JP3220567B2 - 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 and electronic materials, and the like. Usually, when producing an aromatic polycarbonate,
For the purpose of controlling the molecular weight of the aromatic polycarbonate to be produced, a terminal blocking agent (also referred to as a molecular weight controlling agent, a polymerization terminator, a chain terminator, a terminal terminator, etc.) is added to carry out polymerization ( For example, US Pat. No. 3,028,365
issue). Among them, phenol or 4-tert-butylphenol is most generally and widely used as a terminal blocking agent. In addition, in order to maintain the excellent characteristics of the aromatic polycarbonate and further improve the toughness, heat resistance, fluidity, and the like, various reforming methods have been conventionally studied. For example, the modification of an aromatic polycarbonate by blending the aromatic polycarbonate with another polymer or other filler. In this method, at the time of blending, the most important issue is the compatibility of the blend materials. That is, if there is a difficulty in compatibility, a uniform dispersion state is not formed, and the heat resistance of the molded article is reduced, and further, the molded article often has distortion, unevenness, layering, and the like,
This causes a decrease in strength and poor appearance.

[0003] As a terminal blocking agent, phenol or 4-
Aromatic polycarbonates produced using tert-butylphenol have good compatibility with relatively polar polymers such as polyesters, but have relatively poor compatibility with relatively non-polar polymers such as polystyrene. Has difficulties. Therefore, when such an aromatic polycarbonate and polystyrene are blended, various compatibilizers and the like are blended to increase the compatibility. However, since the blend of the aromatic polycarbonate and polystyrene is a simple mixture type, the resulting composition is not always satisfactory in physical properties or processing.

[0004] As another modification method, there is a modification method by copolymerization of an aromatic polycarbonate with another polymer or monomer. In this method, an aromatic polycarbonate having a reactive group (for example, a hydroxy group or an unsaturated hydrocarbon group) in a molecular chain is used. For example, as an end capping agent, 1 having an unsaturated hydrocarbon bond
Aromatic polycarbonates produced using a monovalent hydroxy compound or a carbonic acid derivative thereof, or a monovalent aliphatic carboxylic acid chloride having an unsaturated hydrocarbon bond are known to undergo addition polymerization with various vinyl compounds. (JP-B-48-25076). However, the aromatic polycarbonate described in the publication is a residue in which the molecular chain terminal is derived from a monovalent aliphatic hydroxy compound or a carbonic acid derivative thereof, or an aliphatic carboxylic acid, and the heat resistance of the aromatic polycarbonate ( Glass transition point (Tg) is low.

[0005] JP-B-48-25076 also discloses an aromatic polycarbonate having a residue derived from vinyl phenol at a molecular chain terminal. However, vinyl phenol, which is a terminal blocking agent used in producing the aromatic polycarbonate, has an extremely high reactivity of a vinyl group, and thus has a problem that the reaction mixture gels during the aromatic polycarbonate production reaction. It was difficult to stably produce an aromatic polycarbonate having a residue derived from vinyl phenol at the molecular chain terminal. At present, there is a strong demand for an aromatic polycarbonate which can be produced stably and has an unsaturated hydrocarbon group as a reactive group at the molecular chain terminal.

[0006]

An object of the present invention is to provide a new aromatic polycarbonate having an unsaturated hydrocarbon group at the terminal of the molecular chain, which solves the above-mentioned problems.

[0007]

Means for Solving the Problems The present inventors have made intensive studies on aromatic polycarbonates, and as a result, have reached the present invention. That is, in the present invention, at least one of the terminal groups has a structure represented by the general formula (1) or the general formula (2)
It relates to an aromatic polycarbonate which is a group represented by

[0008]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom or an alkyl group, and Ar represents a divalent aromatic group, provided that all of R _{1 to} R ₅ are hydrogen. In the case of an atom, Ar does not become an unsubstituted phenylene group)

[0009]

Embedded image (Wherein, R ₆ , R ₇ and R ₈ represent a hydrogen atom or an alkyl group, and Ar ′ represents a divalent aromatic group.
₇ and R ₈ are not hydrogen atoms at the same time)

In the group represented by the general formula (1),
R₁, R_Two, R_Three, R_FourAnd R_FiveIs a hydrogen atom or
Represents an alkyl group, preferably a hydrogen atom or carbon number
Represents an alkyl group of 1 to 4. Also, R₁, R_Two, R_Three,
R_FourAnd R_FiveCan be the same or different
It may be. Smell represented by general formula (2)
And R₆, R₇And R₈Is a hydrogen atom or an alkyl
And preferably represents a hydrogen atom or a group having 1 to 4 carbon atoms.
Represents an alkyl group. Also, R₆, R₇And R₈Is
Each may be the same or different
No. Where R₇And R₈Simultaneously become hydrogen atoms
There is no. R ₁~ R₈As a specific example of the alkyl group represented by
For example, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec-
Butyl group and the like.

