JPH0726005A - Production of aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To reduce the coloration of an arom. polycarbonate by subjecting an arom. dihydroxy compd. and a carbonic diester to melt polycondensation in the presence of a catalyst comprising at least one specific compd. having an Al-contg. six-membered ring. CONSTITUTION:An arom. polycarbonate not colored is produced by feeding 1mol of an arom. dihydroxy compd. [e.g. 2,2-bis(4-hydroxyphenyl)propane], 1 to 1.3mol of a carbonic diester (e.g. diphenyl carbonate), 10<-8>-10<-1>mol of at least one compd. having an Al-contg. six-membered ring (or rings) selected from compds. of formulas I-IV (wherein R1, R2, R3, X, Z, X1, and Z1 are each 1-20C alkyl, 6-20C cycloalkyl, 6-20C aryl, etc.; Y and Y1 are each H, 1-20C alkyl, etc.; and m and n are each 0 or an integer provided m+n is 3), and 10<-8>-10<-1>mol of an amine deriv. (e.g. a quaternary ammonium hydroxide) into a reactor, stirring under heating to dissolve the contents in the reactor, polycondensing the contents under a reduced pressure at 250-330 deg.C, and adding 10-1,000ppm phosphorus compd. and 0.001-5 pts.wt. phenolic stabilizer (based on the resulting polymer) to the polymer in a melting state.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing polycarbonate. More specifically, polymerization reaction rate, hue,
The present invention relates to a method for producing a polycarbonate having excellent heat resistance and the like.

[0002]

2. Description of the Related Art Polycarbonate is widely used because it is excellent in mechanical properties such as impact resistance, heat resistance and transparency. As a method for producing such a polycarbonate, a method of directly reacting an aromatic dihydroxy compound such as bisphenol with phosgene (interfacial method), or an aromatic dihydroxy compound such as bisphenol and a diaryl carbonate such as diphenyl carbonate in a molten state Methods such as transesterification (melting method) are known.

Of the above-mentioned production methods, a method for producing a polycarbonate by a transesterification reaction between an aromatic dihydroxy compound and a diaryl carbonate will be described. In this method, as a catalyst, an organic acid salt of a metal, an inorganic acid salt, A method in which an aromatic dihydroxy compound and a diaryl carbonate are finally heated to 250 to 330 ° C. under reduced pressure using an oxide, a hydroxide, a hydride, an alcoholate, or the like to perform a transesterification reaction while melting. is there.

This method has the advantage of being able to produce polycarbonate at a lower cost than the above-mentioned interfacial method, but on the other hand, it has the problem that the hue is unfavorable because the polymer is exposed to high temperatures for a long time. It was Various catalysts have been proposed to improve the hue, but they are still inadequate because they are inferior to polycarbonate polymerized by the interfacial method.

In the melt polymerization method, the reaction is carried out at high temperature under reduced pressure in the presence of a catalyst, so that the polymer is easily colored. Therefore, several catalyst systems aimed at producing a polycarbonate having a low degree of coloration, such as a system in which a tetraalkylammonium hydroxide is combined with an alkali metal or alkaline earth metal compound have been proposed. However, when an alkali or alkaline earth metal compound is used, a component insoluble in a solvent such as methylene chloride may be produced in the polymer by a side reaction depending on the reaction conditions. In particular, this phenomenon becomes remarkable when the molecular weight of polycarbonate is increased. Therefore, when a casting film is produced from a high molecular weight polycarbonate, a resin containing such an insoluble component cannot be used.

Further, when the obtained polycarbonate is melt-molded, the degree of polymerization of the polycarbonate may be largely lowered. In this case, various catalyst deactivators have been proposed, but they may cause another kind of side reaction and are not yet a sufficiently satisfactory solution.

[0007]

DISCLOSURE OF THE INVENTION The present invention has a problem that it is soluble in a solvent such as methylene chloride even when it is colored with a small amount and has a high molecular weight by a melt polymerization method, and the polymerization degree is lowered during melt molding processing. Aims to manufacture polycarbonate that is difficult to cause.

[0008]

According to the present invention, when a polycarbonate is produced by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a catalyst, the catalyst has the following formulas (I) and (II): And (III) and (IV), which is at least one aluminum-containing six-membered cyclic compound selected from the group consisting of compounds.

[0009]

[Chemical 2]

[Wherein R ₁ , R ₂ , R ₃ , X, Z, X ₁ ,
Each Z ₁ is independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. Y and Y ₁ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, and a carbon atom having 6 to 20 carbon atoms.
Selected from the aralkyl groups of. Moreover, m and n are 0 or an integer, and m + n = 3. The aromatic dihydroxy compound that can be used in the present invention is not particularly limited,
The compound shown by following formula (A) can be mentioned.

[0011]

[Chemical 3]

Here, R ₄ and R ₅ are the same or different,
It is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms. As the hydrocarbon group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms is preferable. Examples of such an aliphatic hydrocarbon group include an alkyl group, an alkenyl group and the like, and a methyl group, an ethyl group, a propyl group and the like are exemplified. Further, examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and naphthyl group. Examples of the halogen atom include chlorine, bromine and iodine.

R ₆ is a divalent hydrocarbon group having 4 to 20 carbon atoms, and examples thereof include an aliphatic hydrocarbon group such as an alkylene group and an alkenylene group, and examples thereof include a butylene group and a pentylene group.

