JPH08231843A - Production of polycarbonate composition - Google Patents

Abstract

PURPOSE: To obtain a high-quality polycarbonate composition excellent in hue and molding stability at a high polymerization rate stably for a long time with an easily maintainable apparatus excellent in sealability in a high vacuum. CONSTITUTION: The polycarbonate composition is prepared by a process comprising the polymerization step at least partially consisting of the step of polymerizing a product obtained by melt-kneading an aromatic dihydroxy compound and a diaryl carbonate or a polymer intermediate obtained by reacting an aromatic dihydroxy compound with a dialyl carbonate while allowing the product or polymer intermediate in a melt state to freely fall from a perforated plate and the step of kneading the falling product in a melt state together with a thermoplastic resin and a heat stabilizer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polycarbonate composition. In detail, it has excellent production efficiency and little heat deterioration of polycarbonate during production.
The present invention relates to a method for producing a polycarbonate composition having an excellent hue and excellent stability during molding.

[0002]

2. Description of the Related Art Polycarbonate is known as an engineering plastic excellent in heat resistance, impact resistance and transparency, and is widely used in many fields. Above all, in recent years, polymer alloy products in which polycarbonate and other resins are mixed have been increasing, and are widely used in the fields of home appliances and automobiles.

Conventionally, polymer alloy products comprising polycarbonate and other resins have been produced by kneading polycarbonate produced by the interfacial polycondensation method using phosgene and other resins with an extruder.

However, in this production method, since the polycarbonate production method is an interfacial polycondensation method, toxic phosgene must be used, hydrogen chloride and sodium chloride produced as by-products, and methylene chloride used in large quantities as a solvent. In addition to manufacturing problems such as corrosion of the equipment due to chlorine-containing compounds such as, the obtained polycarbonate has impurities such as sodium chloride and methylene chloride remaining, and there is also a problem in the physical properties of the product. Further, when kneading with other resin in an extruder, since polycarbonate pellets or powders are used, a high temperature is required for melting, so there is a problem that heat degradation of the polycarbonate or coloring of the alloy product occurs. Further, since the stability during molding is poor, there is a problem that the Izod impact strength is reduced or fluctuated, and the appearance of the molded product is deteriorated.

In order to solve the problems caused by these polycarbonate production methods, a method for producing polycarbonate by a melt polymerization method has been proposed. The melt polycondensation method is a method of transesterifying an aromatic dihydroxy compound and a diaryl carbonate, for example, bisphenol A and diphenyl carbonate in a molten state, and polymerizing while extracting phenol by-produced. Unlike the interfacial polycondensation method, a solvent is used. While it has the advantage of not using it, the viscosity of the polymer increases with the progress of polymerization, making it difficult to efficiently extract by-products such as phenol from the system, making it difficult to raise the degree of polymerization. There was a problem. Therefore, in recent years, various measures have been taken to extract phenol and the like from a polymer having a high viscosity. For example, Japanese Patent Publication 50-1
No. 9600 discloses a screw type polymerization device having a vent portion, and Japanese Patent Publication No. 53-5718 discloses a thin film evaporation type reactor such as a screw evaporator or a centrifugal thin film evaporator. Japanese Patent Laid-Open No. 2-153923 discloses a method in which a thin film type evaporator and a horizontal stirring polymerization tank are used in combination.

However, a drawback that these polymerization vessels, including the conventional stirring tank type, have in common is that the polymerization vessel main body has a rotation driving portion, and when the polymerization is carried out under a high vacuum, this driving is performed. Since it is not possible to completely seal the part, it was impossible to prevent the leakage of a small amount of oxygen, and coloring of the product was unavoidable. When using a seal liquid to prevent oxygen from leaking, mixing of the seal liquid is unavoidable,
After all, deterioration of product quality was unavoidable. Further, even when the sealing property at the beginning of operation is high, the sealing property is deteriorated during continuous operation for a long time, which causes serious problems in maintenance.

Further, also in the production of alloys of polycarbonate and other resins, while the polycarbonate is in a molten state, the polycarbonate obtained by the melt polymerization method in which the thin film type evaporator and the horizontal stirring polymerization tank are combined is used. There has been proposed a method in which a resin other than polycarbonate is added (Japanese Patent Laid-Open No. 5-239331). In this method, since the polycarbonate is already in a molten state, it occurs because the above-mentioned polycarbonate is melted at a high temperature, although the problems of thermal deterioration of the polycarbonate and coloring of alloy products can be reduced, but the drawbacks of the aforementioned polymerization vessel itself are Nothing was solved, and deterioration of quality such as stability of operation, hue of the product, and stability at the time of molding was unavoidable.

By the way, the main body does not have a rotary drive portion,
A method of polymerizing while dropping from a porous plate is known as a method for producing a resin other than polycarbonate. For example, U.S. Pat. No. 3,110,547 discloses a method in which a polyester is dropped into a thread in a vacuum to produce a polyester having a desired molecular weight. In the specification, since the quality of polyester is deteriorated when the dropped yarn is circulated again, the polymerization is completed in one pass without being circulated.

However, regarding such a method,
Many drawbacks have been pointed out. For example, Japanese Patent Publication 48-83
Japanese Patent No. 55 discloses the following regarding a method of polycondensing while spinning from a spinneret in a vacuum. If a fiber having a sufficiently high fiber-forming ability is not supplied, the yarn during polymerization is easily cut in the reactor, and the quality variation of the polycondensate becomes severe. The low-molecular-weight condensate scattered from the yarn contaminates the spinneret surface, making it difficult for the yarn to eject directly from the spinneret. . The monitoring window tends to become cloudy and difficult to monitor, so that it is easy to lose the time to replace the mouthpiece. In this publication, as a method for producing polyester and polyamide, it is described that a method of polymerizing while flowing a polymer along a porous object vertically arranged in a reaction vessel is preferable, but polycarbonate is completely described. Not not.

As a method of removing the monomer remaining in the polymerization product, which is not a polymerization method, a method of dropping a lactam heavy synthetic organism into a thread form from a perforated plate is described in US Pat.
719776. However, many drawbacks have been pointed out in this method as well. For example, in Japanese Patent Laid-Open No. 53-17569, US Pat.
The following inconveniences have been pointed out for the method of 719776. If the evaporation of the volatiles is small, the filamentous material can be formed, but if the evaporation is large, the filamentous material is foamed, and smooth operation is difficult. It can only be applied to materials with a relatively narrow range of specific viscosities to form filaments. When an inert gas or the like is introduced into the tower, neighboring filaments come into contact with each other due to the turbulence of the air flow. In addition, in JP-A-53-17569, in order to solve these disadvantages, a method in which a linear support is provided in the longitudinal direction and a highly viscous substance is flown down along the support is described as polyethylene terephthalate or polybutylene. It has been proposed for polyesters such as terephthalate and polyamides such as nylon 6 and nylon 66, but aromatic polycarbonate is not described.

Further, in Japanese Patent Publication No. 14127/1992, there are two methods of continuous polycondensation of polyester, that is, two methods of performing polycondensation while dropping, that is, a method of spinning from a spinneret and a method of polymerizing while extruding a film from a slit. It is described that it is difficult for any of these methods to proceed with polycondensation. Further, the publication proposes a method in which a thin film is held between at least two wires from a slit-shaped supply port, and the polycondensation is continuously carried out by moving the film in one direction in the longitudinal direction. In this publication, of course, nothing is mentioned about aromatic polycarbonate.

As described above, the method of polymerizing while dropping from the perforated plate is known as a method for producing polyester or polyamide, but is not known at all as a method for producing aromatic polycarbonate. As a method for producing polyester or polyamide, the method of polymerizing while dropping it has been pointed out to have many drawbacks such as pore clogging.

[0013]

DISCLOSURE OF THE INVENTION The present invention is a device for producing a polycarbonate composition, which is excellent in sealing property under high vacuum and is easy to maintain, stable for a long time, stable in hue and molding. An object of the present invention is to provide a method for producing a high-quality polycarbonate composition having excellent properties.

[0014]

Means for Solving the Problems The present inventors have found that the object can be achieved by carrying out polymerization using a specific production method, and completed the present invention.

That is, according to the present invention, (1) a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate is freed from a perforated plate in a molten state. After the polymerization step including all or a part of the step of polymerizing while dropping it, the (A) thermoplastic resin and (B) heat stabilizer are added and kneaded while in a molten state. (2) The blending amount of the thermoplastic resin (A) with respect to the polycarbonate is in the range of 1:99 to 99: 1, and the addition amount of the heat stabilizer (B) is 0 with respect to 100 parts by weight of the polycarbonate. In the range of 0.0005 to 0.5 part by weight, the method for producing a polycarbonate composition according to (1) above, (3) (A The method for producing a polycarbonate composition according to (1) or (2) above, wherein the thermoplastic resin is an ABS resin, (4) The polycarbonate according to (3) above, wherein the ABS resin is an ABS resin having an ash content of 0.1% by weight or less. Method for producing composition, (5) ABS resin and (B) heat stabilizer together with (C)
A method for producing a polycarbonate composition according to any one of (1) to (4), characterized in that a phosphorus-based flame retardant is added and kneaded. (6) (C) The amount of the phosphorus-based flame retardant added is polycarbonate and (A). The method for producing a polycarbonate composition according to the above (5), characterized in that it is in the range of 1 to 25 parts by weight with respect to the total amount of 100 parts by weight with the thermoplastic resin, (7) (B) heat stabilizer. Is phosphite diester and /
Alternatively, the method for producing the polycarbonate composition according to any one of (1) to (6) above, which is a phosphorous acid monoester, (8) (B) the heat stabilizer is selected from (a) a phosphorous acid diester and a phosphorous acid monoester. And (b) a phenolic stabilizer, one or more compounds selected from a phosphite triester, and a phosphinic acid diester. It provides a method.

