CN104204032A - Method for manufacturing polycarbonate resin - Google Patents
Method for manufacturing polycarbonate resin Download PDFInfo
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- CN104204032A CN104204032A CN201380016901.3A CN201380016901A CN104204032A CN 104204032 A CN104204032 A CN 104204032A CN 201380016901 A CN201380016901 A CN 201380016901A CN 104204032 A CN104204032 A CN 104204032A
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- polycarbonate resin
- manufacture method
- stir shaft
- scraper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/205—General preparatory processes characterised by the apparatus used
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Polyesters Or Polycarbonates (AREA)
Abstract
Provided is a method for manufacturing a polycarbonate resin that is capable of keeping the quality thereof, wherein the formation of foreign matters is prevented and, therefore, the obtained polycarbonate resin is hardly contaminated with foreign matters. The method for manufacturing a polycarbonate resin whereby the polycarbonate resin is continuously manufactured by employing a plurality of reaction devices, characterized in that at least one of the reaction devices, said reaction device being designed so that the viscosity-average molecular weight of the polycarbonate resin at the outlet of the reaction device attains 10,000 or greater, is provided with an agitation axis and a scraper.
Description
Technical field
The present invention relates to the manufacture method of polycarbonate resin, specifically, the dirt settling relating on the stir shaft that makes polycondensation reaction device reduces, suppresses the manufacture method that foreign matter is sneaked into the polycarbonate resin of goods.
Background technology
As the manufacture method of polycarbonate resin, the known scorification that dihydroxy compound and carbonic diester carry out polycondensation etc. that makes.
In the method, as described in Patent Document 1, known following method: use plural reaction unit, carry out polycondensation continuously and manufacture polycarbonate resin.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-146050 communique
Summary of the invention
The problem that invention will solve
Yet, in above-mentioned successive polymerization, along with polyreaction is carried out, after reaction unit in the molecular weight of the polycarbonate resin that generates increase.Therefore, if polyreaction carry out, after reaction unit in there is full-bodied polycarbonate resin.
Now, along with the viscosity of polycarbonate resin increases, in reaction unit, there is polycarbonate resin adhering on stir shaft etc.In the few situation such as this polycarbonate resin adhering to and contacting of other polycarbonate resin, can carry out at leisure polycondensation, viscosity improves, and is bonded to sometimes on stir shaft etc.In addition, this set thing easily becomes the high branching amount thing with many branched structures.
The set thing of above-mentioned polycarbonate resin is poor with the consistency of the polycarbonate resin of conventionally manufacturing, and the situation of xanthochromia is many.Therefore, if split away off etc. and depart from from stir shaft etc., as foreign matter, mix in polycarbonate resin, become the reason that tone worsens, foreign matter increases.In addition, in the large situation of this lower junk, sometimes also can make to be arranged at the breakages such as polymer filter in reaction unit.
Therefore, the object of the invention is to, in the manufacture of polycarbonate resin, suppress the generation of foreign matter, keep the quality of resulting polycarbonate resin.
For solving the scheme of problem
That is, the present invention has following main points.
(1) manufacture method for polycarbonate resin, it is to use 2 above reaction units to manufacture continuously the method for polycarbonate resin, it is characterized in that,
At least one reaction unit reaching in the reaction unit that more than 10,000 modes sets according to the viscosity-average molecular weight of the polycarbonate resin in above-mentioned reaction unit exit possesses stir shaft and scraper.
(2) manufacture method of the polycarbonate resin as described in above-mentioned (1), is characterized in that, above-mentioned polycarbonate resin makes carbonic diester and dihydroxy compound under the existence of transesterification catalyst, carry out polycondensation to obtain.
(3) manufacture method of the polycarbonate resin as described in above-mentioned (2), is characterized in that, above-mentioned carbonic diester freely replaces or without at least one in the diphenyl carbonate of replacement and the group of dialkyl carbonate composition for choosing.
(4) manufacture method of the polycarbonate resin as described in above-mentioned (2) or (3), it is characterized in that, above-mentioned dihydroxy compound be in molecule, have an above aromatic nucleus and two hydroxyls respectively with the aromatic dihydroxy compound of aromatic nucleus bonding.
(5) manufacture method of the polycarbonate resin as described in any one of above-mentioned (2)～(4), it is characterized in that, above-mentioned transesterification catalyst is for selecting the compound of freely growing the formula periodic table of elements the 1st family's element (not comprising hydrogen), at least one basic cpd in the group that compound, alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound and the amine compound of the long formula periodic table of elements the 2nd family's element form.
(6) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(5), is characterized in that, the scraping portion of above-mentioned scraper and the distance of above-mentioned stir shaft are below 30mm.
(7) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(6), is characterized in that, the scraping portion of above-mentioned scraper and the distance of above-mentioned stir shaft are more than 1mm.
(8) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(7), is characterized in that, the reaction unit that possesses above-mentioned stir shaft and scraper is horizontal reactor.
(9) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(8), is characterized in that, the scraping portion of above-mentioned scraper is positioned at the below at above-mentioned stir shaft Zhou center.
(10) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(9), is characterized in that, the length of the scraping portion of above-mentioned scraper is more than 3% below 30% with respect to the overall length of above-mentioned stir shaft.
(11) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(10), is characterized in that, the circumferential speed of above-mentioned stir shaft is below the above 15cm/s of 5cm/s.
