WO1995002624A1

WO1995002624A1 - Process for producing polycarbonate

Info

Publication number: WO1995002624A1
Application number: PCT/JP1994/001146
Authority: WO
Inventors: Mitsunori Itoh; Toru Bando
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 1993-07-14
Filing date: 1994-07-13
Publication date: 1995-01-26
Also published as: JPH0726011A

Abstract

A process for producing a polycarbonate by the transesterification between a carbonic diester and a dihydric phenol, which comprises using an alkali metal amide having at least one hydrogen atom thereof substituted as a polycondensation catalyst, thereby producing a chemically stable polycarbonate having excellent thermal stability and hydrolysis resistance and a sufficiently high molecular weight at a good productivity.

Description

Specification

Manufacturing method of polycarbonate

An object of the present invention is to produce a high-molecular-weight polycarbonate suitable for use in various mechanical parts, optical discs, electric / electronic equipment parts, automobile parts, and the like with high productivity without deteriorating the physical properties of the polycarbonate by a transesterification reaction. It relates to a manufacturing method. Technology background

Polycarbonate is an engineering plastic with excellent transparency, heat resistance and impact resistance, and has been widely used in the industrial field for applications such as various mechanical parts, optical discs, electric and electronic equipment parts, and automobile parts.

As a generally used method for producing such a polycarbonate, there is an interfacial polycondensation method in which a divalent phenol such as bisphenol A is directly reacted with phosgene in a solvent mainly comprising methylene chloride. However, this interfacial polycondensation method has a problem that toxic phosgene gas and methylene chloride as a chlorine impurity source are used in the production process. As a method for solving this problem, there is a melt polymerization method by a transesterification reaction between a carbonic acid diester and a divalent phenol.

In the production of polycarbonate by this transesterification reaction, a basic catalyst such as an alkali metal or alkaline earth metal carbonate, acetate or hydroxide has conventionally been used as a reaction catalyst. In addition, recently, for example, a method using a barium compound and a borate ester as a catalyst described in Japanese Patent Application Laid-Open No. 3-209328, and a method described in Japanese Patent Application Laid-Open No. A method using an electron-donating amine as a catalyst, an electron-donating amine compound described in JP-A-5-1145, etc., and an element of Group IIb, IVb, or Vb of the periodic table. There is a method of using the compound containing as a catalyst. However, these catalysts The basic nature of the catalyst reduces the chemical stability of the carbonate bond, and therefore, if these catalysts remain in the final product, polycarbonate, they will be thermally stable. This leads to deterioration of physical properties such as properties and hydrolysis resistance. In addition, when melt polycondensation is performed under the conditions of high temperature and high vacuum using these catalysts, there is a problem that the obtained polycarbonate is colored.

As a means of preventing the deterioration of the physical properties of these final products, there is a method of reducing the amount of the above-mentioned catalyst.However, this method slows down the polymerization rate and requires a long time for the production, thus reducing the productivity. As a result, there is a problem that the product cost increases. On the other hand, when a metal salt having no basicity is used as a catalyst, there is a problem that the polymerization activity is low and the polymer cannot be put to practical use, though the physical properties of the polyester are not reduced.

In order to solve these problems, for example, Japanese Patent Application Laid-Open No. Hei 4-175368 proposes a method of adding an acidic compound to a system at the end of polymerization to neutralize a basic catalyst. However, according to this method, there are problems that the operation becomes complicated, or there is a possibility that the added acid substance may remain and deteriorate the physical properties of the polycarbonate. Is hard to say.

JP-A-63-179926 and JP-A-63-23036 disclose a melt polycondensation method using a beryllium compound or a magnesium compound as a catalyst. It is reported that colorless and transparent polycarbonate can be obtained by performing the method. However, according to the examples described in these publications, polycarbonates having a sufficiently high molecular weight have not been obtained in any of the catalyst systems. Disclosure of the invention

The present invention provides a production method capable of producing a high-quality, sufficiently high-molecular-weight polycarbonate with high productivity using a highly active catalyst when producing a polycarbonate by a transesterification reaction. The purpose is to:

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, it has been found that a small amount of an amide of an alkali metal substituted with at least one hydrogen atom exhibits high polycondensation activity. However, they have found that by using this as a catalyst, it is possible to obtain a sufficient high molecular weight product without deteriorating the physical properties of polycarbonate, and based on this finding, have completed the present invention.

