JPH07258400A - Aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To obtain an aromatic polycarbonate excellent in melt flow. CONSTITUTION:This carbonate is one wherein at least either terminal group is represented by the formula (wherein R1 and R2 are each cycloalkyl; and R3 is hydrogen, alkyl, cycloalkyl, alkoxyl or halogen).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to aromatic polycarbonates. More specifically, it relates to an aromatic polycarbonate having a group having a specific structure as an end group.

[0002]

2. Description of the Related Art Conventionally, aromatic polycarbonate has been
It is known as an engineering plastic excellent in transparency, heat resistance, mechanical strength, dimensional stability, etc., and is widely used as parts for automobiles, electric products and the like. Usually, when an aromatic polycarbonate is produced, polymerization is carried out by adding an end capping agent (also called a molecular weight regulator or chain terminator) for the purpose of controlling the molecular weight of the aromatic polycarbonate produced. (Eg, US Pat. No. 3,028,365). Among them, phenol or p-tert-butylphenol is generally widely used as the end capping agent. However, since aromatic polycarbonate produced using phenol or p-tert-butylphenol as an endcapping agent has a very high melt viscosity and poor melt flowability, when producing a molded article,
In order to secure sufficient fluidity, melt molding has been performed under high temperature conditions. However, when manufacturing a thin molded product or a molded product having a complicated shape, the fluidity at the time of melting is still insufficient, it is easy to cause unfilling in the mold, and it is difficult to obtain a precision molded product. There is a problem.

Aromatic polycarbonates have been produced by using a cycloalkyl group-substituted phenol derivative as an end-capping agent (US Pat. No. 4,699,971).
However, for example, the melt flowability of an aromatic polycarbonate produced by using 4-cyclohexylphenol as an end capping agent is not sufficient. Recently, aromatic polycarbonates having excellent melt fluidity are required in fields requiring precise processability required for substrates for optical devices such as data storage discs or audio compact discs. Has become. Currently,
There is a strong demand for aromatic polycarbonates having excellent melt fluidity.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art and to provide an aromatic polycarbonate having excellent melt fluidity.

[0005]

The present inventors have arrived at the present invention as a result of extensive studies on aromatic polycarbonates. That is, the present invention relates to an aromatic polycarbonate in which at least one of the terminal groups is a group represented by the general formula (1) (formula 2).

[0006]

[Chemical 2] (In the formula, R ₁ and R ₂ represent a cycloalkyl group,
₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom)

In the general formula (1), R ₁ and R ₂ each represent a cycloalkyl group, preferably 5 to 14 total carbon atoms which may be mono- or polysubstituted with an alkyl group having 1 to 8 carbon atoms. Is more preferable, and a cycloalkyl group having a total carbon number of 6 to 12 is more preferable. R
Specific examples of ₁ and R ₂ include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotetradecyl group, 2-methylcyclohexyl group. Group, 4-methylcyclohexyl group, 3-ethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4-n-hexylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 3,3,3 Examples thereof include a 5-trimethylcyclohexyl group, but the present invention is not limited thereto. Particularly preferred is a cyclohexyl group.

In the general formula (1), R ₃ is a hydrogen atom,
Represents an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom, preferably a hydrogen atom or a carbon number of 1 to
An alkyl group having 8 carbon atoms, a cycloalkyl group having 5 to 14 carbon atoms, which may be mono- or polysubstituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, It is a bromine atom, and more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a chlorine atom, or a bromine atom.

Specific examples of R ₃ include, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, neopentyl group, n-hexyl group, 2-ethylbutyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group , Cycloundecyl group, cyclododecyl group, cyclotetradecyl group, 2-methylcyclohexyl group, 4-methylcyclohexyl group, 3-ethylcyclohexyl group, 4-tert
-Butylcyclohexyl group, 4-n-hexylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,5
-Dimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, n-pentyloxy group, isopentyloxy group, n -Hexyloxy group, n-octyloxy group, 2
Examples thereof include, but are not limited to, an ethylhexyloxy group, a fluorine atom, a chlorine atom and a bromine atom. Particularly preferably, a hydrogen atom, a methyl group,
A cyclohexyl group, a methoxy group and a chlorine atom. Further, the substitution position of R ₃ is an ortho position or a meta position with respect to the —O (C═O) O— group, and an ortho position is particularly preferable.

Suitable compounds for use in producing an aromatic polycarbonate in which at least one of the terminal groups of the present invention is a group represented by the general formula (1) are represented by the general formula (1-A) The compound represented by 3) can be mentioned.

[0011]

[Chemical 3] (In the formula, R ₁ , R ₂ and R ₃ have the same meanings as described above, Y represents an —OH group, an —OM group, an —OCOZ group, M represents a metal ion, and Z represents a halogen atom.)