(12) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(11), is characterized in that, the diameter of above-mentioned stir shaft is below the above 600mm of 200mm.
(13) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(12), is characterized in that, the viscosity-average molecular weight of above-mentioned polycarbonate resin is more than 18,000.
(14) manufacture method of the polycarbonate resin as described in any one of above-mentioned (1)～(13), is characterized in that, the melt viscosity of above-mentioned polycarbonate resin is below 50,000 pools.
The effect of invention
According to the present invention, scraper is disposed near the stir shaft in reactor, therefore can scraping be attached to the polycarbonate resin of stir shaft.Thus, can prevent from, as the sneaking into of the foreign matter of high molecular thing or high branching amount thing, can manufacturing efficiently the polymkeric substance of few foreign, stably the stable polycarbonate resin of quality bills of materials.In addition, can also prevent from being arranged at the breakage of the polymer filter in reaction unit.
Accompanying drawing explanation
Fig. 1 is the example of polycondensation schema that the example of polycondensation reaction device is shown.
In Fig. 2, being (a) cross-sectional view that disposes the polycondensation reaction device of scraper, is (b) the b-b sectional view of the cross-sectional view of (a).
In Fig. 3, (a), (b), (c) and (d) be respectively the figure that the situation of the dirt settling that is attached to stir shaft in embodiment and comparative example is shown.
Embodiment
The present invention uses 2 above polycondensation reaction devices to manufacture continuously the manufacture method of the polycarbonate resin of polycarbonate resin.
(polycarbonate resin)
Polycarbonate resin as the manufacturing object thing in the present invention is preferably by making carbonic diester and dihydroxy compound carry out the polymer compound that polycondensation (transesterification reaction) is manufactured.
(carbonic diester)
As carbonic diester, can enumerate and such as diphenyl carbonate (DPC), dimethyl benzyl etc., replace the dialkyl carbonates such as diphenyl carbonate, methylcarbonate, diethyl carbonate, dimethyl dicarbonate butyl ester.These carbonic diesters can be used separately, or can mix two or more use.
In addition, above-mentioned carbonic diester can be preferably its 50 % by mole following, further preferably 30 % by mole of following amounts are replaced by dicarboxylic acid or dicarboxylic ester.
As representational dicarboxylic acid or dicarboxylic ester, can enumerate terephthalic acid, m-phthalic acid, terephthaldehyde's diphenyl phthalate, diphenylisophthalate etc.When the dicarboxylic acid by such or dicarboxylic ester displacement, obtain polyestercarbonate.
With respect to above-mentioned aromatic dihydroxy compound, excessively use these carbonic diesters (comprise dicarboxylic acid or dicarboxylic ester after above-mentioned displacement, below identical).That is, with respect to dihydroxy compound, with 1.01～1.30 times of amounts (mol ratio), be preferably 1.02～1.20 times of amounts (mol ratio) and use carbonic diester.If mol ratio is too small, the terminal hydroxyl amount of resulting polycarbonate resin increases, and the thermostability of polycarbonate resin is tending towards variation.And, if mol ratio is excessive, the speed of response of transesterification reaction reduces, and is sometimes difficult to generate the polycarbonate resin with desired molecular weight, and the remaining quantity of the carbonic diester in polycarbonate resin increases, cause sometimes producing when forming process or while making products formed peculiar smell.
(dihydroxy compound)
Dihydroxy compound is the compound in molecule with two hydroxyls, in the present invention, in dihydroxy compound, preferably use in molecule, have an above aromatic nucleus and two hydroxyls respectively with the aromatic dihydroxy compound of aromatic nucleus bonding.
Concrete example as aromatic dihydroxy compound, can enumerate for example 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 (4-hydroxyl-3 of 2-, 5-3,5-dimethylphenyl) propane, 2, two (4-hydroxyl-3 of 2-, 5-dibromo phenyl) propane, 4, two (4-hydroxy phenyl) heptane, 1 of 4-, the bisphenols such as 1-bis(4-hydroxyphenyl) cyclohexane; 4,4 '-dihydroxybiphenyl, 3,3 ', 5,5 '-tetramethyl--4, the 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, preferably 2, two (4-hydroxy phenyl) propane (being dihydroxyphenyl propane (being hereinafter sometimes referred to as " BPA ")) of 2-.These aromatic dihydroxy compounds can be used separately, or can mix two or more use.
(transesterification catalyst)
In above-mentioned transesterification reaction, use transesterification catalyst.As this transesterification catalyst, conventionally can enumerate the catalyzer using when utilizing ester-interchange method to manufacture polycarbonate, be not particularly limited.In general, for example can enumerate at least one basic cpd selecting in the group of freely growing the compound of the formula periodic table of elements the 1st family's element (not comprising hydrogen) (being hereinafter sometimes referred to as " the 1st family's element (not comprising hydrogen) "), the compound of long period Xing 2 family's elements (being hereinafter sometimes referred to as " the 2nd family's element "), alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound and amine compound composition.
In these transesterification catalysts, in practicality, be preferably selected from least one compound in the group that the compound of compound He 2 family's elements of You 1 family's element (not comprising hydrogen) forms.These transesterification catalysts can be used separately, also can be used in combination of two or more.
