CN104169326A - Process for manufacturing aromatic polycarbonate and manufacturing facility - Google Patents
Process for manufacturing aromatic polycarbonate and manufacturing facility Download PDFInfo
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- CN104169326A CN104169326A CN201380015697.3A CN201380015697A CN104169326A CN 104169326 A CN104169326 A CN 104169326A CN 201380015697 A CN201380015697 A CN 201380015697A CN 104169326 A CN104169326 A CN 104169326A
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- aromatic
- dihydroxy compound
- aromatic dihydroxy
- compound
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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
Abstract
Provided are: a process for manufacturing an aromatic polycarbonate, said process being capable of both saving heat resources in manufacturing and minimizing the decomposition of an aromatic dihydroxyl compound; and a facility therefor. A process for manufacturing an aromatic polycarbonate from a carbonic diester and an aromatic dihydroxyl compound as the raw materials through a polycondensation step, characterized by making a molten carbonic diester flow which is a melt flow of the carbonic diester join a molten aromatic dihydroxyl compound flow which is a melt flow of the aromatic dihydroxyl compound, mixing both flows together in a line to prepare a molten raw material for a polycarbonate resin, and then subjecting the molten raw material to continuous polycondensation in a polycondensation reactor. A manufacturing facility which is to be used in the process and which is provided with a raw material preparing unit, a polycondensation reactor, and so on. is provided.
Description
Technical field
The present invention relates to the manufacture method of aromatic copolycarbonate, specifically, the present invention relates to use manufacture method and the producing apparatus of the aromatic copolycarbonate of the producing apparatus possess specific raw material preparation facilities and polycondensation reaction device.
Background technology
In the situation that manufacture aromatic copolycarbonate through take carbonic diester and aromatic dihydroxy compound as the polymerization process that raw material carries out polymerization, as the carbonic diester of raw material and aromatic dihydroxy compound in last operation separately manufactured go out after, be transported to polymerization process and carry out polymerization.
These raw materials are molten state during the manufactured stage going out in last operation separately, temporarily cooling, solidify after, in this polymerization process, heat, melting, mixing.
In polymerization process, heat and make two kinds of equal meltings of raw material, if keep the molten state in last operation to be supplied to unchangeably in polymerization process, can save time cooling, heating, and contribute to save thermal resource.
As such method, known have keep molten state to be supplied to unchangeably the method (referring to patent documentation 1) of polymerization tank aromatic dihydroxy compound.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 6-32886 communique
Summary of the invention
Invent problem to be solved
Aromatic dihydroxy compound is deficient in stability at high temperature, sometimes decomposes.For example, use in the situation of dihydroxyphenyl propane as aromatic dihydroxy compound, if remain on high temperature more than fusing point, observe the trend that stability has variation.The result of this situation basis reference example 3 is hereinafter also obviously known.
Its reason is because carry out pyrolysis under hot effect, and 1 molecule phenol is departed from from dihydroxyphenyl propane.Isopropenyl phenol (IPP) after 1 molecule phenol departs from causes resulting aromatic copolycarbonate yellowing, and therefore expectation suppresses this decomposition reaction as much as possible.
Therefore, aromatic dihydroxy compound preferably shortens the time that remains on high temperature as much as possible.
Therefore, the object of the present invention is to provide and when manufacturing aromatic copolycarbonate, realize the decomposition of saving thermal resource and suppressing aromatic dihydroxy compound, can stably manufacture the manufacture method of the aromatic copolycarbonate that tone is good and the producing apparatus using in this manufacture method.
For the method for dealing with problems
(1) a kind of manufacture method of aromatic copolycarbonate, it is to manufacture the method for aromatic copolycarbonate through take polycondensation step that carbonic diester and aromatic dihydroxy compound carry out polycondensation as raw material, it is characterized in that, by making to converge with being incorporated in pipe arrangement as the melting carbonic diester stream of the melts fluid of described carbonic diester with as the melting aromatic dihydroxy compound stream of the melts fluid of described aromatic dihydroxy compound, mix, prepare thus polycarbonate resin fused raw material, then make described polycarbonate resin fused raw material in polycondensation reaction device, carry out continuously polycondensation.
(2) manufacture method of the aromatic copolycarbonate as described in above-mentioned (1), wherein, described polycondensation step is the operation that makes carbonic diester and aromatic dihydroxy compound carry out polycondensation under the existence of transesterification catalyst.
(3) manufacture method of the aromatic copolycarbonate as described in above-mentioned (2), wherein, 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), the basic cpd of at least one 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.
(4) manufacture method of the aromatic copolycarbonate as described in any one in above-mentioned (1)～(3), wherein, carbonic diester choosing freely replace or the group of unsubstituted diphenyl carbonate and dialkyl carbonate composition at least one.
(5) manufacture method of the aromatic copolycarbonate as described in any one in above-mentioned (1)～(4), wherein, aromatic dihydroxy compound is two (4-hydroxy phenyl) propane of 2,2-.
(6) manufacture method of the aromatic copolycarbonate as described in any one in above-mentioned (1)～(5), wherein, the time that described aromatic dihydroxy compound is melts is in 20 minutes.
(7) manufacture method of the aromatic copolycarbonate as described in any one in above-mentioned (1)～(6), wherein, the content of the aromatic monohydroxy compound in the melts of described aromatic dihydroxy compound is below 1 % by weight.
(8) manufacture method of the aromatic copolycarbonate as described in any one in above-mentioned (1)～(7), wherein, the temperature of described melting aromatic dihydroxy compound stream is below 180 ℃.
(9) manufacture method of the aromatic copolycarbonate as described in any one in above-mentioned (1)～(8), wherein, described aromatic dihydroxy compound at least comprises and the aromatic dihydroxy compound from containing aromatic monohydroxy compound, removes the aromatic dihydroxy compound after aromatic monohydroxy compound.
(10) manufacture method of the aromatic copolycarbonate as described in above-mentioned (9), wherein, described in remove aromatic monohydroxy compound method be distillation.
(11) manufacture method of the aromatic copolycarbonate as described in any one in above-mentioned (1)～(10), wherein, utilizes static mixer to carry out the preparation of described aromatic polycarbonate resin fused raw material.
(12) producing apparatus for aromatic copolycarbonate, it is the producing apparatus of the aromatic copolycarbonate that uses in the manufacture method described in any one in above-mentioned (1)～(11), it is characterized in that,
This producing apparatus possesses:
Raw material preparation facilities, it converges as the melting carbonic diester stream of the melts fluid of described carbonic diester with as the melting aromatic dihydroxy compound stream of the melts fluid of described aromatic dihydroxy compound by making, and prepares thus polycarbonate resin fused raw material in pipe arrangement; With
Polycondensation reaction device, is used the polycarbonate resin fused raw material of preparing in described raw material preparation facilities to carry out continuously polycondensation.
(13) producing apparatus of the aromatic copolycarbonate as described in above-mentioned (12), wherein, this producing apparatus further possesses aromatic dihydroxy compound purification devices, this purification devices is removed aromatic monohydroxy compound from the aromatic dihydroxy compound that contains aromatic monohydroxy compound, then with the form of melting aromatic dihydroxy compound, send to described raw material preparation facilities, form thus described melting aromatic dihydroxy compound stream.
