CN101668792B - Method for producing aromatic polycarbonate resin composition - Google Patents

Abstract

The present invention provides a method for producing an aromatic polycarbonate resin composition, wherein an aromatic polycarbonate resin composition having stable quality is produced by uniformly mixing an additive such as a heat stabilizer with the aromatic polycarbonate resin. The method for producing the aromatic polycarbonate resin composition comprises the steps of: a polycarbonate supply step of continuously supplying an aromatic polycarbonate in a molten state to an extruder; an extrusion step of mixing an aromatic polycarbonate with a heat stabilizer by an extruder and extruding the mixture from the extruder; a granulation step of granulating the aromatic polycarbonate extruded by the extruder to form granules of the aromatic polycarbonate; and a pellet circulation supply step of collecting pellets of a part of the aromatic polycarbonate, continuously adding a heat stabilizer to the pellets, and continuously supplying the pellets to an extruder to which the aromatic polycarbonate is supplied in the polycarbonate supply step.

Description

Method for producing aromatic polycarbonate resin composition

technical field

The present invention relates to a method for producing an aromatic polycarbonate resin composition. More specifically, the present invention relates to a method for producing an aromatic polycarbonate resin composition based on a transesterification reaction.

Background technique

In recent years, aromatic polycarbonate resins have been widely used in office automation parts, automobile parts, building materials, etc. as engineering plastics that are excellent in mechanical properties such as impact resistance, and also excellent in heat resistance, transparency, and the like. In particular, it is widely used in applications such as optical lenses as optical materials, optical discs for recording, sheets, bottles, etc., in order to exert its characteristics such as impact resistance and transparency.

As a method for producing such an aromatic polycarbonate resin, a so-called melting method has been known in the past, that is, transesterifying an aromatic diol and a carbonic acid diester in a molten state, and converting low-molecular-weight polycarbonate such as phenol produced as a by-product A method of continuously obtaining aromatic polycarbonate resin while removing substances out of the system.

Here, when an aromatic polycarbonate resin is used as a material, in order to maintain and improve its performance, it is often used after adding various heat stabilizers. These heat stabilizers are generally mixed into aromatic polycarbonates by a kneading method using an extruder and dispersed and homogenized (see Patent Document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 8-259687

Contents of the invention

However, for example, when producing an aromatic polycarbonate resin by a melt method, the aromatic polycarbonate resin in a molten state and various additives such as heat stabilizers are usually mixed in an extruder installed at the end of the production line. . Then, the aromatic polycarbonate resin extruded from the extruder is molded into pellets of a predetermined size to become a product.

However, most of the additives added to the aromatic polycarbonate resin are in the form of powder or liquid, and the amount thereof is extremely small. Therefore, when the aromatic polycarbonate resin and additives are mixed with an extruder, there are many cases in which the distribution of the additives is not uniform and the uniform mixing is not possible.

In this case, a method of adding to the extruder in the form of a masterbatch composed of additives and appropriate polymers in advance is conceivable. However, when preparing a masterbatch using a mixer such as a Henschel mixer, powdery additives are often classified and cannot be uniformly dispersed. Also, liquid additives are sometimes separated after preparing the masterbatch.

In addition, since the above-mentioned melting method is generally a method for continuously producing aromatic polycarbonate resins, transitional products are generated during product switching and the like. However, such transitional products are out-of-class products and are usually disposed of as production losses.

However, it is not ideal to dispose of such production waste products from the viewpoint of raw material utilization rate of products and resource conservation, and it is desirable to utilize them effectively. However, when such production waste products are recycled, the heat stability of the product may deteriorate and the commodity value may decrease.

The object of the present invention is to provide a method for producing an aromatic polycarbonate resin composition, wherein additives such as heat stabilizers are uniformly mixed with the aromatic polycarbonate resin to produce a stable quality aromatic polycarbonate resin composition. thing.

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies and found that if the aromatic polycarbonate pellets containing a heat stabilizer are pneumatically conveyed using a branch pipe branched from the pneumatic conveying pipe, After the thermal stabilizer is continuously supplied to the extruder, the above-mentioned production loss can be effectively used, and the influence of the production loss on quality can be minimized. Based on these findings, the present invention has been completed.

In this way, the present invention can provide a method for producing an aromatic polycarbonate resin composition, which is a method for producing an aromatic polycarbonate resin composition containing a heat stabilizer, which is characterized in that it includes the following steps: polycarbonate supply A process of continuously supplying the aromatic polycarbonate in a molten state to an extruder; an extrusion process of mixing the aromatic polycarbonate supplied in the polycarbonate supply process with a heat stabilizer using an extruder, and extruded by an extruder; the granulation process, the aromatic polycarbonate extruded by the extruder in the extrusion process is granulated to form particles of the aromatic polycarbonate; and the granule circulation supply process is divided into Partially aromatic polycarbonate pellets pelletized in the pelletizing process, the heat stabilizer is continuously added to the pellets, and the pellets with the heat stabilizer added are continuously supplied to the extruder, and the extruder This is an extruder that supplies aromatic polycarbonate in the polycarbonate supply process.

Here, in the method for producing the aromatic polycarbonate resin composition to which the present invention is applied, it is preferable to further include pneumatic conveying of the pellets of the aromatic polycarbonate granulated in the granulation process through the conveying pipe. In the conveying step, the pellets of the partially aromatic polycarbonate obtained in the granulation step are pneumatically conveyed through a branch pipe branched from the conveying pipe.

Then, in the production method of the aromatic polycarbonate resin composition to which the present invention is applied, it is preferable that the heat stabilizer added to the pellets of the aromatic polycarbonate in the pellet circulation supply step is in a liquid state. Here, in the pellet circulation supply step, the heat stabilizer added to the pellets of the aromatic polycarbonate is preferably an acidic compound or a derivative thereof. Furthermore, the heat stabilizer is preferably liquid sulfonic acid or its ester which may have an alkyl substituent having 1 to 10 carbon atoms.

Then, in the production method of the aromatic polycarbonate resin composition to which the present invention is applied, it is preferable to use 0.001 to 1 part by weight of The heat stabilizer is continuously added to the particles of the aromatic polycarbonate.