The consumption of transesterification catalyst is preferably 1 * 10 conventionally with respect to 1 mole of dihydroxy compound
-9mole～1 * 10
-1mole, more preferably 1 * 10
-7mole～1 * 10
-3mole, further preferably with 1 * 10
-7mole～1 * 10
-5mole use.
As the compound of above-mentioned the 1st family's element (not comprising hydrogen), can enumerate the mineral compound such as the 1st family's element oxyhydroxide of (not comprising hydrogen), carbonate, bicarbonate compound; The organic compound such as salt of the 1st family's element (not comprising hydrogen) and alcohols, phenols, organic carboxyl acid class; Etc..As the 1st family's element (not comprising hydrogen), can enumerate for example lithium, sodium, potassium, rubidium, caesium herein.In the compound of these the 1st family's elements (not comprising hydrogen), preferred Cesium compound and potassium compound, particularly preferably cesium carbonate, cesium bicarbonate, cesium hydroxide, potassium acetate, salt of wormwood.
In addition, as the compound of above-mentioned the 2nd family's element, can enumerate the mineral compound such as oxyhydroxide such as beryllium, magnesium, calcium, strontium, barium etc., carbonate; Salt of beryllium, magnesium, calcium, strontium, barium etc. and alcohols, phenols, organic carboxyl acid class etc.In the compound of these the 2nd family's elements (not comprising hydrogen), preferably magnesium compound.
As above-mentioned alkaline boron compound, can enumerate sodium salt, sylvite, lithium salts, calcium salt, magnesium salts, barium salt, strontium salt of boron compound etc.Herein, as boron compound, can enumerate such as 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.
In addition, as above-mentioned alkaline phosphating compound, can enumerate 3 valency phosphorus compounds such as triethyl phosphine, three n-propyl phosphines, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine, three (to tert-butyl-phenyl) phosphine, tributylphosphine or by these compound derivings quaternary alkylphosphonium salt etc.Wherein, triphenylphosphine, three (to tert-butyl-phenyl) phosphine etc.
As above-mentioned alkaline ammonium compound, can enumerate such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethylammonium ethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, triethyl ammonium hydroxide, triethyl benzylic hydrogens ammonium oxide, triethyl phenyl ammonium hydroxide, tributyl benzylic hydrogens ammonium oxide, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl ammonium hydroxide, methyl triphenyl ammonium hydroxide, butyl triphenyl ammonium hydroxide etc.Wherein, preferred Tetramethylammonium hydroxide etc.
In addition, as above-mentioned amine compound, can enumerate for example 4-aminopyridine, PA, 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.
(manufacture of polycarbonate resin)
Next, the manufacture method of polycarbonate resin is described.
Polycarbonate resin obtains by following manner: in raw material preparation facilities, preparation, as the above-mentioned dihydroxy compound of raw material and the mixture of carbonic diester (raw material preparation section), makes these raw mixtures under the existence of above-mentioned transesterification catalyst, in reaction unit, carry out polycondensation (polycondensation step).
As reactive mode, can use batch-type, continous way, their combination etc., in the present invention, raw material preparation section and polycondensation step carry out with continous way.After polycondensation step, through the operation of after reaction is stopped, the unreacting material in polymerization liquid, byproduct of reaction devolatilization being removed; Add the operation of thermo-stabilizer, release agent, pigment etc.; Form as required the operation of the particle of specified particle diameter; Etc., thereby produce polycarbonate resin.
(polycondensation step)
Raw mixture is sent in more than 2 reaction unit shown in Fig. 1 under molten state, for polycondensation.This polycondensation is conventionally more than 2, carry out continuously in preferably 3～7 reactors.As concrete reaction conditions, be temperature: 150 ℃～320 ℃, pressure: normal pressure～0.01Torr (1.3Pa), mean residence time: 5 minutes～300 minutes; Be preferably temperature: 180 ℃～310 ℃, pressure: 20Torr～0.05Torr (2.7kPa～6.7Pa), mean residence time: 60 minutes～150 minutes.
In more than 2 reaction units, in order more effectively will to carry out along with polycondensation, the monohydroxy compounds such as phenol of by-product are removed to system, in above-mentioned reaction conditions, periodically set higher temperature, high vacuum more for.It should be noted that, in order to prevent that the qualities such as tone of resulting polycarbonate resin from reducing, and preferably sets low temperature, short residence time(SRT) as much as possible.
In the present invention, 2 above reactors that comprise vertical reactor are set conventionally, increase the molecular-weight average of polycarbonate resin.Conventionally arrange 3～6, preferably arrange 4～5.
As concrete example, 3 vertical reactor 11a, 11b, 11c and 1 horizontal reactor 11d in Fig. 1, have been used.
Melts to initial vertical reactor 11a feeding mixt A starts polycondensation under the existence of above-mentioned transesterification catalyst.Next, reaction mixture is sent to vertical reactor 11b, vertical reactor 11c, horizontal reactor 11d successively, carries out polycondensation.Now, though by-product phenol, it is liquefied in heat exchanger, and is sent to phenol storage 13.Phenol in phenol storage 13 is by suitable treatment, as the raw material of dihydroxy compound, carbonic diester compound etc., is reused.
As the reactor of the back segment of a group reaction device, use horizontal reactor 11d.This is because along with polycondensation is carried out, viscosity rise therefore becomes high viscosity in back segment, can make the stirring under high viscosity be more prone to.
