JPH0770306A - Production of polycarbonate - Google Patents

Abstract

PURPOSE:To produce a polycarbonate contg. only small amts. of residual catalysts and excellent in qualities, such as hydrolysis resistance, at high reaction rate and productivity. CONSTITUTION:A polycarbonate is produced by the transesterification of a dihydroxy compd. with a carbonic diester in the presence of an active-hydrogen- contg. heterocyclic nitrogen compd. and a metal compd. as the catalysts provided the heterocyclic compd. and/or the metal compd. is premixed with the dihydroxy compd. or the diester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polycarbonate, which is preferably used in the electric / electronic field, the automobile field and the like. More specifically, the present invention relates to a method for producing a polycarbonate capable of producing a high-quality polycarbonate with a short reaction time and high productivity.

[0002]

2. Description of the Related Art Polycarbonate is an engineering plastic excellent in transparency, heat resistance and impact resistance.
Currently, it is a resin widely used in the industrial field. As a method for producing polycarbonate, an interfacial method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene, or a melting method in which an aromatic dihydroxy compound such as bisphenol A and a carbonic acid diester such as diphenyl carbonate are transesterified in a molten state The law is known.

However, in the interfacial method, toxic phosgene must be used in the production process, the equipment is corroded by chlorine-containing compounds such as hydrogen chloride and sodium chloride produced as a by-product, and hydroxylation remaining in the resin. There is a problem that it is difficult to separate impurities such as sodium that adversely affect the physical properties of the polymer. On the other hand, the melting method has the advantages of not adversely affecting the environment as described above as compared with the interfacial method, and has the advantage that a polycarbonate can be produced at a low cost, but it is usually used at a high temperature of 280 ° C to 310 ° C. Since the reaction is carried out for a long time, there is a problem that the coloring cannot be prevented. In addition, since a basic catalyst is often used, there is a problem that the obtained polycarbonate has poor hydrolysis resistance.

In the melting method, in order to prevent coloration, a method using a specific catalyst (Japanese Patent Publication No. 61-39972, Japanese Patent Application Laid-Open No. 63-223036, etc.), a method of adding an antioxidant in the latter stage of the reaction ( Japanese Patent Laid-Open No. 61-151236
JP-A-62-158719, etc.), and a method of using a twin-screw vent type kneading extruder in the latter stage of the reaction (JP-A-6-61).
1-62522, etc.), a method of using a horizontal stirring polymerization tank (Japanese Patent Laid-Open No. 2-153925, etc.) and the like have been proposed, but they have not been completely solved.

Further, in order to improve the hydrolysis resistance of the obtained polycarbonate, it has been conventionally known to neutralize with an acid such as dimethylsulfate, and recently, p-
A technique of neutralizing with an acid such as toluenesulfonic acid and neutralizing an excess acid with an epoxy compound (JP-A-4-1-1).
No. 75368, etc.) are known, but they have not been completely solved yet.

[0006]

The object of the present invention is to provide a polycarbonate which has a small amount of residual catalyst and is excellent in quality such as hydrolysis resistance, and has a fast reaction rate and excellent productivity. To provide a manufacturing method of.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventor has found that a nitrogen-containing heterocyclic compound containing active hydrogen and a metal as a catalyst are used as a catalyst when a polycarbonate is produced by a transesterification method. It is possible to reduce the amount of the catalyst remaining in the polycarbonate by rapidly contacting at least one of the raw material monomers with the catalyst and then performing the polycondensation reaction, and the polycondensation reaction proceeds rapidly. Based on this finding, the present invention has been completed.

That is, according to the present invention, when the active hydrogen-containing nitrogen-containing heterocyclic compound and the metal compound are used as catalysts and the polycarbonate is produced by the transesterification reaction between the dihydroxy compound as the monomer raw material and the carbonic acid diester, the dihydroxy compound is previously prepared. A method for producing a polycarbonate, comprising mixing a compound or the carbonic acid diester with the active hydrogen-containing nitrogen-containing heterocyclic compound and / or the metal compound and bringing them into contact with each other.