That is, the present invention is characterized in that in producing a polycarbonate from a carbonic acid diester and a divalent phenol by a transesterification reaction, an amide of an alkali metal substituted with at least one hydrogen atom is used as a polycondensation catalyst. It provides a method for producing polycarbonate. BEST MODE FOR CARRYING OUT THE INVENTION

Preferable specific examples of the alkali metal amide used as the polycondensation catalyst in the production method of the present invention include, for example, those represented by the following general formula (I).

O o

R ¹

Awakening (I)

R

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a trialkylsilyl group (where each alkyl group has 1 carbon atom; ) Or a triarylsilyl group (wherein each aryl group is an aryl group having 6 to 12 carbon atoms), and both R ¹ and R ² are hydrogen atoms And M represents an alkali metal. ]

In the above formula, M is an alkali metal of lithium, sodium, potassium, norebidium, cesium or francium, of which sodium and lithium are particularly preferred, and sodium is particularly preferred. Particularly preferred examples of R ¹ and R ² include, for example, a trimethylsilyl group, an isopropyl group and an ethyl group.

Representative examples of these alkali metal amides include, for example, methyl lithium amide, ethyl lithium amide, propyl lithium amide, butyl lithium amide, benzyl lithium amide, methyl sodium amide, methyl sodium amide , Propyl sodium amide, butyl sodium amide, benzyl sodium amide , Methyl potassium amide, ethyl potassium amide, propyl potassium amide, butyl potassium amide, benzyl potassium amide, dimethyl lithium amide, dimethyl lithium amide, dipropyl lithium amide, dibutyl lithium amide , Dibenzyl lithium amide, dimethyl sodium amide, getyl sodium amide, dipropyl sodium amide, dibutyl sodium amide, dibenzyl sodium amide, dimethyl potassium amide, getyl potassium amide, dipropyl potassium amide, dibutyl Alkali metal amides having an alkyl group such as potassium amide and dibenzyl potassium amide, phenyllithium amide, naphthyllithium amide, tolyllithium amide, phenylnatrim Mid, naphthyl sodium amide, tolyl sodium amide, phenyl potassium amide, naphthyl potassium amide, tolyl potassium amide, diphenyl lithium amide, dinaphthyl lithium amide, ditolyl lithium amide, diphenyl sodium amide Alkali metal amide having an aryl group such as dinaphthyl sodium amide, ditolyl sodium amide, diphenyl potassium amide, dinaphthyl potassium amide, ditolyl potassium amide, and (trimethylsilyl) lithium Amide, (triethylsilyl) lithium amide, (triprovirsilyl) lithium amide, (tributylsilyl) lithium amide, (tribenzylsilyl) lithium amide, (trimethylsilyl) sodium amide, (Rethylsilyl) sodium amide, (triprovirsilyl) sodium amide, (triptysilyl) sodium amide, (tribenzylsilyl) sodium amide, (trimethylsilyl) potassium amide, (triethylsilyl) potassium amide, (Virsilyl) potassium amide, (Tributylsilyl) potassium amide, (Tribenzylsilyl) potassium amide, Bis (trimethylsilyl) lithium amide, Bis (tritylsilyl) lithium amide, Bis (triprovylsilyl) lithium amide Bis (tributylsilyl) lithium amide, bis (tribenzylsilyl) lithium amide, bis (trimethylsilyl) sodium amide, bis (triethylsilyl) natriamide Scan (triprolidine building silyl) sodium Ami, bis (tributyl Chirushiriru) sodium Ami, bis (tribenzylsilyl) sodium Ami Tris (silyl) potassium amide, bis (trimethylsilyl) potassium amide, bis (tripylsilyl) potassium amide, bis (tripyrylsilyl) potassium amide, bis (tribenzylsilyl) potassium amide, bis (tribenzylsilyl) potassium amide, etc. Amide of alkali metal having a group, (triphenylsilyl) lithium amide, (trinaphthylsilyl) lithium amide, (tritrisilyl) lithium amide, (triphenylsilyl) sodium amide, (trinaphthylsilyl) sodium amide , (Tritrisilyl) sodium amide, (triphenylsilyl) potassium amide, (trinaphthylsilyl) potassium amide, (tritolylsilyl) potassium amide, bis (triphenyl) Lil) lithium amide, bis (trinaphthylsilyl) lithium amide, bis (tritolylsilyl) lithium amide, bis (triphenylsilyl) sodium amide, bis (trinaphthylsilyl) sodium amide, bis (tritolylsilyl) ) Examples include alkali metal amides having a triarylsilyl group, such as sodium amide, potassium bis (triphenylsilyl) amide, potassium bis (trinaphthylsilyl) amide, and potassium bis (tritolylsilyl) amide. Can be