In the compound represented by the general formula (1-A) according to the present invention, Y is --OH group, --OM group, --OCOZ.
Represents a group, M represents a metal ion, and Z represents a halogen atom. M is preferably a monovalent or divalent alkali metal ion or alkaline earth metal ion, and specific examples thereof include lithium ion, sodium ion, potassium ion and calcium ion.
Z is preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom.

The compound represented by the general formula (1-A) can be produced by a known method. That is, for example, in the general formula (1-A), the compound in which Y is represented by an —OH group is about 2 mol of the same kind in the presence of an acid, relative to 1 mol of the phenol derivative substituted with R _3. It can be produced by reacting different cycloalkene derivatives. In the general formula (1-A), Y is -OCOZ.
In the compound represented by the group, for example, a compound in which Z is a chlorine atom is a compound in which Y is a —OH group,
It can be produced by reacting phosgene. In addition, in the general formula (1-A), the compound in which Y is an -OM group is a compound in which Y is an -OH group, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide in an aqueous solution. It can be produced by reacting with an alkali metal base or an alkaline earth base.

In the aromatic polycarbonate in which at least one of the terminal groups of the present invention is a group represented by the general formula (1), the group represented by the general formula (1) is typically as follows. The groups shown can be mentioned, but of course the present invention is not limited thereto. Example number group 1. 2,4-dicyclopentylphenyloxycarbonyloxy group 1. 2,4-dicyclohexylphenyloxycarbonyloxy group 3. 2,4-dicycloheptylphenyloxycarbonyloxy group 4. 2,4-dicyclodecylphenyloxycarbonyloxy group 5. 2,4-dicyclotetradecylphenyloxycarbonyloxy group 6. 2-cyclohexyl-4- (4'-methylcyclohexyl) phenyloxycarbonyloxy group 7. 2-Cyclohexyl-4-cyclododecylphenyloxycarbonyloxy group 8. 2-cyclodecyl-4- (3'-ethylcyclohexyl) phenyloxycarbonyloxy group

9. 2-cyclohexyl-4- (4'-tert-butylcyclohexyl) phenyloxycarbonyloxy group 10. 2-cyclopentyl-4-cyclohexyl-6-n-propylphenyloxycarbonyloxy group 11. 2,4-dicyclohexyl-5-methylphenyloxycarbonyloxy group 12. 2,4-dicyclohexyl-6-methylphenyloxycarbonyloxy group 13. 2,4-Dicyclohexyl-6-ethylphenyloxycarbonyloxy group 14. 2-Cyclooctyl-4-cyclohexyl-6-n-butylphenyloxycarbonyloxy group 15. 2,4-dicyclohexyl-6-methoxyphenyloxycarbonyloxy group 16. 2-cyclohexyl-4-cycloheptyl-6-ethoxyphenyloxycarbonyloxy group

17. 2,4-dicyclopentyl-6-fluorophenyloxycarbonyloxy group 18. 2,4-dicyclohexyl-6-chlorophenyloxycarbonyloxy group 19. 2,4-dicyclohexyl-6-bromophenyloxycarbonyloxy group 20. 2,4,6-tricyclohexylphenyloxycarbonyloxy group 21. 2,6-dicyclopentyl-4-cyclohexylphenyloxycarbonyloxy group 22. 2,6-dicyclohexyl-4- (4′-methylcyclohexyl) phenyloxycarbonyloxy group 23. 2,4-dicyclohexyl-6-cycloundecylphenyloxycarbonyloxy group 24. 2-cyclopentyl-4-cyclohexyl-6-cyclooctylphenyloxycarbonyloxy group

The aromatic polycarbonate of the present invention can be produced from at least one aromatic dihydroxy compound, a carbonate precursor and at least one compound represented by the general formula (1-A). As a manufacturing method thereof, for example, "Encyclopedia of Polymer Science a
nd Technology "vol.10, Polycarbonate, Interscience
Publishing, p.710-764 (1969), H. Schnell, "Chemistr
y andPhysics of Polycarbonate ", Interscience Publi
The method described in shing, p. 31-76 (1964), for example, the interfacial polymerization method, the solution polymerization method, or the transesterification method can be used, and the interfacial polymerization method is a preferable production method.

When the novel aromatic polycarbonate having a terminal group of the present invention is produced, the compound represented by the general formula (1-A) acts as a terminal blocking agent to produce the aromatic polycarbonate of the present invention. Helps control or adjust the molecular weight of the aromatic polycarbonate in the process. The end capping agent and the aromatic dihydroxy compound form a carbonate bond by the action of the carbonate precursor to produce an aromatic polycarbonate having an end group represented by the general formula (1) of the present invention. . The endcapping agent represented by the general formula (1-A) is generally prepared by first reacting an aromatic dihydroxy compound with a carbonate precursor by
That is, it may be present together with the aromatic dihydroxy compound prior to the addition of the carbonate precursor, or may be sequentially and continuously supplied with the addition of the carbonate precursor.