The dihydroxy compound used in the present invention is not particularly limited, and various dihydroxy compounds including conventionally known compounds can be used. The dihydroxy compounds may be used alone or in combination of two or more.

Here, examples of the dihydroxy compound used as the monomer raw material in the present invention include aromatic dihydroxy compounds, aliphatic dihydroxy compounds, bisesters of these compounds, and biscarbonates.

Specific examples of the aromatic dihydroxy compound preferably used in the present invention include, for example, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-2,
2'-dimethylbiphenyl, 4,4'-dihydroxy-
3,3'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl, 3,3 '
-Dihydroxybiphenyls such as difluoro-4,4'-dihydroxybiphenyl; bis (4-hydroxyphenyl) ether, bis (3-fluoro-4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether Bis (hydroxyaryl) etc.
Ethers; bis (hydroxyaryl) ketones such as 4,4'-dihydroxybenzophenone; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4)
-Bis (hydroxyaryl) sulfides such as -hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, bis (3-phenyl-4-)
Bis (hydroxyaryl) sulfoxides such as hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone, etc. Bis (hydroxyaryl) sulfones; bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo) -4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl)
-1-phenylmethane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane , 1,1-bis (4-
Hydroxyphenyl) ethane, 1,1-bis (2-te
rt-Butyl-4-hydroxy-3-methylphenyl)
Ethane, 1-phenyl-1,1-bis (4-fluoro-
4-hydroxyphenyl) ethane, 1,1-bis (4-
Hydroxyphenyl) -1-phenylethane, 2- (3
-Methyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -2,2,2-triphenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,3 5-
Dimethyl-4-hydroxyphenyl) propane, 1,1
-Bis (2-tert-butyl-4-hydroxy-5-
Methylphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane,
2,2-bis (3-bromo-4-hydroxyphenyl)
Propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-
Dichloro-4-hydroxyphenyl) propane, 2,2
-Bis (3,5-dibromo-4-hydroxyphenyl)
Propane, 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3-
Hydroxyphenyl) hexafluoropropane, 2,2
-Bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 1,1-bis ( 2-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-
tert-Butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4)
-Hydroxy-5-methylphenyl) isobutane, 1,
1-bis (2-tert-amyl-4-hydroxy-5
-Methylphenyl) butane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 2,2-bis ( 4-hydroxyphenyl) -4-methylpentane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (2-tert-butyl-
4-hydroxy-5-methylphenyl) heptane, 2,
2-bis (4-hydroxyphenyl) octane, 1,2
-Bis (hydroxyaryl) alkanes such as bis (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4
-Hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl- Bis (hydroxyaryl) cycloalkanes such as 4-hydroxyphenyl) cyclohexane; 1,1 ′
Bis {(hydroxyaryl) methyl} benzenes such as -bis (4-hydroxyphenyl) -p-diisopropylbenzene and 1,1'-bis (4-hydroxyphenyl) -m-diisopropylbenzene; resorcin, 3-
Methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-tert-
Butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,3,4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin, catechol, hydroquinone, 3-methylhydroquinone,
3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-tert-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,4 , 6-Tetra-tert-butylhydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6-tetrafluorohydroquinone,
Examples thereof include unsubstituted or halogen- and alkyl-substituted dihydroxybenzenes such as 2,3,5,6-tetrabromohydroquinone.

Specific examples of the aliphatic dihydroxy compound used in the present invention include butane-1,4.
-Diol, 2,2-dimethylpropane-1,3-diol, hexane-1,6-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, N, N-methyldiethanolamine, cyclohexane Examples include -1,3-diol, cyclohexane-1,4-diol, 1,4-dimethylolcyclohexane, p-xylylene glycol, and 2,2-bis (4-hydroxycyclohexyl) propane.

Further, in the present invention, the dihydroxy compound is 2,2,2 ', 2'-tetrahydro-
Spiro compounds such as 3,3,3 ', 3'-tetramethyl-1,1'-spirobi- [1H-indene] -6,6'-diol can also be used.

Further, instead of a part of the dihydroxy compound, a dihydric alcohol such as a hydroxyalkyl ester of biphenyldicarboxylic acid or a hydroxyalkyl ester of bicyclohexyldicarboxylic acid may be used. In this case, polyester carbonate is obtained.

