JP3238992B2 - Aromatic polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to aromatic polycarbonates. More specifically, the present invention relates to an aromatic polycarbonate having a group having a specific structure as a terminal group.

[0002]

2. Description of the Related Art Conventionally, aromatic polycarbonates have been
It is known as an engineering plastic having excellent transparency, heat resistance, mechanical strength, dimensional stability, and the like, and is widely used as a component of automobiles, electric products, and the like. Usually, when producing an aromatic polycarbonate, polymerization is carried out by adding a terminal blocking agent (also referred to as a molecular weight regulator or a chain terminator) in order to regulate the molecular weight of the produced aromatic polycarbonate. (Eg, US Pat. No. 3,028,365). Among them, phenol or p-tert-butylphenol is generally and widely used as a terminal blocking agent. However, an aromatic polycarbonate produced using phenol or p-tert-butylphenol as a terminal blocking agent has a problem in weather resistance (for example, heat hydrolysis resistance).

Further, for example, a C _m H _{2m + 1} O-group (m is 3
A method for producing an aromatic polycarbonate by using a phenol derivative having a para-position (indicating an integer of 10 to 10) as a terminal blocking agent has been proposed (JP-A-63-258).
922). However, for example, an aromatic polycarbonate produced using pn-hexyloxyphenol has a problem in weather resistance (for example, heat hydrolysis resistance). At present, there is a demand for an aromatic polycarbonate having excellent weather resistance (for example, heat hydrolysis resistance).

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the problems of the prior art and to provide an aromatic polycarbonate having excellent thermal hydrolysis resistance.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on aromatic polycarbonates, and have reached the present invention. 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]

Embedded image (Wherein R1, R2 and R3 represent an aryl group,
X1 and X2 represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and among R1, R2 and R3,
Except that two or more have an alkoxyaryl group
Good . )

In the group represented by the general formula (1) according to the present invention, R1, R2 and R3 represent an aryl group,
However, two or more of R1, R2, and R3 are simultaneously
Excludes cases having a oxyaryl group. The aryl group may be further mono- or polysubstituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom. More preferably, the total carbon number is 6-1.
2 aryl groups. Specific examples of R1, R2 and R3 include, for example, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl,
3-ethylphenyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group,
4-n-pentylphenyl group, 4-n-heptylphenyl group, 4-tert-octylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl Group, 4-ethoxyphenyl group, 3-isopropoxyphenyl group, 4-n
-Butoxyphenyl group, 4-n-hexyloxyphenyl group, 4-n-octyloxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-diethoxyphenyl group,
4-fluorophenyl group, 2-fluorophenyl group, 4
-Chlorophenyl group, 3-chlorophenyl group, 4-bromophenyl group, 3,5-dichlorophenyl group, 2-chloro-4-methylphenyl group, 4-chloro-2-methylphenyl group, 2-naphthyl group, 1-naphthyl Examples include, but are not limited to, groups.

In the group represented by the general formula (1), X ₁
And X ₂ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom or a bromine atom. Represents As a preferred compound used for 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), a compound represented by the general formula (1-A) The compounds represented may be mentioned.

[0009]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , X ₁ and X ₂ represent the same meaning as described above, Y represents an —OH group, an —OM group, or an —OCOZ group, M represents a metal ion, and Z represents a halogen. Represents an atom)

In the compound represented by the general formula (1-A) according to the present invention, Y represents -OH group, -OM group, -OCOS
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 an alkaline earth metal ion,
Lithium ion, sodium ion, potassium ion,
Specific examples include calcium ions,
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. For example, in the general formula (1-A), a compound in which Y is represented by an -OH group can be produced, for example, by the method described in J. Org. Chem., 58, 3748 (1993). That is, it can be produced by allowing a phenol derivative to act on a triphenylmethanol derivative in the presence of an acid catalyst.

In the general formula (1-A), Y is-
In the compound represented by the OCOZ group, for example, a compound in which Z is a chlorine atom is a compound in which Y is an -OH group,
For example, it can be produced by the action of phosgene.
In the general formula (1-A), a compound in which Y is an —OM group is a compound in which Y is an —OH group, for example, sodium hydroxide, potassium hydroxide, or calcium hydroxide in an aqueous solution. And alkali metal bases or alkaline earth bases. 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) typically includes the following groups. However, the present invention is of course not limited to these.

