JPH07247349A - Production of aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To produce an aromatic polycarbonate having a low nitrogen content, good hue and excellent heat stability. CONSTITUTION:The process for producing an aromatic polycarbonate from an aromatic dihydroxy compound, a carbonate precursor, a base, water and a aromatic halohydrocarbon, comprises the steps of performing the interfacial polymerization reaction at 70 deg.C or below to form an oligomer and further performing the interfacial polymerization at a temperature equal to or higher than that in the above step to form an aromatic polycarbonate, and wherein the amount of the aromatic halohydrocarbon used is 0.4-4 l per mol of the aromatic dihydroxy compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic polycarbonate. More specifically, it relates to a method for producing a high molecular weight aromatic polycarbonate having a low nitrogen content, excellent thermal stability, and good color tone.

[0002]

2. Description of the Related Art Conventionally, aromatic dihydroxy compounds,
Using carbonate precursors, bases, water, organic solvents, polycarbonate generation catalysts (also called polymerization catalysts, polycondensation catalysts, etc.) and end caps (also called molecular weight regulators, polymerization terminators, chain terminators, etc.) Methods for producing aromatic polycarbonates are known. US Patent No. 3
No. 275601 uses bisphenol A as an aromatic dihydroxy compound, phosgene as a carbonate precursor, sodium hydroxide as a 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 an aromatic polycarbonate is described. However, since dichloromethane has a low boiling point and is easily volatilized, it is difficult to say that it is a preferable organic solvent from an environmental point of view.

In Japanese Patent Publication No. 38-14498, there is produced a highly polymerized polycarbonate characterized by reacting a dihydroxy compound with phosgene in the presence of a halogenated aromatic hydrocarbon and an aqueous alkali solution to cause polycondensation. The method is described. In this publication, the amount of the halogenated aromatic hydrocarbon used is 20 to 30% by weight with respect to the amount of the dihydroxy compound, the amount of phosgene used is 1.52 times the equivalent amount with respect to the amount of the dihydroxy compound, and
It is described that the amount of sodium hydroxide used is appropriately 2.05 times the amount of the dihydroxy compound used. However, as a result of additional tests by the present inventors, it was found that it is difficult to terminate the polycondensation reaction by this method, and it is difficult to obtain a desired high-molecular weight polycarbonate. Further, the halogenated aromatic hydrocarbon solution containing polycarbonate obtained by this polycondensation reaction contains a large amount of impurities such as an electrolyte, but it is difficult to remove the electrolyte from this solution by washing. It was

In Japanese Patent Publication No. 41-21472, an interface between a dihydroxy compound and phosgene in the presence of an organic solvent consisting of an aromatic hydrocarbon or a chlorinated aromatic hydrocarbon and an aqueous alkaline solution is used. It describes a method for producing granular polycarbonate having a uniform composition, which is characterized by allowing an activator to coexist and polycondensate. In this publication, the amount of chlorinated aromatic hydrocarbon used is 23.6% by weight based on the amount of dihydroxy compound used, the amount of phosgene used is 1.51 times equivalent to the amount used of dihydroxy compound, and water. The amount of sodium oxide used is 2.05 times equivalent to the amount of dihydroxy compound used. However, as a result of additional tests by the present inventors, it was found that it is difficult to terminate the polycondensation reaction by this method, and it is difficult to obtain a desired high-molecular weight polycarbonate. Also,
Polycarbonate granules obtained by this polycondensation reaction,
Although it contains a large amount of impurities such as an electrolyte, it was difficult to remove the electrolyte from this granular material by washing.

[0005] Japanese Unexamined Patent Publication (Kokai) No. 50-122595 discloses a method for producing an aromatic polycarbonate by an interfacial polymerization method, which is characterized in that a chlorinated aromatic hydrocarbon is used as a solvent to synthesize the aromatic polycarbonate in two steps. The method is described. In this method, in the first step, an aqueous alkali metal solution of at least one aromatic dihydroxy compound and phosgene are added to an aromatic dihydroxy compound at an OH concentration of 0.01 to 0.1% by weight in an aqueous phase. 0.1-2.
In the presence of 5 mol% trialkylamine, and 70
The reaction is carried out at a temperature higher than ℃ for a residence time of 5 minutes or less, and then, in the second step, further trialkylamine is appropriately added to adjust the OH concentration of the aqueous phase to 0.20 to 0.50% by weight.
And the polycondensation is carried out at a temperature higher than 80 ° C. and a residence time longer than 1 minute. However, the aromatic polycarbonate obtained by this method has a high nitrogen content and is poor in thermal stability. In addition, the polycarbonate obtained by any of the above methods has poor color tone and poor thermal stability. At present, there is a demand for a method for producing a high molecular weight aromatic polycarbonate which does not use dichloromethane as an organic solvent, has a low nitrogen content, is excellent in thermal stability, and has a good color tone.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a high molecular weight aromatic polycarbonate having excellent detergency, low nitrogen content, excellent thermal stability and good color tone. It is to be.

