CN101668792B

CN101668792B - Method for production of aromatic polycarbonate resin composition

Info

Publication number: CN101668792B
Application number: CN2008800137755A
Authority: CN
Inventors: 熊泽胜久; 田浦隆之; 山本正规
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Chemical Corp; Mitsubishi Rayon Co Ltd
Priority date: 2007-04-27
Filing date: 2008-04-25
Publication date: 2012-07-25
Anticipated expiration: 2028-04-25
Also published as: CN101668792A; WO2008136440A1

Abstract

Disclosed is a method for producing an aromatic polycarbonate resin composition having stabilized quality by mixing an aromatic polycarbonate resin with an additive such as a thermal stabilizer homogeneously. Specifically disclosed is a method for producing an aromatic polycarbonate resin composition, which comprises the following steps: a polycarbonate feed step for feeding an aromatic polycarbonate in a molten state to an extruder continuously; an extrusion step for mixing the aromatic polycarbonate with a thermal stabilizer in the extruder and extruding the mixture from the extruder; a pellet formation step for pelletizing the aromatic polycarbonate extruded from the extruder to form a pellet of the aromatic polycarbonate; and a pellet circulation/feed step for collecting a part of the aromatic polycarbonate pellets, and continuously feeding the pellet impregnated with the thermal stabilizer to the extruder into which the aromatic polycarbonate is to be fed in the polycarbonate feed step, while impregnating the pellet with the thermal stabilizer continuously.

Description

The method of manufacture of aromatic copolycarbonate resin composition

Technical field

The present invention relates to the method for manufacture of aromatic copolycarbonate resin composition, in more detail, the present invention relates to method of manufacture based on the aromatic copolycarbonate resin composition of transesterification reaction.

Background technology

In recent years, aromatic polycarbonate resin is widely used in office automation parts, trolley part, material of construction etc. as also excellent engineering plastics such as mechanical characteristics excellence such as shock-resistance and thermotolerance, the transparencys.Particularly be widely used in as optics with the optical lens of material and record with purposes such as CD, sheet material, bottles, to bring into play characteristics such as its shock-resistance and the transparency.

Method of manufacture as such aromatic polycarbonate resin; Past is with regard to known so-called scorification; Promptly under molten state, make aromatic diol and carbonic diester generation transesterify, when the low molecular weight substances such as phenol that will generate as by product are removed to outside the system, obtain the method for aromatic polycarbonate resin continuously.

At this, use under the situation of aromatic polycarbonate resin as material, in order to keep and to improve its performance, be used after adding various thermo-stabilizers mostly.These thermo-stabilizers are mixed in the aromatic copolycarbonate through the mixing method of utilizing forcing machine usually and are disperseed and homogenizing (referring to patent documentation 1).

Patent documentation 1: japanese kokai publication hei 8-259687 communique

Summary of the invention

Yet, for example make under the situation of aromatic polycarbonate resin with scorification, in being located at the forcing machine of making the line back segment, various additives such as the aromatic polycarbonate resin of molten state and thermo-stabilizer are mixed usually.Then, the aromatic polycarbonate resin of being extruded by forcing machine is shaped to the particle of predetermined size, becomes product.

But the additive that is added into aromatic polycarbonate resin is Powdered or liquid form mostly, and its consumption is few.Therefore, when utilizing forcing machine mixed aromatic polycarbonate resin and additive, can deposit under many circumstances distribution of additives uneven, can not mixed uniformly problem.

In this case, can consider to add the method in the forcing machine to the form of the masterbatch that constitutes by additive and suitable polymkeric substance in advance.But when for example using mixing machine such as Henschel mixer to prepare masterbatch, under a lot of situation, pulverous additive can classification and can't obtain uniform dispersion state.And liquid additive also can separate behind the preparation masterbatch sometimes.

And,, therefore in the processes such as switching of product, can produce the transition article because above-mentioned scorification is normally made the method for aromatic polycarbonate resin continuously.And such transition article are off-specification material, thereby can be processed as production loss article usually.

But from the raw material availability of product and the aspect that economizes on resources, it is nonideal disposing such production loss article, and hope can utilize effectively.Yet, if with such production loss article cycling and reutilization, the variation of the thermostability of product meeting sometimes, commodity value reduces.

The object of the present invention is to provide a kind of method of manufacture of aromatic copolycarbonate resin composition, wherein,, produce the stable aromatic copolycarbonate resin composition of quality additive and aromatic polycarbonate resin uniform mixing such as thermo-stabilizers.

In order to solve above-mentioned problem, the inventor has carried out deep research, and the result finds; If utilize the branch road pipe arrangement that diverges to by air conveying pipe arrangement to carry out air conveying to the aromatic copolycarbonate particle that includes thermo-stabilizer; And after wherein adding thermo-stabilizer, supply to continuously in the forcing machine, then can also effectively utilize above-mentioned production loss article; These production loss article are dropped to bottom line to the influence of quality, accomplished the present invention based on these discoveries.

Like this; The present invention can provide a kind of method of manufacture of aromatic copolycarbonate resin composition; It is the method for manufacture that contains the aromatic copolycarbonate resin composition of thermo-stabilizer; It is characterized in that comprising following operation: polycarbonate is supplied with operation, is supplied to the aromatic copolycarbonate of molten state in the forcing machine continuously; Extrude operation, utilize forcing machine to supply with the aromatic copolycarbonate that supply comes in the operation and mix, and extrude by forcing machine with thermo-stabilizer at polycarbonate; Granulating working procedure, the aromatic copolycarbonate granulation that will in extruding operation, extrude, the particle of formation aromatic copolycarbonate by forcing machine; Operation is supplied with in circulation with particle; Divide the particle that is taken at the partially aromatic polycarbonate after the granulation in the granulating working procedure; Continuously thermo-stabilizer is being added in particle; To add the particle that thermo-stabilizer is arranged simultaneously and be supplied to continuously in the forcing machine, this forcing machine is to supply with the forcing machine that is supplied to aromatic copolycarbonate in the operation at polycarbonate.

Here; In the method for manufacture of the aromatic copolycarbonate resin composition that the present invention was suitable for; Preferred comprise that also the particle through the aromatic copolycarbonate after carrying pipe arrangement to granulation in granulating working procedure carries out air conveying air conveying operation, and through carrying out air conveying by the branch road pipe arrangement of carrying pipe arrangement to diverge to the particle of the partially aromatic polycarbonate that in granulating working procedure, obtains.

Then, in the method for manufacture of the aromatic copolycarbonate resin composition that the present invention was suitable for, preferably supply with the particulate thermo-stabilizer that is adding in the operation in aromatic copolycarbonate and be liquid state in the particle circulation.Here, the particle circulation is supplied with in the operation, is adding in the particulate thermo-stabilizer of aromatic copolycarbonate being preferably the acidic cpd or derivatives thereof.And thermo-stabilizer is preferably liquid and can have sulfonic acid or its ester that carbonatoms is 1～10 alkyl substituent.

