JP3162493B2 - Aromatic polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to aromatic polycarbonates, and more particularly to branched aromatic polycarbonates.

[0002]

2. Description of the Related Art Aromatic polycarbonate has transparency comparable to that of glass, and combines outstanding impact resistance with excellent properties such as heat resistance, flame retardancy, electrical properties, dimensional stability, and weather resistance. It is an engineering plastic that has been widely used at present. Aromatic polycarbonates are usually industrially inexpensive and readily available 2,2-bis (4'-hydroxyphenyl) propane [also known as bisphenol A]
And the like, and a carbonate precursor such as phosgene, and is a linear polymer in which the aromatic dihydroxy compounds are bonded to each other by a carbonate bond. These linear aromatic polycarbonates differ from most other thermoplastic polymers in melt flow properties.

Most thermoplastic polymers exhibit non-Newtonian flow properties over almost all melt processing conditions (Newtonian flow is defined as the type of flow that occurs in a liquid system where the shear rate is directly proportional to the shear stress). . However, in contrast to most thermoplastic polymers, linear aromatic polycarbonates made from aromatic dihydroxy compounds behave as Newtonian fluids in the molten state at normal processing temperatures and therefore have a defined extrusion volume. However, there is a problem that it is difficult to produce a large hollow molded body by a blow molding method due to a large stress required for obtaining the same, and a low melt elasticity or a low melt strength. Melt elasticity is the strain of molecules due to shear stress applied during blow molding, or the elastic energy stored in the melt that recovers from alignment, and the melt strength is easy to explain as the strength of the molten strand, Both of these properties demonstrate the ability of the melt to support stresses, both of which are extruded, especially in extrusion blow molding. It is an important factor in the case of).

[0004] On the other hand, thermoplastic, randomly branched aromatic polycarbonates exhibit non-Newtonian flow properties, have excellent melt elasticity and melt strength, and, due to such properties, have a linear shape. It is known that aromatic polycarbonates are suitable as materials for producing hollow molded articles such as bottles which are not easily produced. It is known that a branched aromatic polycarbonate having such properties is derived from a trivalent or tetravalent phenol compound, an aromatic dihydroxy compound and a carbonate precursor (US Pat. No. 27,682). . US Pat. No. Re. 27,682 discloses several trivalent or tetravalent phenol compounds, such as 1,1,
1-tris (4′-hydroxyphenyl) ethane is disclosed to be a useful branching agent for making branched polycarbonates. Although the branched aromatic polycarbonate using the trivalent phenol compound as a branching agent shows improved flow characteristics in a molten state, it is obtained more efficiently than a linear aromatic polycarbonate produced from ordinary bisphenol A. There are some problems such as the hue of the resin to be obtained and the transparency of the molded article being inferior. At present, there has been a strong demand for an aromatic polycarbonate which has improved melting characteristics and improved hue, which has improved these problems.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate which has good melting properties, is suitable as a material for blow molding, and has a good hue.

[0006]

Means for Solving the Problems In order to meet the above-mentioned demands, the present inventors have made intensive studies on aromatic polycarbonates, and as a result, have reached the present invention. That is, the present invention relates to a branched aromatic polycarbonate derived from at least one of an aromatic dihydroxy compound, a carbonate precursor and a phenol compound represented by the general formula (1).

[0007]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group, and X ₁ and X ₂ represent a single bond, an alkylene group , Represents an oxygen atom or a sulfur atom)

The phenolic compound represented by the general formula (1) according to the present invention has an effect as a branching component. Preferred compounds are those represented by the general formula (1-a):
Compounds represented by (1-b) and (1-c) (Formula 4) can be exemplified.

[0009]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group, and X ₁ and X ₂ represent a single bond, an alkylene group , Represents an oxygen atom or a sulfur atom)

In the general formulas (1-a) to (1-c),
The substitution position of each hydroxyl group is preferably an ortho position, a meta position, or a para position with respect to X ₁ or X ₂ , and the substituents R _{1 to} R
The substitution position of ₆ is an ortho position to X ₁ or X ₂ ,
The meta or para position is preferred. R ₁ , R ₂ , R
₃ , R ₄ , R ₅ and R ₆ are a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkoxy group or an aryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl Group, tert-octyl group, cyclohexyl group and the like can be mentioned as specific examples.

As the alkoxy group, an alkoxy group having 1 to 8 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-
Propoxy group, n-butoxy group, isobutoxy group, n-
Specific examples include a pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, and an n-octyloxy group. As the aryl group, a phenyl group,
Examples include a naphthyl group, a phenyl group having a substituent or a naphthyl group having a substituent, and examples of the substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, and a phenyl group. And the like. More preferred R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R
₆ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a phenyl group, and a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are Are particularly preferred.