After the polycarbonate resin obtaining in this polycondensation step by devolatilization and be cooled.
As above-mentioned vertical and horizontal reactor, use such as stirring tank reactor, film reactor, centrifugal thin film evaporation reactor, the mixing reactor of Surface Renewal type twin shaft, double-shaft horizontal stirred reactor, wet wall type reactor, in free-falling, carry out the porous template reactor of polymerization, on one side along silk screen (ワ イ ヤ ー) Yi Bian fall to carrying out the porous template reactor with silk screen etc. of polymerization.Wherein, as reactor, preferably stir grooved reaction unit, double-shaft horizontal stirring reaction device.
As the form of the stirring rake of vertical reactor, can enumerate such as vane wheel oar, impeller oar, method Dare (Pfaudler) oar, anchor oar, general can formula (full zone) oar (manufactures of Shinko pantec society), SANMELER oar (manufactures of Mitsubishi Heavy Industries Ltd industry society), Maxblend oar (manufacture of Sumitomo hoisting machinery industry society), ribbon oar, torsion grid oars (the ね じ り grid wing) (manufacture of Hitachi society) etc.Wherein, as stirring rake, preferred Maxblend oar (Sumitomo hoisting machinery industry society manufactures), ribbon oar.
In the present invention, horizontal reactor refers to that the turning axle of stirring rake is the reactor of horizontal (horizontal direction).As the stirring rake of horizontal reactor, can enumerate the stirring rake of single-shaft variants such as rondelle, blade type; HVR, SCR, N-SCR (manufacture of Mitsubishi Heavy Industries Ltd industry society), Bivolac (Sumitomo hoisting machinery industry society manufactures); Or the stirring rake of the biaxial types such as spectacle oar, grid oar (manufacture of Hitachi society); Etc..
It should be noted that, the transesterification catalyst using in the polycondensation of dihydroxy compound and carbonic diester is conventionally sometimes made in advance the aqueous solution and is used.Concentration to the aqueous solution is not particularly limited, and the solubleness according to transesterification catalyst in water is adjusted into any concentration.In addition, also can replace water and select other solvents such as acetone, alcohol, toluene, phenol.
Proterties to water used in the dissolving of transesterification catalyst is not particularly limited, as long as the kind of contained impurity and concentration are necessarily, conventionally preferably uses distilled water, deionized water etc.
In manufacture method of the present invention, use 2 above reaction units to manufacture continuously polycarbonate resin, the viscosity-average molecular weight of the polycarbonate resin in the exit of the reaction unit forming is that at least one in more than 10,000 reaction units possesses stir shaft and scraper (Scraper).
It should be noted that, the viscosity-average molecular weight of above-mentioned polycarbonate resin is preferably more than 14,000, more preferably more than 18,000.If viscosity-average molecular weight is less than 10,000, be difficult to be created in adhering on stir shaft 15, therefore do not need to arrange scraper.On the other hand, the upper limit of viscosity-average molecular weight is preferably 30,000, more preferably 28,000.Also can be greater than 30,000, but be 30,000 enough as the viscosity-average molecular weight of the polycarbonate resin of target.
In general, the material in the polymerization way on stir shaft in easy attachment reaction device (being hereinafter sometimes referred to as " material in polymerization way "), but because material in this polymerization way is sent here successively, therefore can strip down immediately.Yet, though be difficult on stir shaft adhere to the material in polymerization way, once adhere to, be difficult to sometimes peel off.If possess above-mentioned scraper at this position, for peeling off material in the polymerization way that is difficult to peel off, be effective.As example, the situation that scraper 14 is installed in horizontal reactor 11d is shown in to (a) of Fig. 2.
Horizontal reactor 11d shown in Fig. 2 (a) is provided with the device of stirring rake 16 on the stir shaft 15 of horizontal arrangement, from sending into mouthful 17 polymerization fused solutions that insert, while being stirred oar 16 stirrings, carry out polycondensation, and be discharged to outside from relief outlet 18.In order to make outside discharge easier, near the situation that is not provided with stirring rake 16 this relief outlet 18 on stir shaft 15 is more.In this case, in polymerization way, material is attached near the stir shaft 15 of this relief outlet 18, is easily difficult to peel off.Therefore, by above-mentioned scraper being set near the stir shaft that is not provided with stirring rake 16 15 in relief outlet 18 sides, can carry out the scraping of this dirt settling, can prevent that material in this polymerization way from carrying out polymerization and being bonded on stir shaft 15 under the state having adhered to.
In addition, though not shown, but the in the situation that of vertical reactor, in the near interface polymerization way of polymer fluid, material easily adheres to, if above-mentioned scraper is set near stir shaft 15 therefore nearby, can be attached to the scraping of the dirt settling of this part, can prevent that material in this polymerization way from carrying out polymerization and being bonded on stir shaft under the state having adhered to.
The above-mentioned reactor that possesses scraper need to be to arrange at least 1 in the reactor in scope in the viscosity-average molecular weight in above-mentioned reaction unit exit.The reactor that meets this condition has two when above, and scraper is preferably all set, and by least arranging in especially easily producing the reactor adhering to, can effectively prevent set.As this reactor, from the aspect of viscosity-average molecular weight, be preferably the horizontal reactor of last configuration.