In producing the aromatic polycarbonate of the present invention, the compound represented by the general formula (1-A) may be used alone or in combination. Furthermore, the compound represented by the general formula (1-A) can also be used in combination with other known terminal blocking agents within a range that does not impair the desired effects of the present invention. When another known end-capping agent is used in combination, the proportion of the compound represented by the general formula (1-A) in all the end-capping agents is preferably 30 mol% or more, and 60 mol% or more. Is more preferable.

Examples of the terminal blocking agent other than the compound represented by the general formula (1-A) include monovalent hydroxyaromatic compounds, haloformate derivatives of monovalent hydroxyaromatic compounds, and monovalent carboxyl groups. And a monovalent carbonyl halide derivative. Examples of the monovalent hydroxyaromatic compound include phenol and p
-Cresol, o-ethylphenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-cumylphenol, p-cyclohexylphenol, p-octylphenol, p-nonylphenol, 2,4-xylenol, p -Methoxyphenol, p-hexyloxyphenol, p-decyloxyphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, p-bromophenol, pentabromophenol, pentachlorophenol, p-phenylphenol, p -Isopropenylphenol, 2,4-di (1-methyl-1-phenylethyl) phenol, β-naphthol, α-naphthol, p
-(2 ', 4', 4'-trimethylchromanyl) phenol,
Phenols such as 2- (4′-methoxyphenyl) -2- (4 ″ -hydroxyphenyl) propane. As the haloformate derivative of a monovalent hydroxyaromatic compound, the monovalent hydroxyaromatic compound described above is used. Haloformate derivatives and the like.

Examples of the compound having a monovalent carboxyl group include 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-
Fatty acids such as dimethylcaproic acid and phenoxyacetic acid, benzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, p-propyloxybenzoic acid, p-butoxybenzoic acid, p-hexyloxybenzoic acid, p- Benzoic acids such as octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid and p-chlorobenzoic acid. The monovalent carbonyl halide derivative is, for example, a halide derivative of the above-mentioned compound having a monovalent carboxyl group.
In addition, the above-mentioned monovalent hydroxyaromatic compound or an alkali metal (for example, lithium, sodium, potassium) salt or alkaline earth metal (for example, calcium) salt of a compound having a monovalent carboxyl group is also used as the terminal blocking agent. Can be used.

The amount of the end-capping agent used can be changed according to the average molecular weight of the target aromatic polycarbonate. In the present invention, the compound represented by the general formula (1-A) is used alone or in combination with two or more other known end-capping agents. When the compound described above is used in combination with another known end-capping agent, the total number of moles of those compounds is the amount of the end-capping agent used. The relationship between the amount of end-capping agent used and the average molecular weight of aromatic polycarbonate is that the average molecular weight of aromatic polycarbonate generally decreases as the amount of end-capping agent used increases, and the amount of end-capping agent used decreases. As a result, the average molecular weight tends to increase.

The aromatic polycarbonate of the present invention can have an arbitrary molecular weight depending on the amount of the end-capping agent used, but the processability of the aromatic polycarbonate produced is
Considering physical properties such as heat resistance and mechanical strength, about 1500
A weight average molecular weight of 0 to about 150,000 is preferred, a weight average molecular weight of about 20,000 to about 100,000 is more preferred, and a weight average molecular weight of about 30,000 to about 7,000 is preferred.
A weight average molecular weight of 0 is particularly preferred. The amount of the end-capping agent used for producing the aromatic polycarbonate having the weight average molecular weight in the above range is about 1 to about 10 mol% based on the amount of the aromatic dihydroxy compound used. More preferably, about 1.5 to about 7 mol% is more preferably used.

Examples of the aromatic dihydroxy compound used in producing the aromatic polycarbonate of the present invention include compounds represented by the general formula (2) or the general formula (3). HO-Ar ¹ -X-Ar ² -OH (2) HO-Ar ³ -OH (3) (In the formula, Ar ¹ , Ar ² and Ar ³ represent a divalent aromatic group, and X represents Ar ¹ and linking a group) formula that links Ar ² in (2) and the general formula (3), Ar ^1, Ar ² and Ar ³ each represent a divalent aromatic group, preferably a phenylene group, or a substituted It is a substituted phenylene group having a group. Examples of the substituent of the substituted phenylene group include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, a halogen atom and a nitro group.

Ar ¹ and Ar ² are both p-phenylene group, m-phenylene group or o-phenylene group which may have a substituent, or one of them is a p-phenylene group and one of them is m. A -phenylene group or an o-phenylene group is preferred, and it is particularly preferred that both Ar ¹ and Ar ² are p-phenylene groups. Ar ³ is a p-phenylene group, m-phenylene group or o-phenylene group which may have a substituent, and preferably a p-phenylene group or m-phenylene group.