In the groups represented by the general formulas (1) and (2), Ar and Ar ′ represent a divalent aromatic group. The divalent aromatic group refers to an optionally substituted 2
A phenylene group which may have a substituent or a phenylene group which may have a substituent 2
Represents a valent fused polycyclic aromatic group. More preferably, a 1,2-phenylene group which may have a substituent, 1,3-
Represents a phenylene group or a 1,4-phenylene group. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom, and preferably include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, and a bromine atom. . Specific examples of the above substituents include
For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy Group, sec
-A butoxy group, a fluorine atom, a chlorine atom, a bromine atom and the like.

In the groups represented by the general formulas (1) and (2), the divalent aromatic groups represented by Ar and Ar ′ may be monosubstituted by the above-mentioned substituents. It may be polysubstituted. In the group represented by the general formula (1), when all of R _{1 to} R ₅ are hydrogen atoms, A
r does not become an unsubstituted phenylene group. Further, in the groups represented by the general formulas (1) and (2),
When R ₄ and R ₅ , and R ₇ and R ₈ are different groups, the configuration of the double bond may be either cis- or trans-form, or may be a mixture of cis- and trans-forms. In producing the aromatic polycarbonate of the present invention in which at least one of the terminal groups is a group represented by the general formula (1) or (2), a preferred terminal blocking agent includes a compound represented by the general formula (1- A) (Formula 5) or the general formula (2-A)
The compound represented by (Chem. 5) can be mentioned.

[0013]

Embedded image (Wherein, R _{1 to} R ₈ , Ar and Ar ′ represent the same meaning as described above, and W represents an —OH group, a —OM group, a —OCOZ group, a —C
An OOH group, a -COOM group or a -COZ group, M represents a metal ion, and Z represents a halogen atom.

Formulas (1-A) and (2-A)
In the compound represented by, W is an —OH group, —OM
Represents a group, —OCOZ group, —COOH group, —COOM group or —COZ group, M represents a metal ion, and Z represents a halogen atom. M is preferably an alkali metal ion or a 1/2 equivalent alkaline earth metal ion, and specific examples thereof include a lithium ion, a sodium ion, a potassium ion, and a calcium ion. Z is
Preferably a fluorine atom, a chlorine atom, a bromine atom,
More preferably, it is a chlorine atom.

Formulas (1-A) and (2-A)
In the above, some of the compounds in which W is represented by an —OH group or —COOH group are commercially available, and can be obtained by known methods, for example, Beilstein 4th supplementary volume, 6th edition.
Volume, p.3771-3970, 6313-6375, Volume 9, p.2051-214
2, Volume 10, pages 1034 to 1039, etc. For example, in the general formula (1-A), W is an —OH group, and Ar is 3-methyl-1,4-
A compound which is a phenylene group and all of R _{1 to} R ₅ are hydrogen atoms is obtained by adding 3-methylphenol [“m-cresol”] and 2-propenyl chloride [“allyl chloride”] in an aqueous sodium hydroxide solution. It can be manufactured by acting. Further, for example, in the general formula (2-A), W is an —OH group, and Ar ′ is 2
-Ethoxy-1,4-phenylene, R ₆ and R ₇ are hydrogen atoms, and R ₈ is a methyl group is 1,2-diethoxy-4- (trans-1′-propenyl) benzene With methylmagnesium iodide.

Formulas (1-A) and (2-A)
In the compounds in which W is represented by an —OCOZ group, for example, a compound in which Z is a chlorine atom,
The compound can be produced by, for example, allowing phosgene to act on a compound that is a group. In the general formulas (1-A) and (2-A), among compounds in which W is represented by a —COZ group, for example, a compound in which Z is a chlorine atom is represented by W
Is a -COOH group, for example, by reacting with thionyl chloride or oxalyl chloride. Further, the general formula (1-A) and the general formula (2-
In A), compounds in which W is a -OM or -COOM group include compounds in which W is a -OH or -COOH group, for example, sodium hydroxide, potassium hydroxide, and calcium hydroxide in an aqueous solution. And alkali metal bases or alkaline earth metal bases.

