JPH0782361A - Aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To obtain an aromatic polycarbonate having excellent melt flow. CONSTITUTION:The aromatic polycarbonate is a polycarbonate at least one of whose terminals is a group of the formula (wherein R is alkyl or aralkyl; and p is an integer of 1-8).

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, an end capping agent (also called a molecular weight regulator or a chain terminator) is added for the purpose of controlling the molecular weight of the aromatic polycarbonate produced. Polymerization has been done (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 end-capping agent has a very high melt viscosity and poor melt fluidity, it has a sufficient fluidity when producing a molded article. In order to secure the temperature, 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.

Recently, aromatic polycarbonates having excellent melt fluidity are used in the field where precision workability required for substrates for optical devices such as data storage discs or audio compact discs is required. Is needed. C _m H _{2m + 1} as the end sealant
-X (however, m represents an integer of 8 to 20, and X represents -COO.
A method for producing an aromatic polycarbonate by using a chain-like aliphatic carboxylic acid derivative represented by H or —COCl etc.) as a terminal blocking agent has been proposed (JP-A-51-34992). ). However, the melt flowability of an aromatic polycarbonate produced by using these carboxylic acid derivatives (for example, n-capryl chloride) as an endcapping agent is not sufficient. Further, a chain-like aliphatic carboxylic acid represented by R ₁ COX ′ (provided that R ₁ represents a branched alkyl group having 4 to 7 carbon atoms and X ′ represents a halogen or a hydroxyl group) as a terminal blocking agent. Aromatic polycarbonates using acid derivatives are known (Japanese Patent Application Laid-Open No. Sho 5)
9-4645). However, the melt fluidity of an aromatic polycarbonate produced by using such a carboxylic acid derivative (for example, isovaleryl chloride) as an end capping agent is not sufficient. At present, there is a strong demand for aromatic polycarbonates having excellent melt fluidity.

[0005]

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.

[0006]

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).

[0007]

[Chemical 2] (In the formula, R is an alkyl group or an aralkyl group, and p is 1
In the group represented by the general formula (1) according to the present invention, R represents an alkyl group or an aralkyl group, and the aryl group in the aralkyl group further has 1 carbon atom.
It may be mono-substituted or poly-substituted with an alkyl group having 8 to 8, an alkoxy group having 1 to 8 carbons, or a halogen atom. Preferably, R is an alkyl group having 1 to 16 carbon atoms or an aralkyl group having 7 to 16 carbon atoms in total, and more preferably an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms in total. .

Specific examples of R include, for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, neopentyl group Group, n-
Hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 2-methylhexyl group, 2,4- Dimethylpentyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 5
-Methylheptyl group, 2-ethylhexyl group, 1,3-
Dimethylhexyl group, n-nonyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 3,7-dimethyloctyl group, n-
Undecyl group, n-dodecyl group, n-tridecyl group, n
-Tetradecyl group, n-pentadecyl group, n-hexadecyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, 4-methylcyclohexyl group , 3-ethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 3,3,5
-Trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4-n-hexylcyclohexyl group, benzyl group, phenethyl group, α-methylbenzyl group, 4-
Examples thereof include a methylbenzyl group, a 3-methylbenzyl group, a 2-methylbenzyl group, a 4-methoxybenzyl group, a 4-chlorobenzyl group, a 3-chlorobenzyl group and a 2-chlorobenzyl group, but are not limited thereto. Not something.

In the general formula (1), p represents an integer of 1-8, preferably 1-6. At least one of the terminal groups of the present invention is a compound represented by the general formula (1-A) (Chemical Formula 3) as a suitable compound used for producing an aromatic polycarbonate having a group represented by the general formula (1). Mention may be made of the compounds represented.

[0010]

[Chemical 3] (In the formula, R and p have the same meanings as described above, and Y is -C.
OOH group, -COOM group, -COOZ group, M represents a metal ion, and Z represents a halogen atom).
In the compound represented by —A), Y is a —COOH group,
Represents a -COOM group or a -COOZ group, M represents a metal ion, Z represents a halogen atom, and M is preferably a monovalent or divalent alkali metal ion or alkaline earth metal ion, Specific examples thereof include lithium ion, sodium ion, potassium ion, and calcium ion, and Z is preferably
Fluorine atom, chlorine atom, bromine atom can be mentioned,
More preferably, it is a chlorine atom.