(14) producing apparatus of the aromatic copolycarbonate as described in above-mentioned (12) or (13), wherein, the volume that the stream of the described melting aromatic dihydroxy compound from described raw material preparation facilities and described melting carbonic diester flow converges to the stream till described polycondensation reaction device entrance is 0.5m
3above.
(15) producing apparatus of the aromatic copolycarbonate as described in any one in above-mentioned (12)～(14), wherein,
To from exporting to of described aromatic dihydroxy compound purification devices, make the volume of the stream till described melting aromatic dihydroxy compound stream and described melting carbonic diester stream converge described raw material preparation facilities be made as V1,
The volume of the stream till the entrance that converges to described polycondensation reaction device of the described melting aromatic dihydroxy compound stream from described raw material preparation facilities and described melting carbonic diester stream is made as to V2,
V1 and the ratio V1/V2 of V2 are below 0.5.
(16) producing apparatus of the aromatic copolycarbonate as described in any one in above-mentioned (12)～(15) wherein, possesses static mixer in described raw material preparation facilities.
Invention effect
The present invention was provided with raw material preparation facilities before polycondensation reaction device, can shorten the time of the melting aromatic dihydroxy compound that keeps the condition of high temperature.Further, the fusing point of polycarbonate resin fused raw material (mixture of aromatic dihydroxy compound and carbonic diester) is lower than the fusing point of aromatic dihydroxy compound, mixed melt temperature can be reduced near the fusing point of mixture, therefore can suppress the decomposition of aromatic dihydroxy compound.
; in the manufacture method and producing apparatus of aromatic copolycarbonate of the present invention; while manufacturing aromatic copolycarbonate, can save thermal resource, and can suppress the decomposition of aromatic dihydroxy compound, can stably manufacture the aromatic copolycarbonate that tone is good.
Accompanying drawing explanation
Fig. 1 means the example of schema of a part of the producing apparatus of aromatic copolycarbonate.
Fig. 2 means the graphic representation of the result of reference example 3 (thermostability of BPA).
Fig. 3 is to the outlet P from aromatic dihydroxy compound purification devices till the stream pipe arrangement of fluidic junction Q and from fluidic junction Q till the example of the collocation method of the stream pipe arrangement of the entrance S of polycondensation reaction device configuration insulation pipe arrangement.
Fig. 4 is to the outlet P from aromatic dihydroxy compound purification devices till the stream pipe arrangement of fluidic junction Q and from fluidic junction Q till other example of the collocation method of the stream pipe arrangement of the entrance S of polycondensation reaction device configuration insulation pipe arrangement.
Embodiment
The producing apparatus using in the manufacture method of aromatic copolycarbonate involved in the present invention and this manufacture method is for take carbonic diester and aromatic dihydroxy compound as raw material, through using transesterification catalyst to carry out the polycondensation step of polycondensation (transesterification reaction), thereby manufacture aromatic copolycarbonate.
(aromatic copolycarbonate)
Aromatic copolycarbonate as the manufacturing object thing in the present invention refers to by making carbonic diester and aromatic dihydroxy compound carry out the polymer compound that polycondensation is manufactured.
(carbonic diester)
As carbonic diester, can enumerate for example diphenyl carbonate (being sometimes referred to as DPC below); Carboxylol ester etc. is with substituent diphenyl carbonate; The dialkyl carbonates such as methylcarbonate, diethyl carbonate, dimethyl dicarbonate butyl ester.These carbonic diesters can be used separately, or it is two or more to mix use.
In addition, can be with di-carboxylic acid or di-carboxylic acid ester interchange carbonic diester, replacement amount be preferably 50 % by mole of carbonic diester following, more preferably below 30 % by mole.
As representational di-carboxylic acid or dicarboxylic esters, can enumerate terephthalic acid, m-phthalic acid, terephthaldehyde's diphenyl phthalate, diphenylisophthalate etc.In the situation of replacing with di-carboxylic acid or dicarboxylic esters like this, can obtain polyestercarbonate.
With respect to aromatic dihydroxy compound, use these excessive carbonic diesters (comprising di-carboxylic acid or dicarboxylic esters after above-mentioned displacement, lower same).That is, with respect to aromatic 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 aromatic copolycarbonate increases, and the thermostability of aromatic copolycarbonate is tending towards variation.And, if mol ratio is excessive, the speed of response of transesterify reduces, and is sometimes difficult to generate the aromatic copolycarbonate with desired molecular weight, and the residual quantity of the carbonic diester in resin increases, cause sometimes producing when forming process or while making products formed peculiar smell.
(aromatic dihydroxy compound)
Aromatic dihydroxy compound is in molecule, to have the compound that 1 above aromatic nucleus and 2 hydroxyls are combined into aromatic nucleus respectively.Concrete example as such 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 (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 sometimes referred to as BPA below)) of 2-.These aromatic dihydroxy compounds can be used separately, or it is two or more to mix use.
(transesterification catalyst)
In above-mentioned transesterification reaction, used transesterification catalyst.Transesterification catalyst is not particularly limited, can enumerates the catalyzer using while conventionally utilizing ester-interchange method to manufacture polycarbonate.In general, for example can enumerate at least one the basic cpd in the group of compound, the compound of growing the formula periodic table of elements the 2nd family's element (being hereinafter sometimes referred to as " the 2nd family's element "), alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound and amine compound composition that choosing freely grow 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) ").
Among these transesterification catalysts, from practicality aspect, consider to be preferably selected from least one compound 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 may be used alone, can also be used in combination two or more.
With respect to 1 mole of aromatic dihydroxy compound, the consumption of transesterification catalyst is conventionally preferably with 1 * 10
-9～1 * 10
-1mole, more preferably with 1 * 10
-7～1 * 10
-3mole, further preferably with 1 * 10
-7～1 * 10
-5mole scope use.
As the 1st family's element compound of (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 that the 1st family's element (not comprising hydrogen) and alcohols, phenols, organic carboxyl acid class form; Etc..As the 1st family's element (not comprising hydrogen), can enumerate for example lithium, sodium, potassium, rubidium, caesium herein.Among the compound of these the 1st family's elements (not comprising hydrogen), preferably Cesium compound and potassium compound, particularly preferably cesium carbonate, cesium bicarbonate, cesium hydroxide, potassium acetate, salt of wormwood.
In addition, as the compound of the 2nd family's element, can enumerate the mineral compound such as oxyhydroxide such as beryllium, magnesium, calcium, strontium, barium etc., carbonate; The salt that beryllium, magnesium, calcium, strontium, barium etc. and alcohols, phenols, organic carboxyl acid class form; Etc..Among the compound of these the 2nd family's elements, preferably magnesium compound.
As 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.
As alkaline phosphating compound, can enumerate the phosphorus compound of trivalents 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, be carried out quaternary alkylphosphonium salt etc.Wherein, triphenylphosphine, three (to tert-butyl-phenyl) phosphine etc.
As alkaline ammonium compound, can enumerate such as 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.Wherein, preferred tetramethyl ammonium hydroxide etc.
As amine compound, can enumerate for example 4-aminopyridine, PA, N, N-dimethyl-4-aminopyridine, 4-diethylin pyridine, 2 hydroxy pyrimidine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylamino imidazoles, 2-methoxyl group imidazoles, imidazoles, 2-mercaptoimidazole, glyoxal ethyline, quinolylamine etc.
