JPH083307A - Production of aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To obtain an aromatic polycarbonate having low impurity content and useful as an engineering plastic by using exclusively a halogen-free hydrocarbon as an organic solvent without using a halogenated hydrocarbon having environmental pollution problem. CONSTITUTION:This polycarbonate is produced from (A) at least two kinds of aromatic dihydroxy compounds as aromatic dihydroxy compound and (B) a carbonate precursor using (C) exclusively a halogen-free hydrocarbon as an organic solvent. Preferably, a compound of the component A is (i) 2,2-bis (4'- hydroxyphenyl) propane, the molar ratio of the compound (i) to the other compound (ii) is (5-95):(95-5) and the component C is a halogen-free aromatic hydrocarbon such as toluene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic polycarbonate. More specifically, it relates to a method for producing an aromatic polycarbonate using a non-halogenated hydrocarbon as an organic solvent.

[0002]

2. Description of the Related Art Aromatic polycarbonates are widely used as engineering plastics in the fields of automobiles, electricity and optics. The aromatic polycarbonate is produced by an interfacial polymerization method using a carbonyl halide compound such as phosgene as a carbonate precursor, a transesterification method using a carbonic acid diester such as diphenyl carbonate as a carbonate precursor, and the like. The transesterification method is a method for producing an aromatic polycarbonate in a molten state without using an organic solvent, and thus it is a method capable of solving an environmental conservation problem based on an organic solvent, but in the molten state. Since the polymerization reaction is carried out, there is a problem that the physical properties of the aromatic polycarbonate produced are deteriorated due to heat deterioration or the like. When an aromatic polycarbonate is produced by an interfacial polymerization method, usually, an alkali metal or alkaline earth metal base aqueous solution of an aromatic dihydroxy compound and an carbonyl halide compound are subjected to interfacial polycondensation using a halogenated hydrocarbon such as dichloromethane as a solvent. .

Halogenated hydrocarbons such as dichloromethane have a high ability to dissolve aromatic polycarbonate,
Therefore, it is used as a particularly useful organic solvent when an aromatic polycarbonate is produced by an interfacial polymerization method. However, in recent years, halogenated hydrocarbons have been widely taken up in environmental pollution problems, and it is said that it is preferable to reduce the use thereof as much as possible. Further, when a halogenated hydrocarbon is used, if a small amount of the halogenated hydrocarbon remains in the polymer, an acidic substance such as hydrogen halide is generated during the molding process, which may cause deterioration of the physical properties of the polymer, a molding machine, etc. It is known to cause metal corrosion, and is particularly regarded as a problem when reusing a thermoplastic polymer for recycling molding or the like. Further, when producing an aromatic polycarbonate using dichloromethane, impurities such as salts remain in the resulting aromatic polycarbonate because water containing impurities such as salts dissolves in the dichloromethane phase after completion of polymerization. The problem arises.

As described above, a method for producing an aromatic polycarbonate has been disclosed in which the amount of halogenated hydrocarbon used is reduced in order to suppress environmental pollution and deterioration of physical properties of the polymer. For example, in JP-A-4-126715, in the production of a polycarbonate by an interfacial polycondensation reaction, (a) methylene chloride (dichloromethane) 60 to 99% by volume, and (b) a carbon number of 5 to 20.
Of aliphatic or alicyclic hydrocarbons and / or substituted or unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms 40 to
A method for producing a polycarbonate is disclosed, which comprises using 1% by volume of a mixed solvent. However, the production method uses 60 to 99% by volume of a halogen-based hydrocarbon, and the suppression of environmental pollution and the deterioration of the physical properties of the polymer is still insufficient.

Also disclosed is a method for producing an aromatic polycarbonate which uses an aromatic hydrocarbon as an organic solvent without using a halogenated hydrocarbon. For example, in JP-B-41-21472, when a dioxy compound and phosgene are reacted in the presence of one kind of aromatic hydrocarbon and an alkaline aqueous solution, a polycondensation reaction is caused by coexisting a surfactant. Disclosed is a method for producing a granular polycarbonate having a uniform composition. However, according to the production method, the aromatic polycarbonate is obtained in the form of a granular body or a small lump, and it is difficult to remove impurities such as salts generated by the polymerization reaction from the aromatic polycarbonate. At present, there is a demand for a method for producing an aromatic polycarbonate that does not use halogenated hydrocarbons and that contains less impurities that cause deterioration of the physical properties of the polymer.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems of the prior art and to provide a method for producing an aromatic polycarbonate containing less impurities without using a halogenated hydrocarbon solvent. It is provided.