Of these, aromatic dihydroxy compounds are preferably used in the present invention.

Examples of the carbonic acid diester used as a monomer raw material in the present invention include diaryl carbonate compounds, dialkyl carbonate compounds, and alkylaryl carbonate compounds.
Specific examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate,
Examples thereof include dinaphthyl carbonate and bis (biphenylyl) carbonate. In addition, specific examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. On the other hand, specific examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate and cyclohexyl phenyl carbonate. Of these, diaryl carbonate compounds such as diphenyl carbonate are preferably used.

The amount of the carbonic acid diester used is usually 0.9 to 1.50 mol, preferably 0.95 to 1.25 mol, and more preferably 1.
It is from 02 to 1.20 mol.

If necessary, a dicarboxylic acid or a dicarboxylic acid ester may be used instead of a part of the carbonic acid diester. In this case, polyester carbonate is obtained. Examples of the dicarboxylic acid and dicarboxylic acid ester include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, diphenyl isophthalate, diphenyl terephthalate, isophthalic acid dichloride, and terephthalic acid dichloride; succinic acid, glutaric acid, adipic acid, pimelic acid. , Speric acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, diphenyl sebacate, diphenyl decanedioate, and other aliphatic dicarboxylic acids; cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid,
1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-
Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid diphenyl, 1,2-cyclobutanedicarboxylic acid diphenyl,
1,3-Cyclobutanedicarboxylic acid diphenyl, 1,2
Examples thereof include alicyclic dicarboxylic acids such as diphenyl cyclopentanedicarboxylate, diphenyl 1,2-cyclohexanedicarboxylate, diphenyl 1,3-cyclohexanedicarboxylate, and diphenyl 1,4-cyclohexanedicarboxylate. The amount of the dicarboxylic acid and dicarboxylic acid ester used is, for example, 50 mol% or less, preferably 30 mol% or less of the carbonic acid diester.

In the present invention, a two-component catalyst comprising an active hydrogen-containing nitrogen-containing heterocyclic compound and a metal compound is used as the transesterification catalyst.

As the active hydrogen-containing nitrogen-containing heterocyclic compound, for example, a compound having all-keto tautomerism represented by the following formula is particularly preferably used.

[0021]

[Chemical 1] Examples of such compounds having all-keto tautomerism include hydroxy-substituted nitrogen-containing heterocyclic compounds and mercapto-substituted nitrogen-containing heterocyclic compounds.

Specific examples of the hydroxy-substituted nitrogen-containing heterocyclic compound include 2-hydroxypyridine, 4-hydroxypyridine, 2-hydroxyquinoline, 4-hydroxyquinoline, 5-hydroxyquinoline, 7-hydroxyquinoline and 1-hydroxyisoquinoline. , 3-hydroxyisoquinoline, 6-hydroxyisoquinoline, 8-hydroxyisoquinoline, 2-hydroxyquinoxaline, 5-
Hydroxyquinoxaline, 6-hydroxyquinoxaline, 4-hydroxycinnoline, 5-hydroxycinnoline, 8-hydroxycinnoline, 2-hydroxypyrazine, 2-hydroxypyrimidine, 4-hydroxypyrimidine, 3-hydroxypyridazine, 4-hydroxypyridazine , 2-hydroxytriazine and the like.

Specific examples of the mercapto-substituted nitrogen-containing heterocyclic compound include 2-mercaptopyridine, 4-mercaptopyridine, 2-mercaptoquinoline, 4-mercaptoquinoline, 5-mercaptoquinoline, 7-mercaptoquinoline and 1-mercaptoisoquinoline. , 3-mercaptoisoquinoline, 6-mercaptoisoquinoline, 8-mercaptoisoquinoline, 2-mercaptoquinoxaline, 5-
Mercaptoquinoxaline, 6-mercaptoquinoxaline, 4-mercaptocinnoline, 5-mercaptocinnoline, 8-mercaptocinnoline, 2-mercaptopyrazine, 2-mercaptopyrimidine, 4-mercaptopyrimidine, 3-mercaptopyridazine, 4-mercaptopyridazine , 2-mercaptotriazine and the like.

