JP2833981B2 - Method for producing copolymerized polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a copolymerized polycarbonate. More specifically, when using a carbonic acid diester and a plurality of types of aromatic dihydroxy compounds and performing copolymerization by a transesterification method, the color tone is excellent,
The present invention relates to a method for producing a copolymerized polycarbonate capable of increasing the molecular weight.

[0002]

2. Description of the Related Art In order to improve the heat resistance of polycarbonate using one kind of bisphenol represented by bisphenol A, production of a polycarbonate copolymer using a specific kind of bisphenol has been attempted, and optical components,
It has begun to be suitably used for mechanical parts, electric / electronic parts, automobile parts and the like. As the specific bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene is known, and a copolymerized polycarbonate containing this as a copolymer component is known to have high heat resistance (US Pat. No. 3,546,165). ).

As a method for producing a copolymerized polycarbonate containing 9,9-bis (4-hydroxyphenyl) fluorene as a copolymerization component, an interfacial polycondensation method using a solvent is well known. For example, a method using 1,2-dichloroethane or chloroform as a solvent (U.S. Pat.
5, Japanese Patent Application Laid-Open No. 63-182336), a method of using an aqueous potassium hydroxide solution and methylene chloride to solve problems such as molding heat stability and mold rust during molding (Japanese Patent Application No. 4-3023).
No. 58). However, when an attempt is made to produce a polycarbonate copolymer using a solvent in this way, the obtained copolymer is difficult to crystallize, so it is difficult to isolate the polymer from the solvent, and the productivity is low. It decreases significantly.

On the other hand, there is a so-called transesterification method in which a dihydroxy compound and diphenyl carbonate are usually melt-polycondensed without using a solvent. The transesterification method (melt polymerization method) for producing polycarbonate generally has an advantage that it can be produced at lower cost than the above-mentioned interfacial polycondensation method.
Since the reaction is carried out at a high temperature of 0 ° C. for a long time, there is a major drawback that the problem of resin coloring cannot be avoided. In order to reduce coloring in such a melting method, various improved techniques have been proposed. For example, Japanese Patent Publication No. 61-399
No. 72, JP-A-63-223036 and the like disclose a method using a specific catalyst. Also, Japanese Unexamined Patent Publication No.
JP-A-151236 and JP-A-62-158719 disclose a method of adding an antioxidant at a later stage of the reaction. Japanese Patent Application Laid-Open No. 61-62522 discloses a twin-screw vented kneading extruder in the latter stage of the reaction.
No. 3925 discloses a process improvement technique such as using a horizontal stirring polymerization tank. Further, Japanese Unexamined Patent Publication No.
175722 discloses a method for reducing the content of hydrolyzable chlorine in a monomer to a certain level or less. In order to improve the hydrolysis resistance of this polycarbonate, it has been conventionally known that the polycarbonate is neutralized with a volatile acid such as dimethyl sulfate, and recently, neutralization with an acid such as p-toluenesulfonic acid. And a method of neutralizing excess acid with epoxy (JP-A-4-175368) is known. However, in general, this problem has not been completely solved, and a satisfactory polycarbonate has not yet been obtained. Also, in the case of producing a polycarbonate copolymer using 9,9-bis (4-hydroxyphenyl) fluorene as a copolymer component by a transesterification method, the reaction temperature must be higher in the latter half of the polymerization reaction. As a necessity, it was found that the color tone of the copolymer was remarkably reduced, and it was difficult to increase the molecular weight.

[0005]

Accordingly, the present invention is directed to a copolymer for producing a polycarbonate copolymer having 9,9-bis (4-hydroxyphenyl) fluorene as a copolymer component by this transesterification method. It is an object of the present invention to solve the problems of the lowering of the color tone and the difficulty of polymerizing.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve this problem, and as a result, during the transesterification reaction between the first copolymerization component and the carbonic acid diester, the first esterification reaction was carried out.
It has been found that it is effective to add 9,9-bis (4-hydroxyphenyl) fluorene as the second copolymer component after the copolymer component reaches a certain reaction rate or more. The invention has been completed.