[0007]

[Means for Solving the Problems] The inventors of the present invention have made extensive studies in order to solve the above problems, and arrived at the present invention. That is, the present invention uses a non-halogenated hydrocarbon as an organic solvent when producing an aromatic polycarbonate from an aromatic dihydroxy compound and a carbonate precursor, and at least two kinds of aromatic dihydroxy compounds as the aromatic dihydroxy compound. The present invention relates to a method for producing an aromatic polycarbonate, which comprises using

The present invention will be described in detail below. In the method for producing an aromatic polycarbonate of the present invention, at least two kinds of aromatic dihydroxy compounds, a carbonate precursor, a non-halogenated hydrocarbon solvent, an alkali metal or alkaline earth metal base, a polymerization catalyst, a molecular weight modifier and a branching agent are included if desired. Use agents. The aromatic dihydroxy compound according to the production method of the present invention is at least two kinds of aromatic dihydroxy compounds, and preferably, the aromatic compound represented by the general formula (1), (2) or (3) At least two aromatic dihydroxy compounds selected from dihydroxy compounds. HO-Ar ¹ -X-Ar ² -OH (1) HO-Ar ³ -OH (2) (wherein Ar ¹ , Ar ² and Ar ³ are aromatic groups, and X is A
represents a linking group that links r ¹ and Ar ² )

[0009]

Embedded image (In the formula, R ¹ and R ² are alkyl groups, aryl groups or halogen atoms, R ^{3 to} R ¹⁰ are hydrogen atoms or alkyl groups, 1 and m are integers from 0 to 3, and n is 0 or 1.
Represents, and 1 + m is an integer of 0 to 4)

In the general formulas (1) and (2), A
Each of r ¹ , Ar ² and Ar ³ represents an aromatic group, preferably a phenylene group, and the phenylene group may have a substituent. Examples of the substituent include a halogen atom, a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group and an alkoxy group. Preferred are a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group, and more preferred are a halogen atom selected from chlorine or bromine, an alkyl group having 1 to 5 carbon atoms, and a cyclo group having 5 to 8 carbon atoms. Alkyl group, C6-C12 aryl group, C1-C1
5 is an alkoxy group.

Ar ¹ and Ar ² are preferably both
1,4-phenylene group, 1,3-phenylene group or 1,2-
A phenylene group, or one is a 1,4-phenylene group and the other is a 1,3-phenylene group or a 1,2-phenylene group, and more preferably both Ar ¹ and Ar ² are 1,4-
It is a phenylene group. Ar ³ is preferably a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group, more preferably a 1,4-phenylene group or
It is a 1,3-phenylene group.

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

Specific examples of the aromatic dihydroxy compound represented by the general formula (1) or (2) include bis (4-hydroxyphenyl) methane, 1,1-bis (4'-hydroxyphenyl) ethane and 1 , 2-bis (4'-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,1-bis (4'-hydroxyphenyl) -1-phenylethane, 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"], 2- (4'-hydroxyphenyl) -2- (3'-hydroxy Phenyl) propane, 2,2-bis (4'-hydroxyphenyl) butane, 1,1-bis (4'-
Hydroxyphenyl) butane, 1,1-bis (4′-hydroxyphenyl) -2-methylpropane, 2,2-bis (4′-hydroxyphenyl) -3-methylbutane, 2,2-bis (4′-hydroxy) Phenyl) pentane, 3,3-bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxyphenyl) heptane, 2,2-bis (4'-hydroxyphenyl)
Octane, 2,2-bis (3'-methyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-ethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-n -Propyl-
4'-hydroxyphenyl) propane, 2,2-bis (3'-isopropyl-4'-hydroxyphenyl) propane, 2,2-
Bis (3'-sec-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-tert-butyl-4'-hydroxyphenyl) propane,

2,2-bis (3'-cyclohexyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-allyl-4 '
-Hydroxyphenyl) propane, 2,2-bis (3'-methoxy-4'-hydroxyphenyl) propane, 2,2-bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane, 2,2 -Bis (2 ', 3', 5 ', 6'-tetramethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-chloro-4'-
Hydroxyphenyl) propane, 2,2-bis (3 ', 5'-dichloro-4'-hydroxyphenyl) propane, 2,2-bis (3'-bromo-4'-hydroxyphenyl) propane, 2,
2-bis (3 ', 5'-dibromo-4'-hydroxyphenyl) propane, 2,2-bis (2', 6'-dibromo-3 ', 5'-dimethyl-
4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl) cyanomethane, 1-cyano-3,3-bis (4 '
-Hydroxyphenyl) butane, bis (hydroxyaryl) alkanes such as 2,2-bis (4'-hydroxyphenyl) hexafluoropropane,

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

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

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

In the aromatic dihydroxy compound represented by the general formula (3) according to the present invention, R ¹ and R ² represent an alkyl group, an aryl group or a halogen atom, and R ³
To R ¹⁰ represents a hydrogen atom or an alkyl group. R ¹ and R ² are preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and more preferably an alkyl group having 1 to 8 carbon atoms or a halogen atom. . R ^{3 to} R ¹⁰ are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In addition, the bonding position of the hydroxy group bonded to the aromatic ring is not particularly limited, and the o-position or m may be respectively attached to two carbon atoms on the condensed aromatic ring.
It is in the -position, and the bonding positions of the hydroxy groups in the two aromatic rings may be different from each other. l and m represent an integer of 0 to 3, l + m is an integer of 0 to 4, and preferably an integer of 0 to 2. Further, n represents 0 or 1.