Some of the compounds represented by the general formula (1-A) are commercially available and can be produced by known methods. For example, the general formula (1-
In A), the compound in which Y is a —COOH group and p is 1 can be produced by reacting chloroacetic acid with an alcohol in the presence of a base. Further, in the compound represented by the general formula (1-A), in which Y is a —COOZ group, for example, a compound in which Z is a chlorine atom is Y
Can be produced by reacting a compound in which is a —COOH group with, for example, thionyl chloride or oxalyl chloride. In the general formula (1-A), Y is -C.
The compound represented by the OOM group is produced by reacting a compound in which Y is a -COOH group with an alkali metal base such as sodium hydroxide, potassium hydroxide or calcium hydroxide or an alkaline earth base in an aqueous solution. can do.

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 shown below. Examples thereof include groups, but of course, the present invention is not limited thereto. Example number 1. Methoxymethylcarbonyl group 2. Ethoxymethylcarbonyl group 3. Isopropoxymethylcarbonyl group 4. n-butoxymethylcarbonyl group 5. n-hexyloxymethylcarbonyl group 6. Cyclohexyloxymethylcarbonyl group 7. (2-Cyclohexylethyl) oxymethylcarbonyl group 8. n-heptyloxymethylcarbonyl group 9. n-octyloxymethylcarbonyl group 10. n-decyloxymethylcarbonyl group 11. n-dodecyloxymethylcarbonyl group 12. n-hexadecyloxymethylcarbonyl group 13. Benzyloxymethylcarbonyl group 14. 2-methoxyethylcarbonyl group 15. 2-ethoxyethylcarbonyl group

16. 2-n-butoxyethylcarbonyl group 17. 2- (2'-ethylhexyloxy) ethylcarbonyl group 18. 2-n-decyloxyethylcarbonyl group 19. 3-ethoxypropylcarbonyl group 20. 3-n-pentyloxypropyl carbonyl group 21. 4-isopropoxybutylcarbonyl group 22. 4-n-pentyloxybutyl carbonyl group 23. 4-cycloheptyloxybutylcarbonyl group 24. 4- (4'-methylbenzyl) oxybutylcarbonyl group 25. 5-methoxypentylcarbonyl group 26. 5-isobutoxypentylcarbonyl group 27. 5-n-heptyloxypentylcarbonyl group 28. 6-Ethoxyhexylcarbonyl group 29. 6-n-butoxyhexylcarbonyl group 30. 6-n-decyloxyhexylcarbonyl group 31. 6- (4'-methoxybenzyl) oxyhexylcarbonyl group 32. 7-Methoxyheptylcarbonyl group 33. 8-Ethoxyoctylcarbonyl group 34. 8- (4'-chlorobenzyl) oxyoctylcarbonyl 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 Tech-nology "vol.10, Polycarbonate, Interscien
ce Publishing, p.710-764 (1969), H. Schnell, "Chemis
try and Physics of Polycarbonate ", Interscience Pu
The method described in b-lishing, p.33-41 (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. . In the production of the novel aromatic polycarbonate having a terminal group of the present invention, the compound represented by the general formula (1-A) acts as an end-capping agent, and the aromatic polycarbonate is produced in the production process of the aromatic polycarbonate of the present invention. Helps control or adjust the molecular weight of the group polycarbonate. The end capping agent and the aromatic dihydroxy compound form an ester 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 end-capping agent represented by the general formula (1-A) is generally used in the reaction of an aromatic dihydroxy compound with a carbonate precursor first, that is, prior to the addition of the carbonate precursor. It may be present together with the dihydroxy compound, or it may be sequentially and continuously supplied with the addition of the carbonate precursor. In the production of the aromatic polycarbonate of the present invention, the compound represented by the general formula (1-A) can 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%
The above is more preferable.

Examples of the end capping agent other than the compound represented by the general formula (1-A) include a monovalent hydroxyaromatic compound, a monovalent hydroxyaromatic compound haloformate derivative, and a monovalent carboxyl group. 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, pn-octylphenol, p-isooctylphenol, pn- Nonylphenol,
2,4-xylenol, p-methoxyphenol, p-
n-hexyloxyphenol, pn-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-
Phenols such as (2 ′, 4 ′, 4′-trimethylchromanyl) phenol and 2- (4′-methoxyphenyl) -2- (4 ″ -hydroxyphenyl) propane.
Examples of the monovalent hydroxyaromatic compound haloformate derivative include the monovalent hydroxyaromatic compound haloformate derivatives described above.