In addition, it is preferable to supply 0.5 to 5 parts by weight of the pellets of the aromatic polycarbonate to which the heat stabilizer is added with respect to 100 parts by weight of the aromatic polycarbonate supplied to the extruder in the pellet circulation supply process. extruder.

In addition, in the method for producing an aromatic polycarbonate resin composition to which the present invention is applied, it is preferable that the viscosity-average molecular weight (Mv ₁ ) of the aromatic polycarbonate granulated in the granulation step is not greater than that in the extrusion step. Viscosity-average molecular weight (Mv ₂ ) of aromatic polycarbonate in a molten state mixed with a heat stabilizer in an extruder (ie Mv ₁ ≤ Mv ₂ ).

In addition, it is preferable to mix a heat stabilizer in an amount of 0.002 parts by weight or less with respect to 100 parts by weight of the aromatic polycarbonate in the extrusion step.

Furthermore, it is preferable that the aromatic polycarbonate supplied to the extruder in the polycarbonate supplying step is obtained by polycondensation reaction of an aromatic dihydroxy compound and a carbonic acid diester using a basic compound as a catalyst.

The present invention can produce an aromatic polycarbonate resin composition with stable quality. In addition, the present invention can also be expected to improve the utilization rate of raw materials by a simple method and contribute to saving resources.

Description of drawings

FIG. 1 shows an example of a production apparatus of an aromatic polycarbonate resin composition.

FIG. 2 shows an example of an aromatic polycarbonate resin composition manufacturing apparatus in the case of using two or more mixers and adding additives such as heat stabilizers.

Symbol Description

2a...1st raw material preparation tank, 2b...2nd raw material preparation tank, 3a, 3b...anchor type stirring impeller, 4a...raw material supply pump, 5a...catalyst supply port, 6a.. .1st vertical reactor, 6b...2nd vertical reactor, 6c...3rd vertical reactor, 7a, 7b, 7c...Maxblend paddle, 8a, 8b, 8c, 8d.. .distillation tube, 9a...4th horizontal reactor, 10a...grid paddle (lattice wing), 11a...extruder, 12a, 12b, 12c...additive supply line, 13a... Cooling tank (strand bath), 14a... strand pelletizer, 15a... screening machine, 16a, 16b, 16c... product storage bin, 21a, 21b... mixer, 22a, 22b... The thermal stabilizer supply port, 81a, 81b, 81c, 81d ... condenser, 82a, 82b, 82c, 82d ... are connected to piping of the decompression device.

Detailed ways

Next, specific embodiments of the present invention (hereinafter referred to as embodiments of the invention) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement various deformation|transformation within the range of the summary. In addition, the drawings used are for describing embodiments of the present invention, and do not show actual dimensions.

(polycarbonate resin)

In the present invention, the polycarbonate resin is produced by melt polycondensation based on a transesterification reaction between an aromatic dihydroxy compound and a carbonic acid diester.

Next, a method for producing a polycarbonate resin by continuously performing a melt polycondensation reaction in the presence of a transesterification catalyst using an aromatic dihydroxy compound and a diester carbonate as raw materials will be described.

(aromatic dihydroxy compound)

Examples of the aromatic dihydroxy compound used in the embodiment of the present invention include compounds represented by the following general formula (1).

Formula (1)

Here, in the general formula (1), A is a single bond or a linear, branched or cyclic divalent hydrocarbon group with 1 to 10 carbon atoms that may have a substituent, or a -O- , -S-, -CO- or a divalent group represented by -SO ₂ -. X and Y are each independently a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms. p and q are integers of 0-2 each independently. It should be noted that X and Y may be the same or different, and p and q may be the same or different.

Specific examples of aromatic dihydroxy compounds include bis(4-hydroxydiphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3 -methylphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, 1,1-bis(4-hydroxyphenyl)cyclohexyl Bisphenols such as alkanes; 4,4'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl and other biphenols; bis(4-hydroxybenzene base) sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ketone, etc.

Among these, 2,2-bis(4-hydroxyphenyl)propane ("bisphenol A", hereinafter sometimes abbreviated as BPA) is preferable. These aromatic dihydroxy compounds may be used alone or in combination of two or more.

(dicarbonate)

Examples of the diester carbonate used in the embodiment of the present invention include compounds represented by the following general formula (2).

Formula (2)

Here, in the general formula (2), A' is a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. The two A's may be the same or different.

In addition, examples of the substituent on A' include 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, and an ethylene group. group, cyano group, ester group, amido group, nitro group, etc.

As specific examples of carbonic diesters, for example, substituted diphenyl carbonates such as diphenyl carbonate and dibenzyl carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate; base ester.

Among these, diphenyl carbonate (hereinafter sometimes abbreviated as DPC) and substituted diphenyl carbonate are preferable. These carbonic diesters may be used alone or in combination of two or more.

In addition, the above-mentioned carbonic acid diester may be replaced with a dicarboxylic acid or a dicarboxylic acid ester in an amount of preferably 50 mol % or less, more preferably 30 mol % or less.

As typical dicarboxylic acid or dicarboxylic acid ester, terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, etc. are mentioned, for example. When substituting such dicarboxylic acid or dicarboxylic acid ester, polyester carbonate can be obtained.

These carbonic acid diesters (including the above-mentioned substituted dicarboxylic acid or dicarboxylic acid ester; the same applies hereinafter) are used in excess relative to the dihydroxy compound.

That is, the molar ratio of the diester carbonate to be used is preferably 1.01 or more, particularly preferably 1.02 or more, and preferably 1.30 or less, particularly preferably 1.20 or less, relative to the aromatic dihydroxy compound. When the said molar ratio is less than 1.01, the polycarbonate resin obtained will have many terminal OH groups, and thermal stability of a resin will tend to deteriorate. And, when the molar ratio is greater than 1.30, the reaction rate of transesterification decreases, and the production of polycarbonate resin with desired molecular weight tends to be difficult, and the residual amount of carbonic acid diester in the resin becomes large, and sometimes it is difficult to Or it causes an odor when it is made into a molded product, so it is not preferable.

(transesterification catalyst)

The transesterification catalyst used in the embodiment of the present invention is not particularly limited, and examples thereof include catalysts generally used for producing aromatic polycarbonates by a transesterification method. In general, basic compounds such as alkali metal compounds, beryllium or magnesium compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, or amine compounds can be mentioned, for example.