(manufacture of the manufacture of aromatic dihydroxy compound, particularly BPA)
Aromatic dihydroxy compound, particularly BPA can manufacture as follows.That is, use phenol (being sometimes referred to as " PL " below) and acetone as raw material, via building-up reactions operation, low boiling, remove operation, crystallization/separation circuit, heating and melting operation, phenol (PL) and remove operation manufacture.
Then, each operation is described respectively.
Building-up reactions operation is under the existence of an acidic catalyst, to make phenol (PL) and acetone carry out condensation reaction and the operation that generates BPA.Raw material PL used herein and acetone are to react under PL compares the condition of stoichiometric quantity surplus.PL counts 3～30, is preferably 5～20 with the ratio of PL/ acetone with the mol ratio of acetone.Building-up reactions operation is generally 30 ℃～100 ℃ in temperature of reaction, be preferably under the condition that 50 ℃～90 ℃ and reaction pressure be generally normal pressure～5kg/cm2G and carry out.
As an acidic catalyst, can use the mineral acids such as hydrochloric acid, organic acid, ion exchange resin etc.While making spent ion exchange resin as above-mentioned an acidic catalyst, be not particularly limited, but be preferably gel-type and degree of crosslinking is 1%～8%, is preferably 2%～6% sulfonic acid ion exchange resin.
Sulfonic acid cation exchange resin both can directly be used, and also can use as required the sulfonic acid cation exchange resin after modification.As the compound for above-mentioned modification, can enumerate compound having sulfydryl etc.
As the compound with sulfydryl, since can using in the past, become known for ω-pyridyl alkane thiols such as amino-alkane mercaptan such as 2-aminoothyl mercaptan in the purposes of above-mentioned modification, 2-(4-pyridyl) sulfur alcohol, easily by hydrolysis etc., show the compounds such as thiazolidines such as 2 of sulfydryl, 2-dimethylthiazole alkane.
In the reaction mixture generating, conventionally, except BPA, also contain the by products such as unreacted PL, unreacted acetone, catalyzer, water generation reaction and coloring material in above-mentioned building-up reactions operation.
Lowly boil that to remove operation be from resulting reaction mixture building-up reactions operation, to remove the operation of low boiling point component and catalyzer.The low boiling point component of indication refers to water generation reaction, unreacted acetone and the material approaching with their boiling points herein.In this operation, these low boiling point components can be by removing from above-mentioned reaction mixture such as underpressure distillation etc., and the solids component such as catalyzer can be waited from above-mentioned reaction mixture and be removed by filtration.It should be noted that, while using fix bed catalyst reactor, do not need specially Removal of catalyst.Underpressure distillation is preferably that 50mmHg～300mmHg, temperature are to carry out under the condition of 70 ℃～130 ℃ at pressure, more preferably at pressure, be that 100mmHg～200mmHg, temperature are to carry out under 80 ℃～120 ℃ conditions, sometimes there is azeotropic in unreacted PL, and its part is removed to outside system when underpressure distillation.
Above-mentioned crystallization/separation circuit is cooling by carrying out at the low mixed solution that obtains in removing operation of boiling, and makes the affixture crystallization of BPA and PL and carries out separated operation.From the viewpoint of improving workability preferably before this crystallization/separation circuit, by distillation, remove phenol or append phenol and the concentration of the BPA in the mixed solution obtaining in above-mentioned low boiling point component is removed operation is adjusted in advance to 10 % by weight～50 % by weight, is preferably 20 % by weight～40 % by weight, the yield of above-mentioned affixture crystallization can be improved like this, and the apparent viscosity of pulp-like mixed solution can be regulated.
In crystallization/separation circuit cooling conventionally 45 ℃～60 ℃, preferably at 50 ℃～55 ℃, carry out.Cooling by this, the crystallization of the affixture of BPA and PL, system becomes pulp-like.
Utilize the heat exchanger externally arranging or the evaporation of water latent heat adding in crystallization machine to carry out heat extraction, carry out thus cooling.Then, the mother liquor that the liquid separation of this pulp-like is become to affixture crystallization and contains byproduct of reaction by filtration, centrifugation etc., supplies affixture crystallization to subsequent processing.Part or all of the mother liquor being separated is recycled to building-up reactions operation via mother liquid disposal operation described later, as the phenol of raw material part or all and use, and then realize and improve reaction yield.
The operation of heating and melting is carried out in the crystallization that above-mentioned heating and melting operation is the affixture to obtaining in crystallization/separation circuit.The composition of this affixture crystallization is: BPA is 45 % by weight～70 % by weight, be preferably 50 % by weight～60 % by weight; PL is 55 % by weight～30 % by weight, be preferably 50 % by weight～40 % by weight.This crystallization is heated to 100 ℃～160 ℃, is preferably 110 ℃～150 ℃ and make after its melting for to subsequent processing.
It is in the fused solution from obtaining heating and melting operation, to remove the operation that for example obtains melting BPA for the aromatic monohydroxy compound of PL that above-mentioned PL removes operation.At PL, remove operation, by methods such as underpressure distillation, from the solution obtaining, remove PL, affixture crystallization is dissociated, thereby can reclaim highly purified BPA.This underpressure distillation preferably pressure be 10mmHg～100mmHg, temperature be under the condition of 150 ℃～220 ℃ (they being more preferably that 20mmHg～80mmHg, temperature are 160 ℃～200 ℃ at pressure) and the temperature of high 10 ℃ of the fusing point of the mixed solution of the BPA existing at least than system and PL under carry out.Also proposed also to carry out the method that steam stripped (Steam Stripping) is removed residual PL except underpressure distillation.
(manufacture method of aromatic copolycarbonate and producing apparatus)
The manufacture of aromatic copolycarbonate is according to carrying out as follows: in raw material preparation facilities, preparation is as the aromatic dihydroxy compound of raw material and the mixture of carbonic diester compound (raw material preparation section), under the existence of above-mentioned catalyst for ester exchange reaction, make these compounds in polycondensation reaction device, 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 that reaction is stopped and the unreacting material in polymerization liquid, byproduct of reaction volatilization are removed; Add the operation of thermo-stabilizer, release agent, tinting material etc.; Form as required the operation etc. of the particle of predetermined particle diameter, thereby produce aromatic copolycarbonate.
(raw material preparation section)
Raw material preparation section carries out in raw material preparation facilities, but owing to carrying out with continous way, therefore, as the device using, can use the continuous mixers such as static mixer (Static Mixer) in this operation.
In addition, aromatic dihydroxy compound and the carbonic diester to raw material preparation facilities, supplied with are supplied with continuously with molten state.That is, using and deliver to this raw material preparation facilities as the melting carbonic diester stream of the melts fluid of carbonic diester with as the mode of the melting aromatic dihydroxy compound stream of the melts fluid of aromatic dihydroxy compound, two kinds of fluids converge and mixed.Thus, the fused raw material that can prepare polycarbonate resin.
Above-mentioned melting carbonic diester stream can be by making carbonic diester melting, in pipe arrangement, flow to raw material preparation facilities generates.Therefore conventionally, when being made of, carbonic diester in molten state, if start not carry out cooling and directly use the carbonic diester of molten state from the manufacturing installation of carbonic diester, can realize saving thermal resource.
In addition, above-mentioned melting aromatic dihydroxy compound stream can be by making aromatic dihydroxy compound melting, in pipe arrangement, flow to raw material preparation facilities and generate.On the other hand, easily there is thermolysis in the melting aromatic dihydroxy compound of the condition of high temperature, therefore preferably do not keep for a long time this condition of high temperature.