As described above, various types of polymerizers having no main body having a rotational driving portion are known as polymerizers for polymerizing resins other than polycarbonate.
Since the melt polycondensation reaction of polycarbonate is significantly different from the melt polycondensation reaction of polyester or polyamide, it is difficult to apply a high-viscosity polymerizer for the production of polyamide or polyester to the method for manufacturing polycarbonate. The major differences between polyamide, polyester and polycarbonate are as follows. First, the melt viscosity, which is an important factor in the melt polycondensation polymerization reactor design, is extremely high in the case of polycarbonate. That is, the melt viscosity of polyamide or polyester in the latter stage of polymerization is usually several hundred to several thousand poise under the conditions of the polymerization temperature and rarely exceeds 3000 poise, whereas the melt viscosity of polycarbonate in the latter stage of polymerization is tens of thousands of poise. Reach up to. Secondly, melt polycondensation of polyamide, polyester, and polycarbonate are all equilibrium reactions, but the equilibrium constants differ greatly. Normally, the equilibrium constant of polyamide is 10 ² order and the equilibrium constant of polyester is about 1, whereas the equilibrium constant of polycarbonate is 10 to ¹ order. Extremely small. The fact that the equilibrium constant is small means that the polymerization does not proceed unless the by-product is removed more efficiently from the outside of the system. Therefore, the reaction of the polycarbonate needs to extract the by-product out of the system much more efficiently than the reaction of the polyester or the polyamide, and this is extremely difficult for the polycarbonate having a high melt viscosity.

However, according to the present invention, it has been surprisingly revealed that polycarbonate can be polymerized without causing any problems in the conventional method of polymerizing while dropping polyester or polyamide while spinning. That is, since there is no variation in quality due to the cutting of the yarn, a high quality polycarbonate can be stably manufactured. Furthermore, since the spinneret is not contaminated by the low molecular weight condensate at all, it does not hinder the yarn from being ejected directly below, and does not stop the operation for exchanging the spinneret. Therefore, it is possible to operate stably for a very long period of time.

Phenomena in the reaction of polycarbonate,
The reason for these apparent differences from the reaction in polyesters and polyamides is not clear. However, regarding the fact that the contamination of the die does not occur at all, it is possible that the low molecular weight condensate is effectively washed by the by-produced phenols in the reaction of polycarbonate, and water, polyamide or by-product such as ethylene glycol is produced. It is speculated that the reaction may be fundamentally different from the reaction of polyester, but such an effect could not be predicted at all from the polymerization reaction of polyester or polyamide.

Further, the method of polymerizing while freely falling from the perforated plate of the present invention does not need to have a rotation driving part in the gas phase part of the polymerization vessel and is excellent in sealing property under high vacuum, It has become clear that high-quality polycarbonate that is easy to maintain and is colorless and transparent can be produced. That is, by using the manufacturing method of the present invention,
Conventionally occurred when performing melt polycondensation of polycarbonate,
All of the problems mentioned above can be solved.

In the present invention, a method for producing a polycarbonate by using a single polymerization vessel that is allowed to polymerize while freely falling from a porous plate, and a polycarbonate is produced by using a plurality of polymerization vessels that are allowed to polymerize while freely falling from a porous plate. For example, a method of producing a polycarbonate by combining a polymerization vessel in which polymerization is performed while freely falling from a porous plate and another polymerization vessel is possible.

Preferred embodiments of the method of polymerizing while freely falling from the perforated plate and the method of combining with other methods are a method of using a stirred tank type polymerization device in the pre-polymerization step and a free fall from the perforated plate in the post-polymerization step. There is a method of combining a polymerization vessel in which the polymerization is performed while the polymerization is performed. By this method, high quality polycarbonate can be efficiently produced. Since it is not necessary to carry out the prepolymerization step in a high vacuum, it is possible to perform polymerization in a high volume efficiency without impairing the quality even in a stirred tank type polymerizer. In the post-polymerization step in which the degree of polymerization is further increased, a method of performing free-fall polymerization is particularly advantageous. By combining these polymerization methods,
High quality polycarbonate can be efficiently produced.

Further, a polymerization method using a stirred tank type polymerization device in the pre-polymerization step, a polymerization method in which the intermediate wall polymerization step is performed by dropping it in a wall type, and a post-polymerization step step in which the porous plate is freely dropped to perform polymerization A method of combining the methods is also a preferred embodiment of the present invention. It is not necessary to carry out the pre-polymerization step in the first half of the polymerization in a high vacuum in general, and as described above, the polymerization can be performed with high volume efficiency without impairing the quality even in a stirred tank type polymerization device. In the intermediate polymerization process where the degree of polymerization of the polymer is not so high, the method of polymerizing while dropping it in a painted wall type can efficiently give latent heat of vaporization of aromatic monohydroxy compounds, etc., because a large heat transfer area can be taken. , Is advantageous. In the post-polymerization step for further increasing the degree of polymerization, it is particularly advantageous to carry out the polymerization while freely falling from the porous plate. By combining these polymerization methods, high quality polycarbonate can be efficiently produced. In the present invention, since the polymerization method and the polycarbonate after the polymerization are kneaded by adding a thermoplastic resin or the like while the polycarbonate is in a molten state, there is little deterioration of the polycarbonate, and a high-quality polycarbonate composition having particularly excellent hue Can be manufactured. Furthermore, by combining a specific heat-resistant stabilizer and a specific ABS resin, a polycarbonate composition having significantly improved stability in molding in addition to the above properties can be produced.

The present invention will be described in detail below.

In the present invention, the aromatic dihydroxy compound is a compound represented by HO-Ar-OH (wherein Ar represents a divalent aromatic group).

The aromatic group Ar is preferably, for example, -A.
r ¹ -Y-Ar ^2- (In the formula, Ar ¹ and Ar ² each independently represent a divalent carbocyclic or heterocyclic aromatic group having 5 to 70 carbon atoms, and Y is the number of carbon atoms. It represents a divalent alkane group having 1 to 30).

In the divalent aromatic groups Ar ¹ and Ar ² , 1
One or more hydrogen atoms are other substituents that do not adversely affect the reaction, for example, 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, It may be substituted with a cyano group, an ester group, an amide group, a nitro group or the like.

Preferred specific examples of the heterocyclic aromatic group include aromatic groups having one or more ring-forming nitrogen atoms, oxygen atoms or sulfur atoms.

The divalent aromatic groups Ar ¹ and Ar ² are, for example,
It represents a group such as a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted pyridylene. The substituents here are as described above.

The divalent alkane group Y is, for example, an organic group represented by the following chemical formula 1.

[0030]

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(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms.
Of the above, a cycloalkyl group having 5 to 10 ring carbon atoms, a carbocyclic aromatic group having 5 to 10 ring carbon atoms, and a carbocyclic aralkyl group having 6 to 10 carbon atoms. k is 3 to 1
Represents an integer of 1, R ⁵ and R ⁶ are individually selected for each X and, independently of each other, represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and X represents carbon. In addition, R ¹ , R ² ,
In R ³ , R ⁴ , R ⁵ , and R ⁶ , other substituents such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms are used as long as one or more hydrogen atoms do not adversely affect the reaction. 1
It may be substituted with an alkoxy group of 0, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group or the like. ) Examples of such a divalent aromatic group Ar include those represented by the following chemical formula 2.

[0032]

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(In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms in the ring. An alkyl group or a phenyl group, m and n
Is an integer of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and n is 2 to 4
In the case of, each R ⁸ may be the same or different. ) Furthermore, a divalent aromatic group Ar is, -Ar ¹ -Z-Ar ² -
(In the formula, Ar ¹ and Ar ² are as described above, Z is a single bond or —O—, —CO—, —S—, —SO ₂ —, —SO—,
It represents a divalent group such as —COO— and —CON (R ¹ ) —. However, R ¹ is as described above. ) May be shown.

As such a divalent aromatic group Ar,
For example, a compound represented by the following chemical formula 3 may be mentioned.

[0035]

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(In the formula, R ⁷ , R ⁸ , m and n are as described above.) Further, specific examples of the divalent aromatic group Ar include substituted or unsubstituted phenylene, substituted or unsubstituted phenylene. Examples thereof include substituted naphthylene and substituted or unsubstituted pyridylene.

The aromatic dihydroxy compound used in the present invention may be a single kind or two or more kinds. A typical example of the aromatic dihydroxy compound is bisphenol A.

The diaryl carbonate used in the present invention is represented by the following chemical formula 4.

[0039]

[Chemical 4]

(In the formula, Ar ³ and Ar ⁴ each represent a monovalent aromatic group.) Ar ³ and Ar ⁴ represent a monovalent carbocyclic or heterocyclic aromatic group. ³ , in Ar ⁴ , another substituent in which one or more hydrogen atoms do not adversely affect the reaction, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group It may be substituted with a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group or the like. Ar
³ and Ar ⁴ may be the same or different.

Typical examples of the monovalent aromatic groups Ar ³ and Ar ⁴ include phenyl group, naphthyl group, biphenyl group and pyridyl group. These may be substituted with one or more types of the above-mentioned substituents.

Preferred Ar ³ and Ar ⁴ are, for example, the following chemical formula 5 and the like.

[0043]

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Representative examples of the diaryl carbonate include substituted or unsubstituted diphenyl carbonates represented by the following chemical formula 6.