In the compound represented by the general formula (1) according to the present invention, X ₁ and X ₂ represent a single bond, an alkylene group,
Represents an oxygen atom or a sulfur atom. As the alkylene group, an alkylene group having 1 to 8 carbon atoms is preferable, and a methylene group, a 1,1-ethylidene group, a 1,2-ethylene group,
3-propylene group, 2,2-propylidene group, 1,4-
Butylene, 2,2-butylidene, 1,5-pentylidene, 3,3-pentylidene, 2,2-isopentylidene, 1,6-hexylene, 2,2-isohexylidene, 1,7 Specific examples include -heptylene group, 1,8-octylene group, 1,1-cyclopentylidene group, 1,1-cyclohexylidene group and the like. Particularly preferably, X ₁ and X ₂ are a single bond, a methylene group, a 2,2-propylidene group, an oxygen atom or a sulfur atom. Representative specific examples of the compound represented by the general formula (1) according to the present invention include the following compounds, but of course, the present invention is not limited thereto.

Exemplary Compound No. Compound 1 1. 1,2-dihydroxy-3,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 2. 1,2-dihydroxy-3,6-bis [α-methyl-α- (3′-hydroxyphenyl) ethyl] benzene, 3. 1,2-dihydroxy-3,6-bis [(2'-hydroxy-5'-tert-butylphenyl) methyl] benzene; 4. 1,2-dihydroxy-3,6-bis [(2'-hydroxy-3 ', 5'-dimethylphenyl) methyl] benzene; 5. 1,2-dihydroxy-3,6-bis [(2'-hydroxy-5'-ethoxyphenyl) methyl] benzene, 6. 1,2-dihydroxy-3,6-bis [(2'-hydroxy-5'-phenylphenyl) methyl] benzene, 7. 1,2-dihydroxy-3,6-bis [(2'-hydroxy-5'-chlorophenyl) methyl] benzene; 8. 1,3-dihydroxy-4,6-bis [(3'-methoxy-4'-hydroxyphenyl) methyl] benzene, 9. 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,3-dihydroxy-4,6-bis [α-methyl-α- (3′-hydroxyphenyl) ethyl] benzene,

[0014] 11. 11. 1,3-dihydroxy-4,6-bis [α-methyl-α- (3′-ethyl-4′-hydroxyphenyl) ethyl] benzene, 12. 1,3-dihydroxy-4,6-bis [α-methyl-α- (3′-isopropyl-4′-hydroxyphenyl) ethyl] benzene, 13. 1,3-dihydroxy-4,6-bis [α-methyl-α- (3′-cyclohexyl-4′-hydroxyphenyl) ethyl] benzene; 14. 1,3-dihydroxy-4,6-bis [α-methyl-α- (2′-methyl-4′-hydroxyphenyl) ethyl] benzene, 15. 1,3-dihydroxy-4,6-bis [α-methyl-α- (3 ′, 5′-dimethyl-4′-hydroxyphenyl) ethyl] benzene, 16. 1,3-dihydroxy-4,6-bis [α-methyl-α- (3′-fluoro-4′-hydroxyphenyl) ethyl] benzene, 17. 1,3-dihydroxy-4,6-bis [α-methyl-α- (3 ′, 5′-dichloro-4′-hydroxyphenyl) ethyl] benzene, 18. 1,3-dihydroxy-4,6-bis [α-methyl-α- (3′-phenyl-4′-hydroxyphenyl) ethyl] benzene; 1,3-dihydroxy-4- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -6- [α-methyl-α- (3′-methyl-4′-hydroxyphenyl) ethyl Benzene, 20. 1,3-dihydroxy-4- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -6- [α-methyl-α- (3′-chloro-4′-hydroxyphenyl) ethyl 〕benzene,

21. 1,3-dihydroxy-4- [α-methyl-α- (3′-chloro-4′-hydroxyphenyl) ethyl] -6- [α-methyl-α- (3′-methyl-4′-hydroxy 22. phenyl) ethyl] benzene; 22. 1,4-dihydroxy-2,5-bis (3'-hydroxyphenyl) benzene, 23. 1,4-dihydroxy-2,5-bis (2'-methyl-4'-hydroxyphenyl) benzene, 25. 1,4-dihydroxy-2,5-bis [(3 ', 5'-dimethyl-2'-hydroxyphenyl) methyl] benzene, 25. 1,4-dihydroxy-2,5-bis [(4'-hydroxyphenyl) methyl] benzene, 26. 1,4-dihydroxy-2,5-bis [(3'-hydroxyphenyl) methyl] benzene, 28. 1,4-dihydroxy-2,5-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 29. 1,4-dihydroxy-2,5-bis [α-methyl-α- (3′-hydroxyphenyl) ethyl] benzene, 29. 1,4-dihydroxy-2,5-bis [(4'-hydroxyphenyl) oxy] benzene, 30. 1,4-dihydroxy-2,5-bis [(3'-methyl-4'-hydroxyphenyl) oxy] benzene; 32. 1,4-dihydroxy-2,5-bis [(3'-chloro-4'-hydroxyphenyl) oxy] benzene; 1,4-dihydroxy-2,5-bis [(4'-hydroxyphenyl) thio] benzene,