At least one of the terminal groups has the general formula (1)
Alternatively, in the aromatic polycarbonate of the present invention, which is a group represented by the general formula (2), as the group represented by the general formula (1) or (2), the following groups are typically given. However, the present invention is of course not limited to these. In the following groups, when a geometric isomer is present, the configuration of the double bond includes any of the cis and trans geometric isomers. Illustrative number 1.2- (2'-propenyl) -4-ethylphenyl group 2.2- (2'-propenyl) -6-sec-butylphenyl group 3.2- (2'-propenyl) -3,5 , 6-trimethylphenyl group 4.2- (2'-propenyl) -4-isopropoxyphenyl group 5.2- (2'-propenyl) -6-methoxyphenyl group 6.2- (2'-propenyl)- 4-bromophenyl group 7.2- (2'-propenyl) -4,6-dichlorophenyl group 8.2- (2'-propenyl) -6-ethoxy-4-methylphenyl group 9.2- (2'- Propenyl) -3-chloro-6-methoxyphenyl group 10.2- (2′-propenyl) -4,5,6-trichloro-3-methoxyphenyl group

11.2- (1'-methyl-2'-propenyl) -4-methylphenyl group 12.2- (1'-methyl-2'-propenyl) -4,
6-dimethylphenyl group 13.2- (1′-methyl-2′-propenyl) -6
Methoxyphenyl group 14.2- (1 ', 1'-dimethyl-2'-propenyl) phenyl group 15.2- (2'-methyl-2'-propenyl) phenyl group 16.2- (2'-methyl- 2'-propenyl) -4-
Methoxyphenyl group 17.2- (2'-butenyl) phenyl group 18.3- (2'-propenyl) -2-methoxyphenyl group 19.3- (2'-propenyl) -4-methoxyphenyl group 20.3 -(2'-propenyl) -6-n-propoxyphenyl group 21.4- (2'-propenyl) -3-methylphenyl group 22.4- (2'-propenyl) -2-methoxyphenyl group 23.4 -(2'-propenyl) -2,6-dimethylphenyl group 24.4- (1'-methyl-2'-propenyl) -2,
6-dimethylphenyl group 25.4- (1′-methyl-2′-butenyl) -2,6
-Dimethylphenyl group 26.4- (2'-methyl-2'-propenyl) phenyl group 27.4- (2'-butenyl) -2,6-dimethylphenyl group 28.4- (2'-butenyl) phenyl Group 29.4- (3'-methyl-2'-butenyl) phenyl group 30.4- (2'-pentenyl) -2,6-dimethylphenyl group

31.4- (3'-methyl-2'-pentenyl) phenyl group 32.2- (1'-propenyl) phenyl group 33.2- (1'-propenyl) -4-methylphenyl group 2- (1'-propenyl) -3,5-dimethylphenyl group 35.2- (1'-propenyl) -4-methoxyphenyl group 36.2- (1'-propenyl) -4-isopropoxyphenyl group 37 .2- (1'-propenyl) -6-methoxyphenyl group 38.2- (1'-propenyl) -3,4,6-trichlorophenyl group 39.2- (1'-propenyl) -6-ethoxy- 4-
Methylphenyl group 40.2- (1'-butenyl) phenyl group 41.2- (1'-ethyl-1'-propenyl) phenyl group 42.2- (1'-isopropyl-2'-methyl-1 '
-Propenyl) phenyl group 43.2- (2'-methyl-1'-propenyl) phenyl group 44.3- (1'-propenyl) -4-methoxyphenyl group 45.3- (1'-propenyl) -6 -Ethoxyphenyl group 46.3- (1'-propenyl) -6-n-butoxyphenyl group 47.4- (1'-propenyl) phenyl group 48.4- (1'-propenyl) -2-methoxyphenyl group 49.4- (1'-propenyl) -2-ethoxyphenyl group 50.4- (1'-propenyl) -2-n-propoxyphenyl group 51.4- (1'-propenyl) -2-n-butoxy Phenyl group 52.4- (1'-butenyl) phenyl group 53.4- (3'-methyl-1'-butenyl) phenyl group

The aromatic polycarbonate of the present invention is produced from at least one aromatic dihydroxy compound, a carbonate precursor and at least one compound represented by the general formula (1-A) or the general formula (2-A). can do. As a manufacturing method, for example, "Encyclopedi
a of Polymer Science and Technology ", vol.10," Poly
carbonate ", Interscience Publishing, p.710-725 (196
9), H. Schnell, "Chemistry and Physics of Polycarbo
nate ", Interscience Publishing, p31-51 (1964), for example, an interfacial polymerization method, a solution polymerization method, and a transesterification method, and the interfacial polymerization method and the solution polymerization method are preferred production methods. It is.