[0045]

[Chemical 6]

(In the formula, R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
An alkoxy group having 10 or a cycloalkyl group having 5 to 10 ring carbon atoms or a phenyl group, and p and q are 1 to
When R is an integer of 5 and p is 2 or more, each R ⁹ may be different, and when q is 2 or more,
Each R ¹⁰ may be different. ) Among these diphenyl carbonates, unsubstituted diphenyl carbonate, ditolyl carbonate, di-t
Symmetrical diaryl carbonates such as lower alkyl-substituted diphenyl carbonates such as -butyl phenyl carbonate are preferred, but diphenyl carbonate, which is the simplest diaryl carbonate, is particularly preferred.

These diaryl carbonates may be used alone or in combination of two or more.

The use ratio (charge ratio) of the aromatic dihydroxy compound and the diaryl carbonate differs depending on the kind of the aromatic dihydroxy compound and the diaryl carbonate used, the polymerization temperature and other polymerization conditions. The diaryl carbonate is the aromatic dihydroxy compound. It is usually 0.9 to 2.5 mol, and preferably 0.1 to 1 mol.
It is used in a proportion of 95 to 2.0 mol, more preferably 0.98 to 1.5 mol.

The polycarbonate obtained by the method of the present invention has a number average molecular weight of usually 500 to 100,000, preferably 500 to 30,000.

In the present invention, the molten mixture of the aromatic dihydroxy compound and the diaryl carbonate means a state in which the aromatic dihydroxy compound and the diaryl carbonate are heated and mixed to be uniform. The molten mixture can be obtained by heating a mixture of an aromatic dihydroxy compound and a diaryl carbonate at 150 to 200 ° C. Further, the polymerization intermediate means a polycondensate having a lower molecular weight than the polycarbonate produced in the present invention, which is obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate. That is, the molecular weight range of the polymerization intermediate defined in the present invention varies depending on the molecular weight of the finally produced polycarbonate. For example, when the number average molecular weight of the polycarbonate to be produced is 10,000, the molecular weight range of the polymerization intermediate is less than 10,000,
The number average molecular weight of the polycarbonate produced is 20,000.
At that time, the molecular weight range of the polymerization intermediate is less than 20,000.

In the present invention, a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate is polymerized in a molten state while freely falling from a porous plate, Produces polycarbonate.

In the present invention, "freely drop" means
It refers to the state of dropping without contacting a drop resistance object such as a guide or a wall. The shape of the melt when it is allowed to fall freely is a film shape, a thread shape, a droplet shape, a mist shape, or the like. While freely falling, phenol and the like generated by the polycondensation reaction are extracted.

The shape of the holes in the perforated plate of the present invention is not particularly limited, and is usually selected from a circular shape, an oval shape, a triangular shape, a slit shape, a polygonal shape, a star shape and the like. Cross-sectional area of the hole is usually 0.01～100Cm ^2, preferably 0.05～10Cm ^2, particularly preferably from 0.1 to 5 cm ^2. The distance between the holes is usually 1 to 500 mm, preferably 5 to 100 mm in terms of the distance between the centers of the holes.

The molten mixture or the polymerization intermediate can be freely dropped through the porous plate by dropping the liquid mixture or the self-weight, or by applying pressure using a pump or the like to melt the molten mixture from the porous plate. Examples include a method of extruding a mixture or a polymerization intermediate.

The number of pores is not particularly limited, and it varies depending on the conditions such as reaction temperature and pressure, the amount of catalyst, the range of molecular weight to be polymerized, etc., but usually 100 kg / h of polymer is used.
r 10 to 10 ⁵ holes are required for manufacturing.

After passing through the holes, the height of the free fall is preferably 0.3 to 50 m, more preferably 0.5 to 20 m.

The flow rate of the molten mixture or the polymerization intermediate which passes through the holes varies depending on the molecular weight of the molten mixture or the polymerization intermediate, but is usually 10 to ⁴ to 10 ⁴ liters / hr, preferably 10 to 10 per hole. ^{2-10 2} l / h
r, particularly preferably 0.1 to 50 liters / hr.

The time required for free fall is not particularly limited, but is usually in the range of 0.01 seconds to 10 hours.

In the present invention, the polymer after being dropped freely may be dropped as it is to the liquid reservoir, or may be forcibly taken into the liquid reservoir by a winder or the like. Further, the polymerized product after freely falling may be extracted as it is, but it is also a preferable method to circulate the polymerized product and polymerize it while freely falling again. In this case, the residence time can be lengthened according to the reaction time required for the polycondensation reaction in the liquid reservoir, the circulation line or the like after being dropped freely. In addition, since the novel liquid surface area that can be formed in a unit time can be made large by performing the circulation while freely dropping, it becomes easy to sufficiently proceed the polymerization to a desired molecular weight.

In a preferred embodiment of the present invention, a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate is continuously supplied and polymerized in a molten state while freely falling from a perforated plate, and the weight dropped is dropped. There is a method in which a part of the coalescence is circulated and polymerized while freely falling again to continuously withdraw the polycarbonate. At this time, it is one of the great advantages of the present invention that the porous plate can be stably operated for a long period of time without being contaminated with a low condensate.

In the present invention, when a polycarbonate is produced by reacting an aromatic dihydroxy compound with a diaryl carbonate, the reaction temperature is usually 50 to 3
It is selected in the temperature range of 50 ° C, preferably 100 to 290 ° C.

Aromatic monohydroxy compounds are produced as the reaction progresses, but the reaction rate can be increased by removing them from the reaction system. Therefore, nitrogen,
Introduce an inert gas that does not adversely affect the reaction, such as argon, helium, carbon dioxide or lower hydrocarbon gas,
A method of removing the produced aromatic monohydroxy compound by entraining these gases, a method of carrying out a reaction under reduced pressure, and the like are preferably used. The preferred reaction pressure is
Depending on the molecular weight of the molten mixture or the polymerization intermediate, 50 mm in the number average molecular weight range of 1000 or less.
The range of Hg to atmospheric pressure is preferable, and the number average molecular weight is 1000.
In the range of ˜2000, the range of 3 mmHg to 80 mmHg is preferable, and in the range of the number average molecular weight of 2,000 or more, 20 mmHg or less, particularly 10 mmHg or less is preferable.

A particularly preferable method is a method of carrying out the reaction under reduced pressure and while introducing the above-mentioned inert gas.
By this method, there is no inconvenience that neighboring yarns come into contact with each other due to turbulence of the air flow, and the degree of polymerization can be efficiently increased.

The melt polycondensation reaction can be carried out without adding a catalyst, but in order to increase the polymerization rate, it is carried out in the presence of a catalyst, if necessary. The polymerization catalyst is not particularly limited as long as it is used in this field, but hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide. Kinds; alkali metal salts, alkaline earth metal salts, quaternary ammonium salts of hydrides of boron or aluminum such as lithium aluminum hydride, sodium borohydride, tetramethylammonium borohydride;
Lithium hydrides, sodium hydrides, calcium hydrides and other alkali metal and alkaline earth metal hydrides; lithium methoxide, sodium ethoxide, calcium methoxide and other alkali metal and alkaline earth metal alkoxides; lithium Phenoxide, sodium phenoxide, magnesium phenoxide, LiO
-Ar-OLi, NaO-Ar-ONa (Ar is an aryl group) and other alkali metal and alkaline earth metal aryloxides; lithium acetate, calcium acetate, sodium benzoate and other alkali metal and alkaline earth metal organic acids Salts; zinc compounds such as zinc oxide, zinc acetate, zinc phenoxide; boron oxide, boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate, (R ¹ R ² R ³ R ⁴ ) NB (R ¹ R ² R ³ R ⁴ ) or (R ¹ R ² R ³ R
⁴ ) Boron compounds such as ammonium borate or phosphonium borate represented by PB (R ¹ R ² R ³ R ⁴ ) (R ¹ , R ² , R ³ and R ⁴ are as described above); oxidation Compounds of silicon such as silicon, sodium silicate, tetraalkyl silicon, tetraaryl silicon, diphenyl-ethyl-ethoxy silicon; germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide, germanium phenoxide; tin oxide, Compounds of tin such as dialkyltin oxide, dialkyltin carboxylate, tin acetate, ethyltin tributoxide and other alkoxy groups or aryloxy groups, tin compounds such as organotin compounds; lead oxide, lead acetate, lead carbonate, basic Carbonate, lead and organic lead alkoxides or aryloxides Lead compounds; onium compounds such as quaternary ammonium salts, quaternary phosphonium salts, and quaternary arsonium salts; antimony compounds such as antimony oxide and antimony acetate; manganese acetate, manganese carbonate, manganese borate, etc. Compounds of titanium; titanium compounds such as titanium oxide, titanium alkoxides or aryloxides; catalysts such as zirconium acetate, zirconium oxide, zirconium alkoxides or aryloxides, zirconium compounds such as zirconium acetylacetone.

When a catalyst is used, these catalysts may be used alone or in combination of two or more. The amount of these catalysts used is usually selected in the range of 10 to ⁸ to 1% by weight, preferably 10 to ⁷ to 10 to ¹ % by weight, based on the starting aromatic dihydroxy compound.

An example of a preferable polymerization vessel used in the present invention is
A description will be given based on the figure.