In addition to the compounds having all-keto tautomerism as described above, examples of compounds suitably used as the active hydrogen-containing nitrogen-containing heterocyclic compound include amino-substituted nitrogen-containing heterocyclic compounds.

Specific examples of the amino-substituted nitrogen-containing heterocyclic compound include 2-aminopyridine, 4-aminopyridine and 2
-Aminoquinoline, 4-aminoquinoline, 5-aminoquinoline, 7-aminoquinoline, 1-aminoisoquinoline, 3-aminoisoquinoline, 6-aminoisoquinoline, 8-aminoisoquinoline, 2-aminoquinoxaline, 5-aminoquinoxaline, 6 -Aminoquinoxaline, 4-aminocinnoline, 5-aminocinnoline, 8
-Aminocinnoline, 2-aminopyrazine, 2-aminopyrimidine, 4-aminopyrimidine, 3-aminopyridazine, 4-aminopyridazine, 2-aminotriazine and the like can be mentioned.

The nitrogen-containing heterocycle of these compounds may have a substituent such as an alkyl group, a halogen, a cyano group, a nitro group or a methoxy group. These active hydrogen-containing nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.

The active hydrogen-containing nitrogen-containing heterocyclic compound is used in an amount of 10 ^-7 to 1 mol, preferably 10 ^-6 to 10 ^-1 mol, per 1 mol of the dihydroxy compound. If it is less than 10 ^-7 mol, the reaction rate improving effect may be insufficient, and if it is too large, the cost may increase.

As the metal compound, a simple substance of alkali metal or alkaline earth metal, oxide, hydroxide, amide compound, alcoholate, phenolate, ZnO, P
basic metal compounds such as bO and Sb ₂ O ₃ , organic titanium compounds, soluble manganese compounds, Ca, Mg, Zn, P
Examples thereof include acetate salts of b, Mn, Cd, and Co. Among them, manganese acetate, magnesium acetate and the like are preferably used.

These metal compounds may be used alone or in combination of two or more.

The amount of the metal compound used is usually in the range of 10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 10 ^-3 mol, per 1 mol of the dihydroxy compound. If it is less than 10 ^-8 mol, the reaction rate improving effect may be insufficient,
Too much will lead to higher costs.

The ratio of the above-mentioned two kinds of catalyst components used is such that the active hydrogen-containing nitrogen-containing heterocyclic compound / metal compound (molar ratio) is 1.
It is desirable to set it to 0 ⁴ to 10 ^-3 , preferably 10 ³ to 10 ^-1 .

In the present invention, prior to the transesterification reaction between the dihydroxy compound and the carbonic acid diester, one monomer raw material, that is, the above dihydroxy compound or the above carbonic acid diester, is used in advance as a pretreatment step. The nitrogen-containing heterocyclic compound containing active hydrogen and / or the metal compound is mixed and brought into contact. In particular, it is preferable to bring the dihydroxy compound and the metal compound into contact with each other.

The contact time is not particularly limited, but usually 10 minutes to 3 hours is sufficient, and preferably 15 minutes to.
It's an hour. If the contact time is less than 10 minutes, the effect of improving the reaction rate in the transesterification reaction may be insufficient, while if the contact time is too long, the time required for all the steps of polycarbonate production will be long, resulting in It will affect the sex.

The temperature at the time of contact is usually 100 to 2
The temperature is preferably 50 ° C., more preferably 100 to
It is 180 ° C. If it is less than 100 ° C, the effect of improving the reaction rate in the transesterification reaction may be insufficient,
If it exceeds 250 ° C, the monomer component used for the contact, that is, the dihydroxy compound or the carbonic acid diester may be decomposed.

The contact is preferably carried out by stirring a mixture of one of the monomer raw materials and at least one of the catalyst components under an inert atmosphere such as nitrogen.

