JP5589560B2 - Method for producing aromatic polycarbonate resin - Google Patents

Description

  The present invention relates to a method for producing an aromatic polycarbonate resin. More specifically, the present invention relates to a method for switching and producing a plurality of types of aromatic polycarbonate resins having different structural units by using the same production series and without performing a washing operation in the middle.

Aromatic polycarbonate is excellent in mechanical properties such as impact resistance, heat resistance, transparency and the like, and is widely used for various mechanical parts, optical disks, automobile parts and the like.
As a method for producing such an aromatic polycarbonate, an alkaline aqueous solution of dihydroxy compounds represented by 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”) and carbonyl chloride are used. A method of reacting at a phase interface in the presence of an organic solvent (interface method), and a method of polycondensation reaction of dihydroxy compounds and carbonic acid diester represented by diphenyl carbonate in a molten state in the presence of a transesterification catalyst ( Melting method) is known. Among them, the melting method by transesterification has advantages that it can produce an aromatic polycarbonate at a lower cost than the interface method and can handle many types of dihydroxy compounds.

In general, since aromatic polycarbonate is used in many applications, a plurality of types of aromatic polycarbonate are required depending on the application. On the other hand, when an aromatic polycarbonate is produced by the above-described melting method, it is usually performed by a production apparatus in which a plurality of reaction vessels are connected in series under reduced pressure.
In the case of producing a plurality of types of aromatic polycarbonates, in Patent Document 1, in a production apparatus in which a plurality of reaction vessels are connected, bisphenol A and diphenyl carbonate are polycondensed in a single series in the preceding reaction vessel (previous term). A method for continuously producing a plurality of varieties of aromatic polycarbonate by reporting a polymerization step) and a subsequent polycondensation reaction (late polymerization step) in a plurality of series has been reported. Further, in Patent Document 2, by using a reaction apparatus having a single series of primary tanks and a plurality of polymerization series, additional diphenyl carbonate is added before the first reaction tank of the polymerization series, thereby allowing a plurality of varieties. A process for continuously producing such aromatic polycarbonate has been reported.

JP 2004-26916 A International Publication No. 2008/12987 Pamphlet

However, in Patent Documents 1 and 2, although it is effective to produce aromatic polycarbonate resins having the same structural unit in various molecular weight regions, a plurality of types of aromatic polycarbonate resins having different structural units are produced. In order to produce multiple types of aromatic polycarbonate resins, the production equipment is divided for each structural unit, or the production equipment is temporarily stopped and the washing operation is performed. Until now, there has been only a method of producing an aromatic polycarbonate resin, and there has been a problem that the construction cost of the production equipment is increased and a cleaning operation is essential.
Under such circumstances, the object of the present invention is that the same manufacturing equipment is used, and the manufacturing equipment is not temporarily stopped and the cleaning operation is not performed. An object is to produce a plurality of types of aromatic polycarbonate resins having different structural units by reducing the number of products (hereinafter sometimes referred to as switching loss). Furthermore, another object of the present invention is to produce a plurality of types of aromatic polycarbonate resins having different structures with excellent color tone.

The present invention relates to a method for producing an aromatic polycarbonate resin according to the following <1> to < 4 >.
<1> A method for producing an aromatic polycarbonate resin, wherein a plurality of types of aromatic polycarbonate resins having different structural units are produced using the same production equipment,
At least one of a plurality of types of aromatic polycarbonate resins having different structural units has a structural unit represented by the following general formula (1) or general formula (2),
An aromatic polycarbonate resin A having a melt viscosity of 400 Pa · s or less at 300 ° C. and a shear rate of 912 sec ⁻¹ is produced, and then an aromatic polycarbonate having a structural unit different from the structural unit of the aromatic polycarbonate resin A A method for producing an aromatic polycarbonate resin for producing resin B.


(In General Formula (1) and General Formula (2), X represents a single bond, a carbonyl group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom. 2), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group, and R ₃ and R ₄ are each represented by Independently, it represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.
<2> Before producing the aromatic polycarbonate resin A, an aromatic polycarbonate having the same structural unit as the aromatic polycarbonate resin A and having a melt viscosity at 300 ° C. and a shear rate of 912 sec ⁻¹ exceeds 400 Pa · s. The method for producing an aromatic polycarbonate resin according to <1>, wherein the resin is produced.
<3> The substituted or unsubstituted alkylidene group of X in the general formula (1) or the general formula (2) is
The method for producing an aromatic polycarbonate resin according to < 1> , wherein
(R ₅ and R ₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and Z represents a substituted or unsubstituted aryl group. A polymethylene group having 4 to 20 carbon atoms is shown.)
<4> At least one of a plurality of types of aromatic polycarbonate resins having different structural units has the structural units of both the general formula (1) and the general formula (2), and the general formulas (1) and (2 The aromatic according to any one of <1> to < 3> , which is an aromatic polycarbonate resin having 50% by weight or more of the structural unit represented by the general formula (2) with respect to the total amount of the structural unit represented by A method for producing a polycarbonate resin.

  According to the present invention, a plurality of types of aromatic polycarbonate resins having different structural units can be continuously produced in the same production facility without temporarily stopping the production facility and performing a washing operation. . Furthermore, the obtained aromatic polycarbonate resin is excellent in color tone.

It is a schematic diagram of the aromatic polycarbonate resin manufacturing equipment of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The present invention is a method for producing an aromatic polycarbonate resin, wherein a plurality of types of aromatic polycarbonate resins having different structural units are produced with the same production equipment,
An aromatic polycarbonate resin A having a melt viscosity of 400 Pa · s or less at 300 ° C. and a shear rate of 912 sec ⁻¹ is produced, and then an aromatic polycarbonate resin B having a structural unit different from the structural unit of the aromatic polycarbonate resin A Relates to a method for producing an aromatic polycarbonate resin (hereinafter sometimes referred to as “the production method of the present invention”).

  The “same production equipment” as used in the present invention means equipment capable of consistently performing from raw material preparation through polymerization reaction to production of aromatic polycarbonate resin, and even in a batch reaction system. A reaction method may be used. Further, a plurality of reaction vessels may be provided as long as they are continuously connected by piping or the like. Even if it is understood that the polymerization process generally has a plurality of series such that the reaction liquid branches into a plurality of series during the polymerization reaction, each series of the plurality of series is the “Same manufacturing equipment”.