Among these transesterification catalysts, alkali metal compounds or alkaline earth metal compounds are more effective from the viewpoint of uniformly dispersing a small amount of heat stabilizer in the aromatic polycarbonate resin composition, which is the object of the embodiment of the present invention. These transesterification catalysts may be used individually by 1 type, and may use it in combination of 2 or more types.

With regard to the amount of the transesterification catalyst used, it is generally preferred to use 1×10 ^-9 mol or more, particularly preferably 1×10 ^-7 mol or more, and preferably 1×10 ^-1 mol with respect to 1 mol of the aromatic dihydroxy compound. Mole or less, particularly preferably 1×10 ^-2 mole or less.

Examples of the alkali metal compound include inorganic alkali metal compounds such as hydroxides, carbonates, and bicarbonates of alkali metals; organic alkali metal compounds such as salts of alkali metals and alcohols, phenols, and organic carboxylic acids; and the like. Here, examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium.

Among these alkali metal compounds, cesium compounds are preferable, and cesium carbonate, cesium bicarbonate, and cesium hydroxide are particularly preferable.

Examples of beryllium or magnesium compounds and alkaline earth metal compounds include inorganic alkaline earth metal compounds such as beryllium, magnesium, and alkaline earth metal hydroxides and carbonates; salts of these metals with alcohols, phenols, and organic carboxylic acids wait. Here, examples of alkaline earth metals include calcium, strontium, and barium.

Examples of basic boron compounds include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, barium salts, and strontium salts of boron compounds. Here, examples of the boron compound include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron Boron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyl Triphenylboron, butyltriphenylboron, etc.

As the basic phosphorus compound, for example, trivalent phosphorus compounds such as triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, or trivalent phosphorus compounds derived from these Compound-derived quaternary phosphonium salts, etc.

As basic ammonium compounds, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylammonium hydroxide, Methylbenzylammonium, Trimethylphenylammonium Hydroxide, Triethylmethylammonium Hydroxide, Triethylbenzylammonium Hydroxide, Triethylphenylammonium Hydroxide, Tributylbenzylammonium Hydroxide , Tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, etc.

Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxy Pyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, etc.

(Manufacturing method of aromatic polycarbonate)

Next, the production method of the aromatic polycarbonate will be described.

The production of the aromatic polycarbonate is carried out by preparing a mixture containing the raw material aromatic dihydroxy compound and the raw material carbonic acid diester (raw material preparation process), and using two or more reactors in the presence of a transesterification catalyst to melt The state causes the mixture of these compounds to polycondense in a multi-stage manner (polycondensation process). The reaction system may be a batch type, a continuous type, or a combination of a batch type and a continuous type, and the continuous type is preferable from the viewpoint of productivity and quality stability. In the case of a continuous type, the reactor generally consists of two or more reactors arranged in series, preferably two or more vertical reactors followed by at least one horizontal reactor.

In the embodiment of the present invention, an extruder is used to add a heat stabilizer after the polycondensation step, and it is preferable to use a twin-screw extruder having a vent port capable of devolatilizing and removing unreacted raw materials and reaction by-products in the reaction liquid. Exit.

Next, each step of the production method of the aromatic polycarbonate will be described.

(Raw material preparation process)

Usually, under the atmosphere of inert gas such as nitrogen or argon, using a batch, semi-batch or continuous stirred tank type device, the aromatic dihydroxy compound and carbonic acid diester used as raw materials for aromatic polycarbonate Prepare a molten mixture. For example, in the case of using bisphenol A as the aromatic dihydroxy compound and diphenyl carbonate as the diester carbonate, the temperature of melt mixing is selected from preferably 120° C. or higher, particularly preferably 125° C. or higher and preferably 180° C. Below, especially preferably, it is the range of 160 degreeC or less.

At this time, the mixing ratio of the aromatic dihydroxy compound and the carbonic acid diester is adjusted so that the carbonic acid diester is excessive, and adjusted so that the ratio of the carbonic acid diester is preferably 1.01 mol or more, based on 1 mol of the aromatic dihydroxy compound. It is particularly preferably 1.02 moles or more and preferably 1.30 moles or less, particularly preferably 1.20 moles or less.

(polycondensation process)

The polycondensation by the transesterification reaction of an aromatic dihydroxy compound and a carbonic acid diester is performed continuously in the multi-stage system of two or more stages normally, Preferably it is 3-7 stages.

Specific reaction conditions range from 150°C to 320°C in temperature, from normal pressure to 0.01 Torr (1.3Pa) in pressure, and from 5 minutes to 150 minutes in average residence time in one stage.

When the polycondensation process is carried out in multiple stages, in order to more effectively discharge the phenol produced as a by-product as the polycondensation reaction progresses, the temperature and vacuum are generally set step by step within the above-mentioned reaction conditions. . In addition, in order to prevent the fall of quality, such as the color tone of the aromatic polycarbonate resin obtained, it is preferable to set it as low temperature as possible and short residence time.

When carrying out the polycondensation step in a multi-stage system, it is preferable to install two or more vertical reactors followed by at least one reactor with excellent thin film evaporation performance to increase the average molecular weight of the aromatic polycarbonate resin. Usually, 3 to 6 reactors are installed, preferably 4 to 5 reactors.

Here, as a reactor excellent in thin film evaporation performance, for example, a thin film reactor, a centrifugal thin film evaporation reactor, a surface renewal type twin-screw kneading reactor, a twin-screw horizontal stirring reactor, a wetted wall reactor, A perforated plate reactor in which polymerization is performed while free falling, a perforated plate reactor with a wire in which polymerization is performed while falling along a wire, etc.

As the form of the stirring paddle of the vertical reactor, for example, a turbo paddle, an impeller paddle, a three-blade backward curved (Pfaudler) paddle, an anchor paddle, and a full zone (full zone) paddle (manufactured by KOBELCOECO-SOLUTIONS Co., Ltd.) , SANMELER propeller (manufactured by Mitsubishi Heavy Industries, Ltd.), Maxblend propeller (manufactured by Sumiju Machinery Systems Co., Ltd.), propeller belt propeller, and propeller grid propeller (manufactured by Hitachi Industrial Equipment Technology Co., Ltd.), etc.