Then, the rest of the catalyst and the monomer raw material are usually added to the mixture which has undergone this pretreatment step to carry out the transesterification reaction. For example, when the dihydroxy compound and the metal compound are brought into contact with each other in the pretreatment step, after the contact is finished, a carbonic acid diester and an active hydrogen-containing nitrogen-containing heterocyclic compound are added to the mixture of the dihydroxy compound and the metal compound to carry out transesterification. Perform the reaction.

The reaction temperature of the transesterification reaction is not particularly limited, but is usually in the range of 100 to 330 ° C., preferably 160 to 300 ° C., and more preferably about 180 ° C. to 300 ° C. according to the progress of the reaction. A method of raising the temperature to about ℃ is desirable. If the temperature of this transesterification reaction is lower than 100 ° C., the progress of the reaction is slow, and if it exceeds 330 ° C., the polycarbonate may be thermally deteriorated, which is not preferable.

The pressure during the transesterification reaction is set according to the reaction temperature according to the vapor pressure of the monomer used.
This is not limited as long as it is set so that the reaction can be efficiently performed. Usually, in the initial stage of the reaction, the atmospheric pressure or the pressurized state of 1 to 50 atm (760 to 38,000 torr) is kept, and in the latter stage of the reaction, the reduced pressure state, preferably 0.01 to 100 finally.
It is desirable to reduce the pressure to torr and distill off the alcohols and phenols generated from the carbonic acid diester by the transesterification reaction.

The reaction time of the transesterification reaction may be carried out until a polycarbonate having a target molecular weight is obtained, and is usually about 0.2 to 10 hours.

The transesterification reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, and if necessary, a branching agent, a terminal terminator, an antioxidant or the like may be added, or an inert solvent may be added. May be used.

As the branching agent that can be used in the present invention, a polyfunctional compound having three or more functional groups in one molecule is used. Examples of such a polyfunctional compound include phloroglucin, Pyrogallol, 1,
1,1-tris (4-hydroxyphenyl) methane,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (4-hydroxyphenyl) propane, 1,1,1-tris (3-methyl-4-hydroxyphenyl) ethane, 4 , 6-dimethyl-2,4,6
-Tris (4-hydroxyphenyl) -2-heptene,
4,6-Dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6
-Tris (4-hydroxyphenyl) -3-heptene,
1,3,5-Tris (2-hydroxyphenyl) benzene, 1,3,5-tris (4-hydroxyphenyl) benzene, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4- Bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis [α
-(4-Hydroxyphenyl) isopropyl] phenol, 2,6-bis (2'-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4- Dihydroxyphenyl)
Propane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α
-Methyl-α, α ', α'-tris (4-hydroxyphenyl) -1,4-diethylbenzene, hexakis [4
-{Α- (4-hydroxyphenyl) isopropyl} phenyl] -o-terephthalic acid ester, tetrakis (4
-Hydroxyphenyl) methane, tetrakis [4- {α
-(4-hydroxyphenyl) isopropyl} phenoxy] methane, 1,4-bis [(4 ', 4 "-dihydroxytriphenyl) methyl] benzene, 2,4-dihydroxybenzoic acid, trimellitic acid, trimesic acid, pyromellitic acid , Cyanuric acid chloride, 3,3-bis (3-methyl-
4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3,3-bis (4-hydroxyaryl) oxindole, 5-chloroisatin, 5,7-
Examples include dichloroisatin and 5-bromoisatin phloroglyside.

As the terminal terminator which can be used in the present invention, on-butylphenol and mn-
Butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-
Isobutylphenol, ot-butylphenol, m
-T-butylphenol, pt-butylphenol,
on-pentylphenol, m-n-pentylphenol, pn-pentylphenol, on-hexylphenol, m-n-hexylphenol, pn-hexylphenol, o-cyclohexylphenol, m
-Cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, mn-nonylphenol, pn-nonylphenol, o-cumylphenol, m- Cumylphenol, p-cumylphenol, o-naphthylphenol,
m-naphthylphenol, p-naphthylphenol,
2,6-di-t-butylphenol, 2,5-di-t-
Butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, 1-benzyl-4- (hydroxybenzyl) benzene, Dibenzyl-4- (4-hydroxybenzyl) benzene, as well as 2,2,4-trimethyl-4- (4-hydroxyphenyl) chroman, 2,4,4-trimethyl-4- (4-
Examples include monohydric phenols such as chroman derivatives such as hydroxyphenyl) chroman.

