JP3205123B2 - Method for producing aromatic polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing polycarbonate. More specifically, the present invention relates to a method for producing a polycarbonate having improved hue, hydrolysis resistance, heat resistance and the like by using a specific catalyst.

[0002]

2. Description of the Related Art Polycarbonate is widely used because of its excellent 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 (interface method), or a method in which an aromatic dihydroxy compound such as bisphenol and a diaryl carbonate such as diphenyl carbonate are melted. A method of transesterification (melting method) and the like are known.

This method has the advantage that polycarbonate can be produced at a lower cost than the above-mentioned interface method, but on the other hand, the hue is not favorable, or a strongly basic catalyst remains in the polycarbonate. Therefore, there is a problem that the polymer has poor melt stability and hydrolysis resistance.

[0004] In order to improve the hydrolysis resistance and the melt stability of such polycarbonates, a method of kneading a high-boiling acidic compound in a molten state after polymerization to inactivate catalyst residues after polymerization has been conventionally performed. Was. However, in this method, it is necessary to uniformly knead a small amount of an acidic compound in a high-viscosity polymer, so that the production process becomes complicated,
Since the time to receive the thermal history of the polymer becomes long, it is not preferable in terms of hue.

Japanese Patent Application Laid-Open No. 2-124934 discloses a technique of polymerizing polycarbonate using a ternary catalyst of an alkali metal compound, boric acid and tetramethylammonium hydroxide. Although these catalyst systems are superior in hydrolysis resistance as a melting method conventionally, they are inferior to the interface method and are not yet sufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polycarbonate having excellent hue, hydrolysis resistance, melt stability and heat resistance.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, it has been found that polycarbonate produced by a melt polymerization method using a specific catalyst has hydrolysis resistance and melt stability. The present invention was found to have excellent properties and excellent hue, and reached the present invention.

That is, in the present invention, the ester moiety has carbon atoms.
A monovalent aliphatic hydrocarbon group having 1 to 12 or 5 to 5 carbon atoms
Aroma which is obtained by melt-polymerizing an aromatic dihydroxy compound and a diaryl carbonate in the presence of an acidic phosphoric ester salt and / or an acidic phosphite salt selected from 12 monovalent alicyclic hydrocarbon groups. 1 is a method for producing an aromatic polycarbonate.

Hereinafter, the present invention will be described in detail. The aromatic dihydroxy compound that can be used in the present invention is not particularly limited, and examples thereof include a compound represented by the following formula (I).

[0010]

Embedded image

In the formula, X is

[0012]

Embedded image It is.

Here, R ₂ and R ₃ 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 and an alkenyl group, and examples include a methyl group, an ethyl group, and a propyl group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a naphthyl group. Examples of the halogen atom include chlorine, bromine and iodine.

R ₄ 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, such as a butylene group and a pentylene group.

In the formula, R ₅ and R ₆ are the same or different and are 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 specifically, a methyl group, an ethyl group, and a propyl group. Examples of the aromatic group include a substituted or unsubstituted phenyl group and a naphthyl group. Examples of the halogen atom include chlorine, bromine and iodine.

In the formula, m and n are the same or different and represent 0 or an integer of 1 to 4.

Specifically, the following compounds can be mentioned. 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,
Dihydroxydiaryl sulfides such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;
4,4'-dihydroxydiphenylsulfoxide, 4,
Dihydroxydiarylsulfoxides such as 4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;4,4'-dihydroxydiphenylsulfone;
Dihydroxydiaryl sulfones such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;
Dihydroxydiaryls such as 9-bis (4-hydroxyphenyl) fluorene; Of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferably used. These aromatic dihydroxy compounds can be used alone or in combination.

Further, as the diaryl carbonate,
The carbonate is not particularly limited as long as it has an optionally substituted aryl group having 6 to 20 carbon atoms. Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, Naphthyl carbonate, bis (diphenyl) carbonate and the like can be mentioned. Of these, diphenyl carbonate is particularly preferably used. These diaryl carbonates can be used alone or in combination. The diaryl carbonate as described above is used in an amount of usually 1.0 to 1.30 mol, preferably 1.0 to 1 mol of the aromatic dihydroxy compound.
Desirably, it is used in an amount of 1 to 1.20 mol.

