsified in the presence of a polycarbonate-forming catalyst. The present invention relates to a method for producing an aromatic polycarbonate.

In the production method of the present invention, an aromatic dihydroxy compound, a carbonate precursor, an alkali metal or alkaline earth metal base, water, an organic solvent and a polycarbonate generating catalyst are used. In the production method of the present invention, the aromatic dihydroxy compound used is preferably a compound represented by the formula (1) or the formula (2). HO-Ar ¹ -Y-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 Y is Ar ¹ Represents a linking group that connects Ar ² )

In the formula (1) or the formula (2), Ar ¹ ,
Ar ² and Ar ³ are each a divalent aromatic group, preferably a substituted or unsubstituted phenylene group. The substituent of the substituted phenylene group is a halogen atom, a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group or the like. Ar ¹ and Ar
² is preferably both p-phenylene group, m-phenylene group or o-phenylene group, or one is p-
-Phenylene group, one of which is m-phenylene group or o
A phenylene group. Ar ¹ and Ar ² are particularly preferably both 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. Y is a linking group that connects Ar ¹ and Ar ² , and is a single bond or a divalent hydrocarbon group, or —O—,
-S -, - SO -, - SO 2 -, - a group containing atoms other than carbon and hydrogen CO- like. Examples of the divalent hydrocarbon group include an alkylidene group such as a methylene group, an ethylene group, a 2,2-propylidene group and a cyclohexylidene group, an alkylidene group substituted with an aryl group, an aromatic group and other unsaturated groups. It is a hydrocarbon group containing a hydrocarbon group of.

Specific examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) methane, bis (3-methyl-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, 1,3
-Bis (4'-hydroxyphenyl) -1,1-dimethylpropane, 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"], 2- (4'-
Hydroxyphenyl) -2- (3 "-hydroxyphenyl) propane, 1,1-bis (4'-hydroxyphenyl) -2-methylpropane, 2,2-bis (4'-hydroxyphenyl) butane, 1,1 -Bis (4'-hydroxyphenyl) -3-methylbutane, 2,2-bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxyphenyl) -4-methylpentane,
2,2-bis (4'-hydroxyphenyl) hexane,
4,4-bis (4'-hydroxyphenyl) heptane,
2,2-bis (4'-hydroxyphenyl) octane,
2,2-bis (4'-hydroxyphenyl) nonane,

Bis (3,5-dimethyl-4-hydroxyphenyl) methane, 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, 3,3-
Bis (hydroxyaryl) alkanes such as bis (4′-hydroxyphenyl) -1-cyanobutane and 2,2-bis (4′-hydroxyphenyl) hexafluoropropane,

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 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) cycloheptane,
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,
Bis (hydroxyaryl) cycloalkanes such as 2,2-bis (4′-hydroxyphenyl) adamantane,
4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether,
Bis (hydroxyaryl) ethers such as 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,
Bis (hydroxyaryl) sulfides such as 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-
Bis (hydroxyaryl) sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 3,3′-dimethyl-
4,4'-dihydroxydiphenyl sulfone, 3,3 '
-Bis (hydroxyaryl) sulfones such as diphenyl-4,4'-dihydroxydiphenylsulfone and 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) ketone, bis (3- Bis (hydroxyaryl) ketones such as methyl-4-hydroxyphenyl) ketone,

Further, 3,3,3 ', 3'-tetramethyl-6,6'-dihydroxyspiro (bis) indane ["spirobiindane bisphenol"], 3,
3 ', 4,4'-tetrahydro-4,4,4', 4'-
Tetramethyl-2,2'-spirobi (2H-1-benzopyran) -7,7'-diol ["spirobichroman"], 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 (3′-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,
2,6-dihydroxydibenzo-p-dioxin, 2,
6-dihydroxythianthrene, 2,7-dihydroxyphenoxathiin, 9,10-dimethyl-2,7-dihydroxyphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, 4,
4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6
-Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dihydroxypyrene, hydroquinone, resorcin and the like. An aromatic dihydroxy compound containing an ester bond, which is produced by a reaction of 2 mol of bisphenol A and 1 mol of isophthaloyl chloride or terephthaloyl chloride is also useful. These may be used alone or in combination. The aromatic dihydroxy compound preferably used in the production method of the present invention is bisphenol A.

The carbonate precursor used in the production method of the present invention is preferably a carbonyl halide compound or a haloformate compound. As the carbonyl halide compound, carbonyl chloride called phosgene is usually used. Also useful are carbonyl halide compounds derived from halogens other than chlorine, such as carbonyl bromide, carbonyl iodide and carbonyl fluoride. Further, compounds having an ability to form a haloformate group, for example, trichloromethylchloroformate which is a dimer of phosgene and bis (trichloromethyl) carbonate which is a trimer of phosgene are also useful. These may be used alone or in combination.
Usually, the preferred carbonyl halide compound used is phosgene.

The haloformate compound is a mono- or bis-haloformate compound or an oligomeric haloformate compound, and is typically a compound represented by the formula (3). X- (O-R-O-C (= O)) _n- O-R-O-X (3) (In the formula, X represents a hydrogen atom or a halocarbonyl group,
At least one X is a halocarbonyl group and R is 2
Represents a valent aliphatic group or aromatic group, and n represents 0 or a positive integer) The compound represented by the formula (3) is a mono- or bishaloformate compound derived from an aliphatic dihydroxy compound, or It is an oligomeric haloformate compound, a mono- or bishaloformate compound derived from an aromatic dihydroxy compound, or an oligomeric haloformate compound. The oligomeric haloformate compounds may have R groups having different structures in the same molecule. These haloformate compounds may be used alone or as a mixture, and may be used in combination with a carbonyl halide compound. In equation (3),
The divalent aliphatic group R is an alkylene group having 2 to 20 carbon atoms,
A cycloalkylene group having 4 to 12 carbon atoms or a group represented by the formula (4). —R′—Ar ⁴ —R′— (4) (In the formula, R ′ represents an alkylene group having 1 to 6 carbon atoms, and A
r ⁴ represents a divalent aromatic group having 6 to 12 carbon atoms)