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, a carbonyl halide as a carbonate precursor in a two-phase mixed solvent of at least one aromatic dihydroxy compound, an alkali metal base or an alkaline earth metal base, water and an organic solvent substantially insoluble in water. A compound or / and a haloformate compound is optionally added to a polycarbonate-forming catalyst (for example, a tertiary amine in the presence of at least one compound represented by the general formula (1-A) or the general formula (2-A)). Quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, or nitrogen-containing heterocyclic compounds and salts thereof,
And a compound having an amide group) to produce an aromatic polycarbonate.

In producing the aromatic polycarbonate of the present invention, a known solution polymerization method can be used. For example, in a pyridine solution, an aromatic dihydroxy compound, a carbonyl halide compound and / or a haloformate compound as a carbonate precursor, and a compound represented by the general formula (1-A) or the general formula (2-A) By operating at 0 to about 50 ° C., an aromatic polycarbonate can be produced. Furthermore,
When producing the aromatic polycarbonate of the present invention,
Known transesterification methods can also be used. For example, an aromatic dihydroxy compound, a carbonate compound (for example, diphenyl carbonate) as a carbonate precursor, and a compound represented by the general formula (1-A) or the general formula (2-
A mixture of the compounds represented by A) is treated at about 60 to about 300 ° C.
At normal pressure, under pressure or under reduced pressure, if necessary, in the presence of a transesterification catalyst (eg, metal oxide, metal hydroxide, metal carbonate, etc.),
Aromatic polycarbonate can be produced.

In producing the aromatic polycarbonate of the present invention, the compound represented by the general formula (1-A) or (2-A) acts as a terminal blocking agent, Helps to adjust the molecular weight of The terminal blocking agent and the aromatic dihydroxy compound are combined with the general formula (1) of the present invention by the action of a carbonate precursor.
Alternatively, an aromatic polycarbonate having a terminal group represented by the general formula (2) is produced. In producing the aromatic polycarbonate of the present invention by an interfacial polymerization method or a solution polymerization method, the compound represented by the general formula (1-A) or the general formula (2-A) can act at any time. . That is, in the reaction of the aromatic dihydroxy compound and the carbonate precursor, it may be present together with the aromatic dihydroxy compound first, that is, before the carbonate precursor is acted on, or the aromatic dihydroxy compound and the carbonate precursor may be present. It may act during or after the reaction. Further, with the progress of the reaction between the aromatic dihydroxy compound and the carbonate precursor, the compound represented by the general formula (1-A) or the general formula (2-A) can be successively and continuously applied.

In producing the aromatic polycarbonate of the present invention, the compounds represented by formula (1-A) or (2-A) may be used alone or in combination. Furthermore, the general formula (1-A) or the general formula (2
The compound represented by -A) can be used in combination with other known terminal blocking agents as long as the 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) or the general formula (2-A) in all the terminal blocking agents is 30 mol% or more. It is more preferably 60 mol% or more. Examples of the known terminal blocking agent include a monovalent aromatic hydroxy compound, a haloformate derivative of a monovalent aromatic hydroxy compound, a carboxylic acid halide derivative of a monovalent carboxylic acid and a monovalent carboxylic acid, and the like. .

As the monovalent aromatic hydroxy compound,
For example, phenol, 4-cresol, 2-ethylphenol, 4-ethylphenol, 4-isopropylphenol, 4-tert-butylphenol, 4-cumylphenol, 4-cyclohexylphenol, 4-n-octylphenol, 4-isooctylphenol , 4-n
-Nonylphenol, 2,4-xylenol, 4-methoxyphenol, 4-n-hexyloxyphenol,
4-n-decyloxyphenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol,
-Bromophenol, pentabromophenol, pentachlorophenol, 4-phenylphenol, 2,4-
Di (1-methyl-1-phenylethyl) phenol, β
Naphthol, α-naphthol, 4- (2 ′, 4 ′,
4′-trimethylchromanyl) phenol, 2- (4 ′
And phenols such as -methoxyphenyl) -2- (4 "-hydroxyphenyl) propane. Examples of the haloformate derivative of the monovalent aromatic hydroxy compound include, for example, the haloformate derivative of the above-described monovalent aromatic hydroxy compound. (For example, chloroformate derivatives, bromoformate derivatives, etc.).