X is a linking group for connecting Ar ¹ and Ar ² , which is a single bond or a divalent hydrocarbon group, and further --O.
-, - S -, - SO -, - SO 2 -, - it may be a group containing atoms other than carbon and hydrogen CO- like. Examples of the divalent hydrocarbon group include a saturated hydrocarbon group, for example, an alkylidene group such as methylene, ethylene, 2,2-propylidene, cyclohexylidene and the like, but a group substituted with an aryl group is also included. Further, it may be a hydrocarbon group containing an aromatic group or other unsaturated hydrocarbon group.

Specific examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane and bis (2
-Methyl-4-hydroxyphenyl) methane, bis (3
-Methyl-4-hydroxyphenyl) methane, 1,1-
Bis (4'-hydroxyphenyl) ethane, 1,2-bis (4'-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,1-bis (4'-hydroxyphenyl) -1-phenylethane, 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"], 1,3-bis ( 4'-hydroxyphenyl)
-1,1-dimethylpropane, 2- (4'-hydroxyphenyl) -2- (3'-hydroxyphenyl) propane,
1,1-bis (4'-hydroxyphenyl) butane, 2,
2-bis (4'-hydroxyphenyl) butane, 1,1-
Bis (4'-hydroxyphenyl) -3-methylbutane,

2,2-bis (4'-hydroxyphenyl)
Pentane, 3,3-bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxyphenyl) -4
-Methylpentane, 2,2-bis (4'-hydroxyphenyl) hexane, 4,4-bis (4'-hydroxyphenyl) heptane, 2,2-bis (4'-hydroxyphenyl) octane, 2,2- Bis (4'-hydroxyphenyl) nonane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3'-methyl-4'-hydroxyphenyl) propane, 2,2-bis ( 3'-ethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-n-propyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-isopropyl-4'-hydroxyphenyl) ) Propane, 2,2-bis (3'-sec-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-tert-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-cyclohexyl 4'-hydroxyphenyl) propane,

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

1,1-bis (4'-hydroxyphenyl)
Cyclopentane, 1,1-bis (4'-hydroxyphenyl
) Cyclohexane, 1,1-bis (3'-methyl-4'-
Hydroxyphenyl) cyclohexane, 1,1-bis
(3 ', 5'-dimethyl-4'-hydroxyphenyl) cyclo
Hexane, 1,1-bis (3 ', 5'-dichloro-4'-hydr
Roxyphenyl) cyclohexane, 1,1-bis (4'-
Hydroxyphenyl) -4-methylcyclohexane,
1,1-bis (4'-hydroxyphenyl) -3,3,5
-Trimethylcyclohexane, 1,1-bis (4'-hydr
Roxyphenyl) cycloheptane, 1,1-bis (4'-
Hydroxyphenyl) cyclooctane, 1,1-bis
(4'-Hydroxyphenyl) cyclononane, 1,1-bi
Sus (4'-hydroxyphenyl) cyclododecane, 2,2
-Bis (4'-hydroxyphenyl) norbornane, 8,
8-bis (4'-hydroxy15nyl) tricyclo [5.
2.1.0 ^2.6] Decane, 2,2-bis (4'-hydroxy
Biphenyl (hydroxy aryl) such as cyclophenyl adamantane
Le) cycloalkanes,

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

Further, 6,6'-dihydroxy-2,2 ',
3,3′-Tetrahydro-3,3,3 ′, 3′-tetramethyl-1,1′-spirobi (1H-indene) [“spirobiindanebisphenol”], 7,7-dihydroxy-
3,3 ′, 4,4′-tetrahydro-4,4,4 ′, 4′-tetramethyl-2,2′-spirobi (2H-1-benzopyran) [“spirobichroman”], trans-2, 3-bis (4'-hydroxyphenyl) -2-butene, 9,9-
Bis (4'-hydroxyphenyl) fluorene, 3,3-
Bis (4'-hydroxyphenyl) -2-butanone, 1,
6-bis (4'-hydroxyphenyl) -1,6-hexanedione, 1,1-dichloro-2,2-bis (4'-hydroxyphenyl) ethylene, 1,1-dibromo-2,2
-Bis (4'-hydroxyphenyl) ethylene, 1,1-
Dichloro-2,2-bis (3'-phenoxy-4'-hydroxyphenyl) ethylene, α, α, α ', α'-tetramethyl-α, α'-bis (4-hydroxyphenyl)-
p-xylene, α, α, α ′, α′-tetramethyl-
α, α′-bis (4-hydroxyphenyl) -m-xylene,

3,3-bis (4-hydroxyphenyl)
Phthalide, 4,4'-dihydroxybiphenyl, 1,4-
Examples thereof include dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, hydroquinone and resorcin. Further, for example, bisphenols containing an ester bond produced by reacting 2 mol of bisphenol A with 1 mol of isophthaloyl chloride or terephthaloyl chloride are also useful. These may be used alone or in combination. Particularly preferred aromatic dihydroxy compounds are bis (hydroxyaryl) alkanes and bis (hydroxyaryl)
Cycloalkanes, of which bisphenol A is preferable.