Then; In the method for manufacture of the aromatic copolycarbonate resin composition that the present invention was suitable for; Preferably in the particle circulating process; With respect to the particle of 100 weight part aromatic copolycarbonates, make the thermo-stabilizer of 0.001 weight part～1 weight part add particle continuously in aromatic copolycarbonate.

In addition, preferably supply with in the operation, be supplied to the aromatic copolycarbonate of forcing machine with respect to 100 weight parts in particle circulation, with pellet supply that 0.5 weight part～5 weight parts are adding the aromatic copolycarbonate that thermo-stabilizer is arranged to forcing machine.

And, in the method for manufacture of the aromatic copolycarbonate resin composition that the present invention was suitable for, the preferred viscosity-average molecular weight (Mv of the aromatic copolycarbonate after the granulation in granulating working procedure ₁) be not more than in extruding operation the viscosity-average molecular weight (Mv with the aromatic copolycarbonate of thermo-stabilizer blended molten state in forcing machine ₂) (be Mv ₁≤Mv ₂).

In addition, preferably in extruding operation, with respect to 100 weight part aromatic copolycarbonates, with the amount mixture heat stablizer below 0.002 weight part.

And the aromatic copolycarbonate that preferably in polycarbonate is supplied with operation, is supplied to forcing machine is to be that catalyzer and the polycondensation through aromatic dihydroxy compound and carbonic diester obtain with the basic cpd.

The present invention can the stable aromatic copolycarbonate resin composition of quality bills of materials.And, can expect that also the present invention improves raw material availability with easy method, help to economize on resources.

Description of drawings

Fig. 1 representes an example of the manufacturing installation of aromatic copolycarbonate resin composition.

The example that Fig. 2 representes to use 2 above stirrers, adding the manufacturing installation of the aromatic copolycarbonate resin composition in the situation of additives such as thermo-stabilizer.

Nomenclature

2a... the 1st feedstock production groove, 2b... the 2nd feedstock production groove, 3a, 3b... anchor type stirring rake, 4a... raw material supplying pump, 5a... catalyzer supplying opening, 6a... the 1st vertical reactor, 6b... the 2nd vertical reactor, 6c... the 3rd vertical reactor, 7a, 7b, 7c...Maxblend oar, 8a; 8b, 8c, 8d... still tube, 9a... the 4th horizontal reactor, 10a... grid oar (the grid wing), 11a... forcing machine, 12a; 12b, 12c... additive supply line, 13a... cooling tank (strand bath), 14a... line material cutter, 15a... sieve apparatus, 16a, 16b; 16c... product bunker, 21a, 21b... stirrer, 22a, 22b... thermo-stabilizer supplying opening, 81a; 81b, 81c, 81d... condensing surface, 82a; 82b, 82c, 82d... are connected to the pipe arrangement of reliever.

Embodiment

Below, specific embodiments of the invention (below be called the working of an invention mode) is elaborated.Need to prove that the present invention is not limited to following embodiment, can in the scope of its main points, carry out various distortion and implement.And employed accompanying drawing is in order embodiment of the present invention to be described, not to be represented physical size.

(polycarbonate resin)

Among the present invention, polycarbonate resin is to make through the melt phase polycondensation based on the transesterification reaction of aromatic dihydroxy compound and carbonic diester.

Below, to through using aromatic dihydroxy compound and carbonic diester, in the presence of transesterification catalyst, carry out melt polycondensation reaction continuously and make the method for polycarbonate resin and describe as raw material.

(aromatic dihydroxy compound)

As the aromatic dihydroxy compound that uses in embodiments of the present invention, can enumerate the compound shown in the formula (1).

General formula (1)

Here, in the general formula (1), A be singly-bound or have substituting group also can carbonatoms be 1～10 straight chain shape, branched or cyclic divalent alkyl, or with-O-,-S-,-CO-or-SO ₂The divalent group of-expression.X and Y are that halogen atom or carbonatoms are 1～6 alkyl independently of one another.P and q are 0～2 integer independently of one another.Need to prove that X and Y can be the same or different, p and q can be the same or different.

As the concrete example of aromatic dihydroxy compound, for example can enumerate two (4-hydroxy diphenyl) methane, 2, two (4-hydroxy phenyl) propane, 2 of 2-; Two (the 4-hydroxy-3-methyl phenyl) propane, 2 of 2-, two (4-hydroxyl-3-tert-butyl-phenyl) propane, 2 of 2-, two (the 4-hydroxyls-3 of 2-; The 5-3,5-dimethylphenyl) propane, 2, two (4-hydroxyl-3, the 5-dibromo phenyl) propane, 4 of 2-; Two (4-hydroxy phenyl) heptane, 1 of 4-, bisphenols such as 1-bis(4-hydroxyphenyl) cyclohexane; 4,4 '-dihydroxybiphenyl, 3,3 ', 5,5 '-tetramethyl--4, biphenyl phenols such as 4 '-dihydroxybiphenyl; Two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) ketone etc.

Among these, preferred 2, two (4-hydroxy phenyl) propane of 2-(" dihydroxyphenyl propane ", below abbreviate BPA sometimes as).These aromatic dihydroxy compounds can use separately, perhaps can mix two or more the use.

(carbonic diester)

As the carbonic diester that uses in embodiments of the present invention, can enumerate the compound shown in the formula (2).

General formula (2)

Here, in the general formula (2), A ' for have substituting group also can carbonatoms be 1～10 straight chain shape, branched or cyclic 1 valency alkyl.2 A ' can be identical, also can be different.

Need to prove,, can enumerate halogen atom, carbonatoms and be 1～10 alkyl, carbonatoms and be 1～10 alkoxyl group, phenyl, phenoxy, vinyl, cyanic acid, ester group, carboxamido-group, nitro etc. as the substituting group on the A '.

As the concrete example of carbonic diester, for example can enumerate diphenyl carbonate, dimethyl benzyl etc. and be with substituent diphenyl carbonate; Dialkyl carbonates such as methylcarbonate, diethyl carbonate, dimethyl dicarbonate butyl ester.

Among these, preferred diphenyl carbonate (the following DPC that abbreviates as sometimes), be with substituent diphenyl carbonate.These carbonic diesters can use separately, perhaps can mix two or more the use.

And, can replace preferred 50 moles below the %, the further above-mentioned carbonic diester of preferred 30 moles of amounts below the % with dicarboxylicacid or dicarboxylic ester.

As representational dicarboxylicacid or dicarboxylic ester, for example can enumerate terephthalic acid, m-phthalic acid, terephthaldehyde's diphenyl phthalate, diphenylisophthalate etc.Under the situation of replacing with such dicarboxylicacid or dicarboxylic ester, can obtain polyestercarbonate.

These carbonic diesters (comprise dicarboxylicacid or dicarboxylic ester after the above-mentioned replacement.Below identical) excessively use with respect to dihydroxy compound.

