JPH0841189A - Copolycarbonate - Google Patents

Abstract

PURPOSE:To obtain a copolycarbonate excellent in both heat resistance and heat stability. CONSTITUTION:This copolycarbonate comprises structural units derived from an aromatic dihydroxy compound represented by the formula: HO-Ar<1>-X-Ar<2>-OH and structural units derived from an aromatic dihydroxy compound represented by the formula. In the formulas, Ar<1> and Ar<2> are each an aromatic group; X is an oxygen or sulfuration; R is a hydrocarbon group or a halogen atom; and n is an integer of 0-3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to copolycarbonates. More specifically, it relates to a copolycarbonate containing a specific structural unit.

[0002]

Polycarbonate is widely used as an engineering plastic in the fields of automobiles, electricity and optics. Currently widely used polycarbonates are usually produced from 2,2-bis (4'-hydroxyphenyl) propane and carbonyl halide compounds such as phosgene. Polycarbonate produced from 2,2-bis (4'-hydroxyphenyl) propane is a resin having well-balanced properties such as transparency, heat resistance, low moisture permeability, impact resistance, and dimensional stability. However, in recent years, as a polycarbonate used for optical applications,
In addition to excellent optical characteristics such as light transmittance, higher heat resistance (deflection temperature under load) is required.

As described above, various aromatic dihydroxy compounds are used to provide a polycarbonate having more excellent heat resistance than the aromatic polycarbonate produced from 2,2-bis (4'-hydroxyphenyl) propane. A polycarbonate produced by the method is proposed. Polycarbonate with relatively high heat resistance derived from 2,2-bis (4'-hydroxyphenyl) propane and 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane Polycarbonates are disclosed. [Journal of Polym
er Science) Part A, Vol. 3, p. 3209 (1965), U.S. Pat. No. 4,552,949, JP-A-63-314235,
JP-A-4-345618, etc.]. However, aromatic polycarbonates derived from these 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspirobiindane have high heat resistance, but thermal stability (weight loss temperature). Since it is not so high, there is a problem that it is difficult to set conditions during molding. At present, a polycarbonate having both high heat resistance (deflection temperature under load) and excellent thermal stability (high temperature for weight loss) is desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a copolycarbonate having both heat resistance and thermal stability, which overcomes the above problems of the prior art.

[0005]

[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 is derived from the structural unit (a) derived from the aromatic dihydroxy compound represented by the general formula (1) and the aromatic dihydroxy compound represented by the general formula (2) (chemical formula 2). And a copolymerized polycarbonate containing the structural unit (b). HO-Ar ¹ -X-Ar ² -OH (1) (In the formula, Ar ¹ and Ar ² represent an aromatic group, and X represents an oxygen atom or a sulfur atom.)

[0006]

Embedded image (In the formula, R is a hydrocarbon or a halogen atom, and n is 0 to
Represents the integer of 3)

The present invention will be described in detail below. The copolycarbonate of the present invention has a structural unit (a) derived from an aromatic dihydroxy compound represented by the general formula (1) and a structure unit derived from an aromatic dihydroxy compound represented by the general formula (2). It is a copolycarbonate containing a unit (b). Furthermore, the copolymerized polycarbonate of the present invention may optionally contain a structural unit derived from an aromatic dihydroxy compound represented by the general formula (3) as the structural unit (c). ^{HO-Ar 3 -X'-Ar 4} -OH (3) ( in the formula, the Ar ³ and Ar ⁴ aromatic group, X 'is Ar ³ and A
In copolycarbonate of oxygen atoms and represents a linking group other than a sulfur atom) present invention connects the r ^4, each of the structural units (a), and (b) (c) are respectively represented by the formula (4) Are linked by a group. -(C = O)-(4) A carbonate bond is formed by linking each structural unit (a), (b) and (c) with the group represented by Formula (4). The group represented by the formula (4) is a group derived from a carbonate precursor.

The molecular weight of the copolycarbonate of the present invention is not particularly limited, but the weight average molecular weight is usually 5,000 to 100,000 as the standard polystyrene-equivalent molecular weight measured by GPC (gel permeation chromatography). And preferably 10
000-90000, more preferably 1500
It is 0 to 80,000. The polydispersity index represented as the ratio of the weight average molecular weight to the number average molecular weight is not particularly limited, but is preferably 3.0 or less,
It is more preferably 1.5 to 3.0, and even more preferably 2.0 to 3.0.

In the structural unit (a) according to the present invention, the structural unit derived from the aromatic dihydroxy compound represented by the general formula (1) is the structural unit represented by the general formula (1-a). . —O—Ar ¹ —X—Ar ² —O— (1-a) [wherein Ar ¹ , Ar ² and X have the same meanings as in formula (1)] are represented by formula (1). In the aromatic dihydroxy compound, Ar ¹ and Ar ² represent an aromatic group, preferably
It is a phenylene group, and the phenylene group may have a substituent. As the substituent, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group,
An aryl group, an alkoxy group, etc. can be mentioned. 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. An alkyl group, an aryl group having 6 to 12 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms.

Ar ¹ and Ar ² are preferably both a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group, or one of which is a 1,4-phenylene group. , The other is a 1,3-phenylene group or a 1,2-phenylene group, and more preferably both are a 1,4-phenylene group or
A 1,3-phenylene group, or one is a 1,4-phenylene group and the other is a 1,3-phenylene group. In addition, X represents an oxygen atom or a sulfur atom.