[0007]

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 provides a method for producing an aromatic polycarbonate using an aromatic dihydroxy compound, a carbonate precursor, a base, water and at least one halogenated aromatic hydrocarbon, wherein (A) a temperature of 70 ° C. or lower. And a step of performing an interfacial polymerization reaction at a temperature equal to or higher than the temperature of the step (A) to form an aromatic polycarbonate. The amount of the group hydrocarbon used is 0.4 to 4 with respect to the aromatic dihydroxy compound.
The present invention relates to a method for producing an aromatic polycarbonate, which is characterized in that it is liter / mole.

In the production method of the present invention, an aromatic dihydroxy compound, a carbonate precursor, a base, water and a halogenated aromatic hydrocarbon are used. The aromatic dihydroxy compound used in the production 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 linking a group) equation linking the Ar ² in (1) or formula (2), Ar ^1, Ar ² and a
Each r ³ is a divalent aromatic group, preferably an unsubstituted or substituted 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
Are preferably p-phenylene group, m-phenylene group or o-phenylene group, or p-phenylene group.
A phenylene group, one of which is an m-phenylene group or o-
It is a phenylene group. Ar ¹ and Ar ² are particularly preferably
Both are p-phenylene groups.

Ar ³ is a p-phenylene group, an m-phenylene group or an o-phenylene group, preferably a p-phenylene group or an 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
It is a group containing atoms other than carbon and hydrogen, such as-and -CO-. 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-
Methyl butane, 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 [5,5
2,1,0 ^2,6 ] decane, bis (hydroxyaryl) cycloalkanes such as 2,2-bis (4′-hydroxyphenyl) adamantane,

Bis (hydroxyaryl) ethers such as 4,4'-dihydroxydiphenyl ether, 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'-dihydroxy Diphenyl sulfide, 3,
Bis (hydroxyaryl) sulfides such as 3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-4,4'- Bis (hydroxyaryl) sulfoxides such as dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone,
Bis such as 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfone, 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfone, 3,3'-dichloro-4,4'-dihydroxydiphenyl sulfone (Hydroxyaryl) sulfones, bis (4-hydroxyphenyl) ketone, bis (3-methyl-4-hydroxyphenyl) ketone and other bis (hydroxyaryl) ketones,

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 a bis (hydroxyaryl) alkane, particularly preferably 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 Rs having different structures in the same molecule. These haloformate compounds may be used alone or in combination. Further, the haloformate compound may be used in combination with the carbonyl halide compound.

In the formula (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 and 1,3-
Propanediol, 1,4-butanediol, 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 R 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 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. The amount of the carbonate precursor used is preferably about 1.0 to 1.5 times equivalent, and more preferably about 1.0 to 1.4 times equivalent to the amount of the aromatic dihydroxy compound used. Yes, and more preferably about 1.05-1.3 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 as a solution by dissolving it in a gas state or a halogenated aromatic hydrocarbon. When a haloformate compound is used, it is preferably used as a solution in a liquid state, a solid state, or dissolved in a halogenated aromatic hydrocarbon.

The base used in the production method of the present invention is preferably an alkali metal or alkaline earth metal base. For example, hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate,
Examples thereof include carbonates such as calcium carbonate and potassium carbonate, sodium hydrogen carbonate and the like. These may be used alone or in combination. The preferred base is sodium hydroxide or potassium hydroxide. The amount of base used is
The amount of the aromatic dihydroxy compound used is preferably about 1.0 to 2.0 times equivalent, and more preferably
It is about 1.05-1.8 times equivalent, and more preferably,
It is about 1.1 to 1.6 times equivalent. The base is usually used as an aqueous solution. Further, the aromatic dihydroxy compound may be dissolved in the aqueous base solution before use. In this case, sodium sulfite, sodium hydrosulfite, sodium borohydride or the like may be added as an antioxidant.

The total amount of the base may be used in the step (A), a part of the amount may be used in the step (A), and the remaining amount may be added in the step (B). In addition, the base is the step (A)
Alternatively, in the step (B), the whole amount of the used amount may be added at once, or may be added intermittently or continuously. Further, the base may be added intermittently or continuously while controlling the pH of the reaction mixture to a constant value or a constant range. When some bases are used in step (A) and the remaining bases are added in step (B), the amount of base used in step (A) is preferably about 25 equivalents of the total amount of base used. % Or more, more preferably about 5 of the total amount of the base used.
It is 0 equivalent% or more.

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. Further, the amount of water used when preparing the base aqueous solution of the aromatic dihydroxy compound may be the amount necessary for dissolving the aromatic dihydroxy compound and the base or more. For example, when the aromatic dihydroxy compound is bisphenol A, its amount is bisphenol A1.
It is about 0.8 to 2.2 liters per mole.