Examples of the carbonate precursor include carbonyl halide compounds, haloformate compounds, dialkyl carbonate compounds, diaryl carbonate compounds,
Alkylaryl carbonate compounds may be mentioned, with preference given to carbonyl halide compounds and haloformate compounds. Examples of the carbonyl halide compound include carbonyl chloride, which is usually called phosgene, carbonyl bromide, carbonyl iodide, carbonyl fluoride, and a mixture thereof. Furthermore, phosgene dimer trichloromethyl chloroformate and phosgene trimer bis (trichloromethyl)
Carbonates can also be used.

As the haloformate compound, a mono- or bis-haloformate compound and an oligomeric mono- or bis-haloformate compound are used, and a typical example thereof is a compound represented by the general formula (4). W- [OR'-OC (= O)] _n -OR'-OW (4) (In the formula, W represents a hydrogen atom or a halocarbonyl group,
At least one W is a halocarbonyl group, R ′ represents a divalent aliphatic group or an aromatic group, and n represents 0 or a positive integer.) The compound represented by the general formula (4) is Mono- or bishaloformate compounds derived from aliphatic dihydroxy compounds, mono- or bishaloformate compounds derived from aromatic dihydroxy compounds, and oligomeric mono- or bishaloformate compounds of these compounds. In the case of an oligomeric mono- or bishaloformate compound, R's having different structures in the same molecule
It may have a group. These haloformate compounds may be used alone or in combination of two or more,
Further, it can be used in combination with a carbonyl halide compound.

In the general formula (4), R'is a divalent group derived from an aliphatic dihydroxy compound or an aromatic dihydroxy compound. Examples of the aliphatic dihydroxy compound include dihydroxyalkane, dihydroxycycloalkane, and the compound represented by the general formula (5). HO-R "-Ar ⁴ -R" -OH (5) (In the formula, R "represents an alkylene group having 1 to 6 carbon atoms, and A
r ⁴ represents a divalent aromatic group having 6 to 12 carbon atoms) The aliphatic dihydroxy compound is preferably a dihydroxyalkane having 2 to 20 carbon atoms, a dihydroxycycloalkane having 4 to 12 carbon atoms, and a general formula ( The dihydroxy compound represented by 5) can be mentioned.

Specific examples of the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-
Nonanediol, 1,10-decanediol, 1,11
-Undecanediol, 1,12-dodecanediol,
Dipentyl glycols such as neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, 2,
Dihydroxycycloalkanes such as 2-bis (4'-hydroxycyclohexyl) propane, 1,2-bis (hydroxymethyl) benzene, 1,3-bis (hydroxymethyl) benzene, 1,4-bis (hydroxymethyl) benzene, 1,4-bis (2'-hydroxyethyl) benzene, 1,4-bis (3'-hydroxypropyl) benzene, 1,4-bis (4'-hydroxybutyl) benzene,
1,4-bis (5'-hydroxypentyl) benzene,
Examples thereof include dihydroxy compounds such as 1,4-bis (6'-hydroxyhexyl) benzene.

Examples of the aromatic dihydroxy compound include the aromatic dihydroxy compounds represented by the above general formula (2) or general formula (3), such as bisphenol A and hydroquinone. Examples of the dialkyl carbonate compound, diaryl carbonate compound, and alkylaryl carbonate compound include dimethyl carbonate, diphenyl carbonate, methylphenyl carbonate compound, diphenyl carbonate substituted with a halogen atom, a nitro group, and the like. These may be used alone or in combination.

When the aromatic polycarbonate of the present invention is produced by the interfacial polymerization method, a carbonyl halide compound and / or a haloformate compound is preferably used as the carbonate precursor. The carbonate precursor may be used in any state of gas, liquid and solid. When a carbonyl halide compound is used, it is preferably dissolved in a gas state or an organic solvent and used as an organic solvent solution, and when a haloformate compound is used, it is dissolved in an organic solvent in a solid state or an organic solvent. It is preferably used as a solution.

When the aromatic polycarbonate of the present invention is produced by the interfacial polymerization method, for example, when a carbonyl halide compound is used as a carbonate precursor, the amount thereof is about 1 relative to the amount of the aromatic dihydroxy compound. It is preferable to use it in an amount of 0.0 to about 1.3 times. When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method, a known method can be used. For example, in a two-phase mixed solvent of at least one aromatic dihydroxy compound and an alkali metal or alkaline earth metal base, water and an organic solvent substantially insoluble in water, a carbonyl halide compound and / or a halogenate compound is generally used. A method for producing an aromatic polycarbonate by allowing it to act in the presence of a compound represented by the formula (1-A), more preferably a method for producing it in the presence of a polycarbonate-forming catalyst.