That is, the gist of the present invention is that the general formula (1)

[0008]

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(Where X ¹ and Y ¹ each independently represent hydrogen, a halogen atom or an organic group having 1 to 8 carbon atoms;
m and n are each independently an integer of 1 to 4, but when a plurality is present, X ¹ and Y ¹ may be different from each other. (1) and a general formula (2)

[0010]

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(Where A is an alkylidene group having 2 to 15 carbon atoms, an alkylene group having 1 to 15 carbon atoms,
5, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 15 carbon atoms, and 7 carbon atoms
To 15 arylalkylene groups, single bond, -S-, -S
_{O -, - SO 2 -,} - O -, - CO- or formula

[0012]

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X ² and Y ² each independently represent hydrogen, a halogen atom, or an organic group having 1 to 8 carbon atoms, and p and q each independently represent an integer of 1 to 4 However, when there is a plurality, X ² and Y ² may be different from each other. In producing a copolymerized polycarbonate from the aromatic dihydroxy compound (2) represented by the formula (2) and the carbonic acid diester by a transesterification method, the aromatic dihydroxy compound (2) and the carbonic acid diester are subjected to a transesterification reaction as a first step, After the reaction rate of the aromatic dihydroxy compound (2) becomes 50% or more, the second step is a method for producing a copolymerized polycarbonate by adding the aromatic dihydroxy compound (1) and further subjecting it to a transesterification reaction.

The compound represented by the general formula (1) is used in the present invention.
The aromatic dihydroxy compound is 9,9-bis (4-
(Hydroxyphenyl) fluorene or a derivative thereof
, X ¹And Y¹Are independently hydrogen and halogen atoms
(Eg, chlorine, bromine, fluorine, iodine) or 1 to 1 carbon atoms
8 organic groups (typically methyl, ethyl, propyl
Group, n-butyl group, isobutyl group, amyl group, isoamido group
And hexyl groups), and m and n are each independently
It is selected from an integer of 1 to 4. X when m or n is 2 or more
¹Or Y¹May be the same or different. What
The fluorene group has a nuclear substituent in order to obtain the raw material.
Is not selected, but as the copolymerization component in the present invention.
9,9-bis having a nucleus-substituted fluorene group
(4-Hydroxyphenyl) fluorene may be used.

Next, the aromatic dihydroxy compound represented by the general formula (2) used in the present invention will be described.
A in the general formula (2) represents an alkylene group having 1 to 15 carbon atoms or an alkylidene group having 2 to 15 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, ethylidene group, isopropylidene group). A cycloalkylene group having 5 to 15 carbon atoms or a cycloalkylidene group having 5 to 15 carbon atoms (eg, cyclopentylene group, cyclohexylene group, cyclopentylidene group, cyclohexylidene group), carbon number 7-15
, A single bond, -S-, -SO
—, —SO ₂ —, —O—, —CO— or a bond represented by the above formula (3). X ² and Y ² each represent hydrogen, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group) , Amyl group, isoamyl group, hexyl group, etc.), and X ² and Y ² may be the same or different. p and q are selected from integers of 1 to 4, and may be the same or different. When p or q is plural, X ²
Or, Y ² may be the same or different.

As the aromatic dihydroxy compound represented by the general formula (2), bis (4-hydroxyphenyl) methane; bis (3-methyl-4-hydroxyphenyl) methane; bis (3-chloro-4-hydroxy) Phenyl) methane; bis (3,5-dibromo-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl)
Ethane; 1,1-bis (2-t-butyl-4-hydroxy-3-methylphenyl) ethane; 1-phenyl-1,
1-bis (2-fluoro-4-hydroxy-3-methylphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A: BPA);
2,2-bis (3-methyl-4-hydroxyphenyl)
Propane; 2,2-bis (2-methyl-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (2-t-butyl- 4-hydroxy-5-methylphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2,2-bis (3-bromo-4-hydroxyphenyl) propane;
2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dichloro-
4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane;
2,2-bis (4-hydroxyphenyl) octane; bis (4-hydroxyphenyl) phenylmethane; 1,1
-Bis (4-hydroxy-t-butylphenyl) propane; 2,2-bis (3-bromo-4-hydroxy-5-
Chlorophenyl) propane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4-hydroxyphenyl) butane;
1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane; 1,1-bis (2-t-butyl-4-
1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) isobutane; 1,1-bis (2-t-amyl-4)
-Hydroxy-5-methylphenyl) butane; 2,2-
Bis (3,5-dichloro-4-hydroxyphenyl) butane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane; 4,4-bis (4-hydroxyphenyl) heptane; 1,1 -Bis (2-t-butyl-4
Bis (hydroxyaryl) alkanes such as -hydroxy-5-methylphenyl) heptane; 1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1-
Bis (4-hydroxyphenyl) cyclohexane; 1,
1-bis (3-methyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (3-cyclohexyl-4-)
1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) -3,
Bis (hydroxyaryl) cycloalkanes such as 3,5-trimethylcyclohexane; bis (4-hydroxyphenyl) ether; bis (hydroxyaryl) ethers such as bis (4-hydroxy-3-methylphenyl) ether; bis ( 4-hydroxyphenyl) sulfide; bis (3-methyl-4-hydroxyphenyl)
Bis (hydroxyaryl) sulfides such as sulfide; bis (4-hydroxyphenyl) sulfoxide;
Bis (3-methyl-4-hydroxyphenyl) sulfoxide; bis (3-phenyl-4-hydroxyphenyl)
Bis (hydroxyaryl) sulfoxides such as sulfoxide; bis (4hydroxyphenyl) sulfone; bis (3-methyl-4-hydroxyphenyl) sulfone;
Bis (hydroxyaryl) sulfones such as bis (3-phenyl-4-hydroxyphenyl) sulfone;
4,4'-dihydroxy-2,2'-dimethylbiphenyl;4,4'-dihydroxy-3,3'-dimethylbiphenyl;4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl;
And dihydroxybiphenyls such as 3,3'-difluoro-4,4'-dihydroxybiphenyl.
These aromatic dihydroxy compounds can be used alone or in combination of two or more.