Specific examples of the aromatic dihydroxy compound represented by the general formula (3) include 6,6'-dihydroxy-3,3,3.
3 ', 3'-tetramethylspirobiindane, 6,6'-dihydroxy-3,3,3', 3 ', 5,5'-hexamethylspirobiindane, 6,6'-dihydroxy-3,3 , 3 ', 3'5,5', 7,7'-Octamethylspirobiindane, 6,6'-dihydroxy-3,3,3 ', 3'
-Tetramethyl-5,5 ', 7,7'-tetraethylspirobiindane, 6,6'-dihydroxy-3,3,3', 3 ', 5,5'-hexamethyl-7,7'-dibromospiro Biindane, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-5,5'-dichlorospirobiindane, 6,6'-dihydroxy-3,3,3', 3'- Tetramethyl-5,5'-dibromospirobiindane, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-5,5', 7,7'-tetrachlorospirobiindane, 6 , 6'-Dihydroxy-3,3,3 ', 3'
-Tetramethyl-5,5 ', 7,7'-tetrabromospirobiindane, 6,6'-dihydroxy-2,3,3', 5,5'7,7'-heptamethyl-3,3'- Diethylspirobiindane, 6,6'-dihydroxy-2,2'-dimethyl-3,3,3 ', 3'-tetraethyl-7,7'
-Di-n-octylspirobiindane, 6,6'-dihydroxy-2,2 ', 3,3'-tetramethyl-3,3'-diisopropyl-
5,5 ', 7,7'-tetra-n-propylspirobiindane,
6,6'-dihydroxy-2,2,2 ', 5,5'-pentamethyl-2'-
Ethyl-3,3'-diisopropyl-3,3'-di-sec-butyl-7,7'-di-n-butylspirobiindane, 6,6'-dihydroxy-5,5 ', 7,7' -Tetramethyl-2,2-diethyl-2 '
2'-di-n-propyl-3,3'-di (1 "-ethylpropyl) -3,3'-di (1 '"-propylbutyl) spirobiindane, 7,7'-dihydroxy-3,3 ', 4,4'-Tetrahydro-
4,4,4 ', 4'-tetramethyl-2,2'-spirobi (2H-1-benzopyran) etc. can be mentioned.

In the manufacturing method of the present invention, at least 2
The aromatic dihydroxy compound of the species may be used in a solid state, may be used as an alkali metal or alkaline earth metal basic aqueous solution, may be used as an organic solvent solution, or may be an aqueous suspension. Or may be used as an organic solvent suspension. When the aromatic dihydroxy compound is used as an alkaline metal or alkaline earth metal basic aqueous solution, a reducing agent such as sodium sulfite, sodium hydrosulfite, or sodium borohydride is added as an antioxidant during the preparation of the aqueous solution. You can also

The water used for preparing the alkaline metal or alkaline earth metal basic aqueous solution is not particularly limited, but distilled water, deionized water or the like is preferably used. Further, the amount of water for preparing the alkaline metal or alkaline earth metal basic aqueous solution of the aromatic dihydroxy compound is preferably the minimum amount necessary for dissolving the aromatic dihydroxy compound.

The molecular weight of the aromatic polycarbonate produced by the production method of the present invention is not particularly limited, and is usually the weight as a standard polystyrene-equivalent molecular weight measured by GPC (gel permeation chromatography). Average molecular weight is 5,000 to 100,000
The degree is preferably about 10,000 to 90,000, and more preferably about 15,000 to 80,000. The molecular weight distribution represented by the polydispersity index (Mw / Mn) is preferably about 1.9 to 2.8, more preferably about 2.0 to 2.6.

In the manufacturing method of the present invention, at least 2
As the kind of aromatic dihydroxy compound, a combination of various aromatic dihydroxy compounds can be used, the combination of aromatic dihydroxy compounds is not particularly limited, 2,2-bis (4'-hydroxy A combination of phenyl) propane with an aromatic dihydroxy compound other than 2,2-bis (4'-hydroxyphenyl) propane is preferred. As aromatic dihydroxy compounds other than 2,2-bis (4'-hydroxyphenyl) propane, 1,1-bis (4'-hydroxyphenyl) -1-phenylethane and 2,2-bis (3 ', 5 '-Dimethyl-4'-hydroxyphenyl) propane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 2,2-bis (4'-hydroxyphenyl) -4-methylpentane, 2,2-bis ( 4'-hydroxyphenyl) butane, 2,2-bis (4'-hydroxyphenyl)
-3-methylbutane, 2,2-bis (4'-hydroxyphenyl) heptane, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 1,1-bis (4'-hydroxyphenyl) -3, 3,5-Trimethylcyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane, hydroquinone, resorcin Etc. are preferred.