In addition, a horizontal reactor refers to a reactor in which the rotation axis of the stirring blade is horizontal (horizontal direction). As the stirring impeller of the horizontal reactor, for example, single-shaft stirring impellers such as disc type and impeller type; ), or spectacle-shaped paddles, grid paddles (manufactured by Hitachi Industrial Equipment Technology Co., Ltd.) and other biaxial stirring paddles.

It should be noted that the transesterification catalyst used for the polycondensation of aromatic dihydroxy compounds and carbonic acid diesters is usually prepared in advance as an aqueous solution. The concentration of the aqueous catalyst solution is not particularly limited, and may be adjusted to any concentration according to the solubility of the catalyst in water. In addition, other organic solvents such as acetone, alcohol, toluene, and phenol may be used instead of water.

The water used for dissolving the catalyst is not particularly limited as long as the type and concentration of impurities contained therein are constant, and distilled water, deionized water, etc. are usually preferably used.

(manufacturing device)

Next, an example of the manufacturing method of the aromatic polycarbonate resin composition to which the embodiment of this invention is applied is demonstrated concretely based on drawing.

FIG. 1 is a schematic diagram showing an example of a production apparatus of an aromatic polycarbonate resin composition. In the production device shown in Figure 1, the production of aromatic polycarbonate goes through the following steps: the raw material preparation process of preparing the raw material aromatic dihydroxy compound and the raw material carbonic acid diester; using two or more reactors to make these raw materials in a molten state Polycondensation process in which polycondensation reaction occurs.

Then, stop the reaction, go through the process of devolatilizing and removing unreacted raw materials and reaction by-products in the polymerization reaction solution; add heat stabilizers, anti-sticking agents, colorants, etc.; make the aromatic polycarbonate resin into a predetermined After the step of reducing the size of the pellets, pellets of the aromatic polycarbonate resin composition are molded.

In the raw material preparation step, a first raw material preparation tank 2a, a second raw material preparation tank 2b connected in series, and a raw material supply pump 4a for supplying the prepared raw material to the polycondensation step are provided. The first raw material preparation tank 2a and the second raw material preparation tank 2b are respectively provided with, for example, anchor type stirring blades 3a and 3b.

Then, to the first raw material preparation tank 2a, DPC is supplied in a molten state from the DPC supply port 1a-1, and bisphenol A (hereinafter sometimes referred to as BPA) which is an aromatic dihydroxy compound is supplied in a powder state from the BPA supply port 1b. , bisphenol A dissolved in the molten diphenyl carbonate.

Next, in the polycondensation step, the first vertical reactor 6a, the second vertical reactor 6b, and the third vertical reactor 6c connected in series, and the rear stage of the third vertical reactor 6c connected in series are provided. The 4th horizontal reactor 9a. Maxblend paddles 7a, 7b, and 7c are installed in the first vertical reactor 6a, the second vertical reactor 6b, and the third vertical reactor 6c, respectively. In addition, a grid paddle 10a is provided in the fourth horizontal reactor 9a.

It should be noted that distillation pipes 8 a , 8 b , 8 c , and 8 d for discharging by-products and the like generated in the polycondensation reaction are respectively installed on the four reactors. The distillation pipes 8a, 8b, 8c, and 8d are respectively connected to the condensers 81a, 81b, 81c, and 81d, and each reactor is maintained at a predetermined reduced pressure by means of connection pipes 82a, 82b, 82c, and 82d connected to the pressure reducing device. state.

In the production apparatus of the aromatic polycarbonate resin composition shown in FIG. 1 , the DPC melt prepared at a predetermined temperature under a nitrogen atmosphere and the BPA powder weighed under a nitrogen atmosphere are supplied from the DPC supply port 1a-1 and The BPA supply port 1b continuously supplies to the 1st raw material preparation tank 2a. When the liquid level of the first raw material preparation tank 2a exceeds the same height as the highest level in the transfer piping, the raw material mixture is sent to the second raw material preparation tank 2b.

Next, the raw material mixture is continuously supplied to the first vertical reactor 6a via the raw material supply pump 4a. In addition, an aqueous solution of cesium carbonate as a catalyst was continuously supplied from the catalyst supply port 5a in the middle of the transfer piping of the raw material mixture.

In the first vertical reactor 6a, under a nitrogen atmosphere, for example, under the conditions of a temperature of 220°C and a pressure of 13.33kPa (100Torr), the rotation speed of the Maxblend paddle 7a is kept at 160rpm, and the by-product phenol is distilled off from the distillation tube 8a. , keep the liquid level constant, so that the average residence time is 60 minutes, carry out the polycondensation reaction. Then, the polymerization reaction solution discharged from the first vertical reactor 6a is sequentially and continuously supplied to the second vertical reactor 6b, the third vertical reactor 6c, and the fourth horizontal reactor 9a to perform polycondensation reaction. The reaction conditions in each reactor are usually set to high temperature, high vacuum, and low stirring speed as the polycondensation reaction progresses, and can be appropriately adjusted according to the required performance (for example, desired molecular weight, etc.). During the polycondensation reaction, the liquid level is controlled so that the average residence time in each reactor is, for example, about 60 minutes. In each reactor, by-product phenol is distilled from the distillation tubes 8b, 8c, and 8d.

In addition, in embodiment of this invention, by-products, such as phenol, are liquefied and recovered continuously from the condensers 81a and 81b respectively installed in the 1st vertical reactor 6a and the 2nd vertical reactor 6b. In addition, a cold trap (not shown) is provided between the condensers 81c and 81d respectively installed in the third vertical reactor 6c and the fourth horizontal reactor 9a and the connecting pipes 82c and 82d connected to the decompression device. , continuous condensation-solidification recovery of by-products.

Then, the aromatic polycarbonate extracted from the fourth horizontal reactor 9a was supplied to the twin-screw extruder 11a having three stages of vents while maintaining a molten state. The following various additives are supplied to the extruder 11a from the additive supply lines 12a, 12b, 12c, respectively: for example, heat stabilizers, antioxidants, weather-resistant agents, anti-blocking agents, lubricants, antistatic agents, plasticizers, Pigments, dyes, fillers, reinforcements, flame retardants, polymers such as other resins or rubbers, etc.

Here, examples of the heat stabilizer include phosphorus-based stabilizers, hindered phenol-based stabilizers, sulfur-based stabilizers, epoxy-based stabilizers, hindered amine-based stabilizers, and the like. Specific examples of preferable thermal stabilizers are described later.