Aromatic dihydroxy compound be preferably 20 minutes the time of the melts of the condition of high temperature with interior, more preferably 5～15 minutes.
Aromatic dihydroxy compound, was therefore considered not carry out from the manufacturing installation of melting aromatic dihydroxy compound cooling and is directly used the melting aromatic dihydroxy compound of molten state in molten state in the manufactured moment going out.But, just manufacture in melting aromatic dihydroxy compound in the near future and contain phenol, the state of the mixed melting thing in the aromatic dihydroxy compound containing phenol (following, to be sometimes referred to as " the 1st mixed melting thing ").The fusing point of the 1st mixed melting thing is lower than the fusing point of independent aromatic dihydroxy compound, if near the temperature fusing point of the 1st mixed melting thing, aromatic dihydroxy compound is difficult for decomposing.
On the other hand, in polycondensation, preferably remove the aromatic monohydroxy compounds such as phenol.Therefore, preferably carry out purification procedures, this operation is removed phenol from above-mentioned the 1st mixed melting thing, obtains melting aromatic dihydroxy compound.
Above-mentioned purification procedures is undertaken by aromatic dihydroxy compound purification devices.In this device, above-mentioned the 1st mixed melting thing is further applied to heat, remove phenol, thereby obtain melting aromatic dihydroxy compound.Then, this melting aromatic dihydroxy compound is sent to raw material preparation facilities, can be formed thus melting aromatic dihydroxy compound stream.
The amount of the aromatic monohydroxy compound (comprising phenol) in the melting aromatic dihydroxy compound obtaining in purification procedures is preferably below 1 % by weight, 0.5～0.01 % by weight more preferably.
Above-mentioned purification procedures conventionally under reduced pressure, be preferably under 10mmHg～100mmHg, more preferably under 20mmHg～80mmHg, carry out at pressure.And be preferably at 120 ℃～240 ℃, more preferably 150 ℃～220 ℃ and carry out in temperature.In addition, preferably at least than the temperature of high 10 ℃ of the fusing point of the 1st mixed melting thing, carry out.
Use Fig. 1 that above-mentioned operation is described.
First, the 1st mixed melting thing A is delivered to aromatic dihydroxy compound purification devices 11, carry out purifying, phenol is removed in distillation.Then, the melting aromatic dihydroxy compound after purifying is sent and forms melting aromatic dihydroxy compound stream A ', delivers to raw material preparation facilities 12.
In addition, melting carbonic diester stream B is directly delivered to raw material preparation facilities 12.
Melting aromatic dihydroxy compound stream A ' and melting carbonic diester stream B are mixed by the fluidic junction Q of raw material preparation facilities 12, in the interior formation mixture C of raw material preparation facilities 12.Mixture C is sent to polycondensation reaction device 13 through the outlet R of raw material preparation facilities 12.
(polycondensation step)
The aromatic dihydroxy compound of the molten state obtaining in above-mentioned operation and the mixture C of carbonic diester are (following, be sometimes referred to as " the 2nd mixed melting thing ") as polycarbonate resin fused raw material, delivered to continuously in the 1st polycondensation reaction device 13 polycondensation reaction devices such as grade of Fig. 1, add transesterification catalyst etc. simultaneously, carry out continuously polycondensation.It should be noted that, the 2nd section of later polycondensation reaction device is not shown in Figure 1.
This polycondensation be generally 2 stages above, preferably with the multisegment mode of 3 sections～7 sections, carry out continuously.Concrete reaction conditions is 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.
For multisegment mode, in each polycondensation reaction device, in order more effectively will to carry out along with polycondensation, the phenol of by-product is removed to system, in above-mentioned reaction conditions, periodically sets higher temperature, high vacuum more for.It should be noted that, in order to prevent that the qualities such as tone of resulting aromatic copolycarbonate from reducing, and preferably sets low temperature, short residence time(SRT) as much as possible.
While carrying out polycondensation step with multisegment mode, 2 above reaction units that comprise vertical reaction device are set conventionally, thereby increase the viscosity-average molecular weight of aromatic copolycarbonate.Reaction unit conventionally arranges 3～6, preferably arranges 4～5.
As reaction unit, can use such as stirring grooved reaction unit, film reaction unit, centrifugal thin film evaporation reaction unit, the mixing reaction unit of Surface Renewal type twin shaft, double-shaft horizontal stirring reaction device, wet wall type reaction unit, the free-falling orifice plate type reaction unit that carries out polymerization simultaneously, carry out being with of polymerization porous template wiry reaction unit etc. when falling along wire.Wherein, preferably stir grooved reaction unit, double-shaft horizontal stirring reaction device.
As the form of the stirring rake of vertical reaction device, can enumerate such as vane wheel oar, blade oar, three leaf swept-back (Pfaudler) oars, anchor formula oar, general can formula (full zone) oar (manufacture of Shinko Pantec company), SANMELER oar (Mitsubishi Heavy Industry Ltd.'s manufacture), MAXBLEND oar (Sumitomo Heavy Industries, Ltd's manufacture), ribbon oar, turn round grid oar (Hitachi Ltd.'s manufacture) etc.Wherein, preferred MAXBLEND oar (Sumitomo Heavy Industries, Ltd's manufacture), ribbon oar.
In addition, horizontal reacting device refers to the device that the turning axle of stirring rake is horizontal (horizontal direction).As the stirring rake of horizontal reacting device, can enumerate single-shaft variant stirring rakes such as rondelle, blade type, cartwheel pattern; The biaxial type stirring rakes such as HVR, SCR, N-SCR (Mitsubishi Heavy Industry Ltd.'s manufacture), BIVOLAK (Sumitomo Heavy Industries, Ltd's manufacture) or glasses oar, grid oar (Hitachi Ltd.'s manufacture).Wherein, preferred cartwheel pattern, glasses oar, grid oar (Hitachi Ltd.'s manufacture).
It should be noted that, the transesterification catalyst using in the polycondensation of aromatic dihydroxy compound and carbonic diester compound is preferably prepared with aqueous solution form conventionally in advance.Concentration for aqueous catalyst solution is not particularly limited, and can the solubleness in water be adjusted into concentration arbitrarily according to catalyzer.And, also can select other solvents such as acetone, ethanol, toluene, phenol to replace water.
Proterties for the water for catalyst-solvent is not particularly limited, as long as kind and the constant concentration of contained impurity are preferably used distilled water or deionized water etc. conventionally.
(optimum condition of the producing apparatus aspect of aromatic copolycarbonate)
Utilize above-mentioned aromatic dihydroxy compound purification devices, can obtain the melting aromatic dihydroxy compound after purifying.
As mentioned above, if easily there is thermolysis in the melting aromatic dihydroxy compound condition of high temperature.Therefore,, when melting aromatic dihydroxy compound is formed to melting aromatic dihydroxy compound stream A ', owing to keeping the condition of high temperature, therefore easily there is thermolysis.
On the other hand, the fusing point of the mixture of aromatic dihydroxy compound and carbonic diester is lower than independent aromatic dihydroxy compound, by making near temperature as the 2nd mixed melting thing of the melts of this mixture fusing point in the 2nd mixed melting thing, can to suppress the thermolysis of aromatic dihydroxy compound.Therefore, from melting aromatic dihydroxy compound out of aromatic dihydroxy compound purification devices stream A ' to flow the distance that B converges preferably short as far as possible with above-mentioned melting carbonic diester.