The composition ratio of at least two kinds of aromatic dihydroxy compounds is not particularly limited, but one of at least two kinds of aromatic dihydroxy compounds is 2,2-bis (4 In the case of'-hydroxyphenyl) propane, the composition ratio of 2,2-bis (4'-hydroxyphenyl) propane and the other aromatic dihydroxy compound is preferably 2,2-bis (4'-hydroxyphenyl).
Propane is 5 to 95 mol%, other aromatic dihydroxy compound is 95 to 5 mol%, more preferably 2,2-bis (4′-hydroxyphenyl) propane is 10 to 90 mol%, other aromatic The group dihydroxy compound is 90 to 10 mol%, more preferably 2,2-bis (4′-hydroxyphenyl) propane is 15 to 85 mol%, and the other aromatic dihydroxy compound is 85 to 15 mol%. is there.

Examples of the carbonate precursor used in the production method of the present invention include a carbonyl halide compound, a haloformate derivative of an aromatic dihydroxy compound, and a haloformate derivative of an aliphatic dihydroxy compound. Specific examples thereof include carbonyl chloride (phosgene), carbonyl bromide, carbonyl iodide and mixtures thereof, trichloromethyl chloroformate which is a dimer of carbonyl chloride, and 3 of carbonyl chloride.
Carbonyl halide compounds such as bis (trichloromethyl) carbonate which is a monomer, 2,2-bis (4'-chlorocarbonyloxyphenyl) propane, 1,4-bis (chlorocarbonyloxy) benzene, 1,3-bis Haloformate derivatives of aromatic dihydroxy compounds such as (chlorocarbonyloxy) benzene, haloformate derivatives of aliphatic dihydroxy compounds such as 1,2-bis (chlorocarbonyloxy) ethane and 1,4-bis (chlorocarbonyloxy) butane Can be mentioned.

Examples of the base used in the production method of the present invention include hydroxides, carbonates and hydrogen carbonates of alkali metals or alkaline earth metals such as sodium, potassium and calcium.

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

Further, in the production method of the present invention, if desired, an acid halide derivative of an aliphatic dicarboxylic acid and / or an aromatic dicarboxylic acid can be used together with the carbonate precursor. When the acid halide derivative is used, the obtained aromatic polycarbonate is an aromatic polyester carbonate having both ester bond and carbonate bond. Preferably, 50 mol% or less of the acid halide derivative is used with respect to the carbonate precursor, and more preferably 30 mol% or less of the acid halide is used.

The non-halogenated hydrocarbon used in the production method of the present invention represents a hydrocarbon containing no halogen atom, preferably a hydrocarbon having a melting point of room temperature or lower and a boiling point of room temperature or higher. Specific examples of the non-halogenated hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, 2-methylpentane, 3-methylpentane and 2,2-dimethyl. Pentane, 2,3-dimethylpentane, 2,2,3-trimethylpentane, 2,3,4-trimethylpentane,
2,2,3,4-tetramethylpentane, 2,2,3
3-tetramethylpentane, 2-methylhexane, 3-
Methylhexane, 2,2-dimethylhexane, 2,3-
Dimethylhexane, 2,4-dimethylhexane, 2,5
-Dimethylhexane, 2,2,3-trimethylhexane, 2,2,4-trimethylhexane, 2,2,5-trimethylhexane, 2,3,4-trimethylhexane,
2,3,5-trimethylhexane, 2,3,3-trimethylhexane, 2,4,4-trimethylhexane, 2,
Non-halogen aliphatic hydrocarbons such as 4,5-trimethylhexane,

Benzene, toluene, 1,2-dimethylbenzene (o-xylene), 1,3-dimethylbenzene (m-xylene), 1,4-dimethylbenzene (p-xylene), ethylbenzene, 1,2-diethylbenzene. , 1,3-diethylbenzene, 1,4-diethylbenzene, 1-methyl-2-ethylbenzene, 1-methyl-
3-ethylbenzene, 1-methyl-4-ethylbenzene, methoxybenzene (anisole), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-
Dimethoxybenzene, 1-methyl-2-methoxybenzene, 1-methyl-3-methoxybenzene, 1-methyl-
Mention may be made of non-halogenated aromatic hydrocarbons such as 4-methoxybenzene. These non-halogenated hydrocarbons may be used alone or in combination. It is preferably a non-halogenated aliphatic hydrocarbon having 1 to 8 carbon atoms or a non-halogenated aromatic hydrocarbon having 6 to 8 carbon atoms, and more preferably a non-halogenated aromatic hydrocarbon having 6 to 8 carbon atoms. Is.