In the formula (3), specific examples of the aliphatic dihydroxy compound in which R is an aliphatic group include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 3 -Methyl-1,5-
Pentanediol, 1,6-hexanediol, 1,5
-Hexanediol, 1,7-heptanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 1,3-cyclohexane Diol, 1,4-cyclohexanediol, 2,
2-bis (4'-hydroxycyclohexyl) propane, xylylenediol, 1,4-bis (2'-hydroxyethyl) benzene, 1,4-bis (3'-hydroxypropyl) benzene, 1,4-bis ( 4′-hydroxybutyl) benzene, 1,4-bis (5′-hydroxypentyl) benzene, 1,4-bis (6′-hydroxyhexyl) benzene and the like. In the formula (3), the aromatic dihydroxy compound in which R is an aromatic group is represented by the formula (1)
Alternatively, it is an aromatic dihydroxy compound represented by the formula (2), and examples thereof include bisphenol A and hydroquinone.

The carbonate precursor which is particularly preferably used in the production method of the present invention is phosgene, bischloroformate of bisphenol A or bisphenol A.
Is an oligomeric chloroformate compound of. When using a carbonyl halide compound, the amount of the carbonate precursor to be used is, relative to the aromatic dihydroxy compound,
About 0.9 to 2.0 times mol is preferable, and about 1.0 to 1.5
A double mole is more preferable. When a haloformate compound is used, the number of haloformate groups contained in the haloformate compound is about 0.9 with respect to the number of hydroxy groups contained in the haloformate compound and the aromatic dihydroxy compound.
~ 1.5 times equivalents are preferable, and about 1.0 to 1.3 times equivalents are more preferable. The carbonate precursor can be used in any state of gas, liquid and solid. When a carbonyl halide compound is used, it is preferably used in a gaseous state or as an organic solvent solution dissolved in an organic solvent. When a haloformate compound is used, it is preferably used in a liquid state, a solid state or as an organic solvent solution dissolved in an organic solvent.

In the production method of the present invention, the alkali metal or alkaline earth metal base (hereinafter abbreviated as base) used is usually an alkali metal or alkali such as sodium hydroxide, potassium hydroxide or calcium hydroxide. It is a hydroxide of an earth metal. These may be used alone or in combination. The preferred base is sodium hydroxide or potassium hydroxide. The amount of the base used is preferably about 1.0 to about the aromatic dihydroxy compound.
It is 1.6 times equivalent. The base is usually used as an aqueous solution. Further, the aromatic dihydroxy compound may be dissolved in this aqueous solution before use. In this case, sodium sulfite, sodium hydrosulfite, sodium borohydride or the like may be added as an antioxidant. As for the base, the whole amount thereof may be added in advance before the reaction, or a part of the amount may be added in advance before the reaction,
The remaining amount may be added during the reaction. At that time, it may be added intermittently or continuously, and may be added while controlling the pH to a constant value or a constant range.

The water used in the production method of the present invention is distilled water, ion-exchanged water, recovered water produced in producing an aromatic polycarbonate, or the like, and may be a mixture thereof. The water is preferably
Used as an aqueous base solution and / or an aqueous base solution of an aromatic dihydroxy compound. The amount of water used is usually about 0.5 to 5 liters per 1 mol of the aromatic dihydroxy compound. When an aqueous base solution of an aromatic dihydroxy compound is prepared, the amount of water used may be at least the amount required to dissolve the aromatic dihydroxy compound and the base. For example, when the aromatic dihydroxy compound is bisphenol A, the amount thereof is about 0.8 to 2.2 liters per 1 mol of bisphenol A.

The organic solvent used in the production method of the present invention should be one that is substantially inert to the reaction, is substantially insoluble in water, and dissolves the aromatic polycarbonate. Good. The organic solvent is, for example,
With an aliphatic chlorinated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane, dichloropropane, an aromatic chlorinated hydrocarbon such as chlorobenzene, dichlorobenzene, or a mixture thereof. is there. Also, for those chlorinated hydrocarbons or mixtures thereof,
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 may be used. A particularly preferred organic solvent is dichloromethane. Further, the organic solvent used in the production method of the present invention may be a recovered organic solvent produced when producing the aromatic polycarbonate. Further, an organic solvent obtained by mixing the recovered organic solvent and a new organic solvent may be used. The amount of the organic solvent used is usually preferably such that the concentration of the aromatic polycarbonate in the organic solvent solution containing the aromatic polycarbonate at the end of the polymerization is about 5 to 35% by weight, and about 10%. More preferably, it is used in an amount of 20% by weight.

The polycarbonate-forming catalyst used in the production method of the present invention includes a tertiary amine, a quaternary ammonium salt, a tertiary phosphine, a quaternary phosphonium salt, a nitrogen-containing heterocyclic compound and a salt thereof, an imino ether and a salt thereof, Examples thereof include compounds having an amide group. Specific examples of the polycarbonate generation catalyst include trimethylamine, triethylamine, tri-n-propylamine, diethyl-n-propylamine, tri-n-butylamine, tri-n-hexylamine, N, N-dimethylbenzylamine, N, N. ，
N ', N'-tetramethyl-1,4-tetramethylenediamine, N, N, N', N'-tetra-n-butyl-
1,6-hexamethylenediamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylaniline, N, N-diethylaniline, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, N, N′-dimethylpiperazine, N-ethylpiperidine, N-methylmorpholine, 1,4-diazabicyclo [2,2,2] octane, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium bromide , Methyltriethylammonium chloride, phenyltriethylammonium chloride, tetramethylammonium hydroxide, triethyl-n-octadecylammonium chloride, benzyl Tri-n-butylammonium chloride, cyclohexyltrimethylammonium bromide, benzyltrimethylammonium fluoride, tetra-n-butylammonium fluoride, benzyldimethylphenylammonium chloride, tetra-n-heptylammonium iodide, m-trifluoromethylphenyltrimethyl Ammonium bromide, triethylphosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, diphenylbenzylphosphine, tris (p-chlorophenyl) phosphine, phenylnaphthylbenzylphosphine, tetra (hydroxymethyl) phosphonium chloride, benzyltriethylphosphonium chloride, benzyltriphenyl Phenylphospho Umchloride, 4-methylpyridine, 1-methylimidazole, 1,2-dimethylimidazole, 3-methylpyridazine, 4,6-dimethylpyrimidine, 1-cyclohexyl-3,5-dimethylpyrazole, 2,3,5,6 -Such as tetramethylpyrazine. These may be used alone or in combination.