FIG. 1 and FIG. 2 are specific examples of a polymerization vessel for achieving the method of the present invention. In FIG. 1, a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate is supplied from a raw material supply port 1 and passes through a porous plate 3 to form a polymerization reactor. The molten mixture or the polymerization intermediate 4 is introduced into the inside of the film, the thread, the droplet, or the atomized state and freely falls. The inside of the polymerization vessel is controlled to a predetermined pressure, and an aromatic monohydroxy compound distilled from a molten mixture or a polymerization intermediate, an inert gas such as nitrogen introduced from the gas supply port 5 as necessary. Are discharged from the vent port 6. The polymer is discharged from the discharge port 9 by the discharge pump 8. Polymerizer body 10
Etc. are heated by a heater or a jacket and kept warm.

Further, in FIG. 2, a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate is supplied from a raw material supply port 1 to a circulation line 2. The molten mixture or polymerization intermediate 4 is introduced into the polymerization vessel through the porous plate 3 and falls freely in the form of film, thread, droplet, or mist. The inside of the polymerization vessel is controlled to a predetermined pressure, and an aromatic monohydroxy compound distilled from a molten mixture or a polymerization intermediate, an inert gas such as nitrogen introduced from the gas supply port 5 as necessary. Are discharged from the vent port 6. The melted mixture or polymerization intermediate, which has fallen freely in the form of film, thread, droplet, or mist and reached the bottom of the polymerization vessel, is supplied from the porous plate 3 to the inside of the polymerization vessel again through a circulation line 2 equipped with a circulation pump 7. To be done. The polymer having reached the predetermined molecular weight is discharged from the discharge port 9 by the discharge pump 8. The main body 10 of the polymerization vessel, the circulation line 2 and the like are heated and kept warm by a heater or a jacket.

When the polymerization vessel of FIG. 2 is used in a batch system, a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate is used as a raw material supply port 1. Polymerization is performed after all the components have been supplied from the above, and after reaching a predetermined degree of polymerization, the polymer is discharged from the discharge port 9. When used in a continuous manner, a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate is continuously fed from a raw material feed port 1 to form a polymerization vessel. The polymer having a predetermined molecular weight is continuously withdrawn from the outlet 9 while controlling so that the amount of the polymer melt therein is kept constant.

The polymerization vessel used in the method of the present invention may be equipped with a stirrer or the like at the bottom of the polymerization vessel, but it is not always necessary. Therefore, it is possible to eliminate the rotation drive part in the main body of the polymerization vessel, and it is possible to carry out the polymerization under a well-sealed condition even under a high vacuum. The sealing performance of the rotary drive unit of the circulation pump provided in the circulation line is better than that in the case where the main body of the polymerizer has the rotary drive unit because of the liquid head.

The method of the present invention can be carried out with one polymerization vessel, but may be carried out with two or more polymerization vessels. Also, 1
It is also possible to divide the polymerized group of the group into a vertical type or a horizontal type to form a multistage polymerization vessel.

In the present invention, the step of increasing the molecular weight from the molten mixture of the aromatic dihydroxy compound and the diaryl carbonate to the polycarbonate can be carried out by a method in which all of them are polymerized while freely falling from the perforated plate. It is also possible to carry out it in combination with the above polymerization method.

Further, in the present invention, after the completion of the polymerization, a thermoplastic resin, a heat-resistant stabilizer and the like are added and kneaded while in a molten state, but a widely known technique can be used and the method is not particularly limited. As a result, it is not necessary to remelt the cooled polycarbonate to add the thermoplastic resin, the heat-resistant stabilizer and the like, and it is possible to minimize the thermal deterioration due to heating. Specific addition methods include a method of adding in a line from the final polymerization device to the kneading machine, a method of adding with a hopper of the kneading machine, a method of adding from an injection port or an input port of the kneading machine, and the like. It can be added in any state of body, pellet, molten state, solution and the like. Examples of the kneading method include a method using an in-line mixer such as a polymer mixer, a single-screw or multi-screw extruder, a kneader or a kneading extruder.

The thermoplastic resin (A) used in the present invention is not particularly limited as long as it is a resin that can be mixed with polycarbonate. For example, specifically, aromatic vinyl resins such as polystyrene, poly-α-methylstyrene, styrene / maleic anhydride copolymer, styrene / acrylonitrile copolymer, styrene / methyl methacrylate copolymer, styrene / butadiene -Acrylonitrile copolymer (ABS resin), AES resin, rubber-containing graft copolymer such as AAS resin, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, etc. Polyolefin resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyester resin such as paraoxybenzoyl polyester, nylon 6, nylon 66, nylon 6
Polyamide resin such as 10, nylon 11 and nylon 12, acrylic resin such as polymethylmethacrylate, diene rubber such as polybutadiene and polyisoprene, polyphenylene sulfide, polyphenylene ether, polyoxymethylene, polysulfone, polyether sulfone, polyether ether Examples include polyether resins such as ketones and thermoplastic polyurethanes. Above all, A
BS resin, polyethylene terephthalate, polybutylene terephthalate, polypropylene, styrene-acrylonitrile copolymer and polybutadiene are preferable, and A is particularly preferable.
BS resin is preferred. Above all, ABS having an ash content of 0.1% by weight or less is preferable because it does not deteriorate the polycarbonate. When the ash content is 0.1% by weight or more, the molecular weight of the polycarbonate is lowered during production or molding, impact resistance is lowered, and silver is likely to be generated on the surface of the molded product.

In the present invention, the blending amount of the thermoplastic resin (A) with respect to the polycarbonate is preferably in the range of 1:99 to 99: 1 (A): polycarbonate, more preferably 10:90 to 90:10. The range of 10:90 to 50:50 is particularly preferable.

The heat-resistant stabilizer (B) used in the present invention is not particularly limited, and those usable for polycarbonate can be used. For example, phosphorus-based stabilizers, phenol-based stabilizers, sulfur-based stabilizers, epoxy-based stabilizers, hindered amine-based stabilizers and the like can be used.

Examples of the phosphorus-based stabilizer include phosphoric acid, phosphorous acid ester, phosphinic acid ester, phosphoric acid ester and phosphonic acid ester. Specifically, examples of the phosphoric acids include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphinic acids represented by the following chemical formulas 7 and phosphonic acids represented by the chemical formula 8. . Specific examples thereof include phenylphosphonic acid. These compounds may be used alone or in a mixture.

[0078]

[Chemical 7]

[0079]

Embedded image

(Wherein R ¹¹ is an alkyl group such as ethyl group, butyl group, octyl group, cyclohexyl group, 2-ethylhexyl group, decyl group, tridecyl group, lauryl group, pentaerythritol group, stearyl group, phenyl group, An aryl group such as a naphthyl group, or a tolyl group, a pt-butylphenyl group, a 2,4-di-t-butylphenyl group,
An alkylaryl group such as a 2,6-di-t-butylphenyl group, a paranonylphenyl group and a dinonylphenyl group is shown. ) Examples of the phosphite ester include phosphite triester,
Examples of the phosphite diester and phosphite monoester are represented by the following chemical formulas 9.

[0081]

[Chemical 9]

(Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ ,
R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , and R ²³ may be the same or different in the compound, and include hydrogen, ethyl group, butyl group,
Alkyl groups such as octyl group, cyclohexyl group, 2-ethylhexyl group, decyl group, tridecyl group, lauryl group, pentaerythritol group, stearyl group, aryl groups such as phenyl group, naphthyl group, or tolyl group, p-t
An alkylaryl group such as -butylphenyl group, 2,4-di-t-butylphenyl group, 2,6-di-t-butylphenyl group, paranonylphenyl group, dinonylphenyl group, R ¹⁷ and R ²⁴ represents alkylene, arylene, or arylalkylene. ) Specific examples thereof include tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2,4-di-t-butylphenyl) phosphite. Phenyl phosphite, tetraphenyl dipropylene glycol phosphite, tetra (tridecyl) 4,4′-isopropylidene diphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl 4-methylphenyl) pentaerythritol diphosphite, distearyl, pentaerythritol diphosphite, hydrogenation Bisfu Nord A · pentaerythritol diphosphite polymer, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite. Of these, those having a 2,4-di-t-butylphenyl group and a 2,6-di-t-butylphenyl group are particularly preferable because they improve the hydrolysis resistance of the polycarbonate, and specific examples include tris. (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl 4-methylphenyl) penta As erythritol diphosphite, preferred specific examples of the phosphite diester are aromatic phosphite diesters such as diphenyl hydrogen phosphite, bis (nonylphenyl) hydrogen phosphite, and bis (2,4-di- t-butylphenyl) hydrogen phosphite, dicresyl hydrogen phosphite, (bis (pt- Butylphenyl) hydrogen phosphite, bis (p-hexylphenyl) hydrogen phosphite and the like.

Preferred specific examples of the phosphorous acid monoester include phenyl dihydrogen phosphite, nonylphenyl dihydrogen phosphite and 2,4-di-t.
-Butylphenyl dihydrogen phosphite and the like. These compounds may be used alone or in a mixture.

Examples of the phosphinic acid esters include phosphinic acid diesters and phosphinic acid monoesters, which are represented by the following chemical formulas 10. Specific examples of such compounds include tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphinate.
Is mentioned. These compounds may be used alone or in a mixture.