In the present invention, the ester moiety is used as a catalyst.
A monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or carbon
Using number 5-12 monovalent alicyclic acidic phosphate salt and / or acid phosphite salts selected from hydrocarbon groups of, but ester moiety in such salt having a carbon number of 1-12 monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms preferably. Examples of the aliphatic hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group and a propenyl group, and an alkenyl group. Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. etc. can be mentioned, et al. are.

As the cation component, I on the periodic table
Examples include metals from groups a to VIII and groups Ib to VIb and oniums such as quaternary ammonium and phosphonium, and elements of group Ia and group IIa and onium are preferably used.

[0021] ester moiety arbitrariness preferred mono-ester than diesters.

[0022] More specifically, as phosphoric acid ester salts, sodium dimethyl phosphate, dibutyl, sodium dihexyl phosphate, didecyl sodium phosphate,-phosphate dimethyl lithium phosphate di-butyllithium, phosphoric acid di decyl lithium, dimethyl potassium phosphate, potassium phosphate, dibutyl, didecyl potassium phosphate, monomethyl phosphate, mono-butyl magnesium phosphate, mono decyl magnesium phosphate, monobutyl calcium phosphate, monodecyl calcium phosphate,-phosphate Monomethyl strontium, monobutyl strontium phosphate, monodecyl strontium phosphate, and monobutyl barium phosphate are exemplified.

The phosphite salts include dimethyl lithium phosphite, dibutyl lithium phosphite, dihexyl lithium phosphite, dimethyl sodium phosphite, diethyl sodium phosphite, dibutyl sodium phosphite, phosphorus phosphite Sodium dicyclohexyl acid, sodium didecyl phosphite, dimethyl potassium phosphite ,
Dibutyl potassium phosphite , didecyl potassium phosphite, monobutyl magnesium phosphite, monodecyl magnesium phosphite, monobutyl calcium phosphite, monodecyl calcium phosphite, monomethyl strontium phosphite, phosphorous acid Monobutyl strontium, monodecyl strontium phosphite, monobutyl barium phosphite and the like can be mentioned.

Particularly preferred are sodium dibutyl phosphate, potassium didecyl phosphate, monobutyl magnesium phosphate, potassium monodecyl phosphate, sodium dibutyl phosphite, potassium didecyl phosphite, and monobutyl magnesium phosphite.

These compounds can be used alone or in combination.
10 ^-8 to 10 ^-1 mole, preferably 10 ^{-7, based on the} mole
It is used in an amount of from 10 to ² mol.

Further, the present invention provides, as a co-catalyst, an alkali metal compound other than an alkali metal phosphate and an alkali metal phosphite, and an alkali metal compound other than an alkali metal phosphate and an alkaline earth metal phosphite. It is also preferable to use at least one compound selected from the group consisting of alkaline earth metal compounds, other nitrogen-containing basic compounds, boric acid compounds, phosphonium compounds, aluminum compounds and the like at the same time.

As such an alkali metal compound,
Specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate,
Lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride,
Lithium borohydride, sodium borohydride,
Sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, Potassium salts, lithium salts and the like are used.

Further, as the alkaline earth metal compound,
Specifically, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, acetic acid Calcium, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like are used.

As the nitrogen-containing basic compound, for example, a nitrogen-containing compound which is easily decomposed or volatile at a high temperature, specifically, tetramethylammonium hydroxide (Me ₄ N
OH), tetraethylammonium hydroxide (Et
₄ NOH), tetrabutylammonium hydroxide alkyl, aryl, ammonium hydroxide oxides having like Aruariru group such as (Bu ₄ NOH), trimethylbenzylammonium hydroxide (phenyl _{-CH 2 (Me) 3 NOH)} , trimethylamine, triethylamine , Tertiary amines such as dimethylbenzylamine and triphenylamine, secondary amines represented by R ₂ NH (where R is an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and toluyl); RN
Primary amines represented by H ₂ (wherein R is the same as described above), imidazoles such as 2-methylimidazole, 2-phenylimidazole, or ammonia, tetramethylammonium borohydride (Me ₄ NB)
H ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh)
Basic salts such as ₄ ) are used. Of these,
Tetraalkylammonium hydroxides, in particular, tetraalkylammonium hydroxides for electronic use with little metal impurities are preferred.

