JPH07138356A - Production of aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To produce an arom. polycarbonate with melt properties suitable for blow molding, etc. CONSTITUTION:This arom. polycarbonate is produced by subjecting a reactional system contg. 1mol of at least one arom. dihydroxy compd., a carbonate precursor, an alkali or alkaline earth metal base, water, and 0.1-1.0l of an org. solvent to interfacial polymn. in the presence of a polycarbonate-forming catalyst to form an oligomer, continuing the interfacial polymn. until the wt.-average mol.wt. of the resuling prepolymer reaches 20-99% of that of the objective arom. polycarbonate, adding 0.2-2.0l of the org. solvent to the system, and further continuing the polymn.

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, 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 terminator, etc.) (Also referred to as)) are known to produce aromatic polycarbonates. U.S. Pat. No. 3,275,601 describes 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 as a terminal blocking agent. -A method for producing aromatic polycarbonates using butylphenol is described. This method involves adding phosgene before adding
Aromatic polycarbonate is produced by allowing all of the organic solvent to be present in the reaction system.

US Pat. No. 4,529,791 describes a method for producing a polycarbonate resin having improved optical properties by an interfacial polymerization reaction. In this method, a polycarbonate oligomer is formed by the reaction of at least one aromatic dihydroxy compound and phosgene in the presence of an organic solvent, then a polycarbonate-forming catalyst is added, and a polycarbonate resin is obtained by a polycondensation reaction of the oligomer. The method is characterized by adding an organic solvent in a volume of 25 to 125% of the initial amount after the phosgenation and before the polycondensation reaction. This method produces an aromatic polycarbonate by adding an organic solvent after supplying phosgene and before the polycondensation reaction, that is, before adding the polycarbonate-forming catalyst.

Japanese Unexamined Patent Publication (Kokai) No. 5-209049 describes a method for producing an aromatic polycarbonate by an interfacial polymerization reaction of at least one aromatic dihydroxy compound and a carbonyl halide in the presence of a polycarbonate-forming catalyst. . This method is a method of performing conversion in a two-phase system consisting of water and an organic solvent while continuously administering a carbonyl halide, and the amount of the organic solvent at the start of polycondensation is the same as that at the start of polycondensation. Range from 10 to 70% of the amount of organic solvent required at the polymerization temperature to dissolve the amount of polycarbonate that can be generated from the amount of aromatic dihydroxy compound, and at least 20% of the carbonyl halide. After administration,
A method for producing an aromatic polycarbonate, which comprises adding the remaining amount of an organic solvent sufficient to keep the produced polycarbonate at least in a solution state. According to this method, a carbonyl halide is supplied in the presence of a polycarbonate generation catalyst to produce an aromatic polycarbonate. However, even if any of the above methods is used, an aromatic polycarbonate having melt characteristics suitable for a blow molding material or the like cannot be produced. At present, there is a demand for a method for suitably producing an aromatic polycarbonate having a melting property suitable for a blow molding material or the like.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an aromatic polycarbonate having melt characteristics suitable for blow molding materials and the like.

[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 relates to (A) at least one aromatic dihydroxy compound, a carbonate precursor, an alkali metal or alkaline earth metal base, water and 0.1 to 1.0 liter of 1 mol of the aromatic dihydroxy compound. In a reaction system containing an organic solvent, an interfacial polymerization reaction is carried out in the absence of a polycarbonate-forming catalyst to form an oligomer, and (B) the weight average molecular weight of the prepolymer is
2 of the weight average molecular weight of the obtained aromatic polycarbonate
The interfacial polymerization reaction is continued until it becomes 0 to 99%, and (C) is then 0.2 per 1 mol of the aromatic dihydroxy compound.
The present invention relates to a method for producing an aromatic polycarbonate, which comprises adding an organic solvent of up to 2.0 liters and further performing an interfacial polymerization reaction.