The phenolic compound of the present invention represented by the general formula (1) can be produced by a method known per se. That is, for example, the compound of Exemplified Compound No. 4 (melting point: 227 ° C.) reacts with 1,2-dihydroxy-3,6-bis (hydroxymethyl) benzene and excess 2,4-dimethylphenol in the presence of hydrogen chloride. It can be manufactured by doing. The compound of Exemplified Compound No. 9 (melting point: 218 ° C.) can be produced by reacting about 2 mol of 4-isopropenylphenol with 1 mol of resorcinol in the presence of hydrogen chloride. The compound of Exemplified Compound No. 23 (melting point: 310 ° C.) was prepared from 1,4-benzoquinone 1 in concentrated sulfuric acid in the presence of aluminum chloride.
It can be produced by allowing about 2 mol of 3-methylphenol to act on the mol. The compound of Exemplified Compound No. 29 (melting point: 234 ° C.) is 2,5-bis (4 ′
-Hydroxyphenyloxy) -1,4-benzoquinone can be produced, for example, by treating with a reducing agent such as tin chloride.

The amount of the phenolic compound represented by the general formula (1) must be sufficient to produce a substantially branched aromatic polycarbonate. Usually, when the amount of the compound represented by the general formula (1) is less than 0.01 mol% based on the aromatic dihydroxy compound, the obtained aromatic polycarbonate is suitable for extrusion molding or extrusion blow molding in a molten state. On the other hand, if it does not show non-Newtonian behavior, on the other hand, if it exceeds 5 mol%, it is not preferable because gelation occurs during molding. For these reasons, the compound represented by the general formula (1) is preferably used in an amount of 0.01 to 5 mol%, preferably 0.02 to 3 mol%, based on the aromatic dihydroxy compound. More preferably, it is particularly preferably 0.03 to 2 mol%. One or more compounds represented by the general formula (1) can be used. The compound represented by the general formula (1) can be used in combination with another branching agent as long as the desired effect of the present invention is not impaired. In this case, the proportion of the compound represented by the general formula (1) according to the present invention in all the branching agents is preferably 50 mol% or more, more preferably 60 mol% or more, and 70 mol% or more. % Is particularly preferable.

Examples of the branching agent other than the compound represented by the general formula (1) which can be used in the present invention include, for example, three or more aromatic hydroxy groups, chloroformate groups, carboxylic acid groups, carboxylic acid chlorides. Compounds having groups or active halogen atoms can be mentioned. Specific examples include phloroglucinol, 1,1,4,4-tetrakis (4′-hydroxyphenyl) cyclohexane,
3,5-tris (4'-hydroxyphenyl) benzene, 1,1,2-tris (4'-hydroxyphenyl)
Propane, α, α, α ′, α′-tetrakis (4′-hydroxyphenyl) -1,4-diethylbenzene, 1-
Hydroxy-2,4-bis [α-methyl-α- (4′-
Hydroxyphenyl) ethyl] benzene, 2,2,5
5-tetrakis (4'-hydroxyphenyl) hexane, 1,1,2,3-tetrakis (4'-hydroxyphenyl) propane, 2- (4'-hydroxyphenyl)
-2- (2 ", 4" -dihydroxyphenyl) propane, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4, 6-tris (4′-hydroxyphenyl) heptane, 1,4-bis (4 ′, 4 ″ -dihydroxytriphenylmethyl) benzene, 3,3 ′, 5,5′-tetrahydroxydiphenyl ether, tris (4-hydroxy Phenyl) phosphine, 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.

The aromatic dihydroxy compound used in producing the aromatic polycarbonate compound of the present invention includes a compound represented by the general formula (2). HO-R-OH (2) (wherein, R is an aromatic hydrocarbon group, or a halogen atom,
A substituted aromatic hydrocarbon group having a substituent such as a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group or an alkoxy group) In the above general formula (2), R is preferably a group represented by the general formula (3) − Ar ¹ -X-Ar ^2- (3) (wherein, Ar ¹ and Ar ² are each a monocyclic divalent aromatic group,
X is a group linking Ar ¹ and Ar ² ). In the above general formula (3), Ar ¹ and Ar ² are
Each is a monocyclic divalent aromatic group, preferably a phenylene group or a substituted phenylene group having a substituent,
Examples of the substituent include a hydrocarbon group such as an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, a halogen, a nitro group, and an alkoxy group.