Specific examples of the aromatic dihydroxy compound represented by the general formula (1) include 4,4'-dihydroxydiphenyl sulfide, 4,3'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3. '-Dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-diethyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-dichlorodiphenyl sulfide, 4,4'-dihydroxy-3,3'-
Dibromodiphenyl sulfide, 4,4'-dihydroxy-
3,3 ', 5,5'-Tetramethyldiphenyl sulfide, 4,4'-
Dihydroxy-3,3'-dimethyl-5,5'-di-tert-butyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-
Dimethoxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethoxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 4,
4'-dihydroxy-2,2 ', 3,3', 5,5 ', 6,6'-hexamethyldiphenyl sulfide, 4,4'-dihydroxy-3,3', 5,
Dihydroxydiphenyl sulfides such as 5'-tetrabromodiphenyl sulfide,

4,4'-dihydroxydiphenyl ether,
4,3'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-3,3'-diethyldiphenyl ether, 4,4 '
-Dihydroxy-3,3'-dichlorodiphenyl ether,
4,4'-dihydroxy-3,3'-dibromodiphenyl ether, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethyldiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyl- 5,5'-di-tert-butyldiphenyl ether, 4,4'-
Dihydroxy-3,3'-dimethoxydiphenyl ether,
4,4'-dihydroxy-3,3'-dimethoxydiphenyl ether, 4,4'-dihydroxy-3,3'-diphenyldiphenyl ether, 4,4'-dihydroxy-2,2 ', 3,3', 5,5 ', 6,
Examples thereof include dihydroxydiphenyl ethers such as 6'-hexamethyldiphenyl ether and 4,4'-dihydroxy-3,3 ', 5,5'-tetrabromodiphenyl ether. In the structural unit (b) according to the present invention, the structural unit derived from the aromatic dihydroxy compound represented by the general formula (2) is a structural unit represented by the general formula (2-a) (chemical formula 3). is there.

[0013]

Embedded image [In the Formula, R and n represent the same meaning as general formula (2).]

In the aromatic dihydroxy compound represented by the general formula (2), R represents a hydrocarbon group or a halogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a halogen atom. More preferably, it is an alkyl group having 1 to 4 carbon atoms. Further, n represents an integer of 0 to 3, and preferably an integer of 0 to 2. As a specific example of R,
Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group.

Specific examples of the compound represented by the general formula (2) include 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane and 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'-dibromospirobiindane, 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 Examples include 5,5 ', 7,7'-tetrabromospirobiindane and the like. Preferably, 6,6'-dihydroxy-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'- Alkyl-substituted 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane such as octamethylspirobiindane, and more preferably 6,6'-dihydroxy-3,3,
It is 3 ', 3'-tetramethylspirobiindane.

Further, the copolymerized polycarbonate of the present invention may optionally contain a structural unit represented by the structural unit (c), which is derived from the aromatic dihydroxy compound represented by the general formula (3). . Structural unit (c)
Is a structural unit represented by general formula (3-a). —O—Ar ³ —X′—Ar ⁴ —O— (3-a) [wherein Ar ³ , Ar ⁴ and X ′ have the same meanings as in formula (3)] In the aromatic dihydroxy compound described above, Ar ³ and Ar ⁴ represent an aromatic group, and preferably,
It is a phenylene group, and the phenylene group may have a substituent. As the substituent, a halogen atom, a nitro group,
Examples thereof include 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. An alkyl group, an aryl group having 6 to 12 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Ar ³ and Ar ⁴ are preferably both 1,4-phenylene group, 1,3-phenylene group or 1,2-phenylene group, or one of them is 1,4-phenylene group,
The other is a 1,3-phenylene group or a 1,2-phenylene group, and more preferably, both Ar ³ and Ar ⁴ are a 1,4-phenylene group or a 1,3-phenylene group, or one is 1, It is a 4-phenylene group, and the other is a 1,3-phenylene group.

In the aromatic dihydroxy compound represented by the general formula (3), X'represents a connecting group excluding an oxygen atom and a sulfur atom connecting Ar ³ and Ar ⁴ . As the linking group, a single bond, a divalent hydrocarbon group or -SO-, -SO
_2- , -CO- group, etc. can be mentioned. The divalent hydrocarbon group means a saturated hydrocarbon group such as a methylene group,
Examples thereof include an alkylidene group such as an ethylene group, a 2,2-propylidene group, and a 1,1-cyclohexylidene group. An alkylidene group substituted with an aryl group (eg, 1-phenyl-
1,1-ethylene group), and may be a divalent hydrocarbon group containing an aromatic group or other unsaturated hydrocarbon group. Of these, an alkylidene group having 1 to 8 carbon atoms and a cycloalkylidene group having 4 to 10 carbon atoms are preferable, and an alkylidene group having 2 to 6 carbon atoms and a cycloalkylidene group having 5 to 8 carbon atoms are more preferable.

