JP3434636B2 - Manufacturing method of polycarbonate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to a polycarbonate.
For details on the production method of resin series,
It relates to the production method of excellent polycarbonate resin.
is there. [0002] 2. Description of the Related Art Polycarbonate has heat resistance and impact resistance.
Engineering plastics with excellent transparency and transparency
And widely used in many fields
Polycarbonate and ABS resin mixed and polymer
-Alloyed polycarbonate resin is also
Widely used in the automotive field and the like. [0003] About the production method of this polycarbonate
In the past, various studies have been conducted, and among them, aromatic dihydric
Roxy compounds such as 2,2-bis (4-hydroxyf
Enyl) propane (hereinafter referred to as bisphenol A)
An interfacial polycondensation method between phenol and phosgene has been industrialized. Only
However, in this interfacial polycondensation method,
The use of hydrogen chloride and salts
Sodium chloride and methyle chloride used in large quantities as a solvent
Equipment may be corroded by chlorine-containing compounds such as
Impurities such as sodium chloride that adversely affect physical properties
And difficulties in separating residual methylene chloride.
Was. On the other hand, aromatic dihydroxy compounds and diali
Polycarbonate from polycarbonate
As a method, for example, bisphenol A and diphenyl
Transesterification of carbonate in the molten state
The melt polycondensation method of polymerizing while extracting
Known from. Melt polycondensation is different from interfacial polycondensation.
And has the advantage of not using a solvent.
As the polymer proceeds, the viscosity of the polymer increases,
It becomes difficult to efficiently extract knoll etc. out of the system,
There is an essential problem that it is difficult to increase the degree of polymerization. Conventionally, polycarbonate has been melt-polycondensed.
Various types of polymerization reactors are known as polymerization reactors for production.
ing. A method using a tank-type polymerization vessel equipped with a stirrer,
It is widely known. However, the stirring tank type
Combiners have the advantages of high volumetric efficiency and simplicity.
However, on a small scale, polymerization can proceed efficiently.
However, on an industrial scale, as described above,
It is difficult to efficiently extract by-product phenol out of the system
And it is difficult to increase the degree of polymerization.
You. That is, a large-scale stirred tank type polymerization vessel
Usually means that the ratio of liquid volume to evaporation area is small scale
Larger than in the case of
Becomes In this case, reduce the degree of vacuum to increase the degree of polymerization.
Even if raised, the lower part of the stirring tank is substantially higher due to the differential pressure
It is polymerized by pressure, and phenol etc. is efficiently extracted.
It becomes difficult to shake. In order to solve this problem, a high viscosity po
There are various ideas for extracting phenol etc. from limers.
Have been. For example, in Japanese Patent Publication No. 50-19600
Is a screw-type polymerization vessel with a vent,
Japanese Patent Application Laid-Open No. 53-5718 discloses a thin film evaporation type reactor, for example,
For example, screw evaporators and centrifugal thin film evaporators are described.
Furthermore, Japanese Patent Application Laid-Open No. 2-153923 discloses a thin film type.
A method using a combination of an evaporator and a horizontal stirring polymerization tank
It is shown. These polymerization vessels are common, including the stirred tank type.
The drawback is that the polymerization reactor body has a rotary drive part,
If the polymerization is carried out under high vacuum, this drive
Leakage of a small amount of oxygen because it cannot be completely sealed
Cannot prevent coloration of the product.
Was. When using seal liquid to prevent oxygen leakage
Inevitably results in poor product quality
The bottom was inevitable. In addition, high sealing performance at the beginning of operation
The sealability decreases during long-term operation.
And maintenance problems were serious. Accordingly, polycarbonate is prepared by a melt polymerization method.
When manufacturing the glass, the sealing performance under high vacuum is excellent.
Easy maintenance and stable color for a long time
Produce excellent high quality polycarbonate at high polymerization rate
The advent of a way to do this was desired. Meanwhile, polycarbonate
Polycarbonate resin consisting of a resin and ABS resin
Is conventionally manufactured by the interfacial polycondensation method using phosgene.
Polycarbonate and ABS resin using extruder
It is manufactured by kneading. However, this manufacturing method
Has a problem derived from the above-mentioned interfacial polycondensation method.
When kneading with ABS resin in an extruder,
Use carbonate pellets or powder
Requires high temperature for dissolution, and heat degradation of polycarbonate
And the coloring of alloy products became a problem. Also, the pair obtained
The molding stability is poor due to the poor thermal stability of the product.
The impact strength is reduced or fluctuated, and the appearance of molded products is poor.
And so on. Further, the problems of the conventional methods are solved.
Therefore, the polycarbonate obtained by the melt polymerization method,
Polycarbonate while polycarbonate is in the molten state
(For example, Japanese Patent Application Laid-Open No. H5-223933).
No. 1) and melting of oligocarbonate and ABS resin
Mixing during the process of forming polycarbonate under reduced pressure
(Japanese Patent Application Laid-Open No. 6-220295) has been proposed.
ing. However, in these methods, for example, the former
According to the method, the polycarbonate is already in a molten state.
To melt the above polycarbonate at high temperature.
Heat deterioration of the polycarbonate produced and coloring of alloy products
Although the problem can be reduced, the above-mentioned known as a melt polymerization vessel is used.
Using a thin-film evaporator and a horizontal stirring polymerization tank in combination
The above-mentioned drawbacks of the polymerization reactor itself are
Operating stability, product hue, molding stability, etc.
A decline in quality was inevitable. Also in the latter way
Is related to the problem of thermal degradation during melting of oligocarbonate.
In addition, since an evaporating extruder is used as a polymerization device,
As mentioned above, driving stability, product hue, molding stability
Deterioration of quality was inevitable. By the way, the main body does not have a rotary drive part,
The method of polymerizing while dropping from the perforated plate is polycarbonate
It is known as a method for producing resins other than carbonate. An example
For example, in U.S. Pat.
The polymer is dropped in a thread into a vacuum to form a polymer of the desired molecular weight.
A method for making an ester is disclosed. In the specification
Circulates the dropped yarn again, the polyester product
To reduce the quality, complete the polymerization in one pass without circulation.
Has been completed. However, with regard to such methods
Has many drawbacks. For example,
No. 8355 discloses that spinning is performed from a spinneret into a vacuum.