[0012] 1. 1. 4- (triphenylmethyl) phenyl group 2. 4- (triphenylmethyl) -2-methylphenyl group 3. 4- (triphenylmethyl) -2,6-dimethylphenyl group 4. 4- (triphenylmethyl) -2-chlorophenyl group 5. 4-[(4′-methylphenyl) bisphenylmethyl] phenyl group 6. 4- [phenylbis (4'-tert-butylphenyl) methyl] phenyl group 7. 4- [phenylbis (4′-tert-butylphenyl) methyl] -2-methoxyphenyl group 4-[(4 "-methoxyphenyl) bis (4'-
8. tert-butylphenyl) methyl] phenyl group 4-[(4 "-chlorophenyl) bis (4'-te
rt-butylphenyl) methyl] phenyl group 4- [tris (4′-tert-butylphenyl)
[Methyl] phenyl group 4- [tris (4′-tert-butylphenyl)
Methyl] -2-chlorophenyl group 12. 4- [tris (4′-tert-octylphenyl) methyl] phenyl group 4- [tris (4'-chlorophenyl) methyl] phenyl 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). Examples of the production method include “Encyclopedia of Polymer Science a
nd Tech-nology "vol.10, Polycarbonate, Interscien
ce Publishing, p.710-764 (1969), H. Schnell, "Chemis
try and Physics of Polycarbonate ", Interscience Pu
b-lishing, p.33-41 (1964), for example, an interfacial polymerization method, a solution polymerization method, or a transesterification method can be used.In particular, the interfacial polymerization method is a preferable production method. .

In producing the aromatic polycarbonate having a novel terminal group according to the present invention, the compound represented by the general formula (1-A) acts as a terminal blocking agent to produce the aromatic polycarbonate according to the present invention. In the process, it helps to control or adjust the molecular weight of the aromatic polycarbonate. The terminal blocking agent and the aromatic dihydroxy compound form a carbonate bond by the action of a carbonate precursor to produce an aromatic polycarbonate having a terminal group represented by the general formula (1) of the present invention. . General formula (1-A)
Is generally the first in the reaction between the aromatic dihydroxy compound and the carbonate precursor, that is, prior to the addition of the carbonate precursor,
It may be present together with the aromatic dihydroxy compound, or it may be supplied sequentially and continuously with the addition of the carbonate precursor.

In producing the aromatic polycarbonate of the present invention, the compounds represented by the general formula (1-A) can be used alone or in combination. Furthermore, the general formula (1-
The compound represented by A) can be used in combination with other known terminal blocking agents as long as the desired effects of the present invention are not impaired. When another known terminal blocking agent is used in combination, the proportion of the compound represented by the general formula (1-A) in all terminal blocking agents is preferably 30 mol% or more, and more preferably 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 compounds having a monovalent carboxyl group And monovalent carbonyl halide derivatives.

As the monovalent hydroxy aromatic compound,
For example, phenol, p-cresol, o-ethylphenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-cumylphenol, p-cyclohexylphenol, p-n-octylphenol, p-isooctylphenol , Pn
-Nonylphenol, 2,4-xylenol, p-methoxyphenol, pn-hexyloxyphenol,
p-n-decyloxyphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, p
-Bromophenol, pentabromophenol, pentachlorophenol, p-phenylphenol, p-isopropenylphenol, 2,4-di (1-methyl-1-
Phenylethyl) phenol, β-naphthol, α-naphthol, p- (2 ′, 4 ′, 4′-trimethylchromanyl)
Phenol, 2- (4'-methoxyphenyl) -2- (4 "
-Hydroxyphenyl) propane and the like. Examples of the haloformate derivative of a monovalent hydroxy aromatic compound include the above-described haloformate derivatives of a monovalent hydroxy aromatic compound.

Compounds having a monovalent carboxyl group include, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid, 3-methylbutyric acid, 3,3 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, pn-propyloxybenzoic acid, pn-butoxybenzoic acid, pn-hexyl Oxybenzoic acid, pn
Octyloxybenzoic acid, p-phenylbenzoic acid, p
-Benzoic acids such as benzylbenzoic acid and p-chlorobenzoic acid. As the monovalent carbonyl halide derivative,
And halide derivatives of the above compounds having a monovalent carboxyl group. In addition, the alkali metal (for example, lithium, sodium, potassium) of the above-mentioned monovalent hydroxy aromatic compound or the compound having a monovalent carboxyl group is used.
Salts, alkaline earth metal (eg, calcium) salts can also be used as endcapping agents.