That is, with respect to aromatic dihydroxy compound, the mol ratio of employed carbonic diester is preferably more than 1.01, is preferably more than 1.02 especially, and is preferably below 1.30, is preferably below 1.20 especially.Said mol ratio was less than 1.01 o'clock, and the terminal OH base of resulting polycarbonate resin becomes many, and the thermostability of resin aggravates.And said mol ratio was greater than 1.30 o'clock, and the speed of response of transesterify reduces; The polycarbonate resin that production has desired molecular weight is tending towards difficulty; And the remaining quantitative change of the carbonic diester in the resin is many, when shaping adds man-hour or processes molding, causes peculiar smell sometimes, thereby not preferred.

(transesterification catalyst)

Do not limit the transesterification catalyst that uses in the embodiment of the present invention is special, can enumerate the catalyzer that uses when utilizing ester-interchange method to make aromatic copolycarbonate usually.In general, for example can enumerate basic cpds such as alkali metal cpd, beryllium or magnesium compound, alkaline earth metal cpds, alkaline boron cpd, alkaline phosphating compound, alkaline ammonium compound or amine compound.

In these transesterification catalysts, from the purpose of embodiment of the present invention---the aspect that a spot of thermo-stabilizer is dispersed in the aromatic copolycarbonate resin composition is considered that the effect of alkali metal cpd or alkaline earth metal cpds is better.These transesterification catalysts can use a kind of, also can make up two or more the use.

About the consumption of transesterification catalyst, with respect to 1 mole of aromatic dihydroxy compound, transesterification catalyst preferably uses 1 * 10 usually ^-9More than the mole, preferred especially 1 * 10 ^-7More than the mole, and, preferably use 1 * 10 ^-1Below the mole, preferred especially 1 * 10 ^-2Below the mole.

As alkali metal cpd, can enumerate inorganic base metal compounds such as alkali-metal oxyhydroxide, carbonate, bicarbonate compound; The organic alkali metal compounds such as salt of basic metal and alcohols, phenol, organic carboxyl acid class etc.As basic metal, for example can enumerate lithium, sodium, potassium, rubidium, caesium here.

Among these alkali metal cpds, preferred caesium cpd, preferred especially cesium carbonate, cesium bicarbonate, cesium hydroxide.

As beryllium or magnesium compound and alkaline earth metal cpds, for example can enumerate the mineral alkali earth metal compound such as oxyhydroxide, carbonate of beryllium, magnesium, alkaline-earth metal; The salt of these metals and alcohols, phenols, organic carboxyl acid class etc.As earth alkali metal, can enumerate calcium, strontium, barium here.

As alkaline boron cpd, can enumerate sodium salt, sylvite, lithium salts, calcium salt, magnesium salts, barium salt, strontium salt of boron cpd etc.Here; As boron cpd, for example can enumerate tetramethyl-boron, tetraethyl-boron, tetrapropyl boron, tetrabutyl boron, trimethylammonium ethyl boron, trimethyl benzyl boron, trimethylphenyl boron, triethyl methyl boron, triethyl benzyl boron, triethyl phenyl boron, tributyl benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyl triphenyl-boron, methyl triphenyl boron, butyl triphenyl boron etc.

As the alkaline phosphating compound, for example can enumerate 3 valency phosphorus compounds such as triethyl phosphine, three n-propyl phosphines, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine, tributylphosphine or by these compound derivings De quaternary alkylphosphonium salt etc.

As alkaline ammonium compound, for example can enumerate tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide trimethylammonium ethyl ammonium, benzyltrimethyl ammonium hydroxide, hydroxide trimethylphenyl ammonium, hydroxide triethyl ammonium methyl, hydroxide triethyl hexadecyldimethyl benzyl ammonium, hydroxide triethyl phenyl ammonium, hydroxide tributyl hexadecyldimethyl benzyl ammonium, hydroxide tributyl phenyl ammonium, hydroxide tetraphenyl ammonium, hydroxide benzyl triphenyl ammonium, hydroxide methyl triphenyl ammonium, hydroxide butyl triphenyl ammonium etc.

As amine compound; For example can enumerate 4-aminopyridine, 2-EL-970, N, N-dimethyl--4-aminopyridine, 4-diethyl amino yl pyridines, 2 hydroxy pyrimidine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylamino imidazoles, 2-methoxyl group imidazoles, imidazoles, 2-mercaptoimidazole, glyoxal ethyline, quinolylamine etc.

(method of manufacture of aromatic copolycarbonate)

Method of manufacture in the face of aromatic copolycarbonate describes down.

The manufacturing of aromatic copolycarbonate is carried out as follows: preparation comprises the mixture (preparation of raw material operation) of raw material aromatic dihydroxy compound and material carbon acid diesters; In the presence of catalyst for ester exchange reaction; Use the reactor drum more than 2, the mixture that makes these compounds with molten state is with multistage mode generation polycondensation (polycondensation step).Reactive mode can be any in the combination of batch-type, continous way or batch-type and continous way, the preferred continous way from the aspect of productivity and quality stability.Under the situation of continous way, reactor drum generally is made up of the reactor drum that series connection more than 2 is provided with, and preferably uses 2 above vertical reactors and is connected at least 1 horizontal reactor thereafter.

In the embodiment of the present invention, use forcing machine, the preferred double-screw type forcing machine that uses with the venting port that can the unreacting material in the reaction solution and byproduct of reaction devolatilization be removed in order behind polycondensation step, to add thermo-stabilizer.

Then, each operation to the method for manufacture of aromatic copolycarbonate describes.

(preparation of raw material operation)

Usually under inert gas atmosphere such as nitrogen, argon, use the device of the stirring grooved of batch-type, semibatch or continous way, will be prepared into molten mixture as the aromatic dihydroxy compound and the carbonic diester of the raw material of aromatic copolycarbonate.For example; Use dihydroxyphenyl propane as aromatic dihydroxy compound, use under the situation of diphenyl carbonate as carbonic diester, the temperature of melting mixing is selected from and is preferably more than 120 ℃, is preferably more than 125 ℃ especially and is preferably below 180 ℃, is preferably especially the scope below 160 ℃.

At this moment; The blending ratio of aromatic dihydroxy compound and carbonic diester is adjusted so that carbonic diester is excessive; And adjust to respect to 1 mole of aromatic dihydroxy compound, the ratio that makes carbonic diester is preferred more than 1.01 moles, preferred especially more than 1.02 moles and preferred below 1.30 moles, preferred especially below 1.20 moles.

(polycondensation step)

Carry out continuously with the multisegment mode that is generally more than 2 stages, is preferably 3 sections～7 sections based on the polycondensation of the transesterification reaction of aromatic dihydroxy compound and carbonic diester.

As concrete reaction conditions, scope is following: temperature is 150 ℃～320 ℃, and pressure is normal pressure～0.01Torr (1.3Pa), and the mean residence time in 1 stage is 5 minutes～150 minutes.