The melt viscosity in the reaction unit exit of the above-mentioned reactor that possesses scraper be 500 pools above, be preferably 1000 pools above, more preferably more than 5000 pools.If melt viscosity is less than 500 pools, be difficult to be created in adhering on stir shaft 15, therefore do not need to arrange scraper.On the other hand, on melt viscosity, be limited to 50,000 pools, be preferably 30,000 pools, more preferably 25,000 moor, most preferably be 15,000 pools.If melt viscosity surpasses 50,000 pools, on this scraper, also likely produce dirt settling, thereby not preferred.
The temperature of the polycarbonate resin in the reaction unit exit of the above-mentioned reactor that possesses scraper be 260 ℃ above, be preferably 265 ℃ above, more preferably more than 270 ℃.If the temperature of polycarbonate resin is lower than 260 ℃, the melt viscosity of polycarbonate resin becomes too high, also likely produces dirt settling on this scraper, thereby not preferred.On the other hand, the temperature of polycarbonate resin on be limited to 320 ℃, be preferably 310 ℃, most preferably be 300 ℃.If the temperature of polycarbonate resin surpasses 320 ℃, polycarbonate resin xanthochromia likely, thereby not preferred.
As shown in Fig. 2 (b), the leading section of above-mentioned scraper 14 attenuates, thereby forms scraping portion, and be disposed at above-mentioned stir shaft 15 near.By making leading section thin as blade, can more easily carry out the peeling off of dirt settling of above-mentioned stir shaft 15.
Preferably making the 14a of scraping portion of above-mentioned scraper 14 and the distance of above-mentioned stir shaft 15 is below 30mm, more preferably below 20mm.If surpass 30mm, likely cannot fully carry out peeling off of dirt settling.On the other hand, the distance of preferred above-mentioned scraping portion and above-mentioned stir shaft 15 is more than 1mm, more preferably more than 5mm.If be less than 1mm, above-mentioned scraping portion likely contacts with above-mentioned stir shaft 15.
The 14a of scraping portion of above-mentioned scraper 14 is preferably placed at the below at above-mentioned stir shaft Zhou center.By like this, the dirt settling of scraping can again not contact stir shaft and can fall to below.
The length of the 14a of scraping portion of above-mentioned scraper 14 is preferably below 30%, more preferably below 20% with respect to the overall length of stir shaft 15.If than 30% length, resin is attached to scraper central part, likely produces set thing on scraper.On the other hand, the lower limit of the length of the 14a of scraping portion is preferably 3%, more preferably 5% with respect to the overall length of stir shaft.If shorter than 3%, dirt settling scraping efficiency likely reduces.It should be noted that, it is prerequisite that the length of the 14a of scraping portion of above-mentioned scraper 14 be take the length not contacting with stirring rake 16.
In the situation that horizontal reactor possesses above-mentioned scraper 14, the setting position of scraper is preferably compared and is positioned at outlet side with center.This be because, be more that viscosity-average molecular weight is larger in downstream side, more easily produce dirt settling.
The circumferential speed of above-mentioned stir shaft 15 be preferably 5cm/s above, more preferably 7cm/s above, more preferably more than 8cm/s.If slower than 5cm/s, stir shaft strength decreased, the in the situation that of long time running, stir shaft likely can be lost.On the other hand, the upper limit of circumferential speed is preferably 15cm/s, 10cm/s more preferably.Faster than 15cm/s in the situation that, be attached to material in the polymerization way of stir shaft 15 before falling below stir shaft 15, be raised to turning axle above, sometimes cannot peel off but and adhere on the contrary.
The diameter of above-mentioned stir shaft 15 be preferably 200mm above, more preferably 300mm above, more preferably more than 400mm.If be less than 200mm, stir shaft strength decreased, the in the situation that of long time running, stir shaft likely can be lost.On the other hand, the upper limit of the diameter of stir shaft 15 is preferably 600mm, 500mm more preferably.If be greater than 600mm, even if the circumferential speed of stir shaft 15 is in above-mentioned scope, the linear speed on stir shaft 15 surfaces is also too fast, is attached to material in the polymerization way of stir shaft 15 and sometimes cannot peels off but and adhere on the contrary.
The material of above-mentioned scraper 14 is preferably stainless steel, and more preferably SUS304, SUS304L, SUS310S, SUS316, SUS316L, most preferably be SUS316L, SUS310S.
In addition, surface treatment has been carried out on the surface of above-mentioned scraper 14 conventionally, preferred surface treatment is polishing grinding, electrolytic polishing, acid treatment, heat treated, various plating, coating processing, and preferred surface treatment is to carry out electrolytic polishing processing after polishing is ground.In addition, about the surfaceness of above-mentioned scraper 14, surfaceness (Rmax) be preferably 100 μ m following, more preferably 10 μ m following, most preferably be below 1 μ m.This surfaceness (Rmax) is if excessive, and the dirt settling stripping down can residue on scraper, and foreign matter likely increases.(Rmax) is low for preferred surface roughness, but due to constructional difficulties, thereby more than being preferably 0.01 μ m, more preferably more than 0.1 μ m.As the surfaceness of above-mentioned scraper 14, be that 0.1 μ m is enough above.
Embodiment
Below, by embodiments of the invention, describe in more detail, but be not construed to and be defined in this.Each evaluation method about polycarbonate resin, describes below.
