TW200528488A - A method of producing organic solution of refined polycarbonicester and high purity polycarbonic ester - Google Patents

Abstract

This invention relates to a method of producing organic solution of refined polycarbonic ester and high purity polycarbonic ester by using such organic solution of refined polycarbonic ester. The method comprise: mixing a crude polycarbonate organic solution after the polycondensation by an interfacial polycondensation method which contains water-soluble impurities, with an aqueous washing liquid to form an emulsion; and performing purification using a condensor. The manufacturing process performs the operation while controlling a draw-out amount of the polycarbonate organic solution whose moisture has been removed and which is drawn out from the condensor and a discharge amount of the aqueous solution from the condensor top which contains the impurities along with part of the polycarbonate organic solution, so that the polycarbonate organic solution and the aqueous washing liquid may not form a interface substantially by separating into two phases of the organic phase and the aqueous phase at least in the element section inside the condensor to prevent the adhesion and gathing of impurity. By operating as in the above, the manufacturing process produces the purified polycarbonate organic solution efficiently and produces the high-purity polycarbonate using such purified organic solution.

Description

200528488 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a crude polycarbonate organic solution containing water-soluble impurities obtained by an interfacial polycondensation method, and washed with an aqueous cleaning solution to produce a refined product. Method for polycarbonate organic solution and method for producing high-purity polycarbonate using the refined polycarbonate organic solution; more specifically, the present invention relates to a crude product containing water-soluble impurities obtained by an interfacial polycondensation method Polycarbonate organic solution is emulsified by mixing with an aqueous cleaning solution. When the emulsion is separated into an organic phase and an aqueous phase containing impurities using an I condenser to produce a purified polycarbonate organic solution, the coagulation is performed. The device operates under specific operating conditions. At least the component part in the condenser can prevent the adhesion and aggregation of impurities with intermediate specific gravity, and can stably perform the separation operation. At the same time, it can effectively produce a refined polycarbonate organic solution, and A method for producing a high-purity polycarbonate using the purified polycarbonate organic solution.

The manufacturing method of polycarbonate is an interfacial polycondensation method using a halogen-based organic solvent such as dichloromethane; when the interfacial polycondensation method is used to produce polycarbonate, after the polycondensation reaction is completed, an organic solution containing polycarbonate and an aqueous solution are obtained. Mixture; The organic solution containing polycarbonate is usually in the state of an emulsion. It is necessary to separate the emulsion into an organic solution of polycarbonate and an aqueous solution containing impurities. In addition, after the reaction is completed, impurities such as sodium, unreacted monomers, and catalysts remain in the polycarbonate organic solution, which is generally performed in -4- 200528488 (2) Polycarbonate organic solution, adding alkali The alkaline aqueous solution, acidic aqueous solution, pure water, etc. are removed by stirring and washing; further, for the purpose of improving the washing efficiency, the mixture of the crude polycarbonate organic solution and the washing liquid is vigorously stirred to emulsify. In the past, methods for re-separating the emulsion thus obtained include a liquid-liquid centrifugation method, a standing separation method, or a condensate separation method. However, the centrifugal separation method not only has high equipment costs and maintenance costs, but also has a rotating part. It is necessary to prepare a preparatory machine due to the failure of the solvent and abrasion, sintering of the accumulated resin due to the scattering of the dichloromethane of the reaction solvent, and the failure of the separator repeatedly, etc., and the standing separation method also has a slow sedimentation speed. For this reason, it is necessary to have the disadvantage of a large standing separation tank. Therefore, a cohesive separation method has been developed to solve these problems. For example, there is a method of separating a polycarbonate resin liquid by filtering the contact angle with water at 40 ° C or less (for example, refer to Japanese Patent Publication No. 46-4 1). No. 622); However, in this method, it is difficult to remove fine water droplets, and it is necessary to repeatedly pass through the filter layer; after the separation, there may be contamination from the filter material layer; further, it needs to pass from the filter material to the separation. For longer periods, a larger standing separation tank is necessary. There are aqueous layers in the range of pH 2 to 14, emulsifying polycarbonate organic solutions, passing fiber layers with a thickness of 10 to 5000 mm at a space velocity of 0.01 to 2 cm / sec, and an apparent density of 0.2 to 0.7 g / m £. Disclosure of a method for separating two phases (for example, refer to Japanese Patent Application Laid-Open No. 5 5-1 043 1 6); however, in this method, the thickness of the filter material layer is too thick, and there are problems such as pressure loss due to filling. 0 -5- 200528488 (3) In addition, a polycarbonate solution and an aqueous cleaning solution are mixed with a mixer to form a mixed solution in an oil-in-water emulsified state, and then separated into a polycarbonate solution phase by passing through a filter layer. The method of washing the polycarbonate solution with the aqueous washing liquid phase is disclosed (for example, refer to Japanese Patent Application Laid-Open No. 7-3 0 9940); however, 'this method uses a large amount of aqueous washing liquid phase, its drainage Processing increases costs and is not suitable.