In each reactor drum when carrying out polycondensation step, more effectively discharge, in above-mentioned reaction conditions, be set at more high temperature, high vacuum more usually step by step for the phenol that will be along with the carrying out of polycondensation generates as by product with multistage.Need to prove that the reduction for the qualities such as tone that prevent resulting aromatic polycarbonate resin preferably is set at low temperature, short residence time(SRT) as far as possible.

Carry out with multisegment mode under the situation of polycondensation step, 2 above vertical reactors and the reactor drum that is connected at least 1 thin film evaporation excellent performance thereafter preferably are set, so that the molecular-weight average of aromatic polycarbonate resin increases.Reactor drum is provided with 3～6 usually, is preferably 4～5.

Here; As the reactor drum of thin film evaporation excellent performance, for example can use film reactor, centrifugal thin film evaporation reactor drum, Surface Renewal type twin-screw mixer reactor drum, the horizontal stirred reactor of twin screw, wet wall type reactor drum, free-fallingly carry out polymeric porous template reactor drum simultaneously, carry out polymeric band porous template wiry reactor drum etc. when falling along wire.

As the form of the stirring rake of vertical reactor, for example can enumerate turbine oar, impeller oar, three leaf swept-back (Pfaudler) oars, anchor oar, general can formula (full zone) oar (KOBELCOECO-SOLUTIONS of Co., Ltd. manufacturing), SANMELER oar (Mitsubishi Heavy Industry Ltd.'s manufacturing), Maxblend oar (Mitsushige Maching Co., Ltd.'s manufacturing), ribbon oar, spiral grid oar (Hitachi Plant Technologies, Ltd's manufacturing) etc.

And horizontal reactor is meant that the turning axle of stirring rake is the reactor drum of horizontal (horizontal direction).As the stirring rake of horizontal reactor, for example can enumerate single-shaft variant stirring rakes such as rondelle, impeller type; HVR, SCR, N-SCR (Mitsubishi Heavy Industry Ltd.'s manufacturing), Bivolac (Mitsushige Maching Co., Ltd.'s manufacturing) or spectacle oar, grid oar biaxial type stirring rakes such as (Hitachi Plant Technologies, Ltd's manufacturings).

Need to prove that the transesterification catalyst that is used for the polycondensation of aromatic dihydroxy compound and carbonic diester is prepared into the aqueous solution usually in advance.Do not limit the concentration of aqueous catalyst solution is special, be adjusted into concentration arbitrarily according to the solubleness of catalyzer in water.And, also can use other organic solvent such as acetone, alcohol, toluene, phenol to replace water.

Do not limit the water that is used for catalyst-solvent is special, if the kind and the constant concentration of the impurity that is contained, preferred usually zero(ppm) water, the deionized water etc. of using.

(manufacturing installation)

Next, specify based on the example of accompanying drawing the method for manufacture of the aromatic copolycarbonate resin composition that embodiment of the present invention was suitable for.

Fig. 1 is the synoptic diagram of an example that shows the manufacturing installation of aromatic copolycarbonate resin composition.In the manufacturing installation shown in Figure 1, the following operation of the manufacturing of aromatic copolycarbonate process: the preparation of raw material operation of preparation raw material aromatic dihydroxy compound and material carbon acid diesters; Use 2 above reactor drums to make these raw materials that the polycondensation step of polycondensation take place under molten state.

Then, stopped reaction is through the operation that the unreacting material in the polymerization liquid and byproduct of reaction devolatilization are removed; Add the operation of thermo-stabilizer, release agent, tinting material etc.; After making aromatic polycarbonate resin form the particulate operation of predetermined particle diameter, be shaped to the particle of aromatic copolycarbonate resin composition.

In the preparation of raw material operation, be provided with the 1st feedstock production groove 2a, the 2nd feedstock production groove 2b that is connected in series and be used for raw material supplying pump 4a the raw material supplying for preparing to polycondensation step.Be respectively equipped with for example anchor

type stirring rake

3a, 3b among the 1st feedstock production groove 2a and the 2nd feedstock production groove 2b.

And; In the 1st feedstock production groove 2a; 1a-1 supplies with DPC with molten state by the DPC supplying opening, supplies with the dihydroxyphenyl propane (the following BPA that is designated as sometimes) as aromatic dihydroxy compound by BPA supplying opening 1b with pulverulence, and dihydroxyphenyl propane is dissolved in the diphenyl carbonate after the fusion.

Then, in polycondensation step, be provided with the 1st vertical reactor 6a, the 2nd vertical reactor 6b and the 3rd vertical reactor 6c that is connected in series and the 4th horizontal reactor 9a that is connected in series in the back segment of the 3rd vertical reactor 6c.In the 1st vertical reactor 6a, the 2nd vertical reactor 6b and the 3rd vertical reactor 6c, be respectively equipped with

Maxblend oar

7a, 7b, 7c.And, in the 4th horizontal reactor 9a, be provided with grid oar 10a.

Need to prove, be separately installed with still

tube

8a, 8b, 8c, the 8d that is used for the discharges such as by product of polycondensation generation on 4 reactor drums.Still

tube

8a, 8b, 8c, 8d are connected with condensing

surface

81a, 81b, 81c, 81d respectively, and, utilize the connecting

pipings

82a, 82b, 82c, the 82d that link to each other with reliever to make each reactor drum remain on predetermined decompression state.

In the manufacturing installation of aromatic copolycarbonate resin composition shown in Figure 1, with under the nitrogen atmosphere under the DPC fused solution of predetermined temperature preparation and nitrogen atmosphere the BPA powder after the weighing supply to continuously the 1st feedstock production groove 2a from DPC supplying opening 1a-1 and BPA supplying opening 1b respectively.When the liquid level of the 1st feedstock production groove 2a surpass with carry pipe arrangement in the identical height of most significant digit the time, raw mix is transported to the 2nd feedstock production groove 2b.

Then, raw mix is supplied among the 1st vertical reactor 6a via raw material supplying pump 4a continuously.In addition, supply with cesium carbonate aqueous solution continuously by the catalyzer supplying opening 5a in the conveying pipe arrangement way of raw mix as catalyzer.

Among the 1st vertical reactor 6a; Under nitrogen atmosphere, under the condition of for example 220 ℃ of temperature, pressure 13.33kPa (100Torr), keeping the rotating speed of Maxblend oar 7a is 160rpm; When removing by-product phenol from still tube 8a distillation; Keep liquid level constant,, carry out polycondensation so that mean residence time is 60 minutes.Then, the polymerization liquid of discharging from the 1st vertical reactor 6a then supplies to the 2nd vertical reactor 6b, the 3rd vertical reactor 6c, the 4th horizontal reactor 9a successively continuously, carries out polycondensation.For the reaction conditions in each reactor drum, usually be set at high temperature, high vacuum, low stirring velocity respectively along with the carrying out of polycondensation, can suitably adjust according to desired performance (for example, desired molecular weight etc.).During polycondensation, the control liquid level is so that the mean residence time in each reactor drum in addition, in each reactor drum, distills out by-product phenol by still

tube

8b, 8c, 8d for for example about 60 minutes.