The amount of the terminal blocking agent used can be changed according to the desired average molecular weight of the aromatic polycarbonate. In the present invention, the compound represented by the general formula (1-A) is used alone or in combination of two or more, or in combination with another known terminal blocking agent. When the compound is used in combination with another known terminal blocking agent, the total mole number of those compounds is used as the amount of the terminal blocking agent. The relationship between the amount of the terminal blocking agent and the average molecular weight of the aromatic polycarbonate generally indicates that as the amount of the terminal blocking agent increases, the average molecular weight of the aromatic polycarbonate decreases, and the amount of the terminal blocking agent decreases. Accordingly, the average molecular weight tends to increase. The aromatic polycarbonate of the present invention,
An arbitrary molecular weight can be obtained depending on the amount of the end-capping agent used. However, considering the physical properties such as moldability, heat resistance, and mechanical strength of the produced aromatic polycarbonate, about 15
Preferably it has a weight average molecular weight of 000 to about 150,000, more preferably about 20,000 to about 100,000. The amount of the terminal blocking agent required to produce an aromatic polycarbonate having a weight average molecular weight in the above range is from 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 used.

As the aromatic dihydroxy compound used for producing the aromatic polycarbonate of the present invention, a compound represented by the general formula (2) or (3) can be mentioned. HO-Ar ₁ -X-Ar ₂ -OH (2) HO-Ar ₃ -OH (3) (wherein, 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 each a p-phenylene group, an m-phenylene group or an o-phenylene group which may have a substituent, or one is a p-phenylene group and the other is a p-phenylene group. It is preferably an m-phenylene group or an o-phenylene group, and particularly preferably both Ar ₁ and Ar ₂ are both p-phenylene groups. Ar ₃ is a p-phenylene group, an m-phenylene group or an o-phenylene group which may have a substituent, and is preferably a p-phenylene group or an m-phenylene group. X is a linking group linking Ar ₁ and Ar ₂ , and is a single bond or a divalent hydrocarbon group, and further includes —O—, —S—, —SO—, and —SO—.
It may be a group containing atoms other than carbon and hydrogen, such as _2- and -CO-. The divalent hydrocarbon group includes a saturated hydrocarbon group, for example, an alkylidene group such as methylene, ethylene, 2,2-propylidene, cyclohexylidene, etc., but also includes a group substituted with an aryl group or the like. ,Also,
A hydrocarbon group containing an aromatic group or another unsaturated hydrocarbon group may be used.

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-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-bis (2 ', 6'
-Dibromo-3 ', 5'-dimethyl-4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl)
Bis (hydroxyaryl) alkanes such as cyanomethane, 1-cyano-3,3-bis (4′-hydroxyphenyl) butane, 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 ]
Bis (hydroxyaryl) cycloalkanes such as decane and 2,2-bis (4′-hydroxyphenyl) adamantane;

Bis (hydroxyaryl) ethers such as 4,4'-dihydroxydiphenyl ether, 3,3'-dimethyl-4,4'-dihydroxydiphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether; -Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dicyclohexyl-4,4'-dihydroxydiphenyl sulfide, 3,
3′-diphenyl-4,4′-dihydroxydiphenyl sulfide, 3,3 ′, 5,5′-tetramethyl-4,
Bis (hydroxyaryl) sulfides such as 4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 3,3'-dimethyl-4,4 '
Bis (hydroxyaryl) sulfoxides such as -dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 3,3'-dimethyl-4,
Bis (hydroxyaryl) sulfones such as 4′-dihydroxydiphenylsulfone, 3,3′-diphenyl-4,4′-dihydroxydiphenylsulfone, and 3,3′-dichloro-4,4′-dihydroxydiphenylsulfone; Bis (hydroxyaryl) ketones such as 4-hydroxyphenyl) ketone and bis (3-methyl-4-hydroxyphenyl) ketone;

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-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,
Hydroquinone, resorcin and the like can be mentioned. Furthermore,
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. A particularly preferred aromatic dihydroxy compound is bisphenol A.

Examples of the carbonate precursor include carbonyl halide compounds, haloformate compounds, dialkyl carbonate compounds, diaryl carbonate compounds,
Alkyl aryl carbonate compounds can be mentioned, and preferred are carbonyl halide compounds and haloformate compounds. Examples of the carbonyl halide compound include carbonyl chloride, carbonyl bromide, carbonyl iodide, carbonyl fluoride, and mixtures thereof, which are usually called phosgene. Furthermore, phosgene dimer trichloromethylchloroformate and phosgene trimer bis (trichloromethyl)
Carbonates can also be used. As the haloformate compound, a mono- or bis-haloformate compound or an oligomeric mono- or bis-haloformate compound is used, and typically, a compound represented by the general formula (4) can be mentioned.