The following description relates to the method of polycondensation. Fiber-forming ability
Unless a sufficiently large one is supplied, the yarn being polymerized in the reactor
Are easily cut, and the quality of the polycondensate fluctuates greatly. Thread
Low molecular weight condensate scattered from the
Is difficult to eject directly from below the base,
Drops and bundles flow down into thick fibers to hinder the reaction.
The monitoring window is easily cloudy, making it difficult to monitor.
Replacement time is easy to lose. In this publication, the polyester
Vertically in the reaction vessel for the production of
While flowing down the polymer along the porous body
It is described that the method of causing
No mention is made of nates. [0011] Further, although not a polymerization method, it remains in the polymerization product.
Lactam polysynthesis
US Patent No. 2 discloses a method of dropping a material from a perforated plate onto a yarn.
No. 719776. But
However, this method has many drawbacks. example
For example, Japanese Patent Application Laid-Open No. 53-17569 discloses U.S. Pat.
The following disadvantages are pointed out regarding the method of 719776
Have been. If the evaporation of volatiles is low, a thread is formed
Even if it can be done, if there is much evaporation, the yarn will foam
It is difficult to drive smoothly. Formed thread
Substances with a specific viscosity in a relatively narrow range
Applicable only to Place to introduce inert gas, etc. into the tower
If the airflow is turbulent, neighboring yarns will come into contact with each other and collect.
You. Note that, in Japanese Patent Application Laid-Open No. 53-17569,
In order to solve the inconvenience of
In accordance with this, a method of flowing high viscosity material down
Ethylene terephthalate, polybutylene terephthalate
Like polyesters, nylon 6, nylon 66
Has been proposed for various polyamides.
There is no mention of the site. Also, Japanese Patent Publication No. 4-14127 discloses a
Regarding the continuous polycondensation method of
Two methods of performing the condensation, namely spinning from the spinneret
Polymerized while extruding into a film from the slit
It is described that it is difficult for any of the methods to advance polycondensation.
Have been. The publication also states that a small number of slit-shaped supply ports
Hold a thin film between at least two wires, and
The method of continuous polycondensation by moving
Proposed. In this publication, of course,
No mention is made of Bonate. As described above, do not drop from the perforated plate.
The method of polymerization is made of polyester or polyamide.
Although it is known as a manufacturing method, polycarbonate
It is not known as a production method at all. Also, Polyester
As a method for producing polyester and polyamide, polymerization
This method has many drawbacks such as blockage of holes. [0014] SUMMARY OF THE INVENTION The present invention relates to a melt polycondensation
Polycarbonate and ABS resin
Hue and molding stability when producing carbonate resin
Polycarbonate resin with excellent properties, etc. under high vacuum
Excellent sealing performance and easy maintenance.
Produced in a stable manner, with a high polymerization rate and excellent productivity
The purpose is to provide a way to do it. [0015] Means for Solving the Problems The present inventors have solved the above problems.
As a result of intensive studies to solve the problem, the specific ABS tree
Polymerize using a specific manufacturing method
To achieve the goal, and to complete the present invention.
Was. That is, the present invention relates to a polycarbonate-based resin.
In the melt polymerization method, (A) the metal content is 10^-8-10
^-1Weight% of ABS resin and (B) polycarbonate resin
Free of molten mixture with polymer from perforated plate in molten state
Polycarbonate characterized in that it is polymerized while falling onto
It is intended to provide a method for producing a carbonate resin. As described above, the main body has a rotary drive portion.
The type of polymerization vessel that does not use resin other than polycarbonate
Although various known as a polymerization vessel for polymerizing
The melt polycondensation reaction of polycarbonate
It is very different from the melt polycondensation reaction of polyamide.
High viscosity polymerization for the production of lamides and polyesters
Is difficult to apply to the production of polycarbonate
No. Large polyamide, polyester and polycarbonate
The differences are as follows. First, polymerization of melt polycondensation
Melt viscosity is an important factor in vessel design
Extremely high for nate. That is, polyamide, poly
Melt viscosity of ester in late stage of polymerization depends on polymerization temperature
And usually in the hundreds to thousands of poise, over 3000 poise
Is unlikely to be possible, whereas polycarbonate
The melt viscosity in the late stage of polymerization reaches tens of thousands poise. second
Of polyamide, polyester and polycarbonate
All melt polycondensations are equilibrium reactions, but the equilibrium constant
Each is very different. Usually the equilibrium constant of polyamide
Is 10^TwoOrder, the equilibrium constant of the polyester is about 1.
On the other hand, the equilibrium constant of polycarbonate is 10^-1Oh
And polycarbonate even in the same polycondensation reaction.
The equilibrium constant is extremely small. If the equilibrium constant is small
This means that unless by-products are extracted more efficiently outside the system,
Means that the progress does not progress. Therefore, polycarbonate
The reaction of the nate is more than that of the polyester or polyamide.
It is necessary to extract by-products out of the system much more efficiently.
This is extremely true for polycarbonates with high melt viscosities.
It is difficult. However, according to the present invention, surprisingly,
While spinning polyester and polyamides
Polycarbonate without any problems of the polymerization method
It was found that the nate could be polymerized. That is, the yarn
High quality because there is no quality variation due to strip cutting
Can be produced stably. Plus, low
No contamination of the die due to condensate
Without interfering with the injection of the article directly below,
There is no need to stop operation for replacement. Therefore, very
It can be operated stably for a long time. A phenomenon in the reaction of the polycarbonate;
This is a phenomenon in the reaction of polyester and polyamide
The reasons for these apparent differences are not clear. However
If there is no contamination of the base,
Pheno by-product in the polycarbonate reaction
Tools effectively wash low molecular weight condensates,
Or polyamide or poly which by-produces ethylene glycol, etc.
It is presumed that this is fundamentally different from the ester reaction.
It can be seen that this effect is
It could not be foreseen at all from the polymerization reaction. In addition, in the present invention, the metal content
To add ABS resin in a specific range to the polymerization system
The polymerization rate of polycarbonate is greatly improved,
The surprising fact that productivity is improved comes to light
Was. Generally, ABS resin degrades polycarbonate
Known to have a certain metal content in a certain range
The use of ABS resin in
It has been found to promote polymerization. This is completely predictable
Although the reason is not well understood, this polymerization method
So, probably, ABS resin is polycarbonate
Melt mixing affects the shape of the falling yarn, etc.