Ar ¹ and Ar ² are both p-phenylene groups, m
-A phenylene group or an o-phenylene group, or one is a p-phenylene group, and one is an m-phenylene group or an o-phenylene group, and particularly, both Ar ¹ and Ar ² are p-phenylene groups. Preferably it is. X
Is a group linking Ar ¹ and Ar ² , and is a single bond or a divalent hydrocarbon group, furthermore, —O—, —S—, and —SO
A group containing atoms other than carbon and hydrogen, such as —, —SO ₂ —, and —CO—, may also be used. 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. Alternatively, 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, 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”], 2- (4′-hydroxyphenyl) -2- (3′-hydroxyphenyl) propane, 2,2-bis (4′- (Hydroxyphenyl) butane, 1,1-bis (4′-hydroxyphenyl) isobutane, 2,2-bis (4′-hydroxyphenyl) octane, 2,2-bis (3′-methyl-4′-hydroxyphenyl) Propane, 2,2-bis (3′-ethyl-
4′-hydroxyphenyl) propane, 2,2-bis (3′-n-propyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-isopropyl-4′-hydroxyphenyl) propane, 2-bis (3'-se
c-butyl-4'-hydroxyphenyl) propane,
2,2-bis (3'-tert-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-cyclohexyl-4'-hydroxyphenyl) propane, 2,2-
Bis (3′-allyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-methoxy-4′-hydroxyphenyl) propane, 2,2-bis (3 ′, 5′-dimethyl-4 ′) -Hydroxyphenyl) propane, 2,2
-Bis (2 ', 3', 5 ', 6'-tetramethyl-4'
-Hydroxyphenyl) propane, 2,2-bis (3 ′
-Chloro-4'-hydroxyphenyl) propane, 2,
2-bis (3 ', 5'-dichloro-4'-hydroxyphenyl) propane, 2,2-bis (3'-bromo-4'
-Hydroxyphenyl) propane, 2,2-bis (3 ', 5'-dibromo-4'-hydroxyphenyl)
Propane, 2,2-bis (2 ′, 6′-dibromo-
3 ', 5'dimethyl-4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl) cyanomethane,
Bis (hydroxyaryl) alkanes such as 1-cyano-3,3-bis (4′-hydroxyphenyl) butane and 2,2-bis (4′-hydroxyphenyl) hexafluoropropane;

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (3'-methyl-4'-hydroxyphenyl) cyclohexane , 1,1
-Bis (4'-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4'-hydroxyphenyl) cycloheptane, 1,1-bis (4'-
Bis (hydroxyaryl) cycloalkanes such as hydroxyphenyl) cyclooctane and 2,2-bis (4′-hydroxyphenyl) adamantane, 4,4′-
Bis (hydroxyaryl) ethers such as dihydroxydiphenylether, 4,4'-dihydroxy-3,3'-dimethyldiphenylether, ethylene glycol bis (4-hydroxyphenyl) ether, 4,4'-
Dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide,
4,4'-dihydroxy-3,3'-dicyclohexyldiphenyl sulfide, 4,4'-dihydroxy-3,
Bis (hydroxyaryl) sulfides such as 3'-diphenyldiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-
Bis (hydroxyaryl) sulfoxides such as 3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-
Bis (hydroxyaryl) sulfones such as 3,3′-dimethyldiphenylsulfone; bis (hydroxyaryl) ketones such as bis (4-hydroxyphenyl) ketone and bis (4-hydroxy-3-methylphenyl) ketone;

Further, 6,6'-dihydroxy-3,
3,3 ′, 3′-tetramethylspiro (bis) indane [“spirobiindanebisphenol”], trans-
2,3-bis (4'-hydroxyphenyl) -2-butene, 9,9-bis (4'-hydroxyphenyl) fluorene, 3,3-bis (4'-hydroxyphenyl) -2
-Butanone, 1,6-bis (4'-hydroxyphenyl) -1,6-hexanedione, 1,1-dichloro-
2,2-bis (4′-hydroxyphenyl) ethylene,
1,1-dibromo-2,2-bis (4′-hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis (5′-phenoxy-4′-hydroxyphenyl) ethylene, α, α, α ', Α'-tetramethyl-α, α'-
Bis (4-hydroxyphenyl) -p-xylene, α,
α, α ′, α′-tetramethyl-α, α′-bis (4-
(Hydroxyphenyl) -m-xylene, 4,4′-dihydroxydiphenyl and the like. In addition to the above aromatic dihydroxy compounds, hydroquinone, resorcin, and the like are also used. These may be used alone or in combination of two or more. A particularly preferred aromatic dihydroxy compound is bisphenol A. Further, for example, bisphenols (aromatic dihydroxy compounds) containing an ester bond which can be produced by reacting 2 mol of bisphenol A with 1 mol of isophthaloyl chloride or terephthaloyl chloride are also useful.