The halogenated aromatic hydrocarbon 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. To do. Specific examples of the halogenated aromatic hydrocarbon include chlorobenzene, o-, and m.
-Or p-dichlorobenzene, o-, m- or p-
Chlorotoluene, o-, m- or p-chloronitrobenzene, fluorobenzene, bromobenzene, o-, m
-Or p-bromochlorobenzene, o-, m- or p-chlorofluorobenzene, 1,2,3-, 1,2,
4- or 1,3,5-trichlorobenzene and the like.
These may be used alone or in combination of two or more. In addition, to these halogenated aromatic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, hexane, heptane, octane,
You may mix and use aliphatic hydrocarbons, such as cyclohexane. When the aromatic hydrocarbon or the aliphatic hydrocarbon is mixed and used, the amount thereof is preferably 50% by weight or less, more preferably 30% by weight based on the amount of the halogenated aromatic hydrocarbon used. It is not more than 10% by weight, preferably not more than 10% by weight. The halogenated aromatic hydrocarbons are preferably chlorinated aromatic hydrocarbons, particularly preferably chlorobenzene or o-dichlorobenzene.

Further, the halogenated aromatic hydrocarbon used in the production method of the present invention may be a recovered halogenated aromatic hydrocarbon produced in producing an aromatic polycarbonate. Further, a mixture of the recovered halogenated aromatic hydrocarbon and a new halogenated aromatic hydrocarbon may be used. The amount of the halogenated aromatic hydrocarbon used is preferably 0.4 with respect to the aromatic dihydroxy compound.
To 4 liters / mole, and more preferably 0.6 to
3 liters / mole, more preferably 0.8 to
2 liters / mole. The halogenated aromatic hydrocarbon may be used in the whole amount in the step (A), or a part of the halogenated aromatic hydrocarbon may be used in the step (A) and the remaining amount may be added in the step (B). Good. Further, the halogenated aromatic hydrocarbon may be added at once in the step (A) or the step (B) at once, or may be added intermittently or continuously. When a part of the halogenated aromatic hydrocarbon is used in the step (A) and the rest is added in the step (B), the amount of the halogenated aromatic hydrocarbon used in the step (A) is preferably all. About 30% by weight or more of the amount used,
More preferably, it is about 50% by weight or more.

The production method of the present invention may be carried out without using a polycarbonate-forming catalyst or may be carried out using a polycarbonate-forming catalyst. When a polycarbonate-forming catalyst is used, it may be used in the step (A) or the step (B). Further, it may be used in both step (A) and step (B). Particularly preferably, the production method of the present invention is carried out without using a polycarbonate-forming catalyst, or is carried out without using in step (A) but in step (B).

Polycarbonate-forming catalysts suitable for the production method of the present invention include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, nitrogen-containing heterocyclic compounds and salts thereof, imino ethers and salts thereof, and amide groups. And the like. Specific examples of the polycarbonate generation catalyst include trimethylamine, triethylamine, and 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-dimethylcyclohexylamine, 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, benzyltrimethylammonium fluoride, benzyldimethylphenylammonium chloride, tetra-n-heptylammonium iodide,
m-trifluoromethylphenyltrimethylammonium bromide, triethylphosphine, triphenylphosphine, diphenylbutylphosphine, tetra (hydroxymethyl) phosphonium chloride, benzyltriethylphosphonium chloride, benzyltriphenylphosphonium chloride, 4-methylpyridine, 1-methylimidazole, 1,2-dimethylimidazole, 3
-Methylpyridazine, 4,6-dimethylpyrimidine, 1
-Cyclohexyl-3,5-dimethylpyrazole, 2,
3,5,6-tetramethylpyrazine and the like. These polycarbonate-forming catalysts may be used alone,
Moreover, you may use together two or more.

The polycarbonate-forming catalyst is preferably a tertiary amine, more preferably having a total carbon number of 3 to 3.
30 tertiary amines, particularly preferably triethylamine. When a polycarbonate-forming catalyst is used, its amount may be about 0.0005 mol% or more based on the number of moles of the aromatic dihydroxy compound. Also,
Even if the amount is too large, no significant effect can be expected.
The amount of the polycarbonate-forming catalyst is preferably about 0.0005 based on the number of moles of the aromatic dihydroxy compound.
~ 5 mol%, more preferably about 0.001-2
Mol%, and more preferably about 0.005 to 1 mol%. The polycarbonate-forming catalyst may be used in a liquid state or a solid state, and may be used as a halogenated aromatic hydrocarbon solution or aqueous solution.

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- (2 ',
4 ', 4'-Trimethylchromanyl) phenol, 2- (4'
-Methoxyphenyl) -2- (4 "-hydroxyphenyl) propane and the like, or their alkali metal salts and alkaline earth metal salts. The haloformate derivative of a monovalent aromatic hydroxy compound is the above-mentioned 1
And haloformate derivatives of valent aromatic hydroxy compounds.

Examples of the monovalent carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid, 3-methylbutyric acid and 3,3-dimethylbutyric acid. , 4-methylvaleric acid, 3,
3-dimethylvaleric acid, 4-methylcaproic acid, 3,5-
Fatty acids such as dimethylcaproic acid and phenoxyacetic acid or their alkali metal salts and alkaline earth metal salts,
Benzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, p-butoxybenzoic acid, p-octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid,
Benzoic acids such as p-chlorobenzoic acid and their alkali 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 1
5,000 to 150,000, preferably about 200
It is 00 to 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 10.0 mol% based on the number of moles of the aromatic dihydroxy compound. Yes, preferably about 1.5-7.0 mol%. The terminal blocking agent may be used in a solid state or a liquid state, and may be used as a halogenated aromatic hydrocarbon solution, an aqueous solution or an aqueous base solution. The timing of adding the terminal blocking agent is not particularly limited, and may be added in advance before the reaction, or may be added at an arbitrary point in the reaction.