The amount of the non-halogenated hydrocarbon used is preferably such that the concentration of the aromatic polycarbonate in the non-halogenated hydrocarbon solution at the end of the polymerization is about 5 to 50% by weight,
More preferred is an amount of about 10 to 40% by weight, about 15 to
An amount of 35% by weight is more preferable. If the concentration of aromatic polycarbonate in the non-halogenated hydrocarbon solution is too low, large amounts of non-halogenated hydrocarbons may be required. In addition, when the concentration of the aromatic polycarbonate in the non-halogenated hydrocarbon solution is close to the saturated concentration, precipitation of the aromatic polycarbonate may occur during the polymerization process, and the aromatic polycarbonate in the form of granules or small particles may not be formed. Since it may be obtained, it may be difficult to remove impurities in the aromatic polycarbonate. It also reduces the amount of non-halogenated hydrocarbons at the start of the reaction,
The non-halogenated hydrocarbon may be added at any time during the polymerization reaction, or the non-halogenated hydrocarbon may be added after the molecular weight is increased by the polymerization reaction and the viscosity is increased.

In the production method of the present invention, a polymerization catalyst optionally used is a tertiary amine, a quaternary ammonium salt,
Examples thereof include a tertiary phosphine, a quaternary phosphonium salt, or a nitrogen-containing heterocyclic compound and a salt thereof, an imino ether and a salt thereof, and a compound having an amide group. A tertiary amine or a quaternary ammonium salt is preferable, a tertiary amine is more preferable, and a still more preferable.
It is a trialkylamine. The trialkylamine has no branch on the carbon atoms at the 1-position and 2-position,
A trialkylamine in which the alkyl group has 1 to 4 carbon atoms is preferable, and specific examples thereof include triethylamine, tri-n-propylamine, diethyl-n-propylamine, and tri-n-butylamine. Triethylamine is particularly preferable because it is easily available and has a catalytic effect. The amount of the polymerization catalyst may be about 0.005 mol% or more, preferably 0.01 to 1.5 mol%, based on the total number of moles of the aromatic dihydroxy compound used.

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

Examples of the alkali metal or alkaline earth metal salt of the monovalent hydroxyaromatic compound include sodium salt and potassium salt of the above monovalent hydroxyaromatic compound,
Examples thereof include calcium salts, and examples of the monovalent hydroxyaromatic compound haloformate derivative include the above monovalent hydroxyaromatic compound chloroformates and bromoformates.

As the monovalent carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid, 3-methylbutyric acid, 3,3-dimethylbutyric acid, 4-methylvaleric acid, 3,3
-Dimethylvaleric acid, 4-methylcaproic acid, 2,4-dimethylvaleric acid, 3,5-dimethylcaproic acid, aliphatic carboxylic acids such as phenoxyacetic acid, benzoic acid, 4-propoxybenzoic acid, 4-butoxybenzoic acid , 4-pentyloxybenzoic acid, 4-hexyloxybenzoic acid, 4-octyloxybenzoic acid and the like.

Examples of the alkali metal or alkaline earth metal salt of a monovalent carboxylic acid include the sodium salt, potassium salt and calcium salt of the above-mentioned monovalent carboxylic acid. Examples thereof include acid halide derivatives of monovalent carboxylic acid. Examples thereof include chlorides and bromides of the above monovalent carboxylic acids. The amount of the molecular weight modifier used is usually, relative to the total number of moles of the aromatic dihydroxy compound used,
1 to 10 mol%, preferably 1.5 to 8 mol%
And more preferably 2 to 5 mol%.

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

The production method of the present invention is usually carried out at about 10 ° C. to the boiling temperature of the non-halogenated hydrocarbon used in the reaction. If the reaction temperature is excessively low, the reaction between the aromatic dihydroxy compound and the haloformate may not proceed efficiently, and the reaction efficiency of the polymerization reaction may decrease.
Further, an excessively high reaction temperature may cause a side reaction such as decomposition of the polymerization catalyst during the polymerization reaction. Preferably,
It is about 10 to 100 ° C, and more preferably about 10 to 100 ° C.
It is 70 ° C. The production method of the present invention is usually carried out under atmospheric pressure, and can be carried out under conditions below atmospheric pressure or above atmospheric pressure, if desired.