Among these alkali metal amides, for example, bis (trimethylsilyl) lithium amide, bis (trimethylsilyl) sodium amide, bis (isopropyl) lithium amide, bis (isopropyl) sodium amide, getyllithium amide and getyllithium amide Chill sodium amide is preferably used.

In the production method of the present invention, one of the above-mentioned amides of alkali metal may be used alone, or two or more may be used in combination.

The amount of § Mi de of the Al force Li metal used in the manufacturing process as the polycondensation catalyst of the present invention, with respect to divalent Fuwenoru 1 mole of the main raw material, 1 0 - ^8-1 0 ¹ mole are preferred . If the amount of alkali metal amide used is less than 10 to ⁸ mol, the catalytic effect may be insufficient, while if it exceeds ¹⁰ to ¹ mol, the physical properties of the final product polycarbonate, especially heat resistance In some cases, may cause a decrease in the hydrolysis and hydrolysis resistance. Particularly preferred amount is 1 0- ^7-1 0- ⁴ mol.

In the present invention, the alkali metal amide is used as a solid It is administered as a solution using hydrofuran, toluene or the like as a solvent in the reaction raw material mixture. When the alkali metal amide is used as a solution, the concentration of the solution is not particularly limited as long as it is equal to or lower than the saturation concentration of the alkali metal amide to be used. A range of saturation concentrations is preferred.

In addition, according to the purpose, in addition to the alkali metal amide used in the present invention, other polycondensation catalysts, such as other conventionally used alkali metal compounds, may be used in the present invention without affecting the effect of the present invention. In addition, an alkaline earth metal compound, an amine, a quaternary ammonium salt or the like assimilating basic compound, boric acid, a borate ester or the like can be used in combination.

The carbonic acid diester used in the present invention is not particularly limited, and various carbonic acid diesters including known ones can be used.As the carbonic acid diester, one kind may be used alone, or two or more kinds may be used in combination. Is also good. Typical examples of the carbonic diester used are diphenyl carbonate, ditolyl carbonate, bis (clophenyl) carbonate, dinaphthyl carbonate, bis (biphenylyl) carbonate, getyl carbonate, dimethyl carbonate, dibutyl gar. Carbonate and dicyclohexyl carbonate. Among them, diphenyl carbonate is preferably used.

The amount of the carbonic acid diester to be used is 0.90 to 1.50 mol, preferably 0.95 to 1.25 mol, per 1 mol of the dihydric phenol. However, in order to reduce the physical properties of the polycarbonate, particularly the terminal hydroxyl groups as much as possible to eliminate the adverse effect on the hue, the carbonic acid diester is used in an amount of 1.01 to 1.50 with respect to 1 mol of divalent phenol. Mole, preferably from 1.015 to 1.20 mole.

If necessary, a reactive derivative of dicarboxylic acid or dicarboxylic acid may be used instead of part of the carbonic acid diester. In this case, a polyester carbonate is obtained.