The production method of the present invention can produce a branched aromatic polycarbonate by using a branching agent. 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, 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 and the like.

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 a halogenated aromatic hydrocarbon solution, an aqueous solution or an aqueous base 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 branching agents may be used alone or in combination.

In step (A) of the manufacturing method of the present invention, 70
The interfacial polymerization reaction is carried out at a temperature of not higher than 0 ° C to form an oligomer. The oligomer in the present specification means a low molecular weight initial product, and preferably has a weight average molecular weight of 10,000 or less, more preferably a weight average molecular weight of 7 or less.
000 or less. The temperature of step (A) is preferably 10 to 70 ° C, more preferably 20 to 6 ° C.
5 ° C., more preferably 25 to 60 ° C.,
Particularly preferably, it is 30 to 60 ° C. When the temperature in the step (A) exceeds 70 ° C., the aromatic polycarbonate obtained has a poor color tone.

Next, in step (B) of the production method of the present invention, the oligomer obtained in step (A) is further subjected to an interfacial polymerization reaction to form an aromatic polycarbonate. At that time, the temperature of the step (B) is a temperature of the step (A) or higher, preferably [temperature of the step (A) or higher] to 100 ° C., and more preferably [step (A A)
Or higher] to 95 ° C, and more preferably [higher than or equal to the temperature of step (A)] to 90 ° C.
When the temperature of the step (B) is lower than the temperature of the step (A), it becomes difficult to obtain a high molecular weight aromatic polycarbonate. 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, 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. Usually, it is preferable that the stirring is 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. 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, and those 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 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 are paddles, propellers, turbines or chi-type blades or other simple stirring devices, homogenizers, homomixers, high-speed stirrers such as mixers, static mixers,
A stirring device such as a colloid mill, an orifice mixer, a flow jet mixer, and an ultrasonic emulsifying device can be optionally provided.

The production method of the present invention can be carried out batchwise by using a tank reactor. For example, a carbonate precursor or a halogenated aromatic hydrocarbon solution of a carbonate precursor is supplied to a reaction system containing an aromatic dihydroxy compound, a base, water and a halogenated aromatic hydrocarbon, and interfacial polymerization is performed at a temperature of 70 ° C. or lower. The reaction is carried out to form an oligomer, and step (A) is carried out. that time,
The reaction time of step (A) is preferably about 1 second to 200.
Minutes, more preferably about 30 seconds to 150 minutes, further preferably about 1 minute to 100 minutes, and particularly preferably about 7 minutes to 80 minutes.

Then, an interfacial polymerization reaction is further carried out at a temperature higher than the temperature of the step (A) to form an aromatic polycarbonate, and the step (B) is carried out. At that time, process (B)
The reaction time is preferably about 1 minute to 600 minutes,
It is more preferably about 5 minutes to 300 minutes, even more preferably about 10 minutes to 200 minutes, and particularly preferably
It is about 30 minutes to 120 minutes. At that time, if desired, a polycarbonate generation catalyst, an end capping agent and / or a branching agent may be used. In addition, the base may be used in the entire amount in the step (A), a part of the amount may be used in the step (A), and the remaining amount may be used in the step (B).

The production method of the present invention can be carried out in a semi-batch method by using a tank reactor. For example,
An aqueous base solution of an aromatic dihydroxy compound, a halogenated aromatic hydrocarbon and a carbonate precursor, or a halogenated aromatic hydrocarbon solution of a carbonate precursor is continuously supplied to a reaction system, and an interfacial polymerization reaction is performed at a temperature of 70 ° C. or lower. Is carried out to form an oligomer, and step (A) is carried out. At that time, the reaction time of the step (A) is the same as in the case of the batch type. Further, the subsequent operation is the same as that of the batch type.

The production method of the present invention can also 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 base aqueous solution containing an aromatic dihydroxy compound, a carbonate precursor and a halogenated aromatic hydrocarbon, or a halogenated aromatic hydrocarbon solution of a carbonate precursor is continuously supplied to a first tank at a temperature of 70 ° C. or lower. In the step (A), an interfacial polymerization reaction is carried out to form an oligomer. After a certain residence time in the first tank, the reaction mixture is continuously discharged into the second tank. At that time, the residence time of the first tank, that is, the reaction time of the step (A) is preferably about 1 second to 200 minutes, more preferably about 10 seconds to 150 minutes, and further preferably It is about 1 minute to 100 minutes, particularly preferably about 7 minutes to 80 minutes.