The method for producing an aromatic polycarbonate of the present invention can be carried out in a batch system, a semi-batch system, or a continuous system.
The reactor used in the production method of the present invention is a 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 may optionally be equipped with various stirring devices. As the stirring device, a stirring device such as a paddle blade, a propeller blade, a turbine blade, a lattice blade or a chi-type blade,
Examples thereof include a homogenizer, a mixer, a high-speed stirrer such as a homomixer, a static mixer, an orifice mixer, and the like.

When the method for producing an aromatic polycarbonate of the present invention is carried out batchwise, a non-halogenated hydrocarbon is usually added to a basic aqueous solution or suspension of an aromatic dihydroxy compound by using a tank reactor. In the presence of, the carbonate precursor is fed to carry out the reaction. When carrying out the method for producing an aromatic polycarbonate of the present invention in a semi-batch method,
Usually, a basic aqueous solution or suspension of an aromatic dihydroxy compound, a non-halogenated hydrocarbon and a carbonate precursor are simultaneously supplied to a reactor such as a packed column, a static mixer, an orifice mixer, etc. to bring them into contact with each other, and then from the reactor. It is possible to employ a method in which the reaction mixture flowing out is supplied to a tank reactor or the like and the polymerization is carried out batchwise.

When the aromatic polycarbonate of the present invention is produced in a continuous manner, it can be carried out by using a tank-type continuous reaction apparatus in which several tank-type reaction apparatuses are continuously connected. For example, a basic aqueous solution or suspension containing an aromatic dihydroxy compound, a carbonate precursor and a non-halogenated hydrocarbon, or a non-halogenated hydrocarbon of a carbonate precursor is supplied to the first tank. After a certain residence time in the first tank, the reaction mixture is continuously discharged into the second tank. Similarly, after a certain residence time, the reaction mixture can be continuously discharged to the next reactor to produce an aromatic polycarbonate. Furthermore, the production method of the present invention can be carried out continuously by using a tubular reactor. In this case, the production method of the present invention can be carried out by the same operation as in the case of using the tank type continuous reaction device.

The aromatic polycarbonate obtained by the production method of the present invention is an aromatic polycarbonate obtained by an interfacial polymerization method, but compared with an aromatic polycarbonate produced by using an ordinary halogenated hydrocarbon solvent. The content of impurities is low. Here, the impurities are
Salts (halogens of alkali metals or alkaline earth metals, carbonates, hydrogencarbonates, etc.) that are by-produced when an aromatic polycarbonate is produced by an interfacial polymerization method, and metal ions based on such salts, such as aromatic The content of impurities can be measured by measuring the amount of sodium in the polycarbonate. According to the production method of the present invention, the amount of water (containing impurities) in the organic solvent phase at the end of the polymerization is very small, and therefore the content of impurities in the finally obtained aromatic polycarbonate is Also few. The aromatic polycarbonate produced by the production method of the present invention has a low content of impurities,
It is excellent in color tone, heat stability and oxidation stability, and is particularly useful as a molding material for optical materials.

The aromatic polycarbonate obtained by the production method of the present invention is an aromatic polycarbonate derived from at least two kinds of aromatic dihydroxy compounds, and is a copolycarbonate. Here, the higher-order structure in the copolymerization of the aromatic polycarbonate may be random copolymerization, alternating copolymerization, or block copolymerization. The aromatic polycarbonate obtained by the production method of the present invention may be further used as a molding material by blending it with an aromatic polycarbonate derived from 2,2-bis (4′-hydroxyphenyl) propane, if desired. It is possible. Furthermore, it can be used as a molding material in combination with other polymers.

Other polymers include polyethylene, polypropylene, polystyrene, ABS resin, polymethylmethacrylate, polytrifluoroethylene, polytetrafluoroethylene, polyacetal, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polyamide, polyimide and polyamide. Examples thereof include imide, polyether imide, polysulfone, polyether sulfone, paraoxybenzoyl-based polyester, polyarylate, and polysulfide.

The aromatic polycarbonate obtained by the production method of the present invention may be used alone or in a mixture with another polymer, and further, a known method may be used during or after the production of the aromatic polycarbonate by a known method. Add known additives such as heat stabilizers, antioxidants, UV absorbers, mold release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, barium sulfate, TiO _{2 and the} like. Good.

The aromatic polycarbonate obtained by the production method of the present invention, alone or in a state of being mixed with another polymer, may be added with the above-mentioned additives as a molding material to obtain a chassis for electric equipment or the like. It can be molded into housing materials, electronic parts, automobile parts, substrates for information recording media such as compact discs, optical materials such as lenses for cameras and glasses, building materials in place of glass, and the like. The aromatic polycarbonate of the present invention is thermoplastic, and can be injection-molded, extrusion-molded, blow-molded, impregnated with a filler or the like in a molten state, and can be easily molded by a known molding method.