Examples of such reactive derivatives of dicarponic acid or dicarboxylic acid include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, diphenyl isophthalate, diphenyl terephthalate, diphthalic isophthalate, and dichloride terephthalic acid; Aliphatic dicarboxylic acids such as citric acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sevanic acid, decandioic acid, dodecandioic acid, diphenyl sebacate, diphenyl decandioate, and 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-cyclopentane Diphenyl dicarboxylate, 1,2-cyclohexane Diphenyl dicarboxylate And alicyclic dicarboxylic acids such as diphenyl 1,1,3-cyclohexanedicarboxylate and diphenyl 1,4-cyclohexanedicarboxylate.

The amount of the dicarboxylic acid and the reactive derivative of the dicarboxylic acid to be used is, for example, 50 mol% or less, preferably 30 mol% or less of the polyester carbonate.

The divalent phenol used in the present invention is not particularly limited, and various divalent phenols including conventionally known ones can be used.In addition, only one type of the divalent phenol may be used alone, Two or more can be used in combination. Typical examples of the divalent phenol suitably used in the present invention include those represented by the following general formula (II).

[Wherein, R ³ and R ⁴ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms or 6 to 6 carbon atoms: substituted or unsubstituted with I 2 A and b are each independently an integer from 0 to 4, X is a single bond, — 0 one, — CO—, one S—, one SO—, one S 0 ₂ —, — CR ⁵ R ⁶ — (where R ⁵ and R ⁶ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms) It is a mono group.), Carbon number 5 1 to 11 1,1-cycloalkylidene group, 2 to 12 carbon atoms, ω-alkylene group or one R ⁷ R ⁸ C—Y—CR ⁷ R ⁸ — (where Y is a phenylene group , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group. ]

Specific examples of the divalent phenol represented by the general formula (II) include, for example, 4,4-dihydroxybiphenyl, 4,4′-dihydroxy-1,2,2′-dimethylbiphenyl, 4,4 'Dihydroxy-1,3'-dimethylbiphenyl, 4,4'-dihydroxy-1,3'dicyclohexylbiphenyl, 3,3' difluoro mouth 4,4'-dihydroxybisif Enyl, bis (4-hydroxyphenyl) ether, bis (3-fluoro-4-hydroxyphenyl) ether, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide, bis (3-methyl-) 4-Hydroxyphenyl) sulfide, Bis (4-Hydroxyphenyl) sulfoxide, Bis (3-methyl-1-4-hydroxyphenyl) sulfoxide, Bis (3-Fenyl-4) (Hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-14-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) methane, Bis (3-methyl-4-hydroxyphenyl) methane, Bis (3-chloro-4-phenyloxymethane) methane, Bis (3,5-dibutanol 4-hydroxyhydroxyphenyl) methane, 1,1-bis (4 —Hydroxyphenyl) 11-Phenylmethane, 1,1-bis (4-hydroxyphenyl) 1,1,1-Diphenylmethane, 1,1-bis (2-tert-butyl14-hydroxy-5) —Methylphenyl) 1-1-phenylmethane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (2-tert-butyl-4-) Hydroxy-3-methylphenyl) ethane, 1-Phenyl-1-, 1-bis (3-Fluoro-4-4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -111-phenylethane, 2- (3-Methyl-4-hydroxydroxyphenyl) 1-1- (4-Hydroxyphenyl) 111-phenylethane, 2,2-bis (4-hydroxydroxyphenyl) propane, .2,2-bis (3-methyl-14-phenyl) Droxifue Nil) Pro. 2-bis (2-methyl-14-hydroxyphenyl) propane, 11-bis (2-tert-butyl-14-hydroxy-15-methylphenyl) propane, 2,2-bis (3 —Chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 22—bis (3-bromo-14-hydroxyphenyl) propane, 2,2-bis (35 —Difluoro-4-hydroxyphenyl) propane, 22-bis (3,5-dichloro-4-hydroxyphenyl) propane, 22-bis (3,5-dibutene 4-hydroxyphenyl) propane, 2, 2— bis (3-bromo-4-arsenide de port carboxymethyl one 5- black port phenyl) flop ⁰ emissions, 2 2- bis (3-arsenide Dorokishifue two Le) to hexa full O b propane, 2 2- bis (3-Fuweniru one 4-arsenide Dorokishifu Eniru) up ⁰ , 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 1,1-bis (2-butyl 4-hydroxy-1-5-methylphenyl) butane , 11-bis (2-tert-butyl_4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-1-5-methylphenyl) isobutane, 1 1- Bis (2-tert-amylol 4-hydroxyl-5-methylphenyl) butane, 2,2-bis (35-diclo-4-hydroxyphenyl) butane, 22-bis (3,5-jib 4-Hydroxyphenyl) butane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (2-tert-butyl-14-hydroxy-5-methylphenyl) heptane, 2,2-bis (4— Hydroxyphenyl) oct 1,1-bis (4-hydroxyphenyl) cyclopentane, 11-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1 1 —Bis (3-cyclohexyl-1-hydroxyphenyl) cyclohexane, 11-bis (3-phenyl-14-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenyl) ethane, 1, 1'-bis (4-hydroxyphenyl) 1 p-diisopropylbenzene, 11'-bis (4-hydroxyphenyl) 1 m-diisopropylbenzene and the like. A particularly preferred divalent phenol is 2,2-bis (4-hydroxyphenyl) propane.