Similarly, after a certain residence time, the reaction mixture is continuously discharged into the next reaction vessel to form an aromatic polycarbonate and the step (B) is carried out. The residence time after the second tank, that is, the reaction time of step (B) is preferably about 1 minute to 600 minutes, and more preferably,
It is about 5 minutes to 300 minutes, more preferably about 10 minutes to 200 minutes, and particularly preferably about 30 minutes to 120 minutes.
Minutes. The temperature of the second and subsequent tanks is a temperature equal to or higher than the temperature of the step (A). At that time, if desired, a polycarbonate generation catalyst, an end capping agent and / or a branching agent may be used. The base may be used in the entire amount in the step (A), or a part of the amount may be used in the step (A) and the remaining amount may be used in the step (B). 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. Furthermore, the production method of the present invention can be carried out continuously by using a tubular reactor. In this case, the production method of the present invention can be carried out by the same operation as in the case of using the tank type continuous reaction device.

The production method of the present invention can be carried out in a semi-batch type or a continuous type by using a continuous reaction apparatus in which reaction apparatuses 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 and / or a packed tower or the like is installed,
The interfacial polymerization reaction is performed at a temperature of not higher than 0 ° C. to continuously form an oligomer, and step (A) is performed. Next, using a tank reactor and / or a tubular reactor or the like, an interfacial polymerization reaction is carried out at a temperature higher than the temperature of the step (A) to form an aromatic polycarbonate, and the step (B) is carried out. It At that time, if desired, a polycarbonate-forming catalyst,
End caps and / or branching agents may be used.
The base may be used in its entire amount in the step (A),
Further, a part of the amount may be used in the step (A) and the remaining amount may be used in the step (B). Step (A) and step (B)
The residence time of is the same as in the case of the continuous type using a tank type continuous reaction device. 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 washed by a continuous operation or a batch operation. As the washing treatment of the reaction mixture, the organic phase composed of the aromatic polycarbonate and the halogenated aromatic hydrocarbon is separated from the aqueous phase. The obtained organic phase may be diluted with an organic solvent, if necessary. The organic solvent used at that time is the above-mentioned halogenated aromatic hydrocarbon, aromatic hydrocarbon or aliphatic hydrocarbon. The organic phase is optionally washed with water or a dilute aqueous alkaline solution and then 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. At that time, the organic phase may be subjected to the above-mentioned washing treatment while maintaining the reaction temperature in the step (B), at a temperature higher than the reaction temperature in the step (B), or in the step (B). The washing treatment may be carried out at a temperature lower than the reaction temperature in 1.

Then, the aromatic polycarbonate is recovered from the washed organic phase containing the aromatic polycarbonate by a continuous operation or a batch operation. The aromatic polycarbonate is recovered by gradually heating the organic phase containing the aromatic polycarbonate while continuously evaporating the halogenated aromatic hydrocarbons in the extruder, thereby directly heating the aromatic polycarbonate from the molten state. There are a method of pelletizing, a method of cooling an organic phase containing an aromatic polycarbonate, crushing the obtained gel-like material, and then removing a halogenated aromatic hydrocarbon in water.

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 used alone or in a mixture with another polymer in a known manner during or after the production of the aromatic polycarbonate by a known method such as pigments, dyes, processing and heat stability. Agents, antioxidants, hydrolysis stabilizers, impact stabilizers, UV absorbers,
One or more known additives such as release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, barium sulfate and TiO ₂ may be added.

The aromatic polycarbonate produced by the method of the present invention is soluble in a specific organic solvent (for example, a halogenated hydrocarbon solvent), and is processed into a molded product such as a film from the organic solvent solution. can do. The aromatic polycarbonate produced by the method of the present invention is thermoplastic and can be easily molded 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, is optionally added with the above-mentioned additive to obtain a chassis or a housing material for electric equipment, an electronic material, etc. It can be molded into parts, automobile parts, building materials as a substitute for glass, information recording medium bases such as data storage disks or audio compact disks, and optical materials such as lenses of cameras or glasses.

[0048]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Example 1 A 10-liter baffled flask equipped with a jacket was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 912 g of bisphenol A (4.
0 mol), 20.7 g of p-tert-butylphenol (3.44 mol% with respect to bisphenol A), 4 liters of chlorobenzene and 4 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 2.2 liters of an aqueous solution of 464 g (11.6 mol) of sodium hydroxide were supplied, and bisphenol A was dissolved at 30 ° C. 487 g of phosgene in this mixture with stirring
(4.92 mol) was supplied over 30 minutes to obtain an oligomer solution. Meanwhile, cooling water was flown through the jacket to keep the temperature of the reaction mixture at 40 ° C or lower. Next, after adding 0.65 g of triethylamine (0.16 mol% relative to bisphenol A), warm water of 90 ° C. was poured into the jacket,
The reaction was terminated by stirring for another 60 minutes. At that time, the temperature of the reaction mixture reached 80 ° C. 10 minutes after starting flowing hot water through the jacket, and maintained at 80 ° C. as it was. Then, the reaction mixture was allowed to stand still at 80 ° C., the organic phase was separated, neutralized with 5 L of 1/2 N hydrochloric acid, and then washed with 5 L of water three times. The conductivity was 10 μS or less, and the electrolyte was removed. The chlorobenzene solution of the aromatic polycarbonate thus obtained was cooled to room temperature and ground. Then, add 5 liters of water, 40-75 ℃, 40-80m
Chlorobenzene was removed under the condition of mHg to obtain an aromatic polycarbonate powder.