Examples of the monovalent carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid,
-Methylbutyric acid, 3,3-dimethylbutyric acid, 4-methylvaleric acid, 3,3-dimethylvaleric acid, 4-methylcaproic acid,
Fatty acids such as 2,4-dimethylvaleric acid, 3,5-dimethylcaproic acid and phenoxyacetic acid, benzoic acid, 4-methylbenzoic acid, 4-tert-butylbenzoic acid, 4-n-propyloxybenzoic acid, -N-butoxybenzoic acid, 4-
Benzoic acids such as n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-phenylbenzoic acid, 4-benzylbenzoic acid and 4-chlorobenzoic acid are exemplified.
Examples of the carboxylic acid halide derivative of a monovalent carboxylic acid include the above-mentioned carboxylic acid halide derivatives of a monovalent carboxylic acid (for example, carboxylic acid chloride derivatives, carboxylic acid bromide derivatives, and the like). In addition, alkali metal (for example, lithium, sodium, potassium) salt or alkaline earth metal (for example, calcium) salt of the above-mentioned monovalent aromatic hydroxy compound or monovalent carboxylic acid can also be used as a terminal blocking agent.

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) or the general formula (2-A) is used alone, or two or more of them are used together, or used together with another known terminal blocking agent. However, when the terminal capping agents having different structures are used in combination, the total number of moles of the terminal capping agents is used as the amount of the terminal capping agent. In general, the average molecular weight of the aromatic polycarbonate decreases with an increase in the amount of the terminal capping agent, and the amount of the terminal capping agent decreases between the amount of the terminal capping agent and the average molecular weight of the aromatic polycarbonate. There is a tendency that the average molecular weight increases with the decrease in the molecular weight. The aromatic polycarbonate of the present invention can have an arbitrary molecular weight depending on the amount of the terminal blocking agent used, but in consideration of the moldability, heat resistance, and physical properties such as mechanical strength of the produced aromatic polycarbonate, Preferably, the weight average molecular weight is from about 15,000 to about 150,000, and from about 20,000 to about 10
More preferably, the weight average molecular weight is 0000.
The amount of the terminal blocking agent required to produce an aromatic polycarbonate having a weight average molecular weight in the above range is about 1 to about 1 based on the amount of the aromatic dihydroxy compound used.
It is preferably 0 mol%, and more preferably about 1.5 to about 7.0 mol%.

The aromatic dihydroxy compound used for producing the aromatic polycarbonate of the present invention may be a compound represented by the following general formula (3) or (4). HO-Ar ₁ -X-Ar ₂ -OH (3) HO-Ar ₃ -OH (4) (wherein, Ar ₁ , Ar ₂ and Ar ₃ represent a divalent aromatic group, and X represents Ar ₁ and Ar ₂ represents a linking group linking) the general formula (3) and general formula (4), Ar _1, Ar ₂
And Ar ₃ each represent a divalent aromatic group, and are preferably a phenylene group which may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, a halogen atom, and a nitro group.

In the general formula (3), Ar ₁ and Ar ₂ each represent a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group, each of which may have a substituent; Alternatively, one of the 1,4-, which may have a substituent
A phenylene group, one of which is preferably a 1,3-phenylene group or a 1,2-phenylene group which may have a substituent, and both Ar ₁ and Ar ₂ have a substituent. Particularly preferred is a 1,4-phenylene group. In the general formula (4), Ar ₃ is preferably an optionally substituted 1,4-phenylene group, 1,3-phenylene group or 1,2-phenylene group, and has a substituent. 1,4-phenylene group or 1,
More preferably, it is a 3-phenylene group. In the general formula (3), X is a linking group linking Ar ₁ and Ar ₂ , and is a single bond or a divalent hydrocarbon group, and furthermore, —
O -, - S -, - SO -, - SO 2 -, - it may be a group containing atoms other than carbon and hydrogen CO- like. The divalent hydrocarbon group includes a saturated hydrocarbon group, for example, an alkylidene group such as a methylene group, an ethylene group, a 2,2-propylidene group, and a cyclohexylidene group. Further, a hydrocarbon group substituted with an aryl group or the like is also included, and further,
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"], 1,1-bis (4'-hydroxyphenyl) butane, 1,3-bis (4'-hydroxyphenyl) -3-methylbutane , 2- (4'-hydroxyphenyl) -2- (3'-hydroxyphenyl) propane, 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'-hydroxy Phenyl) 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-3,3-bis (4'-hydroxyphenyl) butane,
Bis (hydroxyaryl) alkanes such as 2,2-bis (4′-hydroxyphenyl) hexafluoropropane,