The production method of the present invention can be applied to a polycarbonate of an aromatic dihydroxy compound other than the aromatic dihydroxy compound represented by the general formula (2), but the aromatic dihydroxy compound represented by the general formula (2) can be used. The effect is great when polycarbonates, especially bis (hydroxyaryl) alkanes, are used, and bisphenol A is a typical and most preferred one. In addition, as the aromatic dihydroxy compound other than the aromatic dihydroxy compound represented by the general formula (2),
Examples include dihydroxybenzenes, halogen and alkyl-substituted dihydroxybenzenes. For example, resorcin, 5-methylresorcin, 5-ethylresorcin, 5
-Propyl resorcinol, 5-butyl resorcinol, 5-t
-Butyl resorcin, 5-phenyl resorcin, 5-cumyl resorcin; 2,4,5,6-tetrafluororesorcin; 2,4,5,6-tetrabromoresorcin; catechol, hydroquinone, 3-methylhydroquinone, 3- Ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone; 2,5-dichlorohydroquinone;
2,3,5,6-tetramethylhydroquinone; 2,
3,5,6-tetra-t-butylhydroquinone; 2,
3,5,6-tetrafluorohydroquinone; 2,3
5,6-tetrabromohydroquinone and the like.

Examples of the aliphatic dihydroxy compound which can be used in place of the aromatic dihydroxy compound (2) of the general formula (2) include butane-1,4-diol;
-Dimethylpropane-1,3-diol; hexane-
1,6-diol; diethylene glycol; triethylene glycol; tetraethylene glycol; octaethylene glycol; dipropylene glycol; N, N-methyldiethanolamine; cyclohexane-1,3-diol; cyclohexane-1,4-diol; , 4-
Dimethylolcyclohexane; p-xylylene glycol; 2,2-bis- (4-hydroxycyclohexyl)
-Ethoxylated or propoxylated products of propane and dihydric alcohols or phenols, such as bis-oxyethyl-bisphenol A; bis-oxyethyl-tetrachlorobisphenol A; bis-oxyethyl-tetrachlorohydroquinone and the like. These aromatic or aliphatic dihydroxy compounds can be used in combination with the aromatic dihydroxy compound of the general formula (2).

On the other hand, there are various types of carbonate diester used in the present invention, and at least one compound selected from diaryl carbonate compounds, dialkyl carbonate compounds and alkylaryl ester carbonate compounds. The diaryl carbonate compound is represented by the general formula (4)

[0020]

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[In the formula, Ar ² represents an aryl group. Or a compound represented by the general formula (5)

[0022]

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[In the formula, Ar ¹ represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound, and Ar ² is the same as the above. ] It is a compound represented by these. The dialkyl carbonate compound is represented by the general formula (6)

[0024]

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[In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms. Or a compound represented by the general formula (7)

[0026]

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Wherein R ¹ and Ar ¹ are the same as above. ] It is a compound represented by these. Further, the alkyl aryl carbonate compound is represented by the general formula (8)

[0028]

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Wherein R ¹ and Ar ² are the same as above. Or a compound represented by the general formula (9)

[0030]

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Wherein R ¹ , Ar ¹ and Ar ² are the same as above. ] It is a compound represented by these. Here, as the diaryl carbonate compound, for example, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, bisphenol A bisphenyl carbonate and the like can be mentioned. . Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate. Examples of the alkyl aryl carbonate compound include, for example, methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate,
Cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate and the like can be mentioned. In the present invention, the carbonic acid diester used is appropriately selected from the above compounds, and diphenyl carbonate is most preferably used.