Example 2 A tank-type continuous reactor was used in which four jacketed 4-liter baffled flasks equipped with a three-stage six-blade stirrer and a reflux condenser were connected in series by an overflow outlet. did. Cooling water was flowed through the jacket of the first tank so that the temperature inside the flask was maintained at 40 ° C, and hot water of 90 ° C was flowed through the jackets of the second, third, and fourth tanks to keep the temperature of the reaction mixture. Was maintained at 80 ° C. Under stirring, in the first tank, bisphenol A3653
g (16 mol), p-tert-butylphenol 82.7
g (0.55 mol), sodium hydroxide 1856 g (4
6.4 mol), sodium hydrosulfite 7.2
g in 24 kg of water, a total weight of 29.6 kg of an aqueous solution, phosgene, and chlorobenzene were added to 123.g.
3 g / min, 8.11 g / min (0.082 mol / min), 7
Delivered at 3.8 g / min. After a residence time of about 30 minutes, the oligomer solution was discharged into the second tank at a rate of 205.2 g / min. 2.27 g (0.0224 mol) of triethylamine was added to the second tank from the time when discharge to the second tank started.
210 ml of a chlorobenzene solution of was supplied at 1 ml / min. In the second tank, after a residence time of about 30 minutes, the reaction mixture was discharged into the third tank, and thereafter, in the third and fourth tanks, the reaction containing aromatic polycarbonate from the fourth tank after the same residence time. The mixture was drained. Continuous operation was performed for 4 hours from the time when the supply to the first tank was started. Meanwhile, the fourth
When the weight average molecular weight of the aromatic polycarbonate continuously discharged from the tank was measured every 30 minutes, the same result was always obtained and it was stable. Then, the reaction mixture discharged from the fourth tank was allowed to stand to separate the organic phase. The obtained organic phase was placed in a 40 liter flask, heated to 80 ° C., neutralized with 20 liters of 1 / 2N hydrochloric acid, and then washed with 20 liters of water three times, and the conductivity of the wash water was 10 μS. Below, the electrolyte was removed. The chlorobenzene solution of the aromatic polycarbonate thus obtained was cooled to room temperature and ground. Next, 20 liters of water was added, and chlorobenzene was removed under the conditions of 40 to 75 ° C. and 40 to 80 mmHg to obtain an aromatic polycarbonate powder or granule.

Example 3 A 12 liter baffled flask equipped with a jacket was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 912 g of bisphenol A (4.
(0 mol), 6 liters of chlorobenzene and 4 liters of water were added, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.8 g of sodium hydrosulfite and 400 g (1
Then, 1.5 liter of an aqueous solution of 0 mol) was supplied and bisphenol A was dissolved at 30 ° C. Phosgene (495 g, 5.0 mol) was added to the mixture under stirring for 60 minutes to obtain an oligomer solution. Meanwhile, the temperature of the reaction mixture was 3
The temperature rose from 0 ° C to 55 ° C. Then, 20.7 g of p-tert-butylphenol (3.
44 mol%), 0.65 g of triethylamine (0.16 mol% with respect to bisphenol A) and 0.7 liter of an aqueous solution of 80 g (2 mol) of sodium hydroxide were added, and then warm water of 80 ° C. was poured into the jacket, The reaction was terminated by stirring for another 60 minutes. At that time, the temperature of the reaction mixture was 70 minutes after 7 minutes from the start of flowing hot water into the jacket.
The temperature reached 70 ° C and was maintained at 70 ° C. The subsequent operation was performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder or granule.

Example 4 A 10-liter baffled flask equipped with a jacket was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 438 g of bisphenol A (1.
(92 mol) and 3 liters of water were added, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.8 g of sodium hydrosulfite and 192 g (4.8 mol) of sodium hydroxide were added to the above suspension as an aqueous solution 1.
Bisphenol A was dissolved at 30 ° C. by supplying 5 liters. With stirring, 4 liters of a chlorobenzene solution in which 735 g (2.08 mol) of bischloroformate of bisphenol A was dissolved was added to this mixture, and the mixture was heated to about 1 at 35 ° C.
Stir for 0 minutes to obtain an oligomer solution. Next, p-tert
100 ml of a chlorobenzene solution of 20.7 g of butylphenol (3.44 mol% with respect to bisphenol A)
After addition of the above, warm water of 95 ° C. was flown through the jacket, and the mixture was stirred for another 90 minutes to terminate the reaction. The temperature of the reaction mixture is 9 minutes after 15 minutes from the start of flowing hot water into the jacket.
The temperature reached 0 ° C and was maintained at 90 ° C. The subsequent operation was performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder or granule.