In the formula, R ₇ and R ₈ are the same or different and each is a halogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of the hydrocarbon group include an aliphatic hydrocarbon group having 1 to 12 carbon atoms and an aromatic group having 6 to 12 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group and an alkenyl group, and more specific examples include a methyl group, an ethyl group and a propyl group. Further, examples of the aromatic group include a substituted or unsubstituted phenyl group and naphthyl group. Examples of the halogen atom include chlorine, bromine and iodine.

In the formula, a and b are the same or different and each represents 0 or an integer of 1 to 4.

Specific examples include the compounds shown below. Bis (4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxyphenyl) propane, 2,2
-Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4
-Hydroxy-3-methylphenyl) propane, 1,1
-Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-t-butylphenyl) propane and 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether Dihydroxy aryl ethers such as
4,4'-dihydroxydiphenyl sulfide, 4,
Dihydroxydiarylsulfides such as 4'-dihydroxy-3,3'-dimethyldiphenylsulfide,
4,4'-dihydroxydiphenyl sulfoxide, 4,
Dihydroxy diaryl sulfoxides such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,
Dihydroxydiarylsulfones such as 4'-dihydroxy-3,3'-dimethyldiphenylsulfone, 9,
Examples thereof include dihydroxydiaryls such as 9-bis (4-hydroxyphenyl) fluorene.

Of these, 2,2-bis (4-
Hydroxyphenyl) propane (bisphenol A) is preferably used. These aromatic dihydroxy compounds can be used alone or in combination.

The diaryl carbonate has 6 to 2 carbon atoms.
It is not particularly limited as long as it is a carbonate having an optionally substituted aryl group of 0, but specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (Diphenyl) carbonate etc. can be mentioned. Of these, diphenyl carbonate is particularly preferably used. These diaryl carbonates can be used alone or in combination. The above diaryl carbonate is usually 1.0 to 1.30 mol, preferably 1.01 to 1.2, relative to 1 mol of the aromatic dihydroxy compound.
It is preferably used in an amount of 0 mol.

The aluminum-containing six-membered cyclic compound used in the present invention is

[0020]

[Chemical 4]

[In the formula, R _{1 to} R ₃ , X, Z, X ₁ and Z ₁ are each independently an alkyl group having 1 to 20 carbon atoms and 6 to 6 carbon atoms.
It is selected from the group consisting of a cycloalkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aralkyl group having 6 to 20 carbon atoms. Y and Y ₁ are each independently a hydrogen atom or 1 to 2 carbon atoms.
0 alkyl group, cycloalkyl group having 6 to 20 carbon atoms,
It is selected from an aryl group having 6 to 20 carbon atoms and an aralkyl group having 6 to 20 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group and a propyl group. Examples thereof include a cyclohexyl group as a cycloalkyl group, a phenyl group and a naphthyl group as an aryl group, and a xylyl group as an aralkyl group.

More specifically, preferred examples of the formula (I) include cyclic aluminum oxide methoxide, cyclic aluminum oxide isopropoxide, cyclic aluminum oxide n-butoxide, cyclic aluminum oxide n-hexyl oxide, and cyclic aluminum oxide. Examples include octyl oxide and cyclic aluminum oxide stearyl oxide.

As the formula (II), aluminum dimethoxymethylacetoacetate, aluminum dibutoxymethylacetoacetate, aluminum dioctyloxymethylacetoacetate, aluminum didecyloxymethylacetoacetate, aluminum diisopropoxyethylacetoacetate, Aluminum dipentyloxyethyl acetoacetate, aluminum dinonyloxyethyl acetoacetate, aluminum ditridecyloxyethyl acetoacetate, aluminum diethoxybutyl acetoacetate, aluminum dibutoxybutyl acetoacetate, aluminum diheptyloxybutyl acetoacetate Aluminum, didecyloxybutyl acetoacetate, distearyloxybutyl acetoacetate Minium, dipropoxyhexyl acetoacetate aluminum, dihexyloxyhexyl acetoacetate aluminum, dinonyloxyhexyl acetoacetate aluminum, ditetradecyloxyhexyl acetoacetate aluminum, dimethoxydecyl acetoacetate aluminum, dibutoxydecyl acetoacetate Aluminum tartrate, dioctyl oxydecyl acetoacetate aluminum, ditetradecyl oxydecyl acetoacetate aluminum, diisopropoxy tetradecyl acetoacetate aluminum, dibutoxy tetradecyl acetoacetate aluminum,
Dioctyloxytetradecylacetoacetate aluminum, ditetradecyloxytetradecylacetoacetate aluminum, diphenoxymethylacetoacetate aluminum, diphenoxypropylacetoacetate aluminum, diphenoxyhexadecylacetoacetate aluminum, diethoxyphenylacetoacetate Aluminum tartrate, dibutoxynaphthyl acetoacetate aluminum, dihexyloxyphenyl acetoacetate aluminum, ditetradecyloxyphenyl acetoacetate aluminum, dimethoxymethyl (2
-Methylacetoacetate) aluminum, dibutoxymethyl (2-ethylacetoacetate) aluminum,
Examples include didecyloxyhexyl (2-phenylacetoacetate) aluminum, dinonyloxyphenyl (2-decylacetoacetate) aluminum, dioctyloxytolyl (2-butylacetoacetate) aluminum, and the like.