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (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,
Bis (hydroxyaryl) sulfoxides such as 4'-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) -1,4-xylene,
α, α, α ′, α′-tetramethyl-α, α′-bis (4′-hydroxyphenyl) -1,3-xylene,
3,3-bis (4-hydroxyphenyl) phthalide,
4,4′-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,
Examples thereof include 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, hydroquinone, and resorcin. Further, for example, an aromatic dihydroxy compound containing an ester bond 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 of two or more.
Particularly preferably used aromatic dihydroxy compound,
Bisphenol A.

Examples of the carbonate precursor include a carbonyl halide compound, a haloformate compound, and a carbonate compound. As the carbonyl halide compound, carbonyl chloride called phosgene is usually used, but a carbonyl halide compound derived from a halogen other than chlorine, for example, carbonyl bromide, carbonyl iodide, carbonyl fluoride, or a mixture thereof May be used. Further, a compound having an ability to form a haloformate group, for example, trichloromethylchloroformate which is a dimer of phosgene or bis (trichloromethyl) carbonate which is a trimer of phosgene may be used. Preference is given to using phosgene. As the haloformate compound, a mono- or bis-haloformate compound or an oligomeric mono- or bis-haloformate compound is used, and typically, the compound represented by the general formula (5) can be mentioned. X ′-(OR′-OC (＝ O)) _n —OR′-OX ′ (5) (wherein, X ′ represents a hydrogen atom or a halocarbonyl group, and at least one X ′ 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 (5) includes a mono- or bishaloformate compound derived from an aliphatic dihydroxy compound, a mono- or bishaloformate compound derived from an aromatic dihydroxy compound, and An oligomeric mono- or bis-haloformate compound of the compound. In the general formula (5), R ′ is a divalent group derived from an aliphatic dihydroxy compound or an aromatic dihydroxy compound. Examples of the aliphatic dihydroxy compound for deriving an aliphatic group to R ′ in the general formula (5) include a dihydroxyalkane, a dihydroxycycloalkane, and a compound represented by the general formula (6). _{"4 -R -Ar" -OH (6} ) ( 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)

Preferred are dihydroxyalkanes having 2 to 20 carbon atoms, dihydroxycycloalkanes having 4 to 12 carbon atoms, and dihydroxy compounds represented by the general formula (6). Specific examples 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, neo Pentyl glycol, 2-ethyl-1,6-hexanediol,
Dihydroxyalkanes such as 2-methyl-1,3-propanediol, 1,3-dihydroxycyclohexane,
Dihydroxycycloalkanes such as 1,4-dihydroxycyclohexane and 2,2-bis (4′-hydroxycyclohexyl) propane, 1,2-bis (hydroxymethyl) benzene, 1,3-bis (hydroxymethyl) benzene, 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.

As the aromatic dihydroxy compound for deriving an aromatic group to R ′ in the general formula (5), the aromatic dihydroxy compound represented by the aforementioned general formula (3) or (4) (for example, , Bisphenol A, hydroquinone, etc.). In the case of an oligomeric mono- or bishaloformate compound,
The same molecule may have R ′ groups having different structures.
These haloformate compounds can be used alone,
Alternatively, a plurality of them may be used in combination, and further, it may be used in combination with a carbonyl halide compound.