Example 5 A 15-liter jacketed 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), 20.7 g of p-tert-butylphenol (3.44 mol% with respect to bisphenol A), 7.2 liters of o-dichlorobenzene and 4 liters of water were added, and nitrogen was added to remove oxygen in the flask. Purged. Next, to the above suspension, 1.8 g of sodium hydrosulfite and 2.2 liters of an aqueous solution of 464 g (11.6 mol) of sodium hydroxide were supplied, and bisphenol A was dissolved at 30 ° C. With stirring, 487 g (4.92 mol) of phosgene was supplied to this mixture over 30 minutes to obtain an oligomer solution. Meanwhile, the temperature of the reaction mixture is 30
The temperature rose from ℃ to 65 ℃. Next, after adding 0.65 g of triethylamine (0.16 mol% relative to bisphenol A), warm water of 90 ° C. was poured into the jacket,
The reaction was terminated by stirring for another 60 minutes. At that time, the temperature of the reaction mixture reached 80 ° C. 5 minutes after starting flowing hot water through the jacket, and maintained at 80 ° C. as it was. The subsequent operation was performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder or granule.

Example 6 A 20 liter baffled flask equipped with a jacket was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 912 g of bisphenol A (4.
0 mol), 20.7 g of p-tert-butylphenol (3.44 mol% with respect to bisphenol A), 14 liters of chlorobenzene and 4 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 2.2 liter of an aqueous solution of 464 g (11.6 mol) of sodium hydroxide were supplied, and bisphenol A was added at 30 ° C.
Was dissolved. To this mixture, with stirring, 475 g of phosgene
(4.8 mol) was fed for 60 minutes to obtain an oligomer solution. Meanwhile, cooling water was flown through the jacket to keep the temperature of the reaction mixture at 30 ° C. Next, triethylamine 1.
After adding 21 g (0.3 mol% with respect to bisphenol A), warm water of 60 ° C. was poured into the jacket, and further 9
The reaction was terminated by stirring for 0 minutes. At that time, the temperature of the reaction mixture reached 55 ° C. 15 minutes after starting flowing hot water through the jacket, and maintained at 55 ° C. as it was. The subsequent operation was performed in the same manner as in Example 1 to obtain an aromatic polycarbonate powder or granule.

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, 2.2 liters of an aqueous solution containing 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 30 ° C. To this mixture, with stirring, 467 g (4.72 mol) of phosgene
For 30 minutes. Meanwhile, the temperature of the reaction mixture is 3
Raised to 9 ° C. Next, 0.65 g of triethylamine
(0.16 mol% relative to bisphenol A) was added and stirred for 60 minutes to terminate the reaction. The temperature of the reaction mixture during that time was 30 ° C. Then, the reaction mixture was allowed to stand still, the organic phase was separated, neutralized with 5 L of 1/2 N hydrochloric acid, and then washed 3 times with 5 L of water.
The conductivity of the wash water was 10 μS or less, and the electrolyte was removed. To the dichloromethane solution of the aromatic polycarbonate thus obtained, 2 liters of toluene and 5 liters of water were added, and the mixture was heated to 98 ° C. to distill off dichloromethane and toluene to obtain a granular material of aromatic polycarbonate.

Comparative Example 2 (Method described in Japanese Examined Patent Publication No. 38-14498) A 10-liter baffled flask equipped with a jacket was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 912 g of bisphenol A (4.
(0 mol) 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 liter of an aqueous solution of 4.8 g of sodium hydrosulfite and 320 g (8 mol) of sodium hydroxide was supplied, warm water was poured into the jacket, and the mixture was heated to 40 ° C. to dissolve bisphenol A. did. Next, 255 ml of chlorobenzene was added. With stirring, 98.9 g (1 mol) of phosgene was fed to this mixture in 30 minutes. in the meantime,
Pour cooling water into the jacket and raise the temperature of the reaction mixture to 30 ° C.
Kept at. Next, while adding 1324 g of a 25.4 wt% sodium hydroxide aqueous solution (8.41 mol of sodium hydroxide), 500 g (5.06 mol) of phosgene at the same time.
For 90 minutes. Then, after stirring for 30 minutes, warm water was flown through the jacket to bring the temperature of the reaction mixture to 80 ° C. over 1 hour, and the mixture was further stirred at 80 ° C. for 1 hour. Then, the reaction mixture was allowed to stand while maintaining the temperature at 80 ° C., and the organic phase was separated. Chlorobenzene 3.4 was added to the obtained organic phase.
After the addition of 1 liter, the mixture was neutralized with 5 liters of 1/2 N hydrochloric acid and washed 10 times with 5 liters of water, but the conductivity of the washing water was not 10 μS or less, and washing was extremely difficult. The chlorobenzene solution of the obtained aromatic polycarbonate was cooled to room temperature and ground. Next, 5 liters of water was added, and chlorobenzene was removed under the conditions of 40 to 75 ° C. and 40 to 80 mmHg to obtain a granular material of aromatic polycarbonate.