The polycarbonate-forming catalyst is preferably a tertiary amine, more preferably a total carbon number of 3 to.
30 tertiary amines, particularly preferably triethylamine. The amount of the polycarbonate-forming catalyst used is
About 0.0 based on the number of moles of the aromatic dihydroxy compound
It may be 005 mol% or more. The amount is 0.0005
If it is excessively less than mol%, the aromatic polycarbonate obtained will have a high content of cyclic oligomers. Even if the amount is excessively large, a remarkable effect cannot be expected. The amount of the polycarbonate-forming catalyst is preferably about 0.0005 to about 5 mol%, more preferably about 0.001 to about 2 mol%, based on the number of moles of the aromatic dihydroxy compound. Preferably, it is about 0.005 to about 1 mol%. The polycarbonate production catalyst may be used in a liquid state or a solid state, and may be used as an organic solvent solution or an aqueous solution. The polycarbonate-forming catalyst may be added in advance before the reaction, or may be added after the oligomer is formed and before the emulsified state. In addition, until the emulsified state,
It may be added intermittently or continuously. When a carbonyl halide compound is used as the carbonate precursor, the polycarbonate generation catalyst is preferably added after supplying the carbonyl halide compound.

The production method of the present invention can be carried out without using an end-capping agent, but it is preferable to use an end-capping agent because the molecular weight can be easily controlled. The endcapping agent suitable for the production method of the present invention is a monovalent aromatic hydroxy compound, a monovalent aromatic hydroxy compound haloformate derivative, a monovalent carboxylic acid, or a monovalent carboxylic acid halide derivative. Monovalent aromatic hydroxy compounds include, for example, phenol, p-cresol, o-ethylphenol, p-ethylphenol,
p-isopropylphenol, p-tert-butylphenol, p-cumylphenol, p-cyclohexylphenol, p-octylphenol, p-nonylphenol, 2,4-xylenol, p-methoxyphenol,
p-hexyloxyphenol, p-decyloxyphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, p-bromophenol, pentabromophenol, pentachlorophenol, p-
Phenylphenol, p-isopropenylphenol,
2,4-di (1'-methyl-1'-phenylethyl) phenol, β-naphthol, α-naphthol, p-
Phenols such as (2 ′, 4 ′, 4′-trimethylchromanyl) phenol, 2- (4′-methoxyphenyl) -2- (4 ″ -hydroxyphenyl) propane or their alkali metal salts and alkaline earths The haloformate derivative of a monovalent aromatic hydroxy compound is the haloformate derivative of a monovalent aromatic hydroxy compound described above.

The monovalent carboxylic acid is, for example, 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-
Dimethyl valeric acid, 3,5-dimethylcaproic acid, fatty acids such as phenoxyacetic acid or their alkali metal salts and alkaline earth metal salts, benzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, p- Benzoic acids such as propyloxybenzoic acid, p-butoxybenzoic acid, p-hexyloxybenzoic acid, p-octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid and p-chlorobenzoic acid, or alkalis thereof. Metal salts and alkaline earth metal salts. The monovalent carboxylic acid halide derivative is, for example, the above monovalent carboxylic acid halide derivative.

These may be used alone or in combination. The endcapping agent preferably used is phenol, p
-Tert-butylphenol or p-cumylphenol. The amount of the end-capping agent used is determined according to the weight average molecular weight of the aromatic polycarbonate produced. The weight average molecular weight of the aromatic polycarbonate is about 1500.
0 to about 150,000, preferably about 20,000
Is about 100,000. The amount of the end capping agent required for producing the aromatic polycarbonate having the weight average molecular weight in the above range is about 1.0 to about 10.0 mol% based on the number of moles of the aromatic dihydroxy compound. And preferably about 1.5 to about 7.0 mol%. The terminal blocking agent may be used in a solid state or a liquid state, and may be used as an organic solvent solution, an aqueous solution or a basic aqueous solution. There is no particular limitation on the timing of adding the terminal blocking agent, and the terminal blocking agent may be added in advance before the reaction or at any time during the reaction.

In the production method of the present invention, an interfacial polymerization reaction is carried out in a reaction system containing an aromatic dihydroxy compound, a carbonate precursor, a base, water and an organic solvent to form an oligomer, and then the oligomer is emulsified. And a method for producing an aromatic polycarbonate by causing an interfacial polymerization reaction while maintaining an emulsified state, in the presence of a polycarbonate-forming catalyst, a method for producing an aromatic polycarbonate, wherein the oligomer is in an emulsified state. Is.