As the carbonate compound, a dialkyl carbonate compound, an alkylaryl carbonate compound, a diaryl carbonate compound, a bisalkyl carbonate derivative of an aromatic dihydroxy compound, an alkyl aryl carbonate derivative, and a bisaryl carbonate derivative are used. Examples of the dialkyl carbonate compound, alkylaryl carbonate compound, diaryl carbonate compound include dimethyl carbonate, methylphenyl carbonate, diphenyl carbonate, and an alkyl group, a halogen atom, and a bis (substituted phenyl) carbonate having a substituent such as a nitro group [for example, Bis (4-methylphenyl) carbonate,
Bis (4-chlorophenyl) carbonate, bis (4-
Nitrophenyl) carbonate, etc.]. Examples of the bisalkyl carbonate derivative, alkylaryl carbonate derivative, and bisaryl carbonate derivative of the aromatic dihydroxy compound include, for example, the aromatic dihydroxy compound represented by the general formula (3) or (4) described above (for example, A bismethyl carbonate derivative such as bisphenol A and hydroquinone), a methylphenyl carbonate derivative, a bisphenyl carbonate derivative, and a bis (substituted phenyl) carbonate derivative having a substituent such as an alkyl group, a halogen atom, or a nitro group [for example, bis (4- Methylphenyl) carbonate derivative, bis (4-chlorophenyl) carbonate derivative, bis (4-nitrophenyl) carbonate derivative, etc.]. These carbonate compounds are:
They may be used alone or in combination.

The aromatic polycarbonate of the present invention can be converted into a branched aromatic polycarbonate by adding a branching agent at the time of production, if desired.
As a branching agent, a phenolic hydroxy group, a haloformate group, a carboxyl group, a carbonyl halide group,
Compounds having three or more active halogen atoms are exemplified. 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, 1,4-bis (4 ', 4 "-dihydroxytriphenylmethyl) benzene, 3,3', 5,5'-tetrahydroxydiphenyl ether, trimesic acid trichloride, cyanuric chloride, 3,3- Screw (4 '
-Hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3,3-bis (4'-hydroxy-3 '
-Methylphenyl) -2-oxo-2,3-dihydroindole and the like. The amount of 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 includes an aromatic polyester carbonate, and at least one aromatic dihydroxy compound [for example, represented by the general formula (3) or (4)] Compound), carbonate precursor (for example, phosgene),
Aromatic or aliphatic divalent carboxylic acids or carboxylic acid halide derivatives of divalent carboxylic acids (for example, isophthalic acid, terephthalic acid, isophthalic dichloride, terephthalic dichloride, adipic acid described in U.S. Pat. No. 3,169,121); Pimelic acid, suberic acid, azelaic acid, sebacic acid), an acid binder and a compound represented by the general formula (1-
A) or a compound represented by the general formula (2-A),
Aromatic polyester carbonates can be produced by known methods, for example, the methods described in U.S. Pat. No. 3,169,121, U.S. Pat. No. 4,156,069, and U.K. Pat. At this time, the amount of the aromatic or aliphatic divalent carboxylic acid or the carboxylic acid halide derivative of the divalent carboxylic acid used is preferably about 30 to 80 mol% based on the aromatic dihydroxy compound.

The aromatic polycarbonate of the present invention may be used during or after the production of the aromatic polycarbonate for the purpose of imparting light resistance, weather resistance, flame retardancy, mold release and other properties during processing. In a known manner, dyes, pigments,
Various additives such as antioxidants, ultraviolet absorbers, release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, barium sulfate, and TiO ₂ may be added. The aromatic polycarbonate of the present invention may be used alone or mixed with other aromatic polycarbonates or other polymers, and further, if desired, various additives may be added thereto, for example, chassis and housing materials for electric equipment, electronic components, automobiles, and the like. It can be formed into parts, substrates for information recording media such as compact disks, optical materials such as lenses for cameras and glasses, building materials in place of glass, and the like.
The aromatic polycarbonate of the present invention is thermoplastic,
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 a cast film can be produced from a solution of the aromatic polycarbonate in an organic solvent. Since the aromatic polycarbonate of the present invention can be produced by a known method, industrialization is extremely easy. In addition, the aromatic polycarbonate of the present invention maintains the excellent characteristics of the aromatic polycarbonate produced using phenol or 4-tert-butylphenol as a terminal blocking agent, and furthermore, has a reactive activity on the molecular chain terminal. Since it is an aromatic polycarbonate having an unsaturated hydrocarbon group as a functional group, it can be used as a raw material of a block copolymer using an unsaturated hydrocarbon group.

[0043]

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. In addition, the molecular weight of each aromatic polycarbonate produced in each Example was GPC [gel permeation chromatography, manufactured by Showa Denko KK, GPC system-1.
1]. In addition, the glass transition point (T
g, ° C.) is DSC [manufactured by Mac Science Co., Ltd.,
SC-3100], and the heating rate was measured at 16 ° C./min.