As the formula (III), dimethoxymono (2,
4-pentanedionate) aluminum, propoxybis (2,4-pentanedionate) aluminum, dibutoxymono (2,4-pentanedionate) aluminum, decyloxybis (2,4-pentanedionate)
Aluminum, ditridecyl mono (2,4-pentanedionate) aluminum, methoxybis (3-phenyl-2,4-pentanedionate) aluminum, diethoxymono (3-methyl-2,4-pentanedionate)
Aluminum, propoxybis (3-ethyl-2,4-
Pentanedionate) aluminum, dibutoxymono (3-hexyl-2,4-pentanedionate) aluminum, nonyloxybis (3-decyl-2,4-pentanedionate) aluminum, dimethoxymono (1-
Phenyl-1,3-butanedionate) aluminum,
Ethoxybis (1-phenyl-1,3-butanedionate) aluminum, dipropoxymono (1-phenyl-
1,3-butanedionate) Aluminum, hexyloxybis (1-phenyl-1,3-butanedionate)
Aluminum, ditridecyloxymono (1-phenyl-1,3-butanedionate) aluminum, ethoxybis (2,2,6,6-tetramethyl-3,5-heptanedionate) aluminum, dibutoxymono (2,2
2,6,6-Tetramethyl-3,5-heptanedionate) aluminum, hexyloxybis (2,2,6,
6-Tetramethyl-3,5-heptanedionate) aluminum, ditridecyloxymono (2,2,6,6-
Tetramethyl-3,5-heptanedionate) aluminum, methoxybis [4,4,4-trifluoro-1-
(2-furyl) -1,3-pentanedionate] aluminum, dipropoxymono [4,4,4-trifluoro-
1- (2-furyl) -1,3-pentanedionate] aluminum, butoxybis [4,4,4-trifluoro-
1- (2-furyl) -1,3-pentanedionate] aluminum, dihexyloxymono [4,4,4-trifluoro-1- (2-furyl) -1,3-pentanedionate] aluminum, didecyl Oxymono [4,4,4
-Trifluoro-1- (2-furyl) -1,3-pentanedionate] aluminum, diethoxymono (1,3-
Diphenyl-1,3-propanedionate) aluminum, butoxybis (1,3-diphenyl-1,3-propanedionate) aluminum, dimethoxymono (1,
1,5,5,5-hexafluoro-2,4-pentanedionate) aluminum, ethoxybis (1,1,5,
5,5-hexafluoro-2,4-pentanedionate)
Aluminum, dibutoxy mono (1, 1, 5, 5, 5-
Hexafluoro-2,4-pentanedionate) aluminum, hexyloxybis (1,1,5,5,5-hexafluoro-2,4-pentanedionate) aluminum, didecyloxymono (1,1,5,5) , 5-hexafluoro-2,4-pentanedionate) aluminum,
Diethoxy mono (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate) aluminum,
Butoxybis (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate) aluminum, dipentyloxymono (1,1,1-trifluoro-5,5
-Dimethyl-2,4-hexanedionate) aluminum, nonyloxybis (1,1,1-trifluoro-5,
5-dimethyl-2,4-hexanedionate) aluminum, ditetradecyloxymono (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate) aluminum, dimethoxymono (1,1) , 1-trifluoro-2,4-pentanedionate) aluminum,
Examples thereof include butoxybis (1,1,1-trifluoro-2,4-pentanedionate) aluminum and dihexyloxymono (1,1,1-trifluoro-2,4-pentanedionate) aluminum.

As formula (IV), tris (methylacetoacetate) aluminum, tris (butylacetoacetate) aluminum, tris (hexylacetoacetate) aluminum, tris (decylacetoacetate)
Aluminum, tris (ethyl-2-methylacetoacetate) aluminum, tris (butyl-2-propylacetoacetate) aluminum, tris (nonyl-2)
-Cyclohexylacetoacetate) aluminum, Tris (2,4-pentanedionate) aluminum, Tris (3-methyl-2,4-pentanedionate) aluminum, Tris (3-butyl-2,4-pentanedionate) Aluminum, tris (3-phenyl-2,4
-Pentane dionate) Aluminum, Tris (2,
2,6,6-Tetramethyl-3,5-heptadionate) aluminum, tris (1,1,1,2,2,3,3)
3-heptafluoro-7,7-dimethyl-4,6-octanedionate) aluminum, tris (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate) aluminum, tris (4 4,4-Trifluoro-1-phenyl-1,3-butanedionate) aluminum, mono (2,4-pentanedionate) bis (ethylacetoacetate) aluminum, mono (2,4-pentanedionate) bis (Butyl acetoacetate) aluminum, mono (2,4-pentanedionate) bis (decyl acetoacetate) aluminum, mono (2, 4-
4-Pentanedionate) bis (hexadecylacetoacetate) aluminum, bis (2,4-pentanedionate) mono (methylacetoacetate) aluminum, bis (2,4-pentanedionate) mono (nonylacetoacetate) Tart) Aluminum, bis (2,4-pentanedionate) mono (tridecyl acetoacetate)
Aluminum, mono (3-methyl-2,4-pentanedionate) bis (ethylacetoacetate) aluminum, bis (3-butyl-2,4-pentanedionate)
Aluminum mono (butylacetoacetate), mono (3-phenyl-2,4-pentanedionate) bis (hexylacetoacetate) aluminum, bis (1,3-diphenyl-1,3-propanedionate)
Mono (2,4-pentanedionate) aluminum, mono (3-methyl-2,4-pentanedionate) bis (2,4-pentanedionate) aluminum, bis (3-butyl-2,4-pentanedio) Nato) mono (2,4-pentanedionate) aluminum, mono (3-phenyl-2,4-pentanedionate) bis (2,4-pentanedionate) aluminum, bis (2,2,6,6- Tetramethyl-3,5-heptanedionate) mono (2,4-pentanedionate) aluminum and the like can be mentioned.