(fish-eye number)
By at 130 ℃, the polycarbonate resin particle after dry 5 hours, 320 ℃ of extrusion mouldings, obtains the film of wide 140mm, thick 70 μ m.In extrusion moulding, used the single screw extrusion machine that diameter is 30mm (manufacture of Isuzu Kakoki society).Next, use optical foreign matter inspection units (Dia Instruments Co., Ltd., manufacture, GX40K) to measure flake (the size 50 μ m～500 μ m) number of the film of the wide 80mm * long 1.7m * thick 70 μ m that select at Liao Congmo center.That is, use the light quantity of 800mV, the fish-eye number in the scope of the light quantity of absorbed 100mV～300mV is made as to (A), the number of the scope of light quantity more than 300mV is made as to (B), by following formula (1), calculate.Mensuration is carried out 2 times, and its mean value is shown.
Fish-eye number=(A)-(B) (1)
(axle adheres to Thickness Evaluation)
The mean thickness that is attached to the polycarbonate resin of axle is used polymer flow dynamic simulated (manufacture of ANSYS society, ANSYS Fluent) to carry out instrumentation, evaluation.
(viscosity-average molecular weight)
Polycarbonate resin is dissolved in methylene dichloride, prepares dichloromethane solution (concentration (C) is 0.6g/dl).Use this dichloromethane solution of determination of ubbelohde viscometer at the specific viscosity (η of 20 ℃ of temperature
sp), by following formula, calculate viscosity-average molecular weight (Mv).
η
sp/C＝[η](1+0.28η
sp)
[η]＝1.23×10
-4×(Mv)
0.83
(melt viscosity)
Use possesses the capillary rheometer that mode diameter is 1mm φ * 30mm (manufacture of Japan Jing Ji society) by being heated to 280 ℃ at 120 ℃ of polycarbonate resins of dry 5 hours, with velocity of shear 122 (sec
-1) mensuration melt viscosity.
(comparative example 1)
Diphenyl carbonate (manufacture of Mitsubishi Chemical society) and dihydroxyphenyl propane (manufacture of Mitsubishi Chemical society) are mixed to the fused solution of raw materials mixture at 155 ℃ of temperature with certain mol ratio (DPC/BPA=1.050).The flow of next, take 4400kg/ hour is supplied to continuously to control by raw material ingress pipe and is 220 ℃, 13.3 * 10
3the capacity 10m of Pa
3the 1st vertical mixing reactor in, according to mean residence time, be the mode of 60 minutes, be controlled at the aperture of the set valve of the polymkeric substance vent line of reactor bottom, liquid level is kept to certain simultaneously.In addition, in the supply that starts raw material molten solution, with respect to 1 mole of dihydroxyphenyl propane, using the ratio of 0.5 μ mol (as amount of metal, being 1.0 μ mol with respect to 1 mole of dihydroxyphenyl propane) and supply with continuously cesium carbonate aqueous solution as catalyzer.
Next the reaction solution of discharging from reactor bottom is successively continuously fed to the 2nd, the 3rd vertical mixing reactor (capacity 10m
3) and the 4th horizontal reactor (capacity 15m
3), from the polymkeric substance relief outlet of the 4th reactor bottom, be discharged from.The 4th reactor has been used double-shaft horizontal reactor.The circumferential speed of the stir shaft of the 4th polymerization tank is that the diameter of 8.8cm/s, stir shaft is 560mm.
Then, the polymkeric substance that polymkeric substance relief outlet from the 4th reactor bottom is discharged is directly delivered to and in mould outlet, is provided with the twin screw extruder of polymer filter (society of JSW manufactures screw diameter 0.174m, L/D=39 (herein with molten state, L refers to the diameter of screw rod, D refers to the overall length of screw rod)), using butyl p-toluenesulfonate (being 5 times of molar weights with respect to the cesium carbonate using as catalyzer) continuous mixing, from mould, with line material shape, discharge, with cutting unit, cut off, obtain polycarbonate resin particle (viscosity-average molecular weight (Mv) 21,000).
Reaction conditions in the 2nd～4th reactor is respectively (260 ℃, 4.00 * 10 of the 2nd reactors
3pa, 75rpm), the 3rd reactor (270 ℃, 200Pa, 75rpm), the 4th reactor (280 ℃, 67Pa, 4rpm), when reaction is carried out, be made as high temperature, high vacuum.In addition, during reaction, according to the 2nd and the mean residence time of the 3rd reactor be that 60 minutes, the mean residence time of the 4th reactor are that the mode of 90 minutes is carried out liquid level control, also carried out the distillation of the phenol of by-product simultaneously and removed.Now, the viscosity-average molecular weight of the 4th reactor outlet reaction solution (Mv) is 21,000, at the melt viscosities of 280 ℃, is approximately 10,000 pools.
In addition, all reactors all do not arrange scraper.
As the polymer filter in reactor, (Japanese Pall society manufactures, filtering precision is the metal non-woven fabric type (material: SUS316L) of 20 μ m to have used the commercially available product of leaf dish-type polymer filter.
Running starts after latter approximately 1 day, in the end near the stir shaft that the is not provided with stirring rake relief outlet 18 of the horizontal reactor 11d of configuration, has produced dirt settling.The fish-eye number of polycarbonate resin particle is now 36.