Specific examples of the aromatic dihydroxy compound represented by the general formula (3) 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'-
Hydroxyphenyl) propane, 2,2-bis (4'-hydroxyphenyl) butane, 1,1-bis (4'-hydroxyphenyl) butane, 1,1-bis (4'-hydroxyphenyl)-
2-methylpropane, 2,2-bis (4'-hydroxyphenyl) -3-methylbutane, 2,2-bis (4'-hydroxyphenyl) pentane, 3,3-bis (4'-hydroxyphenyl)
Pentane, 2,2-bis (4'-hydroxyphenyl) heptane, 2,2-bis (4'-hydroxyphenyl) octane, 2,
2-bis (3'-methyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-ethyl-4'-hydroxyphenyl)
Propane, 2,2-bis (3'-n-propyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-isopropyl-
4'-hydroxyphenyl) propane, 2,2-bis (3'-se
c-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'-hydroxy Phenyl) 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 (3'-methyl-4'-hydroxyphenyl) cyclohexane , 1,1-bis (3 ', 5'-dimethyl-
4'-hydroxyphenyl) cyclohexane, 1,1-bis (3 ', 5'-dichloro-4'-hydroxyphenyl) cyclohexane, 1,1-bis (4'-hydroxyphenyl) -4-methylcyclohexane, 1, 1-bis (4'-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4'-
Hydroxyphenyl) cycloheptane, 1,1-bis (4'-
Hydroxyphenyl) cyclooctane, 1,1-bis (4'-
Hydroxyphenyl) cyclononane, 1,1-bis (4'-hydroxyphenyl) cyclododecane, 2,2-bis (4'-hydroxyphenyl) norbornane, 8,8-bis (4'-hydroxyphenyl) tricyclo (5.2. 1.0 ^2.6 ] decane, 2,
Bis (hydroxyaryl) cycloalkanes such as 2-bis (4'-hydroxyphenyl) adamantane, bis (such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, etc. (Hydroxyaryl) sulfoxides, bis (hydroxyaryl) sulfones such as 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, bis (4-hydroxyphenyl) ketone, bis Bis (hydroxyaryl) ketones such as (3-methyl-4-hydroxyphenyl) ketone,

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 and the like can be mentioned. Further, an aromatic dihydroxy compound containing an ester bond, which can be produced by reacting 2 mol of bisphenol A with 1 mol of isophthaloyl chloride or terephthaloyl chloride, is also useful. These may be used alone or in combination. As the aromatic dihydroxy compound, bis (hydroxyaryl) alkanes and bis (hydroxyaryl) cycloalkanes are preferable, bis (hydroxyaryl) alkanes are more preferable, and bisphenol A is further preferable.

The copolycarbonate of the present invention is a copolycarbonate containing structural units (a) and (b) and, if desired, a component (c), and, if desired, the structural unit (a). , (B) and (c) may be included. As the other structural unit, a branched structural unit composed of a terminal group, a trivalent or higher valent group,
Structural units derived from bifunctional compounds other than the aromatic dihydroxy compounds represented by the general formulas (1) to (3), groups other than the carbonyl group represented by the formula (4), and the like. Examples of the bifunctional compound other than the aromatic dihydroxy compounds represented by the general formulas (1) to (3) include an aliphatic dihydroxy compound, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an aromatic diamine, an aliphatic diamine, and an aromatic compound. Examples of such compounds include group diisocyanates and aliphatic diisocyanates.
Examples of the group other than the carbonyl group represented by the formula (4) include groups such as imino group, ester group, ether group, imide group and amide group.

These structural units (a), (b), (c)
The content of the structural unit other than the group represented by the formula (4) is a structural unit derived from a bifunctional compound other than the aromatic dihydroxy compounds represented by the general formulas (1) to (3). Is about 20 mol% or less, preferably 15 mol% based on the total number of structural units in the copolymerized polycarbonate.
It is at most mol%, more preferably at most 10 mol%.
Further, the content of groups other than the carbonyl group represented by the formula (4) is 20 mol% or less, preferably, with respect to the number of moles of the carbonyl group represented by the formula (4) in the copolycarbonate. 15 mol% or less, more preferably 10 mol%
It is the following.

The ratio of the structural units (a) and (b) in the copolycarbonate according to the present invention [the ratio of the structural unit (a) or (b) to the sum of the structural units (a) and (b)] is Although not particularly limited, preferably,
The structural unit (a) is 10 to 90 mol%, the structural unit (b) is 90 to 10 mol%, more preferably the structural unit (a) is 20 to 80 mol% and the structural unit (b) is 80 to 90 mol%. Two
It is 0 mol%, and more preferably, the structural unit (a) is 30 to 70 mol%, and the structural unit (b) is 70 to 30.
Mol%. When the copolymerized polycarbonate of the present invention comprises structural units (a), (b) and (c), the ratio of (c) to the sum of structural units (a) and (b) is particularly limited. However, preferably, the sum of the structural units (a) and (b) is 20 to 95 mol%, the structural unit (c) is 80 to 5 mol%, and more preferably the structural unit (a ) And (b) is 25 to 90 mol%,
The structural unit (c) is 75 to 10 mol%, more preferably the sum of the structural units (a) and (b) is 40 to 90 mol%, and the structural unit (c) is 60 to 10 mol%. is there.