Further, as the divalent phenol, a monocyclic compound represented by the following general formula (III) can also be used.

(R ⁹ ¾ ^> f (0H) ₂ (III)

(In the formula, R ⁹ is each independently a halogen atom or an alkyl group having 1 to 10 carbon atoms or a halogenated alkyl group, and c is an integer of 0 to 4.)

Specific examples of the divalent phenol represented by the general formula (III) include, for example, resorcinol, 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, and 3-tert-butyl. Resorcinol, 3-phenylresorcinol, 3-cumylresorcinol, 2,3,4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, catechol, hide-mouth quinone, 3 —Methylhydroquinone, 3-Ethylhydroquinone, 3-Propylhydroquinone, 3-Butylhydroquinone, 3-tert-Butylhydrid quinone, 3-Phenylhydroquinone, 3-Cumylhydroquinone, 2,3,5,6 -Tetramethylhydroquinone, 2,3,4,6-tetra-tert-butylhydroquinone, 2,3,5,6-tetrafluorohigh Droquinone, 2,3,5,6-tetrabromohydroquinone and the like can be mentioned.

Further, in the present invention, 2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1-spirobilo [1H-indene] 16,6 'as a divalent phenol -Spiro compounds such as diols can also be used. If necessary, an alicyclic diol and an aliphatic diol may be used in addition to such a divalent phenol.

Further, a dihydric alcohol such as a hydroxyalkyl ester of biphenyldicarboxylic acid or a hydroxyalkylester of bicyclohexyldicarboxylic acid may be used instead of a part of the dihydric phenol. Again, the polyester carb A net is obtained.