Increases the diffusion rate of phenol and reduces phenol.
This is considered to be due to the
Metal has some interaction with polycarbonate polymerization
It is estimated that they are using As described above, the production method of the present invention relates to
It is not necessary to have a rotary drive in the gas phase, and
Controllability and easy maintenance.
High quality polycarbonate with excellent hue and molding stability
It has become clear that a resin can be produced. That is,
By using the manufacturing method of the present invention, as described above,
All problems can be solved. Hereinafter, the present invention will be described in detail. Book
(A) ABS resin of the invention^-8-10^-1Wt% gold
The genus is not particularly limited as long as it contains a genus. Metal component
Although not particularly limited, for example, sodium, potassium
Lium, magnesium, calcium, aluminum, iron
And the like. When the metal content is higher than the above range
Can easily progress the decomposition reaction of polycarbonate,
It is not preferable because the degree of accuracy does not increase, and it is smaller than the above range.
In this case, the effect of improving the polymerization rate of polycarbonate is small.
Not very good. Preferably, 10^-8~ 5 × 10^-2of
In the range, more preferably 10^-8-10^-2In the range
You. Metal content can be easily measured by atomic absorption method etc.
You. The method for producing the ABS resin is not particularly limited.
Bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization
ABS resin manufactured by known methods such as
Can be used. A produced by a suspension polymerization method or an emulsion polymerization method
BS resin generally contains a large amount of metal, and is used as a salting-out agent.
The metal content is reduced by devising the type of
Preferably. Types and ratios of copolymer components of ABS resin
Rate, type and ratio of rubber component, graft ratio, molecular weight, etc.
The requirements for the polycarbonate resin obtained are not limited to
Selected by performance. (B) The polycarbonate prepoly of the present invention
The mer usually comprises a repeating unit represented by the following chemical formula 1.
And its terminal group is not particularly limited, but generally, it is aromatic.
A hydroxyl group (-OH) directly linked to a group
2 comprises an aryl carbonate group shown in FIG.
It may have a terminal group. [0023] Embedded image (In the formula, Ar represents a divalent aromatic group.) [0025] Embedded image (Wherein, Ar¹Represents a monovalent aromatic group
You. ) In the polycarbonate prepolymer of the present invention, Ar
And Ar¹May be of a single type
Good, even if it consists of two or more types
No. Molar ratio of hydroxyl group to aryl carbonate group
Is not particularly limited. In general, the closer the molar ratio is to 1, the higher the weight
Fast joint speed. The aromatic group Ar is preferably, for example,
It is represented by -Ar^Two-Y-Ar^Three− (Wherein, Ar^TwoAnd Ar^ThreeAre each independently charcoal
Divalent carbocyclic or heterocyclic aromatic compounds having a prime number of 5 to 70
Represents an aromatic group, and Y is a divalent alkyl having 1 to 30 carbon atoms.
Represents a can group. ) Divalent aromatic group Ar^Two, Ar^ThreeOne or more water
Other substituents whose elemental atoms do not adversely affect the reaction, for example
For example, a halogen atom, an alkyl group having 1 to 10 carbon atoms,
Alkoxy groups of the formulas 1 to 10, phenyl groups, phenoxy
Group, vinyl group, cyano group, ester group, amide group, nitro
It may be substituted by a group such as b. As a preferred specific example of the heterocyclic aromatic group,
Is one or more ring-forming nitrogen, oxygen or sulfur
An aromatic group having a yellow atom can be mentioned. Bivalent good
Aromatic group Ar^Two, Ar^ThreeIs, for example, a substituted or unsubstituted
Phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted
Or an unsubstituted group such as pyridylene. Replace here
The groups are as described above. The divalent alkane group Y is, for example,
Is an organic group represented by [0030] Embedded image Where R¹, R^Two, R^Three, R^FourAre each
Independently hydrogen, an alkyl group having 1 to 10 carbon atoms,
10 alkoxy groups, cycloalkyl having 5 to 10 ring carbon atoms
Alkyl group, a carbocyclic aromatic group having 5 to 10 ring carbon atoms,
Represents a carbocyclic aralkyl group having 6 to 10 carbon atoms. k is 3
Represents an integer of from 1 to 11;^FiveAnd R⁶Is for each X
Selected individually and independently of one another, hydrogen or carbon number 1
And X represents an alkyl group, and X represents carbon. Also,
R¹, R^Two, R^Three, R^Four, R^Five, R⁶At least one
Other positions are not affected by the hydrogen atom above.
Substituent, for example, halogen atom, alkyl having 1 to 10 carbon atoms
Group, an alkoxy group having 1 to 10 carbon atoms, a phenyl group,
Nonoxy group, vinyl group, cyano group, ester group, amide
May be substituted by a group, nitro group, etc.
No. ) Examples of such a divalent aromatic group Ar include, for example,
Those represented by Chemical Formula 4 are exemplified. [0032] Embedded image (Where R⁷, R⁸Are independently hydrogen sources
Atom, halogen atom, alkyl group having 1 to 10 carbon atoms, carbon
An alkoxy group having 1 to 10 carbon atoms,
A cycloalkyl group or a phenyl group, m and n
Is an integer of 1 to 4, and when m is 2 to 4, each R⁷Is it
They may be the same or different, and n is 2 to 4.
In the case of⁸Are the same but different
You may. ) Further, the divalent aromatic group Ar is represented by the following formula.
There may be. -Ar^Two-Z-Ar^Three− (Wherein, Ar^Two, Ar^ThreeIs as described above, Z is a single bond,
Or -O-, -CO-, -S-, -SO_Two-, -S
O-, -COO-, -CON (R¹)-And other divalent groups
Represents Where R¹Is as described above. ) Examples of such a divalent aromatic group include the following:
Are shown. [0035] Embedded imageWhere R⁷, R⁸, M and n are as described above.
It is as follows. ) Further, specific examples of the divalent aromatic group Ar include substitution and substitution.