Therefore, by the outlet P from aromatic dihydroxy compound purification devices 11 till the volume of the stream of the fluidic junction Q that the above-mentioned melting aromatic dihydroxy compound stream A ' of making raw material preparation facilities 12 and above-mentioned melting carbonic diester stream B converge is made as V1 (scope of the dotted line of the V1 of Fig. 1 is interior), by from fluidic junction Q till the volume of the stream of the entrance S of polycondensation reaction device 13 is made as the V2 scope of the dotted line of the V2 of Fig. 1 (in), now the ratio of V1 and V2, be that V1/V2 is preferably below 0.5, more preferably below 0.2.If be greater than 0.5, melting aromatic dihydroxy compound has the trend of easy generation thermolysis.On the other hand, above-mentioned ratio is preferably more than 0.01 conventionally.If above-mentioned ratio is less than 0.01, mean that V2 is excessive, sometimes cause equipment larger.
Preferable volume as V2 is 0.5m
3～10m
3, 1m more preferably
3～5m
3.
It should be noted that, at fluidic junction Q, between the entrance S of polycondensation reaction device 13, also can be provided with tank.Wherein, the volume of this tank also forms from fluidic junction Q till a part for the volume V 2 of the stream of the entrance S of polycondensation reaction device 13 in this case.
More than in the pipe arrangement of above-mentioned melting aromatic dihydroxy compound stream A ', linear velocity is preferably 0.3 meter per second, more preferably more than 0.5 meter per second.And in this pipe arrangement linear velocity be preferably 3.0 meter per seconds following, more preferably 2.0 meter per seconds following, most preferably be below 1.5 meter per seconds.It is elongated that linear velocity hour is joined intraductal retention time, and thermolysis likely easily occurs melting aromatic dihydroxy compound.Pressure-losses when linear velocity is larger in pipe arrangement increases, and must exceedingly improve the ability of liquid-feeding pump, due to the heat of friction with pipe arrangement or the heat release in liquid-feeding pump, likely generates impurity.
More than in the pipe arrangement of above-mentioned the 2nd mixed melting thing, linear velocity is preferably 0.3 meter per second, more preferably more than 0.5 meter per second.And in this pipe arrangement linear velocity be preferably 3.0 meter per seconds following, more preferably 2.0 meter per seconds following, most preferably be below 1.5 meter per seconds.It is elongated that linear velocity hour is joined intraductal retention time, and thermolysis likely easily occurs melting aromatic dihydroxy compound.Pressure-losses when linear velocity is larger in pipe arrangement increases, and must exceedingly improve the ability of liquid-feeding pump, due to the heat of friction with pipe arrangement or the heat release in liquid-feeding pump, likely generates impurity.
The temperature of above-mentioned the 1st mixed melting thing be preferably 230 ℃ following, more preferably 220 ℃ following, most preferably be 200 ℃ following, be particularly preferably below 180 ℃.If excess Temperature, the thermolysis of the 1st mixed melting thing A is carried out, and sometimes causes impurity in purifying aromatic dihydroxy compound to increase.And it is above, more preferably high more than 10 ℃ than the fusing point of the 1st mixed melting thing A that this temperature is preferably the fusing point of the 1st mixed melting thing A.
In addition, the temperature of the melting aromatic dihydroxy compound stream A ' obtaining in aromatic dihydroxy compound purification devices 11 is preferably below 220 ℃, more preferably below 210 ℃, more preferably below 200 ℃.If excess Temperature, thermolysis is carried out, and sometimes causes impurity level to increase.And, more than this temperature is preferably the fusing point of aromatic dihydroxy compound.
Below the temperature of above-mentioned melting carbonic diester stream B is preferably 130 ℃, more preferably below 110 ℃.And more than this temperature is preferably 85 ℃, more preferably more than 90 ℃.If excess Temperature, the temperature of above-mentioned the 2nd mixed melting thing raises, and the thermolysis of aromatic dihydroxy compound is carried out, and likely causes impurity to increase, if temperature is too low, likely cause having aromatic dihydroxy compound to separate out in above-mentioned the 2nd mixed melting thing.
Further, the temperature of above-mentioned the 2nd mixed melting thing be preferably 180 ℃ following, more preferably 160 ℃ following, more preferably below 155 ℃.If excess Temperature, the thermolysis of aromatic dihydroxy compound is carried out, and sometimes causes impurity to increase.And more than this temperature is preferably the fusing point of the 2nd mixed melting thing C.
From the outlet P of aromatic dihydroxy compound purification devices 11 till the distance of the fluidic junction Q that the above-mentioned melting aromatic dihydroxy compound stream raw material preparation facilities 12 and above-mentioned melting carbonic diester stream converge be preferably 5m more than, more preferably more than 10m.And this distance is preferably below 100m, more preferably below 50m.Pipe arrangement distance is more short better, if but too short, aspect configuration, likely cause machine cannot be set.If pipe arrangement distance is long, the thermolysis of aromatic dihydroxy compound is carried out, and likely causes impurity to increase.
From fluidic junction Q till the pipe arrangement of the entrance S of polycondensation reaction device 13 distance be preferably 50m more than, more preferably more than 100m.And this distance is preferably below 500m, more preferably below 300m.Pipe arrangement distance is more short better, if but too short, aspect configuration, likely cause machine cannot be set.If pipe arrangement distance is long, the thermolysis of aromatic dihydroxy compound is carried out, and likely causes impurity to increase.
For the outlet P from aromatic dihydroxy compound purification devices 11, till the stream of fluidic junction Q, melting carbonic diester flow to the stream of fluidic junction Q and from fluidic junction Q till the stream of the entrance S of polycondensation reaction device 13, the periphery that is preferably shown in stream pipe arrangement 14 according to Fig. 3 arranges insulation pipe arrangement 15.Now, if the vertical pipe arrangement of stream pipe arrangement 14, the preferred concentric circles with stream pipe arrangement 14 arranges insulation pipe arrangement 15 symmetrically.If the horizontal pipe arrangement of stream pipe arrangement 14, preferably according to shown in Fig. 4, insulation pipe arrangement 15 being arranged on below lower part of stream pipe arrangement 14.If stream pipe arrangement 14 is for horizontal pipe arrangement and with the concentric circles of stream pipe arrangement 14, insulation pipe arrangement 15 is set as shown in Figure 3, likely excessively use thermal medium, likely cause the thermolysis of aromatic dihydroxy compound carry out and impurity is increased.In addition, preferred circulation steam or heated oil in insulation pipe arrangement 15.
The difference of the insulation interior temperature of pipe arrangement 15 and the interior temperature of stream pipe arrangement 14 be preferably 50 ℃ following, more preferably 30 ℃ below, more preferably below 10 ℃.If difference is excessive likely makes the thermolysis of aromatic dihydroxy compound carry out, impurity increases.
Embodiment
Below, by embodiments of the invention, further describe, but be not construed to and be defined in this.Each evaluation method for polycarbonate resin describes.
(1) viscosity-average molecular weight
The dichloromethane solution (concentration (C) is 0.6 Grams Per Minute liter) of preparing aromatic copolycarbonate, using this solution of determination of ubbelohde viscometer is the specific viscosity (η of 20 ℃ in temperature
sp), by following formula, calculate viscosity-average molecular weight (Mv).