In addition, the “aromatic polycarbonate resin having different structural units” in the present invention refers to an aromatic polycarbonate resin in which a part or all of the structural units constituting the aromatic polycarbonate resin are different. As used herein, “part of the structural unit” means that a part of the structural unit constituting the aromatic polycarbonate resin has another structural unit. For example, dihydroxy of the general formula (3) described later Bisphenol A type polycarbonate resin produced from a compound and a carbonic acid diester, a dihydroxy compound of the same general formula (3), and a copolymerized aromatic polycarbonate resin produced from a dihydroxy compound of the following general formula (4) and a carbonic acid diester Is included in the “aromatic polycarbonate resin having different structural units” in the present invention. Further, “all” of the structural units mentioned here means that the structural units are completely different. For example, the bisphenol A type polycarbonate resin having the structural unit represented by the general formula (1) and the aromatic polycarbonate resin having the structural unit represented by the general formula (2) are referred to as “aromatic polycarbonate having different structural units” in the present invention. Included in “resin”.
Moreover, even if the structural units constituting the aromatic polycarbonate resin are the same, there are a plurality of structural units and the structural ratios are different. For example, an aromatic polycarbonate resin composed of a structural unit (30% by weight) represented by the general formula (1) and a structural unit (70% by weight) represented by the general formula (2), and a structure represented by the general formula (1) The aromatic polycarbonate resin composed of the unit (50% by weight) and the structural unit (50% by weight) represented by the general formula (2) is an “aromatic polycarbonate resin having different structural units” in the present invention.
On the other hand, the “aromatic polycarbonate resin having the same structural unit” as used in the present invention is an aromatic polycarbonate having the same structural unit and all the structural units constituting the aromatic polycarbonate resin. Refers to resin.
In the present invention, “production switching” refers to switching to production of an aromatic polycarbonate resin having a different structural unit by changing an aromatic dihydroxy compound as a raw material, a catalyst, or production conditions.

In the production method of the present invention, when switching to production of an aromatic polycarbonate resin having a different structural unit, the melt viscosity of the aromatic polycarbonate resin before switching at 300 ° C. and a shear rate of 912 sec ⁻¹ is 400 Pa · s or less. There is. (Hereinafter, the aromatic polycarbonate having the specific viscosity may be referred to as aromatic polycarbonate A.)
Since the melt viscosity of the aromatic polycarbonate resin before switching is in the above range, an aromatic polycarbonate resin having a structural unit different from the aromatic polycarbonate A (hereinafter, referred to as “aromatic polycarbonate B” may be referred to hereinafter). )), Excessive mixing of the aromatic polycarbonate A into the aromatic polycarbonate B can be suppressed, and the aromatic polycarbonate B can be stably produced.
As a result, it is possible to continuously produce a plurality of types of aromatic polycarbonates without temporarily stopping the production facility and performing a washing operation with a solvent such as phenol.

More specifically, in the production method of the present invention, an aromatic polycarbonate resin A having a melt viscosity of 400 Pa · s or less at 300 ° C. and a shear rate of 912 sec ⁻¹ is produced, and then the structure of the aromatic polycarbonate resin A An aromatic polycarbonate resin B having a structural unit different from the unit is produced.
Further, in the above, before producing the aromatic polycarbonate resin A, an aromatic having the same structural unit as the aromatic polycarbonate resin A and having a melt viscosity at 300 ° C. and a shear rate of 912 sec ⁻¹ exceeds 400 Pa · s. It is preferable to produce a polycarbonate resin.

The aromatic polycarbonate resin according to the present invention can be produced by using the following aromatic dihydroxy compound and carbonic acid diester as raw materials and performing a melt polycondensation reaction in the presence of a transesterification catalyst.
Hereinafter, a general method for producing an aromatic polycarbonate resin according to the present invention will be described first.

(Aromatic dihydroxy compounds)
Examples of the aromatic dihydroxy compound that is a raw material of the aromatic polycarbonate resin according to the present invention include aromatic dihydroxy compounds represented by the following general formula (3).

Here, in the general formula (1), X represents a single bond, a carbonyl group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom.

  Another example of the aromatic dihydroxy compound that is a raw material of the aromatic polycarbonate resin according to the present invention is an aromatic dihydroxy compound represented by the following general formula (4).

Here, in the general formula (4), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group, and R ₃ And R ₄ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.
Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ₁ and R ₂ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the substituted or unsubstituted aryl group include: A phenyl group, a benzyl group, a tolyl group, 4-methylphenyl group, a naphthyl group, etc. are mentioned.
Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ₃ and R ₄ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the substituted or unsubstituted aryl group include: A phenyl group, a benzyl group, a tolyl group, 4-methylphenyl group, a naphthyl group, etc. are mentioned.
Among these, R ₁ and R ₂ are preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a methyl group. R ₃ and R ₄ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a hydrogen atom or a methyl group.

In General Formula (3) or General Formula (4), X represents a single bond, a carbonyl group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom. Examples of the substituted or unsubstituted sulfur atom include —S— and —SO ₂ —. In addition, a substituted or unsubstituted alkylidene group is

Indicates. Here, R ₅ and R ₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and Z is substituted or unsubstituted. A substituted polymethylene group having 4 to 20 carbon atoms is shown.
Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ₅ and R ₆ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the substituted or unsubstituted aryl group include a phenyl group, a benzyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.
Among these, R ₅ and R ₆ are preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a methyl group.
Z is bonded to the carbon to which two phenyl groups are bonded in the general formula (3) or (4) to form a substituted or unsubstituted divalent carbocycle. Examples of the divalent carbocycle include a cycloalkylidene group such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group (preferably a carbon number of 5 To 12 carbon atoms). Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a methyl-substituted product of a cyclohexylidene group, a cyclododecylidene group, or a cyclohexylidene group is preferable.

  Specific examples of the aromatic dihydroxy compound represented by the general formula (3) include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 1,1-bis (4-hydroxyphenyl) cyclohexane. 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) adamantane, 1,1-bis (4-hydroxyphenyl) cyclododecane, , 4-bis (4-hydroxyphenyl) adamantane, 5,5-bis (4-hydroxyphenyl) hexahydro-4,7-methanoindane, 2,2-bis (4-hydroxyphenyl) sulfone, 2,2-bis ( 4-hydroxyphenyl) sulfide and the like.

  Among these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferably used. In addition, the aromatic dihydroxy compound represented by General formula (3) can be used 1 type or in mixture of 2 or more types.