Heat stabilizers may be used alone or in combination. The addition amount is not particularly limited, but usually 0.0001 to 0.5 parts by weight, preferably 0.001 to 0.2 parts by weight of the heat stabilizer is used per 100 parts by weight of the aromatic polycarbonate. Wherein, when the thermal stabilizer is supplied in a liquid state, the amount used is not more than 0.005 parts by weight, preferably not more than 0.002 parts by weight, more preferably not more than 0.001 parts by weight.

Here, in the embodiment of the present invention, as will be described later, the thermal stabilizer is continuously added to the aromatic polycarbonate pellets, and is then continuously supplied to the extruder 11a from the additive supply line 12a.

The aromatic polycarbonate and the thermal stabilizer are melt-mixed inside the extruder 11a and extruded from the outlet. When the aromatic polycarbonate is extruded from the extruder 11a, it is extruded into a strand form through a hole (not shown) provided in the outlet portion.

Then, the strand-shaped aromatic polycarbonate is cooled by cooling water through the cooling tank 13a, granulated by the strand pelletizer 14a, dehydrated by the sieving machine 15a, and introduced into the product storage bins 16a and 16b.

In addition, in a preferred embodiment of the present invention, a part of the final product (that is, the aromatic polycarbonate resin composition (aromatic polycarbonate pellets) as a product) also passes through a branch pipe branched from the pneumatic conveying pipe. Induct product silo 16c.

The aromatic polycarbonate pellets can be pneumatically conveyed by supplying compressed air or an inert gas such as nitrogen to the pneumatic conveying pipe by a compressor (not shown).

(continuous addition of heat stabilizer)

In the embodiment of the present invention, the aromatic polycarbonate pellets stored in the product silo 16c are supplied to the agitator 21a in an appropriate manner through a pneumatic conveying pipe, preferably continuously. In order to continuously supply to the mixer 21a stably, a hopper and a quantitative feeder for supplying aromatic polycarbonate particles can also be equipped, and the product storage bin 16c is intermittently supplied to the hopper, and the quantitative feeder is used to continuously feed the polycarbonate pellets from the hopper. The aromatic polycarbonate pellets are supplied to the mixer 21a, which is not shown in FIG. 1 .

The thermal stabilizer is continuously supplied to the mixer 21a through the thermal stabilizer supply port 22a. Then, in the mixer 21a, the heat stabilizer is continuously added to the aromatic polycarbonate pellets. The stirring time is preferably 1 minute to 20 minutes, more preferably 5 minutes to 10 minutes. If the stirring time is too long, the apparatus tends to be too large, and if the stirring time is too short, the addition to the entire aromatic polycarbonate particles tends to be insufficient.

In this case, the amount of the thermal stabilizer continuously added to the aromatic polycarbonate pellets in the mixer 21a is not particularly limited, but usually the thermal stabilizer is 0.001 wt. 1 part by weight, preferably 0.005 part by weight to 0.5 part by weight, more preferably 0.01 part by weight to 0.2 part by weight.

When the amount of the thermal stabilizer added to the aromatic polycarbonate pellets is too large, the dispersibility of the thermal stabilizer in the extruder 11a decreases, and the aromatic polycarbonate obtained as a product may suffer from poor color tone and uneven quality. tendency. Furthermore, when the amount of the heat stabilizer added to the aromatic polycarbonate pellets is too small, the feed amount of the pellets supplied into the extruder 11a tends to increase in order to secure a predetermined amount of the heat stabilizer. In this case, a large amount of aromatic polycarbonate pellets having a previous heat history are fed into the extruder 11a. As a result, not only the color tone of the aromatic polycarbonate obtained as a product deteriorates, but also the operation of the extruder 11a becomes unstable, which tends to place an excessive load on the mixer 21a.

(continuous addition of aromatic polycarbonate pellets)

Then, as described above, the aromatic polycarbonate pellets to which the heat stabilizer is continuously added in the mixer 21a are continuously circulated and supplied to the extruder 11a through the additive supply line 12a, and are mixed with the molten aromatic polycarbonate in the extruder 11a. Polycarbonate mixed together.

In addition, here, "attachment" refers to a state in which the heat stabilizer is attached to the aromatic polycarbonate pellets by mixing.

The mixer 21a is not particularly limited, as long as it is capable of continuous mixing, for example, a ribbon mixer etc. are mentioned. In addition, since the oxygen entrained when feeding the aromatic polycarbonate pellets to the extruder 11a will lead to a decrease in product quality, it is preferable to operate under an inert gas atmosphere such as nitrogen. In particular, introduction of nitrogen into the mixer 21a is effective in suppressing thermal deterioration of the product.

In addition, two or more types of thermal stabilizers may be supplied to the mixer 21a, and additives other than thermal stabilizers such as a release agent, a colorant, and an ultraviolet absorber may be simultaneously supplied.

In addition, the additive supplied from the additive supply line 12b, 12c can also be supplied by the method similar to the additive supply line 12a.

When the aromatic polycarbonate supplied to the extruder 11a from the fourth horizontal reactor 9a is 100 parts by weight, the amount of the aromatic polycarbonate resin composition continuously circulated and supplied to the extruder 11a Usually, it is 0.1 weight part - 10 weight part, Preferably it is 0.5 weight part - 5 weight part, More preferably, it is 1 weight part - 4 weight part. When the amount of the aromatic polycarbonate resin composition circulated and supplied to the extruder 11a is too small, the effects of the present invention are hardly produced, and when too large, the thermal stability of the product tends to deteriorate.

Furthermore, the size, shape, etc. of the aromatic polycarbonate pellets are not particularly limited, and the pellets are generally preferably processed to have a maximum length of 20 mm or less. In addition, granular, amorphous, tabular, and cylindrical particles can be used, and among them, granular and cylindrical shapes are preferable from the viewpoint of easy availability, and cylindrical shapes are particularly preferable.

As described above, in the embodiment of the present invention, a part of the granulated aromatic polycarbonate pellets as a product is taken out, a heat stabilizer is continuously added thereto, and then the heat stabilizer attached to the pellets is continuously added to the pellets. supplied to the extruder. Therefore, it is possible to uniformly mix the thermal stabilizer and the molten aromatic polycarbonate resin in the extruder. In addition, by continuously supplying the heat stabilizer-added pellets to the extruder, an aromatic polycarbonate resin composition with stable quality can be obtained without causing deterioration and separation of the heat stabilizer.