[0085]

[Chemical 10]

(In the formula, R ²⁵ is an ethyl group, a butyl group, an octyl group, a cyclohexyl group, a 2-ethylhexyl group, a decyl group, a tridecyl group, a lauryl group, a pentaerythritol group, a stearyl group or the like, a phenyl group, An aryl group such as a naphthyl group, or a tolyl group, a pt-butylphenyl group, a 2,4-di-t-butylphenyl group,
An alkylaryl group such as a 2,6-di-t-butylphenyl group, a paranonylphenyl group and a dinonylphenyl group, wherein R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³¹ and R ³² are the same in the compound. The same or different, hydrogen, ethyl group,
Alkyl groups such as butyl group, octyl group, cyclohexyl group, 2-ethylhexyl group, decyl group, tridecyl group, lauryl group, pentaerythritol group and stearyl group,
Aryl group such as phenyl group and naphthyl group, or tolyl group, pt-butylphenyl group, 2,4-di-t-butylphenyl group, 2,6-di-t-butylphenyl group, paranonylphenyl group , An alkylaryl group such as a dinonylphenyl group, and R ³⁰ represents alkylene, arylene, or arylalkylene. ) Examples of phosphoric acid esters include phosphoric acid diesters and phosphoric acid monoesters, which are represented by the following chemical formulas 11.

[0087]

[Chemical 11]

(Wherein R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ ,
R ¹⁹ , R ²¹ , R ²³ and R ²⁴ are the same as above. ) As specific examples of these, as specific examples of phosphoric acid diesters, for example, diphenyl hydrogen phosphate,
Bis (nonylphenyl) hydrogen phosphate, bis (2,4-di-t-butylphenyl) hydrogen phosphate, dicresyl hydrogen phosphate,
(Bis (p-t-butylphenyl) hydrogen phosphate, bis (p-hexylphenyl) hydrogen phosphate, etc. may be mentioned.

Specific examples of the phosphoric acid monoester include phenyl dihydrogen phosphate, nonylphenyl dihydrogen phosphate, 2,4-di-t-butylphenyl dihydrogen phosphate and the like. These compounds may be used alone or in a mixture.

Examples of the phosphonates include phosphonate monoesters, which are represented by the following chemical formulas 12.

[0091]

[Chemical 12]

(Wherein R ²⁵ , R ²⁷ , R ²⁹ , R ³⁰ , R ³¹ ,
R ³² is the same as the above) The phenolic stabilizer is represented by the following chemical formula 13.

[0093]

[Chemical 13]

[0094] (wherein, R ³³ is a hydrogen atom, a hydroxyl group, indicates an alkoxyl group or an optionally substituted hydrocarbon residue, R ³³ may be the same or different. However, R ³³
Of these, at least one represents a hydrocarbon residue which may have a substituent. ) Specifically, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-p-anisole, 2,6
-Di-t-butyl-4-ethylphenol, 2,2'-
Methylene bis (6-t-butyl-p-cresol),
2,2'-methylenebis (4-ethyl-6-t-butyl-p-phenol), 4,4'-methylenebis (6-t
-Butyl-p-cresol), 4,4'-butylidene bis (6-t-butyl-m-cresol), tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4']
-Hydroxyphenyl) propionate] methane,
4,4′-thiobis (6-t-butyl-m-cresol), stearyl-β- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate, 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3
-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and the like. To be

Preferred phenolic stabilizers are represented by the following chemical formula 14.

[0096]

Embedded image

(In the formula, R ³⁴ represents a methyl group or a t-butyl group, R ³⁵ represents a t-butyl group, A represents a b-valent hydrocarbon or heterocyclic residue having 1 to 30 carbon atoms, and a represents An integer from 1 to 4,
b represents an integer of 1 or more. ) Specifically, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, stearyl-β- (3,5-di-t-butyl-). 4-hydroxyphenyl) propionate, triethylene glycol-
Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and the like can be mentioned.

A phenolic stabilizer further containing a P atom,
For example, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis (3,5-
Examples also include calcium di-t-butyl-4-hydroxybenzylphosphonate). These phenolic stabilizers may be used alone or in a mixture.

As the sulfur stabilizer, the following chemical formula 15 is used.
And a thioether compound represented by the following chemical formula 16 and the like.

[0100]

[Chemical 15]

(In the formula, R ³⁶ is the same as R ^11. R ³⁷ is the same as R ^12. )

[0102]

Embedded image

(In the formula, R ³⁸ and R ³⁹ represent a C12 to C18 alkyl group.) Specific examples thereof include benzenesulfinic acid, p-toluenesulfinic acid,
Examples thereof include benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and methyl, ethyl, butyl, octyl and phenyl esters of these acids. Also,
Dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-
3,3′-thiodipropionate, pentaerythritol (β-laurylthiopropionate) and the like can be mentioned. These sulfur stabilizers may be used alone,
You may use it in a mixture.

Examples of the epoxy stabilizer include fats and oils such as epoxidized soybean oil and epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, bisphenol A diglycidyl ether, and tetrabromobisphenol A diester. Glycidyl ether, phthalic acid diglycidyl ester,
Hexahydrophthalic acid diglycidyl ester and other glycidyl compounds, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate,
3,4-epoxy-6-methylcyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate,
2,3-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4- (3,4-
Epoxy-5-methylcyclohexyl) butyl-3,4
-Epoxycyclohexanecarboxylate, 3,4-
Epoxy cyclohexyl ethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate,
Bisepoxycyclohexyl adipate, octadecyl-2,2'-dimethyl-3,4-epoxycyclohexanecarboxylate, N-butyl-2,2'-dimethyl-3,4-epoxycyclohexanecarboxylate,
Cyclohexyl-2-methyl-3,4-epoxycyclohexanecarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexanecarboxylate, octadecyl-3,4-epoxycyclohexanecarboxylate, 2-ethylhexyl −
3,4-epoxycyclohexanecarboxylate,
4,6-Dimethyl-2,3-epoxycyclohexyl-
3,4-epoxycyclohexanecarboxylate, diethyl-4,5-epoxy-cis-1,2-cyclohexanecarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2- Cyclohexane carboxylate, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3, -methyl-5-t-butyl-
Epoxycyclohexane compounds such as 1,2-epoxycyclohexane, bisepoxydicyclopentadienyl ether, butadiene diepoxide, tetraphenyl ene nepoxide, epoxidized polybutadiene, 4,5-epoxy tetrahydrophthalic anhydride, 3-t- Butyl-
Examples include 4,5-epoxy tetrahydrophthalic anhydride and the like. These epoxy stabilizers may be used alone or in a mixture.

Examples of the hindered amine stabilizer include bis (2,2,6,6-tetramethyl-4-biperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-
4-biperidyl) sebacate, 2- (3,5-di-t-
Butyl-4-hydroxybenzyl) -2-n butylmalonate bis (1,2,2,6,6-pentamethyl-4-biperidyl) tetraxy (2,2,6,6-tetramethyl-4-biperidyl) 1 , 2,3,4-butanetetracarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) poropionyloxy}
Ethyl] -4- {3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionyloxy} -2,2
6,6-tetramethylpiperidine, 8-benzyl-7,
7,9,9-Tetramethyl-3-octyl-1,2,3
-Triazaspiro {4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and the like can be mentioned. These may be used alone or in a mixture.

These heat resistance stabilizers may be used alone or in combination. Among these, phosphorus-based and sulfur-based stabilizers having an active hydrogen group and sulfinic acid or sulfonic acid esters are preferably used. Examples of the phosphorus-based stabilizer having an active hydrogen group include the aforementioned phosphoric acids, phosphinic acids, phosphonic acids, phosphorous acid diesters, phosphorous acid monoesters, phosphinic acid monoesters, phosphoric acid diesters, phosphorus. Examples thereof include acid monoesters and phosphonic acid monoesters. Examples of the sulfur-based stabilizer having an active hydrogen group include sulfinic acids and sulfonic acids. Among these, phosphorus-based stabilizers having an active hydrogen group are preferable, and phosphorous acid diesters and phosphorous acid monoesters are particularly preferable. The addition amount is not particularly limited, but generally polycarbonate 10
It is used in an amount of 0.0005 to 0.5 part by weight, preferably 0.0005 to 0.2 part by weight, based on 0 part by weight.
0.0005 for heat-resistant stabilizers having active hydrogen groups
It is preferably used in the range of
A range of 0.0005 to 0.009 parts by weight is particularly preferable.

When the heat-resistant stabilizer is used in combination, the heat-resistant stabilizer can be freely combined, but is selected from the phosphorus-based or sulfur-based stabilizers having the above-mentioned active hydrogen groups and the sulfinic acid or sulfonic acid esters. One or more stabilizers and one or more stabilizers selected from other phosphorus-based stabilizers, phenol-based stabilizers, sulfur-based stabilizers, epoxy-based stabilizers, hindered amine-based stabilizers, etc. Is preferred. Among them, one or more stabilizers selected from phosphorus-based and sulfur-based stabilizers having active hydrogen groups and esters of sulfinic acid or sulfonic acid, and phosphorous acid triesters, phosphinic acid diesters, and phenolic stabilizers. It is particularly preferable to combine one or more stabilizers selected from among, further, phosphite diesters, one or more stabilizers and phosphite triesters selected from phosphite monoesters, It is particularly preferable to combine with one or more stabilizers selected from phosphinic acid diesters and phenolic stabilizers. When used in combination with these stabilizers, coloring and long-term heat aging resistance of polycarbonate during recycling molding are improved. The addition amount of these stabilizers is not particularly limited, but one or more kinds selected from phosphorus-based and sulfur-based stabilizers having an active hydrogen group and esters of sulfinic acid or sulfonic acid with respect to 100 parts by weight of polycarbonate. The stabilizer is generally in the range of 0.0005 to 0.015 parts by weight, preferably 0.0005 to 0.009, and the stabilizer to be used in combination is generally 0.0005 to 0.2.
It is in the range of parts by weight, preferably 0.0005 to 0.1.
Parts by weight, more preferably 0.001 to 0.05 parts by weight.