Z ′ — (OR—O—C (＝ O)) _n —O—R′—O—Z ′ (4) (wherein, Z ′ represents a hydrogen atom or a halocarbonyl group; At least one Z ′ 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 a mono- or bis-halo compound derived from an aliphatic dihydroxy compound. Formate compounds, mono- or bis-haloformate compounds derived from aromatic dihydroxy compounds, and oligomeric mono- or bis-haloformate compounds of these compounds. In the case of an oligomeric mono- or bishaloformate compound, the same molecule may have R 'groups having different structures in the same molecule. These haloformate compounds may be used alone or in combination of two or more, and further, may 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 formula (5). _{"4 -R -Ar" -OH (5} ) ( wherein HO-R, R "represents an alkylene group having 1 to 6 carbon atoms, A
r ₄ represents a divalent aromatic group having 6 to 12 carbon atoms) As the aliphatic dihydroxy compound, preferably, 2 to 2 carbon atoms are used.
Examples thereof include 20 dihydroxyalkanes, dihydroxycycloalkanes having 4 to 12 carbon atoms, and dihydroxy compounds represented by the general formula (5).

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,
Dihydroxyalkanes 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 ′ Dihydroxy compounds such as -hydroxypentyl) benzene and 1,4-bis (6'-hydroxyhexyl) benzene.

Examples of the aromatic dihydroxy compound include the aromatic dihydroxy compounds represented by the aforementioned general formula (2) or (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 an interfacial polymerization method, a carbonyl halide compound and / or a haloformate compound are preferably used as a carbonate precursor. Carbonate precursors can be gas, liquid,
It may be used in any solid state. When using a carbonyl halide compound, it is preferable to use a gaseous state or dissolved in an organic solvent to be used as an organic solvent solution, and when using a haloformate compound,
It is preferable to use a solid state or a solution in an organic solvent as an organic solvent solution.

When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method, a known method can be used. That is, 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 haloformate compound Is reacted in the presence of the compound represented by the general formula (1-A) to produce an aromatic polycarbonate, more preferably in the presence of a polycarbonate-forming catalyst.
When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method, as a carbonate precursor, for example,
When a carbonyl halide compound is used, the amount used is about 1.0 to the amount of the aromatic dihydroxy compound.
It is preferably used in an amount of about 1.3 to about 1.3 moles.

The organic solvent can be arbitrarily used as long as it is substantially insoluble in water and inert to the reaction and dissolves the aromatic polycarbonate. Preferred organic solvents include, for example, dichloromethane, chloroform, 1,2-dichloroethane, 1,2-
Aliphatic chlorinated hydrocarbon solvents such as dichloroethylene, trichloroethane, tetrachloroethane, dichloropropane, or chlorinated hydrocarbon solvents such as aromatic chlorinated hydrocarbon solvents such as chlorobenzene and dichlorobenzene, or mixtures thereof. No. Further, a mixed solvent of these chlorinated hydrocarbon solvents and aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene, or aliphatic hydrocarbon solvents such as hexane, heptane, and cyclohexane may be used. A particularly preferred organic solvent is dichloromethane. The amount of the organic solvent used is usually
When 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 about 3
It is preferable to use an organic solvent so as to be 5% by weight.

The amount of the organic solvent and water used in the reaction may be an amount necessary to maintain the reaction mixture in a substantially uniform emulsified state. , About 0.4 to about 1.5: 1. Examples of the alkali metal or alkaline earth metal base (hereinafter abbreviated as base) used in producing the aromatic polycarbonate of the present invention include sodium hydroxide, potassium hydroxide, and calcium hydroxide. . 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 before use in the reaction. In this case, a basic aqueous solution of an aromatic dihydroxy compound may be prepared by adding a reducing agent such as sodium sulfite, sodium hydrosulfite, or sodium borohydride as an antioxidant.