Furthermore, there is a disclosure of a method for separating an aqueous emulsion in oil with a metal filter material (for example, refer to Japanese Patent Application Laid-Open No. 2 01-3 1 7 5 5); however, in terms of the amount of water, its separation performance does not change. full. In a method for producing a polycarbonate resin by an interfacial polycondensation method, a polycarbonate-containing solution is washed with an aqueous washing solution, and when the washing solution is separated from the polycarbonate-containing solution, The method of separating the polycarbonate-containing organic solution and the cleaning solution from each other in the condenser of the filling material (see, for example, Japanese Patent Publication No. 2002-528580).

However, the operating conditions under which the separation operation is performed in the condenser are not disclosed, so the present invention is not described. [Summary of the Invention] [Disclosure of the Invention] Under the present circumstances, the present invention provides a crude polycarbonate organic solution containing water-soluble impurities obtained by an interfacial polycondensation method, emulsified with aqueous washing and liquid mixing, and used a condenser. The emulsion is separated into an organic phase and an aqueous phase; when producing a refined polycarbonate organic solution, by operating the condenser under specific operating conditions, at least the element portion in the condenser can prevent- 6- 200528488 (4) Stops the adhesion and aggregation of impurities with intermediate specific gravity, and can stably perform the separation operation; at the same time, it can effectively produce a refined polycarbonate organic solution, and use the refined polycarbonate organic solution to produce high-purity polycarbonate The ester method is for the purpose. Working colleagues of the present invention, in order to solve the above-mentioned problems, after in-depth discussion and continuous research, it was found that the polycarbonate organic solution and the aqueous cleaning solution were separated into an organic phase and water by at least the element part in the condenser. The two phases of the phase can substantially not form an interface, which is the operating condition of the condenser and can achieve the above-mentioned purpose. The present invention has been completed based on this discovery. The present invention is constituted by the following. (1) A method for producing a refined polycarbonate organic solution, characterized in that a crude polycarbonate organic solution that has been subjected to a polycondensation reaction by an interfacial polycondensation method is mixed with an aqueous washing solution to emulsify; and the obtained emulsion is emulsified; In the method of introducing a condenser to obtain a purified polycarbonate organic solution by removing water, the amount of the polycarbonate organic solution from which water is removed from the condenser is controlled and the content of the polycarbonate organic solution discharged from the top of the condenser is contained. The discharge amount of the aqueous solution containing a part of the impurities of the polycarbonate organic solution enables the polycarbonate organic solution and the aqueous cleaning solution to be separated into two phases of the organic phase and the water phase in at least the element portion of the condenser. Substantially no interface is formed; a polycarbonate organic solution with water removed is obtained. (2) The method for producing a purified polycarbonate organic solution as described in (1) above, wherein the discharge amount of the aqueous solution containing impurities containing a part of the polycarbonate organic solution discharged from the top of the condenser is controlled to be supplied The amount of the aqueous washing solution is 1 to 1.5 times. 