  Specific examples of the aromatic dihydroxy compound represented by the general formula (4) include 2,2-bis (4-hydroxy-3-methylphenyl) propane and 1,1-bis (4-hydroxy-). 3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,5,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) adamantane, 1 , 1-bis (4-hydroxy-3-methylphenyl) cyclododecane, 1,4-bis (4-hydroxy-3-methylphenyl) adamantane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-cyclohexyl) Enyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 5,5-bis (4-hydroxy-3-methylphenyl) hexahydro-4,7-methanoindane, 2,2-bis ( 4-hydroxy-3-methylphenyl) sulfone, 2,2-bis (4-hydroxy-3-methylphenyl) sulfide, 3,3′-dimethylbiphenol, 2,2-bis (4-hydroxy-3,5- Dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylcyclohexane 1,1-bis (4-hydroxy-3,5-dimethylphenyl) adamantane, 1,1-bis (4-hydroxy-3,5- Methylphenyl) cyclododecane, 1,4-bis (4-hydroxy-3,5-dimethylphenyl) adamantane, 2,2-bis (3-ethyl-4-hydroxy-5-methylphenyl) propane, 2,2- Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (4-hydroxy-) 3-methyl-5-phenylphenyl) propane, 2,2-bis (3,5-diethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propane, 2,2-bis (3,5-di-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5) -Diphenylphenyl) propane, 5,5-bis (4-hydroxy-3,5-dimethylphenyl) hexahydro-4,7-methanoindane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) sulfone, Examples include 2,2-bis (4-hydroxy-3,5-dimethylphenyl) sulfide, 3,3 ′, 5,5′-tetramethylbiphenol, and the like.

  Among these, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-) Methylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,5,5-trimethylcyclohexane, 5,5-bis (4-hydroxy-3-methylphenyl) hexahydro-4, 7-methanoindane, 3,3′-dimethylbiphenol, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3,5- Methylphenyl) -3,5,5-trimethylcyclohexane, 5,5-bis (4-hydroxy-3,5-dimethylphenyl) hexahydro-4,7-methanoindane, 3,3 ′, 5,5′-tetramethyl Biphenol and the like are preferred.

  Among these, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and 1,1-bis (4- Hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclododecane, 1,1 -Bis (4-hydroxy-3-methylphenyl) -3,5,5-trimethylcyclohexane is more preferred, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydride) Xy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane, and 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclododecane Most preferred. In addition, the aromatic dihydroxy compound represented by General formula (4) can be used 1 type or in mixture of 2 or more types.

(Carbonated diester)
Examples of the carbonic acid diester that is a raw material of the aromatic polycarbonate resin according to the present invention include compounds represented by the following general formula (5).

Here, in the general formula (5), A ′ is an optionally substituted linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. Two A ′ may be the same or different from each other.
In addition, as a substituent on A ′, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, and an ester group Amide group, nitro group and the like.

Specific examples of the carbonic acid diester compound include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.
Among these, diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) and substituted diphenyl carbonate are preferable. These carbonic acid diesters can be used alone or in admixture of two or more.

Moreover, the amount of the carbonic acid diester compound is preferably 50 mol% or less, more preferably 30 mol% or less, and may be substituted with dicarboxylic acid or dicarboxylic acid ester.
Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

  In the production method of the present invention, the amount of these carbonic acid diesters (including the above-mentioned substituted dicarboxylic acid or dicarboxylic acid ester; the same shall apply hereinafter) is usually such that the carbonic acid diester compound is used per 1 mol of the aromatic dihydroxy compound. It is used in a ratio of 1.01 mol to 1.30 mol, preferably 1.02 mol to 1.20 mol. If the molar ratio of the carbonic acid diester is excessively small, the transesterification reaction rate decreases, making it difficult to produce an aromatic polycarbonate resin having a desired molecular weight, or increasing the terminal hydroxyl group concentration of the resulting aromatic polycarbonate resin. The thermal stability tends to deteriorate. In addition, when the molar ratio of the carbonic acid diester is excessively large, the transesterification reaction rate decreases, and it becomes difficult to produce an aromatic polycarbonate resin having a desired molecular weight. The remaining amount is increased, which may cause odors during molding or molding, which is not preferable.

(Transesterification catalyst)
Examples of the transesterification catalyst used in the production method of the present invention include a catalyst usually used for producing an aromatic polycarbonate resin by a transesterification method, and are not particularly limited.
In general, for example, basic compounds such as alkali metal compounds, alkaline earth metal compounds, beryllium compounds, magnesium compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used. Among these, alkali metal compounds and alkaline earth metal compounds are preferable for practical use. These transesterification catalysts may be used alone or in combination of two or more.

The amount of transesterification catalyst used is usually in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol with respect to 1 mol of the total aromatic dihydroxy compound, but is an aromatic polycarbonate excellent in molding characteristics and hue. In order to obtain a resin, the amount of the transesterification catalyst is preferably 1.0 × 10 ⁻⁸ mol based on 1 mol of the wholly aromatic dihydroxy compound when an alkali metal compound and / or an alkaline earth metal compound is used. -1 × 10 ⁻⁴ mol, more preferably 1.0 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol, and particularly preferably 1.0 × 10 ⁻⁷ mol to 5.0. It is in the range of × 10 ⁻⁶ mol. If the amount is less than the above lower limit amount, the polymerization activity necessary for producing an aromatic polycarbonate resin having a desired molecular weight cannot be obtained. If the amount is more than this amount, the polymer hue deteriorates, and the amount of branching components is too large to flow. The aromatic polycarbonate resin excellent in target melting characteristics cannot be produced.

Examples of the alkali metal compound include inorganic alkali metal compounds such as alkali metal hydroxides, carbonates and hydrogencarbonate compounds; organic alkali metal compounds such as salts with alkali metal alcohols, phenols and organic carboxylic acids. It is done. Here, as an alkali metal, lithium, sodium, potassium, rubidium, cesium etc. are mentioned, for example.
Among these alkali metal compounds, cesium compounds are preferable, and cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide are particularly preferable.

  Examples of the alkaline earth metal compound include inorganic alkaline earth metal compounds such as alkaline earth metal hydroxides and carbonates; alkaline earth metal alcohols, phenols, salts with organic carboxylic acids, and the like. It is done. Here, examples of the alkaline earth metal include calcium, strontium, barium and the like.

  Examples of the beryllium compound and magnesium compound include inorganic metal compounds such as metal hydroxides and carbonates; salts of the metals with alcohols, phenols, and organic carboxylic acids.

  Examples of basic boron compounds include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, barium salts, strontium salts, and the like of boron compounds. Here, as the boron compound, for example, tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributyl Examples include benzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron.

  Examples of the basic phosphorus compound include trivalent phosphine compounds such as triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, and tributylphosphine, or derivatives thereof. And quaternary phosphonium salts.

  Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

(Catalyst deactivator)
In the present invention, a catalyst deactivator for neutralizing and deactivating the catalyst may be added after the transesterification reaction. The heat resistance and hydrolysis resistance of the aromatic polycarbonate resin obtained by such treatment are improved.
As such a catalyst deactivator, an acidic compound having a pKa of 3 or less, such as sulfonic acid and sulfonic acid ester, is preferable. Specifically, benzenesulfonic acid, p-toluenesulfonic acid, methyl benzenesulfonate, benzenesulfone Examples include ethyl acetate, propyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, and butyl p-toluenesulfonate.
Among these, p-toluenesulfonic acid and butyl p-toluenesulfonate are preferably used.

<Production process of aromatic polycarbonate resin>
Next, a specific manufacturing process of the aromatic polycarbonate resin to which the manufacturing method of the present invention is applied will be described.
The process for producing an aromatic polycarbonate resin is to prepare a raw material mixed melt of an aromatic dihydroxy compound and a carbonic acid diester (raw step), and melt the raw material mixed melt in the presence of a transesterification reaction catalyst. It is carried out by performing a polycondensation reaction in multiple stages using a plurality of reaction vessels in a state (polycondensation step). The reaction system may be any of a batch system, a continuous system, or a combination of a batch system and a continuous system. As the reaction tank, a plurality of vertical stirring reaction tanks and, if necessary, at least one horizontal stirring reaction tank subsequent thereto are used. Usually, these reaction tanks are installed in series and processed continuously.
After the polycondensation step, the reaction is stopped, the unreacted raw materials and reaction by-products in the polycondensation reaction liquid are devolatilized and removed, the heat stabilizer, the release agent, the colorant, etc. are added, the aromatic polycarbonate A step of forming a resin with a predetermined particle size may be added as appropriate.
Next, each process of the manufacturing method will be described.

(Primary process)
Aromatic dihydroxy compounds and carbonic acid diester compounds used as raw materials for aromatic polycarbonate resins are usually batch, semi-batch or continuous stirring tank type devices in an inert gas atmosphere such as nitrogen or argon. It is prepared as a raw material mixed melt. For example, when bisphenol A is used as the aromatic dihydroxy compound and diphenyl carbonate is used as the carbonic acid diester compound, the melt mixing temperature is usually selected from the range of 120 ° C. to 180 ° C., preferably 125 ° C. to 160 ° C.
Hereinafter, the case where bisphenol A is used as an aromatic dihydroxy compound and diphenyl carbonate is used as a raw material as a carbonic acid diester compound will be described as an example.
Under the present circumstances, the ratio of an aromatic dihydroxy compound and a carbonic acid diester compound is adjusted so that a carbonic acid diester compound may become excess, and a carbonic acid diester compound is 1.01 mol-1 normally with respect to 1 mol of aromatic dihydroxy compounds. .30 mol, preferably 1.02 mol to 1.20 mol.

(Polycondensation process)
The polycondensation by the transesterification reaction between the aromatic dihydroxy compound and the carbonic acid diester compound is usually carried out continuously in a multistage manner of two or more stages, preferably 3 to 7 stages. Specific reaction conditions for each stage are temperature: 150 ° C. to 320 ° C., pressure: normal pressure to 0.01 Torr (1.3 Pa), and average residence time: 5 minutes to 150 minutes.
In each multi-stage reaction tank, in order to more effectively remove aromatic monohydroxy compounds such as phenol as a by-product from the system as the transesterification proceeds, the reaction temperature is increased stepwise in the above reaction conditions. Set to a higher vacuum.

When the polycondensation step is performed in a multistage manner, usually, a plurality of reaction vessels including a vertical stirring reaction vessel are provided to increase the average molecular weight of the aromatic polycarbonate resin. The reaction tank is usually installed in 2 to 6 groups, preferably 4 to 5 groups.
Here, as a reaction tank, for example, a stirring tank type reaction tank, a thin film reaction tank, a centrifugal thin film evaporation reaction tank, a surface renewal type biaxial kneading reaction tank, a biaxial horizontal type stirring reaction tank, a wet wall reaction tank, a free tank A perforated plate type reaction vessel that polycondenses while dropping, a perforated plate type reaction vessel with wire that polycondenses while dropping along a wire, and the like are used.

  The types of stirring blades in the vertical stirring reaction tank include, for example, turbine blades, paddle blades, fiddler blades, anchor blades, full zone blades (manufactured by Shinko Environmental Solution Co., Ltd.), Sun Meller blades (manufactured by Mitsubishi Heavy Industries, Ltd.), Max blend blades (manufactured by Sumitomo Heavy Industries, Ltd.), helical ribbon blades, twisted lattice blades (manufactured by Hitachi Plant Technology Co., Ltd.), and the like.

  Moreover, a horizontal stirring reaction tank means that the rotating shaft of a stirring blade is a horizontal type (horizontal direction). As a stirring blade of a horizontal stirring reaction tank, for example, a uniaxial stirring blade such as a disk type or a paddle type, HVR, SCR, N-SCR (manufactured by Mitsubishi Heavy Industries, Ltd.), Vivolak (Sumitomo Heavy Industries, Ltd.) )), Or biaxial stirring blades such as spectacle blades and lattice blades (manufactured by Hitachi Plant Technology Co., Ltd.).

  In addition, the transesterification catalyst used for the polycondensation of an aromatic dihydroxy compound and a carbonic acid diester compound may usually be prepared as a solution in advance. The concentration of the catalyst solution is not particularly limited, and is adjusted to an arbitrary concentration according to the solubility of the catalyst in the solvent. As the solvent, acetone, alcohol, toluene, phenol, water and the like can be appropriately selected.

  When water is selected as the solvent for the catalyst, the nature of the water is not particularly limited as long as the type and concentration of impurities contained are constant, but usually distilled water or deionized water is preferably used.

(Aromatic polycarbonate resin)
Next, the aromatic polycarbonate resin produced by the production method of the present invention (hereinafter sometimes referred to as “the aromatic polycarbonate resin according to the present invention”) will be described.

  The aromatic polycarbonate resin according to the present invention is derived from the aromatic dihydroxy compound represented by the general formula (3) or the general formula (4), and contains at least the following general formula (1) or general formula (2) in the molecule. A typical example is one having a structural unit represented by

Here, in the general formula (1), X represents a single bond, a carbonyl group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom.

Here, in the general formula (2), R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group, and R ₃ And R ₄ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X represents a single bond, a carbonyl group, a substituted or An unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom is shown.