The amount of such a catalyst used is in the range of 10 ^-8 to 10 ^-1 mol per mol of the aromatic dihydroxy compound.

The larger the amount of such a catalyst used, the more preferable it is for the reaction, but it is not preferable for the physical properties of the polymer (for example, haze, polymer color tone, etc.). Accordingly, in the above sense, preferably 10 ^-7 to 10 ^-1 mol, more preferably 10 ^-7 to 1
It is in the range of 0 ^-2 mol.

As the amine derivative compound used in the present invention, quaternary ammonium hydroxide, quaternary ammonium carboxylate, quaternary ammonium tetrafluoroborate, quaternary ammonium borohydride,
Examples thereof include quaternary ammonium hexafluorophosphate, intramolecular quaternary ammonium carboxylate, and tertiary amine.

Preferred quaternary ammonium hydroxides are tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetradecylammonium hydroxide and tetramethylammonium hydroxide. Stearyl ammonium hydroxide, butyl trimethyl ammonium hydroxide, dibutyl diethyl ammonium hydroxide, hexyl trimethyl ammonium hydroxide, hexyl triethyl ammonium hydroxide, nonyl trimethyl ammonium hydroxide, nonyl tributyl ammonium hydroxide, decyl trimethyl ammonium hydroxide, decyl triethyl ammonium Hi Rokishido, stearyltrimethylammonium hydroxide, lauryltrimethylammonium hydroxide, phenyl trimethyl ammonium hydroxide, tolyl triethylammonium hydroxide, benzyltrimethylammonium hydroxide,
Examples thereof include benzyltributylammonium hydroxide, cyclohexyltrimethylammonium hydroxide and cyclohexyltrihexylammonium hydroxide.

Preferred examples of the quaternary ammonium carboxylate are tetramethylammonium acetate, tetraethylammonium acetate, tetrapropylammonium acetate, tetrabutylammonium propionate, tetrahexylammonium propionate, tetradecylammonium propionate,
Tetrastearyl ammonium myristate, butyl trimethyl ammonium stearate, dibutyl diethyl ammonium stearate, hexyl trimethyl ammonium oleate, hexyl triethyl ammonium oleate, nonyl trimethyl ammonium acetate, nonyl tributyl ammonium acetate, decyl trimethyl ammonium propionate, decyl triethyl ammonium propioate Nate, stearyl trimethyl ammonium lactate, lauryl trimethyl ammonium lactate, phenyl trimethyl ammonium palmitate, tolyl triethyl ammonium palmitate, benzyl trimethyl ammonium behenate, benzyl tributyl ammonium behenate, cyclohexyl trimethyl ammonium Seteto, cyclohexyl trihexyl ammonium acetate are.

Preferred examples of the quaternary ammonium tetrafluoroborate are tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrahexylammonium tetrafluoroborate, Tetradecyl ammonium tetrafluoroborate, tetrastearyl ammonium tetrafluoroborate, butyl trimethyl ammonium tetrafluoroborate, dibutyl diethyl ammonium tetrafluoroborate, hexyl trimethyl ammonium tetrafluoroborate, hexyl triethyl ammonium tetrafluoroborate, nonyl trimethyl ammonium tetrafluoroborate, nonyl triborate Tylammonium tetrafluoroborate, decyltrimethylammonium tetrafluoroborate, decyltriethylammonium tetrafluoroborate, stearyltrimethylammonium tetrafluoroborate, lauryltrimethylammonium tetrafluoroborate, phenyltrimethylammonium tetrafluoroborate, tolyltriethylammonium tetrafluoroborate, benzyltrimethyl Examples thereof include ammonium tetrafluoroborate, benzyltributylammonium tetrafluoroborate, cyclohexyltrimethylammonium tetrafluoroborate, and cyclohexyltrihexylammonium tetrafluoroborate.

Preferred examples of the quaternary ammonium borohydride include tetramethylammonium borohydride, tetraethylammonium borohydride, tetrapropylammonium borohydride, tetrabutylammonium borohydride, tetrahexylammonium borohydride and tetradecylammonium borohydride. , Tetrastearyl ammonium borohydride, butyl trimethyl ammonium borohydride, dibutyl diethyl ammonium borohydride, hexyl trimethyl ammonium borohydride, hexyl triethyl ammonium borohydride, nonyl trimethyl ammonium borohydride, nonyl tributyl ammonium borohydride, decyl trihydrate Chill ammonium borohydride, decyl triethyl ammonium borohydride,
Stearyl trimethyl ammonium borohydride,
Examples thereof include lauryltrimethylammonium borohydride, phenyltrimethylammonium borohydride, tolyltriethylammonium borohydride, benzyltrimethylammonium borohydride, benzyltributylammonium borohydride, cyclohexyltrimethylammonium borohydride, cyclohexyltrihexylammonium borohydride.

Preferred examples of the quaternary ammonium hexafluorophosphate are tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetrahexylammonium hexafluorophosphate. , Tetradecyl ammonium hexafluorophosphate, tetrastearyl ammonium hexafluorophosphate, butyltrimethylammonium hexafluorophosphate, dibutyldiethylammonium hexafluorophosphate, hexyltrimethylammonium hexafluorophosphate, hexyltriethylammonium hexafluorophosphate, nonyl Limethylammonium hexafluorophosphate, nonyltributylammonium hexafluorophosphate, decyltrimethylammonium hexafluorophosphate, decyltriethylammonium hexafluorophosphate, stearyltrimethylammonium hexafluorophosphate, lauryltrimethylammonium hexafluorophosphate, phenyltrimethylammonium hexafluorophosphate, tolyl Trimethylammonium hexafluorophosphate,
Examples thereof include benzyltrimethylammonium hexafluorophosphate, benzyltributylammonium hexafluorophosphate, cyclohexyltrimethylammonium hexafluorophosphate, and cyclohexyltrihexylmonium hexafluorophosphate.