In the production method of the present invention, an aromatic dihydroxy compound, a carbonate precursor, an alkali metal or alkaline earth metal base, water and an organic solvent are used.
The aromatic dihydroxy compound used in the method of the present invention is preferably a compound represented by formula (1) or 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 In Formula (1) or Formula (2), which represents a linking group for connecting Ar ₂ , Ar ₁ , Ar ₂ and Ar ₃
Are each a divalent aromatic group, preferably a substituted or unsubstituted phenylene group. As the substituent of the substituted phenylene group, a halogen atom, a nitro group, an alkyl group,
Examples thereof include a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group and an alkoxy group. Ar ₁ and Ar ₂ are
Preferably, both are a p-phenylene group, an m-phenylene group or an o-phenylene group, or one is a p-phenylene group and the other is an m-phenylene group or an o-phenylene group. Particularly preferred, Ar ₁ and Ar ₂ are 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 and 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 (4'-hydroxyphenyl) -1-
Bis (hydroxyaryl) alkanes such as 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 [5,2,1,02,6]
Decane, bis (hydroxyaryl) cycloalkanes such as 2,2-bis (4′-hydroxyphenyl) adamantane, 4,4′-dihydroxydiphenyl ether,
Bis (hydroxyaryl) ethers such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl 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,
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,

Furthermore, 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 composition, typically a compound represented by 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 An oligomeric haloformate composition, a mono- or bis-haloformate compound derived from an aromatic dihydroxy compound, or an oligomeric haloformate composition. The oligomeric haloformate composition 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. Formula (3)
In the above, 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, the R ′ group represents an alkylene group having 1 to 6 carbon atoms,
The Ar ₄ group represents a divalent aromatic group having 6 to 12 carbon atoms.

In formula (3), specific examples of the aliphatic dihydroxy compound in which the R group is an aliphatic group include ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol. , 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-
Cyclohexanediol, 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 Formula (3), the aromatic dihydroxy compound in which the R group is an aromatic group is an aromatic dihydroxy compound represented by Formula (1) or Formula (2), and examples thereof include bisphenol A and hydroquinone. The carbonate precursor used particularly preferably in the production method of the present invention is
It is a bischloroformate of phosgene, bisphenol A or an oligomeric chloroformate composition of bisphenol A.

When a carbonyl halide compound is used, the amount of the carbonate precursor used is preferably about 0.9 to about 2.0 times the molar amount of the aromatic dihydroxy compound, and about 1.0 to about 1. A 5-fold molar amount is more preferable. When a haloformate compound is used, the number of haloformate groups supplied by the haloformate compound is preferably about 0.9 to about 1.5 times the equivalent of the number of hydroxy groups supplied by the haloformate compound and the aromatic dihydroxy compound, and preferably about 1 It is more preferably from 0.0 to about 1.3 times equivalent. 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.

The alkali metal or alkaline earth metal base (hereinafter abbreviated as base) used in the production method of the present invention 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. based on the aromatic dihydroxy compound.
It is 0 to about 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. The whole amount of the base may be used in step (A), or a part of the amount may be used in step (A) and the remaining amount may be used in step (B) and / or step (C). You may. In addition, it is not necessary to use the entire amount of the base at once in each of the step (A), the step (B), and the step (C), and the base may be intermittently or continuously added to the reaction system. You may add to a reaction system, controlling pH to a fixed value or a fixed 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
It is about 0.5 to about 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, its amount is bisphenol A1.
It is about 0.8 to about 2.2 liters per mole.

The organic solvent used in the production method of the present invention is substantially inert to the reaction, is substantially insoluble in water, and dissolves the aromatic polycarbonate. Good. Examples of the organic solvent include aliphatic chlorinated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane and dichloropropane, and aromatic chlorinated hydrocarbons such as chlorobenzene and dichlorobenzene. Hydrogen, or a mixture thereof may be mentioned. Further, an organic solvent in which an aromatic hydrocarbon such as toluene, xylene and ethylbenzene, an aliphatic hydrocarbon such as hexane, heptane and cyclohexane, and the like are mixed with the chlorinated hydrocarbon or the mixture thereof 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 an aromatic polycarbonate. Further, an organic solvent obtained by mixing the recovered organic solvent and a new organic solvent may be used.

In the method of the present invention, the amount of the organic solvent used differs between the steps (A) and (B) and the step (C). The amount of the organic solvent used in steps (A) and (B) is 0.1 with respect to 1 mol of the aromatic dihydroxy compound.
To 1.0 liter, preferably 0.2 to 0.9
It is 1 liter, and more preferably 0.3 to 0.8 liter. The amount of organic solvent added in step (C) is
0.2-2. To 1 mol of aromatic dihydroxy compound.
It is 0 liter, preferably 0.3 to 1.5 liter, and more preferably 0.5 to 1.0 liter. When the organic solvent is added in step (C), it is not necessary to add the entire amount at once, and the organic solvent may be added intermittently or continuously to the reaction system. The starting time of step (C), that is, the time of adding the organic solvent, is the time when the weight average molecular weight of the prepolymer becomes 20 to 99% of the weight average molecular weight of the aromatic polycarbonate obtained, and preferably, The time is 30 to 95%, more preferably 40 to 90%, and further preferably 50 to 85%.