200528488 (5) (3) — A method for manufacturing a refined polycarbonate organic solution, characterized in that a crude polycarbonate organic solution completed by a polycondensation reaction by an interfacial polycondensation method is mixed with an aqueous cleaning solution to form an opacification. Liquid; introducing the obtained emulsion into a condenser, and removing the water to obtain a purified polycarbonate organic solution; the amount of the crude polycarbonate organic solution supplied into the condenser, and the supplied aqueous washing The total amount of clean liquid is discharged from the inside of the condenser to a static separation tank provided downstream, and the polycarbonate organic solution layer is discharged from the static separation tank, so that at least the element portion in the condenser is collected. The carbonate organic solution and the aqueous cleaning solution are separated into two phases, an organic phase and an aqueous phase, and an interface may not be formed substantially. (4) The method for producing a refined polycarbonate organic solution as described in any one of the items (1) to (3) above, wherein the method of mixing the crude polycarbonate organic solution and the aqueous cleaning solution uses an in-line mixer , Static mixer, or orifice mixer. (5) The method for producing a refined polycarbonate organic solution according to any one of the items (1) to (4) above, wherein the material of the elements in the condenser is glass fiber, carbon fiber, metal fiber, polytetrafluoro Ethylene fibers, polypropylene fibers, polyethylene fibers, pulp fibers, or kapok fibers. (6) The method for producing a refined polycarbonate organic solution according to any one of the items (1) to (5) above, wherein the shape of the element in the condenser is flat, cylindrical, or folded . (7) The method for producing a purified polycarbonate organic solution according to any one of the items (1) to (6) above, wherein the structure of the element in the condenser is a fiber layer installed in a cylindrical box. 200528488 (6) (8) — A method for producing high-purity polycarbonate, characterized in that a purified polycarbonate organic solution obtained by the production method according to any one of the items (1) to (7) is used. [The best form for implementing the invention]

In the present invention, a crude polycarbonate organic solution containing water-soluble impurities obtained by an interfacial polycondensation method is mixed with an aqueous washing liquid to emulsify; the emulsion is separated into an organic phase and an aqueous phase using a condenser; In the case of a polycarbonate organic solution, by operating the condenser under specific operating conditions, at least the element portion in the condenser can prevent the adhesion and aggregation of impurities with a specific gravity in the middle, and can perform a stable separation operation; An effective method for producing a refined polycarbonate organic solution, and a method for producing a high-purity polycarbonate using the refined polycarbonate organic solution.

The interfacial polycondensation method uses divalent phenol as the main component, and adds caustic alkali which is a terminal termination system (also known as molecular weight regulator) and divalent phenylhydrazone dissolved in a small amount, and a branching agent according to demand. The gas or phosgene derivative is produced by reacting in an organic solvent; the obtained crude polycarbonate organic solution is mixed with an aqueous cleaning solution and stirred to 'wash out water-soluble impurities; and then, after the isolation and recovery steps, the polycarbonate is produced. In this interfacial polycondensation method, divalent phenol used as a raw material of polycarbonate includes, for example, a compound represented by general formula (I).