Need to prove that in the embodiment of the present invention, by products such as recovery phenol continuously liquefy from condensing surface 81a, the 81b that is installed on the 1st vertical reactor 6a and the 2nd vertical reactor 6b respectively.And, between the condensing surface 81c, the 81d that are installed on the 3rd vertical reactor 6c and the 4th horizontal reactor 9a respectively and the connecting pipings 82c that links to each other with reliever, 82d, being provided with cold-trap (not shown), by product is reclaimed in condensation continuously-curing.

Then, will keep molten state to be supplied to the double-screw type forcing machine 11a with 3 sections venting ports from the aromatic copolycarbonate that the 4th horizontal reactor 9a extracts out.Respectively following various additives are supplied to the forcing machine 11a from

additive supply line

12a, 12b, 12c: for example, polymkeric substance such as thermo-stabilizer, inhibitor, weather resisting agent, release agent, lubricant, static inhibitor, softening agent, pigment, dyestuff, weighting agent, toughener, fire retardant, other resins or rubber, or the like.

Here, as thermo-stabilizer, for example can enumerate phosphorus is that stablizer, hindered phenol are that stablizer, sulphur are that stablizer, epoxy are that stablizer, hindered amine are stablizer etc.The concrete example of preferred thermo-stabilizer is seen after and is stated.

Thermo-stabilizer can use separately, also can make up use.Do not limit addition is special, but use the thermo-stabilizer of 0.0001 weight part～0.5 weight part, preferred 0.001 weight part～0.2 weight part with respect to 100 weight part aromatic copolycarbonates usually.Wherein supply with under the thermo-stabilizer situation with liquid state, consumption is below 0.005 weight part, is preferably below 0.002 weight part, more preferably below 0.001 weight part.

Here, in the embodiment of the present invention, as after state, thermo-stabilizer is adding in the aromatic copolycarbonate particle continuously, is supplied to continuously among the forcing machine 11a by additive supply line 12a again.

Aromatic copolycarbonate and thermo-stabilizer be melting mixing in the inside of forcing machine 11a, is extruded by export department.Aromatic copolycarbonate is extruded into line material shape through the hole (not shown) of being located at export department when being extruded by forcing machine 11a.

And the aromatic copolycarbonate of line material shape utilizes line material cutter 14a granulation via the cooling tank 13a water cooling that is cooled, remove moisture through sieve apparatus 15a after, import

product bunker

16a, 16b.

And in the preferred implementation of the present invention, the part of this end product aromatic copolycarbonate resin composition (aromatic copolycarbonate particle) of product (promptly as) also imports product bunker 16c through the branch road pipe arrangement that is diverged to by air conveying pipe arrangement.

Supply with through rare gas elementes such as air compressed or nitrogen to this air conveying pipe arrangement through not shown compressor, thereby can carry out air conveying the aromatic copolycarbonate particle.

(adding continuously of thermo-stabilizer)

In the embodiment of the present invention, the aromatic copolycarbonate particle that is stored among the product bunker 16c passes through air conveying pipe arrangement, is supplied in a suitable manner among the stirrer 21a, preferably supplies with continuously.In order stably in stirrer 21a, to supply with continuously; Also can be equipped with and be used to supply with aromatic copolycarbonate particulate hopper and doser; 16c supplies with to hopper discontinuously by the product bunker; Use doser by hopper continuously with the aromatic copolycarbonate pellet supply to stirrer 21a, this does not demonstrate in Fig. 1.

Thermo-stabilizer is supplied among the stirrer 21a through thermo-stabilizer supplying opening 22a continuously.Then, in stirrer 21a, continuously thermo-stabilizer is being added in the aromatic copolycarbonate particle.Churning time is preferably 1 minute～and 20 minutes, further be preferably 5 minutes～10 minutes.When churning time was long, then device often became excessive, when churning time is too short, then was tending towards insufficient to whole the adding of aromatic copolycarbonate particle.

In this case; Do not limit in stirrer 21a, adding continuously in the amount of aromatic copolycarbonate particulate thermo-stabilizer is special; Common particle with respect to 100 weight part aromatic copolycarbonates; Thermo-stabilizer is 0.001 weight part～1 weight part, is preferably 0.005 weight part～0.5 weight part, further is preferably 0.01 weight part～0.2 weight part.

Adding when the amount of aromatic copolycarbonate particulate thermo-stabilizer is too much, then the dispersiveness of thermo-stabilizer in forcing machine 11a reduces, and has the tendency that tone deterioration and streaking etc. appear in the aromatic copolycarbonate that obtains as product.And, adding when the amount of aromatic copolycarbonate particulate thermo-stabilizer is very few, then make the particulate feed rate that is supplied in the forcing machine 11a be tending towards increasing in order to ensure the specified amount of thermo-stabilizer.In this case, cause in forcing machine 11a, supplying with the aromatic copolycarbonate particle of a large amount of before existing thermal histories.The result not only can cause worsening as the tone of the aromatic copolycarbonate of product acquisition, also can cause the running of forcing machine 11a to become unstable, has the tendency that makes stirrer 21a bear HD.

(the aromatic copolycarbonate particulate adds continuously)

Then; As stated; The aromatic copolycarbonate particle that in stirrer 21a, has added thermo-stabilizer continuously circulates continuously through additive supply line 12a and is supplied among the forcing machine 11a, mixes with fusion aromatic copolycarbonate in the forcing machine 11a.

Need to prove,, adding being meant, make the state of thermo-stabilizer attached to this degree on the aromatic copolycarbonate particle through mixing at this.

Do not limit stirrer 21a is special, get final product, for example can enumerate helical ribbon agitator etc. so long as can carry out the blended machine continuously.And,, thereby preferably under inert gas atmospheres such as nitrogen, operate because the oxygen that the aromatic copolycarbonate pellet supply is carried secretly during to forcing machine 11a can cause product quality to reduce.Particularly in stirrer 21a, import the thermal degradation when that nitrogen has suppressed product effectively.

And, can supply with the thermo-stabilizer more than 2 kinds to stirrer 21a, can also supply with the additive beyond the thermo-stabilizer simultaneously, for example release agent, tinting material, UV light absorber etc.

In addition, the additive of being supplied with by

additive supply line

12b, 12c also can be with supplying with the same method of additive supply line 12a.

When establishing when being supplied to aromatic copolycarbonate among the forcing machine 11a and being 100 weight parts by the 4th horizontal reactor 9a; The amount of the aromatic copolycarbonate resin composition of circulation supply is generally 0.1 weight part～10 weight parts continuously in forcing machine 11a; Be preferably 0.5 weight part～5 weight parts, more preferably 1 weight part～4 weight parts.When the amount of the aromatic copolycarbonate resin composition that circulation is supplied with in forcing machine 11a is very few, be difficult for producing effect of the present invention, and too much the time, then the thermostability of product is easy to worsen.