In General Formula (1) or General Formula (2), X represents a single bond, a carbonyl group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom. Examples of the substituted or unsubstituted sulfur atom include —S— and —SO ₂ —. In addition, a substituted or unsubstituted alkylidene group is

Indicates. Here, R ₅ and R ₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and Z is substituted or unsubstituted. A substituted polymethylene group having 4 to 20 carbon atoms is shown.
Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ₅ and R ₆ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the substituted or unsubstituted aryl group include a phenyl group, a benzyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.
Among these, R ₅ and R ₆ are preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a methyl group.
Z is bonded to the carbon to which two phenyl groups are bonded in the general formula (1) or the general formula (2) to form a substituted or unsubstituted divalent carbocycle. Examples of the divalent carbocycle include a cycloalkylidene group such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group (preferably a carbon number of 5 To 12 carbon atoms). Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a methyl-substituted product of a cyclohexylidene group, a cyclododecylidene group, or a cyclohexylidene group is preferable.

  As a preferable example of the aromatic polycarbonate resin containing the structural unit represented by the general formula (1), a bisphenol A type polycarbonate resin made from 2,2-bis (4-hydroxyphenyl) propane (BPA) is used. Can be mentioned.

  A preferred example of the aromatic polycarbonate resin containing the structural unit represented by the general formula (2) is 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter abbreviated as “bisphenol C”). Bisphenol C-type polycarbonate resin, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) Cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane, and / or 1,1-bis (4- An aromatic polycarbonate resin using hydroxy-3,5-dimethylphenyl) cyclododecane as a raw material can be used.

  The aromatic polycarbonate resin to which the present embodiment is applied may have both structural units of the general formula (1) and the general formula (2) as long as the object of the present invention is not hindered. In this case, the ratio of the structural unit represented by the general formula (2) to the total amount of the structural units represented by the general formulas (1) and (2) depends on the type and use of the aromatic polycarbonate resin as the product. However, it is generally 50% by weight or more, preferably 70% by weight or more.

In the present invention, “a plurality of types of aromatic polycarbonate resins having different structural units” are resins having the structural unit of the general formula (1) as the first aromatic polycarbonate resin in the case of two types, for example. The second aromatic polycarbonate resin is a resin having the structural unit of the general formula (2), and the second aromatic polycarbonate resin has the structural units of the general formula (1) and the general formula (2). You may have.
In the present invention, at least one of the aromatic polycarbonate resins having different structural units is composed of the structural unit represented by the general formula (1), that is, only the structural unit represented by the general formula (1). It is preferable.

Next, the continuous production method of a plurality of types of aromatic polycarbonate resins of the present invention will be described.
The production method of the present invention is the same production in which the production of a plurality of types of aromatic polycarbonate resins having different structural units can be performed consistently from the preparation of raw materials through the polymerization reaction to the production of the aromatic polycarbonate resin. It is characterized by using equipment. As described above, the same production equipment in the present invention may be a batch reaction system or a continuous reaction system, and may have a plurality of reaction tanks as long as they are continuously connected by piping or the like.

  For example, as a plurality of types of aromatic polycarbonate resins, an aromatic polycarbonate resin a and an aromatic polycarbonate resin b having different structural units are produced, and the melt viscosity of each of the aromatic polycarbonate resin a and the aromatic polycarbonate b is changed. The production switching of the present invention in the case of production will be specifically described. In addition, each aromatic polycarbonate resin from which the melt viscosity of aromatic polycarbonate resin a differs is resin a (1), resin a (2), ..., resin a (n), and melt viscosity of aromatic polycarbonate resin b. The aromatic polycarbonate resins having different values are designated as resin b (1), resin b (2),..., Resin b (n).

Example 1: Resin a (1) → Resin a (2) → Resin b (1)
Example 2: Resin b (1) → Resin b (2) → Resin a (1)
Example 3: Resin a (1)-> Resin a (2)-> Resin b (1)-> Resin b (2)
Example 4: Resin b (1) → Resin b (2) → Resin a (1) → Resin a (2)
Example 5: Resin a (1) → Resin a (2) → Resin a (3) → Resin b (1)
Example 6: Resin b (1) → Resin b (2) → Resin b (3) → Resin a (1)
Example 7: Resin a (2) → Resin b (1) → Resin b (2) → Resin a (1)
In Example 1 above, the resin a (1) is first manufactured, the manufacturing conditions are changed, the resin a (2) is manufactured, and then the resin b (1) having a different structural unit is manufactured using the same manufacturing equipment. It shows that it went continuously. Moreover, in Example 5, after manufacturing resin a (1) first, manufacturing conditions etc. are changed, resin a (2) and resin a (3) are manufactured in order, and resin b (1 with a different structural unit after that is manufactured. ) Was continuously performed at the same manufacturing facility. Further, in Example 7, after first producing the resin a (2), the resin b (1) having a different structural unit is switched, and the production conditions are changed to produce the resin b (2). It is shown that the resin a (1) having different values was continuously performed in the same production facility.

In the above example, the present invention is characterized in that the aromatic polycarbonate resin (resin a (2) in Example 1, resin b (2) in Example 2, resin b (2), Example 2) before shifting (switching) to an aromatic polycarbonate resin having a different structural unit. Resin a (2) in Example 3, Resin b (2) in Example 4, Resin a (3) in Example 5, Resin b (3) in Example 6, Resin a (2) and Resin b (2) in Example 7 It is necessary that the melt viscosity of the resin be 400 Pa · s, preferably 380 Pa · s (measured at 300 ° C. and a shear rate of 912 sec ⁻¹ ) or less.

  As described above, the aromatic polycarbonate resin remaining in the reaction facility is changed in the structural unit after the change because the melt viscosity of the aromatic polycarbonate resin before the transition to the aromatic polycarbonate resin having a different structural unit is in a specific range. It is possible to entrain and remove to a level that does not impair the physical properties of different aromatic polycarbonate resins.

  On the other hand, when the melt viscosity of the aromatic polycarbonate resin before the transition to the aromatic polycarbonate resin having a different structural unit is high, the change is caused by the accompanying high melt viscosity aromatic polycarbonate resin before the transition remaining in the reaction equipment. There may be a problem that the hue of an aromatic polycarbonate resin having a different structural unit later deteriorates or foreign matter is mixed in.

(manufacturing device)
Next, an aromatic polycarbonate production facility to which the present embodiment is applied will be specifically described with reference to the drawings.
The “same production equipment” as used in the present invention means that, from the raw material preparation to the polymerization reaction as described above, the production of the aromatic polycarbonate resin through the polymerization reaction and the production of the aromatic polycarbonate resin are performed consistently. It can be a batch reaction system or a continuous reaction system.
An example of a continuous reaction type aromatic polycarbonate production apparatus will be described below with reference to FIG.