In addition, a part for approximately 7 days postadhesion things falls in polymer fluid.Immediately the fish-eye number of aromatic polycarbonate resin particle is thereafter 1540.
(embodiment 1)
In horizontal reactor 11d, be provided with as shown in Figure 2 scraper, similarly implement with comparative example 1 in addition.In addition, the shape of scraper front end shown in Fig. 2 (b) attenuates as blade, using this leading section as scraping portion, uses.
The leading section of scraper and the distance of stir shaft are set as 15mm.In addition, the length of the leading section of scraper is made as 6% of stir shaft overall length.
The fish-eye number that running starts the polycarbonate resin particle after approximately 1 day is 25.
In addition, running starts, after 7 days, slightly to have produced dirt settling, but the whereabouts of dirt settling does not occur between scraper and stir shaft.The fish-eye number of polycarbonate resin particle is now 31.Further, the whereabouts of dirt settling does not occur after 2 months in running yet, the fish-eye number of polycarbonate resin particle is now 28.
(comparative example 2～4)
Use above-mentioned polymer flow dynamic simulated, axle dirt settling generation situation has been carried out to probatio inspectionem pecuoarem.That is,, about viscosity-average molecular weight (Mv21,000) and the melt viscosity (10,000 pool) in the exit of horizontal reactor 11d, polymer flow when polymkeric substance is contacted with stir shaft has been implemented simulation.
It should be noted that, in comparative example 2～4, scraper is not set.
About diameter and the circumferential speed of stir shaft, in comparative example 2, be 280mm, 5.1cm/s, in comparative example 3, be 560mm, 8.8cm/s, in comparative example 4, be 430mm, 7.9cm/s.
About making viscosity-average molecular weight (Mv), be 21, the result of polymer flow dynamic simulated when 000 polycarbonate resin melts contacts with stir shaft, comparative example 2 be shown in Fig. 3's (a), comparative example 3 is shown in (b) of Fig. 3, comparative example 4 is shown in (c) of Fig. 3.In addition, about the mean thickness of the dirt settling in polymer flow dynamic simulated, in comparative example 2, be in 33.3mm, comparative example 3, to be in 57.9mm, comparative example 4, to be 49.2mm.
(embodiment 2)
In horizontal reactor 11d, be provided with as shown in Figure 2 scraper, similarly implement simulation with comparative example 3 in addition.In addition, the shape of scraper front end shown in Fig. 2 (b) attenuates as blade, using this leading section as scraping portion.
The leading section of scraper and the distance of stir shaft are set as 10mm.In addition, the length of the leading section of scraper is made as 6% of stir shaft overall length.
By (d) that the results are shown in Fig. 3 of this polymer flow dynamic simulated.In addition, the mean thickness of the dirt settling in polymer flow dynamic simulated is 10.3mm in embodiment 2.
Industrial applicibility
The manufacture method of polycarbonate resin of the present invention can prevent sneaking into as the foreign matter of high molecular thing or high branching amount thing, can efficiently, stably manufacture the polycarbonate resin of few foreign, stay in grade, can also prevent breakage of the polymer filter that arranges in reaction unit etc., industrial applicibility is high.
It should be noted that, the full content of specification sheets, claims, accompanying drawing and the summary of No. 2012-078641, the Japanese patent application of submitting on March 30th, 2012 is quoted so far, as the disclosure of specification sheets of the present invention, charge to the application.
Nomenclature
11a, 11b, 11c vertical reactor
11d horizontal reactor
12 heat exchangers
13 phenol storages
14 scrapers
14a scraper scraping portion
15 stir shafts
16 stirring rakes
17 send into mouth
18 relief outlets
A raw mixture
B polycarbonate resin
Claims (14)
1. a manufacture method for polycarbonate resin, it,, for using 2 above reaction units to manufacture continuously the method for polycarbonate resin, is characterized in that,
At least one reaction unit reaching in the reaction unit that more than 10,000 modes sets according to the viscosity-average molecular weight of the polycarbonate resin in described reaction unit exit possesses stir shaft and scraper.
2. the manufacture method of polycarbonate resin as claimed in claim 1, is characterized in that, described polycarbonate resin makes carbonic diester and dihydroxy compound under the existence of transesterification catalyst, carry out polycondensation to obtain.
3. the manufacture method of polycarbonate resin as claimed in claim 2, is characterized in that, described carbonic diester freely replaces or without at least one in the diphenyl carbonate of replacement and the group of dialkyl carbonate composition for choosing.
4. the manufacture method of polycarbonate resin as claimed in claim 2 or claim 3, is characterized in that, described dihydroxy compound be in molecule, have an above aromatic nucleus and two hydroxyls respectively with the aromatic dihydroxy compound of aromatic nucleus bonding.
5. the manufacture method of the polycarbonate resin as described in any one of claim 2～4, it is characterized in that, described transesterification catalyst is for selecting the compound of freely growing the formula periodic table of elements the 1st family's element (not comprising hydrogen), at least one basic cpd in the group that compound, alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound and the amine compound of the long formula periodic table of elements the 2nd family's element form.
6. the manufacture method of the polycarbonate resin as described in any one of claim 1～5, is characterized in that, the scraping portion of described scraper and the distance of described stir shaft are below 30mm.
7. the manufacture method of the polycarbonate resin as described in any one of claim 1～6, is characterized in that, the scraping portion of described scraper and the distance of described stir shaft are more than 1mm.