And, not limiting aromatic copolycarbonate particulate size, shape etc. are special, it is the size below the 20mm that particle preferably is processed into maximum length usually.And, can use the particle of granular, amorphous, tabular, shape such as cylindric, wherein consider preferably granular, cylindric, especially preferably cylindric from the aspect that is easy to obtain.

As stated, in the embodiment of the present invention, the particle of the aromatic copolycarbonate of part after as the granulation of product is taken out, to wherein adding thermo-stabilizer continuously, then, the thermo-stabilizer that will add on particle supplies in the forcing machine continuously.Therefore thermo-stabilizer is mixed equably with the aromatic polycarbonate resin of molten state.In addition, be supplied to continuously in the forcing machine, can obtain the aromatic copolycarbonate resin composition of stay in grade, and can not cause the rotten of thermo-stabilizer and separate through adding the particle that thermo-stabilizer is arranged.

And in the embodiment of the present invention, the aromatic copolycarbonate particle itself that is supplied by product bunker 16c just contains thermo-stabilizer, is further adding thermo-stabilizer on this basis and is being supplied among the forcing machine 11a.Therefore, the thermostability of resulting aromatic polycarbonate resin is improved significantly, and the quality that has significantly suppressed the finished product reduces.

In the embodiment of the present invention,,, thermo-stabilizer is distributed in the aromatic copolycarbonate resin composition fully even the amount of thermo-stabilizer is less through adopting above-mentioned method.In the embodiment particularly of the present invention; Even the amount at thermo-stabilizer is under the situation below 0.002 weight part with respect to the fusion aromatic polycarbonate resin of 100 weight parts in forcing machine 11a, also can stably thermo-stabilizer be supplied in the aromatic polycarbonate resin.

In the embodiment of the present invention, employed thermo-stabilizer is liquid situation and is to be effective especially under the situation of acidic cpd or derivatives thereof.

Here, to as the not special restriction of the acidic cpd of thermo-stabilizer, for example can enumerate usually the alkaline ester exchange catalysts that in polycondensation, uses is carried out neutral compound (what is called is called as the compound of reaction terminating agent and deactivator).

Specifically, can enumerate hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, Tripyrophosphoric acid, hexanodioic acid, xitix, aspartic acid, nonane diacid, adenosine phosphate, phenylformic acid, formic acid, valeric acid, Hydrocerol A, oxyacetic acid, L-glutamic acid, pentanedioic acid, styracin, succsinic acid, acetate, tartrate, oxalic acid, to Brs such as toluenesulfinic acid, tosic acid, naphthene sulfonic acid, nicotinic acid, TNP, VPP, phthalic acid, terephthalic acid, propionic acid, benzene sulfinic acid, Phenylsulfonic acid, propanedioic acid, toxilic acid and ester class thereof, etheride, salt etc.These can use separately, also can make up more than 2 kinds and use.

Among these acidic cpds, preferably liquid and can have sulfonic acid or its ester that carbonatoms is 1～10 alkyl substituent.As sulfonic acid, for example can enumerate Phenylsulfonic acid, toluenesulphonic acids, naphthene sulfonic acid.As the ester of sulfonic acid, can enumerate the methyl ester of sulfonic acid, the ethyl ester of sulfonic acid, the butyl ester of sulfonic acid, the octyl group ester of sulfonic acid, the phenylester of sulfonic acid etc.Among these, preferred especially butyl p-toluenesulfonate.

In the embodiment of the present invention, preferably wait to add the viscosity-average molecular weight (Mv of the aromatic copolycarbonate in the aromatic copolycarbonate particle of thermo-stabilizer ₁) be not more than the viscosity-average molecular weight (Mv of the fusion aromatic copolycarbonate in the forcing machine 11a ₂).Be preferred Mv ₁≤Mv ₂Wherein, the poor (Mv of viscosity-average molecular weight ₂-Mv ₁) to be advisable below 5,000, be preferably below 3,000, be preferably below 2,000 especially.

Wait to add the viscosity-average molecular weight (Mv of the aromatic copolycarbonate in the aromatic copolycarbonate particle of thermo-stabilizer ₁) excessive viscosity-average molecular weight (Mv greater than the fusion aromatic copolycarbonate in the forcing machine 11a ₂) time, perhaps viscosity-average molecular weight (Mv ₂) and viscosity-average molecular weight (Mv ₁) poor (Mv ₂-Mv ₁) when excessive, then the dispersiveness of thermo-stabilizer is tending towards reducing.

And; In the embodiment of the present invention; With the aromatic copolycarbonate resin composition that uses forcing machine 11a to produce as waiting that the aromatic copolycarbonate particle that is adding thermo-stabilizer utilizes; It is returned among the forcing machine 11a once more, and through adopting such Production Flow Chart, the defective goods (カ Star トミス article) that produce in the terminal stage of the manufacturing of aromatic polycarbonate resin, the production loss article that produce because of the product switching etc. also can be as waiting that the particle that is adding thermo-stabilizer uses.And, this feed rate for the steady heat stablizer, guarantee in molten polymer dispersiveness, prevent the thermal degradation when of recycling article and keep aspect the product quality also to be effective.Its result, the taking into account of stabilization of saving and product quality that can realize improvement, the resource of the raw material availability of product.

Fig. 2 representes to use 2 above stirrers, adding other instances of the manufacturing installation of the aromatic copolycarbonate resin composition in the situation of additives such as thermo-stabilizer.Used identical symbol for the formation identical, omitted its explanation at this with Fig. 1.

In the manufacturing installation of aromatic copolycarbonate resin composition shown in Figure 2, on the manufacturing installation of aromatic copolycarbonate resin composition shown in Figure 1, newly be provided with stirrer 21b.And, be provided with thermo-stabilizer supplying opening 22b in addition.

Through making air conveying pipe arrangement divide the out branch pipe arrangement, can likewise supply with the aromatic copolycarbonate particle with stirrer 21a to stirrer 21b.And, can supply with thermo-stabilizer and other additive by thermo-stabilizer supplying opening 22b, and can in stirrer 21b, they added in the aromatic copolycarbonate particle.

Among the stirrer 21b, added thermo-stabilizer and other additive after, through additive supply line 12b, circulation is supplied among the forcing machine 11a.

Embodiment

Through embodiment concrete mode of the present invention is described below, only otherwise exceed its main points, the present invention just is not limited to these embodiment.

Need to prove that following embodiment and the aromatic copolycarbonate resin composition in the comparative example are analyzed according to following method.

(1) viscosity-average molecular weight (Mv)

Aromatic copolycarbonate resin composition is dissolved in the methylene dichloride, uses the limiting viscosity [η] of determination of ubbelohde viscometer in 20 ℃ methylene dichloride, obtain viscosity-average molecular weight (Mv) according to following mathematical expression (1).