Examples of the boric acid compound include boric acid and boric acid esters. As the borate ester, a general formula

[0031]

A borane represented by B (OR) _n (OH) _{3-n wherein} R is alkyl such as methyl or ethyl, aryl such as phenyl, and n is 1, 2 or 3. Acid esters are used.

Specific examples of such borate esters include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. Is used.

As the phosphonium compound, tetraarylphosphonium hydroxide and / or tetraalkylphosphonium hydroxide is used.
Specifically, tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide, tetratolylphosphonium hydroxide, tetraarylphosphonium hydroxide having another substituted aryl group , Tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetraalkylphosphonium hydroxide having another substituted alkyl group, and the like.

The aluminum compound has the following formula (I)

[0035]

Embedded image A compound represented by the formula: Al (OR ₇ ) ₃ (I) Here, R ₇ has 1 to 2 carbon atoms.
Represents a monovalent hydrocarbon group up to 0, and has 1 to 12 carbon atoms;
A monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms are preferable. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an alkyl group such as a propenyl group, an alkenyl group, and the like.As the alicyclic hydrocarbon group,
Examples thereof include cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and examples of the aromatic group include phenyl group and naphthyl group which may be substituted.

More specifically, the following compounds can be mentioned. Trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tri-n-butyroxyaluminum, tri-sec-butyroxyaluminum, tri-t-butyroxyaluminum, trihexyloxyaluminum, trioctyloxyaluminum, tricyclohexyloxy aluminum,
Examples include aluminum triphenoxy, aluminum trinaphthyloxy, aluminum tris (chlorophenoxy), and aluminum tris (diphenyloxy). These compounds can be used alone or in combination. One mole of the aromatic dihydroxy compound can be used in one mole.
It is used in an amount of 0 ^-8 to 10 ^-1 mol, preferably 10 ^-7 to 10 ^-2 mol.

The method of charging the catalyst system may be either solid or liquid, but is preferably a solution or suspension.
The concentration when the catalyst or cocatalyst is used as a solution or a suspension may be a concentration that can be handled in a liquid state, and is preferably 30% by weight or less, more preferably 20% by weight or less. The concentration of oxygen dissolved in the solution or suspension is 100
ppm or less, more preferably 50 ppm or less, even more preferably 10 ppm or less.
If it exceeds this range, coloring or branched components are likely to be generated due to the influence of dissolved oxygen.

In the present invention, it is also preferable to add various stabilizers in a molten state at least once before, during or after the polymerization. Examples of the stabilizer include an ion-containing acidic compound and / or a derivative formed from the acidic compound, a phenol-based stabilizer, a thioether-based stabilizer, a phosphorus-based stabilizer, a hindered amine-based stabilizer, an epoxy compound, and a salicylic acid-based ultraviolet absorber. Agents, benzotriazole-based ultraviolet absorbers, and the like.

Examples of the ion-containing acidic compound and / or a derivative formed from the acidic compound include sulfurous acid, sulfuric acid, sulfinic acid compounds, sulfonic acid compounds, and derivatives thereof. Specifically, as the sulfuric acid derivatives, dimethyl sulfate, diethyl sulfate, sulfuric acid,
Examples thereof include dipropyl sulfate, dibutyl sulfate, diphenyl sulfate, dimethyl sulfite, diethyl sulfite, and diphenyl sulfite.

Examples of the sulfinic acid compound include benzenesulfinic acid, toluenesulfinic acid, and naphthalene sulfinic acid. Examples of the sulfonic acid compound and its derivative include the following compounds. That is, benzenesulfonic acid, p
-Sulfonic acids such as toluenesulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p- Butyl toluenesulfonate, octyl p-toluenesulfonate, p-
Examples include sulfonic acid esters such as phenyl toluenesulfonic acid and ammonium sulfonic acid salts such as ammonium p-toluenesulfonic acid.