8. the manufacture method of the polycarbonate resin as described in any one of claim 1～7, is characterized in that, the reaction unit that possesses described stir shaft and scraper is horizontal reactor.
9. the manufacture method of the polycarbonate resin as described in any one of claim 1～8, is characterized in that, the scraping portion of described scraper is positioned at the below at described stir shaft Zhou center.
10. the manufacture method of the polycarbonate resin as described in any one of claim 1～9, is characterized in that, the length of the scraping portion of described scraper is more than 3% below 30% with respect to the overall length of described stir shaft.
The manufacture method of 11. polycarbonate resins as described in any one of claim 1～10, is characterized in that, the circumferential speed of described stir shaft is below the above 15cm/s of 5cm/s.
The manufacture method of 12. polycarbonate resins as described in any one of claim 1～11, is characterized in that, the diameter of described stir shaft is below the above 600mm of 200mm.
The manufacture method of 13. polycarbonate resins as described in any one of claim 1～12, is characterized in that, the viscosity-average molecular weight of described polycarbonate resin is more than 18,000.
The manufacture method of 14. polycarbonate resins as described in any one of claim 1～13, is characterized in that, the melt viscosity of described polycarbonate resin is below 50,000 pools.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-078641 | 2012-03-30 | ||
| JP2012078641 | 2012-03-30 | ||
| PCT/JP2013/059671 WO2013147223A1 (en) | 2012-03-30 | 2013-03-29 | Method for manufacturing polycarbonate resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104204032A true CN104204032A (en) | 2014-12-10 |
Family
ID=49260463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380016901.3A Pending CN104204032A (en) | 2012-03-30 | 2013-03-29 | Method for manufacturing polycarbonate resin |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2013227511A (en) |
| KR (1) | KR20140145136A (en) |
| CN (1) | CN104204032A (en) |
| IN (1) | IN2014DN08297A (en) |
| WO (1) | WO2013147223A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018150453A (en) * | 2017-03-13 | 2018-09-27 | 三菱ケミカル株式会社 | Manufacturing method of polybutylene succinate |
| JP7258069B2 (en) * | 2021-03-26 | 2023-04-14 | 旭化成株式会社 | Method for assembling polycarbonate production equipment, and polycarbonate production equipment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4636525Y1 (en) * | 1968-09-17 | 1971-12-15 | ||
| US5055273A (en) * | 1987-12-18 | 1991-10-08 | Davy Mckee Aktiengesellschaft | Apparatus for processing high viscosity materials |
| JPH0636525A (en) * | 1992-07-17 | 1994-02-10 | Sanyo Electric Co Ltd | Music selection circuit of disk reproducing device |
| CN2487736Y (en) * | 2001-05-10 | 2002-04-24 | 天津大学 | Horizontal single drum stirring degassing reactor for producing poly-arbonate |
| CN1249120C (en) * | 2000-11-14 | 2006-04-05 | 帝人株式会社 | Aromatic polycarbonate, process for producing the same, and composition containing the same |
| CN101421329A (en) * | 2006-07-25 | 2009-04-29 | 三菱化学株式会社 | Production method of aromatic polycarbonate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0827265A (en) * | 1994-07-20 | 1996-01-30 | Mitsubishi Chem Corp | Production of aromatic polycarbonate |
| JPH0912703A (en) * | 1995-06-26 | 1997-01-14 | Teijin Ltd | Production of aromatic polycarbonate |
| JPH11310631A (en) * | 1998-04-28 | 1999-11-09 | Daicel Chem Ind Ltd | Manufacture of polycarbonate |
| JP5245311B2 (en) * | 2006-07-25 | 2013-07-24 | 三菱化学株式会社 | Method for producing aromatic polycarbonate |
-
2013
- 2013-03-07 JP JP2013045717A patent/JP2013227511A/en active Pending
- 2013-03-29 KR KR1020147027078A patent/KR20140145136A/en not_active Application Discontinuation
- 2013-03-29 CN CN201380016901.3A patent/CN104204032A/en active Pending
- 2013-03-29 IN IN8297DEN2014 patent/IN2014DN08297A/en unknown
- 2013-03-29 WO PCT/JP2013/059671 patent/WO2013147223A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4636525Y1 (en) * | 1968-09-17 | 1971-12-15 | ||
| US5055273A (en) * | 1987-12-18 | 1991-10-08 | Davy Mckee Aktiengesellschaft | Apparatus for processing high viscosity materials |
| JPH0636525A (en) * | 1992-07-17 | 1994-02-10 | Sanyo Electric Co Ltd | Music selection circuit of disk reproducing device |
| CN1249120C (en) * | 2000-11-14 | 2006-04-05 | 帝人株式会社 | Aromatic polycarbonate, process for producing the same, and composition containing the same |
| CN2487736Y (en) * | 2001-05-10 | 2002-04-24 | 天津大学 | Horizontal single drum stirring degassing reactor for producing poly-arbonate |
| CN101421329A (en) * | 2006-07-25 | 2009-04-29 | 三菱化学株式会社 | Production method of aromatic polycarbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013147223A1 (en) | 2013-10-03 |
| JP2013227511A (en) | 2013-11-07 |
| KR20140145136A (en) | 2014-12-22 |
| IN2014DN08297A (en) | 2015-05-15 |
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