In the step (A) of the production method of the present invention, the interfacial polymerization reaction is carried out in the absence of a polycarbonate-forming catalyst. In the step (B) and / or the step (C),
Although it is possible to carry out the interfacial polymerization reaction without adding the polycarbonate forming catalyst, it is preferable to add the polycarbonate forming catalyst. The polycarbonate generation catalyst suitable for the production method of the present invention is 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-forming catalyst include trimethylamine, triethylamine, tri-n-propylamine and 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-dimethyl Cyclohexylamine, 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-octadecyl Ammonium chloride, benzyltri-n-butylammonium chloride, cyclohexyltrimethylammonium bromide, benzyltrimethylammonium fluoride, tetra-n-butylammonium fluoride,
Benzyldimethylphenylammonium chloride, tetra-n-heptylammonium iodide, m-trifluoromethylphenyltrimethylammonium bromide, triethylphosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, diphenylbenzylphosphine, tris (p-chlorophenyl) Phosphine, phenylnaphthylbenzylphosphine, tetra (hydroxymethyl) phosphonium chloride, benzyltriethylphosphonium chloride, benzyltriphenylphosphonium chloride, 4-methylpyridine, 1-methylimidazole, 1,2-dimethylimidazole, 3-methylpyridazine, 4, 6-dimethylpyrimidine, 1-cyclohexyl-3,5-dimethyl Pyrazole, 2,3,5,6-tetramethyl pyrazine, and the like. These alone
Alternatively, a plurality may be used in combination. The polycarbonate-forming catalyst is preferably a tertiary amine, more preferably
It is a tertiary amine having a total carbon number of 3 to 30, and particularly preferably triethylamine.

When the polycarbonate-forming catalyst is added in step (B) and / or step (C), the amount thereof is about 0.000 relative to the number of moles of the aromatic dihydroxy compound.
It should be 5 mol% or more. Even if the amount is excessively large, a remarkable effect cannot be expected. The amount of polycarbonate-forming catalyst is preferably about 0.0005 to about 5 mol% based on the number of moles of the aromatic dihydroxy compound.
The polycarbonate generation catalyst may be added in a liquid state or a solid state, or may be added as an organic solvent solution or an aqueous solution. In the step (B) or the step (C), it is not necessary to add the entire amount of the polycarbonate-forming catalyst at once, and the catalyst may be added intermittently or continuously to the reaction system.

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 obtained.
The weight average molecular weight of the aromatic polycarbonate is about 150.
00 to about 150,000, preferably about 2000
It is 0 to 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. In the production method of the present invention, when the terminal blocking agent is used, the addition timing is not particularly limited, and it may be added in advance before the reaction, or may be added at an arbitrary point in the reaction. Preferably, the endcapping agent is added in step (C). Moreover, it is not necessary to add the whole amount of the end-capping agent at once, and the end-capping agent may be added intermittently or continuously. Further, in the step (C), the additional organic solvent, the polycarbonate-forming catalyst and the end capping agent may be added to the reaction system at the same time, and may be intermittently or continuously added to the reaction system. .