In the copolymerized polycarbonate of the present invention, the terminal group may be a reactive terminal group such as a hydroxy group, a haloformate group and a carbonic acid ester group.
It may be an inert terminal group sealed with a molecular weight regulator. Here, as the molecular weight modifier, a monovalent hydroxyaromatic compound, an alkali metal or alkaline earth metal salt of a monovalent hydroxyaromatic compound, a haloformate compound of a monovalent hydroxyaromatic compound, a monovalent hydroxyaromatic compound Carbonic acid ester of compound, monovalent carboxylic acid, alkali metal or alkaline earth metal salt of monovalent carboxylic acid,
Examples thereof include acid halides of monovalent carboxylic acids and esters of monovalent carboxylic acids. Specific examples of the molecular weight modifier include the following compounds. That is, as the monovalent hydroxy aromatic compound, phenol, 4-tert-butylphenol, 2-cresol, 3
-Cresol, 4-cresol, 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, etc. The alkali metal or alkaline earth metal salt of a monovalent hydroxyaromatic compound is sodium of the above monovalent hydroxyaromatic compound. Examples thereof include salts, potassium salts, calcium salts and the like.

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,
Aliphatic carboxylic acids such as 3,3-dimethylbutyric acid, 4-methylvaleric acid, 3,3-dimethylvaleric acid, 4-methylcaproic acid, 2,4-dimethylvaleric acid, 3,5-dimethylcaproic acid and phenoxyacetic acid Benzoic acids such as acids, benzoic acid, 4-propoxybenzoic acid, 4-butoxybenzoic acid, 4-pentyloxybenzoic acid, 4-hexyloxybenzoic acid and 4-octyloxybenzoic acid can be mentioned. 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 monovalent carboxylic acid. Examples of the acid halide derivative of a monovalent carboxylic acid include the above monovalent carboxylic acid chlorides and bromides. The amount of terminal groups in the copolymerized polycarbonate is about 1 to 10 mol% based on the total number of moles of the structural unit, preferably 1.5.
-8 mol%, more preferably 2-5 mol%.

The branched structural unit having a trivalent or higher valent group is a structural unit derived from the following compounds used as a branching agent. Here, the branching agent is a compound having three or more phenolic hydroxyl groups, haloformate groups, carboxyl groups, carbonyl halide groups, and active halogen atoms, such as phloroglucinol and 4,6-dimethyl-2. , 4,6-Tris (4'-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) heptane, 1,3,5-tris
(4'-hydroxyphenyl) benzene, 1,1,1-tris (4'-hydroxyphenyl) ethane, 1,3,5-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-chlorocarbonyloxyisophthalate 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 Etc. The content of the branched structural unit in the copolycarbonate is not particularly limited, but is usually preferably 0.05 to 2.0 mol% with respect to the total number of moles of the structural unit. .

The copolycarbonate of the present invention is represented by the aromatic dihydroxy compound represented by the general formula (1), the aromatic dihydroxy compound represented by the general formula (2), and optionally the general formula (3). Aromatic dihydroxy compound,
It is produced from a carbonate precursor. The method for producing the copolycarbonate is classified into the following methods depending on the kind of the compound used as the carbonate precursor. That is, A: a method of using an aromatic dihydroxy compound and a carbonyl halide compound as a carbonate precursor, and B: a method of using an aromatic dihydroxy compound and a carbonic acid diester as a carbonate precursor.

Here, the carbonyl halide compound means carbonyl chloride (phosgene), carbonyl bromide, carbonyl iodide and a mixture thereof, trichloromethyl chloroformate, which is a dimer of carbonyl chloride, and trimethyl chloride. The body is bis (trichloromethyl)
Represents carbonate and the like. The carbonic acid diester represents dialkyl carbonate, diaryl carbonate, alkylaryl carbonate, and a mixture thereof. Specific examples of the carbonic acid diester include diphenyl carbonate, bis (4-methylphenyl) carbonate, bis (2-nitrophenyl) carbonate, bis (4-chlorophenyl) carbonate, and the like, dimethyl carbonate, diethyl carbonate, di-n. Examples thereof include dialkyl carbonates such as propyl carbonate and carbonic acid diesters such as alkyl aryl carbonates such as methylphenyl carbonate, ethylphenyl carbonate and butylphenyl carbonate.

The production method A is usually called a solution polymerization method or an interfacial polymerization method. The solution polymerization method is carried out in the presence of an organic base such as pyridine, in an organic solvent, with an aromatic dihydroxy compound and a carbonyl halide compound (for example,
Phosgene). In the interfacial polymerization method, a reaction with a carbonyl halide compound is carried out under the interfacial conditions of an aqueous solution of an aromatic dihydroxy compound and an alkali metal or alkaline earth metal base and an organic solvent, and a catalyst (for example, triethylamine) is optionally added. ) Is present, the polycondensation reaction is carried out. Manufacturing method B
Is a method generally called transesterification method, which is a method of reacting an aromatic dihydroxy compound and a carbonic acid diester (for example, diphenyl carbonate) in a molten state or a solution state under heating and, optionally, in the presence of a catalyst. .

The method for producing the copolycarbonate of the present invention is not particularly limited, and it can be produced by any production method selected from the transesterification method, the interfacial polymerization method and the solution polymerization method. Generally, the interfacial polymerization method can produce a relatively high molecular weight copolycarbonate, and the transesterification method can produce impurities (particularly alkali metal or alkaline earth metal and halogen-based impurities). It becomes possible to produce a copolycarbonate having an extremely low content. The transesterification method or the interfacial polymerization method is preferred, and the interfacial polymerization method is more preferred.