The following are examples of raw materials that can be used in place of the dihydroxy compound and the carbonic acid diester used in the present invention. For example, diesters of dihydroxy compounds include diacetate of bisphenol A, dipropionate of bisphenol A, dibutylate of bisphenol A, and dibenzoate of bisphenol A. Examples of dicarbonates of dihydroxy compounds include bismethyl carbonate of bisphenol A, bisethyl carbonate of bisphenol A, and bisphenyl carbonate of bisphenol A. Furthermore, as monocarbonates of dihydroxy compounds,
Examples thereof include bisphenol A monomethyl carbonate, bisphenol A monoethyl carbonate, bisphenol A monopropyl carbonate, and bisphenol A monophenyl carbonate. These raw materials can be used in combination with the aromatic dihydroxy compound of the general formula (2) or the diester carbonate.

The method for producing a copolymerized polycarbonate according to the present invention is divided into a first stage and a second stage, which will be described in detail later. As the reaction system, any of a batch system and a continuous system may be used, but when the continuous system is adopted, at least two or more reactors are used, and the above-mentioned two-stage reaction conditions are separately set. preferable. The material and structure of the reactor used in the production method according to the present invention are not particularly limited, as long as they have a normal stirring function. However, since the viscosity is increased in the latter stage of the reaction, those having a high viscosity type stirring function are preferable. The shape of the reactor is not limited to a tank type, but may be an extruder type. Further, as a feature of the reaction according to the present invention, as the reaction proceeds, phenols and alcohols corresponding to the used carbonic acid ester or these esters and an inert solvent are desorbed from the reactor. Can be separated, purified and recycled for use, and it is preferable to have the removal from the reactor and the above-mentioned various treatment facilities.

The catalyst used in the reaction according to the production method of the present invention includes, in addition to a catalyst generally used in a transesterification reaction, a quaternary ammonium cation and a carboxylic acid anion in the molecule described below. An inner salt having an ion is also suitable, and is used alone or in combination. Here, the commonly used transesterification catalyst is, for example, an alkali metal compound (for example, lithium hydroxide, sodium hydroxide,
Potassium hydroxide), alkaline earth metal compounds, nitrogen-containing basic compounds such as amines and quaternary ammonium salts, and boron compounds. When used in combination, among these, a nitrogen-containing basic compound is particularly preferably used because it exhibits basicity and has a characteristic that it does not relatively remain in the reaction system.

When a polymerization catalyst is used in combination, the nitrogen-containing basic compound preferably used includes, for example, trimethylamine, triethylamine, tripropylamine, and the like.
Examples include aliphatic tertiary amine compounds such as tributylamine, tripentylamine, trihexylamine, and dimethylbenzylamine, and aromatic tertiary amine compounds such as toephenylamine. Also, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-aminopyridine, 2-hydroxypyridine, 4-hydroxypyridine, 2-methoxypyridine, 4 Nitrogen-containing heterocyclic compounds such as -methoxypyridine, imidazole, 2-methylimidazole, 4-methylimidazole, 2-dimethylaminoimidazole, 2-methoxyimidazole, 2-mercaptoimidazole, aminoquinoline and diazabicyclooctane (DABCO) No. Further, tetramethyl ammonium hydroxide (Me ₄ NOH), tetraethyl ammonium hydroxide (Et ₄ NOH),
Tetrabutylammonium hydroxide (Bu ₄ NO
H), ammonium hydroxides having an alkyl group, an aryl group, an aralkyl group and the like such as trimethylbenzylammonium hydroxide [C ₆ H ₅ CH ₂ (Me) ₃ NOH]. In addition, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium phenylborate (Bu ₄ NBP)
h _4), basic salts such as tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄₎ and the like. Among these nitrogen-containing basic compounds, trihexylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide and dimethylaminopyridine are preferably used. Further, as the boron compound,
For example, boric acid, trimethyl borate, triethyl borate, tributyl borate, triheptyl borate, triphenyl borate, trinaphthyl borate and the like can be mentioned.