In the present invention, the carbonate precursor includes a carbonyl halide, a haloformate compound,
Any of a dialkyl carbonate compound, a diaryl carbonate compound, and an alkyl aryl carbonate compound may be used. As the carbonyl halide,
Usually, carbonyl chloride called phosgene is used, but carbonyl halide derived from halogen other than chlorine, for example, carbonyl bromide, carbonyl iodide, carbonyl fluoride and the like, and 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 of an aromatic dihydroxy compound (for example, monochloroformate of bisphenol A, bischloroformate of hydroquinone, bischloroformate of bisphenol A, etc.) or an oligomeric aromatic compound Mono- or bis-haloformate compounds of group dihydroxy compounds and mixtures thereof. Dialkyl carbonate compounds, diaryl carbonate compounds, alkylaryl carbonate compounds include dimethyl carbonate, diphenyl carbonate,
Examples include methylphenyl carbonate, diphenyl carbonate substituted with a halogen atom, a nitro group and the like, and a mixture thereof.

In the present invention, the amount of the carbonyl halide compound used is preferably about 1.0 to about 1.3 times the molar amount of the aromatic dihydroxy compound. The use of an extremely small amount of the carbonyl halide compound less than 1.0 mole results in the production of an unreacted aromatic dihydroxy compound, which is a factor of producing an aromatic polycarbonate having a poor color tone. Also, the use of an excessive amount of the carbonyl halide compound more than 1.3-fold mol results in the production of a large amount of an oligomer terminated with a haloformate terminal group,
As a result, the ratio of the haloformate terminal group to the OH group (or phenolate group) of the oligomer in the reaction system becomes excessive in the haloformate terminal group. It is not preferable because an aromatic polycarbonate is formed. The carbonyl halide compound is a gas,
It may be supplied in any state of a liquid and a solution. For example,
When the carbonyl halide compound is phosgene, it is preferably supplied in a gaseous state, but may be dissolved in an organic solvent such as dichloromethane and supplied in an organic solvent solution.

As a method for producing the aromatic polycarbonate of the present invention, a known interfacial polymerization method or transesterification method can be used. In particular, the interfacial polymerization method is a preferable production method. When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method, a carbonyl halide and / or a haloformate compound is preferably used as a carbonate precursor. When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method,
A known method for producing a linear aromatic polycarbonate can be used. For example, an aqueous solution of an aromatic dihydroxy is prepared from at least one aromatic dihydroxy compound and an alkali metal or alkaline earth metal base and water, and is contacted with a carbonyl halide compound such as phosgene in the presence of an organic solvent to form a wire. And the like. The branched aromatic polycarbonate of the present invention can be obtained by, at any point in the above-mentioned method for producing a linear aromatic polycarbonate, a compound represented by the general formula (1): It can be produced by adding a phenol compound or an alkali metal or alkaline earth metal salt thereof.

The organic solvent used for producing the aromatic polycarbonate of the present invention may be any one which is substantially insoluble in water, inert to the reaction, and dissolves the aromatic polycarbonate. Can be used arbitrarily. For example, chlorinated hydrocarbons such as aliphatic chlorinated products such as dichloromethane, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane, and dichloropropane, or aromatic chlorinated products such as chlorobenzene and dichlorobenzene Or mixtures thereof can be mentioned as suitable organic solvents.
Further, an organic solvent in which an aromatic hydrocarbon such as toluene, xylene and ethylbenzene, an aliphatic hydrocarbon such as hexane, heptane, cyclohexane and the like may be mixed with the above chlorinated hydrocarbon or a mixture thereof may be used. A particularly preferred organic solvent is dichloromethane.

The amount of the organic solvent used is usually about 5 to about 5% in the concentration of the aromatic polycarbonate in the organic solvent solution at the end of the polymerization.
Preferably, it is used in an amount of about 35% by weight. When the concentration of the aromatic polycarbonate is extremely low, a large amount of an organic solvent is required, which is not preferable in terms of productivity. Also, when the concentration of the aromatic polycarbonate is close to the saturation concentration, the viscosity of the organic solvent solution becomes extremely high, so that the reaction efficiency of the interfacial polymerization decreases, and the handleability of the organic solvent solution after polymerization deteriorates. Is not preferred. It is particularly preferred to use an organic solvent such that the concentration of the aromatic polycarbonate in the organic solvent solution at the end of the polymerization is about 10 to about 20% by weight.