• 9- 200528488 (7) In the above general formula (I), X1 and X2 are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms; specific examples are methyl, ethyl, N-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl, etc .; X1 and X2 are the same as each other or It can be different; a and b are the substitution numbers of X1 and X2, integers of 0 ~ 4; when χΐ is plural, X1 of the plural may be the same or different from each other, and X2 is plural when X2 is plural Same or different. Υ is a single bond, an alkenyl group having 1 to 8 carbon atoms (for example, methylene, vinyl, propyl, butyl, pentyl, hexyl, etc.), and an Asian radical having 2 to 8 carbon atoms ( For example, ethylene, isopropylidene, etc.), cycloalkenyl with 5 to 15 carbons (such as cyclopentenyl, cyclohexenyl, etc.), cycloalkylene with 5 to 15 carbons (such as cyclo Pentylene, cyclohexylene, etc.), a s-, _SO-,-S02-, ~ 〇 一, a co- bond or a bond represented by formula (Π-1) or formula (II-2)

(Π-1) (Π-2) Here, the divalent phenol 'shown in the above general formula (I) has a variety of considerations, with 2,2-bis (4-monohydroxyphenyl) propane (commonly referred to as bis Phenol A) is most suitable; divalent phenols other than bisphenol A are, for example, bis (4-hydroxybenzene-10-200528488 (8) yl) methane; bis (4-monohydroxyphenyl) phenylmethane; bis (4 Monohydroxyphenyl) naphthylmethane; bis (4-monohydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,5-dichloro-4-hydroxyphenyl) methane; bis (3, 5 dimethyl-4-hydroxyphenyl) methane; 1,1 bis (4-hydroxyphenyl) ethane; 1-naphthyl-i, 1 bis (4-hydroxyphenyl) ethane; 1 — Phenyl-1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2-methyl-1,1-bis (4-hydroxyphenyl) ) Propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis ( 3,5_ dichloro-4 —Cycylphenyl) propanate; 2,2 —bis (3,5 —dibromo-4 — Phenyl) propane; 2,2-bis (3-chloro-4 4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4 4-hydroxyphenyl) propane; 2,2-bis (3 -Fluoro-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) butane; 1,4-bis (4-hydroxy) Phenyl) butane; 2,2-bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxy) Phenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) nonane; 1,1 0-bis (4-hydroxyphenyl) decane Alkanes; 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 2,2-bis (4-monohydroxyphenyl) -1,1,1,3,3 Dihydroxydiarylalkanes such as, 3-hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4_hydroxyphenyl) Cyclohexane; 1,1-bis (4-hydroxyphenyl) cyclodecane and other dihydroxydiarylcycloalkanes; bis (4-hydroxyphenyl); bis (3,5-di Methyl-4-hydroxyphenyl); -11-200528488 (9) bis (3-chloro-4-hydroxyphenyl) and other dihydroxydiaryls, bis (4-hydroxyphenyl) ether; Dihydroxydiaryl ethers such as bis (3,5-dimethyl-1,4-hydroxyphenyl) ether, 4,4 · dihydroxybenzophenone; 3,3 ', 5,5'tetramethyl Di-4,4'-dihydroxybenzophenone and other dihydroxy diaryl ketones, bis (4-monohydroxyphenyl) sulfide; bis (3-methyl-4 4-hydroxyphenyl) sulfide; bis (3,5-Dimethyl-4 monohydroxyphenyl) sulfide and other dihydroxydiaryl sulfides, bis (4-monohydroxyphenyl) aceto and other dihydroxydiaryl aceto, 4, ^ Dihydroxydiphenyls such as dihydroxydiphenyl, dihydroxydiarylfluorenes such as 9,9-bis (4-monohydroxyphenyl) fluorene, etc .; and, two of the general formula (I) Divalent phenols include dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone, 1,5-dihydroxynaphthalene, and dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene. Etc; these divalent phenols can be used separately or in two kinds The combination. Molecular weight regulators can be used as long as they are used by ordinary polycarbonate polymers. Specific examples of monovalent phenols include phenol, p-cresol, p-tert-butylphenol, and p-tert-octylphenol. P-cumylphenol, bromophenol, tribromophenol, nonylphenol, etc. Among them, p-tert-butylphenol and phenol are more suitable from the viewpoints of economical efficiency, ease of availability, and the like. In the present invention, the above-mentioned divalent phenol may be used simultaneously with an appropriate branching agent. This branching agent is a polyvalent phenol having a trivalent or higher valency; specifically, 1,1,1, tris (4 hydroxyphenyl) Ethane, α, α ·, α "—tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α ~ methyl-α (41-hydroxyphenyl) ethyl ] -4- [α ,, α '-(bis (41, -hydroxyphenyl) ethyl] -12-200528488 (10) benzene, pyrogallol, isatin bis (o-cresol), etc .; The amount of these branching agents varies depending on the degree of branching of the target, and is usually about 0.05 to 