In the interfacial polymerization method, in addition to the aromatic dihydroxy compound and the carbonyl halide compound, an organic solvent, a catalyst, water, an alkali metal or alkaline earth metal base, and optionally a molecular weight modifier and a branching agent are used. . Here, the organic solvent is capable of dissolving a haloformate derivative of an aromatic dihydroxy compound represented by any of the general formulas (1) to (3) or a copolycarbonate derived from the haloformate derivative. Any inert organic solvent can be selected and used. For example, dichloromethane, chloroform, 1,
Use of aliphatic halogenated hydrocarbons such as 2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane and dichloropropane, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, or a mixture thereof. Is possible. Aliphatic halogenated hydrocarbons are preferable, and dichloromethane is more preferable.

In the interfacial polymerization method, as a catalyst optionally used, a tertiary amine, a quaternary ammonium salt, a tertiary phosphine, a quaternary phosphonium salt, a nitrogen-containing heterocyclic compound and the like can be mentioned. Preferably, a tertiary amine,
More preferred is trialkylamine, and further preferred is triethylamine. The amount of catalyst used is
It is not particularly limited, and is generally represented by the general formula (1) to
It is about 0.005 to 1.5 mol% with respect to the total number of moles of the aromatic dihydroxy compound represented by (3). Examples of the alkali metal or alkaline earth metal bases (hereinafter abbreviated as bases) include hydroxides or carbonates of alkali metals or alkaline earth metals such as sodium, potassium and calcium.

When the copolymerized polycarbonate of the present invention is produced by the interfacial polymerization method, the molar ratio between the aromatic dihydroxy compound, the carbonyl halide compound and the base is as follows:
According to the formulas (A) and (B) shown below. 1 ≦ β / α ≦ 2 (A) 4β-2α ≦ γ ≦ 4β-α (B) (In the formula, α is a molar amount of an aromatic dihydroxy compound, β is a molar amount of a carbonyl halide compound, and γ is a base. When β / α is less than 1, a copolymerized polycarbonate having a hydroxy end group may be produced. Further, when β / α is larger than 2, a copolycarbonate having a haloformate end group may be produced. When γ is less than (4β-2α), unreacted haloformate groups may remain when the copolymerized polycarbonate is produced. Also, γ is (4β-
If it is larger than α), no particular advantage is found.

The production conditions for producing the copolycarbonate of the present invention by the interfacial polymerization method of the production method A are as follows. First, a basic aqueous solution or suspension containing an aromatic dihydroxy compound, a base and water is prepared. Then, it is brought into contact with a carbonyl halide compound in the presence of an organic solvent to prepare an oligomer whose terminal group is a haloformate group. Then, if desired, a catalyst is added, and the mixture is stirred and mixed under an interfacial condition to carry out a polymerization reaction until a copolycarbonate having a desired molecular weight is obtained. The reaction temperature is about 5 ° C to the boiling point of the organic solvent, preferably about 10 to 40.
Carry out at ° C. The reaction is usually carried out under atmospheric pressure, but it may be carried out under pressure or under reduced pressure. The reaction time varies depending on the amount of catalyst, temperature, etc., but is usually about 5 to 120 minutes.

When the copolymerized polycarbonate of the present invention is produced by the transesterification method of the production method B, an aromatic dihydroxy compound, a carbonic acid diester and optionally a catalyst, an organic solvent, a molecular weight modifier and a branching agent are used. . In the production method B, the catalyst optionally used is
Usually, a catalyst used in a transesterification reaction can be used, for example, an alkali metal or alkaline earth metal compound (a simple substance such as sodium, potassium, or lithium, a hydroxide, a borohydride compound, a benzoate, or a phenoxide. Etc.), boric acid or boric acid ester, nitrogen-containing basic compound, and periodic table [see Chemical Society of Japan, revised handbook, 3rd edition, basic edition, Maruzen Co., Ltd. (1983)] 2.
A catalyst selected from the group consisting of metal atoms belonging to the B, 3B, 4A and 4B groups and compounds thereof (for example, carboxylates, halides, inorganic acid salts, complex compounds, oxides, hydroxides). You can

As the production conditions for producing the copolycarbonate by the production method B, first, the carbonic acid diester is used in an amount of 1 to 1.5 times the mole of the aromatic dihydroxy compound. Preferably, the amount of carbonic acid diester is 1.02 to 1.2 times the molar amount of the aromatic dihydroxy compound, which is a slight excess. The reaction temperature is not particularly limited, but it is preferably carried out under heating. A preferable reaction temperature is 60 to 350 ° C, more preferably 80 to 300 ° C, and further preferably 10
It is 0-280 degreeC. Furthermore, it is also preferable to gradually raise the temperature to about 180 to 300 ° C. as the reaction progresses. If the reaction temperature is excessively lower than about 60 ° C, the reaction progresses slowly, and if it is excessively higher than about 350 ° C, thermal deterioration of the polymer may occur. The pressure at the time of reaction is not particularly limited as long as it is set so that the reaction can be efficiently performed. Usually about 760 in the early stage of the reaction
The pressure is set to atmospheric pressure or increased pressure up to 38,000 mmHg, and the pressure is reduced in the latter stage of the reaction, preferably about 0.01 to 100 mmHg. The reaction time may be such that it reaches the desired molecular weight, and is usually about 0.2 to 10 hours. Although the reaction can be carried out in an air atmosphere, it is preferably carried out in an inert gas atmosphere such as nitrogen gas, helium gas or argon gas.