η
sp/C＝[η](1+0.28η
sp)
[η]＝1.23×10
-4Mv
0.83
(2) the particle YI value of aromatic copolycarbonate
The tone of aromatic copolycarbonate is according to ASTM D1925, the YI value in the reflected light of particle (yellowness index numerical value) to be measured to evaluate.
The spectral photometric colour measuring meter (CM-5) that has used Konica Minolta Co., Ltd to manufacture as determinator.It is 30mm, SCE that condition determination has been selected mensuration diameter.Culture dish is measured with proofreading and correct glass (CM-A212) and embedded determination part, and on cover, zero correction box (CM-A124) carries out zero correction from it, then uses built-in white correcting plate to carry out white and proofreaies and correct.
Use white correcting plate (CM-A210) to measure, confirm L* and be 99.40 ± 0.05, a* is 0.03 ± 0.01, b* for-0.43 ± 0.01, YI value is-0.58 ± 0.01.In the mensuration of particle, by grain packing, at internal diameter, be 30mm, highly for measuring to the degree of depth of 40mm left and right in the cylindrical glass container of 50mm.From Glass Containers, take out particle, and then measure, repeat 2 these operations.To amount to the mean value of measured value of 3 times as the YI value of aromatic copolycarbonate particle.The yellow sense of the less aromatic copolycarbonate of this YI value is fewer, means that tone is more excellent.
(3) the isopropenyl phenol amount in dihydroxyphenyl propane
1g dihydroxyphenyl propane is dissolved in acetone 23ml, ((Shimadzu Corporation manufactures (LC-10AT), post is MCI GEL ODS) (5 μ m), 4.6mmID * 150mmL, detector are 219nm, elutriant: acetonitrile/water=4/6 volume ratio) measure, the isopropenyl phenol amount in dihydroxyphenyl propane has been carried out quantitatively to utilize liquid chromatograph.
(Production Example of DPC (diphenyl carbonate))
To the reactor that temperature is remained on to 150 ℃, supply with continuously commercially available phenol and the pyridine catalyst after melting, and then supply with continuously phosgene gas.Follow the phosgenation reaction of phenol and the hydrogen chloride gas of by-product is cooled to 10 ℃ carries out condensation.In condensate return reactor, uncondensed gas is by alkaline aqueous solution and rear discharge.On the other hand, from reactor, draw off continuously the reaction solution that approximately contains 91 % by weight DPC.The reactivity of the phosgene in reaction process is roughly 100%.
Then, the aqueous sodium hydroxide solution of above-mentioned reaction solution and approximately 5 % by weight is supplied to respectively to Teflon liner manufactures in and tempering tank, at 80 ℃, mix approximately 10 minutes, pH is adjusted into 8.5.By the organic phase standing separation after neutralization, and be delivered to washing tempering tank.In washing tempering tank, utilize the warm water of approximately 30 % by weight that are equivalent to organic phase to clean organic phase, isolate water, thereby obtained rough DPC (containing water 1 % by weight, pyridine 2 % by weight, phenol 8 % by weight and DPC89 % by weight).
Then, above-mentioned rough DPC is supplied to continuously to the stage casing of the low distillation tower that boils with the feed speed of approximately 30 kgs/hr.It is the continuous still battery tower of 8 that the low distillation tower that boils has used theoretical plate number, its internal diameter is 150mm, highly for 4.0m, and on top, there is reflux, in central authorities, there is raw material supplying portion, in concentrated portion and recoverer, filled Sulzer filler (Sulzer packing) (Sumitomo Heavy Industries, Ltd's manufacture).Be that to be about 220 ℃, head temperature be thereby that 80～100 ℃, midsection temperature are to distill these boiling points of dephlegmate, pyridine and phenol lower than the material of DPC under 160 ℃, the reflux ratio condition that is 1 for 20torr, thermal oil temperature in vacuum tightness.From the speed with approximately 26 kgs/hr at the bottom of tower, draw off continuously DPC (containing below water 10 ppm by weight, below pyridine 1 ppm by weight and phenol 50 ppm by weight).
Further, the DPC of liquid at the bottom of the tower as the low distillation tower that boils is supplied with to the paramount distillation tower that boils continuously.Height boils, and to have used theoretical plate number be the continuous still battery tower of 8 to distillation tower, its internal diameter is 200mm, highly for 4.0m, it has reflux, in central authorities, has raw material supplying portion on top, filled Sulzer filler (Sumitomo Heavy Industries, Ltd's manufacture) in concentrated portion and recoverer.In vacuum tightness, be that 20torr, thermal oil temperature are about 240 ℃, head temperature and are about under the condition that 180 ℃, reflux ratio are 0.5 and distill, from top, obtained the fused solution of purifying DPC.
(Production Example of BPA)
In thering is the flow type synthesis reactor of thermoswitch, filled 60L (liter) utilize in 4-pyridine sulfur alcohol and 15% sulfonic group after sulfonic acid type acidic cation-exchange resin (Mitsubishi chemical Co., Ltd manufactures, trade(brand)name Diaion SK-104).The flow that the temperature of take in this synthesis reactor is 80 ℃, 68.2 kgs/hr packs into take phenol: the mixed solution that the ratio of mixture that the mol ratio of acetone is 10:1 mixes commercially available phenol and acetone also makes it reaction.The transformation efficiency of acetone is 80%.For reaction mixture, use distillation tower to remove low boilers (part for unreacted acetone, water, phenol) with the flow of 5.1 kgs/hr, be then cooled to 50 ℃ of crystallizations that make affixture.Then, by filtration, make the crystallization of affixture separated with mother liquor.The flow of the crystallization of affixture is that 16.5 kgs/hr, the flow of mother liquor are 46.5 kgs/hr.After making resulting affixture crystallization again be dissolved in the phenol of 27.2 kgs/hr of flows, be cooled to 50 ℃ and make crystallization, by filtration, make the crystallization of affixture separated with mother liquor.Flow is respectively 11.3 kgs/hr and 32.5 kgs/hr.Make resulting crystallization melting, thereby obtained the mixed melting thing of BPA and phenol, i.e. the 1st mixed melting thing.
[purifying of BPA]
Keep molten state to send into unchangeably in the aromatic dihydroxy compound purification devices 11 shown in Fig. 1 the 1st mixed melting thing obtaining in the Production Example of the BPA above-mentioned.Then, under 180 ℃, the condition of 0.3Torr, distill, thereby obtained the melts of the BPA after purifying.
(reference example 1)
Use device and the pipe arrangement circuit shown in Fig. 1, to raw material preparation section and the 1st polycondensation reaction device, send into.
[raw material preparation section]
The melts of the BPA that purifying obtains in aromatic dihydroxy compound purification devices 11 is carried to raw material preparation facilities via pipe arrangement from outlet P, and formation temperature is that 180 ℃, flow velocity are the melting aromatic dihydroxy compound stream A ' of 0.7 meter per second.
In addition, the fused solution of above-mentioned purifying DPC is carried to raw material preparation facilities via pipe arrangement, formation temperature is that 100 ℃, flow velocity are the melting carbonic diester stream B of 0.8 meter per second.