Next, an inner salt having a zwitterion of a quaternary ammonium cation and a carboxylic acid anion in the molecule will be described. This salt has the general formula (10)

[0037]

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Using an inner salt having a structure represented by the following formula:
It is necessary. Here, in the above equation (10),
R^Two, R^ThreeAnd R^FourIs an alkyl having 1 to 20 carbon atoms
Kill group (for example, methyl group, ethyl group, propyl group, n
-Butyl group, isobutyl group, tert-butyl group, amyl
Group, isoamyl group, tert-amyl group, hexyl group, octyl group
Tyl group, tert-octyl group, nonyl group, etc.), carbon number 6
To 20 aryl groups (for example, phenyl group, naphthyl group
Etc.). These R^Two, R ^ThreeAnd R^FourRespectively
They may be the same or different. Also, R^FiveHas 1 to 1 carbon atoms
20 alkylene groups (for example, methylene group, ethylene
Group, trimethylene group, tetramethylene group, propylene
Group, butylene group, penterylene group, hexylene group, etc.)
Or an arylene group having 6 to 20 carbon atoms (for example, phenyle
Group, naphthalene group, phenanthrene group, etc. or alkylene
And an arylene group are connected).

The inner salt having the structure represented by the general formula (10) has a zwitterion of a quaternary ammonium cation and a carboxylic acid anion in the molecule as described above. It is a compound. The general formula (1)
There are various types of internal salts having the structure represented by 0), for example, glycine betaine, α-alanine betaine, β-alanine betaine, α-butyrobetaine, β-butyrobetaine, and γ-butyrobetaine. Can be Of these, glycine betaine is preferably used. The polymerization catalysts may be used alone, or may be used in combination of two or more kinds or in the form of hydrates depending on the purpose. In the transesterification reaction, the polymerization catalyst is added to the reaction system as a solid or an aqueous solution. In addition, you may use together with the transesterification catalyst normally used depending on the objective.

Further, a simple substance of an alkali metal or alkaline earth metal, an oxide, a hydroxide, an amide compound, an alcoholate, a phenolate, or a basic metal oxide such as lead oxide or antimony oxide, an organic titanium compound, soluble manganese Compound, Ca, Mg, Zn, Pb, Sn, M
n, Cd, Co acetates or nitrogen-containing basic compounds and boron compounds, nitrogen-containing basic compounds and alkali (earth) metal compounds, nitrogen-containing basic compounds and alkali (earth) metal compounds and boron compounds, etc. Combination type catalysts are exemplified.

The amount of the catalyst used in the production method according to the present invention is generally represented by the general formulas (1) and (2) through both the first stage and the second stage or around the first stage. 1 × 10 ^-2 to 1 per mole of both dihydroxy compounds
The amount is ^10-8 mol, preferably ^1-10-3 to ^1-10-7 mol. If the amount of this catalyst is less than 1 × 10 ^-8 mol,
There is a possibility that the catalytic effect is not exhibited. If the amount exceeds 10 ^-2 mol, the physical properties of the final product, polycarbonate,
In particular, heat resistance and hydrolysis resistance may decrease,
In addition, since it leads to an increase in cost, it is not necessary to add more than this.

The manufacturing method according to the present invention is divided into the first stage and the second stage as described above. In the first step, a carbonate is added to the aromatic dihydroxy compound represented by the general formula (2), and the amount of the carbonate used is determined by the amount of the aromatic dihydroxy compound used in the first and second steps. The molar ratio is determined based on the total amount of the aromatic dihydroxy compound.
5 mol is preferable, and more preferably 1.05 to 2.0 mol. The reaction temperature is preferably from 100 to 240 ° C,
160-220 degreeC is more preferable. As described above, the catalyst may be used in the first stage and the second stage separately.
In the first stage, the preferred amount may be added in its entirety. The reaction pressure is preferably from atmospheric pressure or a reduced pressure of about 50 atm to about 50 mmHg, more preferably from atmospheric to 100 mmHg. As the reaction atmosphere, a state in which an inert gas such as nitrogen or argon is constantly allowed to flow is preferable. At the end of the first step, the amount of unreacted terminal groups in the aromatic dihydroxy compound used in the first step was determined to be 50 mol% by analyzing the amount of phenol distilled off in the reaction process.
This is the point in time when the reaction rate becomes below (reaction rate of 50 mol% or more).