In the production apparatus shown in FIG. 1, the aromatic polycarbonate resin undergoes a polycondensation reaction using a plurality of reaction tanks in a molten state with a raw material process for preparing the raw material aromatic dihydroxy compound and carbonic acid diester compound. It manufactures through a polycondensation process.
Thereafter, the step of stopping the reaction and devolatilizing and removing unreacted raw materials and reaction byproducts in the polymerization reaction solution (not shown), and the step of adding a thermal stabilizer, a release agent, a colorant and the like (not shown) ), And through a step (not shown) of forming an aromatic polycarbonate resin into pellets having a predetermined particle size, the pellets of the aromatic polycarbonate resin are formed.

In the raw material adjustment process, a first raw material mixing tank 1a and a second raw material mixing tank 1b connected in series, and a raw material supply pump 2 for supplying the prepared raw material to the polycondensation process are provided. For example, anchor-type stirring blades are provided in the first raw material mixing tank 1a and the second raw material mixing tank 1b, respectively.
In addition, for example, diphenyl carbonate (hereinafter sometimes referred to as “DPC”) as a carbonic acid diester is supplied in a molten state to the first raw material mixing tank 2a, and for example, bisphenol A (hereinafter, “ BPA ”may be described in a powder state, and bisphenol A is dissolved in molten diphenyl carbonate.

Next, in the polycondensation step, the first vertical reaction tank 4a, the second vertical reaction tank 4b, the third vertical reaction tank 4c, the fourth vertical reaction tank 4d, and the fourth vertical mold connected in series. A fifth horizontal reaction tank 6 connected in series is provided downstream of the reaction tank 4d. The first vertical reaction tank 4a, the second vertical reaction tank 4b, and the third vertical reaction tank 4c are each provided with a max blend blade, and the fourth vertical reaction tank 4d is provided with a double helical blade. Yes. The fifth horizontal reaction tank 6 is provided with a stirring blade.
These five reaction tanks are each equipped with a distillation pipe (not shown) for discharging by-products generated by the polycondensation reaction.

  In the apparatus for producing the aromatic polycarbonate resin shown in FIG. 1, a DPC melt prepared at a predetermined temperature in a nitrogen gas atmosphere and a BPA powder weighed in a nitrogen gas atmosphere are continuously supplied to the first raw material mixing tank 1a. To supply. When the liquid level of the first raw material mixing tank 1a exceeds the same height as the highest position in the transfer pipe, the raw material mixture is transferred to the second raw material mixing tank 1b.

Next, the raw material mixture is continuously supplied to the first vertical reactor 4 a via the raw material supply pump 2 and the raw material filter 3. As a catalyst, cesium carbonate in the form of an aqueous solution is continuously supplied from a catalyst supply port (not shown) in the middle of the transfer pipe of the raw material mixture.
In the first vertical reaction tank 4a, under a nitrogen atmosphere, for example, a temperature of 220 ° C., a pressure of 13.33 kPa (100 Torr), a rotating speed of a stirring blade is maintained at 160 rpm, and by-produced phenol is distilled from the distillation pipe. The polycondensation reaction is carried out while keeping the liquid level constant so that the average residence time is 60 minutes.

Next, the polymerization reaction liquid discharged from the first vertical reaction tank 4a is continuously used in the second vertical reaction tank 4b, the third vertical reaction tank 4c, the fourth vertical reaction tank 4d, and the fifth horizontal reaction tank 6. The polycondensation reaction is allowed to proceed continuously. A liquid feed pump 5a is used from the third vertical reaction tank 4c to the fourth vertical reaction tank 4d, and a liquid supply pump 5b is used from the fourth vertical reaction tank 4d to the fifth horizontal reaction tank 6.
The reaction conditions in each reaction tank are set so as to become high temperature, high vacuum, and low stirring speed as the polycondensation reaction proceeds. During the polycondensation reaction, the liquid surface level is controlled so that the average residence time in each reaction tank is, for example, about 60 minutes. In each reaction tank, by-produced phenol is distilled from the distillation pipe.

The aromatic polycarbonate resin discharged from the fifth horizontal reaction tank 6 is supplied to a vented twin screw extruder (not shown) as it is without being cooled and solidified by a liquid feed pump (not shown), and the catalyst is lost. Add butyl p-toluenesulfonate as an activator into the bent twin screw extruder, extrude, extrude into a strand from the vent twin screw extruder, cool with water, and pelletizer (not shown). To obtain a chip-like aromatic polycarbonate resin.
In the devolatilization extrusion process in the vent type twin-screw extruder, the devolatilization process may be performed by injecting a solvent as necessary. In this case, water is used as a preferred solvent.

  Hereinafter, the present invention will be described more specifically based on examples. In addition, this invention is not limited to a following example. The physical properties of the aromatic polycarbonate resin used in the examples were evaluated by the following methods.

(1) Melt Viscosity Aromatic polycarbonate resin dried at 120 ° C. for 5 hours is heated to 300 ° C. using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.) having a die diameter of 1 mmφ × 10 mmL and a shear rate γ = 9. It measured between 12-1824 (sec < ^-1 >), and calculated | required by reading melt viscosity (eta) ^* ₉₁₂ in the shear rate of ₉₁₂ sec < ^-1 >.

(2) Hue Using an injection molding machine J100SS-2 (manufactured by Nippon Steel Works), a plate having a thickness of 3 mm, a length of 100 mm, and a width of 100 mm under conditions of a barrel temperature of 280 ° C. and a mold temperature of 90 ° C. Injection molded. About this injection-molded plate, the tristimulus value XYZ which is the absolute value of the color is measured with a color tester (SC-1-CH manufactured by Suga Test Instruments Co., Ltd.), and the YI value which is an index of yellowness by the following relational expression Was calculated. The larger this YI value, the more yellow it is colored.

Example 1
An aqueous solution of cesium carbonate was added to 6,700 g of BPA and 6,539 g of DPC to prepare a mixture. Cesium carbonate was 1 μmol per 1 mol of BPA. Next, the mixture was charged into a first reaction tank having an internal temperature of 80 ° C. or less and an internal volume of 40 L and equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser.

  Subsequently, the operation of setting the inside of the first reaction tank to 1.33 kPa (10 torr) and then setting it to atmospheric pressure with nitrogen was repeated 5 times, and the inside of the first reaction tank was replaced with nitrogen. After nitrogen substitution, the internal temperature of the first reaction tank was gradually raised through a heat medium having a temperature of 230 ° C. through the heat medium jacket to dissolve the contents. Then, it stirred at 300 rpm, the temperature in a heat-medium jacket was controlled, and the internal temperature of the 1st reaction tank was kept at 220 degreeC. The pressure in the first reaction tank is 101.3 kPa (760 Torr) in absolute pressure over 40 minutes while distilling off the phenol produced as a by-product by the oligomerization reaction of BPA and DPC performed in the first reaction tank. To 13.3 kPa (100 torr).