2 mol% for divalent phenol. When polycarbonate is produced by the interfacial polycondensation method, a polycarbonate main chain is formed. Carbonate bond compounds include, for example, phosgene, triphosgene, bromophosgene, bis (2,4,6-trichlorophenyl) carbonate, bis (2,4 dichlorophenyl) carbonate, bis (2-cyanophenyl) carbonate, trichloromethyl chloroformate, etc. can be used. In the interfacial polycondensation method, the manufacturing steps of polycarbonate are not particularly limited, and it can be produced by the conventional interfacial polycondensation method. Commonly used procedures for carbonates; for example, by performing (A) a preparation step of a divalent phenol polycarbonate oligomer, (B) a polymerization step of the above oligomer, (C) a washing step, and (D) a polymerization step The isolation and recovery steps of carbonate can effectively produce the desired polycarbonate. In addition, in the present invention, the polymer may be directly polymerized without separating the above steps (A) and (B); The production form of the carbonate may be either batch type or continuous type, but continuous type is more suitable; when using this continuous type, it is advantageous to link the steps (A) and (b) above. The steps are briefly described as follows: (A) Step: This step (A) is a step of interfacial polycondensation of divalent phenol and phosgene or phosgene derivative to prepare a divalent phenylfluorene polycarbonate oligomer. -13- 200528488 (11) The method for preparing this divalent phenol polycarbonate oligomer is not limited. For example, the following suitable method can be used. First, the alkaline water containing the above-mentioned divalent phenol containing raw materials is prepared and Inert organic solvents are mixed and stirred while A divalent phenol polycarbonate oligomer is obtained by reacting phosgene or a substance in the coexistence of an aqueous alkali solution and an inert organic solvent. At this time, the concentration of the alkaline aqueous solution is usually 1 to 15 weights. Suitable; In addition, the content of the divalent phenol in the alkaline aqueous solution is selected in a range of 0.5 to 20% by weight; further, the inert organic agent is selected so that the capacity ratio of the organic phase to the water phase can reach 5/1 to 1/7. The reaction temperature is usually 0 ~ 50 ° C, and it is better to choose a range. In this reaction, an alkali aqueous solution containing divalent phenol after reacting phosgene or a phosgene derivative is reacted. Part of the terminal terminator is a catalyst that can make the reaction proceed smoothly. Sodium hydroxide and potassium hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and hydroxide planer used for preparing the above-mentioned alkaline aqueous solution containing divalent phenol are more suitable, and sodium hydroxide is better; There are all kinds; for example, dichloromethane, carbon tetrachloride, 1,1 dichloroethane, 1,2-dichloroethane, 1-trichloroethane, 1,1,2-trichloroethylene Ethyl chloride, 1,1,1, ethane, 1,1,2,2-tetrachloroethane, pentachloroethane, chlorobenzene; toluene, acetophenone, etc .; these organic solvents can be used separately These are used in combination; among them, dichloromethane is most suitable. There are special solutions to derivatize divalent phenol phosgene: the amount of% is usually more suitable for the amount of use, suitable for 5 ~ 40V, more added, and the desired alkali is, for example; the other is trichloro Formethane, 1,12-tetrachloro, and other chlorinated hydrocarbons, but also -14-200528488 (12) The catalyst is a phase-shift catalyst. For example, a suitable tertiary amine or its salt, quaternary ammonium salt, quaternary scale salt, etc. can be used. Wait. Tertiary amines are, for example, triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline, N-methylpiperidine, etc .; and tertiary amine salts are, for example, these tertiary Amine hydrochloride, bromate, etc .; quaternary ammonium salts are, for example, trimethylbenzyl ammonium chloride, triethylbenzyl ammonium chloride, tributylbenzyl ammonium chloride, trioctylmethylammonium Chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, etc .; quaternary scale salts include, for example, tetrabutylscale chloride, tetrabutylammonium bromide, etc .; these catalysts can be used separately, or It can be used in combination of two or more kinds; among the above catalysts, tertiary amine is more suitable, especially triethylamine is more suitable. After the reaction, it is allowed to stand or