In the second step, an aromatic dihydroxy compound represented by the general formula (1) is added to the above reaction system. In this case, if the reaction rate is less than 50 mol%, a high molecular weight polycarbonate having an excellent color tone cannot be produced. The reason for this is unclear. The ratio of the aromatic dihydroxy compound represented by the general formula (1) to the aromatic dihydroxy compound represented by the general formula (2) is determined by the ratio of the aromatic dihydroxy compound represented by the general formula (2) to the desired ratio. It is not particularly limited because it is determined by the purpose of the reforming, but usually,
5 to 95 mol% of the aromatic dihydroxy compound of the general formula (1) is used for the aromatic dihydroxy compound 9 of the general formula (2).
5 to 5 mol% is used. If the total amount of the carbonate ester to be used with respect to the total amount of both aromatic dihydroxy compounds is not used in the first step, the remaining amount is used in the second step. The reaction temperature is preferably from 160 to 380 ° C,
180-360 degreeC is more preferable. The reaction pressure is preferably from atmospheric pressure or a pressurized state (50 atm) to a reduced pressure state of about 0.01 mmHg.

The above transesterification reaction is carried out in the absence of an inert solvent, but may be carried out in the presence of an inert solvent in an amount of 1 to 150% by weight of the obtained PC, if necessary. Here, examples of the inert solvent include diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene,
Aromatic compounds such as methylnaphthalene; gases such as carbon dioxide, nitrous oxide and nitrogen; alkanes such as chlorofluorohydrocarbon, ethane and propane; cyclohexane, tricyclo (5.2.10) decane, cyclooctane and cyclodecane Various substances such as cycloalkane, ethene, and alkene such as propene are exemplified.

A terminal terminator may be used in the reaction system of the first or second step, if necessary. The terminating agent that can be used in the present invention includes on-butylphenol; mn-butylphenol; pn-butylphenol;
o-isobutylphenol; m-isobutylphenol; p-
Isobutylphenol; ot-butylphenol; mt-butylphenol; pt-butylphenol: on-pentylphenol; mn-pentylphenol; pn-pentylphenol; on-hexylphenol; mn-hexylphenol; pn-hexyl Phenol; o-cyclohexylphenol; m-cyclohexylphenol; p-cyclohexylphenol; o-phenylphenol; m-phenylphenol; p-phenylphenol; on-nonylphenol; mn-nonylphenol; pn-nonylphenol;
o-cumylphenol; m-cumylphenol; p-cumylphenol; o-naphthylphenol; m-naphthylphenol; p-naphthylphenol; 2,6-di-t-butylphenol; 2,5-di-t -Butylphenol; 2,4-Di-t-butylphenol; 3,5-Di-t-butylphenol; 2,5-Dicumylphenol; 2,4-Dicumylphenol; 3,5-Dicumylphenol; Formula

[0046]

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As the compound represented by the formula or a cumarone derivative, for example,

[0048]

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And the like. Among such phenols, although not particularly limited in the present invention, pt-butylphenol; p-cumylphenol; p-phenylphenol and the like are preferable. In addition, as another terminal stopper, a carbonic acid diester compound is used in some cases. Specific examples of such a carbonic acid diester compound terminal terminator include carboxybutyphenylphenyl carbonate; methylphenylbutylphenyl carbonate; ethylphenylbutylphenyl carbonate; dibutyldiphenylcarbonate; biphenylphenyl carbonate; dibiphenylcarbonate; cumylphenylphenyl Carbonate; Dicumylphenyl carbonate; Naphthylphenylphenyl carbonate; Dinaphthylphenylcarbonate; Carbopropoxyphenylphenylcarbonate; Carboheptoxyphenylphenylcarbonate; Carbomethoxy-t-butylphenylphenylcarbonate; Carboprotoxyphenylmethylphenylphenylcarbonate; Chromani Lephenyl carbonate; dichromanyl carbonate And the like. Furthermore,

[0050]

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[0051]

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And the like. If necessary, a branching agent can be used in the first or second stage reaction system. The branching agents that can be used in the present invention include phloroglysin; trimellitic acid; 1,1,1-tris (4-
(Hydroxyphenyl) ethane; 1- [α-methyl-α-
(4′-hydroxyphenyl) ethyl] -4- [α ′,
α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; isatin bis (o-cresol) and the like it can.