Need to prove; In the present embodiment; Because the composition in the aromatic copolycarbonate resin composition except that aromatic polycarbonate resin is a trace, therefore the viscosity-average molecular weight (Mv) with the aromatic polycarbonate resin in the aromatic copolycarbonate resin composition is regarded as identical with the viscosity-average molecular weight (Mv) of aromatic copolycarbonate resin composition.

[η]=1.23 * 10 ^-4(Mv) ^0.83Mathematical expression (1)

(2) initial stage tone

Under nitrogen atmosphere in 120 ℃ of dry aromatic poly carbonate resin compositions after 6 hours; The J75EII type injection moulding machine that uses Japan Steel Co., Ltd to make molds the thick operation that is injected into matrix of 60mm * 60mm * 3mm repeatedly with 360 ℃ of resin temperatures, 30 seconds condition of shaping cycle.

Use yellowness index (YI) value of the injection-molded article that colorimetric analysis appearance (Konica Minolta Co., Ltd make CM-3700d) obtains the 6th time～the 15th time injection to measure then, calculate MV and standard deviation.The YI value is more little, explains that tone is good more, and quality is more excellent; Standard deviation is more little, and the account for color inequality is less more, and quality is stable more.

(3) heat stops the tone after testing

In above-mentioned (2), change shaping cycle into 10 minutes from the 16th injection, the operation of duplicate injection moulding obtains the injection-molded article until the 22nd injection.

The YI value of the injection-molded article that the 60mm * 60mm * 3mm that the 20th time～the 22nd time injection is obtained with colorimetric analysis appearance (CM-3700d that Konica Minolta Co., Ltd makes) is thick is measured, and calculates MV.Be worth more for a short time, explain that tone is good more, quality is more excellent.

(embodiment 1)

As the manufacturing installation of aromatic copolycarbonate resin composition, use device shown in Figure 2.

Among Fig. 2, under nitrogen atmosphere, temperature is adjusted among 140 ℃ the 1st feedstock production groove 2a in constant mol ratio (DPC/BPA=1.050) DPC and BPA being supplied to continuously; Form uniform molten state; Wherein, supply with DPC, supply with BPA by BPA supplying opening 1b by DPC supplying opening 1a-1.

Then, through likewise being adjusted into 140 ℃ the 2nd feedstock production groove 2b, using raw material supplying pump 4a to reach and supply to continuously under the constant condition among the 1st vertical reactor 6a in the feed rate of unit time.Then, from catalyzer supplying opening 5a being 0.5 * 10 with respect to 1 mole of BPA ^-6The amount of mole is supplied with the cesium carbonate aqueous solution as catalyzer continuously.

The interior temperature of the 1st vertical reactor 6a is adjusted into 220 ℃, pressure is adjusted into 13.3kPa, the aperture of valve (not shown) of regulating the vent line of being located at trench bottom is so that mean residence time is 1.5 hours, and keeps liquid level constant.

The polymer fluid of being discharged by the 1st vertical reactor 6a then is supplied to the 2nd vertical reactor 6b, the 3rd vertical reactor 6c, the 4th horizontal reactor 9a successively continuously.The interior temperature of the 2nd vertical reactor 6b is that 260 ℃, pressure are that 4kPa, mean residence time are 1.5 hours.The interior temperature of the 3rd vertical reactor 6c is that 270 ℃, pressure are that 70Pa, mean residence time are 1 hour; The interior temperature of the 4th horizontal reactor 9a is that 270 ℃, pressure are that 200Pa, mean residence time are 1.5 hours.

Keep molten state to be supplied to double-screw type forcing machine 11a this aromatic copolycarbonate, time per unit is supplied with 97 weight parts.At this moment; Storage has the aromatic copolycarbonate particle that contains thermo-stabilizer (mean length 3mm, average diameter 3mm, the Mv=15 that utilizes the method identical with following method to produce in advance in product bunker 16c; 000), is supplied to stirrer 21a with time per unit 1.5 weight parts.Need to prove that stirrer 21a uses the helical ribbon agitator of successive type, and the nitrogen that circulated.And the churning time among the stirrer 21a is 8 minutes.

And, supply with butyl p-toluenesulfonate as thermo-stabilizer with small-sized pump of constant delivery type (not shown) with time per unit 0.0005 weight part from thermo-stabilizer supplying opening 22a, adding continuously on the aromatic copolycarbonate particle.Be supplied to continuously among the forcing machine 11a by additive supply line 12a then.

And then, likewise the aromatic copolycarbonate particle is supplied to stirrer 21b (likewise having used the helical ribbon agitator of successive type with stirrer 21a) by product bunker 16c with time per unit 1.5 weight parts with above-mentioned, and the nitrogen that circulated.In addition, the churning time in stirrer 21b is 8 minutes.

Here; Continuously following substances is supplied to stirrer 21b by supplying opening 22b with following speed: supply with as three (2 of thermo-stabilizer with time per unit 0.005 weight part; The 4-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER is supplied with the glyceryl monostearate as release agent with time per unit 0.03 weight part.Then, they are being added continuously on the aromatic copolycarbonate particle, be supplied to continuously among the forcing machine 11a by additive supply line 12b again.

Poly carbonate resin composition cooling curing in cooling tank 13a of under molten state, discharging with line material shape by double-screw type forcing machine 11a; After line material cutter 14a granulation; Remove big or small substandard particle with sieve apparatus 15a, suitably be stored among product bunker 16a～16c.

The viscosity-average molecular weight of resulting poly carbonate resin composition (Mv) is 15000, and the YI=1.28 at initial stage, standard deviation are 0.015, the YI=3.21 after the stop heat stability test.

(embodiment 2)

Aromatic copolycarbonate particulate viscosity-average molecular weight (Mv) in being stored in product bunker 16c is 14500, likewise makes aromatic copolycarbonate resin composition with embodiment 1.

The viscosity-average molecular weight of resulting aromatic copolycarbonate resin composition (Mv) is 15,000, and initial stage tone YI=1.25, standard deviation are 0.013, the YI=3.20 after the stop heat stability test.

(embodiment 3)

Aromatic copolycarbonate particulate viscosity-average molecular weight (Mv) in being stored in product bunker 16c is 27000, likewise makes aromatic copolycarbonate resin composition with embodiment 1.

The viscosity-average molecular weight of resulting aromatic copolycarbonate resin composition (Mv) is 15,400, and initial stage tone YI=1.37, standard deviation are 0.031, the YI=3.43 after the stop heat stability test.

(embodiment 4)

Except the aromatic copolycarbonate particle that is supplied to

stirrer

21a, 21b is supplied with time per unit 3 weight parts respectively, likewise make aromatic copolycarbonate resin composition with embodiment 1.Churning time was respectively 4 minutes.

The viscosity-average molecular weight of resulting aromatic copolycarbonate resin composition (Mv) is 15,000, and initial stage tone YI=1.40, standard deviation are 0.012, the YI=3.65 after the stop heat stability test.