Or unsubstituted phenylene, substituted or unsubstituted naphthyl
And substituted or unsubstituted pyridylene. This
The substituents here do not adversely affect the reaction, for example,
Halogen atom, alkyl group having 1 to 10 carbon atoms, 1 carbon atom
To 10 alkoxy groups, phenyl groups, phenoxy groups,
Nyl, cyano, ester, amide, nitro
And so on. The polycarbonate prepolymer of the present invention
Among them, bisphenol A and substituted vinyl
A group represented by the following formula 6 which is a residue of sphenol A is A
r is 85 to 100 mol% of the whole. [0038] Embedded image (Where R⁷, R⁸, M and n are as described above.
It is as follows. ) In addition, the prepolymer of the present invention is about
In the range of 0.01 to 3 mol%, containing a trivalent aromatic group
You can go out. In addition, the aryl carbonate group
Ar¹Is a monovalent carbocyclic or heterocyclic aromatic group
Where Ar¹, One or more hydrogen atoms
Are other substituents that do not adversely affect the reaction, for example,
Logene atom, alkyl group having 1 to 10 carbon atoms, 1 to 1 carbon atom
10 alkoxy groups, phenyl groups, phenoxy groups, vinyl
Group, cyano group, ester group, amide group, nitro group, etc.
May be replaced. Monovalent aromatic group Ar¹As a typical example of
Phenyl, naphthyl, biphenyl and pyridyl groups
I can list them. These are one or more of the above substituents
May be replaced. Preferred Ar¹as,
For example, the following chemical formula 7 is mentioned. [0041] Embedded imageThe polycarbonate preform used in the present invention
The polymer has a number average molecular weight of usually 300 to 20,000.
Things. The polycarbonate prepolymer of the present invention
The synthesis method is not particularly limited. like this
Examples of the production method include the following method.
You. Aromatic dihydroxy compound and diary
A method using a transesterification method with a carbonate.   Aromatic dihydroxy compounds and diaryl carbonates
With the diaryl carbonate in an excess molar ratio.
The terminal group mainly consists of an aryl carbonate group
Pre-produce polycarbonate oligomer
Of the oligomer and the aromatic dihydroxy compound
A method using the tell exchange method. Aromatic dihydroxy compound and diary
Is converted to an excess of aromatic dihydroxy compound.
The end groups are mainly hydroxyl groups
Polycarbonate oligomers
Beforehand, the reaction between the oligomer and the diaryl carbonate
A method using the steal exchange method.   In the presence of a molecular weight regulator, an aromatic dihydroxy compound
Method using an interfacial polycondensation method between a substance and phosgene. In the above interfacial polycondensation method, the aromatic di
Excess phosgene and aroma relative to hydroxy compound
Reaction with an aromatic monodihydroxy compound (molecular weight regulator)
And the terminal group is mainly aryl carbonate
Polycarbonate oligomers
The oligomer and the aromatic dihydroxy compound
Using a transesterification method. In the case of the transesterification method,
It is also possible to have a molecular weight regulator. The above,
The polycarbonate prepolymer is produced by the method of
When made, these prepolymers contain substantially
It is easy to not contain chlorine compounds,
Polycarbonate obtained from such a prepolymer
Can be made of high quality which is substantially free of chlorine compounds.
You. In addition, as in the above-mentioned method,
Even when using a component such as
Carbonate prepolymer and polycarbonate oligomer
-When the molecular weight is relatively low, chlorine compounds are decomposed and removed.
These prepolymers and oligos
The product should be of high purity, substantially free of chlorine compounds.
Can be Therefore, even if these methods are used,
Polycarbonate contains substantially chlorine compounds
Not be of high quality. The raw material of the polycarbonate prepolymer
The aromatic dihydroxy compound used as a filler is as follows:
It is represented by an equation. HO-Ar-OH (In the formula, Ar is as described above.) The diaryl compound is represented by the following formula (8).
It is. [0049] Embedded image (Wherein, Ar¹Is as described above. ) Representative examples of diaryl carbonates include:
Substituted or unsubstituted diphenyl carbonate represented by 9
And the like. [0051] Embedded image (Where R⁹And R^TenIs independently hydrogen
Atom, halogen primitive, alkyl having 1 to 10 carbon atoms
Group, alkoxy group having 1 to 10 carbon atoms, ring-constituting carbon
Represents a cycloalkyl group or a phenyl group of several 5 to 10,
p and q are integers of 1 to 5, and when p is 2 or more, each R
⁹May be different from each other, and q is 2 or more.
In the case of^TenMay be different
No. ) Among these diphenyl carbonates, diphenyl carbonate
-Carbonate, ditolyl carbonate, di-t-butyl
Lower alkyl-substituted diphenes such as phenyl carbonate
Symmetric diaryl carbonates such as neal carbonate
Are preferred, but the diaryl car
The carbonate diphenyl carbonate is preferred. These diaryl carbonates may be used alone
May be used, or two or more kinds may be used in combination.
However, if two or more types are used, the reaction system becomes complicated, which is an advantage.
No symmetrical diaryl carbonate
Good to be. The transesterification method and the interfacial polycondensation method
The molecular weight regulator used in the formula is represented by the following formula
Aromatic monohydroxy compounds and the like. Ar¹-OH (Ar¹Is as described above. ) Preferred aromatic monohydroxy compounds include, for example,
Phenol, o, m, p-cresol, 2,6-xyle
Knol, pt-butylphenol, p-octylfe
Nol (various octyl groups) can be used.
You. In addition, these aromatic monohydroxy compounds
Along with other molecular weight regulators such as methanol,
Monohydric alcohols such as ethanol: methylchloropho
Haloho such as mate, cyclohexylchloroformate
-Mates: methyl mercaptan, ethyl mercaptan
Monovalent thiols such as: methylchlorothioformate,
Monovalent halothioforme such as ethyl chlorothioformate
Silicates: acetic acid, propionic acid, benzoic acid, acetic anhydride,
Monicals such as cetyl chloride and propionyl chloride
It is also effective to use boric acid or a derivative thereof in combination. Further, for the aromatic dihydroxy compound,
Less than 5 mol% of dibasic acid or its reactive derivative
It is also effective to react. The dibasic acid or its anti-diacid
The reactive derivative is any of aliphatic, aromatic and alicyclic
And specific examples thereof include terephthalic acid and isophthalic acid.