In the production method of the present invention, an oligomer is first formed. The oligomer in the present specification means
It means a low molecular weight initial product. In this step, the interfacial polymerization reaction can be performed without stirring the reaction mixture, but it is preferable to stir the reaction mixture to perform the interfacial polymerization reaction from the viewpoint that the polymerization time can be shortened. At that time, the stirring may be performed to such an extent that the separation of the organic phase and the aqueous phase is prevented. Usually, the stirring condition is preferably such that the organic phase and the aqueous phase are uniformly mixed. In some cases, the interfacial polymerization reaction may be carried out under vigorous stirring conditions. Incidentally, the interfacial polymerization reaction in the present specification includes all reactions that occur when an aromatic polycarbonate is produced by the method of the present invention,
The reactions mainly occur at the interface between the organic phase and the aqueous phase.

Next, the reaction mixture containing the oligomer is emulsified in the presence of the polycarbonate-forming catalyst. The emulsified state in the present specification means, for example, a state in which the organic phase and the aqueous phase do not separate until the interfacial polymerization reaction is completed even if the emulsified state is allowed to stand without stirring or the like.
As a method of obtaining an emulsified state, there are a method of stirring with a stirring device, a method of adding an alkaline aqueous solution, and the like. As the stirring device, a simple stirring device such as a paddle, a propeller, a turbine or a chi-type blade, a homogenizer, a mixer, a high-speed stirrer such as a homomixer, a static mixer, a colloid mill, an orifice mixer, a flow jet mixer, an ultrasonic emulsifying device. Etc. As a method for examining the emulsified state, for example, there is a method of measuring the average droplet diameter of the dispersed phase using a laser diffraction type particle size distribution measuring device (SALD1100 manufactured by Shimadzu Corp.). The average droplet diameter of the dispersed phase in the emulsified state measured by this method is, for example, about several tens of μm.

The emulsified state is preferably a highly emulsified state in which the interfacial polymerization reaction is completed within a few hours, more preferably within a few hours, and even more preferably within one hour. As a stirring device for obtaining such a highly emulsified state, a homogenizer, a mixer,
High-speed stirrer such as homomixer, static mixer,
A stirring device such as a colloid mill, an orifice mixer, a flow jet mixer, and an ultrasonic emulsifying device is preferable. When a high-speed stirrer is used, the stirring speed for obtaining a highly emulsified state is preferably 1000 rpm or more, more preferably 3000 rpm or more, and further preferably 5000 rpm or more. The stirring time for obtaining a highly emulsified state is preferably 30
Seconds or longer, more preferably 1 minute or longer, still more preferably 2 minutes or longer. The above stirring conditions bring the oligomer into an emulsified state, preferably a highly emulsified state.

Then, the emulsified reaction mixture is interfacially polymerized to produce an aromatic polycarbonate. The stirring conditions at that time are not particularly limited, and any of the above stirring devices can be used. Further, after the emulsified state, it is also possible to carry out the interfacial polymerization reaction by allowing it to stand without stirring.

In the production method of the present invention, it is important that the oligomer is emulsified in the presence of the polycarbonate-forming catalyst. In the absence of a polycarbonate-forming catalyst,
When the oligomer is emulsified, the aromatic polycarbonate obtained has a large content of cyclic oligomer. Also, when the polycarbonate-forming catalyst is added after the emulsified state, the resulting aromatic polycarbonate has a large content of cyclic oligomer. Further, the manufacturing method of the present invention, compared with the conventional manufacturing method,
The time required for the reaction can be significantly shortened.

In the production method of the present invention, a branched aromatic polycarbonate can be produced by using a branching agent. The branching agent suitable for the production method of the present invention is
It is a compound having three or more (which may be the same or different) a reactive group selected from an aromatic hydroxy group, a haloformate group, a carboxylic acid group, a carboxylic acid halide group, an active halogen atom and the like. Specific examples of the branching agent include 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, 1,1,2-tris (4′-hydroxyphenyl) propane, α, α, α ′
-Tris (4'-hydroxyphenyl) -1-ethyl-
4-isopropylbenzene, 2,4-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] phenol, 2- (4′-hydroxyphenyl) -2- (2 ″,
4 "-dihydroxyphenyl) propane, tris (4-
Hydroxyphenyl) phosphine, 1,1,4,4-tetrakis (4′-hydroxyphenyl) cyclohexane, 2,2-bis [4 ′, 4′-bis (4 ″ -hydroxyphenyl) cyclohexyl] propane, α, α ，
α ', α'-Tetrakis (4'-hydroxyphenyl)
-1,4-diethylbenzene, 2,2,5,5-tetrakis (4'-hydroxyphenyl) hexane, 1,1,
2,3-Tetrakis (4'-hydroxyphenyl) propane, 1,4-bis (4 ', 4 "-dihydroxytriphenylmethyl) benzene, 3,3', 5,5'-tetrahydroxydiphenyl ether, 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-
Examples include dihydroindole and 3,3-bis (4′-hydroxy-3′-methylphenyl) -2-oxo-2,3-dihydroindole.

The amount of the branching agent used is determined according to the degree of branching of the aromatic polycarbonate produced. Preferably, the amount of the aromatic dihydroxy compound is about 0.
It is 05 to 2.0 mol%. The branching agent may be used in a solid state or a liquid state, and may be used as an organic solvent solution, an aqueous solution or a basic aqueous solution. The timing of adding the branching agent is not particularly limited. The branching agent may be added in advance before the reaction, or may be added at any point in the reaction. These may be used alone or in combination. The production method of the present invention is generally carried out at about 10 ° C to the boiling temperature of the organic solvent used in the reaction. The manufacturing method of the present invention is
Usually carried out at atmospheric pressure, if desired, below atmospheric pressure,
Alternatively, it can be carried out under atmospheric pressure or higher.