  Subsequently, the pressure in the first reaction tank was maintained at 13.3 kPa, and an oligomerization reaction was performed for 80 minutes while further distilling off phenol. After completion of the oligomerization reaction, the inside of the system was restored to absolute pressure of 101.3 kPa with nitrogen, the gauge pressure was increased to 0.2 MPa, and the oligomerization reaction was performed using a transfer pipe heated to 200 ° C. or higher in advance. The obtained oligomer was pumped to a second reaction tank (internal pressure: 0.05 MPa-G) equipped with a stirrer having an internal volume of 40 L controlled to an internal temperature of 240 ° C., a heat medium jacket, a vacuum pump and a reflux condenser.

  Next, the oligomer fed into the second reaction tank was stirred at 38 rpm, the internal temperature was raised with a heating medium jacket, and the inside of the second reaction tank was absolute pressure from 101.3 kPa to 13.3 kPa over 40 minutes. The pressure was reduced to. Thereafter, the temperature increase was continued, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) as an absolute pressure over an additional 40 minutes, and the distilled phenol was removed out of the system. Further, the temperature was increased and the pressure was reduced, and after the absolute pressure in the second reaction tank reached 70 Pa (about 0.5 torr), the polycondensation reaction was carried out while maintaining 70 Pa. The final internal temperature in the second reactor was 285 ° C.

  In the present embodiment, the stirring power of the stirrer provided in the second reaction tank is used as an index of the molecular weight of the aromatic polycarbonate resin. The polycondensation reaction was completed when the agitator in the second reaction tank reached a predetermined stirring power. Next, the inside of the second reaction tank is restored to an absolute pressure of 101.3 kPa with nitrogen and then increased to 0.2 MPa with a gauge pressure, and the aromatic polycarbonate resin is extracted in a strand form from the bottom of the second reaction tank. The mixture was pelletized using a rotary cutter while being cooled in a water bath. The melt viscosity of the obtained aromatic polycarbonate resin was 597 Pa · s, and YI = 2.0.

  At the same time when the pelletization was started, 6,700 g of BPA and 6,583 g of DPC were added and mixed with an aqueous solution of cesium carbonate at 0.5 μmol per 1 mol of BPA in the first reaction tank cooled to 80 ° C. The prepared mixture was charged and manufactured in the same manner as the above manufacturing conditions. The stirring power is adjusted so that the melt viscosity of the aromatic polycarbonate resin produced in the second reaction tank is 357 Pa · s, and the aromatic polycarbonate resin is formed into a strand from the bottom of the second reaction tank with the predetermined stirring power. Extracted with a rotary cutter and pelletized while cooling in a water bath. The melt viscosity of the obtained aromatic polycarbonate resin was 357 Pa · s, and YI = 1.8.

  Next, the aromatic polycarbonate resin having a melt viscosity of 357 Pa · s is extracted in the form of a strand from the bottom of the second reaction tank, and immediately after starting pelletization, in the first reaction tank cooled to 80 ° C. in advance. An aqueous solution of cesium carbonate was added to 6,700 g of bisphenol C (hereinafter referred to as “BPC”) and 5,711 g of DPC to prepare a mixture. The cesium carbonate was 1.5 μmol per 1 mol of BPC. Next, an aromatic polycarbonate resin was produced using the mixture in the same manner as in the production conditions described above. The stirring power is adjusted so that the melt viscosity of the aromatic polycarbonate resin produced in the second reaction tank is 434 Pa · s, and the aromatic polycarbonate resin is formed into a strand from the bottom of the second reaction tank with a predetermined stirring power. Extracted with a rotary cutter and pelletized while cooling in a water bath. The melt viscosity of the obtained aromatic polycarbonate resin was 434 Pa · s, and YI = 2.0.

(Example 2)
In Example 1, after first producing 434 Pa · s aromatic polycarbonate resin using BPC as a raw material, immediately after starting pelletization, BPC 6,700 g and DPC 5, An aqueous solution of cesium carbonate was added to 767 g to prepare a mixture. The cesium carbonate was 1.5 μmol per 1 mol of BPC. Next, the mixture was used in the same production conditions as above to produce an aromatic polycarbonate resin having a melt viscosity of 357 Pa · s and YI = 2.0, and then an aromatic having a melt viscosity of 597 Pa · s using BPA as a raw material. Production was carried out in the same manner as in Example 1 except that the polycarbonate resin was produced. The melt viscosity of the aromatic polycarbonate resin obtained from BPA as a raw material was 597 Pa · s and YI = 2.0.

(Comparative Example 1)
In Example 1, after producing an aromatic polycarbonate resin having a melt viscosity of 597 Pa · s using BPA as a raw material, the same as in Example 1 except that an aromatic polycarbonate resin having a melt viscosity of 434 Pa · s was produced using BPC as a raw material. Manufactured. The melt viscosity of the aromatic polycarbonate resin obtained using BPC as a raw material was 434 Pa · s, and YI = 3.0.

(Comparative Example 2)
In Example 1, manufactured in the same manner as in Example 1 except that a 434 Pa · s aromatic polycarbonate resin was first produced using BPC as a raw material, and then an aromatic polycarbonate resin having a melt viscosity of 597 Pa · s was produced using BPA as a raw material. Went. The melt viscosity of the aromatic polycarbonate resin obtained using BPA as a raw material was 597 Pa · s and YI = 4.0.