In the step (A) of the production method of the present invention, the interfacial polymerization is carried out in the absence of a catalyst for producing a polycarbonate, using 0.1 to 1.0 liter of an organic solvent with respect to 1 mol of the aromatic dihydroxy compound. The reaction takes place and oligomers are formed. In the step (A), the presence of the polycarbonate-forming catalyst makes it difficult to control the molecular weight, which is not preferable. In the step (B), an interfacial polymerization reaction is subsequently carried out to form a prepolymer. Process (B)
As in the step (A), the interfacial polymerization reaction is carried out with a small amount of organic solvent. The prepolymer obtained in step (B) is
The weight average molecular weight thereof corresponds to 20 to 99% of the weight average molecular weight of the obtained aromatic polycarbonate. Next, in step (C), 0.2 to 2.0 liters of an organic solvent is added to 1 mol of the aromatic dihydroxy compound, and an interfacial polymerization reaction is further performed to produce an aromatic polycarbonate. When the organic solvent is added before the weight average molecular weight of the prepolymer obtained in the step (B) becomes 20% of the weight average molecular weight of the obtained aromatic polycarbonate, the effect of the present invention is difficult to obtain.
Further, even after the weight average molecular weight of the prepolymer obtained in the step (B) reached 99% of the weight average molecular weight of the obtained aromatic polycarbonate, the interfacial polymerization reaction was further performed without adding an organic solvent. In this case, the viscosity of the organic solvent solution becomes extremely high, and it becomes difficult to reach the target weight average molecular weight. Incidentally, the oligomer in the present specification means a low molecular weight initial product, and the prepolymer means an aromatic polycarbonate having a weight average molecular weight of about 3,000 or more and before reaching a target weight average molecular weight. To do. The weight average molecular weight of the prepolymer is GP
It is calculated by analysis such as C (gel permeation chromatography).

The aromatic polycarbonate produced by the method of the present invention has melting characteristics suitable for blow molding materials and the like, that is, non-Newtonian flow characteristics. Linear aromatic polycarbonates produced by conventional methods are defined as Newtonian flow in the molten state at normal processing temperatures (Newtonian flow is the type of flow that occurs in a liquid system whose shear rate is directly proportional to shear stress). It is not suitable as a blow molding material or the like. Conventional methods have used branching agents to produce branched aromatic polycarbonates to impart non-Newtonian flow properties. On the other hand, the method of the present invention can produce an aromatic polycarbonate having non-Newtonian flow characteristics without using a branching agent.

In the production method of the present invention, a branching agent may be used if desired. The branching agent suitable for the production method of the present invention has three or more reactive groups 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 (the same or different). ) Has a compound. Specific examples of the branching agent include phloroglucinol and 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 tri Chloride, cyanuric acid chloride, 3,3-bis (4'-hydroxyphenyl) -2-
And oxo-2,3-dihydroindole, 3,3-bis (4'-hydroxy-3'-methylphenyl) -2-oxo-2,3-dihydroindole and the like. These may be used alone or in combination. The amount of the branching agent used is determined according to the degree of branching of the aromatic polycarbonate produced. Preferably, it is about 0.05 to about 2.0 mol% based on the number of moles of the aromatic dihydroxy compound.
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.

The production method of the present invention is usually carried out at about 10 ° C. to the boiling temperature of the organic solvent used in the reaction. The production method of the present invention is usually carried out under atmospheric pressure, and if desired, it can be carried out under atmospheric pressure or above atmospheric pressure. In the production method of the present invention, the interfacial polymerization reaction can be carried out without stirring the reaction mixture, but it is preferable to stir the reaction mixture to carry out the interfacial polymerization reaction from the viewpoint that the polymerization time can be shortened. At that time, it is not necessary to continue stirring from the beginning to the end of the interfacial polymerization reaction, and if necessary, 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. If desired, 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.

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 may be a known reactor such as a tank reactor, a tubular reactor, a packed tower, a static mixer or a strong stirring line mixer, or any combination thereof. And a reaction device. The production method of the present invention can be carried out batchwise by using a tank reactor. For example, 0.1 to 1.0 with respect to 1 mol of an aromatic dihydroxy compound, a base, water, and an aromatic dihydroxy compound.
To a reaction system containing liters of organic solvent, a carbonate precursor or an organic solvent solution of a carbonate precursor is supplied,
An interfacial polymerization reaction is carried out to carry out step (A). After the end of the supply, the interfacial polymerization reaction is further performed, and the step (B) is performed. At this point, the polycarbonate-forming catalyst may be added. Next, the weight average molecular weight of the prepolymer is 20 to 20% of the weight average molecular weight of the obtained aromatic polycarbonate.
When it reaches 99%, 0.2 to 2.0 liters of an organic solvent is added to 1 mol of the aromatic dihydroxy compound, and an interfacial polymerization reaction is further carried out to carry out the step (C). At this time, an end cap and / or a catalyst for generating polycarbonate may be added. The production method of the present invention can be carried out in a semi-batch manner by using a tank reactor. For example, the step (A) is carried out by continuously supplying 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 to an interfacial polymerization reaction. 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, a basic aqueous solution containing an aromatic dihydroxy compound, a carbonate precursor and an organic solvent, or an organic solvent solution of a carbonate precursor is continuously supplied to the first tank. After a certain residence time in the first tank, the reaction mixture is continuously discharged into the second tank. Similarly, after a certain residence time, the reaction mixture is continuously discharged into the next reaction tank to produce an aromatic polycarbonate. At that time, the additional organic solvent is continuously added to an arbitrary reaction tank after the weight average molecular weight of the prepolymer becomes 20% of the weight average molecular weight of the obtained aromatic polycarbonate. In this case, the first tank is the step (A), and one or more reaction tanks from the second tank before the addition of the additional organic solvent are the step (B), and the additional organic solvent is added. One or more reaction tanks after the reaction tank are step (C). Further, the method of using the polycarbonate generation catalyst and the end capping agent is the same as in the case of the batch type. The method using the tank-type continuous reaction apparatus as described above,
Aromatic polycarbonate having a stable molecular weight can be continuously produced.