The alkali metal or alkaline earth metal base (hereinafter abbreviated as base) used for producing the aromatic polycarbonate of the present invention is usually an alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide or the like. Sodium hydroxide and potassium hydroxide are preferred because they are hydroxides of metals or alkaline earth metals and are relatively easily available, and sodium hydroxide is particularly preferred. The base is usually used in the form of an aqueous solution, and the aromatic dihydroxy compound is further dissolved in the aqueous solution and used in the reaction in many cases. In this case, since the basic aqueous solution of the aromatic dihydroxy compound generally tends to be colored, a basic agent of the aromatic dihydroxy compound is added by adding a reducing agent such as sodium sulfite, sodium hydrosulfite or sodium borohydride as an antioxidant. An aqueous solution may be prepared.

Suitable polymerization catalysts (also called polycondensation catalysts) used in the interfacial polymerization method include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts,
Alternatively, examples thereof include a nitrogen-containing heterocyclic compound and a salt thereof, an imino ether and a salt thereof, and a compound having an amide group. Preferably, it is a trialkylamine which is a tertiary amine, more preferably a trialkylamine having no branch on the carbon atom at the 1-position and the 2-position, wherein the alkyl group has 1 to 4 carbon atoms. , Triethylamine, tri-n-propylamine, diethyl-n-propylamine, tri-n-butylamine and the like, and triethylamine is particularly preferred in that it is easily available and has excellent catalytic effects. The amount of the polymerization catalyst used is preferably about 0.0005 to about 0.7 mol% based on the aromatic dihydroxy compound. The polymerization catalyst can be added before or during the reaction when producing the aromatic polycarbonate of the present invention.

The preferred molecular weight regulator (also referred to as a terminal blocking agent) used in the interfacial polymerization method is for regulating the molecular weight in the process of producing an aromatic polycarbonate, and is generally a monovalent hydroxyaromatic. A group compound is used, but a chloroformate compound of a monovalent hydroxy aromatic compound, a compound having a monovalent carboxylic acid group, a chloride compound of a monovalent carboxylic acid, or the like may also be used. As the monovalent hydroxy aromatic compound,
For example, phenol, p-tert-butylphenol, o
-Cresol, m-cresol, p-cresol, o-
Ethylphenol, m-ethylphenol, p-ethylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-octylphenol, m-octylphenol, p-octylphenol, o-nonylphenol, m-nonylphenol, p-nonylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-chlorophenol,
m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, pentabromophenol, pentachlorophenol, β-naphthol, α-naphthol, p- (2 ′,
4 ', 4'-trimethylchromanyl) phenol.

Examples of the monovalent hydroxyaromatic compound chloroformate include the above-described monovalent hydroxyaromatic compound chloroformate derivatives, and examples of the compound having a monovalent carboxylic acid group include: Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid,
Caprylic acid, 2,2-dimethylpropionic acid, 3-methylbutyric acid, 3,3-dimethylbutyric acid, 4-methylvaleric acid,
3,3-dimethylvaleric acid, 4-methylcaproic acid, 2,
Fatty acids such as 4-dimethylvaleric acid, 3,5-dimethylcaproic acid and phenoxyacetic acid, p-propoxybenzoic acid, p
-Butoxybenzoic acid, p-pentyloxybenzoic acid, p
Benzoic acids such as -hexyloxybenzoic acid and p-octyloxybenzoic acid; and the monovalent carboxylic acid chloride compounds include chloride derivatives of the above compounds having a monovalent carboxylic acid group. These may be used alone or as a mixture of two or more. Phenol, p-tert-butyl phenol,
P-cumylphenol is preferred.

The amount of the molecular weight modifier used depends on the average molecular weight of the aromatic polycarbonate to be produced.
In the present invention, the aromatic polycarbonate to be produced can have an arbitrary molecular weight depending on the amount of the molecular weight modifier used, but the molding processability, the thermal decomposition resistance, and the various physical properties such as impact resistance are about 4000 to 60,000. It is preferably a number average molecular weight, more preferably 10,000 to 3000.
More preferably, the number average molecular weight is about 0. The amount of the molecular weight regulator required to produce an aromatic polycarbonate having a number average molecular weight in the above range is about 8.2 to about 0.5 mol% based on the amount of the aromatic dihydroxy compound used. And preferably about 6.65.
It is more preferred to use from about 1.50 mol%. Molecular weight regulator, at least one aromatic dihydroxy compound, an alkali metal or alkaline earth metal base, water,
It may be present in a mixture composed of an organic solvent, or may be supplied to the mixture sequentially and continuously with the supply of the carbonyl halide compound.