Phthalic acid, phthalic acid, naphthalene-1,5-dicarboxylic
Acid, diphenyl-2,2-dicarboxylic acid, cis-1,2
-Cyclohexanedicarboxylic acid, oxalic acid, succinic acid,
Sebacic acid, adipic acid, maleic acid, fumaric acid, etc.
Dibasic acids, amine salts, acid halides, aryl esters
And the like. In the present invention, (A) the metal content is 10
^-8-10^-1Wt% ABS resin and (B) polycarbonate
The ratio of A: B to the toppolymer is 1:99 to 99:99.
1, preferably between 10:90 and 90:10.
In the range, particularly preferably from 10:90 to 50:50.
In range. In the present invention, (A) the metal content is 10^-8~
10^-1Wt% ABS resin and (B) polycarbonate resin
The molten mixture with the repolymer is
Polycarbonate is produced by polymerizing while falling
To produce resin. In the present invention, "freely dropping" means
Drops without contacting a drop-resistant object such as a guide or wall
Means the state to be made. The aromatic when dropped freely
The shape of the polycarbonate prepolymer melt is
Worm, thread, droplet, mist, etc. Let it fall freely
In the meantime, phenol etc. generated by the polycondensation reaction
Will be issued. In the perforated plate of the present invention,
There is no particular limitation, and it is usually circular, oval, triangular,
It is selected from shapes such as a cut, a polygon, and a star. Hole
The cross-sectional area is usually 0.01 to 100 cm^TwoAnd preferred
Or 0.05-10cm^TwoAnd particularly preferably
0.1-5cm^TwoRange. The distance between holes is
The center-to-center distance is usually 1 to 500 mm,
Or 5 to 100 mm. Through this perforated plate, ABS resin and polycarbonate
Allow the molten mixture with the carbonate prepolymer to fall freely
The method of dropping with the liquid head or its own weight
By applying pressure using a method or a pump,
Examples include a method of extruding the molten mixture from a perforated plate.
You. There is no particular limitation on the number of holes, and conditions such as reaction temperature and pressure are not limited.
Condition, amount of catalyst, range of molecular weight to be polymerized, etc.
However, usually, a polymer is produced at, for example, 100 kg / hr.
10-10^FiveHoles are required. [0061] The height at which the material is allowed to fall freely after passing through the hole.
Is preferably from 0.3 to 50 m, more preferably
Is 0.5 to 20 m. The flow through the holes is
Normally one hole, depending on the molecular weight of the carbonate
Per 10^-Four-10^FourLiter / hr, preferably 1
0^-2-10^TwoLiter / hr, particularly preferably 0.1
５０50 liters / hr. The time required to drop freely is particularly limited.
Although not limited, it is usually in the range of 0.01 seconds to 10 hours.
In the present invention, the polymer after freely falling is the
It may be dropped into the liquid reservoir as it is,
It may be taken into the liquid reservoir partly. In addition, fall freely
The polymer after being allowed to be extracted as it is
Circulates and polymerizes while freely falling again
Is also a preferred method. In this case, it was dropped freely
During the reaction necessary for the polycondensation reaction in the later liquid reservoir or circulation line, etc.
The residence time can be lengthened depending on the time. In addition,
Forming in unit time by circulating while falling
Since a large new liquid surface area can be obtained,
It is easy to proceed the polymerization sufficiently to the molecular weight. In a preferred embodiment of the present invention, (A) AB
Melting of S resin and (B) polycarbonate prepolymer
Continuous supply of the mixture, free from the perforated plate in the molten state
The polymer is polymerized while dropping, and part of the polymer dropped is circulated.
Ring and drop freely again to polymerize, polycarbonate
And a method of continuously extracting a sheet-based resin. this
In operation, the perforated plate is stable for a long time without being contaminated by low condensate etc.
What can be done is one of the great advantages of the present invention. In the present invention, the reaction temperature is usually 50
Temperature range from to 350 ° C, preferably from 100 to 290 ° C
Is chosen. As the reaction progresses, aromatic monohydric
Roxy compounds are generated, which are removed outside the reaction system
Doing so increases the reaction rate. Therefore, nitrogen,
Argon, helium, carbon dioxide and lower hydrocarbon gases
Introduce an inert gas that does not adversely affect the reaction
The resulting aromatic monohydroxy compound is
Method of removing by entraining with gas or performing reaction under reduced pressure
The method is preferably used. The preferred reaction pressure is
Polycarbonate in polycarbonate resin to be manufactured
The number average molecular weight is 1000 or less.
In the lower range, a range of 50 mmHg to normal pressure is preferable,
When the number average molecular weight is in the range of 1,000 to 2,000, 3 mm
The range of Hg to 80 mmHg is preferable, and the number average molecular weight is
In the range of 2000 or more, 10 mmHg or less, especially 5 mHg
mHg or less is preferable. A particularly preferred method is to use
In this method, the reaction is performed while introducing an inert gas.
In this way, the nearby yarns are
Can efficiently increase the degree of polymerization without inconvenience such as contact aggregation.
You can do it. In the melt polycondensation reaction, a catalyst is added.
Although it can be carried out without delay, in order to increase the polymerization rate,
It is carried out in the presence of a catalyst as required. As a polymerization catalyst
Is not particularly limited as long as it is used in this field.