These compounds can be used alone or in combination. Of these, [B] pK
As the sulfur-containing acidic compound having an a value of 3 or less and a derivative formed from the acidic compound, a sulfonic acid compound or a derivative thereof is preferably used. In particular, benzenesulfonic acid, butylbenzenesulfonic acid, p-toluenesulfonic acid, Ethyl p-toluenesulfonate and butyl p-toluenesulfonate are preferably used.

Examples of the phenolic stabilizer include, for example, n
-Octadecyl-3- (4-hydroxy-3 ', 5'-
Di-tert-butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-)
Hydroxyphenyl) propionate] methane, 1,
1,3-Tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-tert-butyl) benzylmalonate, 4-hydroxymethyl-2,6-di-tert-butylphenol, etc., which are used alone They may be used alone or in combination of two or more.

As the thioether-based stabilizer, for example,
Dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, pentaerythritol-tetrakis- (β
-Lauryl-thiopropionate) and the like, and these may be used alone or as a mixture of two or more.

Examples of the phosphorus-based stabilizer include bis (2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, diphenyldecyl phosphite,
Arylalkyl phosphites such as phenylisooctyl phosphite and 2-ethylhexyl diphenyl phosphite; trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl diphosphite, and tris (2-chloroethyl ) Trialkyl phosphites such as phosphite and tris (2,3-dichloropropyl) phosphite; tricycloalkyl phosphites such as tricyclohexyl phosphite; triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) Phosphite, tris (2,4-di-t
Tributyl phosphite, tris (hydroxyphenyl) phosphite and other triaryl phosphites; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl phosphate, tris (2-chloroethyl) phosphate Trialkyl phosphates such as tricyclohexyl phosphate; triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate and 2-ethylphenyl diphenyl phosphate; They may be used alone or in combination of two or more.

The hindered amine stabilizers include
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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, tetrakis (2,2 , 6,6-tetramethyl-4
—Piperidyl) 1,2,3,4-butanetetracarboxylate and the like, and these may be used alone or as a mixture of two or more.

In the present invention, a compound having one or more epoxy groups in one molecule is used as the epoxy compound.

Specific examples of such epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxycyclohexylmethyl-
3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylsilohexylcarboxy Rate, bisphenol-A diglycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide , Tetraphenylethylene epoxide, octyl epoxy tartrate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5- Methyl-1,2-epoxycyclohexane, 3-methyl -5-t-butyl-1,2
Epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2
-Methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 '4,4'-Epoxycyclohexylcarboxylate, 4,6-dimethyl-
2,3-epoxycyclohexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-tert-butyl-4,5-
Epoxy tetrahydrophthalic anhydride, diethyl-4,5
-Epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-tert-butyl-4,5-
Epoxy-cis-1,2-cyclohexyldicarboxylate and the like can be mentioned.

Specific examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate. As the benzophenone-based ultraviolet absorber, 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.

As the benzotriazole-based UV absorber, 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole, 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 "94",
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-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate and the like.

These compounds are used in an amount of 10 ^-8 to 10 ^-1 mol, preferably 10 ^-7 to 10 ^-2 mol, per 1 mol of the aromatic dihydroxy compound.

In the present invention, when the above-mentioned aromatic dihydroxy compound and diaryl carbonate are melt-polycondensed to produce a polycarbonate, the reaction system has 10 to 40, preferably 15 to 15 carbon atoms as a terminal blocking agent.
To 40 to 40 mol%, preferably 0.5 to 7 mol%, based on the aromatic organic dihydroxy compound.
Mol%, more preferably 1 to 5 mol%.

As the phenols having 10 to 40 carbon atoms as described above, the following compounds are used. o-
n-butylphenol, p-cyclohexylphenol, o-phenylphenol, m-isobutylphenol, mn-nonylphenol, pt-butylphenol, om-pentylphenol, p-cumylphenol, pm-pentylphenol , O-naphthylphenol, pn-pentylphenol, mn-hexylphenol, 2,6-di-tert-butylphenol,
2,4-di-tert-butylphenol, 3,5-di-tert-
Butylphenol, 2,6-dicumylphenol, 3,
5-Dicumylphenol, 2,2,2-trimethyl-4
Monovalent phenols such as monohydroxychroman derivatives such as-(hydroxyphenyl) chroman are used.