Of these monohydric phenols, although not particularly limited in the present invention, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferable.

Further, as another terminal stopper used in some cases, there is a specific carbonic acid diester compound. Specific examples of the specific carbonic acid diester compound as such an end terminating agent include carbobutoxyphenyl phenyl carbonate, methylphenyl butyl phenyl cartonate, ethyl phenyl butyl phenyl carbonate, dibutyl diphenyl carbonate, biphenylyl phenyl carbonate, cumyl phenyl. Carbonate, dicumyl phenyl carbonate, naphthyl phenyl carbonate,
Examples thereof include dinaphthylphenyl carbonate, carbopropoxyphenylphenyl carbonate, carboheptoxyphenylphenyl carbonate, carbomethoxy-t-butylphenylphenyl carbonate, carbopropoxyphenylmethylphenyl carbonate, chromanylphenyl carbonate and dichromanyl carbonate. In addition, C _7-30 -alkylcarbonyloxybenzene,
C _{7-30 -aliphatic} alcohol, phenyl (C _1-12 -alkoxy) benzoate, phenyl di (C _1-12 -alkoxy) benzoate, phenyl tri (C _1-12 -alkoxy) benzoate, phenyl (C _1-12) -Alkoxy) sulfonate and the like.

The amount of the terminator used is preferably 0.05 mol% to 10 mol% with respect to 1 mol of the dihydroxy compound. Of course, the amount of the end-stopping agent used can be changed according to the molecular weight of the desired polycarbonate, etc., but usually by using the amount in the above range, the hydroxyl group end of the obtained polycarbonate is sufficiently sealed. Therefore, a polycarbonate having sufficiently excellent heat resistance and water resistance is obtained, which is preferable.

The monohydric phenol or carbonic acid diester compound as the above-mentioned terminal terminator may be added in the whole amount to the mixture used in the pretreatment step or to the reaction system of the transesterification reaction after the pretreatment step. Alternatively, a part may be added in advance to the mixture used in the pretreatment step or the reaction system of the transesterification reaction, and the rest may be added as the transesterification reaction proceeds. Further, in some cases, the total amount may be added to the reaction system after the transesterification reaction between the dihydroxy compound and the carbonic acid diester proceeds to some extent.

Examples of the antioxidant that can be used in the present invention are tris (nonylphenyl) phosphite, trisphenylphosphite, 2-ethylhexyldiphenylphosphite, trimethylphosphite, triethylphosphite, tricresylphosphite. Phosphorus antioxidants such as triaryl phosphite are preferably used.

As the inert solvent which can be used in the present invention, aromatic compounds such as diphenyl ether, halogenated diphenyl ether, diphenyl sulfone, benzophenone, polyphenyl ether, dichlorobenzene and methylnaphthalene, carbon dioxide, nitrous oxide. , Gases such as nitrogen, chlorofluorohydrocarbons, alkanes such as ethane and propane, cyclohexane, cycloalkanes such as tricyclo (5,2,10) -decane, cyclooctane and cyclododecane, alkenes such as ethylene and propene, or hexa Various materials such as sulfur fluoride can be used.

In addition, the polycarbonate obtained by the present invention may be blended with well-known additives such as a plasticizer, a pigment, a lubricant, a release agent, a stabilizer and an inorganic filler. You can

Further, the polycarbonate obtained by the present invention can be blended with other polymers such as polyolefin and polystyrene, and particularly OH group, CO
It is effective to use a polyphenylene ether having an OH group or an NH ₂ group at the end, a polyether nitrile, a terminal-modified polysiloxane compound, a modified polypropylene, a modified polystyrene, or the like in combination.

[0051]

The present invention will be described in more detail below with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.