Furthermore, in the embodiment of the present invention, the aromatic polycarbonate pellets supplied from the product silo 16c itself contain a heat stabilizer, and the heat stabilizer is further added thereto and supplied to the extruder 11a. Therefore, the thermal stability of the obtained aromatic polycarbonate resin is remarkably improved, and the deterioration of the quality of a final product is remarkably suppressed.

In an embodiment of the present invention, by adopting the above method, even if the amount of the heat stabilizer is small, the heat stabilizer can be sufficiently dispersed in the aromatic polycarbonate resin composition. In particular, in the embodiment of the present invention, even when the amount of the heat stabilizer is 0.002 parts by weight or less with respect to 100 parts by weight of the molten aromatic polycarbonate resin in the extruder 11a, it is possible to stably transfer heat A stabilizer is supplied to the aromatic polycarbonate resin.

In the embodiment of the present invention, it is particularly effective when the heat stabilizer to be used is liquid or an acidic compound or a derivative thereof.

Here, the acidic compound used as a heat stabilizer is not particularly limited, and examples thereof include compounds that usually neutralize a basic transesterification catalyst used in a polycondensation reaction (so-called reaction terminators and deactivators). compound of).

Specifically, hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphate, benzoic acid , formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid, Picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid and other Bronsted acids and their esters, acid halides, salt etc. These may be used individually or in combination of 2 or more types.

Among these acidic compounds, liquid sulfonic acid or its ester which may have an alkyl substituent having 1 to 10 carbon atoms is preferred. Examples of the sulfonic acid include benzenesulfonic acid, toluenesulfonic acid and naphthalenesulfonic acid. Examples of esters of sulfonic acid include methyl sulfonic acid, ethyl sulfonic acid, butyl sulfonic acid, octyl sulfonic acid, and phenyl sulfonic acid. Among these, butyl p-toluenesulfonate is particularly preferred.

In the embodiment of the present invention, it is preferable that the viscosity-average molecular weight (Mv ₁ ) of the aromatic polycarbonate in the aromatic polycarbonate pellets to be added with a heat stabilizer is not greater than that of the molten aromatic polycarbonate in the extruder 11a. Viscosity average molecular weight (Mv ₂ ). That is, it is preferable that Mv ₁ ≤ Mv ₂ . Among them, the difference in viscosity average molecular weight (Mv ₂ -Mv ₁ ) is preferably 5,000 or less, preferably 3,000 or less, particularly preferably 2,000 or less.

When the viscosity-average molecular weight (Mv ₁ ) of the aromatic polycarbonate in the aromatic polycarbonate pellets to which the heat stabilizer is added is excessively larger than the viscosity-average molecular weight (Mv ₂ ) of the molten aromatic polycarbonate in the extruder 11a , or when the difference (Mv ₂ −Mv ₁ ) between the viscosity average molecular weight (Mv ₂ ) and the viscosity average molecular weight (Mv ₁ ) is too large, the dispersibility of the heat stabilizer tends to decrease.

In addition, in the embodiment of the present invention, the aromatic polycarbonate resin composition produced by using the extruder 11a is used as the aromatic polycarbonate pellets to which the heat stabilizer is added, and it is returned to the extruder 11a again. Among them, by adopting such a production process, residual products (kattomisu products) generated in the final stage of the production of aromatic polycarbonate resins, production loss products caused by product switching, etc. can also be used as pellets to be added with heat stabilizers. to use. Also, it is effective in stabilizing the supply amount of the heat stabilizer, securing the dispersibility in the molten polymer, preventing thermal deterioration of recycled products, and maintaining product quality. As a result, improvement of raw material utilization rate of products, resource saving, and stabilization of product quality can be achieved at the same time.

FIG. 2 shows another example of the production apparatus of the aromatic polycarbonate resin composition in the case of using two or more mixers and adding additives such as heat stabilizers. The same reference numerals are used for the same configuration as in FIG. 1 , and description thereof will be omitted here.

In the production apparatus of the aromatic polycarbonate resin composition shown in FIG. 2, the stirrer 21b is newly installed in the production apparatus of the aromatic polycarbonate resin composition shown in FIG. Furthermore, a thermal stabilizer supply port 22b is provided separately.

The aromatic polycarbonate pellets can be supplied to the agitator 21b similarly to the agitator 21a by branching the pneumatic conveying pipe into the branch pipe. In addition, a thermal stabilizer and other additives can be supplied from the thermal stabilizer supply port 22b, and they can be added to the aromatic polycarbonate pellets in the mixer 21b.

After the heat stabilizer and other additives are added to the mixer 21b, they are circulated and supplied to the extruder 11a through the additive supply line 12b.

Example

The specific forms of the present invention will be described below through examples, but the present invention is not limited to these examples unless the gist thereof is exceeded.

In addition, the aromatic polycarbonate resin composition in the following examples and comparative examples was analyzed by the following method.

(1) Viscosity average molecular weight (Mv)

The aromatic polycarbonate resin composition was dissolved in dichloromethane, and the intrinsic viscosity [η] in dichloromethane at 20°C was measured using an Ubbelohde viscometer, and the viscosity average molecular weight was obtained from the following mathematical formula (1) (Mv).

It should be noted that, in this example, since the components other than the aromatic polycarbonate resin in the aromatic polycarbonate resin composition are trace amounts, the aromatic polycarbonate in the aromatic polycarbonate resin composition The viscosity average molecular weight (Mv) of the resin is considered to be the same as the viscosity average molecular weight (Mv) of the aromatic polycarbonate resin composition.

[η]=1.23×10 ^-4 (Mv) ^0.83 Mathematical formula (1)

(2) Initial tone

After drying the aromatic polycarbonate resin composition at 120°C for 6 hours in a nitrogen atmosphere, molding was repeated using a J75EII injection molding machine manufactured by Nippon Steel Works Co., Ltd. at a resin temperature of 360°C and a molding cycle of 30 seconds. The operation of producing 60mm×60mm×3mm thick injection molding sheet.