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 additional organic solvent is continuously supplied from an arbitrary position in the middle of the pipe after the weight average molecular weight of the prepolymer becomes 20% of the weight average molecular weight of the aromatic polycarbonate obtained. The production method of the present invention is a semi-batch type or a continuous type by using a continuous reaction device in which any combination of reaction devices such as a tank reactor, a tubular reactor, a packed tower, a static mixer or a strong stirring line mixer is used. It can be carried out. For example, in the initial stage of the reaction, a tubular reactor, a packed column, a device for performing initial contact with the reaction solution, or the like is provided to continuously produce the oligomer, and the step (A) is performed. next,
The interfacial polymerization reaction is further carried out using a tank reactor, a tubular reactor, a static mixer or a strong stirring line mixer,
Process (B) is implemented. After that, an additional organic solvent is added to an arbitrary reaction apparatus after the weight average molecular weight of the prepolymer reaches 20% of the weight average molecular weight of the aromatic polycarbonate to be obtained, and the interfacial polymerization reaction is further carried out to carry out the step (C ) Is carried out. The manufacturing method of the present invention is carried out by the above operations.

Next, the reaction mixture containing the aromatic polycarbonate produced by the method of the present invention is treated by a continuous operation or a 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 is recovered by removing the organic solvent by distillation or steam distillation, or by adding an organic solvent (poor solvent) which 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 toluene,
Aromatic hydrocarbons such as xylene, pentane, hexane,
Aliphatic hydrocarbons such as octane, cyclohexane, and methylcyclohexane, alcohols such as methanol, ethanol, propanol, butanol, pentanol, and hexanol, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, and other ketones, ethyl acetate And esters such as 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 another polymer 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 stabilizer, impact stabilizer, UV absorber, mold release agent, organic halogen compound, alkali metal sulfonate, glass fiber, carbon fiber, glass beads, barium sulfate, TiO2, etc. You may add above.

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 a molded product such as a film is produced from the organic solvent. Can be processed into 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 other polymers, if desired, the above additives are added, and chassis and housing materials for electric devices, electronic parts, automobile parts, building materials as a substitute for glass, data storage disks or audio It can be molded into a base of an information recording medium such as a compact disc, an optical material such as a lens of a camera or glasses, and the like.

[0037]

The present invention will be described in more detail by 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% based on bisphenol A), 2.4 liters of dichloromethane (0.6 liters based on 1 mol of bisphenol A)
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 (10.9 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, the mixture was stirred for 30 minutes. Next, 2.8 liters of dichloromethane (bisphenol A
(0.7 liter per 1 mol) was added and stirred for 60 minutes to terminate the reaction. The weight average molecular weight of the prepolymer at the time when dichloromethane was added is shown in Table 1 (Table 1). The reaction mixture was allowed to stand, the organic phase was separated, then neutralized with hydrochloric acid, and washed repeatedly with water until the electrolyte disappeared. To the obtained dichloromethane solution of aromatic polycarbonate, 2 liters of toluene and 5 liters of water were added and heated to 98 ° C. to distill off dichloromethane and toluene to obtain a powder of aromatic polycarbonate.