But not lithium hydroxide, sodium hydroxide, potassium hydroxide
Alkali metals such as ium and calcium hydroxide
Potassium earth metal hydroxides; lithium aluminum hydride
System, sodium borohydride, tetramethyl borohydride
Hydrides of boron and aluminum such as luammonium
Alkali metal salts, alkaline earth metal salts, quaternary ammonium
Lithium hydride, sodium hydride, hydrogen
Alkali metals and alkaline earth metals such as calcium iodide
Hydrogen compounds; lithium methoxide, sodium ethoxide
Oxides, alkali metals such as calcium methoxide and
Alkoxides of alkaline earth metals; lithium phenoki
Sid, sodium phenoxide, magnesium phenoki
Sid, LiO-Ar-OLi, NaO-Ar-ONa
(Ar is an aryl group) alkali metals and alkalis
Earth metal aryloxides; lithium acetate, calcium acetate
Alkali metals such as sodium and sodium benzoate;
Organic salts of alkaline earth metals; zinc oxide, zinc acetate, zinc oxide
Zinc compounds such as lead phenoxide; boron oxide, boron
Acid, sodium borate, trimethyl borate, triborate
Butyl, triphenyl borate, (R¹R^Two R^ThreeR^Four) NB (R¹ R^Two
R^Three R^Four) Or (R¹R^Two R^ThreeR^Four) PB (R¹ R^TwoR^Three R^Four)
Ammonium borates or phosphonium borates
Class (R¹, R^Two, R^Three, R^FourIs as described in Chemical Formula 3)
Silicon compounds; silicon oxide, sodium silicate, tetra
Alkyl silicon, tetraaryl silicon, diphenyl-
Compounds of silicon such as ethyl-ethoxy silicon; oxidation
Germanium, germanium tetrachloride, germanium eth
Germanium such as oxide, germanium phenoxide
Compounds; tin oxide, dialkyltin oxide, dia
Lucyl tin carboxylate, tin acetate, ethyl tint
Alkoxy or aryloxy groups such as riboxide
Of tin such as tin compounds and organotin compounds combined with tin
Compounds: lead oxide, lead acetate, lead carbonate, basic carbonate, lead and
Such as alkoxide or aryloxide of organic and organic lead
A compound of the formula: quaternary ammonium salt, quaternary phosphonium
Onium compounds such as salts and quaternary arsonium salts; acids
Compounds of antimony, such as antimony chloride and antimony acetate
Manganese acetate, manganese carbonate, manganese borate
Which manganese compounds; titanium oxide, titanium alcohol
Compounds of titanium such as oxide or aryloxide;
Of zirconium acetate, zirconium oxide, zirconium
Alkoxide or aryloxide, zirconium acetyl
Catalysts such as zirconium compounds such as luacetone
I can list them. When a catalyst is used, these catalysts are one type.
Or may be used in combination of two or more.
good. The amount of these catalysts used depends on the aromatic di
Usually, 10^-9-10^-1weight
%, Preferably 10^-8-10^-2Weight% range
You. In the polycarbonate resin obtained by the method of the present invention
The number average molecular weight of the polycarbonate is usually 800 to 1
00000. An example of a preferable polymerization vessel used in the present invention is as follows:
A description will be given based on the drawings. 1 and 2 illustrate the method of the present invention.
It is a specific example of a polymerization vessel to be achieved. In FIG. 1, (A) AB
Melting of S resin and (B) polycarbonate prepolymer
The mixture is supplied from the raw material supply port 1 and passes through the perforated plate 3.
Film, thread, droplet, mist
The polymer 4 is formed. The inside of the polymerization vessel is cooled to a predetermined pressure.
Aromatic monophenol distilled from polymer
From the gas supply port 5 if necessary
Introduced inert gas such as nitrogen is exhausted from vent port 6.
Will be issued. The polymer is discharged from the discharge port 9 by the discharge pump 8.
Is discharged. A heater or jacket is used for
It is heated and kept warm by the kit. In FIG. 2, (A) ABS resin and
(B) Melt mixture with polycarbonate prepolymer
Is supplied to the circulation line 2 from the raw material supply port 1 and
3 and introduced into the inside of the polymerization vessel,
The polymer 4 is in the form of droplets or mist. The inside of the polymerization vessel is at a specified pressure.
Aroma controlled by force and distilled from polymer
Aromatic monohydroxy compound etc. and gas supply as needed
Inert gas such as nitrogen introduced from port 5 is vented
Exhausted from 6. Film, thread, droplet, mist
The polymer reaching the bottom of the polymerization vessel is circulated with a circulation pump 7.
Through the ring line 2, the perforated plate 3 is supplied again into the polymerization vessel.
Be paid. When the polymer reaches the specified molecular weight, the
8 through the outlet 9. Polymerizer 10 and circulation
Ring line 2 is heated by a heater or jacket.
And kept warm. When the polymerization vessel of FIG. 2 is used in a batch system,
Are (A) ABS resin and (B) polycarbonate prepo
The molten mixture with the limer is all supplied from the raw material supply port 1.
After the polymerization is performed, and after reaching a predetermined polymerization degree,
It is extracted. When used in a continuous system, (A) ABS
Melt mixing of resin and (B) polycarbonate prepolymer
The compound is continuously supplied from the raw material supply port 1, and the
Predetermined while controlling the amount of polymer to be constant
The polymer that has reached the molecular weight of is continuously extracted from the outlet 9.
put out. The polymerization vessel used in the method of the present invention is a polymerization vessel.
It is possible to equip Tom with a stirrer, etc., but it is especially necessary
is not. Therefore, there is no need for a rotation drive unit in the polymerization reactor body.
Condition, and good sealing even under high vacuum
Can be polymerized. Provided in the circulation line
There is a liquid head for the seal of the rotary drive of the circulation pump.
Therefore, it is better than the case where the polymerization
You. The method of the present invention can be carried out in one polymerization reactor.
It is possible, but two or more units may be used. Also, 1
Multi-stage polymerization vessel by dividing vertical polymerization group into vertical or horizontal type
It is also possible to do. In the present invention, in the molten mixture
Polycarbonate prepolymer to polycarbonate
All the steps to increase the molecular weight from the perforated plate freely
It is also possible to carry out the polymerization method while lowering,
It is also possible to carry out in combination with other polymerization methods. example
For example, a method of polymerizing while freely falling from a perforated plate
And stirred tank type polymerization device, thin film type polymerization device, screw type polymerization
And a method of polymerizing using a horizontal stirring polymerization vessel.
It is also possible to manufacture polycarbonate together.
You. The material of the polymerization vessel for achieving the method of the present invention is particularly
There is no restriction on the
It is selected from lath lining. Scale on the inner surface of the polymerization vessel
Of circulating polymer to prevent
It is also advantageous in the present invention that a wet wall is formed on the inner wall of the polymerization vessel at the portion.
This is one of preferred embodiments. In the present invention, a heat-resistant stabilizer, a mold release
Agents, weathering agents, coloring agents, flame retardants, fillers, acidic compounds, etc.
It may be added. These additives are the same as (A) ABS resin.
May be added at any time, or polycarbonate after the end of polymerization
The system resin may be added during the molten state. Also, Polica
-Pelletize the carbonate resin once and add the additives again.