Any organic solvent may be used as long as it is substantially insoluble in water, inert to the reaction, and capable of dissolving the aromatic polycarbonate. Preferred organic solvents include, for example, dichloromethane, chloroform, 1,2-dichloroethane, 1,2-
Dichloroethylene, trichloroethane, tetrachloroethane, dichloropropane and other aliphatic chlorinated hydrocarbon solvents, or chlorobenzene, dichlorobenzene and other aromatic chlorinated hydrocarbon solvents such as chlorinated hydrocarbon solvents or mixed solvents thereof Can be mentioned. Furthermore, mixed solvents of these chlorinated hydrocarbon solvents and aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, etc., or aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, etc. may be mentioned. A particularly preferred organic solvent is dichloromethane. The amount of the organic solvent used is usually such that the concentration of the aromatic polycarbonate in the organic solvent solution containing the aromatic polycarbonate at the end of the polymerization is about 5 to 5.
It is preferred to use about 35% by weight.

The amounts of the organic solvent and water used in the reaction may be such that the reaction mixture maintains a substantially uniform emulsified state, and the volume ratio of water to the organic phase is usually It is preferably about 0.4 to about 1.5: 1. Examples of alkali metal or alkaline earth metal bases (hereinafter abbreviated as bases) used in producing the aromatic polycarbonate of the present invention include sodium hydroxide, potassium hydroxide and calcium hydroxide. .
The amount of the base used is preferably about 1.0 to about 1.6 times the equivalent amount of the aromatic dihydroxy compound. The base is usually used in the form of an aqueous solution, and it is preferable to dissolve the aromatic dihydroxy compound in the aqueous solution and use it in the reaction. In this case, sodium sulphite, sodium hydrosulfite, sodium borohydride or the like may be added as an antioxidant to prepare a basic aqueous solution of the aromatic dihydroxy compound.

In the interfacial polymerization method, a polycarbonate-forming catalyst (also called a polymerization catalyst) optionally used is a tertiary amine, a quaternary ammonium salt, a tertiary phosphine, a quaternary phosphonium salt, or a nitrogen-containing heterocycle. Examples thereof include compounds and salts thereof, imino ethers and salts thereof, and compounds having an amide group. Preferred are tertiary amines such as triethylamine and tri-n-.
Propylamine, diethyl-n-propylamine, tri-n-butylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N-
Ethyl piperidine and the like can be mentioned. These polycarbonate-forming catalysts can be used alone or in combination. The amount of the polycarbonate-forming catalyst used is preferably about 0.0005 to about 1.5 mol% based on the number of moles of the aromatic dihydroxy compound. The polycarbonate generation catalyst can be added before or during the reaction when producing the aromatic polycarbonate of the present invention. In the interfacial polymerization method, the reaction temperature is preferably about 10 ° C. to the boiling point temperature of the organic solvent used for the reaction to produce the aromatic polycarbonate of the present invention.
The reaction is usually carried out under atmospheric pressure, but if desired, it may be carried out under pressure or under reduced pressure.

When the aromatic polycarbonate of the present invention is produced, a known solution polymerization method can be used. For example, in a pyridine solution, an aromatic dihydroxy compound, a carbonyl halide compound or / and a haloformate compound and a compound represented by the general formula (1-A) can be allowed to act at about 0 to about 50 ° C. to produce them. it can. Using a dialkyl carbonate compound, an alkylaryl carbonate compound or / and a diaryl carbonate compound as the carbonate precursor,
When producing the aromatic polycarbonate of the present invention,
Dialkyl carbonate compound, alkylaryl carbonate compound and / or diaryl carbonate compound, aromatic dihydroxy compound and general formula (1-A)
At a temperature of about 60 to about 300 ° C., under normal pressure, under pressure or under reduced pressure, if necessary, a transesterification catalyst (for example, metal oxide, metal hydroxide, It can be produced by a known transesterification method in the presence of a metal carbonate or the like).

The aromatic polycarbonate of the present invention is
If desired, by adding a branching agent during production,
It may be a branched aromatic polycarbonate. Examples of the branching agent include compounds having three or more phenolic hydroxyl groups, haloformate groups, carboxyl groups, carbonyl halide groups, and active halogen atoms. Specific examples of the branching agent include phloroglucinol, 4,6-dimethyl-2,4,6-tris (4'-
Hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) heptane, 1,3,5-tris (4'-hydroxyphenyl) benzene, 1,1, 1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-hydroxyphenyl) propane, α, α, α′-tris (4′-hydroxyphenyl) -1-ethyl-4- Isopropylbenzene, 2,4-bis [α-methyl-α- (4'-hydroxyphenyl) ethyl] phenol, 2- (4'-hydroxyphenyl) -2- (2 ", 4" -dihydroxyphenyl)
Propane, tris (4-hydroxyphenyl) phosphine, 1,1,4,4-tetrakis (4'-hydroxyphenyl) cyclohexane, 2,2-bis [4 ', 4'-bis (4 "-hydroxyphenyl) cyclohexyl 〕propane,