In the interfacial polymerization method, a polycarbonate forming catalyst (also referred to as a polymerization catalyst) optionally used is a tertiary amine, a quaternary ammonium salt, a tertiary phosphine, a quaternary phosphonium salt, or a nitrogen-containing heterocyclic ring. Examples include compounds and salts thereof, imino ethers and salts thereof, and compounds having an amide group. Preferably, a tertiary amine, for example, triethylamine, tri-n-
Propylamine, diethyl-n-propylamine, tri-n-butylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N-
Ethyl piperidine and the like. These polycarbonate forming catalysts can be used alone or in combination. The amount of the polycarbonate-forming catalyst used is about 0.0005 to about 5 moles of the aromatic dihydroxy compound.
About 1.5 mol% is preferred. The timing of adding the polycarbonate-forming 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 of the organic solvent used in the reaction to produce the aromatic polycarbonate of the present invention. The reaction is usually carried out under atmospheric pressure, but may be carried out under increased or reduced pressure, if desired.

In producing the aromatic polycarbonate of the present invention, a known solution polymerization method can be used. For example, it is possible to produce an aromatic dihydroxy compound, a carbonyl halide compound or / and a haloformate compound and a compound represented by the general formula (1-A) in a pyridine solution at about 0 to about 50 ° C. to produce the compound. it can. Using a dialkyl carbonate compound, an alkylaryl carbonate compound or / and a diaryl carbonate compound as a 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, pressure or reduced pressure, if necessary, with a transesterification catalyst (for example, metal oxide, metal hydroxide, In the presence of a metal carbonate or the like) by a known transesterification method.

The aromatic polycarbonate of the present invention comprises
If desired, by adding a branching agent during production,
It can 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
-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, -Hydroxyphthalic acid, 5-chlorocarbonyloxyphthalic acid, trimesic acid trichloride, cyanuric chloride, 3,3-bis (4'-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3,
3-bis (4'-hydroxy-3'-methylphenyl)
-2-oxo-2,3-dihydroindole and the like. These branching agents can be used alone or in combination. 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 used in an amount of about 0.05 to 2.0 mol% based on the aromatic dihydroxy compound. Is preferred.

Further, the aromatic polycarbonate of the present invention also includes an aromatic polyester carbonate, and at least one aromatic dihydroxy compound [for example, represented by the general formula (2) or (3)] Compound), carbonate precursor (for example, phosgene),
A divalent aromatic or aliphatic carboxylic acid or a halide derivative of the compound (for example, US Pat. No. 3,169,121)
Using the compound represented by the formula (1-A) and isophthalic acid, terephthalic acid, isophthalic dichloride, terephthalic dichloride, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid)
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. 896640). At this time, aromatic or aliphatic 2
The amount of the divalent carboxylic acid or carboxylic acid halide used is
It is preferable to use 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, usually, an organic solvent solution containing the aromatic polycarbonate is separated from an aqueous layer, and then substantially washed with water. After washing until the electrolyte disappears, 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, it is also possible to directly pelletize the aromatic polycarbonate melted under the production conditions or to process it into a molded product.

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

Further, the aromatic polycarbonate of the present invention includes, during or after the production of the aromatic polycarbonate,
In a known manner, dyes, pigments, heat stabilizers, antioxidants, hydrolysis stabilizers, ultraviolet absorbers, release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, sulfuric acid One or more of various additives such as barium and TiO ₂ may be added.

The aromatic polycarbonate of the present invention may be used alone or as a mixture with other polymers and, if desired, various additives may be added to the material to form a chassis or housing material for electric equipment, electronic parts, automobile parts, compact disks, etc. It can be formed into a substrate of an information recording medium, an optical material such as a lens of a camera or an eyeglass, a building material instead of a glass, and the like.
The aromatic polycarbonate of the present invention is thermoplastic,
Injection molding, extrusion molding, blow molding, impregnation into a filler or the like is possible, and molding can be easily performed by a known method. 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 formed into a film or the like.

[0043]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. The molecular weight of each aromatic polycarbonate produced in each of Examples and Comparative Examples was determined by GPC [gel permeation chromatography, Showa Denko KK
Manufactured by GPC System-11]. The glass transition point (Tg, ° C) was measured using a DSC (manufactured by Mac Science Corporation, DSC-3100) at a heating rate of 16 ° C / min. In order to examine the thermal hydrolysis resistance, a cast film (thickness: 30) of each aromatic polycarbonate was used.
μm) was immersed in hot water at 80 ° C. for 120 hours, the weight average molecular weight (Mw) thereof was measured, and before the test (before immersion)
Was determined from the following formula. The smaller the value, the more excellent the heat-resistant hydrolysis property.