The copolymerized polycarbonate of the present invention may be alternating copolymerization, random copolymerization, or block copolymerization. The excellent heat resistance and thermal stability aimed at by the present invention can be achieved with a copolymer having any structure. When the copolymerized polycarbonate is produced as a random copolymer, the general formula (1),
It can be produced by mixing (2) and, if desired, the aromatic dihydroxy compound represented by the general formula (3) and allowing the carbonate precursor to act on the mixture of the aromatic dihydroxy compounds.

When the copolycarbonate is produced as a block copolymer, either the aromatic dihydroxy compound represented by the general formula (1) or the aromatic dihydroxy compound represented by the general formula (2) is used. It can be produced by reacting with a carbonate precursor alone to prepare a polycarbonate oligomer having most of the terminals having a haloformate group or a carbonate ester group, and then reacting the other aromatic dihydroxy compound or its oligomer. It is possible. When the copolymerized polycarbonate is produced as an alternating copolymer, the compound represented by the general formula (1)
A monomer intermediate having a haloformate group or a carbonic acid ester group at its end is produced from either the aromatic dihydroxy compound represented by the formula (1) or the aromatic dihydroxy compound represented by the general formula (2) and the carbonate precursor. However, it can be produced by reacting this intermediate with the other aromatic dihydroxy compound.

The copolycarbonate of the present invention has high heat resistance and is excellent in thermal stability, so that it can be molded under a wide temperature range of molding conditions.
Further, since it is also optically excellent, it is useful as a molding material for materials for optical devices. For example, headlamp lens,
It is useful as a material for various optical devices such as various lenses such as projector lenses, prisms, optical fibers, optical disks, and liquid crystal panels. It is also useful as a modifier for other resins.

The copolymerized polycarbonate of the present invention can be further used, if desired, as a molding material by blending it with an aromatic polycarbonate derived from 2,2-bis (4'-hydroxyphenyl) propane. . In addition, it can be used as a molding material in combination with another polymer. Other polymers include
Polyethylene, polypropylene, polystyrene, ABS
Resin, polymethylmethacrylate, polytrifluoroethylene, polytetrafluoroethylene, polyacetal,
Examples thereof include polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polyamide, polyimide, polyamideimide, polyetherimide, polysulfone, polyether sulfone, paraoxybenzoyl-based polyester, polyarylate, and polysulfide.

The copolymerized polycarbonate of the present invention may be used alone or in a mixture with another polymer, and may be further added with a pigment, a dye, a heat stabilizer, an oxidant by a known method during or after the production of the copolymerized polycarbonate. Known additives such as an inhibitor, an ultraviolet absorber, a release agent, an organic halogen compound, an alkali metal sulfonate, glass fiber, carbon fiber, glass beads, barium sulfate and TiO ₂ may be added. The copolycarbonate of the present invention, alone or in a state of being mixed with other polymers, optionally contains the above-mentioned additives to form a molding material, such as a chassis or housing material for electric equipment, electronic parts, and automobile parts. It can be molded into a substrate of an information recording medium such as an optical disc, an optical material such as a lens of a camera or spectacles, a building material instead of glass, and the like. The copolycarbonate 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.

[0042]

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 weights, deflection temperatures under load, and thermal stability of the polycarbonates produced in each Example and Comparative Example were measured by the following methods. -Molecular weight: A 0.2% by weight chloroform solution of polycarbonate was measured by GPC (gel permeation chromatography) [Showa Denko KK, System-11] to determine the weight average molecular weight. The measured values are standard polystyrene equivalent values. Deflection temperature under load (HDT: ° C): JIS K-720
Compliant with 7. That is, length x width is 110 x 12.6 m
A test piece having a thickness of 3 mm and a thickness of 3 mm was prepared and annealed at 120 ° C. for 4 hours, and then the bending stress was 18.5 kgf / cm.
^The deflection temperature under load was measured at ² . -Thermal stability: Thermogravimetric measuring device (TGA- manufactured by Shimadzu Corporation)
50), in air atmosphere, at a temperature rising rate of 10 ° C./min.
The temperature was measured up to 50 ° C., and the 5% weight loss temperature (TG, ° C.) was used as a measure of thermal stability. It should be noted that additives such as a heat stabilizer were not added to the polycarbonate produced in each of the examples and comparative examples.

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. In this flask, 545 g (2.5 mol) of 4,4'-
Dihydroxydiphenyl sulfide, 770 g (2.5
Mol) of 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane, 25.8 g of 4-tert-butylphenol, 560 g of sodium hydroxide are charged and the mixture is added to A suspension was prepared by adding 6 liters of deionized water. To this suspension was added 6 liters of dichloromethane to give a two phase mixture. 594 g in this two-phase mixture
Of carbonyl chloride was fed with stirring at a feed rate of 9.9 g / min. 0.808 after supply of carbonyl chloride
g of triethylamine was added, and the mixture was further stirred and mixed. After stirring and mixing for 90 minutes, a viscous dichloromethane solution containing a copolycarbonate was obtained.
After separating the reaction mixture, the dichloromethane phase was neutralized with hydrochloric acid, and then washing with deionized water was repeated until substantially no electrolyte was detected in the aqueous washing liquid. Dichloromethane was distilled off from the obtained solution of the copolycarbonate in dichloromethane to obtain a solid copolycarbonate. The physical properties of the obtained copolycarbonate are summarized in Table 1 (Table 1).