centrifuge to separate into an aqueous phase and an organic phase containing a polycarbonate oligomer; the organic phase may be used in the next step without isolating the polycarbonate oligomer. Step (B) is a polymerization step of the polycarbonate oligomer obtained in the above step (A); in the presence of the remaining terminal terminator, the desired catalyst, an alkaline aqueous solution, and an inert organic solvent, the polymerization The carbonate oligomer undergoes interfacial polycondensation with divalent phenol. Specifically, the polycarbonate oligomer solution obtained in the step (A) is mixed with the remaining terminal terminator, the desired catalyst, an inert organic solvent, an alkaline aqueous solution, and an aqueous alkaline solution of divalent phenol. '' Normally at 0 ~ 5 (TC for interfacial polycondensation, more suitable in the range of 5 ~ 40 ° C. -15- 200528488 (13) The base, inert organic solvent, and catalyst used at this time can be the same as the above ( A) The description in the step is the same; Also, in this interfacial polycondensation, the capacity ratio of the organic phase to the water phase is the same as that in the step (A) above. Moreover, this polymerization step can be divided into preliminary polymerization (pre-polymerization) Polymerization with this polymerization (post-polymerization); that is, first, the polycarbonate oligomer solution obtained in the above step (A) is mixed with the remaining terminal terminator, the desired catalyst, an inert organic solvent, and an alkaline aqueous solution. Yu lower

Pre-polymerization (pre-polymerization) at a temperature (for example, a temperature lower than 20 C); then, an alkaline aqueous solution of divalent phenol is added thereto, and the present polymerization is performed at a higher temperature (for example, 20 to 40 ° C) (after polymerization). After the reaction, it is appropriately diluted with an inert organic solvent, and then separated into a water phase and an organic phase containing polycarbonate through operations such as standing or centrifugal separation. (C) Step

This step (C) is a washing step of the crude polycarbonate organic solution separated in the above step (b). The residual monomers, catalysts, and test substances of impurities are removed from the polycarbonate organic solution to obtain The method of high-purity polycarbonate organic solution is performed by extracting impurities on the water phase side by adding 'washing water such as test aqueous solution, acidic aqueous solution, pure water, etc.' to the polycarbonate stack solution; For this washing, only one of these washing operations can be performed. 'Two or more washing methods can also be combined: the number of washing operations can also be set according to demand.' The method of mixing the crude polycarbonate organic solution and the aqueous cleaning solution can be used on any commercially available machine for the purpose of liquid / liquid mixing, in order to obtain the desired stirring efficiency of -16-200528488 (14). Mixers, static mixers, and sharp-hole plate mixers are more suitable; the stirring power of these mixers is also related to the material of the components in the condensers described later, usually 0.1kw / m3 / hi * or more, with 0.2 More than kw / m3 / hr is more suitable, and more than 0.5kw / m3 / hr is more suitable; when the stirring strength is weak, not only cannot be washed sufficiently, but the water in the polycarbonate organic solution after separation is increased, resulting in the resulting polymer. The quality of the carbonate is lowered; more substances which are not suitable in terms of quality are not on the organic phase side but on the water phase side. The water phase of the aqueous cleaning solution when the crude polycarbonate organic solution is mixed with the aqueous cleaning solution is usually 50% by volume or less, more preferably 30 to 3% by volume, and more preferably 20 to 5% by volume; When a large amount of clean liquid is used, more drainage treatment costs are required, which is extremely uneconomical. In the cleaning of the present invention, the relationship between the organic phase (oil phase) and the water phase constituting the emulsion can be either of a water droplet dispersion type in oil and a water droplet dispersion type in water. For fit. In the present invention, the crude polycarbonate organic solution separated from the aqueous phase in the polymerization step is mixed with the aqueous washing liquid to emulsify; it is separated into an