The phosphorus-based flame retardant (C) used in the present invention is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl. Non-halogen phosphates such as phosphate, octyldiphenyl phosphate, tris (chloroethyl) phosphate, bis (2,3dibromopropyl)
2,3-dichloropropyl phosphate, tris (dichloropropyl) phosphate, bis (chloropropyl)
Examples thereof include halogen-containing phosphates such as monooctyl phosphate and condensed phosphates represented by the following chemical formula 17.

[0109]

[Chemical 17]

(In the formula, R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ each independently represent an aryl group or an alkylaryl group such as phenyl, cresyl, xylenyl, propylphenyl and halogenated derivatives thereof. , B represent arylene groups derived from dihydroxy compounds such as resorcinol, hydroquinone, bisphenol A and halogenated derivatives thereof, etc. i ₁ , i ₂ , i ₃ and i ₄ are each independently 0 or 1. , J is 1 to 30
Represents the integer. Among these phosphorus-based flame retardants, tricresyl phosphate and condensed phosphoric acid esters represented by the following chemical formula 18 are preferable (k in the formula is the same as j). These condensed phosphates may have a single degree of polymerization or a mixture of those having different degrees of polymerization, and in the case of the mixture, k is represented by an average value, and k = 1 to 10 is preferable, and 1 to 5 is preferable. Is particularly preferable.

[0111]

Embedded image

In the present invention, the phosphorus-based flame retardant (C) is 100 parts by weight of the total amount of polycarbonate and (A) thermoplastic resin.
It is preferably used in the range of 1 to 25 parts by weight, particularly 5 to 20 parts by weight, relative to parts by weight.

Further, in the present invention, other additives may be added. Examples of other additives include release agents, weathering agents, colorants, flame retardants, fillers, acidic compounds, anti-dripping agents, and the like. These additives may be added at the same time as (A) the thermoplastic resin or the like, or may be pelletized once after the addition of the (A) thermoplastic resin or the like during the molten state after the completion of the polymerization, and other additives may be added as necessary. It is also possible to add and re-melt and knead into a product.

Next, the preferred combination modes of the production method in the present invention are shown below, but the present invention is not limited to these. For example, it is possible to produce a polycarbonate by combining a method of polymerizing while freely falling from a porous plate and a method of polymerizing using a thin film type polymerization device, a screw type polymerization device, a horizontal stirring polymerization device or the like.

Specific examples of preferred combination of the production methods in the present invention include a method of using a stirred tank type polymerization vessel in the pre-polymerization step, a method of polymerizing while freely falling from the porous plate in the post-polymerization step, and two units. The combination of the methods of adding and kneading a thermoplastic resin using the extruder of No. 1 is mentioned. Stirring tank type polymerizers generally have high volume efficiency and high stirring efficiency for low-viscosity substances, but the liquid surface area per liquid volume is small, and stirring efficiency for high-viscosity substances is not necessarily high. Therefore, when the polycarbonate is produced only by the stirred tank type polymerization device, it is difficult to efficiently extract the aromatic monohydroxy compound from the polymer having the increased viscosity in the latter half of the polymerization to proceed the polymerization. Further, since the gas phase portion has a rotation driving portion, polymerization under high vacuum causes a problem of product quality deterioration due to oxygen leakage. However, a high quality polycarbonate can be efficiently produced by combining the method of using the stirred tank type polymerization device in the pre-polymerization step with the method of performing the polymerization while freely dropping from the porous plate in the post-polymerization step. That is, since the pre-polymerization step does not usually need to be carried out in a high vacuum, the stirring tank type polymerizer does not impair the quality, and since the viscosity is low, it is possible to perform polymerization with high stirring efficiency and high volume efficiency. In the polymerization process, it is possible to efficiently extract aromatic monohydroxy compounds, etc. by the method of polymerizing while freely falling from the porous plate, and to proceed with the polymerization, and because of the excellent sealing properties under high vacuum, high quality is achieved. A simple polycarbonate can be easily produced.

In this example, the prepolymerization step means a step of producing a polymerization intermediate having a number average molecular weight of usually 300 to 5000 from an aromatic dihydroxy compound and a diaryl compound, and the postpolymerization step means , A step of producing a polycarbonate having a higher degree of polymerization than the polymerization intermediate obtained in the prepolymerization step.

As the stirring tank type polymerizer, any of the stirring tanks described in, for example, Chapter 11 of the Chemical Equipment Handbook (edited by the Chemical Engineering Society; 1989) can be used. The shape of the tank is not particularly limited, and a vertical type or a horizontal type is usually used.
Further, the shape of the stirring blade is not particularly limited, and the anchor type,
Turbine type, screw type, ribbon type, double blade type and the like are used.

The reaction temperature and reaction time in the prepolymerization step are usually selected in the range of 50 to 350 ° C., preferably 100 to 290 ° C., usually 1 minute to 100 hours, preferably 30 minutes to 50 hours.

The reaction pressure in the prepolymerization step varies depending on the molecular weight of the melt mixture or the polymerization intermediate, but is usually 3 mm.
The range of Hg to normal pressure is preferable, and more preferably 5 mm.
It is in the range of Hg to normal pressure. As the reaction progresses, the produced aromatic monohydroxy compound is efficiently removed to the outside of the reaction system, so that it is inert such as nitrogen, argon, helium, carbon dioxide or lower hydrocarbon gas, which does not adversely affect the reaction. It is also preferable to use a method in which a different gas is introduced and the produced aromatic monohydroxy compound is entrained in these gases.

The prepolymerization step can be carried out by either a batch system or a continuous system. Further, in the prepolymerization step, it is possible to use one agitation type polymerization vessel or a combination of two or more types.

In the prepolymerization step, since the amount of aromatic monohydroxy compound is usually large, it is preferable to provide a heat exchanger, a vaporization chamber or the like as necessary to evaporate the aromatic monohydroxy compound.

The apparatus, the polymerization method, the polymerization conditions and the like of the post-polymerization step in this example, that is, the method of polymerizing while freely falling from the perforated plate are as described above.

Next, a specific example of this method will be described with reference to the drawings.

3 and 4 are examples of processes for achieving the method of the present invention. Although one polymerization vessel is used in FIG. 3, three polymerization vessels are used in the pre-polymerization step and two polymerization vessels are used in the post-polymerization step in FIG. 4, these are merely specific examples, and the present invention is not limited thereto. Not a thing.

In FIG. 3, an extruder is connected after the polymerization apparatus of FIG. 2, and the molten polymer discharged from the discharge port 9 is sent to the hopper port 12 of the extruder 11. on the other hand,
The thermoplastic resin measured by the feeder 22 is added to the addition port 21.
Is supplied to the extruder 11. Further, the heat resistance stabilizer is supplied from the heat resistance stabilizer tank 13 by the liquid feed pump 14 to the inlet 1
Sent to 5. In the extruder 11, the melt polymer, the thermoplastic resin, and the heat resistance stabilizer are uniformly kneaded, then discharged in a strand form from the sixth, cooled in the cooling bath 17, and pelletized by the cutter 18.

In FIG. 4, in the prepolymerization step, the aromatic dihydroxy compound and the diaryl carbonate were fed from the raw material supply ports 1, 1 ′ through the stirring tank type first polymerizer (I) 3 and the stirring tank type first polymerizer ( II) Introduced in 3 '. The stirring tank type first polymerizer (II) 3'is exactly the same as the stirring tank type first polymerizer (I) 3 and can be used by switching when operating in batch. The inside of the polymerization vessel is under an atmosphere of an inert gas such as nitrogen, and is usually controlled at around normal pressure, and the aromatic monohydroxy compound and the like that are distilled out are discharged from the vent ports 2 and 2 ′. The polymerization intermediate 4 obtained by reacting for a predetermined time under stirring is discharged from the discharge ports 5 and 5 ′, transferred by the transfer pump 6 and introduced into the stirring tank type second polymerization device 8 from the supply port 7. .

The inside of the polymerization vessel is controlled under reduced pressure, and the distilling aromatic monohydroxy compound and the like are discharged from the vent port 9. The polymerization intermediate 10 obtained by reacting for a predetermined time under stirring is discharged from the discharge port 11 and transferred to the post-polymerization step by the transfer pump 12.

In the post-polymerization step, the polymerization intermediate 10 produced in the pre-polymerization step is supplied from the supply port 13 to the circulation line 14 and introduced into the inside of the perforated plate type first polymerization vessel 16 through the perforated plate 15. It falls freely in the form of a film, a thread, a droplet, or a mist to become a polymerization intermediate 17. The inside of the polymerization vessel is controlled to a predetermined pressure, and the aromatic monohydroxy compound distilled from the polymerization intermediate and the inert gas such as nitrogen introduced from the gas supply port 18 as necessary are vented. It is discharged from the mouth 19. The polymerization intermediate, which has fallen freely in the form of film, thread, droplet, or mist to reach the bottom of the polymerization vessel, is supplied again from the perforated plate 15 to the inside of the polymerization vessel through a circulation line 14 equipped with a circulation pump 20. . The polymerization intermediate 21 having reached a predetermined molecular weight is discharged from the discharge port 23 by the transfer pump 22, supplied from the supply port 24, introduced into the inside of the porous second polymerization vessel 27 through the perforated plate 26, and the film In the shape of a filament, a filament, a droplet, or a mist, the polymer intermediate 28 falls freely. The inside of the polymerization vessel is controlled to a predetermined pressure, and an aromatic monohydroxy compound distilled from the polymerization intermediate or the like and an inert gas such as nitrogen introduced from the gas supply port 29 as necessary are vented. It is discharged from the mouth 30. The molten polymer 32 is discharged from the discharge port 34 by the discharge pump 33 to the hopper port 3 of the extruder 37.
Sent to 5. On the other hand, the thermoplastic resin melted by the extruder 46 is supplied to the hopper port 36. Further, additives such as a heat resistance stabilizer and a phosphorus-based flame retardant are sent from the additive tank 44 to the injection port 45 by the liquid sending pump 43. In the extruder 37, the molten polymer, the thermoplastic resin, and the additives are uniformly kneaded, then discharged from the die 38 in a strand form, cooled in the cooling bath 39, pelletized by the cutter 40, and then siloed in the transfer line 42. Sent to. In all the steps, each of the polymerization reactor, extruder, circulation line, transfer line, discharge line, etc. is heated by a jacket or heater and kept warm.