It is also possible to melt and knead the product. [0074] DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described by way of examples.
You. The measurement was performed by the following method. Molecular weight: gel permeation chromatography
(GPC) number average molecular weight (hereinafter abbreviated as Mn)
You. ) And weight average molecular weight (hereinafter abbreviated as Mw).
You. Stability during molding: continuous at 250 ° C using an injection molding machine
During molding, the molding was stopped for 20 minutes and allowed to stay.
Started shape. Specimen appearance after stagnation and eye before and after stagnation
The retention rate of the zod impact strength was determined. [0075] Example 1 The reaction was carried out using a polymerization process as shown in FIG.
Responded. The polymerization vessel has 50 holes with a diameter of 7.5 mm.
With a perforated plate that can be freely dropped at a height of 4 m
It is. The extruder is a co-rotating twin screw extruder (45 mmφ, L
/ D = 30) and has a liquid inlet and a vent.
You. ABS tree containing 0.001% by weight of metal
Fat (Styrac ABS prototype manufactured by Asahi Kasei Kogyo Co., Ltd.)
A: butadiene content 15% by weight, unsaturation in the copolymer
27% by weight of sum nitrile compound unit, rubbery substance
30% by weight of bisphenol
A and diphenyl carbonate (based on bisphenol A mole
Polycarbonate of Mn6000 manufactured from 1.05)
30 liters of molten mixture of 70 parts by weight
In the polymerization vessel in advance and the same as this
Is supplied at a rate of 6 liters / hr,
Continuous extraction of molten mixture to keep the level constant
And fed to the extruder. Obtained points after steady state
Molecular weight M of polycarbonate in carbonate-based resin
w was 28,000. The polymerization reactor is operated at a reaction temperature of 240.
° C, reaction pressure 1.5mmHg, circulation flow rate 100 l
/ Hr, nitrogen gas flow rate 2 liter / hr, 10
The polymerization reaction was performed continuously for 00 hours. The extruder has a temperature of 24
The operation was performed at 0 ° C. and a rotation speed of 200 rpm. From liquid inlet
Is a screw with respect to 100 parts by weight of the supplied polycarbonate.
(Nonylphenyl) hydrogen phosphite is 0.0
The solution was dissolved in acetone so as to be 01 parts by weight and injected.
Acetone was extracted from the vent port by reducing the pressure to a vacuum. Push
The polycarbonate composition that came out of the machine was cooled and cooled.
And obtained continuously as pellets. The result
As a result, the hue of the obtained polycarbonate resin is good.
The stability during molding shows that the Izod impact strength retention rate is 67%.
%, And the appearance of the molded product was good. [0077] [Comparative Example 1] In Example 1, a polycarbonate was used without using an ABS resin.
Polymerization was performed using only the carbonate prepolymer. The result
As a result, the molecular weight of the obtained polycarbonate was Mw2200
It was as low as 0. [0078] Comparative Example 2 Including metal instead of ABS resin of Example 1
0.21% by weight (Styrac by Asahi Kasei Corporation)
ABS prototype B: butadiene content 15% by weight, weight
The ratio of the unsaturated nitrile compound unit in the union is 30% by weight.
%, Graft ratio to rubber-like substance is 50%)
Was carried out in the same manner as in Example 1. As a result,
The hue of the carbonate resin is slightly yellowish.
And the molecular weight of polycarbonate is as low as Mw 16600
Was something. [0079] [Comparative Example 3] Horizontal twin-screw agitation instead of perforated plate type polymerization vessel
Except for the production of polycarbonate using a mold polymerization vessel.
An aromatic polycarbonate composition was produced in exactly the same manner as in Example 1.
Built. However, in the case of a horizontal twin-screw polymerization reactor, the internal volume is 30
Liter, L / D = 6, 140 mm rotary diameter biaxial
With stirring blades, reaction temperature 275 ° C, reaction pressure
The conditions were 0.1 mmHg and an internal volume of 10 liters. Cheap
The molecular weight Mw of the polycarbonate after the transition to the steady state operation is 2
5300, low hue, yellowish brown
Was. [0080] Comparative Example 4 Commercially available polycarbonate (Mitsubishi Chemical Industries, Ltd.)
(NOVALEX 7025A: Mw27800) 7
0 parts by weight and 30 parts by weight of the ABS resin used in Comparative Example 2.
And extruder (co-directional twin screw extruder: 45 mmφ, L / D
= 30), temperature 285 ° C., rotation speed 200 rpm
And extruded into pellets. The resulting polycarbonate
The nitrate resin is colored yellow and the polycarbonate in the composition
The Mw of carbonate was also reduced to 25900. Ma
In addition, the stability at the time of molding was as follows.
%, And the appearance of the molded product is a large amount of silver.
And it was inferior. [0081] [Embodiment 2] A polycarbonate as shown in FIG.
A nate-based resin was produced. However, the first polymerization vessel of the stirring tank is
(A) and (B) are switched and operated in batches.
The other polymerization reactor was operated continuously. Stirring tank first polymerization vessel
(A) and (B) have an inner volume of 100 liters,
The internal volume of the polymerization vessel is 50 liters,
Are also anchor type. Perforated plate type first polymerization vessel, and perforated plate
The second type polymerization reactor has a multi-hole having 50 holes having a diameter of 7.5 mm.
Equipped with a perforated plate, the height of free fall is 4m
You. However, only the perforated plate type first polymerization reactor has a circulation line.
ing. In addition, a perforated plate type first polymerization device and a perforated plate type second polymerization device
It has a mixer between the vessels and supplies ABS resin
The second extruder (single screw 30mmφ, L / D = 30) is connected
ing. The first polymerization vessel in the stirring tank was used for both (A) and (B).
At a temperature of 180 ° C, a normal pressure, and a nitrogen gas flow rate of 1 l
This is the condition of the title / hr. Stirring tank first polymerization vessel (A)
In addition, bisphenol A and diphenyl carbonate (versus
80 mol of Sphenol A molar ratio 1.10)
r Melt and mix continuously at 5 liters / hr
It was supplied to the combiner. From the first polymerization vessel (A) to the first
2 While supplying to the polymerization vessel, the first polymerization vessel (B) in the stirring tank
In the same manner as in the first polymerization vessel (A) of the stirring tank, bisphenol A
And diphenyl carbonate are melted and mixed, and the first
When the combiner (A) becomes empty, the first polymerization vessel (B) in the stirring tank
Switched to. Thereafter, the first polymerization vessel of the stirring tank is similarly operated.