The catalyst thus combined is preferable because the polycondensation reaction can proceed at a sufficient speed to produce a high molecular weight polycarbonate with high polymerization activity.
In the presence of such a catalyst, the polycondensation reaction between the aromatic dihydroxy compound and the diaryl carbonate can be carried out under the same conditions as conventionally known polycondensation reaction conditions.

Specifically, the first-stage reaction is carried out at 80 to 25.
0 ° C., preferably 100-230 ° C., more preferably 120-190 ° C., for 0-5 hours, preferably 0 ° C.
The aromatic dihydroxy compound and the diaryl carbonate are reacted under reduced pressure for 4 to 4 hours, more preferably 0 to 3 hours. Next, the reaction temperature is increased while increasing the degree of vacuum in the reaction system, and the reaction between the aromatic dihydroxy compound and the diaryl carbonate is carried out.
A polycondensation reaction between the aromatic dihydroxy compound and the diaryl carbonate is performed at 20 ° C.

The polycondensation reaction as described above may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

The reaction product polycarbonate obtained as described above usually has an intrinsic viscosity (phenol / 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 40/60)) measured at 35 ° C. ) Is 0.1-1.
0, preferably 0.2 to 0.8.

In the present invention, the polycarbonate obtained as described above has ordinary heat stability, an ultraviolet absorber, a releasing agent, a coloring agent, an antistatic agent, a lubricant, an antifogging agent as long as the object of the present invention is not impaired. , Natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like.

[0059]

According to the present invention, a polycarbonate having excellent hydrolysis resistance, melt stability and hue can be efficiently produced.

[0060]

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

The hydrolysis resistance was evaluated by the following method. The polymer sample is pulverized so that the particle size becomes 20 to 50 mesh, 0.3 g of the pulverized sample and 4 ml of water are sealed in a test tube, and this is heat-treated at 130 ° C. for 100 hours. The viscosity average molecular weight was determined from the viscosity, and the molecular weight retention after treatment was determined and evaluated from this value.

The intrinsic viscosity of phenol / 35 ° C.
The measurement was performed with a 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 40/60). The hue was observed by visual observation of the polymerized pellet.

[0063]

Examples 1 to 8, Comparative Example 1 A predetermined amount of bisphenol A, diphenyl carbonate and a catalyst described in Tables 1 and 2 were added to a 300 ml flask equipped with a stirrer and a distilling tube.
The mixture was charged into a stainless steel flask, subjected to degassed nitrogen replacement three times, and then melted at 180 ° C. Next, while maintaining this temperature, the pressure was reduced to 30 mmHg, and for 45 minutes,
The reaction was allowed to proceed for 30 minutes while reducing the pressure to 5 mmHg. The conversion was determined from the amount of phenol distilled out during the initial polymerization reaction, and is shown in Tables 1 and 2. Next 2 over 45 minutes
The temperature was raised to 90 ° C., and finally the late-stage polymerization reaction was performed at 290 ° C. and a pressure of 1 mmHg or less for the times shown in Tables 1 and 2. Tables 1 and 2 show the observation results of intrinsic viscosity and hue of the obtained polycarbonate.

For comparison, Table 2 shows the results when only sodium hydroxide, which is a typical alkali metal compound, was used as a catalyst. From the results, it can be seen that the catalyst system of the present invention has excellent hydrolysis resistance and good hue. It can be seen that a polymer can be produced.

[0065]

[Table 1]

[0066]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-56983 (JP, A) JP-B 46-20503 (JP, B1) JP-B 44-27984 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) C08G 64/00-64/42 C08L 69/00

Claims (1)

(57) [Claims] (1) a monovalent ester having an ester moiety having 1 to 12 carbon atoms;
Aliphatic hydrocarbon group or monovalent alicyclic ring having 5 to 12 carbon atoms
A process for producing an aromatic polycarbonate, comprising melt-polymerizing an aromatic dihydroxy compound and a diaryl carbonate in the presence of an acidic phosphoric acid ester salt and / or an acidic phosphite salt selected from aromatic hydrocarbon groups .