(comparative example 1)

Except the aromatic copolycarbonate particle that will not contain thermo-stabilizer be stored in supply with among the product bunker 16c, likewise make aromatic copolycarbonate resin composition with embodiment 1.

The viscosity-average molecular weight of resulting aromatic copolycarbonate resin composition (Mv) is 15,000, and initial stage tone YI=1.55, standard deviation are 0.017, the YI=3.90 after the stop heat stability test, and the result is inferior to above-mentioned each embodiment.

(comparative example 2)

Except not circulating the nitrogen, likewise make aromatic copolycarbonate resin composition with comparative example 1 to

stirrer

21a, 21b.

The viscosity-average molecular weight of resulting aromatic copolycarbonate resin composition (Mv) is 15,000, and initial stage tone YI=1.59, standard deviation are 0.024, the YI=4.05 after the stop heat stability test, and the result is inferior to above-mentioned each embodiment.

(comparative example 3)

The aromatic copolycarbonate particle that 6 weight parts are stored among the product bunker 16c drops into Henschel mixer, add 0.002 weight part butyl p-toluenesulfonate after, thorough mixing 10 minutes.The particle that so prepares with batch mode is supplied among the stirrer 21a with time per unit 1.5 weight parts.Need to prove, do not supply with the butyl p-toluenesulfonate to stirrer 21a by thermo-stabilizer supplying opening 22a, likewise implement with embodiment 1 except having to use with embodiment 1 identical successive type helical ribbon agitator.

The viscosity-average molecular weight of resulting poly carbonate resin composition (Mv) is 15,000, and initial stage tone YI=1.49, standard deviation are 0.157, the YI=3.77 after the stop heat stability test.

(comparative example 4)

In comparative example 3; To be stored at aromatic copolycarbonate particle 6 weight parts and 0.02 weight part three (2 among the product bunker 16c with Henschel mixer in advance; The 4-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER, 0.12 weight part glyceryl monostearate thorough mixing are 10 minutes; With the batch mode preparation, this particle is supplied to stirrer 21b continuously with time per unit 1.5 weight parts.Need to prove, except do not have to use the successive type helical ribbon agitator identical with embodiment 1 by supplying opening 22b to stirrer 21b supply three (2, the 4-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTERs with beyond the glyceryl monostearate, likewise implement with comparative example 3.The viscosity-average molecular weight of resulting poly carbonate resin composition (Mv) is 15,000, and initial stage tone YI=1.53, standard deviation are 0.170, the YI=3.84 after the stop heat stability test.

Industrial applicibility

The aromatic copolycarbonate resin composition of staies in grade such as the raw material availability that the present invention can manufacture a product is improved, help to economize on resources, thermostability, so the present invention is useful in industry.

Need to prove that the application has quoted the full content of Japanese patent application 2007-120090 number specification sheets, claims, accompanying drawing and summary submitting on April 27th, 2007 at this, be introduced into specification sheets of the present invention with the form of reference.

Claims

1. a method of manufacture that contains the aromatic copolycarbonate resin composition of thermo-stabilizer is characterized in that, this method of manufacture comprises following operation:

Polycarbonate is supplied with operation, is supplied to the aromatic copolycarbonate of molten state in the forcing machine continuously;

Extrude operation, utilize above-mentioned forcing machine, will supply with the aromatic copolycarbonate that supply comes in the operation at polycarbonate and mix, and extrude by this forcing machine with thermo-stabilizer;

Granulating working procedure will be at the above-mentioned aromatic copolycarbonate granulation of being extruded by forcing machine in the operation, the particle of formation aromatic copolycarbonate extruded; With

Operation is supplied with in the particle circulation; Divide the particle that is taken at the partially aromatic polycarbonate after the granulation in the above-mentioned granulating working procedure; Continuously thermo-stabilizer is being added in this particle; Simultaneously this is being added the particle that thermo-stabilizer is arranged and be supplied to continuously in the forcing machine, this forcing machine is to supply with the forcing machine that is supplied to aromatic copolycarbonate in the operation at above-mentioned polycarbonate.

2. the method for manufacture of aromatic copolycarbonate resin composition as claimed in claim 1; It is characterized in that; This method also comprises air conveying operation; In this air conveying operation, the particle through the aromatic copolycarbonate after carrying pipe arrangement to granulation in said granulating working procedure carries out air conveying

And carry out air conveying to the particle of the partially aromatic polycarbonate that in said granulating working procedure, obtains through the branch road pipe arrangement that diverges to by said conveying pipe arrangement.

3. according to claim 1 or claim 2 the method for manufacture of aromatic copolycarbonate resin composition is characterized in that, said particle circulation is supplied with the particulate thermo-stabilizer that adding in the operation in aromatic copolycarbonate for liquid.

4. according to claim 1 or claim 2 the method for manufacture of aromatic copolycarbonate resin composition is characterized in that, said particle circulation supplies with that to add in the particulate thermo-stabilizer of aromatic copolycarbonate in the operation be acidic cpd.

5. according to claim 1 or claim 2 the method for manufacture of aromatic copolycarbonate resin composition is characterized in that said thermo-stabilizer is liquid sulfonic acid or its ester, and this sulfonic acid or its ester to have carbonatoms be 1～10 alkyl substituent or do not have substituting group.

6. according to claim 1 or claim 2 the method for manufacture of aromatic copolycarbonate resin composition; It is characterized in that; Said particle circulation is supplied with in the operation; With respect to the particle of 100 weight part aromatic copolycarbonates, make the thermo-stabilizer of 0.001 weight part～1 weight part add particle continuously in this aromatic copolycarbonate.

7. according to claim 1 or claim 2 the method for manufacture of aromatic copolycarbonate resin composition; It is characterized in that; Said particle circulation is supplied with in the operation; Be supplied to the aromatic copolycarbonate of said forcing machine with respect to 100 weight parts, the pellet supply that 0.5 weight part～5 weight parts are being added the aromatic copolycarbonate that said thermo-stabilizer is arranged is to this forcing machine.

8. according to claim 1 or claim 2 the method for manufacture of aromatic copolycarbonate resin composition is characterized in that the viscosity-average molecular weight Mv of the aromatic copolycarbonate in said granulating working procedure after the granulation ₁Be not more than the viscosity-average molecular weight Mv that extrudes in the operation with thermo-stabilizer aromatic copolycarbonate of blended molten state in said forcing machine said ₂, i.e. Mv ₁≤Mv ₂

9. according to claim 1 or claim 2 the method for manufacture of aromatic copolycarbonate resin composition is characterized in that said extruding in the operation is with respect to 100 weight part aromatic copolycarbonates, with the amount mixture heat stablizer below 0.002 weight part.

10. according to claim 1 or claim 2 the method for manufacture of aromatic copolycarbonate resin composition; It is characterized in that; Said polycarbonate is supplied with in the operation, and to be supplied to aromatic copolycarbonate in the said forcing machine and to be catalyzer with the basic cpd, the polycondensation through aromatic dihydroxy compound and carbonic diester obtains.