Examples 1 to 4 and Comparative Example 1 A compound marked with a circle in Table 1 was added to an ampoule tube, a stirrer chip was put therein, and the tube was sealed under a nitrogen environment. Put this ampoule tube in the oil bath kept at 150 ℃, and
The mixture was stirred for 0 minutes (pretreatment step). Then, in order to carry out the transesterification reaction, the remaining compound marked with ○ is added,
The tube was sealed under a nitrogen environment and reacted at 150 ° C. for 1 hour (transesterification reaction). After completion of the reaction, the produced phenol was quantified by gas chromatography to obtain the reaction rate. The results are shown in Table 1.

[0053]

[Table 1] BPA: Bisphenol A, addition amount = 0.3 g (0.0
013 mol) DPC: diphenyl carbonate, addition amount = 0.56 g
(0.0026 mol) 2-HyPy: 2-hydroxypyridine, addition amount = 2 ×
10 ⁻² mol / mol BPA Mn (OAc) ₂ : manganese acetate, addition amount = 2 × 10 ⁻⁴
Mol / mol BPA

Example 5 The same operation as in Example 3 was performed except that magnesium acetate was used in the same ratio in place of manganese acetate. The reaction rate was 85%.

Comparative Example 2 The same operation as in Example 5 was carried out except that the pre-treatment step of bringing diphenyl carbonate and magnesium acetate into contact with each other was not carried out and the direct transesterification reaction was carried out. The reaction rate was 42%.

Examples 6 and 7, Comparative Examples 3 and 4 Pretreatment step: 228 g of bisphenol A (1.
00 mol), manganese acetate 0.0245 g (0.000
(1 mol), nitrogen substitution was performed 5 times, and 180 ° C for 3 times.
The mixture was stirred for 0 minutes (pretreatment step).

Transesterification reaction: Next, 225 g (1.05 mol) of diphenyl carbonate and 0.001 mol of the compound shown in Table 2 were added to adjust the temperature to 240 ° C., and 1
The vacuum degree was raised to 1 mmHg over time. Then, the temperature was set to 270 ° C., the vacuum degree was set to 1 mmHg, and the reaction was performed for 1 hour. Finally, a viscous and transparent condensate remained in the autoclave.

The condensate obtained is dissolved in methylene chloride,
The viscosity average molecular weight was measured. Further, the obtained viscous and transparent condensate was crushed and press-molded at 270 ° C. to form a sheet, and the hydrolysis resistance was measured. The results are shown in Table 2.

Comparative Example 5 The same operation as in Example 6 was carried out except that the pretreatment of bringing bisphenol A into contact with manganese acetate was not carried out and all the monomer components and the catalyst were simultaneously added to carry out the transesterification reaction. The results are shown in Table 2.

[0060]

[Table 2] 1) Measure [η] in CH ₂ Cl ₂ at 20 ° C.
= 1.23 × 10 ⁻⁵ Mv ^0.83 . 2) Sheet (thickness 3mm) on steam at 121 ℃ 48
The state after the time exposure was visually judged. 3) Since the condensates obtained in Comparative Examples 3 and 4 had a low molecular weight and it was clear that they had no effect of promoting the reaction, hydrolysis resistance was not evaluated. 4) No pretreatment process

[0061]

EFFECTS OF THE INVENTION According to the present invention, when a polycarbonate is produced by the transesterification method, the reaction can be promptly promoted even if the addition amount of the transesterification catalyst is reduced, and the quality such as hydrolysis resistance is improved. It has become possible to produce excellent polycarbonate with high productivity.

Claims (2)

[Claims] 1. A method for producing a polycarbonate by transesterification between a dihydroxy compound as a monomer raw material and a carbonic acid diester using an active hydrogen-containing nitrogen-containing heterocyclic compound and a metal compound as a catalyst, wherein the dihydroxy compound or the carbonic acid is previously prepared. A process for producing a polycarbonate, which comprises mixing a diester and the active hydrogen-containing nitrogen-containing heterocyclic compound and / or the metal compound and bringing them into contact with each other. 2. The polycarbonate according to claim 1, wherein the dihydroxy compound and the metal compound are previously mixed and brought into contact with each other, and then a carbonic acid diester and a nitrogen-containing heterocyclic compound containing active hydrogen are added to the mixture to carry out a transesterification reaction. Manufacturing method.