Examples of tertiary amines include tetramethylamine, tetraethylamine, tetrapropylamine,
Tetrabutylamine, tetrahexylamine, tetradecylamine, tetrastearylamine, butyltrimethylamine, dibutyldiethylamine, hexyltrimethylamine, hexyltriethylamine, nonyltrimethylamine, nonyltributylamine, decyltrimethylamine, decyltriethylamine, stearyltrimethylamine, lauryltrimethylamine, phenyltrimethylamine, tolyl Aliphatic amines such as triethylamine, benzyltrimethylamine, benzyltributylamine, cyclohexyltrimethylamine, cyclohexyltrihexylamine; 1,8-diazabicyclo [5.
4.0] -7-Undecene, 1,5-diazabicyclo [5.3.0] -5-nonene, 1,4-diazabicyclo [2.2.2] octane, 1,2-dimethyl-1,4
Cyclic amines such as 5,6-tetrahydropyrimidine, 4- (2-piperidinoethyl) pyridine, 4-piperidinopyridine; N, N, N ', N'-tetramethylhexamethylenediamine, N, N, N', N'-tetramethyltetramethylenediamine, N, N, N ', N'-tetramethyltrimethylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N', N ″ ―
Examples include polyamines such as pentamethyldiethylenetriamine.

Examples of the intramolecular quaternary ammonium carboxylate include Nissan Manon (registered trademark) BF (NOF Corporation), Nissan Manon BL (NOF Corporation), Nissan Manon LG (NOF Corporation) and Nissan Manon. An amphoteric surfactant such as BDF-R (NOF CORPORATION) can be used.

The amine derivative catalyst can be used in an amount of 10 ^-8 to 10 ^-1 mol per mol of the aromatic dihydroxy compound. The larger the amount of the amine catalyst used, the more preferable it is for the reaction, but it adversely affects the physical properties of the polymer such as hue and haze. Therefore, the preferred range is 10 ^-8 to 10 ^-2 mol, and more preferably 10 ^-7 to 10 ^-2 mol.

If desired, other metal catalyst may be used in combination.
It can also be used. For example, IIB and III of the periodic table
Metal elements belonging to groups B, IVA and IVB and compounds thereof
Selected from among things. Metal compound used as catalyst
For example, Zn (OAc)₂, Zn (OBz)₂
Carboxylate of zinc such as, ZnO, ZnS such as ZnS
Oxides or sulfides, Zn (OH)₂Zinc hydroxide such as
Compound, (C₂H_Five)₂Zn, Ph₂Zn, C₂H_FiveZn
OC₂H_Five, PhZnCl, PhZnOAc, C_FourH₉
Organozinc compounds such as ZnOAc, Zn (OC₂H_Five)
₂, Zn (OPh)₂Alkoxide of zinc such as or
Aryloxide, Zn (acac)₂, Zn (oxi
n)₂Zinc compounds such as zinc chelate compounds
Kind: Ga (OAc)₃, Ga (OBz), GaO (OA
g) carboxylates of gallium such as c), Ga₂O₃Such as
Gallium oxide, Ga (OH)₃Gallium water such as
Oxide, (CH₃)₃Ga, Ph₃Organic gari such as Ga
Um compounds, Ga (OCH₃)₃, Ga (OPh)₃Na
Which gallium alkoxide or aryloxide, G
a (acac)₃Chelate compounds of gallium, etc.
Gallium compounds; In (OAc)₃Such as Injiu
Carboxylate, In₂O₃Oxidation of indium such as
Thing, (C₂H_Five)₃In, Ph₃Organic ink such as In
Indium compound, In (acac)₃Such as indium
Indium compounds such as rate compounds; Ge (OA
c)_Four, Ge (OBz)_FourSuch as germanium carbo
Phosphate, GeO₂Oxides of germanium such as Ge
(OH)₂, Ge (OH)_FourHydroxides such as (C₂H
_Five)_FourGe, Ph_FourGe, [(C_FourH₉)₂GeO]
n, [Ph₂Organic germanium compounds such as GeO] n
Thing, Ge (OCH₃)_Four, Ge (OPh)_FourSuch as gel
A manganese alkoxide or aryloxide
Rumanium compounds; Sn (OAc)₂, Sn (OA
c)_Four, Sn (OBz)₂, Sn (OBz)_FourSuch as
Carboxylic acid salt, (C₂H_Five)_FourSn, Ph_FourSn
Which organotin compound, (C_FourH₉)₂SnO, [(C_Four
H₉)₂SnO] n, [(C₆H₁₇)₂SnO] n,
[(C_FourH₉) Organotinoxy such as PhSnO] n
De, (C_FourH₉)₂Sn (OAc)₂, Dibutyltin
Organic tin carboxylates such as urate, SnO, Sn
O₂Oxides of tin such as Sn (OH)₂, Sn (O
H)_FourSn hydroxides such as Sn (OCH₃)₂, S
n (OCH) ₃, Sn (OC_FourH₉)_Four, Sn (OP
h)₂, Sn (OPh)_Four,