Further, a combination of a method of using a stirred tank type polymerizer in the prepolymerization step, a method of polymerizing while dropping in a wet wall type in an intermediate polymerization step, and a method of polymerizing while freely falling from a perforated plate in a postpolymerization step Is also a preferred embodiment of the present invention.

In the intermediate polymerization step of the specific example of the above combination, the polymerization intermediate obtained in the pre-polymerization step is polymerized in a molten state while dropping in a wet wall system. The method of polymerizing while dropping onto a wet wall makes it possible to efficiently supply latent heat of vaporization of an aromatic monohydroxy compound, etc. because a large heat transfer area can be taken, and since a large evaporation area can be obtained, an aromatic monohydroxy compound can be obtained. And the like can be efficiently extracted to advance the polymerization.

In this example, the prepolymerization step is a step of producing a polymerization intermediate having a number average molecular weight of usually 300 to 5000 from an aromatic dihydroxy compound and a diaryl compound. The intermediate polymerization step is A polymerization intermediate having a higher molecular weight than the polymerization intermediate obtained in the pre-polymerization step, that is, a step of producing a polymerization intermediate having a number average molecular weight of up to about 10,000 is usually used, and the post-polymerization step is an intermediate polymerization step. It is a step of producing a polycarbonate having a higher molecular weight than the produced polymerization intermediate.

The stirring tank type polymerization vessel used in the prepolymerization step, the polymerization method in the prepolymerization step, the polymerization conditions and the like are as described above.

In the intermediate polymerization step, examples of an apparatus for performing polymerization while dropping it in a wet wall system include the reactor described in Chapter 11 on page 461 of Chemical Equipment Handbook (edited by Chemical Engineering Society; 1989). The polymerization vessel may be of a multi-tube type, or the dropped polymer may be circulated and polymerized while being dropped again in a wet wall type.

The reaction temperature and reaction time in the intermediate polymerization step are
Usually at a temperature in the range of 50 to 350 ° C, preferably 100 to 290 ° C, usually for 1 minute to 100 hours, preferably 30.
The preferable reaction pressure of the intermediate polymerization step selected in the range of minutes to 50 hours varies depending on the molecular weight of the melt mixture or the polymerization intermediate, and when the number average molecular weight is 1000 or less, the range of 50 mmHg to normal pressure is preferable, and the number average is In the range of molecular weight of 1000 to 2000, 3 mmHg to 80 m
The range of mHg is preferable, and when the number average molecular weight is 2000 or more, 10 mmHg or less, particularly 5 mmHg or less is preferable. As the reaction progresses, the produced aromatic monohydroxy compound is efficiently removed to the outside of the reaction system, so that it is inert such as nitrogen, argon, helium, carbon dioxide or lower hydrocarbon gas, which does not adversely affect the reaction. It is also preferable to use a method in which a different gas is introduced and the produced aromatic monohydroxy compound is entrained in these gases.

The intermediate polymerization step can be carried out in either a batch system or a continuous system. Further, in the intermediate polymerization step, it is possible to use one polymerization vessel or a combination of two or more polymerization vessels.

In the intermediate polymerization step, the amount of the aromatic monohydroxy compound is usually large, and in order to evaporate the aromatic monohydroxy compound, it is preferable to provide a heat exchanger or a vaporization chamber as necessary.

The apparatus, the polymerization method, the polymerization conditions and the like of the post-polymerization step in this example, that is, the method of freely dropping from the perforated plate to carry out the polymerization are as described above.

There are no particular restrictions on the material of the polymerization vessel for achieving the method of the present invention, and it is usually selected from stainless steel, nickel, glass lining and the like.

It is also one of the preferred embodiments of the present invention to form a wetting wall on the inner wall surface of the polymerization vessel with a part of the circulating polymer in order to prevent the scale from adhering to the inner surface of the polymerization vessel.

[0140]

BEST MODE FOR CARRYING OUT THE INVENTION Examples will be described below. The measurement was performed by the following method.

(1) Number average molecular weight (hereinafter abbreviated as Mn)
And weight average molecular weight (hereinafter abbreviated as Mw): measured by gel permeation chromatography (GPC).

(2) Stability during molding: During continuous molding at 250 ° C. using an injection molding machine (J100E manufactured by Japan Steel Works), molding was stopped for 20 minutes and allowed to stay, and then molding was started again. The appearance of the test piece after retention and the retention rate of Izod impact strength before and after retention were determined.

(3) Measurement of ash content: After washing the platinum crucible with a detergent, it is washed again with pure water. After washing, the crucible is dried with a dryer and then left to cool in a desiccator. The crucible weight and the sample weight were precisely weighed, and the ash content was calculated according to the following formula.

Ash content (wt%) = {(crucible weight after ashing (g) -crucible weight (g)) / (sample weight (g))} ×
100 Example 1 The reaction was carried out using a polymerization process as shown in FIG.
This polymerization vessel is equipped with a perforated plate having 50 holes with a hole diameter of 7.5 mm at a pitch of 30 mm, and the height at which it freely drops is 4 m. The extruder is a twin-screw extruder of the same direction (45 m
mφ, L / D = 30), and has an addition port, a liquid injection port, and a vent port. 30 liters of a polymerization intermediate of Mn6000 produced from bisphenol A and diphenylcarbonate (molar ratio of bisphenol A to 1.05) was charged in a polymerization vessel in advance, and the same Mn6 as the charged one was charged.
000 polymerization intermediates were fed at 6 liters / hr and the molten polymer was continuously fed to the extruder so as to keep the liquid level constant. The molecular weight Mw of the obtained polycarbonate after the steady state was 28,000. The polymerization reactor has a reaction temperature of 250 ° C., a reaction pressure of 1.0 mmHg, and a circulation flow rate of 1
The polymerization reaction was continuously carried out for 1000 hours under the conditions of 00 liter / hr and nitrogen gas flow rate of 2 liter / hr. The extruder was operated at a temperature of 250 ° C. and a rotation speed of 200 rpm. From the addition port, ABS resin (Asahi Kasei Co., Ltd .: Stylak ABS prototype-1: butadiene content 15% by weight,
The proportion of unsaturated nitrile compound units in the copolymer is 27
% By weight, the graft ratio to the rubber-like substance is 50%, and the ash content is 0.05% by weight, and the same amount as the supply polycarbonate is supplied. From the liquid injection port, 100 parts by weight of the supply polycarbonate is mixed with bis (nonylphenyl). ) Hydrogen phosphite was dissolved in acetone and injected so as to be 0.001 part by weight. Acetone was depressurized to a vacuum from the vent port and extracted. The polycarbonate composition discharged from the extruder was continuously obtained as pellets through a cooling bath and a cutter. As a result, the hue of the obtained polycarbonate composition was good, and the M of the polycarbonate in the composition was
The w was 27500, which was almost unchanged. Also,
As for stability during molding, retention rate of Izod impact strength is 65%
The appearance of the molded product was also good.

Example 2 Example 1 was repeated except that 0.02 parts by weight of trisnonylphenylphosphite was used in place of the bis (nonylphenyl) hydrogenphosphite of Example 1. As a result, the obtained polycarbonate composition had a good hue, and the Mw of the polycarbonate in the composition was 2 as well.
The decrease was as low as 7100. Regarding the stability during molding, the Izod impact strength retention was 46%, and the appearance of the molded product was also good.

Example 3 Instead of the ABS resin of Example 1, Stylak ABS prototype-2 (Asahi Kasei Co., Ltd .: butadiene content 15% by weight, the proportion of unsaturated nitrile compound units in the copolymer was Example 1 was repeated, except that 30% by weight, the graft ratio to the rubber-like substance was 50%, and the ash content was 0.45% by weight. As a result, the hue of the obtained polycarbonate composition was good, and the M of the polycarbonate in the composition was
w was slightly reduced to 26600. As for the stability during molding, the Izod impact strength retention rate was 40%, and the appearance of the molded product was almost good although some silver was generated.

Comparative Example 1 50 parts by weight of a commercially available polycarbonate (Mitsubishi Kasei Kogyo Co., Ltd .: Novarex 7025A: Mw27800) and 50 parts by weight of the ABS resin used in Example 3 were mixed and an extruder (coaxial twin screw extrusion) was used. Machine: 45 mmφ, L / D = 30) was used for extrusion pelletization at a temperature of 280 ° C. and a rotation speed of 200 rpm. As a result, the obtained polycarbonate composition was colored yellow and the Mw of the polycarbonate in the composition was also reduced to 25,500. In addition, the stability at the time of molding was significantly low, with the retention of Izod impact strength being 23%, and the appearance of the molded product was also poor because a large amount of silver was generated.