The production 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 or a packed tower, or a reactor in which those reactors are arbitrarily combined. These reactors can optionally be equipped with the agitator mentioned above. The production method of the present invention can be carried out batchwise by using a tank reactor. For example, a carbonate precursor or a solution of a carbonate precursor in an organic solvent is supplied to a reaction system containing an aromatic dihydroxy compound, a base, water and an organic solvent, and an interfacial polymerization reaction is performed to form an oligomer. Next, the oligomer is emulsified in the presence of a polycarbonate generation catalyst, and an interfacial polymerization reaction is further carried out to produce an aromatic polycarbonate.
The production method of the present invention can be carried out in a semi-batch manner by using a tank reactor. For example, an aqueous base solution of an aromatic dihydroxy compound, an organic solvent and a carbonate precursor, or a solution of a carbonate precursor in an organic solvent is continuously supplied to the reaction system to carry out an interfacial polymerization reaction to form an oligomer. Subsequent operations are the same as in the batch type.

The production method of the present invention can be carried out in a continuous manner by using a tank-type continuous reaction apparatus in which several tank-type reactors are continuously connected. For example, an aqueous base solution containing an aromatic dihydroxy compound, a carbonate precursor and an organic solvent, or a solution of a carbonate precursor in an organic solvent is used as a first solution.
Continuously feed the 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 is continuously discharged into the next reaction tank to produce an aromatic polycarbonate. At that time, any one or more reaction tanks are equipped with a stirring device for forming an emulsified state. The polycarbonate-forming catalyst is continuously added to a reaction vessel equipped with a stirring device for forming an emulsified state and / or one or more reaction vessels before the reaction vessel. The method using the tank-type continuous reaction apparatus as described above can continuously produce an aromatic polycarbonate having a stable molecular weight and molecular weight distribution.

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. At that time, the polycarbonate-forming catalyst is continuously supplied from an arbitrary position in the middle of the pipe and / or the portion provided with the stirring device for forming the emulsified state. The production method of the present invention can be carried out in a semi-batch type or a continuous type by using a continuous reaction device in which reaction devices such as a tank reactor, a tubular reactor or a packed tower are arbitrarily combined. For example, at the beginning of the reaction, a tank reactor, a tubular reactor,
An interfacial polymerization reaction is carried out by providing a packed tower and / or a device for making initial contact with the reaction solution, and the oligomer is continuously formed. Next, an emulsified state is obtained by using a tank type reactor or a tube type reactor equipped with a stirring device for making an emulsified state, and an interface is further obtained by using a tank type reactor and / or a tube type reactor. A polymerization reaction is performed to produce an aromatic polycarbonate. At that time, the polycarbonate production catalyst is
It is continuously added to a tank reactor or a tubular reactor equipped with a stirring device for forming an emulsified state, and / or any reactor prior thereto. The manufacturing method of the present invention is carried out by the above operations.

The reaction mixture containing the aromatic polycarbonate produced by the method of the present invention is then treated in a continuous or batch operation to recover the aromatic polycarbonate. As the treatment of the reaction mixture, the organic phase containing the aromatic polycarbonate and the aqueous phase are separated, and the organic phase containing the aromatic polycarbonate is washed with water or a dilute aqueous alkaline solution, if necessary. Next, it is neutralized with a dilute aqueous acid solution. The acid used at that time is a mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid. Then, it is repeatedly washed with water until substantially no electrolyte is present. And
The aromatic polycarbonate is recovered from the washed organic solvent solution of the aromatic polycarbonate by a known method.

The aromatic polycarbonate can be recovered by removing the organic solvent by distillation or steam distillation, or by adding an organic solvent (poor solvent) that does not dissolve the aromatic polycarbonate to the organic solvent solution of the aromatic polycarbonate. Aromatic polycarbonate in the solid state,
There is a method of separating the organic solvent from the obtained organic solvent slurry of aromatic polycarbonate by a method such as filtration. More specifically, the organic solvent is distilled off from the organic solvent solution of the aromatic polycarbonate, and the aromatic polycarbonate is crystallized by bringing the organic solvent solution of the aromatic polycarbonate into a saturated state, and then crushed and dried. To remove the contained organic solvent, heating while removing the organic solvent from the organic solvent solution of the aromatic polycarbonate, the aromatic polycarbonate is directly pelletized from the molten state, the organic solvent solution of the aromatic polycarbonate is warm water A method of pulverizing the gel-like substance produced while removing the organic solvent, adding a poor solvent or a non-solvent to an organic solvent solution of an aromatic polycarbonate, and water and concentrating by heating to obtain a solid-state aroma. Method for obtaining aromatic polycarbonate as an aqueous slurry, using aromatic polycarbonate in an organic solvent solution A method of obtaining a solid state aromatic polycarbonate as a water slurry by evaporating and distilling off an organic solvent added to warm water containing a powder of an aromatic polycarbonate, an organic solvent solution of the aromatic polycarbonate is a powder of the aromatic polycarbonate, and There is a method of obtaining an aromatic polycarbonate in a solid state as a water slurry by evaporating and distilling off an organic solvent while supplying it into warm water containing a poor solvent.

Specific examples of the poor solvent or non-solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, octane, cyclohexane and methylcyclohexane, methanol, ethanol, propanol and butanol. Examples include alcohols such as 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. The aromatic polycarbonate produced by the method of the present invention can be used alone or in a mixture with other polymers as a molding material.
Specific examples of other polymers include polyethylene, polypropylene, polystyrene, ABS resin, polymethylmethacrylate, polytrifluoroethylene, polytetrafluoroethylene, polyacetal, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polyamide, polyimide, polyamideimide. , Polyetherimide, polysulfone, polyether sulfone, paraoxybenzoyl-based polyester, polyarylate, polysulfide and the like. The aromatic polycarbonate produced by the method of the present invention may be a pigment, a dye, a processing and heat stabilizer, an antioxidant, in a known method during or after the production of the aromatic polycarbonate, either alone or mixed with another polymer. , Hydrolysis stabilizers, impact stabilizers, ultraviolet absorbers, mold release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, barium sulfate, TiO _{2 and} other known additives. You may add one or more types.