As the compound having a monovalent carboxyl group, 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-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 benzyl benzoic acid and p-chlorobenzoic acid. As the monovalent carbonyl halide derivative,
Examples thereof include halide derivatives of the above-mentioned 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 compound having a monovalent carboxyl group.
Salts and alkaline earth metal (eg, calcium) salts can also be used as endcapping agents.

The amount of the end-capping agent used can be changed according to the average molecular weight of the desired aromatic polycarbonate. In the present invention, the compound represented by the general formula (1-A) is used alone or in combination, or is used in combination with another known end-capping agent, and is represented by the general formula (1-A). When the compound 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 generally such that the average molecular weight of aromatic polycarbonate decreases as the amount of end-capping agent used increases, and the amount of end-capping agent used decreases. Along with this, the average molecular weight tends to increase. The aromatic polycarbonate of the present invention,
Although an arbitrary molecular weight can be obtained depending on the amount of the end-capping agent used, when considering physical properties such as moldability, heat resistance, and mechanical strength of the aromatic polycarbonate produced, it is about 15
A weight average molecular weight of 000 to about 150,000 is preferred, and a weight average molecular weight of about 20,000 to about 100,000 is more 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 for producing the aromatic polycarbonate of the present invention include compounds represented by the general formula (2) or the general formula (3). HO-Ar ₁ -W-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 W is 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, or one is p-phenylene group and one is m-phenylene group or o-phenylene group. Preferably, Ar ₁
It is particularly preferred that both and Ar ₂ are p-phenylene groups. Ar ₃ is a p-phenylene group, m-phenylene group or o-phenylene group, and preferably a p-phenylene group or m-phenylene group. W is Ar ₁ and Ar ₂
A linking group that binds a single bond or a divalent hydrocarbon group, and further -O-, -S-, -SO-, -SO.
It may be a group containing atoms other than carbon and hydrogen, such as _2- and -CO-. 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. ,Also,
It may be a hydrocarbon group containing an aromatic group or other unsaturated hydrocarbon group.

Specific examples of the aromatic dihydroxy compound include, for example, bis (4-hydroxyphenyl) methane,
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-3,3-bis (4'-hydroxyphenyl) butane, 2,2-bis (4 Bis (hydroxyaryl) alkanes such as'-hydroxyphenyl) hexafluoropropane,

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (3'-methyl-4'-hydroxyphenyl) cyclohexane , 1,1
-Bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) cyclohexane, 1,1-bis (3', 5'-dichloro-4'-hydroxyphenyl) cyclohexane,
1,1-bis (4′-hydroxyphenyl) -4-methylcyclohexane, 1,1-bis (4′-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4′-hydroxyphenyl) cycloheptane, 1,1-bis (4′-hydroxyphenyl) cyclooctane, 1,1-bis (4′-hydroxyphenyl) cyclononane, 1,1-bis ( 4'-hydroxyphenyl) cyclododecane, 2,2-bis (4'-hydroxyphenyl) norbornane, 8,8-bis (4'-hydroxyphenyl) tricyclo [5.2.1.0 ^2.6]
Decane, bis (hydroxyaryl) cycloalkanes such as 2,2-bis (4′-hydroxyphenyl) adamantane, 4,4′-dihydroxydiphenyl ether,
Bis (hydroxyaryl) ethers such as 3,3′-dimethyl-4,4′-dihydroxydiphenyl ether and ethylene glycol bis (4-hydroxyphenyl) ether,

4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dicyclohexyl-
4,4'-dihydroxydiphenyl sulfide, 3,
3'-diphenyl-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetramethyl-4,
Bis (hydroxyaryl) sulfides such as 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-
Bis (hydroxyaryl) sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 3,3′-dimethyl-
4,4'-dihydroxydiphenyl sulfone, 3,3 '
-Bis (hydroxyaryl) sulfones such as diphenyl-4,4'-dihydroxydiphenylsulfone and 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) ketone, bis (3- Bis (hydroxyaryl) ketones such as 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. 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. A particularly preferred aromatic dihydroxy compound is bisphenol A.

As the carbonate precursor, a carbonyl halide compound, a haloformate compound, a dialkyl carbonate compound, a diaryl carbonate compound,
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 typical examples thereof include compounds represented by the general formulas (4) and (Formula 4). .