(Example 3)
Using continuous polymerization equipment as shown in FIG. 1, DPC and BPC were continuously supplied to the raw material preparation tank 1a so that the molar ratio of the raw material DPC and BPC was 1.02. About the raw material molten mixture adjusted in the raw material preparation tanks 1a and 1b, the raw material filter 3 was passed through the liquid feed pump 2 and supplied to the first vertical reaction tank 4a equipped with a stirring blade at 50 kg / hr. . In addition, the aqueous cesium carbonate solution was supplied to the first vertical reactor 4a so as to be 1.2 μmol as cesium carbonate with respect to 1 mol of BPA. From the first vertical reaction tank 4a to the second vertical reaction tank 4b, the third vertical reaction tank 4c, the fourth vertical reaction tank 4d, and the fifth horizontal reaction tank 6, the average residence time in each tank. The polymerization reaction was advanced under the reaction conditions as shown below so as to be 60 minutes, and the by-produced phenol was appropriately discharged from the distillation line.
(First vertical stirring reaction tank 4a): 220 ° C., normal pressure (second vertical stirring reaction tank 4b): 220 ° C., 13.3 kPa
(Third vertical stirring reaction tank 4c): 240 ° C., 2 kPa
(4th vertical stirring reaction tank 4d): 270 ° C., 67 Pa
(Fifth horizontal stirring reaction tank 6): 290 ° C., 67 Pa

  The aromatic polycarbonate resin discharged from the fifth horizontal reaction tank 6 is supplied to a vented twin screw extruder (not shown) as it is without being cooled and solidified by a liquid feed pump (not shown), and the catalyst is lost. 12 ppm of p-toluenesulfonic acid butyl as an activator was added and mixed in the vent type twin screw extruder, devolatilized and extruded, extracted into a strand form from the vent type twin screw extruder, cooled with water, and pelletized (Fig. (Not shown) to obtain a chip-like aromatic polycarbonate resin. The melt viscosity of the obtained aromatic polycarbonate resin was 434 Pa · s, and YI = 1.9.

After producing an aromatic polycarbonate resin under the above production conditions for 1 week, the aqueous cesium carbonate solution was changed to 0.75 μmol as cesium carbonate with respect to 1 mol of BPC, and the conditions of each tank were changed as follows. .
(First vertical stirring reaction tank 4a): 220 ° C., normal pressure (second vertical stirring reaction tank 4b): 220 ° C., 13.3 kPa
(Third vertical stirring reaction tank 4c): 240 ° C., 2 kPa
(4th vertical stirring reaction tank 4d): 270 ° C., 67 Pa
(Fifth horizontal stirring reaction tank 6): 280 ° C., 67 Pa

  The aromatic polycarbonate resin discharged from the fifth horizontal reaction tank 6 is supplied to a vented twin screw extruder (not shown) as it is without being cooled and solidified by a liquid feed pump (not shown), and the catalyst is lost. 7.5 ppm of butyl p-toluenesulfonate as an activator is added and mixed in the vented twin screw extruder, devolatilized, extracted into a strand from the vented twin screw extruder, cooled with water, and pelletized. A chip-like aromatic polycarbonate resin was prepared by using (not shown). The melt viscosity of the obtained aromatic polycarbonate resin was 357 Pa · s, and YI = 1.8.

After preparing an aromatic polycarbonate resin having a melt viscosity of 357 Pa · s using BPC as a raw material for 2 days, the raw material is changed from BPC to BPA, and the cesium carbonate aqueous solution is 0.75 μm as cesium carbonate with respect to 1 mol of BPA. It changed so that it might become a mole, and the conditions of each tank were changed as follows.
(First vertical stirring reaction tank 4a): 220 ° C., normal pressure (second vertical stirring reaction tank 4b): 220 ° C., 13.3 kPa
(Third vertical stirring reaction tank 4c): 240 ° C., 2 kPa
(4th vertical stirring reaction tank 4d): 270 ° C., 67 Pa
(Fifth horizontal stirring reaction tank 6): 290 ° C., 67 Pa

  The aromatic polycarbonate resin discharged from the fifth horizontal reaction tank is supplied to a vented twin-screw extruder (not shown) as it is without being cooled and solidified by a liquid feed pump (not shown) to deactivate the catalyst. 7.5 ppm of butyl p-toluenesulfonate as an agent was added and mixed in the bent type twin screw extruder, devolatilized, extruded into a strand from the bent type twin screw extruder, cooled with water, and pelletized ( A chip-like aromatic polycarbonate resin was obtained. The melt viscosity of the obtained aromatic polycarbonate resin was 597 Pa · s, and YI = 2.0.

(Comparative Example 3)
In Example 3, after producing an aromatic polycarbonate resin having a melt viscosity of 434 Pa · s using BPC as a raw material, an aromatic polycarbonate resin having a melt viscosity of 597 Pa · s was directly produced using BPA as a raw material. It carried out similarly. The melt viscosity of the aromatic polycarbonate resin obtained using BPA as a raw material was 597 Pa · s and YI = 3.0.

  According to the present invention, in the same existing manufacturing facility, a plurality of types of aromatic polycarbonates having different structural units can be continuously manufactured without temporarily stopping the manufacturing facility or performing a cleaning operation. Can do. The present invention can be applied to both a batch reaction system and a continuous reaction system, and the obtained aromatic polycarbonate resin is not inferior to conventional ones in physical properties such as color tone, and an efficient production of an aromatic polycarbonate is possible. Provide a method.

1a, 1b Raw material preparation tank 2, 5a, 5b Liquid feed pump 3 Raw material filter 4a, 4b, 4c, 4d Vertical reaction tank 6 Horizontal reaction tank

Claims (4)

A method for producing an aromatic polycarbonate resin, wherein a plurality of types of aromatic polycarbonate resins having different structural units are produced in the same production facility,
At least one of a plurality of types of aromatic polycarbonate resins having different structural units has a structural unit represented by the following general formula (1) or general formula (2),
An aromatic polycarbonate resin A having a melt viscosity of 400 Pa · s or less at 300 ° C. and a shear rate of 912 sec ⁻¹ is produced, and then an aromatic polycarbonate having a structural unit different from the structural unit of the aromatic polycarbonate resin A A method for producing an aromatic polycarbonate resin, comprising producing resin B.


(In General Formula (1) and General Formula (2), X represents a single bond, a carbonyl group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom. 2), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group, and R ₃ and R ₄ are each represented by Independently, it represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. Before producing the aromatic polycarbonate resin A, produce an aromatic polycarbonate resin having the same structural unit as the aromatic polycarbonate resin A and having a melt viscosity of more than 400 Pa · s at 300 ° C. and a shear rate of 912 sec ⁻¹ . The method for producing an aromatic polycarbonate resin according to claim 1. The substituted or unsubstituted alkylidene group of X in the general formula (1) or the general formula (2) is
The method for producing an aromatic polycarbonate resin according to claim 1 , wherein:
(R ₅ and R ₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and Z represents a substituted or unsubstituted aryl group. A polymethylene group having 4 to 20 carbon atoms is shown.) At least one of a plurality of types of aromatic polycarbonate resins having different structural units has the structural units of both general formula (1) and general formula (2), and is represented by general formulas (1) and (2). The aromatic polycarbonate resin according to any one of claims 1 to 3 , which is an aromatic polycarbonate resin having 50% by weight or more of the structural unit represented by the general formula (2) with respect to the total amount of the structural units to be formed. For producing a polycarbonate resin.