Then use a chromaticity analyzer (CM-3700d manufactured by Konica Minolta Co., Ltd.) to measure the yellowness index (YI) value of the injection molded product obtained from the 6th to 15th injection, and calculate the average value and standard value. deviation. The smaller the YI value, the better the color tone and the better the quality; the smaller the standard deviation, the less uneven the color and the more stable the quality.

(3) Color tone after heat retention test

In the above (2), the molding cycle was changed to 10 minutes from the 16th injection, and the injection molding operation was repeated to obtain injection molded products up to the 22nd injection.

The YI value of the 60 mm x 60 mm x 3 mm thick injection molded product obtained from the 20th to 22nd injection was measured with a colorimeter (CM-3700d manufactured by Konica Minolta Co., Ltd.), and the average value was calculated. . The smaller the value, the better the tone and the better the quality.

(Example 1)

As the production apparatus of the aromatic polycarbonate resin composition, the apparatus shown in FIG. 2 was used.

In Fig. 2, under a nitrogen atmosphere, DPC and BPA are continuously supplied to the first raw material preparation tank 2a whose internal temperature is adjusted to 140° C. at a constant molar ratio (DPC/BPA=1.050) to form a uniform molten state, Among them, DPC is supplied from the DPC supply port 1a-1, and BPA is supplied from the BPA supply port 1b.

Then, through the second raw material preparation tank 2b adjusted to 140°C in the same manner, it is continuously supplied to the first vertical reactor 6a under the condition that the supply amount per unit time becomes constant using the raw material supply pump 4a. Next, an aqueous cesium carbonate solution as a catalyst was continuously supplied from the catalyst supply port 5 a in an amount of 0.5×10 ⁻⁶ moles relative to 1 mole of BPA.

The internal temperature of the first vertical reactor 6a was adjusted to 220° C., the pressure was adjusted to 13.3 kPa, and the opening of the valve (not shown) in the discharge line at the bottom of the tank was adjusted so that the average residence time was 1.5 hours, and Keep the liquid level constant.

The polymerization solution discharged from the first vertical reactor 6a is then continuously supplied to the second vertical reactor 6b, the third vertical reactor 6c, and the fourth horizontal reactor 9a in this order. The inner temperature of the second vertical reactor 6 b was 260° C., the pressure was 4 kPa, and the average residence time was 1.5 hours. The internal temperature of the third vertical reactor 6c was 270°C, the pressure was 70Pa, and the average residence time was 1 hour; the internal temperature of the fourth horizontal reactor 9a was 270°C, the pressure was 200Pa, and the average residence time was 1.5 hours.

This aromatic polycarbonate was supplied to the twin-screw extruder 11a in a molten state at a rate of 97 parts by weight per unit time. At this time, heat stabilizer-containing aromatic polycarbonate pellets (average length 3 mm, average diameter 3 mm, Mv=15,000) manufactured by the same method as described below were previously stored in the product silo 16c, and each 1.5 parts by weight per unit time was supplied to the mixer 21a. In addition, the mixer 21a used the continuous type ribbon mixer, and nitrogen gas flowed. In addition, the stirring time in the stirrer 21a was 8 minutes.

Then, 0.0005 parts by weight of butyl p-toluenesulfonate as a heat stabilizer was supplied from the heat stabilizer supply port 22a by a small quantitative pump (not shown) per unit time, and added continuously to the aromatic polycarbonate pellets. It is then continuously fed into the extruder 11a from the additive supply line 12a.

Further, the aromatic polycarbonate pellets were supplied from the product silo 16c to the mixer 21b at 1.5 parts by weight per unit time (a continuous ribbon mixer was used in the same way as the mixer 21a) in the same manner as above, and nitrogen gas was passed through. In addition, the stirring time in the stirrer 21b was 8 minutes.

Here, the following substances are continuously supplied to the mixer 21b from the supply port 22b at the following speed: 0.005 parts by weight per unit time of tris(2,4-di-tert-butylphenyl)phosphate as a heat stabilizer, Stearic acid monoglyceride was supplied as a release agent at 0.03 parts by weight per unit time. Then, these are continuously added to the aromatic polycarbonate pellets, and then continuously supplied to the extruder 11a from the additive supply line 12b.

The polycarbonate resin composition discharged in the form of strands from the twin-screw extruder 11a in a molten state is cooled and solidified in the cooling tank 13a, and after being pelletized with the strand pelletizer 14a, the size of the polycarbonate resin composition is removed with a sieving machine 15a. The granules of the specifications are properly stored in the product silos 16a-16c.

The obtained polycarbonate resin composition had a viscosity average molecular weight (Mv) of 15,000, an initial YI=1.28, a standard deviation of 0.015, and a YI after the dwell thermal stability test of 3.21.

(Example 2)

An aromatic polycarbonate resin composition was produced in the same manner as in Example 1 except that the viscosity average molecular weight (Mv) of the aromatic polycarbonate pellets stored in the product silo 16c was 14,500.

The obtained aromatic polycarbonate resin composition had a viscosity average molecular weight (Mv) of 15,000, an initial color tone YI=1.25, a standard deviation of 0.013, and YI=3.20 after the dwell heat stability test.

(Example 3)

An aromatic polycarbonate resin composition was produced in the same manner as in Example 1 except that the viscosity average molecular weight (Mv) of the aromatic polycarbonate pellets stored in the product silo 16c was 27,000.

The obtained aromatic polycarbonate resin composition had a viscosity average molecular weight (Mv) of 15,400, an initial color tone YI=1.37, a standard deviation of 0.031, and YI=3.43 after the dwell heat stability test.

(Example 4)

An aromatic polycarbonate resin composition was produced in the same manner as in Example 1, except that the aromatic polycarbonate pellets supplied to the mixers 21a and 21b were each supplied at 3 parts by weight per unit time. The stirring time was 4 minutes respectively.

The obtained aromatic polycarbonate resin composition had a viscosity average molecular weight (Mv) of 15,000, an initial color tone YI=1.40, a standard deviation of 0.012, and YI=3.65 after the dwell heat stability test.

(comparative example 1)

An aromatic polycarbonate resin composition was produced in the same manner as in Example 1, except that aromatic polycarbonate pellets not containing a thermal stabilizer were stored and supplied in the product silo 16c.