Example 1 Production of Aromatic Polycarbonate Having Terminal Group of Example No. 1 A 10-liter baffled flask was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 912 g of bisphenol A (4.0 mol) and 45.7 g of 4- (triphenylmethyl) phenol (0.136 mol,
(3.4 mol% based on bisphenol A), 4 l of dichloromethane and 4 l of deionized water were added to form a suspension, and a nitrogen purge was performed to remove oxygen in the flask. Next, sodium hydrosulfite 1. was added to the suspension.
2 g and 432 g (10.8 mol) of sodium hydroxide
Then, 2.2 l of an aqueous solution in which was dissolved was supplied, and bisphenol A was dissolved at 15 ° C. 495 g of phosgene was added to this solution.
(5.0 mol) was fed in 60 minutes. The reaction temperature rose and reflux of dichloromethane was confirmed. After the supply of phosgene was completed, 0.64 g of triethylamine was added, and the reaction solution was further stirred for 90 minutes to carry out a polymerization reaction. Thereafter, the reaction solution was allowed to stand, the organic layer was separated, neutralized with hydrochloric acid, and washed with deionized water until the electrolyte was exhausted. To a dichloromethane solution of the obtained aromatic polycarbonate, 2 l of toluene and 5 l of water were added, and dichloromethane and toluene were distilled off by heating to 98 ° C.
An aromatic polycarbonate powder was obtained. The number average molecular weight of the obtained aromatic polycarbonate was 20,800, and the weight average molecular weight was 5,1200. Tg was 144 ° C. The reduction rate of Mw was 0.6%.

Example 2 Production of an aromatic polycarbonate having a terminal group of Exemplification No. 2 In Example 1, instead of using 4- (triphenylmethyl) phenol, 4- (triphenylmethyl)-
Except for using 56.1 g of 2-methylphenylchloroformate (3.4 mol% based on bisphenol A),
An aromatic polycarbonate was produced in the same manner as in Example 1. The number average molecular weight of the obtained aromatic polycarbonate was 20,800, and the weight average molecular weight was 51,000.
Tg was 144 ° C. The reduction rate of Mw was 0.5%.

Example 3 Production of an aromatic polycarbonate having a terminal group of Exemplified No. 6 In Example 1, instead of using 4- (triphenylmethyl) phenol, 4- [phenylbis (4'-te
rt-butylphenyl) methyl] phenol 60.9 g
(3.4 mol% based on bisphenol A), and an aromatic polycarbonate was produced in the same manner as in Example 1. The number average molecular weight of the obtained aromatic polycarbonate was 20,800, and the weight average molecular weight was 51,000. Tg was 143 ° C. Mw reduction rate is 0.6
%Met.

Example 4 Production of an aromatic polycarbonate having a terminal group of Exemplification No. 10 In Example 1, instead of using 4- (triphenylmethyl) phenol, 4- [tris (4'-tert-butylphenyl) Methyl] phenol was used in the same manner as in Example 1 except that 68.5 g (3.4 mol% based on bisphenol A) was used to produce an aromatic polycarbonate. The number average molecular weight of the obtained aromatic polycarbonate was 21,900 and the weight average molecular weight was 53400. T
g was 142 ° C. The reduction rate of Mw was 0.5%.

Comparative Example 1 For comparison, in Example 1, instead of using 4- (triphenylmethyl) phenol, 20.4 g of p-tert-butylphenol (3.
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 4 mol%) was used. The number average molecular weight of the obtained aromatic polycarbonate was 21,000, and the weight average molecular weight was 51,000. Tg was 148 ° C.
The reduction rate of Mw was 4.7%.

Comparative Example 2 For comparison, in Example 1, 26.4 g of pn-hexyloxyphenol (3.4 mol% based on bisphenol A) instead of using 4- (triphenylmethyl) phenol. Aromatic polycarbonate was produced in the same manner as in Example 1 except for using. The number average molecular weight of the obtained aromatic polycarbonate was 20,800, and the weight average molecular weight was 51,300. Tg was 136 ° C. The reduction rate of Mw was 4.5%. From the examples and the comparative examples, it was found that the aromatic polycarbonate of the present invention is superior in heat resistance to hydrolysis as compared with an aromatic polycarbonate produced using a known terminal blocking agent.

[0050]

According to the present invention, it has become possible to provide an aromatic polycarbonate excellent in heat hydrolysis resistance.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Satoshi Morikawa (56) References JP-A-6-287293 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (1)

(57) [Claims] 1. An aromatic polycarbonate wherein at least one of the terminal groups is a group represented by the general formula (1). (Wherein R1, R2 and R3 represent an aryl group,
X1 and X2 represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and among R1, R2 and R3,
Excluding the case where two or more have an alkoxy group . )