In the interfacial polymerization method, the reaction temperature is about 1
It is preferable to produce the aromatic polycarbonate of the present invention at a temperature of 0 ° C. to the boiling point of the organic solvent used for the reaction. 10
At a reaction temperature extremely lower than 0 ° C., the reaction rate becomes slow, and a cooling medium or a cooling device is required, which is not practical. If the organic solvent used is dichloromethane, it can be carried out at atmospheric pressure and at a reflux temperature of about 39 ° C. In practice, the reaction usually starts around room temperature and is then raised to near reflux by the heat of reaction. The reaction is usually carried out at atmospheric pressure, but if desired, the reaction may be carried out under elevated or reduced pressure.

Using the dialkyl carbonate compound, the alkylaryl carbonate compound and / or the diaryl carbonate compound, the branched aromatic polycarbonate of the present invention is produced from the aromatic dihydroxy compound and the compound represented by the general formula (1). If you do
A mixture of a dialkyl carbonate compound, an alkylaryl carbonate compound or / and a diaryl carbonate compound, an aromatic dihydroxy compound and a compound represented by the general formula (1) is heated at a temperature of about 60 to about 300 ° C under normal pressure and pressure. Alternatively, it can be produced by a transesterification method under reduced pressure in the presence of a transesterification catalyst (for example, a metal oxide, a hydroxide, a carbonate, or the like) as necessary. In this case, a molecular weight modifier may be added,
In order that the alcohol compound by-produced in the transesterification process and the phenol compound act as a molecular weight regulator, by adjusting the ratio of the amount by which the by-product alcohol compound and the monohydroxy compound such as the phenol compound are removed out of the reaction system, An aromatic polycarbonate having a target molecular weight can be produced.

When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method, usually, an organic solvent solution containing the aromatic polycarbonate is separated from an aqueous layer, and then washed with water until the electrolyte substantially disappears. After doing
The aromatic polycarbonate of the present invention can be obtained by removing the organic solvent from the organic solvent solution by a known method. In addition, the aromatic polycarbonate produced by the transesterification method can be directly pelletized or processed into a molded product from the aromatic polycarbonate melted under transesterification conditions.

The aromatic polycarbonate of the present invention is soluble in a specific organic solvent (eg, a halogenated hydrocarbon solvent such as dichloromethane), and can be processed into a molded product such as a film from the organic solvent. The aromatic polycarbonate of the present invention is thermoplastic and can be easily molded from a melt by a known molding method such as injection molding, extrusion molding, blow molding, or lamination. Further, the aromatic polycarbonate of the present invention can be mixed with another aromatic polycarbonate or a polyester such as polyethylene terephthalate or poly (1,4-butylene terephthalate).

The aromatic polycarbonate of the present invention may be prepared at the time of its production or production for the purpose of imparting thermal stability during processing, light resistance, weather resistance, flame resistance, mold release and other properties. Later, in a known manner, a very wide range of additives, stabilizers, flame retardants and fillers, ie processing and heat stabilizers, antioxidants, UV absorbers, release agents, organohalogen compounds, alkali metal sulphonates , Glass fibers, glass beads, barium sulfate, TiO2 and the like may be added.

[0040]

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. Example 1 A 10-liter baffled flask was provided with a three-stage six-blade stirrer, reflux condenser, and immersion tube for supplying phosgene. In this flask, 912 g (4.0 mol) of bisphenol A was added.
20.66 g of p-tert-butylphenol (0.137
7 mol), 1,3-dihydroxy-4,6-bis [α-
Methyl-α- (4′-hydroxyphenyl) ethyl] benzene (compound of Exemplified Compound No. 9) (7.56 g (0.5 mol% based on bisphenol A)), dichloromethane (4 l) and deionized water (4 l) were added and suspended. The mixture was made into a liquid, and a nitrogen purge 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 was supplied to the suspension, and bisphenol A was dissolved at 15 ° C. To this solution, 495 g (5.0 mol) of phosgene was fed at a rate of 8.25 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 the mixture was heated to about 98 ° C. to distill off dichloromethane and toluene to obtain an aromatic polycarbonate powder. The molecular weight of the obtained aromatic polycarbonate is
Number average molecular weight is 20400, weight average molecular weight is 666
00. Further, the obtained polymer was colorless, and a press sheet produced using this aromatic polycarbonate was colorless and transparent.

Example 2 In Example 1, instead of using 7.56 g of 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 3.78 g was used.
g (0.25 mol% based on bisphenol A), and an aromatic polycarbonate was produced in the same manner as in Example 1. The molecular weight of the obtained aromatic polycarbonate is such that the number average molecular weight is 20,000 and the weight average molecular weight is 5
6100. Further, the obtained polymer was colorless, and a press sheet produced using this aromatic polycarbonate was colorless and transparent.