[0038]

[Chemical 5]

(C_FourH₉)₂Sn (OCH₃)₂Such as
Alkoxides or aryloxy of tin and organotin
Do, SnSO_FourInorganic acid salts of tin, such as Na [Sn
F₃], [(C₂H_Five)_FourN], Pb (OAc)₂, P
b (OAc)_Four, Pb (OBz)₂Lead carvone
Acid salt, PbCO₃2PbCO₃・ Pb (OH)₂Such
Lead Inorganic Acid Salt, Na₂[Pb (OH)₆] Such as lead
Complex compound, PbO, PbO₂, Pb₃O_FourLead acid such as
Compound, Pb (OH)₂Lead hydroxides, such as (C
_FourH ₉)_FourPb, Ph_FourPb, (C₂H_Five)₃PbC
l, Ph₃PbCl, (C₂H _Five)₂PbCl₂, (C
₂H_Five)₃Organic lead compounds such as Pb (OAc), Pb
(OCH₃)_Four, Pb (OPh)_Four, (C_FourH₉)₂P
b (OPh)₂Such as lead and organic lead alkoxides
Or lead compounds such as aryloxide; Zr (OA
c)_Four, Zr (OBz)_FourZirconium carbo such as
Phosphate, ZrO₂Zirconium oxide, such as Zr
(OC_FourH₉)_Four, Zr (OPh)_FourZirconiu such as
Alkoxide or aryloxide, Zr (OA
c)₃(Π-C_FiveH _Five), ZrH₂(Π-C_FiveH_Five)₂
Organozirconium compounds such as Zr (acac)_FourNa
Zirconium such as zirconium chelate
And the like.

These catalysts may be used either individually or in combination of two or more. The amount of the catalyst used is 10 ⁻⁹ to 10 with ^respect to 1 mol of the aromatic dihydroxy compound.
^It can be used in the range of ^-2 mol, preferably 10 ^-9 to 10 ^-2 mol, particularly preferably 10 ^-8 to 10 ^-3 mol. If it deviates from the above-mentioned range of use, there are problems that various properties of the obtained polycarbonate are adversely affected, and the polycondensation reaction does not proceed sufficiently to obtain a high-molecular weight polycarbonate.

In the present invention, if necessary, the following sulfonic acid derivative can be preferably added after the polycondensation end stage.

Examples of such a sulfonic acid derivative include a sulfonic acid ester, a sulfonic acid anhydride, or a mixed acid anhydride of sulfonic acids, for example, a mixed acid anhydride with another sulfonic acid, carboxylic acid, phosphoric acid, or boric acid. Is mentioned.

Examples of the sulfonate ester include methyl methanesulfonate, butyl methanesulfonate, hexyl methanesulfonate, decyl methanesulfonate, tridecyl methanesulfonate, ethyl propane sulfonate, pentyl propane sulfonate, nonyl propane sulfonate, and propane. Phenyl sulfonate, naphthyl propane sulfonate, methyl hexane sulfonate, propyl hexane sulfonate, pentyl hexane sulfonate, tolyl hexane sulfonate, benzyl hexane sulfonate, cyclohexyl hexane sulfonate, methyl benzene sulfonate,
Butyl benzene sulfonate, hexyl benzene sulfonate, octyl benzene sulfonate, xylyl benzene sulfonate, naphthyl benzene sulfonate, hexadecyl benzene sulfonate, methyl p-dodecyl benzene sulfonate, ethyl p-dodecyl benzene sulfonate, p-
Examples thereof include butyl dodecylbenzenesulfonate, phenyl p-dodecylbenzenesulfonate, benzyl p-dodecylbenzenesulfonate, and naphthyl p-dodecylbenzenesulfonate.

Examples of the sulfonic acid anhydride include methanesulfonic acid anhydride, ethanesulfonic acid anhydride, butanesulfonic acid anhydride, hexanesulfonic acid anhydride, nonylsulfonic acid anhydride, decylsulfonic acid anhydride and dodecylsulfonic acid anhydride. Compounds, tetradecylsulfonic anhydride, hexadecylsulfonic anhydride, benzenesulfonic anhydride, toluenesulfonic anhydride, xylenesulfonic anhydride, naphthalenesulfonic anhydride, dodecylbenzenesulfonic anhydride, etc. .

Examples of mixed acid anhydrides of sulfonic acids include methanesulfonyl ethane sulfonate, methane sulfonyl butane sulfonate, methane sulfonyl nonyl sulfonate, methane sulfonyl tetradecyl sulfonate, methane sulfonyl hexadecyl sulfonate, methane sulfonyl benzene sulfonate, hexane sulfonyl decyl sulfonate, Hexanesulfonyl hexadecyl sulfonate, hexane sulfonyl benzene sulfonate, hexane sulfonyl xylene sulfonate, hexane sulfonyl naphthalene sulfonate, hexane sulfonyl dodecyl benzene sulfonate, benzene sulfonyl butane sulfonate, benzene sulfonyl toluene sulfonate, benzene sulfonyl xylene sulfonate, benzene sulfonylna Dripping down sulfonate, etc. benzenesulfonyl dodecylbenzene sulfonates.