Example 2 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, 1.6 liter of dichloromethane (0.4 liter per 1 mol of bisphenol A) and 4 liter of water were placed, and nitrogen purge was performed to remove oxygen in the flask. . Then, 1.5 g of an aqueous solution containing 1.8 g of sodium hydrosulfite and 436 g (10.9 mol) of sodium hydroxide was added to the above suspension, and bisphenol A was added at 15 ° C.
Was dissolved. To this mixture under stirring, 467 g of phosgene
(4.72 mol) was fed in 30 minutes. Then, the mixture was stirred for 30 minutes. Then, p-tert-butylphenol 20.
7 g (3.44 mol% relative to bisphenol A) was added and stirred for 10 minutes. Then dichloromethane 2.4
The reaction was terminated by adding liter (0.6 liter to 1 mol of bisphenol A) and stirring for 40 minutes. Then, the same treatment as in Example 1 was carried out 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, 2 liters of dichloromethane (0.5 liter per 1 mol of bisphenol A) 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 436 g (10.9 mol) of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. To this mixture under stirring, 467 g of phosgene
(4.72 mol) was fed in 30 minutes. Then, the mixture was stirred for 50 minutes. Next, 2 liters of dichloromethane (0.5 liters per 1 mole of bisphenol A), p-tert-
20.7 g of butylphenol (3.44 mol% based on bisphenol A) and 0.32 g of triethylamine
(0.08 mol% relative to bisphenol A) was added and stirred for 20 minutes to terminate the reaction. Then, the same treatment as in Example 1 was carried out to obtain an aromatic polycarbonate powder.

Example 4 A powder of aromatic polycarbonate was obtained in the same manner as in Example 3 except that after supplying phosgene, stirring was performed for 60 minutes instead of stirring for 50 minutes. Example 5 A 10-liter baffled flask was equipped with a three-stage, six-blade stirrer and a reflux condenser. 912 g (4.0 mol) of bisphenol A, 1 liter of dichloromethane (0.25 liter per 1 mol of bisphenol A) and 4 liter of water were put in this flask, and nitrogen purge was performed to remove oxygen in the flask. next,
1.8 g of sodium hydrosulfite in the above suspension
Then, 1.5 liter of an aqueous solution of 436 g (10.9 mol) of sodium hydroxide was supplied, and bisphenol A was dissolved at 15 ° C. To this mixture, with stirring, phosgene 467
g (4.72 mol) was fed in in 30 minutes. Then 30
Stir for minutes. Next, 1 liter of dichloromethane (0.25 liter per 1 mole of bisphenol A), p-te
31.1 g of rt-butylphenol (5.18 mol% relative to bisphenol A) and 0.3 of triethylamine
The reaction was terminated by adding 2 g (0.08 mol% to bisphenol A) and stirring for 20 minutes. Then, the same treatment as in Example 1 was carried out 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. 912 g (4.0 mol) of bisphenol A, 3.4 liters of dichloromethane (0.85 liters per 1 mol of bisphenol A) and 4 liters of water were placed in this flask, and nitrogen purge was performed to remove oxygen in the flask. . Next, sodium hydrosulfite 1.
8 g and sodium hydroxide 436 g (10.9 mol)
1.5 liter of the aqueous solution of bisphenol A was supplied and bisphenol A was dissolved at 15 ° C. To this mixture, under stirring, add phosgene 4
67 g (4.72 mol) were fed in in 30 minutes. After that, 0.32 g of triethylamine (0.08 mol% relative to bisphenol A) was added and stirred for 30 minutes. Next, 4.8 liters of dichloromethane (bisphenol A
1.2 liters per mole) and 13.1 g p-tert-butylphenol (2.
18 mol%) was added and stirred for 30 minutes to terminate the reaction. Then, the same treatment as in Example 1 was carried out to obtain an aromatic polycarbonate powder.

Example 7 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, 2 liters of dichloromethane (0.5 liter per 1 mol of bisphenol A) 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 436 g (10.9 mol) of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. To this mixture under stirring, 467 g of phosgene
(4.72 mol) was fed in 30 minutes. Then, 0.32 g of triethylamine (0.08 mol% with respect to bisphenol A) was added and stirred for 30 minutes. next,
2 l of dichloromethane (0.5 l per mol of bisphenol A) and 20.7 g of p-tert-butylphenol (3.44 mol% relative to bisphenol A) were added and stirred for 30 minutes to terminate the reaction. Then, the same treatment as in Example 1 was carried out to obtain an aromatic polycarbonate powder.