Α, α, α ', α'-tetrakis (4'-hydroxyphenyl) -1,4-diethylbenzene, 2,
2,5,5-tetrakis (4'-hydroxyphenyl) hexane, 1,1,2,3-tetrakis (4'-hydroxyphenyl) propane, 1,4-bis (4 ', 4 "-dihydroxytriphenylmethyl ) Benzene, 3,3 ', 5,5'-
Tetrahydroxydiphenyl ether, 3,5-dihydroxybenzoic acid, 3,5-bis (chlorocarbonyloxy) benzoic acid, 4-hydroxyisophthalic acid, 4-chlorocarbonyloxyisophthalic acid, 5-hydroxyphthalic acid, 5-chlorocarbonyloxy Phthalic acid, trimesic acid trichloride, cyanuric acid 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 can be mentioned. These branching agents may be used alone or in combination of two or more.
The amount of the branching agent used can be changed according to the degree of branching of the desired branched aromatic polycarbonate, and is usually 0.05 with respect to the aromatic dihydroxy compound.
It is preferable to use about 2.0 mol%.

Furthermore, the aromatic polycarbonate of the present invention also includes an aromatic polyester carbonate, which is represented by at least one aromatic dihydroxy compound [for example, represented by the general formula (2) or the general formula (3)]. A compound], a carbonate precursor (for example, phosgene),
Aromatic or aliphatic divalent carboxylic acid or a halide derivative of the compound (for example, US Pat. No. 3,169,121).
The isophthalic acid, terephthalic acid, isophthalic acid dichloride, terephthalic acid dichloride, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid) and the compound represented by the general formula (1-A),
The aromatic polyester carbonate can be produced by a known method (for example, the method described in U.S. Pat. No. 3,169,121, U.S. Pat. No. 4,156,069, and British Patent No. 8,977,640). At this time, the amount of the aromatic or aliphatic divalent carboxylic acid or carboxylic acid halide used is preferably about 30 to 80 mol% based on the aromatic dihydroxy compound.

When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method or a solution polymerization method, the organic solvent solution containing the aromatic polycarbonate is usually separated from the aqueous layer and then washed substantially with water. After washing until the electrolyte is exhausted, the organic solvent is removed from the organic solvent solution by a known method to obtain the aromatic polycarbonate of the present invention. In the case of production by the transesterification method, the aromatic polycarbonate melted under the production conditions can be directly pelletized or processed into a molded product.

The aromatic polycarbonate of the present invention can be used as a molding material by mixing with other aromatic polycarbonate or other polymer. Other polymers include polyethylene, polypropylene, polystyrene, ABS resin, polymethylmethacrylate, polytrifluoroethylene, polytetrafluoroethylene,
Examples thereof include polyacetal, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polyamide, polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, paraoxybenzoyl polyester, polyarylate, and polysulfide.

Further, the aromatic polycarbonate of the present invention has the following properties during or after the production of the aromatic polycarbonate:
By known methods, dyes, pigments, heat stabilizers, antioxidants, hydrolysis stabilizers, UV absorbers, mold release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, sulfuric acid. One or more kinds of various additives such as barium and TiO ₂ may be added. The aromatic polycarbonate of the present invention may be used alone or in a mixture with other polymers, and if desired, various additives may be added thereto, such as chassis and housing materials for electric devices, electronic parts, automobile parts, compact discs, etc. It can be formed into a substrate of an information recording medium, an optical material such as a lens of a camera or spectacles, a building material instead of glass, and the like. The aromatic polycarbonate of the present invention is thermoplastic and can be injection-molded, extruded, blow-molded, impregnated with a filler and the like, and can be easily molded by a known method. Further, the aromatic polycarbonate of the present invention is soluble in a specific organic solvent (for example, a halogenated hydrocarbon solvent such as dichloromethane), and can be cast from the organic solvent solution and molded into a film or the like.

[0051]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples. The molecular weight of each aromatic polycarbonate produced in each of the examples and comparative examples is GPC [gel permeation chromatography, manufactured by Showa Denko KK, GPC].
System-11]. The glass transition point (Tg, ° C) was measured using DSC [manufactured by Mac Science Co., Ltd., DSC-3100] at a heating rate of 16 ° C / min. Melt flow index (MI)
Is a Toyo Seiki S-01 melt indexer,
Measured at a temperature of 280 ° C and a load of 2.16 kg, 10
The weight of the polymer eluted per minute (unit: gram) is shown. The larger the number, the better the melt flowability.