Example 2 A baffled flask having an internal capacity of 20 liters was equipped with a stirrer with a lattice blade and a reflux condenser. 490.
5 g (2.25 mol) of 4,4'-dihydroxydiphenyl sulfide, 16.63 g (0.054 mol) of 6,6'-
Dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane, 296.5 g sodium hydroxide, 25.8 g 4
A suspension was prepared by charging -tert-butylphenol and 6 liters of water. Thereafter, 1168.1 g (2.696 mol) of 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane bischloroformate dissolved in 6 liter of dichloromethane was added to the suspension. Was charged, 0.808 g of triethylamine was further added, and the reaction mixture was stirred and mixed. After 90 minutes, stop stirring and
The phase mixture was separated. Then, the dichloromethane phase was neutralized with an aqueous hydrochloric acid solution and washed with deionized water until no electrolyte was detected in the aqueous washing liquid. After that, dichloromethane was distilled off from the dichloromethane solution of the copolycarbonate to obtain a solid state copolycarbonate. The physical properties of the obtained copolycarbonate are shown in Table 1.

Example 3 In Example 1, 545 g (2.5 mol) of 4,4'-dihydroxydiphenyl sulfide was added to 6,6'-dihydroxy.
770 g of 3,3,3 ', 3'-tetramethylspirobiindane
(2.5 mol) Instead of using, 763 g (3.5 mol) of 4,4'-dihydroxydiphenyl sulfide, 6,6 '
A copolymerized polycarbonate was produced in the same manner as in Example 1 except that 462 g (1.5 mol) of -dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane was used. The physical properties of the obtained copolycarbonate are shown in Table 1.

Example 4 In Example 1, 545 g (2.5 mol) of 4,4'-dihydroxydiphenyl sulfide was added to 6,6'-dihydroxy.
770 g of 3,3,3 ', 3'-tetramethylspirobiindane
(2.5 mol) Instead of using, 327 g (1.5 mol) of 4,4'-dihydroxydiphenyl sulfide, 6,6 '
A copolymeric polycarbonate was produced in the same manner as in Example 1 except that 1078 g (3.5 mol) of -dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane was used. The physical properties of the obtained copolycarbonate are shown in Table 1.

Example 5 In Example 1, 545 g (2.5 mol) of 4,4'-dihydroxydiphenyl sulfide was added to 6,6'-dihydroxy.
770 g of 3,3,3 ', 3'-tetramethylspirobiindane
(2.5 mol) Instead of using, 327 g (1.5 mol) of 4,4'-dihydroxydiphenyl sulfide, 6,6 '
-Dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane was used in an amount of 462 g (1.5 mol), and 2,2-bis (4'-hydroxyphenyl) propane was added in an amount of 456 g (2.
Copolymerized polycarbonate was produced in the same manner as in Example 1 except that 0 mol) was added. The physical properties of the obtained copolycarbonate are shown in Table 1.

Example 6 In Example 1, 545 g (2.5 mol) of 4,4'-dihydroxydiphenyl sulfide was added to 6,6'-dihydroxy.
770 g of 3,3,3 ', 3'-tetramethylspirobiindane
(2.5 mol) Instead of using, 490.5 g (2.25 mol) of 4,4'-dihydroxydiphenyl sulfide, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspiro 693 g (2.25 mol) of biindane was used, and 1,2-bis (4'-hydroxyphenyl) propane was added to 1
A copolycarbonate was produced in the same manner as in Example 1 except that 14 g (0.5 mol) was added. The physical properties of the obtained copolycarbonate are shown in Table 1.

Example 7 Instead of using 545 g (2.5 mol) of 4,4'-dihydroxydiphenyl sulfide in Example 1,
505 g of 4'-dihydroxydiphenyl ether (2.
Copolymerized polycarbonate was produced in the same manner as in Example 1 except that 5 mol) was used. Table 1 shows the physical properties of the obtained copolycarbonate.

Example 8 In Example 1, 545 g (2.5 mol) of 4,4'-dihydroxydiphenyl sulfide was added to 6,6'-dihydroxy.
770 g of 3,3,3 ', 3'-tetramethylspirobiindane
Instead of using (2.5 mol), 707 g (3.5 mol) of 4,4'-dihydroxydiphenyl ether, 6,6'-
Example 1 except that 462 g (1.5 mol) of dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane was used.
A copolycarbonate was produced by the same procedure as described above. The physical properties of the obtained copolycarbonate are shown in Table 1.

Comparative Example 1 A baffled flask having an internal volume of 20 liters was equipped with a stirrer equipped with a lattice blade, a reflux cooling tube, and a dipping tube for blowing phosgene. In this flask, 570 g (2.5 mol)
2,2-bis (4'-hydroxyphenyl) propane and 770 g (2.5 mol) of 6,6'-dihydroxy-3,3,3 ',
3'-Tetramethylspirobiindane, 560 g of sodium hydroxide, 25.8 g of 4-tert-butylphenol and 6 liters of deionized water were charged to form a suspension. Then, 6 liters of dichloromethane was added to the suspension to make a two-phase mixture, and while stirring the two-phase mixture, 594 g of carbonyl chloride was added to the mixture at 9.9 g /
It was fed at a feed rate of minutes. After the completion of the carbonyl chloride supply, 0.808 g of triethylamine was added to the reaction mixture, and the mixture was further stirred and mixed for 90 minutes. After 90 minutes, stirring was stopped, the reaction mixture was separated, the dichloromethane phase was neutralized with aqueous hydrochloric acid and washed with deionized water until the aqueous washings were virtually free of electrolytes. After that, dichloromethane was distilled off from the dichloromethane phase to obtain a solid-state copolycarbonate. The physical properties of the obtained copolycarbonate are shown in Table 1.