The viscosity-average molecular weight (Mv) of the obtained aromatic polycarbonate resin composition was 15,000, the initial color tone YI=1.55, the standard deviation was 0.017, and the YI=3.90 after the dwell heat stability test, the results were inferior to those of the above-mentioned examples. .

(comparative example 2)

An aromatic polycarbonate resin composition was produced in the same manner as in Comparative Example 1 except that nitrogen gas was not passed through the stirrers 21a and 21b.

The viscosity-average molecular weight (Mv) of the obtained aromatic polycarbonate resin composition was 15,000, the initial color tone YI=1.59, the standard deviation was 0.024, and the YI=4.05 after the dwell heat stability test, the results were inferior to those of the above-mentioned examples. .

(comparative example 3)

6 parts by weight of the aromatic polycarbonate pellets stored in the product silo 16c were put into the Henschel mixer, and after adding 0.002 parts by weight of butyl p-toluenesulfonate, they were thoroughly mixed for 10 minutes. The granules thus prepared in a batch manner were fed into the mixer 21a at 1.5 parts by weight per unit time. In addition, it carried out similarly to Example 1 except not having supplied butyl p-toluenesulfonate to the agitator 21a from the thermal stabilizer supply port 22a using the continuous type ribbon mixer similar to Example 1.

The obtained polycarbonate resin composition had a viscosity average molecular weight (Mv) of 15,000, an initial color tone YI=1.49, a standard deviation of 0.157, and YI=3.77 after the residence heat stability test.

(comparative example 4)

In Comparative Example 3, 6 parts by weight of aromatic polycarbonate particles and 0.02 parts by weight of tris(2,4-di-tert-butylphenyl)phosphate stored in the product silo 16c were mixed in advance with a Henschel mixer. 0.12 parts by weight of monoglyceride stearate was thoroughly mixed for 10 minutes to prepare in batches, and the granules were continuously supplied to the mixer 21b at 1.5 parts by weight per unit time. It should be noted that tris(2,4-di-tert-butylphenyl)phosphate and monoglyceryl stearate were not supplied from the supply port 22b to the mixer 21b using the same continuous ribbon mixer as in Example 1. , implemented in the same manner as in Comparative Example 3. The obtained polycarbonate resin composition had a viscosity average molecular weight (Mv) of 15,000, an initial color tone YI=1.53, a standard deviation of 0.170, and YI=3.84 after the dwell heat stability test.

Industrial Applicability

The present invention can produce an aromatic polycarbonate resin composition having improved raw material utilization rate of products, contributing to resource saving, and stable quality such as thermal stability, so the present invention is industrially useful.

It should be noted that this application refers to the Japanese patent application No. 2007-120090 submitted on April 27, 2007, including the specification, claims, drawings and the entire contents of the abstract, which are incorporated into the present invention in the form of reference. manual.

Claims (10)

1. a kind of manufacture method that contains the aromatic polycarbonate resin composition of thermostabilizer, it is characterized in that, this manufacture method comprises following operation: The polycarbonate supply process continuously supplies the molten aromatic polycarbonate to the extruder; In the extruding process, the aromatic polycarbonate supplied in the polycarbonate supplying process and the heat stabilizer are mixed using the above-mentioned extruder, and extruded from the extruder; a granulation process of granulating the aromatic polycarbonate extruded from the extruder in the above extrusion process to form granules of the aromatic polycarbonate; and In the pellet circulation supply process, the particles of the partially aromatic polycarbonate granulated in the above-mentioned granulation process are separated, the thermal stabilizer is continuously added to the pellets, and the pellets to which the thermal stabilizer is added are continuously supplied. To an extruder that is supplied with an aromatic polycarbonate in the polycarbonate supply process described above. 2. The manufacture method of aromatic polycarbonate resin composition as claimed in claim 1, it is characterized in that, the method also comprises pneumatic conveying process, and in this pneumatic conveying process, through conveying piping pair in described granulation process The granulated aromatic polycarbonate particles are conveyed pneumatically, The pellets of the partially aromatic polycarbonate obtained in the granulation step were pneumatically conveyed through a branch pipe branched from the conveyance pipe. 3. The method for producing an aromatic polycarbonate resin composition according to claim 1 or 2, wherein the heat stabilizer added to the particles of the aromatic polycarbonate in the particle circulation supply step is in a liquid state. 4. The method for producing an aromatic polycarbonate resin composition according to claim 1 or 2, wherein the thermal stabilizer added to the particles of the aromatic polycarbonate in the particle circulation supply process is an acidic compound . 5. the manufacture method of aromatic polycarbonate resin composition as claimed in claim 1 or 2 is characterized in that, described thermal stabilizer is liquid sulfonic acid or its ester, and this sulfonic acid or its ester have carbon atom The number of 1-10 alkyl substituents may not have a substituent. 6. The method for producing an aromatic polycarbonate resin composition according to claim 1 or 2, wherein, in the particle circulation supply process, 0.001 The heat stabilizer is continuously added to the particles of the aromatic polycarbonate in parts by weight to 1 part by weight. 7. The method for producing an aromatic polycarbonate resin composition according to claim 1 or 2, wherein, in the pellet circulation supply process, with respect to 100 parts by weight of the aromatic polycarbonate supplied to the extruder For polycarbonate, 0.5 to 5 parts by weight of aromatic polycarbonate pellets to which the heat stabilizer is added is supplied to the extruder. 8. The manufacture method of the aromatic polycarbonate resin composition as claimed in claim 1 or 2, is characterized in that, in described granulation process, the viscosity-average molecular weight _Mv of the aromatic polycarbonate after granulation is not greater than the viscosity average molecular weight Mv ₂ of the aromatic polycarbonate in the molten state mixed with the thermal stabilizer in the extruder in the extrusion process, that is, Mv ₁ ≤ Mv ₂ . 9. The method for producing an aromatic polycarbonate resin composition according to claim 1 or 2, wherein, in the extrusion step, the amount of the aromatic polycarbonate is 0.002 parts by weight or less The amount of mixed heat stabilizer. 10. The method for producing an aromatic polycarbonate resin composition according to claim 1 or 2, wherein in the polycarbonate supply step, the aromatic polycarbonate supplied to the extruder It is obtained by polycondensation reaction of aromatic dihydroxy compound and carbonic acid diester with basic compound as catalyst.

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