Example 1 Production of Aromatic Polycarbonate having Ex. No. 2 End Group A 10-liter baffled flask was equipped with a three-stage six-blade stirrer and reflux condenser, and 912 g of bisphenol A (4. 0 mol), 3,4-dicyclohexylphenol (35.1 g, 0.136 mol, 3.4 mol% based on bisphenol A), dichloromethane (4 liters) and deionized water (4 liters) were added to prepare a suspension, which was placed in the flask. A nitrogen purge was performed to remove the oxygen in. Next, 1.2 g of sodium hydrosulfite and 432 g (10.8 g) of sodium hydroxide were added to the above suspension.
2.2 liter of an aqueous solution in which
The bisphenol A was dissolved at ℃. Phosgene (495 g, 5.0 mol) was fed to the solution in 60 minutes. The reaction temperature rose and the reflux of dichloromethane was confirmed. After the supply of phosgene was completed, 0.64 g of triethylamine was added, and the reaction solution was stirred for another 90 minutes to carry out a polymerization reaction. Then, the reaction solution was allowed to stand still, the organic layer was separated, neutralized with hydrochloric acid, and washed with deionized water until the electrolyte was exhausted. To the obtained aromatic polycarbonate solution in dichloromethane was added 2 liters of toluene and 5 liters of water,
Dichloromethane and toluene were distilled off by heating to 98 ° C to obtain an aromatic polycarbonate powder. The obtained aromatic polycarbonate had a number average molecular weight of 20,800 and a weight average molecular weight of 51,500. T
g was 144 ° C. and MI was 18.5.

Example 2 Preparation of Aromatic Polycarbonate having an Exemplified No. 12 Instead of using 2,4-dicyclohexylphenol in Example 1, 2,4-dicyclohexyl-6-
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 40.0 g of sodium salt of methylphenol (3.4 mol% based on bisphenol A) was used. The number average molecular weight of the obtained aromatic polycarbonate is 2070.
0, the weight average molecular weight was 51300. Tg is 14
It was 3 degreeC and MI was 18.5.

Example 3 Preparation of Aromatic Polycarbonate having an Exemplification No. 15 End group 2,4-dicyclohexyl-6- instead of using 2,4-dicyclohexylphenol
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 39.2 g of methoxyphenol (3.4 mol% based on bisphenol A) was used. The obtained aromatic polycarbonate had a number average molecular weight of 20,700 and a weight average molecular weight of 51,300. Tg is 144 ° C,
The MI was 18.5.

Example 4 Preparation of Aromatic Polycarbonate Having End Group No. 18 In Example 1, instead of using 2,4-dicyclohexylphenol, 2,4-dicyclohexyl-6-
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 48.3 g of chlorophenyl chloroformate (3.4 mol% based on bisphenol A) was used. The number average molecular weight of the obtained aromatic polycarbonate was 2100.
0, the weight average molecular weight was 51,600. Tg is 14
It was 5 degreeC and MI was 18.2.

Example 5 Production of Aromatic Polycarbonate having End Group No. 20 In Example 1, instead of using 2,4-dicyclohexylphenol, 46.2 g (bisphenol A) of 2,4,6-tricyclohexylphenol was used. Against 3.
Aromatic polycarbonate was produced in the same manner as in Example 1 except that 4 mol%) was used. The obtained aromatic polycarbonate had a number average molecular weight of 21,000 and a weight average molecular weight of 51,500. Tg is 145 ° C, MI is 1
It was 9.2.

Comparative Example 1 For comparison, instead of using 2,4-dicyclohexylphenol in Example 1, 20.4 g of p-tert-butylphenol (3.4 relative to bisphenol A)
Aromatic polycarbonate was produced in the same manner as in Example 1 except that (mol%) was used. The obtained aromatic polycarbonate has a number average molecular weight of 21,000 and a weight average molecular weight of 5
It was 1200. Tg is 148 ° C, MI is 1
It was 1.0.

Comparative Example 2 For comparison, instead of using 2,4-dicyclohexylphenol in Example 1, 23.9 g of 4-cyclohexylphenol (3.
Aromatic polycarbonate was produced in the same manner as in Example 1 except that 4 mol%) was used. The obtained aromatic polycarbonate had a number average molecular weight of 20,800 and a weight average molecular weight of 51,300. Tg is 142 ° C, MI is 1
It was 0.2.

From the results of Examples and Comparative Examples, it was found that the aromatic polycarbonate of the present invention has excellent melt flowability as compared with the aromatic polycarbonate produced by using a known end-capping agent. It was

[0060]

According to the present invention, it is possible to provide an aromatic polycarbonate having excellent melt fluidity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomonori Ito 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 Within the corporation

Claims (3)

[Claims] 1. An aromatic polycarbonate in which at least one of the terminal groups is a group represented by the general formula (1) (formula 1). [Chemical 1] (In the formula, R ₁ and R ₂ represent a cycloalkyl group,
₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom) 2. In the general formula (1), R ₁ and R ₂
Is a cycloalkyl group having 5 to 14 carbon atoms, R ₃ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 14 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom. The aromatic polycarbonate according to Item 1. 3. In the general formula (1), R ₁ and R ₂
Is a cycloalkyl group having 6 to 12 carbon atoms, R ₃ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. The aromatic polycarbonate according to Item 1.