Examples of the mixed acid anhydride with carboxylic acid include methanesulfonyl acetate, methanesulfonyl lactate, methanesulfonyl myristate, methanesulfonyl stearate, methanesulfonyl benzoate, methanesulfonyl naphthoate, butanesulfonyl propionate, butanesulfonyl palmyi. Tate, butanesulfonyl oleate, butanesulfonyl behenate, hexanesulfonyl acetate, hexanesulfonyl myristate, hexanesulfonyl stearate, dodecyl sulfonyl propionate, dodecyl sulfonyl palmitate, dodecyl sulfonyl myristate, dodecyl sulfonyl stearate, dodecyl sulfonyl oleate , Toluenesulfonyl acetate, Toluenesulfonyl propionate, Toluene Fonyl stearate, toluene sulfonyl terephthalate, dodecyl benzene sulfonyl propionate, dodecyl benzene sulfonyl lactate, dodecyl benzene sulfonyl succinate, dodecyl benzene sulfonyl palmitate, dodecyl benzene sulfonyl stearate, dodecyl benzene sulfonyl benzoate, dodecyl benzene sulfonyl naphthoate, etc. Is mentioned.

These sulfonic acid derivatives can be used alone or in combination. These may be added separately or may be added simultaneously. In the present invention, as described above, the sulfonic acid derivative is contained in the polycarbonate resin in an amount of 0.1 to 10 equivalents, preferably 0.2 to 7 equivalents, and more preferably 0.3 equivalent, per equivalent of the total polycondensation catalyst.
Add ~ 5 equivalents. Addition of such a sulfonic acid derivative improves the hydrolysis resistance of the polycarbonate during melting or during wet heat treatment.

In the method for producing a polycarbonate according to the present invention, a phosphorus compound may be added if necessary. As such a phosphorus compound, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphorous acid ester can be used.

Specific examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate,
Tributyl phosphate, trioctyl phosphate,
Tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate,
Trialkyl phosphates such as tris (2-chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tricycloalkylphosphates such as tricyclohexylphosphate, triphenylphosphate, tricresylphosphate, tris (nonylphenyl) phosphate, Examples thereof include triaryl phosphates such as 2-ethylphenyldiphenyl phosphate.

Further, examples of the phosphite ester include compounds represented by the following general formula.

P (OR) ₃ (In the formula, R represents an alicyclic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. These may be the same or different.) Examples of the compound represented by the formula include trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, tris (2-ethylhexyl) phosphite, trinonylphosphite, tridecylphosphite, trioctadecylphosphite. Trialkylphosphite such as phyto, tristearyl phosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite, tricycloalkylphosphite such as tricyclohexylphosphite,
Triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite And arylalkyl phosphites such as phenyldidecylphosphite, diphenyldecylphosphite, diphenylisooctylphosphite, phenylisooctylphosphite, and 2-ethylhexyldiphenylphosphite.

Further, as phosphite, distearyl pentaerythrityl diphosphite, bis (2,4
-Di-t-butylphenyl) pentaerythrityl diphosphite and the like.

These compounds can be used alone or in combination. These may be added separately or may be added simultaneously. In the present invention, the phosphorus compound as described above is added to the polycarbonate resin in an amount of 10
~ 1000 ppm, preferably 50-500 ppm.

When the phosphorus compound is added to the polycarbonate, which is the reaction product, these may be added while the polycarbonate is in a molten state, or may be added after pelletizing the polycarbonate once and then remelting. . In the former, these are added while the polycarbonate, which is the reaction product in the molten reactor or extruder obtained after the completion of the polycondensation reaction, is in the molten state.

Specifically, for example, the compound (a) and a phosphorus compound, if necessary, are added to the polycarbonate obtained by the polycondensation reaction in the reactor to form a polycarbonate, which is then pelletized through an extruder. Alternatively, while the polycarbonate obtained by the polycondensation reaction is pelletized from the reactor through the extruder, if necessary, a phosphorus compound is added, and these are kneaded to form a polycarbonate. Obtainable.

In the present invention, the polycarbonate obtained as described above is added to the polycarbonate within a range not impairing the object of the present invention.
Ordinary heat resistance stabilizer, ultraviolet absorber, release agent, colorant, antistatic agent, slip agent, antiblocking agent, lubricant, antifogging agent, natural oil, synthetic oil, wax, as shown below.
You may add an organic type filler, an inorganic type filler, etc. Such additives may be added at the same time as the above phosphorus compound or may be added separately.

Specific examples of such heat-resistant stabilizers include phenol-based stabilizers, organic thioether-based stabilizers, hindered amine-based stabilizers, and the like.

As the phenolic stabilizer, for example, n-
Octadecyl-3- (4-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3', 5'-di-t-butyl-4-]
Hydroxyphenyl) propionate] methane, 1,
1,3-Tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzyl malonate, 4-hydroxymethyl-2,6-di-t-butylphenol, etc. were listed, and these were used alone. You may use, or may mix and use 2 or more types.

Examples of the thioether stabilizers include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, Pentaerythritol-Tetrakis- (β-
Lauryl-thiopropionate) and the like.

These may be used alone or in combination of two or more. Examples of hindered amine stabilizers include bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, bis (1, 2, 2, 6, 6-
Pentamethyl-4-piperidyl) sebacate, 1- [2
-{3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy} -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2 , 4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine,
2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,2)
6-pentamethyl-4-piperidyl) tetrakis (2,2
2,6,6-tetramethyl-4-piperidyl) 1,2,
3,4-butane tetracarboxylate and the like can be mentioned.

These may be used alone or in combination of two or more. These heat stabilizers are used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, and more preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the polycarbonate. It is desirable to be used.