(A), (B) is the second stirring tank while switching batchwise
The polymerization intermediate is continuously supplied to the polymerization vessel at a rate of 5 L / hr.
Continued. The capacity of the second polymerization vessel in the stirred tank reaches 20 liters
Then, post-polymerization to keep the content 20 liters constant
Continuously supply the polymerization intermediate to the perforated plate type first polymerization vessel in the process
Was. The second polymerization vessel in the stirring tank has a reaction temperature of 230 ° C and a reaction pressure of
100 mmHg, nitrogen gas flow rate 2 liter / hr
It is. The perforated plate type first polymerization vessel has a capacity of 10 liters
Once reached, make sure to maintain a constant volume of 10 liters
The polymerization intermediate was continuously supplied to the plate-type second polymerization vessel. Perforated plate
The first type polymerization reactor has a reaction temperature of 240 ° C. and a reaction pressure of 2.5 m.
mHg, nitrogen gas flow rate 1 liter / hr, circulation amount 200
It is a condition of liter / hr. On the other hand, it was melted at 240 ° C. in the second extruder.
ABS resin (Stylac ABS prototype manufactured in Example 1)
Article-1) is supplied 100 weight of polycarbonate oligomer
33.3 parts by weight per part. porous
When the capacity of the plate type second polymerization vessel reaches 2 liters, the contents
Continuously drain the molten polymer to maintain a constant volume of 2 liters
The extruder was fed. Reaction temperature 240 ° C, reaction pressure
0.3 mmHg, nitrogen gas flow rate 1 liter / hr
It is. A perforated plate-type first polymerization reactor after transition to stable steady operation
The polymerized intermediate supplied to Mn has a Mn of 780,
Mn of the polymerization intermediate supplied to the second type polymerization reactor is 5,500.
Met. Also, polycarbonate supplied to the extruder
Mw was 24,000. The extruder is a biaxial pusher in the same direction.
Discharge port (30mmφ, L / D = 30)
Has a mouth, temperature 240 ° C, rotation speed 200rpm
Driven by Polycarbonate is supplied from the hopper mouth
Then, from the liquid inlet, supply polycarbonate 100 weight
Parts by weight of bis (nonylphenyl) hydrogenpho
0.001 parts by weight of sphite, Tris (2,4
0.01 parts by weight of t-butylphenyl) phosphite,
Octadecyl-3- (3,5-di-tert-butyl-4-hi
(Droxyphenyl) propionate is 0.01 part by weight
And condensed phosphate ester flame retardants (E890 manufactured by Daihachi Chemical)
Was adjusted to be 13.5 parts by weight and injected.
Add polytetrafluoroethylene powder (die
(Kin Kogyo Co., Ltd .: F201L) 0.4 parts by weight
Was. The polycarbonate resin discharged from the extruder is cooled
Continuously obtained as pellets
Was. As a result, the hue of the obtained polycarbonate resin
Is good, and the molecular weight of the polycarbonate in the composition is low.
There are few lower parts, and it has good physical properties such as stability during molding and flame retardancy.
Was. [0085] EFFECT OF THE INVENTION Polycarbonate excellent in hue, molding stability, etc.
Neat-based resin has excellent sealing properties under high vacuum and
Easy maintenance, stable polymerization for a long time, high polymerization rate
It can be manufactured in a fast and productive manner.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing one example of a polymerization vessel used in the present invention. FIG. 2 is a schematic view showing an example of a 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 an example of a process for achieving the method of the present invention. DESCRIPTION OF THE SYMBOLS In FIGS. 1 and 2, 1 a raw material supply port 2 a circulation line 3 a perforated plate 4 a polymer in the form of a film, a thread, a droplet, and a mist 5 a gas supply port 6 a vent port 7 a circulation pump 8 a discharge pump 9 Outlet 10 Polymerizer main body In FIG. 3, 1 Raw material supply port 2 Circulation line 3 Perforated plate 4 Film-, thread-, droplet-, or mist-like polymer 5 Gas supply port 6 Vent port 7 Circulation pump 8 Discharge pump 9 Discharge port REFERENCE SIGNS LIST 10 Polymerizer main body 11 Extruder 12 Hopper port 13 Heat resistant stabilizer tank 14 Liquid feed pump 15 Liquid inlet 16 Die 17 Cooling bath 18 Cutter 19 Discharge port 20 Vent port In FIG. 4, 1 Raw material supply port 1 ′ Raw material supply port 2 vent Port 2 'Vent Port 3 Stirring Tank First Polymerizer (A) 3' Stirring Tank First Polymerizer (B) 4 Polymerization Intermediate 5 Outlet 5 'Outlet 6 Transfer Pump 7 Supply Port 8 Stirring Tank Second Polymerizer Body 9 Ben Mouth 10 Polymerization intermediate 11 Outlet 12 Transfer pump 13 Supply port 14 Circulation line 15 Perforated plate 16 Perforated plate type first polymerization device 16 'Perforated plate type polymerization device 17 Film-like, thread-like, droplet-like, and mist-like polymer Reference Signs List 18 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 device 28 film-like, thread-like, droplet-like, and mist-like Polymer 29 Gas supply port 30 Vent port 31 Circulating pump 32 Molten polymer 33 Discharge pump 34 Discharge port 35 Extruder popper port 36 Mixer 37 Extruder 38 Die 39 Cooling bath 40 Cutter 41 Discharge port 42 Transfer line 43 Liquid feed pump 44 Stabilizer tank 45 Liquid injection port 46 Second extruder 47 Additive feeder 48 Addition port

Claims (1)

(57) [Claims 1] In a melt polymerization method of a polycarbonate resin, (A) A having a metal content of 10 ^-8 to 10 ^-1 % by weight.
A method for producing a polycarbonate resin, wherein a molten mixture of a BS resin and (B) a polycarbonate prepolymer is polymerized while being freely dropped from a perforated plate in a molten state.