The aromatic polycarbonate produced by the method of the present invention is soluble in a specific organic solvent (for example, a halogenated hydrocarbon solvent such as dichloromethane), and is molded into a film from the organic solvent solution. It can be processed into a product. The aromatic polycarbonate produced by the method of the present invention is thermoplastic and can be easily molded from a melt by a known molding method such as injection molding, extrusion molding, blow molding, or lamination. Further, the aromatic polycarbonate produced by the method of the present invention, alone or in a state of being mixed with another polymer, optionally, by adding the above-mentioned additive, a chassis or housing material of electric equipment, electronic parts, It can be molded into automobile parts, building materials replacing glass, information recording medium bases such as data storage disks or audio compact disks, and optical materials such as lenses of cameras or spectacles.

[0041]

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. Example 1 A 10-liter baffled flask was equipped with a three-stage, six-blade stirrer and a reflux condenser. In this flask, 912 g of bisphenol A (4.0 mol), p-te
20.7 g of rt-butylphenol (3.44 mol% with respect to bisphenol A), 4 liters of dichloromethane and 4 liters of water were added, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.5 liter of an aqueous solution of 1.8 g of sodium hydrosulfite and 442 g (11.04 mol) of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. With stirring, 471 g (4.76 mol) of phosgene was supplied to this mixture over 30 minutes to obtain an oligomer solution. Next, after adding 0.002 g of triethylamine (0.0005 mol% relative to bisphenol A), the three-stage six-blade stirrer was removed, and an SL type homomixer [made by Tokushu Kika Kogyo Co., Ltd. was used instead. ], And the mixture was stirred at 5000 rpm for 3 minutes to obtain a highly emulsified state. And again SL
The mold homomixer was removed, a 3-stage, 6-blade stirrer was attached, and the mixture was stirred for another 27 minutes to terminate the reaction.
Then, the reaction mixture was allowed to stand, the organic phase was separated, neutralized with hydrochloric acid, and repeatedly washed with water until the electrolyte was exhausted. To the obtained aromatic polycarbonate solution in dichloromethane was added 2 liters of toluene and 5 liters of water.
The mixture was heated to ° C and dichloromethane and toluene were distilled off to obtain an aromatic polycarbonate powder.

Example 2 A 10-liter baffled flask was equipped with a three-stage, six-blade stirrer and a reflux condenser. In this flask, 912 g of bisphenol A (4.0 mol), p-te
20.7 g of rt-butylphenol (3.44 mol% with respect to bisphenol A), 4 liters of dichloromethane and 4 liters of water were added, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.5 liter of an aqueous solution of 1.8 g of sodium hydrosulfite and 442 g (11.04 mol) of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. With stirring, 471 g (4.76 mol) of phosgene was supplied to this mixture over 30 minutes to obtain an oligomer solution. Next, after adding 0.012 g of triethylamine (0.003 mol% with respect to bisphenol A), the three-stage six-blade stirrer was removed, an SL-type homomixer was attached instead, and the mixture was stirred at 7,000 rpm for 2 minutes, A highly emulsified state was set. Then, the SL homomixer was removed again, a three-stage, six-blade stirrer was attached, and stirring was continued for another 28 minutes to terminate the reaction. Subsequent operations were performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder.

Example 3 A 10-liter baffled flask was equipped with a three-stage six-blade stirrer and a reflux condenser. To this flask, 912 g (4.0 mol) of bisphenol A, 4 liters of dichloromethane and 4 liters of water were placed, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.5 liter of an aqueous solution of 1.8 g of sodium hydrosulfite and 442 g (11.04 mol) of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. 471 g of phosgene in this mixture with stirring
(4.76 mol) was supplied for 30 minutes to obtain an oligomer solution. Next, 0.032 g of triethylamine (0.008 mol% based on bisphenol A) and p-tert.
-After adding 50 ml of a dichloromethane solution of 20.7 g of butylphenol (3.44 mol% with respect to bisphenol A), the three-stage, six-blade stirrer was removed, and an SL type homomixer was attached instead, and 3 at 6000 rpm.
The mixture was stirred for a minute to give a highly emulsified state. After that, the interface polymerization reaction was carried out for 27 minutes without stirring, and the reaction was terminated. Subsequent operations were performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder.

Example 4 A 10-liter baffled flask was equipped with a three-stage six-blade stirrer and a reflux condenser. To this flask, 912 g (4.0 mol) of bisphenol A, 4 liters of dichloromethane and 4 liters of water were placed, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.5 liter of an aqueous solution of 1.8 g of sodium hydrosulfite and 442 g (11.04 mol) of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. 471 g of phosgene in this mixture with stirring
(4.76 mol) was supplied for 30 minutes to obtain an oligomer solution. Next, after stirring for 30 minutes, 0.04 g of triethylamine (0.01 mol% based on bisphenol A) was added. Then, the 3-stage, 6-blade stirrer was removed, and an SL-type homomixer was attached instead,
The mixture was stirred at 0 rpm for 3 minutes to give a highly emulsified state. Then, after adding 50 ml of a dichloromethane solution containing 20.7 g of p-tert-butylphenol (3.44 mol% with respect to bisphenol A), the SL-type homomixer was again removed, and a three-stage six-blade stirrer was attached, The reaction was terminated by stirring for another 27 minutes. Subsequent operations were performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder.

Example 5 An SL type homomixer and a reflux condenser were attached to a 10-liter baffled flask. In this flask,
Bisphenol A 438 g (1.92 mol), p-tert
-Butylphenol 20.7 g (3.44 mol% relative to bisphenol A), triethylamine 0.04 g
(0.01 mol% relative to bisphenol A) and water 3
A liter was added and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.8 g of sodium hydrosulfite and 192 sodium hydroxide were added to the above suspension.
1.5 g of an aqueous solution of g (4.8 mol) was supplied, and 1
Bisphenol A was dissolved at 5 ° C. To this mixture, 735 g of bischloroformate of bisphenol A (2.0 g
4 liters of a dichloromethane solution having 8 mol) dissolved therein was added to obtain an oligomer solution. Next, 10000 rpm
The mixture was stirred for 2 minutes to obtain a highly emulsified state, and allowed to stand for 28 minutes without stirring to carry out interfacial polymerization to terminate the reaction.
Subsequent operations were performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder.