[0027]

[Chemical 4] (In the formula, Z ′ represents a hydrogen atom or a halocarbonyl group, and at least one Z ′ is a halocarbonyl group,
R'represents a divalent aliphatic group or aromatic group, and n represents 0 or a positive integer)

The compound represented by the general formula (4) is a mono- or bishaloformate compound derived from an aliphatic dihydroxy compound, a mono- or bishaloformate compound derived from an aromatic dihydroxy compound, and these compounds. It is an oligomeric mono- or bishaloformate compound of the compound. In the case of an oligomeric mono- or bishaloformate compound, R ′ groups having different structures may be contained in the same molecule. These haloformate compounds may be used alone or in combination of two or more, and may also 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 preferably has 2 to 2 carbon atoms.
Examples thereof include 20 dihydroxy alkanes, C 4-12 dihydroxy cycloalkanes, 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, 1,1
2-dodecanediol, neopentyl glycol, 2-
Ethyl-1,6-hexanediol, 2-methyl-1,
Dihydroxyalkane such as 3-propanediol, 1,
Dihydroxycycloalkanes such as 3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane and 2,2-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, 1,4 Examples thereof include dihydroxy compounds such as 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. Carbonate precursors are gases, liquids,
It may be used in any solid state. When using a carbonyl halide compound, 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 preferable to use it as a solution in an organic solvent by dissolving it in a solid state or in an organic solvent.

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, 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 allowed to act in the presence of a compound represented by the general formula (1-A) to produce an aromatic polycarbonate, more preferably a method of producing in the presence of a polycarbonate-forming catalyst.
When producing the aromatic polycarbonate of the present invention by an interfacial polymerization method, as a carbonate precursor, for example,
When the carbonyl halide compound is used, the amount thereof is about 1.0 to the amount of the aromatic dihydroxy compound.
It is preferred to use about 1.3 times the molar amount.

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 organic solvent used is usually
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 preferably used so as to be 5% by weight. The amount of the organic solvent and water used in the reaction may be any amount required to maintain the substantially homogeneous emulsified state of the reaction mixture, and the volume ratio of the water relative organic phase is usually about 0. .4 to about 1.
It is preferably 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. be able to. 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, a reducing agent such as sodium sulfite, sodium hydrosulfite, or sodium borohydride 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 generation catalysts can be used alone or in combination. The amount of the polycarbonate-forming catalyst used is about 0.0005 to the mole number of the aromatic dihydroxy compound.
About 1.5 mol% is preferred. 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 about 1.
It is preferable to produce the aromatic polycarbonate of the present invention at 0 ° C to the boiling temperature of the organic solvent used for the reaction. The reaction is usually carried out under atmospheric pressure, but if desired, it may be carried out under pressure or under reduced pressure. Further, when 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 or / and a haloformate compound and a compound represented by the general formula (1-A) can be produced by reacting at about 0 to about 50 ° C. When the aromatic polycarbonate of the present invention is produced using a dialkyl carbonate compound, an alkylaryl carbonate compound or / and a diaryl carbonate compound as the carbonate precursor, a dialkyl carbonate compound,
A mixture of an alkylaryl carbonate compound or / and a diaryl carbonate compound, an aromatic dihydroxy compound and a compound represented by the general formula (1-A),
At a temperature of about 60 to about 300 ° C., under normal pressure, under pressure or under reduced pressure, optionally in the presence of a transesterification catalyst (eg, metal oxide, metal hydroxide, metal carbonate, etc.),
It can be produced by a known transesterification method.

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-chlorocarbonyloxyphthalic 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 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 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, 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. 897640). At this time, aromatic or aliphatic 2
The amount of carboxylic acid or carboxylic acid halide used is
It is preferable to use about 30 to 80 mol% with respect to 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, the organic solvent solution containing the aromatic polycarbonate is separated from the aqueous layer and then washed with water to substantially eliminate the electrolyte. After the washing, 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 another aromatic polycarbonate or another 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, during or after the production of the aromatic polycarbonate, by a known method, a dye, a pigment, a heat stabilizer,
Antioxidant, hydrolysis stabilizer, ultraviolet absorber, release agent,
Organic halogen compounds, alkali metal sulfonates, glass fibers, carbon fibers, glass beads, barium sulfate, Ti
One or more kinds of various additives such as O 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 equipment, electronic parts, automobile parts, compact discs and the like. 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,
Injection molding, extrusion molding, blow molding, impregnation with a filler and the like are possible, and molding can be easily performed 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.