Comparative Example 2 A flask equipped with a baffle having an internal capacity of 20 liters was equipped with a stirrer equipped with a lattice blade, a reflux cooling tube, and a dipping tube for blowing phosgene. In this flask, 545 g (2.5 mol)
4,4'-dihydroxydiphenyl sulfide and 57
0 g (2.5 mol) 2,2-bis (4'-hydroxyphenyl) propane, 560 g sodium hydroxide, 25.8
An aqueous solution was prepared by charging g of 4-tert-butylphenol and 6 liters of deionized water. Thereafter, 6 liters of dichloromethane was added to the aqueous solution to form a two-phase mixture, and the two-phase mixture was stirred and the mixture was mixed with 59
4 g of carbonyl chloride was fed at a feed rate of 9.9 g / min. After the supply of carbonyl chloride was completed, 0.808 g of triethylamine was added to the reaction mixture, and the mixture was further stirred and mixed for 90 minutes. After 90 minutes, the stirring was stopped, the reaction mixture was separated, the dichloromethane phase was neutralized with aqueous hydrochloric acid and washed with deionized water until the electrolyte was virtually undetectable in the aqueous wash. . After that, dichloromethane was distilled off from the dichloromethane phase to obtain a solid-state copolycarbonate. The physical properties of the obtained copolycarbonate are shown in Table 1.

Comparative Example 3 A baffled flask having an internal capacity of 20 liters was equipped with a stirrer equipped with a lattice blade, a reflux condenser, and a dipping tube for blowing phosgene. In this flask, 1140 g (5.0 mol) of 2,2-bis (4'-hydroxyphenyl) propane,
560 g sodium hydroxide, 25.8 g 4-tert-
An aqueous solution was prepared by charging butylphenol and 6 liters of deionized water. Then, 6 liters of dichloromethane was added to the aqueous solution to form a two-phase mixture.
While stirring the phase mixture, 594 g of carbonyl chloride was fed to the mixture at a feed rate of 9.9 g / min. After the supply of carbonyl chloride was completed, 0.808 g of triethylamine was added to the reaction mixture, and the mixture was further stirred and mixed for 90 minutes. The stirring was then stopped, the reaction mixture was separated, the dichloromethane phase was neutralized with aqueous hydrochloric acid and washed with deionized water until no substantial electrolyte was detected in the aqueous wash. Then, dichloromethane was distilled off from the dichloromethane phase to obtain a solid-state polycarbonate. The physical properties of the obtained polycarbonate are shown in Table 1.

[0054]

[Table 1] A: Proportion (mol%) of structural units derived from the aromatic dihydroxy compound represented by general formula (1) in all structural units B: Aromatic represented by general formula (2) in all structural units Ratio of structural units derived from dihydroxy compound (mol%) C: Ratio of structural units derived from aromatic dihydroxy compound represented by general formula (3) in all structural units (mol%)

As is clear from Table 1, the copolymerized polycarbonate of the present invention has higher heat resistance than the polycarbonate produced from 2,2-bis (4'-hydroxyphenyl) propane (Comparative Example 3). Excellent and 6,6 ′ of Comparative Example 1
-Excellent in thermal stability compared with copolymerized polycarbonate produced from dihydroxy-3,3,3 ', 3'-tetramethylspirobiindane and 2,2-bis (4'-hydroxyphenyl) propane It is understood that there is.

[0056]

EFFECT OF THE INVENTION It has become possible to provide a copolycarbonate having both excellent heat resistance and 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-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A structural unit (a) derived from an aromatic dihydroxy compound represented by the general formula (1), and HO—Ar ¹ —X—Ar ² —OH (1) (wherein Ar ¹ and Ar ² represents an aromatic group and X represents an oxygen atom or a sulfur atom.) A structural unit (b) derived from an aromatic dihydroxy compound represented by the general formula (2) (Chemical formula 1) (In the formula, R is a hydrocarbon group or a halogen atom, and n is 0.
Represents an integer of -30). 2. A structural unit (a), a structural unit (b) and a structural unit (c) derived from an aromatic dihydroxy compound represented by the general formula (3): HO—Ar ³ —X′—Ar ⁴ — OH (3) (wherein Ar ³ and Ar ⁴ are aromatic groups, and X ′ is Ar ³ and A
The copolymerized polycarbonate according to claim 1, further comprising a linking group excluding an oxygen atom and a sulfur atom that link r ⁴ . 3. The structural unit (a) is 10 to 90 mol% and the structural unit (b) is 90 to 10 mol%.
The copolycarbonate described. 4. The sum of structural units (a) and (b) is 20-9.
The copolycarbonate according to claim 2, which is 5 mol% and the structural unit (c) is 80 to 5 mol%.