Example 6 A 10-liter baffled flask was equipped with a three-stage, six-blade stirrer and a reflux condenser. Into this flask, 438 g (1.92 mol) of bisphenol A and 3 liters of water were placed, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.8 g of sodium hydrosulfite and 1 part of sodium hydroxide were added to the above suspension.
1.5 g of an aqueous solution containing 92 g (4.8 mol) was supplied, and bisphenol A was dissolved at 15 ° C. With stirring, add bischloroformate 7 of bisphenol A to this mixture.
4 L of a dichloromethane solution in which 35 g (2.08 mol) was dissolved was added to obtain an oligomer solution. Then 3
After stirring for 0 minutes, p-tert-butylphenol 20.
50 g of a solution of 7 g (3.44 mol% based on bisphenol A) and 0.16 g triethylamine (0.04 mol% based on bisphenol A) in dichloromethane were added. And remove the three-stage six-blade agitator,
Instead, attach SL type homomixer, 10000r
The mixture was stirred at pm for 2 minutes to give a highly emulsified state, and allowed to stand for 28 minutes without stirring to carry out interfacial polymerization to terminate the reaction. Subsequent operations were performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder.

Example 7 A tank-type continuous reactor was used in which three baffled flasks equipped with a reflux condenser were connected in series through outlets for overflow. The first tank and the third tank have a capacity of 4 liters, and are equipped with a three-stage six-blade stirrer,
The second tank had a capacity of 0.5 liter and was equipped with an SL type homomixer. With stirring, in the first tank, bisphenol A 3653 g (16 mol), sodium hydroxide 17
46 g (43.65 mol) and 7.2 g of sodium hydrosulfite dissolved in 18 kg of water Total weight 2
An aqueous solution of 3.4 kg, phosgene, and dichloromethane were added at 97.50 g / min and 7.78 g / min (0.078 g / min, respectively).
6 mol / min), 88.67 g / min. After a residence time of about 30 minutes, the oligomer solution was in the second tank 194.0.
It was discharged at a rate of g / min. From the beginning of discharge to the second tank, p-tert-butylphenol 7 was added to the second tank.
210 ml of a solution of 2.3 g (0.482 mol) and 0.57 g (0.0056 mol) of triethylamine in dichloromethane were fed at 1 ml / min. From the time when the second tank was filled with the oligomer solution, the SL-type homomixer was rotated at 5000 rpm to start stirring. In the second tank, after a residence time of about 4 minutes, the reaction mixture was discharged into the third tank, and in the third tank, the reaction mixture containing the aromatic polycarbonate was discharged after the same residence time as in the first tank. Continuous operation was performed for 4 hours from the time when the supply to the first tank was started. During that time, when the weight average molecular weight of the aromatic polycarbonate continuously discharged from the third tank was measured every 30 minutes, the same result was always obtained and it was stable. afterwards,
The reaction mixture discharged from the third tank was separated, the aqueous phase was removed, the organic phase was neutralized with hydrochloric acid, and washed repeatedly with water until the electrolyte was exhausted. To the obtained aromatic polycarbonate solution in dichloromethane was added 5 liters of toluene and 1 part of water.
2.5 liters were added and heated to 98 ° C. to distill off dichloromethane and toluene to obtain an aromatic polycarbonate powder.

Example 8 A continuous reaction apparatus was used in which the first tank, the second tank and the first tubular reactor were connected in this order via the overflow outlet. The first tank was a 4-liter baffled flask equipped with a three-stage six-blade stirrer and a reflux condenser, and the second tank was a 0.5-liter flask equipped with an SL homomixer and a reflux condenser. It is a flask, and the first tubular reactor is a tubular reactor having an inner diameter of 4 cm and a total length of 3 m. 3653 g of bisphenol A in the first tank under stirring
(16 mol), 1746 g of sodium hydroxide (43.6)
5 mol), 7.2 g of sodium hydrosulfite dissolved in 18 kg of water, an aqueous solution having a total weight of 23.4 kg, phosgene, and dichloromethane are respectively 97.50.
g / min, 7.78 g / min (0.0786 mol / min), 8
It was fed at 8.67 g / min. After a dwell time of about 30 minutes,
The oligomer solution was discharged into the second tank at a rate of 194.0 g / min. From the time when the discharge to the second tank started, 72.3 g (0.48 p-tert-butylphenol) was added to the second tank.
2 mol) and 0.57 g of triethylamine (0.00
210 ml of a dichloromethane solution of 56 mol)
It was supplied at a rate of min / minute. From the time when the second tank was filled with the oligomer solution, the SL-type homomixer was rotated at 5000 rpm to start stirring. After a residence time of about 4 minutes in the second tank, the reaction mixture was discharged into the first tubular reactor.
In the first tubular reactor, the reaction mixture containing the aromatic polycarbonate was discharged after a residence time of about 28 minutes. First
Continuous operation was performed for 4 hours from the time when the supply to the tank was started.
During that time, when the weight average molecular weight of the aromatic polycarbonate continuously discharged from the first tubular reactor was measured every 30 minutes, the same result was always obtained and stable. Subsequent operations were performed in the same manner as in Example 7 to obtain an aromatic polycarbonate powder.