Such heat resistance stabilizer may be added in the form of solid or liquid. Such a heat stabilizer is preferably added while the resulting polycarbonate is in a molten state while being cooled and pelletized from the final polymerization vessel, and in this case the polycarbonate undergoes a small number of thermal history. Further, when the heat treatment such as extrusion molding or pelletizing is performed again, since the polycarbonate contains the heat resistance stabilizer, thermal decomposition can be suppressed.

The UV absorber may be a general UV absorber and is not particularly limited, and examples thereof include salicylic acid UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, cyanoacrylate UV absorbers. And so on.

Specific examples of the salicylic acid type ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate. Benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone, 2,
2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4 -N-octoxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone, 4
-Dodecyloxy-2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the like can be mentioned.

Examples of the benzotriazole type ultraviolet absorber include 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole and 2- (2'-hydroxy-).
3 ', 5'-di-t-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-
5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy 3 ', 5'-di-t-butyl-phenyl) -5-chlorobenzotriazole, 2
-(2'-hydroxy-5'-t-octylphenyl)
Benzotriazole, 2- (2'-hydroxy-3 ',
5'-di-t-amylphenyl) benzotriazole,
2- [2'-hydroxy-3 '-(3 ", 4", 5 ",
6 ″ -tetrahydrophthalimidomethyl) 5′-methylphenyl] benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6
-(2H-benzotriazol-2-yl) phenol] and the like.

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate. These may be used alone or in combination of two or more.

These UV absorbers are usually used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of polycarbonate.
It can be used in an amount of preferably 0.005 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight.

Further, the release agent may be a general release agent and is not particularly limited. For example, examples of the hydrocarbon releasing agent include natural and synthetic paraffins, polyethylene waxes, fluorocarbons and the like.

Polycarbonate 10 is used as the releasing agent.
0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight, and more preferably 0.01 to 0 part by weight.
It can be used in amounts of up to 0.5 parts by weight.

Further, the colorant may be a pigment or a dye. The colorant includes an inorganic colorant and an organic colorant, whichever may be used.
You may use it in combination.

These colorants may be used alone or in combination. These colorants are usually used in an amount of 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × 10 ^{−5 to} 3 parts by weight, and more preferably 1 × 10 ⁻⁵ to 1 part by weight, based on 100 parts by weight of polycarbonate. Can be used.

[0072]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0073]

Examples 1 to 10 and Comparative Examples 1 and 2 228 parts of 2,2-bis (4-hydroxyphenyl) propane (parts represent parts by weight, the same applies hereinafter), diphenyl carbonate 2
08 parts and a predetermined amount of the catalyst shown in Table 1 were charged into a reactor equipped with a stirrer, a pressure reducing device, a distillation column and the like. 18
It was dissolved by stirring at 0 ° C. under a nitrogen atmosphere for 30 minutes. Then, the pressure was gradually reduced and the reaction was carried out while distilling phenol at 100 mmHg for 1 hour.

Further, the temperature is gradually raised and the pressure is reduced, and finally 290
The temperature was raised to 1 ° C., the pressure was reduced to 1 mmHg or less, and polymerization was carried out at the same temperature and the same pressure for 2 hours to produce a polycarbonate resin.

Next, the molten resin was fed into the biaxial ruder (L / D = 20 barrel temperature 300 ° C.) by a gear pump. At this time, the phosphorus compounds and the phenolic stabilizers shown in Table 1 were added in predetermined amounts, if necessary. Physical properties of the obtained polycarbonate are shown in Tables 1 to 3.

For comparison, a polycarbonate was produced in the same manner as in Example 1 except that NaOH (Comparative Example 1) and tetraammonium hydroxide (Comparative Example 2) were used as catalysts. The results are shown in Table 3.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

In the present invention, physical properties were measured as follows.

(I) Intrinsic viscosity [η]: 2 in methylene chloride
It was measured with an Ubbelohde viscometer at 0 ° C.

(Ii) Solubility: 5 g of the polymer was added to 100 ml of methylene chloride, and the mixture was irradiated with ultrasonic waves at 25 ° C. and dissolved. The obtained polymer solution was filtered through a 0.2 μ Millipore filter under a pressure of 0.5 kg / cm ² . When there was no insoluble matter, the filtration was completed within 30 minutes.

(Iii) Polymer color tone (a) Yellowness (YI): An injection-molded plate having a thickness of 3 mm was molded at a cylinder temperature of 310 ° C., an injection pressure of 1000 kg / cm ² , and a mold temperature of 90 ° C. X, Y and Z values are made by Nippon Denshoku Industries Co., Ltd .: “Color and Color Defference Meter ND-100.
The L value and [YI] were determined by a transmission method at 1DP ". (B) Haze: same as above, injection-molded plate was manufactured by Nippon Denshoku Industries Co., Ltd.
Measured with H-200 ".

Claims (2)

[Claims] 1. When producing a polycarbonate by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a catalyst, the catalyst comprises the following formulas (I) and (II):
A method for producing a polycarbonate, comprising at least one aluminum-containing six-membered cyclic compound selected from the group consisting of compounds represented by (III) and (IV). [Chemical 1] [In the formula, R ₁ , R ₂ , R ₃ , X, Z, X ₁ and Z ₁ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. Selected from the group consisting of aryl groups and aralkyl groups having 6 to 20 carbon atoms. Y and Y ₁ are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. In addition, m and n are 0 or an integer,
m + n = 3. ] 2. A catalyst of formula (I), (II), (III)
The method according to claim 1, wherein at least one aluminum-containing six-membered cyclic compound selected from the group consisting of compounds represented by the formulas (4) and (IV) and an amine derivative compound are used.