[0047]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The molecular weight of the aromatic polycarbonate produced in each of the examples and comparative examples and the content of impurities in the aromatic polycarbonate were measured by the following methods. -Molecular weight: 0.2% by weight of aromatic polycarbonate in chloroform was added to GPC (gel permeation chromatography) [Showa Denko KK, System]
-11] to determine the weight average molecular weight and polydispersity index (Mw / Mn). The measured values are standard polystyrene equivalent values. Content of Impurities in Aromatic Polycarbonate As a measure of the content of impurities in the aromatic polycarbonate, the amount of sodium in the aromatic polycarbonate was measured by atomic absorption [Hitachi, Model 180-80].

Example 1 A flask equipped with a baffle having an internal capacity of 20 liters was equipped with a stirrer with a lattice blade, a reflux cooling tube, and a dipping tube for blowing phosgene. Here, 957.6 g (4.2 mol) of 2,2-bis (2-mol) was added. (Four'
-Hydroxyphenyl) propane and 812 g
(2.8 mol) of 1,1-bis (4'-hydroxyphenyl)
1-Phenylethane and 36.12 g of 4-tert-butylphenol were charged. To this flask was added 10 liters of an aqueous solution containing 840 g of sodium hydroxide and 3.1 g of sodium hydrosulfite, and further 7 liters of toluene to form a two-phase mixture. Then 865.55 g of phosgene were introduced into this two-phase mixture with stirring over a period of 60 minutes. After the introduction of phosgene, stirring was continued for another 20 minutes, then 1.13 g of triethylamine was added, and stirring and mixing was continued for another 70 minutes. Next, the stirring was stopped, the reaction solution was separated, the toluene phase was washed with water, neutralized with an aqueous hydrochloric acid solution, and the toluene phase was washed with deionized water until the electrolyte was substantially removed. From a toluene solution of the resulting aromatic polycarbonate. Aromatic polycarbonate was obtained by removing toluene by evaporation. The weight average molecular weight of the obtained aromatic polycarbonate was 45,000, and the polydispersity index (Mw / Mn) was 2.45. Amount of sodium in aromatic polycarbonate is 50p
It was pb. The production conditions and the physical properties of the obtained aromatic polycarbonate are summarized in Table 1 (Table 1).

Examples 2 to 9 The same operations as in Example 1 were carried out using the non-halogenated hydrocarbons shown in Table 1 and the aromatic dihydroxy compound to produce aromatic polycarbonates. Table 1 shows the production conditions and the physical properties of the obtained aromatic polycarbonate.

Example 10 A baffled flask having an internal capacity of 20 liters was equipped with a stirrer with a lattice blade and a reflux condenser. 50 in this flask
0.0 g (1.62 mol) of 6,6'-dihydroxy-3,3,
3 ', 3'-tetramethylspirobiindane and 318.
43 g (1.40 mol) of 2,2-bis (4′-hydroxyphenyl) propane, 33.5064 g of 4-tert-butylphenol are charged, where 371.6 g of sodium hydroxide and 2.9 g are charged. 9 liters of an aqueous solution in which sodium hydrosulfite was dissolved was supplied to obtain a suspension. Next, 1226.06 g (3.4
7 mol) of bischloroformate of 2,2-bis (4'-hydroxyphenyl) propane and 9 liters of toluene were fed. The mixture was stirred, then 1.05 g of triethylamine was added and stirring and mixing was continued for 90 minutes. Next, the stirring was stopped, the reaction solution was separated, the toluene phase was washed with water, then neutralized with an aqueous hydrochloric acid solution, and the toluene phase was washed with deionized water until substantially no electrolyte was detected. Aromatic polycarbonate was obtained by distilling toluene from the obtained toluene solution of aromatic polycarbonate. The reaction conditions and the physical properties of the obtained aromatic polycarbonate are summarized in Table 1.

Example 11 An apparatus having a tank type reactor having an internal capacity of 3 liters having an overflow outlet and three tank type reactors having an internal capacity of 7 liters each having an overflow outlet were connected in series, 3192 g (14 mol) of 2,2-bis (4'-hydroxyphenyl) propane, 103.2 g of 4-tert-
Butylphenol, 2320 g of sodium hydroxide,
8.8 g sodium hydrosulfite and 24
An aqueous phase consisting of kg of water, phosgene, and toluene were respectively added to the first tank-type reactor having an internal volume of 3 liters, at 109.7.
2 g / min (aqueous phase), 8.79 g / min (phosgene), 7
The feed rate was 4.10 g / min (toluene). At the same time as the reaction mixture flows from the first tank type reactor into the second tank type reactor having an internal volume of 7 liters through the overflow outlet, 1712 g of the second tank type reactor.
A suspension consisting of (5.56 mol) 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane and 4630 g of toluene was fed at a feed rate of 25.36 g / min. did. Furthermore, at the same time that the reaction mixture in the second tank reactor flowed into the third tank reactor, triethylamine was supplied to the third tank reactor at a supply rate of 0.02 g / min. The reaction mixture continuously discharged from the fourth tank reactor was then subjected to liquid separation, the toluene phase was washed with water, neutralized with an aqueous hydrochloric acid solution, and then the toluene phase was substantially deionized water. It was washed until no electrolyte was detected. From the obtained toluene solution of the aromatic polycarbonate, toluene was distilled off to obtain a solid aromatic polycarbonate. The reaction conditions and the physical properties of the obtained aromatic polycarbonate are summarized in Table 1.