In the present invention, when producing a polycarbonate, a polyfunctional compound having three or more functional groups in one molecule may be further used in combination as a branching agent. Examples of such polyfunctional compounds 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-14-hydroxyphenyl) ethane, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) 1-Heptene, 4,6-dimethyl-1,2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) 1-3 —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-hydroxy xyphenyl) cyclohexyl] pronogun, 2,4-bis [α- (4-hydroxyphenyl) isopropyl] phenol, 2,6-bis ( 2'-Hydroxy-1 5'-Methylbenzyl-1 4-Methylphenol, 2- (4-Hydroxyphenyl) 1-2- (2,4-Dihydroxyphenyl) propane, α, a ', Hi "-1 Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, na-methyl-α, ', a' — Tris (4-hydroxyphenyl) -1,4-ethylbenzene, hexakis [4- { a- (4-Hydroxyphenyl) isopropyl} phenyl] mono-terephthalate, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- {a- (4-hydroxyphenyl) isopropyl] phenoxy ] Methane, 1,4-bis [(4 ', 4 "—dihydroxytriphenyl) methyl] benzene, 2,4-dihydroxybenzoic acid, trimellitic acid, trimesic acid, pyromellitic acid, cyanuric chloride , 3,3-bis (3-methyl-4-hydroxyphenyl) 1,2-oxo-1,2,3-dihydroindole, 3,3-bis (4-hydroxylaryl) oxyindole, 5-chloroisatin, 5,7 Dichloroisatin, 5-bromoisatin phloroglyside and the like. As a reaction mode of the transesterification reaction between the carbonic acid diester and the dihydric phenol, a melt polycondensation method and a solid phase polycondensation method are suitable. In the case of performing the melt polycondensation method, after mixing the above-mentioned alkali metal amide or a solution thereof as a polycondensation catalyst, a carbonic acid diester and a divalent phenol, gradually reduce the pressure and raise the temperature, and then melt in a molten state at a high temperature under the reduced pressure. Done in The reaction is usually preferably carried out at a temperature ranging from 100 to about 320C. A more preferred reaction temperature is 130 to 300 ° C. When the reaction temperature is lower than 100 ° C., the progress of the polymerization reaction is slow and the production time may be long, which is not economical. On the other hand, when the temperature exceeds 320 ° C., coloring may be caused in the obtained poly-carbonate or a side reaction may occur, and a good product may not be obtained. When the solid-phase polycondensation method is used, the alkali metal amide or a solution thereof, a diester carbonate and a dihydric phenol are mixed, and while the diester carbonate and the dihydric phenol are kept in a solid state, the resulting polycarbonate is produced. The polycondensation is performed by heating to a temperature below the melting point of one carbonate. In any case, at the final stage of the reaction, the degree of reduced pressure is preferably set to 0.1 to 1 mmHg or less, and the phenols and alcohols derived from the above-mentioned diester carbonate generated by the transesterification reaction are taken out of the system. Distill off.

The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon, and if necessary, a terminal terminator, an antioxidant and the like may be added.

Representative examples of preferred end capping agents include phenol, naphthol, cresol, xylenol, p-tert-butylphenol, anisol, p-phenylphenol, black phenol, bromophenol, ethoxyphenol, aminophenol, and cyanophenol. , P-ditrophenol, 3-methyl-6-isopropylphenol, 2-methyl-5-isopropylphenol and the like.

Depending on the intended use, the polycarbonate obtained in this manner may be a commonly used heat stabilizer, ultraviolet absorber, release agent, coloring agent, antistatic agent, slip agent, antiblocking agent, lubricant, Fogging agents, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like may be added.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. It is not limited to these embodiments.

Example 1

In a 100 ml separable flask equipped with a stirrer and a distillation apparatus, 22.8 g (0.1 mol) of 2,2-bis (4-hydroxyphenyl) propane and 21.4 g of diphenyl carbonate (0. 1 mol). Here was added bis (trimethyl silyl) Na preparative Riumuami de 0. 1 8mg (lxl 0_ ⁶ moles). After that, the inside of the apparatus was replaced with argon, and then the inside temperature of the apparatus was set to 240. C, the degree of vacuum was gradually reduced to ImmHg, and the reaction was performed. Thereafter, the temperature in the apparatus was raised to 270 ° C., and polycondensation was performed at 270 ° C. for 120 minutes, and the produced phenol was distilled off to obtain 25 g of a colorless and transparent polycarbonate. When the thermal properties of the obtained polycarbonate were measured, the glass transition point (Tg) was 153. C. The reduced viscosity at 20 ° C of a solution having a concentration of 0.2 g / d1 containing methylene chloride as a solvent was 0.667 dl Zg, and the viscosity average molecular weight calculated from this value was 29,200. Was. Example 2

Polycarbonate was obtained in the same manner as in Example 1, except that bis (isopropyl) lithium amide was used instead of bis (trimethylsilyl) sodium amide. When the thermal properties of the obtained polycarbonate were measured, the glass transition point (Tg) was 152 ° C, the reduced viscosity was 0.667 d 1 / g, and the viscosity average molecular weight was 28,800. .