Example 1 Preparation of Aromatic Polycarbonate Having Terminal Group No. 22 A 10-liter baffled flask was equipped with a three-stage six-blade stirrer and a reflux condenser. In this flask, 912 g (4.0 mol) of bisphenol A and 22.3 g (0.136 mol, bisphenol A) of 4- (2′-propenyl) -2-methoxyphenol [“eugenol”] were added.
3.4 mol%), 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, an aqueous solution in which 1.2 g of sodium hydrosulfite and 432 g (10.8 mol) of sodium hydroxide were dissolved in the above suspension.
2 liters were fed and bisphenol A was dissolved at 15 ° C.
To this solution was added 495 g (5.0 mol) of phosgene in 8.2.
It was fed at a rate of 5 g / min. The reaction temperature rose to 39 ° C., 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 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 the dichloromethane solution of the aromatic polycarbonate thus obtained, 2 l of toluene and 5 l of water were added, and 9
By heating to 8 ° C., dichloromethane and toluene were distilled off to obtain an aromatic polycarbonate powder.
The number average molecular weight of the obtained aromatic polycarbonate is 20.
800 and the weight average molecular weight was 51,000. The glass transition point was 150 ° C.

Example 2 Preparation of an aromatic polycarbonate having a terminal group of Exemplification No. 26 In Example 1, instead of using 4- (2'-propenyl) -2-methoxyphenol, 4- (2'-methyl- 2'-propenyl) benzoic acid chloride 26.4 g
An aromatic polycarbonate was produced according to the method described in Example 1, except that (3.4 mol% based on bisphenol A) was used. The number average molecular weight of the obtained aromatic polycarbonate was 21,100, and the weight average molecular weight was 5130.
It was 0. The glass transition point was 149 ° C.

Example 3 Preparation of Aromatic Polycarbonate Having Terminal Group No. 32 In Example 1, instead of using 4- (2'-propenyl) -2-methoxyphenol 2- (2'-propenyl) phenol , 2- (1′-propenyl) benzoic acid chloride (cis, trans mixture) 24.5 g (3.4 mol% based on bisphenol A)
An aromatic polycarbonate was produced according to the method described in Example 1. The number average molecular weight of the obtained aromatic polycarbonate was 21,000, and the weight average molecular weight was 51,500. The glass transition point was 149 ° C.

Example 4 Preparation of Aromatic Polycarbonate Having Terminal Group No. 45 In Example 1, instead of using 4- (2'-propenyl) -2-methoxyphenol, 3- (trans-
1′-propenyl) -6-ethoxyphenol [“propenyl guaetol”] 24.2 g (bisphenol A
, Based on the method described in Example 1, except that 3.4 mol%) was used.
The number average molecular weight of the obtained aromatic polycarbonate is 20.
800 and the weight average molecular weight was 51200. The glass transition point was 150 ° C.

Example 5 Preparation of an aromatic polycarbonate having a terminal group of Ex. No. 48 In Example 1, 4- (1′-propenyl) was used instead of using 4- (2′-propenyl) -2-methoxyphenol. Aromatic polycarbonate was prepared according to the method described in Example 1 except that 22.3 g (3.4 mol% based on bisphenol A) of 2-methoxyphenol (a mixture of cis and trans) [“isoeugenol”] was used. Manufactured. The number average molecular weight of the obtained aromatic polycarbonate was 20,900, and the weight average molecular weight was 5,1600. The glass transition point was 150 ° C.

[0049]

According to the present invention, it has become possible to stably produce an aromatic polycarbonate having an unsaturated hydrocarbon group as a reactive group at the molecular chain terminal.

──────────────────────────────────────────────────続 き Continuation of 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-5-140441 (JP, A) JP-A-63-15821 (JP, A) JP-B-48-25076 (JP, B1) (58) Fields investigated (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) or (2). Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom or an alkyl group, and Ar represents a divalent aromatic group, provided that all of R _{1 to} R ₅ are hydrogen. In the case of an atom, Ar does not become an unsubstituted phenylene group. (Wherein, R ₆ , R ₇ and R ₈ represent a hydrogen atom or an alkyl group, and Ar ′ represents a divalent aromatic group.
₇ and R ₈ are not hydrogen atoms at the same time)