Comparative Example 2 A polycarbonate composition was produced in exactly the same manner as in Example 3 except that a horizontal biaxial stirring type polymerization vessel was used instead of the porous plate type polymerization vessel to produce the polycarbonate. However, the horizontal biaxial stirring type polymerization vessel has an internal volume of 30 liters and L / D =
6, a biaxial stirring blade having a rotating diameter of 140 mm was used, and the reaction temperature was 295 ° C., the reaction pressure was 0.1 mmHg, and the internal volume was 10 liters. The molecular weight Mw of the polycarbonate after the transition to stable steady operation was 28300, which was slightly yellowish as compared with Example 3. As a result, the obtained polycarbonate composition was colored yellow,
The hue was poor. M of polycarbonate in the composition
w dropped to 26000. In addition, the stability during molding had a low Izod impact strength retention rate of 34%, and the appearance of the molded product was inferior because silver was generated.

Example 4 Polycarbonate was produced by the process as shown in FIG. However, the first polymerization vessel in the stirring tank in the pre-polymerization step was operated batchwise while switching between (I) and (II), and the other polymerization vessels were operated continuously. Stirring tank first polymerizer (I),
The internal volume of (II) is 100 liters, the internal volume of the second agitator polymerization vessel is 50 liters, and the stirring blades are all anchor type.

In the perforated plate type first polymerizer and the perforated plate type second polymerizer in the post-polymerization step, holes having a hole diameter of 7.5 mm were provided at pitches of 30.
It is equipped with a perforated plate having 50 mm, and the height at which it can be freely dropped is 4 m. However, the circulation line is provided only in the perforated plate type first polymerization vessel.

In the first polymerization vessel of the stirring tank in this prepolymerization step, both (I) and (II) are under the conditions of a temperature of 180 ° C., a normal pressure and a seal nitrogen gas flow rate of 1 liter / hr. In the first polymerization vessel (I) of the stirring tank, 8 parts of bisphenol A and diphenyl carbonate (molar ratio of bisphenol A to 1.10) were added.
0 Kg was charged and melt mixed for 4 hours, and continuously supplied to the second polymerization vessel in the stirring tank at 5 liter / hr. While supplying from the stirring tank first polymerization device (I) to the stirring tank second polymerization device, bisphenol A was added to the stirring tank first polymerization device (II) similarly to the stirring tank first polymerization device (I). The diphenyl carbonate was melt-mixed, and when the stirring tank first polymerization device (I) became empty, the stirring tank first polymerization device (II) was switched to. Thereafter, similarly, the stirring tank first polymerizers (I) and (II) were switched batchwise and the polymerization intermediate was continuously supplied to the stirring tank second polymerizer at 5 liters / hr. When the internal volume of the second tank of the stirring tank reached 20 liters, the polymerization intermediate was continuously supplied to the porous plate type first polymerizer in the post-polymerization step so as to keep the internal volume of 20 liters constant. The second polymerization vessel in the stirring tank has a reaction temperature of 2
The conditions are 30 ° C., reaction pressure 100 mmHg, and nitrogen gas flow rate 2 liter / hr. When the internal volume of the porous plate type first polymerization vessel reached 10 liters, the polymerization intermediate was continuously supplied to the porous plate type second polymerization vessel so as to keep the internal volume of 10 liters constant. The perforated plate type first polymerization vessel has a reaction temperature of 250 ° C.,
Reaction pressure 2.0 mmHg, nitrogen gas flow rate 1 liter / h
r and circulation rate of 200 liters / hr. When the internal volume of the porous plate type second polymerization device reached 2 liters, the molten polymer was continuously extracted and supplied to the extruder so that the internal volume was kept constant at 2 liters. The polymerization intermediate supplied to the perforated plate type first polymerization vessel after the transition to stable steady operation also has Mw of 1600, and the Mw of the polymerization intermediate supplied to the perforated plate type second polymerization vessel.
Was 12000. The Mw of the polycarbonate supplied to the extruder was 24000. The extruder is
It was a twin-screw extruder of the same direction (30 mmφ, L / D = 30) having a liquid injection port and an addition port, and was operated at a temperature of 240 ° C. and a rotation speed of 200 rpm. From the hopper mouth, ABS resin melted at 240 ° C. with the second extruder (single screw 30 mmφ, L / D = 30) (styrac AB used in Example 1
S prototype-1) is supplied in an amount of 33.3 parts by weight based on 100 parts by weight of the supplied polycarbonate. From the liquid inlet, 0.001 part by weight of bis (nonylphenyl) hydrogen phosphite and 0.01 part by weight of tris (2,4-di-t-butylphenyl) phosphite are used with respect to 100 parts by weight of supplied polycarbonate. Parts, 0.01 parts by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and 2
Condensed phosphate ester flame retardant represented by 9 (where m is m
= 1 is a mixture of which the main component is, and the average is 1.2)
Was mixed and adjusted to 13.5 parts by weight and injected.
From the addition port, 0.4 parts by weight of polytetrafluoroethylene powder (F201L, Daikin Industries, Ltd.) was added. The polycarbonate composition discharged from the extruder was continuously obtained as pellets through a cooling bath and a cutter. As a result, the hue of the obtained polycarbonate composition was good, the decrease in the molecular weight of the polycarbonate in the composition was small, and it had good physical properties such as stability during molding and flame retardancy.

[0152]

EFFECTS OF THE INVENTION An apparatus which has excellent sealing properties under high vacuum and is easy to maintain, stable for a long time, at a high polymerization rate,
It is possible to produce a high-quality polycarbonate composition having excellent hue and stability during molding.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a polymerization vessel used in the present invention.

FIG. 2 is a schematic view showing another example of the polymerization vessel used in the present invention.

FIG. 3 is a schematic diagram showing an example of a process for achieving the method of the present invention.

FIG. 4 is a schematic diagram showing another example of a process for achieving the method of the present invention.

[Explanation of symbols]

In FIGS. 1, 2 and 3, 1. Raw material supply port 2. Circulation line 3. Perforated plate 4. 4. Film-like, thread-like, droplet-like, atomized melt mixture or polymerization intermediate Gas supply port 6. Vent port 7. Circulation pump 8. Discharge pump 9. Discharge port 10. Polymerizer main body 11. Extruder 12. Hopper mouth 13. Heat-resistant stabilizer tank 14. Liquid delivery pump 15. Inlet 16. Die 17. Cooling bath 18. Cutter 19. Discharge port 20. Vent port 21. Addition port 22. Feeder In FIG. Raw material supply port 1 '. Raw material supply port 2. Vent port 2 '. Vent port 3. Stirring tank first polymerizer (I) 3 '. Stirring tank first polymerizer (II) 4. Polymerization intermediate 5. Discharge port 5 '. Discharge port 6. Transfer pump 7. Supply port 8. Stirring tank 2nd polymerizer main body 9. Vent port 10. Polymerization intermediate 11. Discharge port 12. Transfer pump 13. Supply port 14. Circulation line 15. Perforated plate 16. Perforated plate type first polymerization vessel 16 '. Perforated plate type polymerizer 17. 18. Polymeric intermediates in the form of film, thread, droplet, or mist Gas supply port 19. Vent port 20. Circulation pump 21. Polymerization intermediate 22. Transfer pump 23. Discharge port 24. Supply port 25. Circulation line 26. Perforated plate 27. Perforated plate type second polymerization vessel 28. 29. Film-shaped, thread-shaped, droplet-shaped, and atomized polymerization intermediates Gas supply port 30. Vent port 31. Circulation pump 32. Melt polymer 33. Discharge pump 34. Discharge port 35. Extruder popper mouth 36. Extruder popper port 37. Extruder 38. Die 39. Cooling bath 40. Cutter 41. Discharge port 42. Transfer line 43. Liquid feed pump 44. Stabilizer tank 45. Inlet 46. Second extruder 47. Additive feeder 48. Addition port

Claims (8)

[Claims] 1. A step of polymerizing a molten mixture of an aromatic dihydroxy compound and a diaryl carbonate or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and a diaryl carbonate while freely falling from a porous plate in a molten state. After the polymerization step containing all or part of
A method for producing a polycarbonate composition, which comprises adding (A) a thermoplastic resin and (B) a heat stabilizer during a molten state and kneading. 2. The compounding amount of the thermoplastic resin (A) with respect to the polycarbonate is in the range of 1:99 to 99: 1,
The method for producing a polycarbonate composition according to claim 1, wherein the amount of the heat-resistant stabilizer (B) added is in the range of 0.0005 to 0.5 part by weight based on 100 parts by weight of the polycarbonate. 3. The method for producing a polycarbonate composition according to claim 1, wherein the thermoplastic resin (A) is an ABS resin. 4. The method for producing a polycarbonate composition according to claim 3, wherein the ABS resin is an ABS resin having an ash content of 0.1% by weight or less. 5. The method for producing a polycarbonate composition according to claim 1, wherein (C) a phosphorus flame retardant is added and kneaded together with the ABS resin and the (B) heat stabilizer. 6. The addition amount of the (C) phosphorus-based flame retardant is in the range of 1 to 25 parts by weight with respect to 100 parts by weight of the total amount of the polycarbonate and the (A) thermoplastic resin. A method for producing the polycarbonate composition according to claim 5. 7. The method for producing a polycarbonate composition according to claim 1, wherein the heat-resistant stabilizer (B) is a phosphorous acid diester and / or a phosphorous acid monoester. 8. The heat-resistant stabilizer (B) is one or more compounds selected from (a) phosphite diester and phosphite monoester, and (b) a phenolic stabilizer, phosphite triester and The method for producing a polycarbonate composition according to claim 1, which comprises one or more compounds selected from phosphinic acid diesters.