Comparative Example 1

A polycarbonate was obtained in exactly the same manner as in Example 1 except that sodium amide 0.39 mg (lx10 mol) was used instead of the bis (trimethylsilyl) sodium amide used in Example 1. . When the thermal properties of the obtained polycarbonate were measured, the glass transition point (T g) was 132 ° C. The reduced viscosity at 20 ° C of a solution having a concentration of 0.2 g / d1 using methylene chloride as a solvent is 0.292 dl Zg, and the viscosity average molecular weight calculated from this value is 10,700. Met.

In Examples and Comparative Examples, the glass transition temperature (Tg) was increased using DSC. Measured at a temperature rate of 20 ° CZ, the viscosity average molecular weight (Mv) is

[τ /] = 1. 23 x 10- 4 Μν 0 · 83

It calculated from the formula of. Industrial applications

According to the polycarbonate production method of the present invention, an alkali metal amide in which at least one hydrogen atom has been replaced is used as a polycondensation catalyst, so that it is chemically stable, heat stable, and resistant to heat. High quality polycarbonate having excellent properties such as hydrolyzability can be produced. In addition, since the alkali metal amide has a high polycondensation activity, the polycondensation proceeds rapidly with a small amount of use, and a sufficiently high molecular weight and high quality polycarbonate can be obtained with high productivity. Can be. The polycarbonate obtained by the method of the present invention is suitably used as a raw material for various mechanical parts, optical disks, electric and electronic equipment parts, automobile parts, and the like.

Claims

The scope of the claims

1. The production of polycarbonate from a diester carbonate and a dihydric phenol by transesterification is characterized by the use of an aluminum amide substituted with at least one hydrogen atom as a polycondensation catalyst. Manufacturing method of polycarbonate.

2. The divalent Fuwenoru 1 mole of preparation of polycarbonates according to claim 1, wherein the § Mi de of the Arukari metal 1 0 ^8-1 0 ¹ mols.

3. The amide of the alkali metal is represented by the following general formula R ¹

Marauder (I)

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a trialkylsilyl group (where each alkyl group has 1 carbon atom; Or an alkyl group of 1 to 12) or a triarylsilyl group (each aryl group is an aryl group having 6 to 12 carbon atoms), and both 1 ^ and 1 ^ ² are hydrogen atoms And M represents an alkali metal. ]

3. The method for producing a polycarbonate according to claim 2, which is represented by:

4. The amide of the alkali metal is bis (trimethylsilyl) lithium amide, bis (trimethylsilyl) sodium amide, bis (isopropyl) lithium amide, bis (isopropyl) sodium amide, getyllithium amide or getyllithium amide. 4. The method for producing a polycarbonate according to claim 3, which is tyl sodium amide.

5. The polycarbonate according to claim 4, wherein the amide of the metal is bis (trimethylsilyl) sodium amide or bis (isopropyl) lithium amide. Nate production method c

6. The divalent phenol has the following general formula (II)

Wherein R ³ and R ⁴ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. There, a and b are each independently an integer from 0 to 4, X is a single bond, one hundred and one, -CO-, - S-, -SO-, - S0 2 -, one CR ⁵ R ⁶ - ( Provided that R ⁵ and R ⁶ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.) 5 to 11, 1,1-cycloalkylidene group, α, ω-alkylene group having 2 to 12 carbon atoms or one R ⁷ R ⁸ C—Y—CR7R ⁸ — (where Y is a phenylene group, R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group.

Or the following general formula (I I I)

(R ⁹ ¾H3 + (0H) ₂ (no

(Wherein, R ⁹ is each independently a halogen atom or an alkyl group or a halogenated alkyl group having 1 to 10 carbon atoms, and c is an integer of 0 to 4.)

2. The method for producing a polycarbonate according to claim 1, which is a compound represented by the formula:

7. The carbonic diester is diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, dinaphthylcarbonate, bis (biphenylylyl) carbonate, getylcarbonate, dimethylcarbonate, dibutylcarbonate or dicyclohexyl. Claim 1 which is a carbonate A process for producing carbonate.

8. The process for producing a polycarbonate according to claim 5, wherein said divalent phenol is 2,2-bis (4-hydroxyphenyl) propane and said carbonic acid diester is diphenyl carbonate.