organic phase and an aqueous phase using a condenser; the condenser can promote the emulsion The water droplets are condensed, and the organic phase is separated from the water phase when the solution is circulated. Usually, it is separated in the condenser shell; at this time, there are essentially two phases of the organic phase and the water phase in the shell or the component part in the shell. When the separation operation is performed under the interface state, the intermediate specific gravity materials of impurities, such as metal chlorides, metal hydroxides, degraded monomers and polymers, etc., gather in the casing, which is the main reason for the shortened life of the components in the condenser Not only can't the separation operation be performed stably -17- 200528488 (15), but the precision of refining is reduced, and high-purity refined polycarbonate organic solution cannot be obtained; moreover, the so-called component part inside the casing is Refers to the area between the two horizontal planes in the housing that contains the upper and lower end faces of the element, respectively; therefore, the separation of the organic phase from the water phase through the condenser is at another The separation tank is implemented; the discharge amount of the aqueous solution containing impurities containing a part of the organic solution of the polycarbonate discharged from the top of the condenser must be at least the component part in the shell of the condenser, the organic phase and the water phase. The two phases may not substantially form an interface; thereby, substantially, at least the element portion in the shell of the condenser, the interface forming the two phases of the organic phase and the water phase does not exist; at this time, a separation tank is provided in the previous step, It is also possible to use it for separation (for example, refer to FIG. 1 and FIG. 3), and it is also possible to provide a separation tank on the downstream side of the condenser (for example, refer to FIG. 2); and, an aqueous solution containing impurities containing a part of the polycarbonate organic solution The discharge amount is not particularly limited, and it is sufficient to control the amount to be 1 to 1.5 times the amount of the aqueous cleaning solution supplied; further, by using the amount of the polycarbonate organic solution supplied to the condenser, and the supply The total amount of the aqueous cleaning liquid is discharged from the condenser to a static separation tank provided downstream, so that at least the element part in the shell of the condenser, the two phases of the organic phase and the water phase are substantially formed. Surface also (see FIG. 4) does not occur. As the condenser used, any commercially available form can be used, for example, products of Hexing Industrial Co., Ltd., Polu Co., Ltd., Fuji Filter Co., Ltd., and Asahi Kasei Fiber Co., Ltd. can be used. The condenser is actually equipped with a component with a function of promoting aggregation; the material of the component is not particularly limited, and glass fiber, -18- 200528488 (16) carbon fiber, metal fiber, polytetrafluoroethylene (PTFE) ), Polypropylene (PP), or polyethylene (PE) and other synthetic fibers, pulp, kapok and other organic fibers, porous graphite and other porous materials; especially carbon fibers or glass fibers, more suitable for polycarbonate organic solutions Separated after washing. The shape of the element can be selected from the viewpoint of ease of handling, installation, and cost; flat, cylindrical, and folded shapes can be used. From the point of processing, the cylindrical shape is more suitable. Suitable; Also, the structure of the element may be only the fiber layer; it may be a structure with strength and a retainer; etc .; For the purpose of removing impurities in the fluid and performance, a double-layer or more multilayer structure may also be used; Among them, structurally, it is better to install a fiber layer in a cylindrical box; the thickness of the fiber layer constituting the element can also be set freely according to the performance, for example, the thickness of the fiber layer, the pressure difference ΔP, and the separation performance can be optimized. In addition, the device can be installed in either a vertical direction or a horizontal direction. Next, an embodiment of the separation operation of the present invention using a condenser will be described with reference to the drawings. Figure 1 shows that the polycarbonate-containing reaction