Example 3 In Example 1, instead of using 7.56 g of 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,2 −
Dihydroxy-3,6-bis [2′-hydroxy-
3 ′, 5′-Dimethylphenyl) methyl] benzene (compound of Exemplified Compound No. 4) was used in the same manner as in Example 1 except that 7.56 g (0.5 mol% based on bisphenol A) was used. A group polycarbonate was produced. Regarding the molecular weight of the obtained aromatic polycarbonate, the number average molecular weight was 20,500 and the weight average molecular weight was 63,800.
Further, the obtained polymer was colorless, and a press sheet produced using this aromatic polycarbonate was colorless and transparent.

Example 4 In Example 1, instead of using 7.56 g of 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,4 −
Except that 6.44 g (0.5 mol% based on bisphenol A) of dihydroxy-2,5-bis (2′-methyl-4′-hydroxyphenyl) benzene (compound of Exemplified Compound No. 23) was used. An aromatic polycarbonate was produced in the same manner as in Example 1. As for the molecular weight of the obtained aromatic polycarbonate, the number average molecular weight was 20,500 and the weight average molecular weight was 64,700. Further, the obtained polymer was colorless, and a press sheet produced using this aromatic polycarbonate was colorless and transparent.

Example 5 In Example 1, instead of using 7.56 g of 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene, 1,4 −
Example 1 was repeated except that 6.52 g (0.5 mol% based on bisphenol A) of dihydroxy-2,5-bis [(4'-hydroxyphenyl) oxy] benzene (compound of Exemplified Compound No. 29) was used. In the same manner as in the above, an aromatic polycarbonate was produced. Regarding the molecular weight of the obtained aromatic polycarbonate, the number average molecular weight was 20,400 and the weight average molecular weight was 64,000. Further, the obtained polymer was colorless, and a press sheet produced using this aromatic polycarbonate was colorless and transparent.

Comparative Example 1 For comparison, in Example 1, 1,3 was used as a branching agent.
-Dihydroxy-4,6-bis [α-methyl-α-
(4'-Hydroxyphenyl) ethyl] benzene 7.5
Except for using 6.1 g of 1,1,1-tris (4′-hydroxyphenyl) ethane (0.5 mol% based on bisphenol A) instead of using 6 g, An aromatic polycarbonate was produced. As for the molecular weight of the obtained aromatic polycarbonate, the number average molecular weight was 20400 and the weight average molecular weight was 64700,
The obtained polymer was colored in pale green yellow, and was a polymer having low commercial value in practical use.

Reference Example 1 In Example 1, 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene as a branching agent was added without adding Example 1
By the same operation as described above, a linear aromatic polycarbonate was produced. The molecular weight of the obtained aromatic polycarbonate was such that the number average molecular weight was 21,000 and the weight average molecular weight was 51.
It was 200. The melt flow index (MI) of this aromatic polycarbonate was measured and compared with the melt flow index of the aromatic polycarbonate produced in each Example. The results are shown in Table 1 (Table 1). The melt flow index (MI) was measured at a temperature of 280 ° C. under a load of 2.16 k using an S-01 melt indexer manufactured by Toyo Seiki.
The amount of polymer eluted in 10 minutes, measured in grams (unit:
G). Also, the melt flow index ratio (MIR) is given by the ratio of the melt flow rates at two different shear levels and is a measure of the non-Newtonian flow properties of a polymer. At a test temperature of 280 ° C., respective melt indices [MI (12.5 kg) and MI (2.16 kg)] at a load of 12.5 kg and a load of 2.16 kg were measured by the above-mentioned method, and the ratio was determined. MI of linear aromatic polycarbonate behaving as Newtonian fluid
The R value is usually 6.4 or less, and the MIR value of 7.0 or more indicates that the polymer behaves as a non-Newtonian fluid when melted, indicating that the polymer is suitable for blow molding. I have.

[0047]

[Table 1]

[0048]

According to the present invention, it has become possible to provide a branched aromatic polycarbonate having a melting property suitable for a blow molding material and a good hue.

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

Claims (4)

(57) [Claims] 1. A branched aromatic polycarbonate derived from at least one of an aromatic dihydroxy compound, a carbonate precursor and a phenol compound represented by the general formula (1). Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group, and X ₁ and X ₂ represent a single bond, an alkylene group , Represents an oxygen atom or a sulfur atom) 2. A phenol compound represented by the general formula (1-
The aromatic polycarbonate according to claim 1, which is a compound selected from the group consisting of a), (1-b) and (1-c) (Formula 2). Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group, and X ₁ and X ₂ represent a single bond, an alkylene group , Represents an oxygen atom or a sulfur atom) 3. The method according to claim 1, wherein the amount of the phenol compound is 0.01 to 5 mol% based on the aromatic dihydroxy compound.
Or the aromatic polycarbonate according to 2. 4. The number average molecular weight is 4000 to 60000
The aromatic polycarbonate according to claim 1, 2 or 3, wherein