Further, an antioxidant can be added. Examples of the phosphorus-based antioxidant include tris (nonylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, trimethylphosphite and triethylphosphite. , Tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, distearyl pentaerythyl diphosphite, tris (2-
Trialkylphosphites such as chloroethyl) phosphite and tris (2,3-dichloropropyl) phosphite; tricycloalkylphosphites such as tricyclohexylphosphite; triphenylphosphite;
Tricresyl phosphite, tris (ethylphenyl)
Triaryl phosphites such as phosphite, tris (butylphenyl) phosphite, tris (hydroxyphenyl) phosphite; trimethyl phosphate,
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2-chloroethyl)
Trialkyl phosphates such as phosphate, tris (2,3-dichloropropyl) phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate,
Triaryl phosphates such as 2-ethylphenyldiphenyl phosphate and the like can be mentioned. In addition, plasticizers, pigments, lubricants, release agents, stabilizers, inorganic fillers, and the like, which are ordinary additives, can also be used. In particular, the addition of the above antioxidant is preferably carried out during the reaction.

Hereinafter, the present invention will be described in more detail with reference to Examples. Example 1 Bisphenol A (BPA) 1 was placed in a 1.4 liter nickel steel autoclave (with a stirrer).
82.4 g (0.8 mol) and 225 of diphenyl carbonate
g (1.10 mol), tetramethylammonium hydroxide (TMAH) 2.4 × 10 ^-4 mol was added as a catalyst, and nitrogen substitution was performed 5 times. The mixture was heated to 180 ° C. to melt bisphenol A and diphenyl carbonate. Subsequently, the temperature was increased to 210 ° C., and the degree of vacuum was gradually increased to 200 torr for reaction. 1
After an hour, the reaction rate is 60% calculated from the amount of phenol distilled off.
At which point 70 g of bisphenol fluorene (0.
2 mol), and the temperature was raised to 240 ° C. and 15 torr in 1 hour, the pressure was reduced, and the temperature was further increased to 300 ° C. and 0.3 torr, and the reaction was continued for 2 hours. After the reaction, in the autoclave,
The polymer was taken out and the viscosity average molecular weight was measured in methylene chloride. After removing the solvent, the polymer was press-formed at 300 ° C. to form a 3 mm-thick plate. Various physical properties and copolymer composition ratios were measured by the following measurement methods (the same is applied to the following Examples and Comparative Examples). (1) Viscosity average molecular weight It was measured at 20 ° C. in methylene chloride using a Mv Ubbelohde viscosity tube. The following was used as the relational expression between the intrinsic viscosity and the viscosity average molecular weight. [Η] = 1.23 × 10 ⁻⁵ · Mv ^0.83 (2) YI value YI value was measured using a transmission-type photometer according to JIS K7103-77. (3) Polymer Copolymer Composition Analysis The contents (mol%) of 9,9-bis (4-hydroxyphenyl) fluorene and bisphenol A were determined using high-resolution NMR. The results are shown in Table 1.

Example 2 Bisphenol A in Example 1
The reaction was carried out in the same manner except that bisphenolfluorene was added when the reaction rate reached 70%. The results are shown in Table 1.

Example 3 The temperature after melting bisphenol A and diphenyl carbonate in the first stage in Example 1 was increased to 240 ° C., the degree of vacuum was reduced to 100 torr, and the conversion of bisphenol A became 80%. The same procedure was followed except that bisphenolfluorene was added. The results are shown in Table 1.

Example 4 Bisphenol A in Example 1
And the reaction rate was 96.8 g (0.6 mol).
When it reaches 5%, bisphenolfluorene 140
g (0.4 mol) and the reaction temperature at the end of the second stage is 33
The press molding for measuring the physical properties of the produced polymer was carried out at 330 ° C. except that the temperature was 0 ° C. and the degree of vacuum was 0.3 torr. The results are shown in Table 1.

Example 5 The procedure of Example 1 was repeated except that the catalyst was 5 × 10 ⁻⁵ mol (5 mg) of calcium acetate, and 10 mg of the antioxidant trisnonylphenylphosphite was added together with bisphenolfluorene. The results are shown in Table 1.