Comparative Example 3 (Method described in JP-A No. 50-122595) Continuous reaction in which a 300 ml pump type circulation reactor with a jacket and a 750 ml tubular reactor with a jacket were connected by an overflow pipe. The equipment was used. In this pump type circulation reactor, 3646 g of bisphenol A
(16 mol), p-tert-butylphenol 64.5 g
(0.43 mol), sodium hydroxide 1300 g (3
2.5 mol), sodium hydrosulfite 7.2
g and triethylamine 16.13 g (1 mol% with respect to bisphenol A) dissolved in 19.3 kg of water, a total weight of 24.3 kg of aqueous solution, phosgene, chlorobenzene, and a 45% by weight sodium hydroxide aqueous solution, respectively. 3 g / min, 7.45 g / min (0.075 mol / min
Min), 97.8 g / min, and 0.55 g / min. The OH concentration in the aqueous phase was 0.08% by weight and the temperature of the reaction mixture was 72 ° C. After a residence time of 1.6 minutes, the reaction mixture was discharged into the tubular reactor. The tubular reactor was fed with a 45% by weight aqueous sodium hydroxide solution, and the OH in the aqueous phase was
The concentration was kept between 0.30 and 0.35% by weight. The temperature of the reaction mixture was kept at 83 ° C. by flowing 90 ° C. warm water through the jacket and after a residence time of 4 minutes the reaction mixture was discharged. The subsequent operation is performed in the same manner as in Example 2,
A powder of aromatic polycarbonate was obtained.

Table 1 (Table 1) shows the reaction temperature of step (A), the reaction temperature of step (B) and the use of halogenated aromatic hydrocarbon for the aromatic dihydroxy compound in each of the examples and comparative examples. The amount is shown. Table 2 (Table 1)
The weight average molecular weight (Mw), nitrogen content, 15-second retention YI value, and 5-minute retention YI value of the obtained aromatic polycarbonate in each of Examples and Comparative Examples are shown in Table 1.
The measuring method is as shown below. -Measurement of weight average molecular weight: 0.02 g of aromatic polycarbonate powder is dissolved in 10 g of chloroform. This solution was measured by GPC [gel permeation chromatography, Showa Denko KK-made, GPC system-11] to calculate the weight average molecular weight (Mw). -Measurement of nitrogen content: The nitrogen content of the produced aromatic polycarbonate was measured by a total nitrogen analyzer (TN-10) manufactured by Mitsubishi Kasei Co., Ltd. -Measurement of YI value Aromatic polycarbonate powder was pelletized by an extruder (cylinder temperature 280 ° C). An injection molding machine [PS20E-5AS manufactured by NISSEI PLASTIC INDUSTRIES CO., LTD.
E] and plasticized at 280 ° C., then 15
After being retained for 2 seconds or 5 minutes, injection molded to a thickness of 1 m
m press sheets were prepared. The YI value of this press sheet was measured by a transmission measurement method using a color difference meter manufactured by Suga Test Instruments. The YI value of the press sheet made by staying for 15 seconds is set as the YI value of staying for 15 seconds, and the YI value of the press sheet made by staying for 5 minutes is set as the staying YI value of 5 minutes. The smaller the YI value, the less the coloring is, and the smaller the difference between the 15-second retention YI value and the 5-minute retention YI value, the better the thermal stability.

[0058]

[Table 1]

[0059]

[Table 2]

From the results of Examples 1 to 6, it can be seen that the production method of the present invention can suitably produce an aromatic polycarbonate having a low nitrogen content, a good color tone and excellent thermal stability. Further, the results of Comparative Example 1 show that the aromatic polycarbonate obtained by using dichloromethane as the organic solvent has poor color tone and poor thermal stability. Further, in the method of Comparative Example 2, it is difficult to terminate the polycondensation reaction, a high-molecular-weight aromatic polycarbonate cannot be produced, and the washability of the organic solvent solution containing the aromatic polycarbonate is poor, and further, It can be seen that the color tone is poor and the thermal stability is poor. In addition, it can be seen that the method of Comparative Example 3 has a large nitrogen content, a poor color tone, and poor thermal stability. From the above results, the production method of the present invention makes it possible to produce an aromatic polycarbonate having a low nitrogen content, a good color tone, and excellent thermal stability as compared with the conventional production method. .

[0061]

Industrial Applicability According to the present invention, it is possible to provide a method for producing an aromatic polycarbonate having a low nitrogen content, a good color tone, and good thermal stability.

 ─────────────────────────────────────────────────── (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] 1. A method for producing an aromatic polycarbonate using an aromatic dihydroxy compound, a carbonate precursor, a base, water and at least one halogenated aromatic hydrocarbon, wherein (A) at a temperature of 70 ° C. or lower. An interfacial polymerization reaction to form an oligomer, and (B) a step of further performing an interfacial polymerization reaction at a temperature higher than the temperature of the step (A) to form an aromatic polycarbonate. The amount of the group hydrocarbon used is 0.4 to 4 with respect to the aromatic dihydroxy compound.
A method for producing an aromatic polycarbonate, characterized in that it is liter / mol. 2. The amount of the carbonate precursor used is 1.0 to 1.5 with respect to the amount of the aromatic dihydroxy compound used.
The production method according to claim 1, which is a double equivalent. 3. The production method according to claim 1, wherein the amount of the base used is 1.0 to 2.0 times equivalent to the amount of the aromatic dihydroxy compound used. 4. An aromatic polycarbonate obtained by the production method according to claim 1.