Comparative Example 1 A baffled flask having an internal capacity of 20 liters was equipped with a stirrer with a lattice blade, a reflux cooling tube, and a dipping tube for blowing phosgene, and 862.4 g (2.8 mol) of 6,6'- Dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane and 957.6 g (4.2 mol) of 2,2-bis (4'-hydroxyphenyl) propane were charged. 8 in this flask
A two-phase mixture was prepared by adding 10 liters of an aqueous solution containing 40 g of sodium hydroxide and 3.1 g of sodium hydrosulfite, and further adding 7 liters of dichloromethane. Next, in this aqueous solution, with stirring,
865.55 g of phosgene was introduced over 60 minutes.
After the introduction of phosgene, 36.12 g of 4-tert-butylphenol are added and stirred for a further 20 minutes, then 1.
13 g of triethylamine was added and stirring and mixing was continued for another 70 minutes. Then, the stirring was stopped, the reaction solution was separated, and the dichloromethane phase was washed with deionized water until substantially no electrolyte was detected. Aromatic polycarbonate was obtained by distilling off dichloromethane from the obtained aromatic polycarbonate solution in dichloromethane. The reaction conditions and the physical properties of the obtained aromatic polycarbonate are summarized in Table 1.

Comparative Example 2 A flask equipped with a baffle having an internal capacity of 20 liters was equipped with a stirrer with a lattice blade, a reflux cooling tube, and a dipping tube for blowing phosgene, and 1,596 g (7.0 mol) of 2,2-bis ( Four'
-Hydroxyphenyl) propane was charged. To this flask was added 10 liters of an aqueous solution containing 840 g of sodium hydroxide and 3.1 g of sodium hydrosulfite, and then 7 liters of toluene to form a two-phase mixture. 86 with stirring in this solution
5.55 g of phosgene was introduced over 60 minutes. After the introduction of phosgene, 36.12 g of 4-tert-butylphenol are added and stirred for a further 20 minutes, then 1.13.
g of triethylamine was added and stirring and mixing was continued for another 70 minutes. The reaction mixture becomes a mixture of powdery aromatic polycarbonate, toluene and an aqueous phase, has very poor liquid separation property, has a low molecular weight, and has a chloroformate group remaining at the end of the aromatic polycarbonate. Was found to be incomplete. The reaction conditions and the physical properties of the obtained aromatic polycarbonate are summarized in Table 1.

[0054]

[Table 1]

PC: Polycarbonate BPA: 2,2-bis (4'-hydroxyphenyl) propane BP-AP: 1,1-bis (4'-hydroxyphenyl) -1-
Phenylethane BP-C: 1,1-bis (4'-hydroxyphenyl) cyclohexane TMBPA: 2,2-bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane BP-MEK: 2,2- Bis (4'-hydroxyphenyl) butane TDP: 4,4'-dihydroxydiphenyl sulfide DHDPE: 4,4'-dihydroxydiphenyl ether HQ: hydroquinone SBI: 6,6'-dihydroxy-3,3,3 ', 3'- Tetramethylspirobiindane

[0056]

EFFECTS OF THE INVENTION The production method of the present invention makes it possible to produce an aromatic polycarbonate having a low impurity content without using a halogenated hydrocarbon which is regarded as a problem in terms of environmental protection.

 ─────────────────────────────────────────────────── (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. When an aromatic polycarbonate is produced from an aromatic dihydroxy compound and a carbonate precursor, only a non-halogenated hydrocarbon is used as an organic solvent, and
A method for producing an aromatic polycarbonate, which comprises using at least two kinds of aromatic dihydroxy compounds as the aromatic dihydroxy compound. 2. One of the aromatic dihydroxy compounds is 2,
The method for producing an aromatic polycarbonate according to claim 1, which is 2-bis (4'-hydroxyphenyl) propane. 3. The molar ratio of 2,2-bis (4′-hydroxyphenyl) propane to another aromatic dihydroxy compound is 5.
The method for producing an aromatic polycarbonate according to claim 2, wherein the ratio is from 95 mol% to 95 mol%. 4. The method for producing an aromatic polycarbonate according to claim 1, 2 or 3, wherein the non-halogenated hydrocarbon is a non-halogenated aromatic hydrocarbon.