Example 6 Bisphenol A18 was placed in a glass autoclave (with an agitator) having an internal volume of 8.0 liters.
24 g (8.0 mol) and diphenyl carbonate 2250
g (11.0 mol) was charged and mixed and melted at 140 ° C.
In order to maintain this level, bisphenol A and diphenyl carbonate were 684 g (3.0 mol) and 883 g (4.
At the same time, the mixture was fed at a rate of 1567 g / hour to the next Ni steel autoclave (with a stirrer) while feeding at a rate of 13 mol / hour. The temperature of the autoclave was maintained at 180 ° C., and 65.5 mg / hour of tetramethylammonium hydroxide was fed as a catalyst. The mixture was fed to a subsequent Ni steel autoclave (with a stirrer) while controlling the flow rate so that the residence time was 30 minutes. Here, the temperature was 200 ° C., and the degree of vacuum was 100 torr. The outlet flow rate was controlled so that phenol distills at 507.6 g / h (5.4 mol / h). Here, the hydroxyl group terminal reaction rate of BPA was 90%. Next, the mixture is fed to a Ni steel autoclave (with a stirrer) controlled at 240 ° C. and 20 torr, and at the same time, a mixture of bisphenolfluorene (BPFL) and diphenyl carbonate (DPC) is melted (1050 g / 188.3 g). / Hour feed rate. The outlet flow was controlled so that the residence time was 45 minutes. Subsequently, the mixture was transferred to a horizontal stirrer and the outlet flow rate was controlled so that the residence time was 1 hour at 320 ° C. and 0.5 torr. The polymer discharged from the horizontal stirrer was extruded in water, made into strands, cut, and pelletized. 120 pellets
After drying at 4 ° C. for 4 hours, injection molding was performed at 340 ° C. The results are shown in Table 1.

(Comparative Example 1) The same operation as in Example 1 was carried out except that bisphenol fluorene was added simultaneously with bisphenol A. The results are shown in Table 1.

(Comparative Example 2) The same operation as in Example 1 was carried out except that bisphenol fluorene was added when the reaction rate between bisphenol A and diphenyl carbonate reached 30%. The results are shown in Table 1.

Comparative Example 3 The same operation as in Example 4 was carried out except that bisphenol fluorene was added simultaneously with bisphenol A. The results are shown in Table 1.

[0063]

[Table 1]

[0064]

As described above, the present invention provides a copolymer of an aromatic dihydroxy compound represented by the general formula (1), an aromatic dihydroxy compound represented by the general formula (2) and a carbonate ester by a transesterification method. In the case of production, the reaction between each aromatic dihydroxy compound and the carbonic acid diester is separated, and the reaction rate of the latter is increased to 50% or more, and then the former reaction is carried out. We succeeded in preventing quality deterioration.

Claims (2)

(57) [Claims] 1. A compound of the general formula (1) (Provided that X ¹ and Y ¹ each independently represent hydrogen, a halogen atom or an organic group having 1 to 8 carbon atoms, and m and n each independently represent an integer of 1 to 4;
¹ and Y ¹ may be different from each other. The aromatic dihydroxy compound (1) represented by the formula) and the general formula (2): (However, A is an alkylidene group having 2 to 15 carbon atoms, an alkylene group having 1 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms,
An arylene group having 6 to 15 carbon atoms, an arylalkylene group having 7 to 15 carbon atoms, a single bond, -S-, -SO-, -SO
_2- , -O-, -CO- bond or formula Wherein X ² and Y ² each independently represent hydrogen, a halogen atom, or an organic group having 1 to 8 carbon atoms, and p and q each independently represent an integer of 1 to 4, When there are a plurality, X ² and Y ² may be different from each other. In producing a copolymerized polycarbonate from the aromatic dihydroxy compound (2) represented by the formula (2) and the carbonic acid diester by a transesterification method, the aromatic dihydroxy compound (2) and the carbonic acid diester are subjected to a transesterification reaction as a first step, Aromatic dihydroxy compound (2)
A reaction rate of 50% or more after the addition of the aromatic dihydroxy compound (1) as a second step, followed by a further transesterification reaction. 2. An aromatic dihydroxy compound (1) represented by the general formula (1) and an aromatic dihydroxy compound (2) represented by the general formula (2) are each contained in an amount of 95 to 5 mol% and 5 to 5 mol%.
The method for producing a copolycarbonate according to claim 1, wherein the copolycarbonate is used in a proportion of up to 95 mol%.