Example 8 Four equipped with a three-stage six-blade stirrer and a reflux condenser
A tank-type continuous reactor was used in which four liter baffled flasks were continuously connected by an overflow outlet. Under stirring, in the first tank, bisphenol A3653
g (16 mol), 1746 g of sodium hydroxide (43.
65 mol), sodium hydrosulfite 7.2 g
Was dissolved in 18 kg of water to obtain a total weight of 23.4 kg of an aqueous solution, phosgene, and dichloromethane.
g / min, 7.78 g / min (0.0786 mol / min), 4
4.34 g / min (33.3 ml / min, bisphenol A
(0.5 liter per mol) was supplied. After a residence time of about 30 minutes, the reaction mixture was in the second tank 149.6 g /
Exhausted at the rate of minutes. Thereafter, after the same residence time, they were discharged into the third tank and the fourth tank. From the time when the discharge to the second tank started, 0.567 g of triethylamine was added to the second tank.
210 ml of an aqueous solution of (0.0056 mol) was fed at 1 ml / min. Next, 6 liters of a dichloromethane solution of 62.0 g (0.413 mol) of p-tert-butylphenol was placed in a third tank at 33.3 ml / min (bisphenol A1).
(0.5 liter per mole). When the supply of additional dichloromethane was started, a part of the reaction mixture discharged from the second tank was taken out, and the weight average molecular weight of the prepolymer was measured. The results are shown in Table 1. Continuous operation was performed for 4 hours from the time when the supply to the first tank was started. During that time, when a part of the reaction mixture continuously discharged from the second tank and the fourth tank was taken out every 30 minutes and the weight average molecular weight was measured, the same result was always obtained and stable. Then, the reaction mixture discharged from the fourth 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 dichloromethane solution of aromatic polycarbonate, 5 liters of toluene and 12.5 liters of water were added and heated to 98 ° C. to distill off dichloromethane and toluene to obtain a powder of aromatic polycarbonate.

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 (1 liter with respect to 1 mol of bisphenol A) and 4 liters of water were added, and a nitrogen purge was performed to remove oxygen in the flask. I went. Next, 1.8 g of sodium hydrosulfite and 43 g of sodium hydroxide were added to the above suspension.
1.5 g of an aqueous solution of 6 g (10.9 mol) was supplied, and bisphenol A was dissolved at 15 ° C. To this mixture, with stirring, was added 30% of 467 g (4.72 mol) of phosgene.
Supplied in minutes. After that, 0.32 g of triethylamine
(0.08 mol% relative to bisphenol A) was added and stirred for 60 minutes to terminate the reaction. Then, the same treatment as in Example 1 was carried out to obtain an aromatic polycarbonate powder.

Comparative Example 2 (Method described in US Pat. No. 4,529,791) 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
18.6 g of rt-butylphenol (3.1 mol% based on bisphenol A), 3.3 liters of dichloromethane (0.83 liters based on 1 mol of bisphenol A)
And 3 liters of water were added, and a nitrogen purge was performed to remove oxygen in the flask. Next, to the above suspension, 1.8 g of sodium hydrosulfite and 0.5 liter of an aqueous solution of 486 g (12.15 mol) of sodium hydroxide were supplied. To this mixture, under stirring, 502 g of phosgene
(5.07 mol) was fed in 30 minutes. Next, 3.3 liters of dichloromethane (0.83 liters per 1 mol of bisphenol A) were added. Furthermore, 3.17 g of triethylamine (0.7 with respect to bisphenol A)
(8 mol%) was added and stirred for 60 minutes to terminate the reaction. Then, the same treatment as in Example 1 was carried out to obtain an aromatic polycarbonate powder.

Comparative Example 3 (Method described in JP-A-5-209049) A 10-liter baffled flask was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 912 g (4.0 mol) of bisphenol A, 0.4 g of triethylamine (0.1 g based on bisphenol A)
Mol%), 1.57 liters of dichloromethane (0.4 liters per 1 mole of bisphenol A) and 1.7 water.
A liter was added and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.8 g of sodium hydrosulfite and 436 sodium hydroxide were added to the above suspension.
0.5 l of an aqueous solution of g (10.9 mol) was fed. Phosgene was fed to the mixture under stirring. When 85% of the total amount of phosgene was supplied, 1.57 liters of dichloromethane (for 1 mol of bisphenol A,
0.4 liter) was added. The total supply of phosgene is 4
55 g (4.6 mol), fed over 30 minutes. Then, 16.9 g of phenol (4.5 mol% relative to bisphenol A) was added and stirred for 60 minutes to terminate the reaction. Then, the same treatment as in Example 1 was carried out to obtain an aromatic polycarbonate powder.