Comparative Example 1 (Method described in US Pat. No. 3,275,601) A 10-liter baffled flask was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 912 g of bisphenol A (4.0 mol), p-te
20.7 g of rt-butylphenol (3.44 mol% with respect to bisphenol A), 4 liters of dichloromethane and 4 liters of water were added, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.5 liter of an aqueous solution of 1.8 g of sodium hydrosulfite and 436 g (10.91 mol) of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. To this mixture, with stirring, 467 g (4.72 mol) of phosgene
For 30 minutes. Then, triethylamine 0.
32 g (0.08 mol% relative to bisphenol A) was added and stirred for 60 minutes to terminate the reaction. Subsequent operations were performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder.

Comparative Example 2 (Method described in Japanese Examined Patent Publication No. 37-2198) A 3-liter, six-blade stirrer and a reflux condenser were attached to a 10-liter baffled flask. Into this flask were placed 684 g (3.0 mol) of bisphenol A, 1.8 liters of dichloromethane and 2.1 liters of water,
A nitrogen purge was performed to remove oxygen in the flask.
Next, 1 liter of an aqueous solution of 1.8 g of sodium hydrosulfite and 336 g (8.4 mol) of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. Add phosgene 33 to this mixture with stirring.
6 g (3.4 mol) were fed in 50 minutes. Next, 1 part of the reaction mixture was taken out into a beaker and stirred at 10000 rpm for 1 minute using a SL type homomixer to obtain a highly emulsified state. Return this emulsion to the flask,
Then, the mixture was again stirred with a three-stage six-blade stirrer for 2 hours. Subsequent operations were performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder.

Comparative Example 3 (Method described in JP-A-2-133425) A 10-liter baffled flask was equipped with a three-stage six-blade stirrer and a reflux condenser. To this flask, 912 g (4.0 mol) of bisphenol A, 4 liters of dichloromethane and 4 liters of water were placed, and a nitrogen purge was performed to remove oxygen in the flask. next,
Sodium hydrosulfite 1.8 was added to the above suspension.
g and 2.3 g of an aqueous solution of 400 g (10 mol) of sodium hydroxide were supplied to dissolve bisphenol A. To this mixture, with stirring, 468 g (4.7 g) of phosgene.
3 mol) in 90 minutes. Next, 0.5 liter of a solution of 20.4 g of p-tert-butylphenol (3.39 mol% based on bisphenol A) in dichloromethane and 1.5 liter of an aqueous solution of 96 g of sodium hydroxide were added. Next, using an SL type homomixer, the mixture was stirred at a rotation speed of 6000 rpm for 3 minutes to obtain a highly emulsified state. Then, the mixture was again stirred for 60 minutes by a three-stage, six-blade stirrer. The weight average molecular weight at that time was 41,000 (75% of the target). At that time, 10 ml of an aqueous solution of 0.4 g of triethylamine (0.1 mol% with respect to bisphenol A) was added and stirred for another 60 minutes to terminate the reaction. The subsequent operation is performed in the same manner as in Example 1,
A powder of aromatic polycarbonate was obtained.

In Table 1 (Table 1), the weight average molecular weight (Mw) of the obtained aromatic polycarbonate, the content (% by weight) of the oligomer having a molecular weight of 3000 or less, and the extraction are shown in each Example and each Comparative Example. The content (% by weight) of the cyclic oligomer in the oligomer is shown. The measuring method is as shown below. -Measurement of weight average molecular weight and content of oligomer: The reaction mixture was allowed to stand, the organic phase was separated, and neutralized with hydrochloric acid. The organic phase is washed with water until free of electrolyte, and then dichloromethane is distilled off to obtain an aromatic polycarbonate. 0.02 g of the obtained aromatic polycarbonate is dissolved in 10 g of chloroform. This solution was applied to GPC [gel permeation chromatography, Showa Denko KK
Manufactured by GPC System-11], and the weight average molecular weight (Mw) and the content (% by weight) of the oligomer having a molecular weight of 3000 or less were calculated. -Measurement of content of cyclic oligomer in oligomer: 10 g of polycarbonate powder at room temperature, 100 g of acetone
Stir in 10 hours and extract the oligomer. The oligomer obtained by distilling off acetone was analyzed by high performance liquid chromatography, and the content (% by weight) of the cyclic oligomer in all the extracted oligomers (linear oligomer + cyclic oligomer) was calculated.

[0053]

[Table 1]

From Examples 1 to 8, it can be seen that the production method of the present invention can suitably produce an aromatic polycarbonate having a low content of cyclic oligomer. Moreover, Example 1
8, Comparative Examples 2 and 3 show that in order to produce an aromatic polycarbonate having a low cyclic oligomer content, it is very important to emulsify the oligomer in the presence of a polycarbonate-forming catalyst. In addition, it can be seen from Examples 7 and 8 that the production method of the present invention can be preferably carried out using a continuous reaction apparatus. It can be seen that the production method of Comparative Example 2 does not reach the target weight average molecular weight. It is understood that the conventional production methods of Comparative Examples 1 to 3 can produce only aromatic polycarbonate having a large content of cyclic oligomer. From the above results, the production method of the present invention makes it possible to produce an aromatic polycarbonate having a smaller content of cyclic oligomer as compared with the conventional production method.

[0055]

According to the present invention, it is possible to provide an aromatic polycarbonate having a low content of cyclic oligomer.

 ─────────────────────────────────────────────────── (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, Kanagawa Mitsui Toatsu Chemical Within the corporation

Claims (3)

[Claims] 1. An interfacial polymerization reaction is carried out in a reaction system containing at least one aromatic dihydroxy compound, a carbonate precursor, an alkali metal or alkaline earth metal base, water and an organic solvent to form an oligomer, In a method for producing an aromatic polycarbonate by subjecting an oligomer to an emulsified state and carrying out an interfacial polymerization reaction while maintaining the emulsified state, in the presence of a polycarbonate-forming catalyst, the oligomer is put into an emulsified state. Method for producing aromatic polycarbonate. 2. The manufacturing method according to claim 1, wherein an end-capping agent is used. 3. An aromatic polycarbonate obtained by the method according to claim 1.