Then, these fluids A ' and B are converged, be fed through raw material preparation facilities 12.Now, V1 is 0.16m
3(from the outlet P of aromatic dihydroxy compound purification devices 11 till the distance that makes the fluidic junction Q that above-mentioned melting aromatic dihydroxy compound stream and above-mentioned melting carbonic diester stream converges raw material preparation facilities 12 is 30m).In addition, DPC/BPA is made as 1.03 with molar ratio computing.
After making the temperature of raw material preparation facilities 12 be 150 ℃, making mixed flow homogenizing, resulting the 2nd mixed melting thing C is delivered to the 1st vertical mixing reactor, carry out polycondensation.Now, using V2 is 0.92m
3device.
Melt phase polycondensation is to utilize the apparatus for continously production with 3 vertical mixing reactors and 1 Horizontal stirring reactor to manufacture aromatic copolycarbonate according to following condition.
(the 1st vertical mixing reactor): 220 ℃, 13.3kPa, mean residence time are 60 minutes
(the 2nd vertical mixing reactor): 260 ℃, 4kPa, mean residence time are 60 minutes
(the 3rd vertical mixing reactor): 270 ℃, 200Pa, mean residence time are 30 minutes
(the 1st Horizontal stirring reactor): 280 ℃, 70Pa, mean residence time are 90 minutes
Above-mentioned the 2nd mixed melting thing C is supplied in the 1st vertical mixing reactor continuously.Now before being about to arrive the 1st vertical mixing reactor, take with respect to 1 mole of BPA is 0.5 * 10
-6mole ratio from catalyzer ingress pipe, supply with continuously the cesium carbonate aqueous solution as catalyzer.In addition, the mode that the 1st vertical mixing reactor is 60 minutes according to mean residence time is controlled at the aperture of the valve arranging on the polymkeric substance vent line of trench bottom, makes liquid level keep constant.
And then the polymerization liquid of discharging from the bottom land of the 1st vertical mixing reactor is supplied to the 2nd vertical mixing reactor, the 3rd vertical mixing reactor and the 1st Horizontal stirring reactor successively continuously.According to the mean residence time that makes each reactor, during polyreaction, be that the mode of time is controlled liquid level as mentioned above, and distill the phenol of removing with polyreaction while by-product.
(reference example 2)
The length that changes pipe arrangement, making V1 is 0.55m
3(from the outlet P of aromatic dihydroxy compound purification devices 11 till the distance that makes the fluidic junction Q that above-mentioned melting aromatic dihydroxy compound stream and above-mentioned melting carbonic diester stream converges raw material preparation facilities 12 is 100m), in addition, similarly implement with reference example 1.
(embodiment 1)
According to making the mode that thermal history is identical with reference example 1, use the reactor with stirrer of 200mL to carry out polyreaction.Described in specific as follows.
The BPA116g that outlet P from aromatic dihydroxy compound purification devices is sent is added on the reactor of 200mL with stirrer, at 180 ℃ of interior temperature, under stirring, keeps 5 minutes.Add wherein DPC114.5g (mol ratio is DPC/BPA=1.045) after melting and form the 2nd molten mixture, at 150 ℃ of interior temperature, under stirring, keep 13 minutes.Thereafter, 40 minutes used times were decompressed to 13.3kPa (100Torr) with absolute manometer from 101.3kPa (760Torr) by the pressure in reactor.
Then, the pressure in reactor is held in to 13.3kPa, further phenol is removed in distillation, carries out 80 minutes transesterification reactions simultaneously.Then utilize thermal medium chuck to make interior temperature rise temperature (250 ℃), 40 minutes used times made with absolute manometer, from 101.3kPa, to be decompressed to 13.3kPa in reactor.Thereafter, continue to heat up, further 40 minutes used times made interior pressure from 13.3kPa, be decompressed to 399Pa (3Torr) with absolute manometer, and the phenol distilling out is expelled to outside system.Further, continue to heat up, the absolute pressure in the 2nd reactor arrives 70Pa (about 0.5Torr) afterwards, keeps 70Pa, carries out polycondensation.Final internal temperature in reactor is 280 ℃.When stirrer reaches predefined regulation stirring power, stop polycondensation.
Now the Mv of resulting aromatic copolycarbonate is 21,200, and terminal hydroxyl concentration is 650ppm, and the YI value of tone is 4.2.
(comparative example 1)
According to making the mode that thermal history is identical with reference example 2, use 200mL to carry out polyreaction with the reactor of stirrer.Described in specific as follows.
The BPA that outlet P from aromatic dihydroxy compound purification devices is sent keeps 16 minutes under 180 ℃ of interior temperature, implements similarly to Example 1 in addition.
The YI value that now Mv of resulting aromatic copolycarbonate is 21,400, terminal hydroxyl concentration is 705ppm, tone is 6.2.
[thermostability of BPA]
(reference example 3)
BPA100g is put into glass container made and heat, the thermostability during to 180 ℃, 200 ℃ and 220 ℃ is measured.The results are shown in Fig. 2.
The measuring method of thermostability is undertaken by the increasing amount of utilizing liquid chromatography to measure isopropenyl phenol (IPP).
Shown in reaction formula described as follows (1), IPP is the resolvent of BPA, is the compound that causes yellowing.
Its result is known, and the growing amount of the higher IPP of temperature is larger.
[changing 1]
Industrial applicibility
The present invention can realize saving thermal resource when manufacturing aromatic copolycarbonate, further, can suppress the decomposition of aromatic dihydroxy compound, can stably manufacture aromatic copolycarbonate that tone is good etc., and its industrial applicibility is high.
It should be noted that, the full content of specification sheets, claims, accompanying drawing and the summary that No. 2012-083283, the Japanese patent application submitted on March 30th, 2012 is quoted so far, as the disclosure of specification sheets of the present invention, charges in the application.
The explanation of symbol
11 aromatic dihydroxy compound purification devices
12 raw material preparation facilitiess
13 the 1st polycondensation reaction devices
14 stream pipe arrangements
15 insulation pipe arrangements
A the 1st mixed melting thing
A ' melting aromatic dihydroxy compound stream
B melting carbonic diester stream
C the 2nd mixed melting thing
The outlet of P aromatic dihydroxy compound purification devices
Q fluidic junction
The outlet of R raw material preparation facilities
S the 1st polycondensation reaction device entrance
Claims (16)
1. the manufacture method of an aromatic copolycarbonate, it is to manufacture the method for aromatic copolycarbonate through take polycondensation step that carbonic diester and aromatic dihydroxy compound carry out polycondensation as raw material, it is characterized in that, by making to converge with being incorporated in pipe arrangement as the melting carbonic diester stream of the melts fluid of described carbonic diester with as the melting aromatic dihydroxy compound stream of the melts fluid of described aromatic dihydroxy compound, mix, prepare thus polycarbonate resin fused raw material, then make described polycarbonate resin fused raw material in polycondensation reaction device, carry out continuously polycondensation.
2. the manufacture method of aromatic copolycarbonate as claimed in claim 1, is characterized in that, described polycondensation step is the operation that makes carbonic diester and aromatic dihydroxy compound carry out polycondensation under the existence of transesterification catalyst.
3. the manufacture method of aromatic copolycarbonate as claimed in claim 2, it is characterized in that, described transesterification catalyst does not comprise that for choosing is free the compound of the long formula periodic table of elements the 1st family's element of hydrogen is, the basic cpd of at least one 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.