In Table 1 (Table 1), the weight average molecular weight (Mw) of the prepolymer at the time of adding an organic solvent in each Example and each Comparative Example, the prepolymer relative to the weight average molecular weight of the obtained aromatic polycarbonate is shown. The arrival rate (%) of the weight average molecular weight and the weight average molecular weight (Mw) of the obtained aromatic polycarbonate are shown.

[0048]

[Table 1]

In Table 2 (Table 2), the melt flow index (MI) and the melt flow index ratio (MIR) of the obtained aromatic polycarbonates in each Example and each Comparative Example, the melting at two different shear levels are shown. The flow rate ratio) is shown. The measuring method is as shown below. -Measurement of weight average molecular weight and reaching rate: The reaction mixture is allowed to stand still, the organic phase is separated, neutralized with hydrochloric acid, washed with water until the electrolyte disappears, and then dichloromethane is distilled off to obtain a prepolymer or an aroma. Obtain a group polycarbonate. The obtained prepolymer or aromatic polycarbonate
02 g is dissolved in 10 g of chloroform. This solution
It is measured by GPC [gel permeation chromatography, Showa Denko KK-made, GPC system-11]. The arrival rate (%) is the ratio of the weight average molecular weight (Mw) of the prepolymer to the weight average molecular weight (Mw) of the obtained aromatic polycarbonate. -Melt flow index and melt flow index ratio The melt flow index was measured by Toyo Seiki S-01 melt indexer at a temperature of 280 ° C and a load of 2.16.
It was measured in kg and indicated as the amount of polymer eluted in 10 minutes (unit: gram). Further, the melt flow index ratio is a load of 12.5 kg and a load of 2.
Each melt flow index [MI (12.5 kg), MI (2.16 kg)] at 16 kg was measured and determined as the ratio. A conventional linear aromatic polycarbonate that behaves as a Newtonian fluid has an MIR value of about 6, and an MIR value of 7 or more indicates that it is a polymer that behaves as a non-Newtonian fluid when melted. It is shown that the polymer is suitable for the above.

[0050]

[Table 2]

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 melting property suitable for a blow molding material or the like. From Example 8, it can be seen that the production method of the present invention can be preferably carried out using a tank-type continuous reaction apparatus. It is understood that the conventional production methods of Comparative Examples 1 to 3 cannot produce an aromatic polycarbonate having melt characteristics suitable for a blow molding material or the like. It can be seen that the molecular weight cannot be controlled by the method of supplying phosgene in the presence of the polycarbonate-forming catalyst of Comparative Example 3.

[0052]

As described above, the production method of the present invention makes it possible to favorably produce an aromatic polycarbonate having melting characteristics suitable for a blow molding material and the like as compared with the conventional production methods.

 ─────────────────────────────────────────────────── (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 (4)

[Claims] (A) At least one aromatic dihydroxy compound, a carbonate precursor, an alkali metal or alkaline earth metal base, water, and 0.1 to 1.0 liter of organic per 1 mol of the aromatic dihydroxy compound. In a reaction system containing a solvent, an interfacial polymerization reaction is carried out in the absence of a polycarbonate-forming catalyst to form an oligomer,
(B) Furthermore, the weight average molecular weight of the prepolymer is 20 to 20% of the weight average molecular weight of the obtained aromatic polycarbonate.
The interfacial polymerization reaction is continued until it reaches 99%, and then (C)
0.2-2. To 1 mol of aromatic dihydroxy compound.
A method for producing an aromatic polycarbonate, which comprises adding 0 liter of an organic solvent and further performing an interfacial polymerization reaction. 2. The manufacturing method according to claim 1, wherein an end-capping agent is used. 3. A polycarbonate-forming catalyst is added in step (B) and / or step (C).
The manufacturing method described. 4. An aromatic polycarbonate obtained by the method according to claim 1.