[0041]

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 measured by GPC [gel permeation chromatography, 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. 4 End Group A 3-liter, six-blade stirrer and a reflux condenser were attached to a 10-liter baffled flask. Into this flask, 912 g (4.0 mol) of bisphenol A, 18.0 g of n-butoxyacetic acid (0.136 mol, 3.4 mol% based on bisphenol A), 4 l of dichloromethane and 4 l of deionized water were added and suspended. As a liquid, nitrogen purging was performed to remove oxygen in the flask. Next, 2.2 l of 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.
Was added to dissolve bisphenol A at 15 ° C. 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 dichloromethane solution of aromatic polycarbonate, 2 l of toluene and 5 l of water were added, and the mixture was heated to 98 ° C to distill off dichloromethane and toluene to obtain a powder of aromatic polycarbonate. The obtained aromatic polycarbonate had a number average molecular weight of 20,800 and a weight average molecular weight of 5,1200.
Tg was 142 ° C. and MI was 16.5.

Example 2 Preparation of Aromatic Polycarbonate having an Exemplification No. 6 In Example 1, instead of using 4-n-butoxyacetic acid, 21.5 g of cyclohexyloxyacetic acid (3.4 with respect to bisphenol A) was used. Aromatic polycarbonate was produced in the same manner as in Example 1 except that (mol%) was used.
The number average molecular weight of the obtained aromatic polycarbonate is 20.
800, the weight average molecular weight was 50,800. Tg was 143 ° C and MI was 17.8.

Example 3 Preparation of Aromatic Polycarbonate Having an End Group of Exemplification No. 13 Instead of using 4-n-butoxyacetic acid in Example 1, 25.1 g of benzyloxyacetic acid chloride (3. 4 mol%) except that
An aromatic polycarbonate was produced in the same manner as in Example 1. The obtained aromatic polycarbonate had a number average molecular weight of 20,700 and a weight average molecular weight of 51,000. T
g was 143 ° C. and MI was 16.5.

Example 4 Preparation of Aromatic Polycarbonate having End Group No. 15 In Example 1, instead of using 4-n-butoxyacetic acid, 18.6 g of 3-ethoxypropionic acid chloride was used.
An aromatic polycarbonate was produced in the same manner as in Example 1 except that (3.4 mol% based on bisphenol A) was used. The obtained aromatic polycarbonate had a number average molecular weight of 21,000 and a weight average molecular weight of 5,1200. Tg was 143 ° C and MI was 16.2.

Example 5 Preparation of Aromatic Polycarbonate Having an End Number of Exemplified No. 25 Instead of using 4-n-butoxyacetic acid in Example 1, 19.9 g of 6-methoxyhexanoic acid (3 relative to bisphenol A) Aromatic polycarbonate was produced in the same manner as in Example 1 except that 0.4 mol%) was used. The number average molecular weight of the obtained aromatic polycarbonate was 210.
00, the weight average molecular weight was 51300. Tg is 1
It was 41 degreeC and MI was 18.2.

Example 6 Preparation of Aromatic Polycarbonate having an End Number of Exemplified No. 29 Instead of using 4-n-butoxyacetic acid in Example 1, 27.5 g of 7-n-butoxyheptanoic acid (based on bisphenol A) was used. The aromatic polycarbonate was produced in the same manner as in Example 1 except that the amount of the aromatic polycarbonate was 3.4 mol%. The obtained aromatic polycarbonate had a number average molecular weight of 20,900 and a weight average molecular weight of 51,100. T
g was 140 ° C. and MI was 21.6.

COMPARATIVE EXAMPLE 1 For comparison, in Example 1, instead of using 4-n-butoxyacetic acid, p-tert-butylphenol 20.
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 4 g (3.4 mol% based on bisphenol A) was used. The obtained aromatic polycarbonate had a number average molecular weight of 21,000 and a weight average molecular weight of 51,000. Tg was 148 ° C and MI was 13.0.

Comparative Example 2 For comparison, instead of using 4-n-butoxyacetic acid in Example 1, 25.9 g of n-capryl chloride was used.
An aromatic polycarbonate was produced in the same manner as in Example 1 except that (3.4 mol% based on bisphenol A) 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 was 139 ° C and MI was 14.2.

Comparative Example 3 For comparison, instead of using 4-n-butoxyacetic acid in Example 1, 16.4 g of isovaleryl chloride was used.
An aromatic polycarbonate was produced in the same manner as in Example 1 except that (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 50,800. Tg was 146 ° C and MI was 5.4. From the 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 using a known end-capping agent.

[0051]

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 (1)

[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 is an alkyl group or an aralkyl group, and p is 1
~ Represents an integer of 8)