4. the manufacture method of the aromatic copolycarbonate as described in any one in claim 1～3, is characterized in that, carbonic diester choosing freely replace or the group of unsubstituted diphenyl carbonate and dialkyl carbonate composition at least one.
5. the manufacture method of the aromatic copolycarbonate as described in any one in claim 1～4, is characterized in that, aromatic dihydroxy compound is two (4-hydroxy phenyl) propane of 2,2-.
6. the manufacture method of the aromatic copolycarbonate as described in any one in claim 1～5, is characterized in that, the time that described aromatic dihydroxy compound is melts is in 20 minutes.
7. the manufacture method of the aromatic copolycarbonate as described in any one in claim 1～6, is characterized in that, the content of the aromatic monohydroxy compound in the melts of described aromatic dihydroxy compound is below 1 % by weight.
8. the manufacture method of the aromatic copolycarbonate as described in any one in claim 1～7, is characterized in that, the temperature of described melting aromatic dihydroxy compound stream is below 180 ℃.
9. the manufacture method of the aromatic copolycarbonate as described in any one in claim 1～8, it is characterized in that, described aromatic dihydroxy compound at least comprises removes the aromatic dihydroxy compound after aromatic monohydroxy compound the aromatic dihydroxy compound from containing aromatic monohydroxy compound.
10. the manufacture method of aromatic copolycarbonate as claimed in claim 9, is characterized in that, described in remove aromatic monohydroxy compound method be distillation.
The manufacture method of 11. aromatic copolycarbonates as described in any one in claim 1～10, is characterized in that, utilizes static mixer to carry out the preparation of described aromatic polycarbonate resin fused raw material.
The producing apparatus of 12. 1 kinds of aromatic copolycarbonates, it is the producing apparatus of the aromatic copolycarbonate that uses in the manufacture method described in any one in claim 1～11, it is characterized in that,
This producing apparatus possesses:
Raw material preparation facilities, it converges as the melting carbonic diester stream of the melts fluid of described carbonic diester with as the melting aromatic dihydroxy compound stream of the melts fluid of described aromatic dihydroxy compound by making, and prepares thus polycarbonate resin fused raw material in pipe arrangement; With
Polycondensation reaction device, is used the polycarbonate resin fused raw material of preparing in described raw material preparation facilities to carry out continuously polycondensation.
The producing apparatus of 13. aromatic copolycarbonates as claimed in claim 12, it is characterized in that, this producing apparatus further possesses aromatic dihydroxy compound purification devices, this purification devices is removed aromatic monohydroxy compound from the aromatic dihydroxy compound that contains aromatic monohydroxy compound, then with the form of melting aromatic dihydroxy compound, send to described raw material preparation facilities, form thus described melting aromatic dihydroxy compound stream.
The producing apparatus of 14. aromatic copolycarbonates as described in claim 12 or 13, it is characterized in that, the volume that the described melting aromatic dihydroxy compound stream from described raw material preparation facilities and described melting carbonic diester flow converges to the stream till described polycondensation reaction device entrance is 0.5m
3above.
The producing apparatus of 15. aromatic copolycarbonates as described in any one in claim 12～14, is characterized in that,
To from exporting to of described aromatic dihydroxy compound purification devices, make the volume of the stream till described melting aromatic dihydroxy compound stream and described melting carbonic diester stream converge described raw material preparation facilities be made as V1,
The volume of the stream till the entrance that converges to described polycondensation reaction device of the described melting aromatic dihydroxy compound stream from described raw material preparation facilities and described melting carbonic diester stream is made as to V2,
V1 and the ratio V1/V2 of V2 are below 0.5.
The producing apparatus of 16. aromatic copolycarbonates as described in any one in claim 12～15, is characterized in that possessing static mixer in described raw material preparation facilities.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-083283 | 2012-03-30 | ||
| JP2012083283 | 2012-03-30 | ||
| PCT/JP2013/059667 WO2013147221A1 (en) | 2012-03-30 | 2013-03-29 | Process for manufacturing aromatic polycarbonate and manufacturing facility |
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|---|---|
| CN104169326A true CN104169326A (en) | 2014-11-26 |
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| CN201380015697.3A Pending CN104169326A (en) | 2012-03-30 | 2013-03-29 | Process for manufacturing aromatic polycarbonate and manufacturing facility |
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|---|---|
| JP (1) | JP6167570B2 (en) |
| KR (1) | KR101955064B1 (en) |
| CN (1) | CN104169326A (en) |
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| WO (1) | WO2013147221A1 (en) |
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| CN110577633A (en) * | 2019-09-11 | 2019-12-17 | 利华益维远化学股份有限公司 | polycarbonate production raw material pretreatment system and method |
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| JP6211405B2 (en) * | 2013-12-03 | 2017-10-11 | 旭化成株式会社 | Method for producing aromatic polycarbonate, aromatic polycarbonate, and molded article |
| CN109971147B (en) * | 2014-02-28 | 2022-06-28 | 出光兴产株式会社 | Polycarbonate resin and polycarbonate resin composition |
| JP6627148B2 (en) * | 2014-02-28 | 2020-01-08 | 出光興産株式会社 | Polycarbonate resin and polycarbonate resin composition |
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| CN1466605A (en) * | 2000-09-26 | 2004-01-07 | 三菱化学株式会社 | Process for production of aromatic polycarbonates |
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| JP3187957B2 (en) | 1992-07-16 | 2001-07-16 | 日本ジーイープラスチックス株式会社 | Manufacturing method of aromatic polycarbonate |
| JP3681529B2 (en) * | 1997-12-26 | 2005-08-10 | 日本ジーイープラスチックス株式会社 | Method for producing polycarbonate |
| KR101129202B1 (en) * | 2006-06-15 | 2012-04-16 | 미쓰비시 가가꾸 가부시키가이샤 | Equipment for production of polycarbonate resin and process for production thereof |
| JP5332100B2 (en) * | 2006-07-26 | 2013-11-06 | 三菱化学株式会社 | Continuous production method and production apparatus for aromatic polycarbonate |
| JP5200375B2 (en) * | 2006-12-18 | 2013-06-05 | 三菱化学株式会社 | Method for producing polycarbonate resin |
| CN103992469B (en) * | 2007-12-13 | 2018-03-16 | 三菱化学株式会社 | Makrolon and its article shaped |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1466605A (en) * | 2000-09-26 | 2004-01-07 | 三菱化学株式会社 | Process for production of aromatic polycarbonates |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110577633A (en) * | 2019-09-11 | 2019-12-17 | 利华益维远化学股份有限公司 | polycarbonate production raw material pretreatment system and method |
| WO2021047037A1 (en) * | 2019-09-11 | 2021-03-18 | 利华益维远化学股份有限公司 | System and method for pretreating raw materials for polycarbonate production |
| CN110577633B (en) * | 2019-09-11 | 2023-12-19 | 利华益维远化学股份有限公司 | Pretreatment system and method for polycarbonate production raw materials |
Also Published As
| Publication number | Publication date |
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| KR20140145131A (en) | 2014-12-22 |
| IN2014DN07820A (en) | 2015-05-15 |
| KR101955064B1 (en) | 2019-03-06 |
| JP2013227510A (en) | 2013-11-07 |
| WO2013147221A1 (en) | 2013-10-03 |
| JP6167570B2 (en) | 2017-07-26 |
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