solution from the polymerization step is introduced into the static separation tank in the previous stage, and the crude polycarbonate organic solution in the lower layer with a large specific gravity is discharged by a pump or the like, and an aqueous cleaning solution is added in the middle By emulsifying with a pipeline mixer; passing the emulsion through a condenser to separate the organic phase and the water phase; at the same time, at least the element portion in the condenser prevents the organic phase and the water phase from forming substantially two Phase; the water phase is discharged from the top as a part of the organic phase, and is circulated in the above-mentioned stationary separation tank; the refined organic phase is discharged from the side of the condenser, and conveyed to the next step. An example of implementation. -19- 200528488 (17) At this time, the amount of the aqueous phase containing a part of the organic phase discharged from the top is not particularly limited; as described above, the amount of the aqueous cleaning solution supplied is controlled from i to i. 5 Multiplying is enough; the water phase part in the separation tank is left to be discharged by another method and sent to the drainage treatment step. Fig. 2 shows that after the emulsion is introduced into the condenser and separated into an organic phase and an aqueous phase; at least the element portion in the condenser prevents the organic phase and the aqueous phase from forming two phases; Partial organic phase is discharged 'introduced into a static separation tank installed on the downstream side' and separated at the rear part 'while indicating the refined organic phase discharged from the side of the condenser; It is sufficient that the amount of the water phase of the organic phase is the same as the above; the water phase portion provided in the downstream static separation tank is discharged by another method and sent to the drainage treatment step. FIG. 3 shows an example of an embodiment using a condenser which is washed with alkali and acid, and washed with water in series; in this case, the water phase part in the stationary separation tank is also discharged and transported by another method. Go to the drainage treatment step. FIG. 4 shows the total amount of the polycarbonate organic solution supplied to the condenser and the amount of the aqueous cleaning solution supplied to the condenser from the condenser to a stationary separation tank provided downstream, and discharged. The implementation of the present invention in which at least the element portion in the condenser separates the polycarbonate organic solution and the aqueous cleaning solution into two phases, an organic phase and an aqueous phase, does not substantially form an interface, and performs a separation operation in the static separation tank. Type: in this case, the water phase part in the standing separation tank is also discharged by another method and sent to the drainage treatment step. (D) Step: -20- 200528488 (18) This (D) step is a step of isolation and recovery of the polycarbonate; specifically, for example, the purified polycarbonate obtained by the above-mentioned step (C) after washing treatment After the organic solution is concentrated, the obtained flakes are subjected to a pulverization treatment and a drying treatment such as vacuum drying to obtain a high-purity polycarbonate of the product; further, the polycarbonate is melt-kneaded with an extruder or the like, and extruded. When pressed and granulated, a granular form can be obtained. From the viewpoint of mechanical strength and moldability, polycarbonate is more suitable for a viscosity average molecular weight (Mv) in the range of 10,000 to 100,000, more preferably 1 2000 to 40,000, and most preferably 1 3000 to 30,000; Yes, the viscosity average molecular weight (Mv) is determined by using a Uberlaude viscometer at 20 ° C for dichloromethane solution, and the intrinsic viscosity [7?] Is obtained from it, according to [77] = 1.23χ 10 · 値 calculated by the formula of 5Mν 0.83. [Embodiments] [Examples] Next, the present invention will be described in detail with examples as follows; the scope of the present invention is not limited to these examples; the determination of the water content in polycarbonate organic solutions (polymer solutions) is based on Karl Fischer. [Manufacturing Example 1] (1) Production of polycarbonate oligomer A bisphenol A (BPA) was dissolved in a 6 wt% sodium hydroxide aqueous solution to obtain a 14.5 wt% BPA-NaOH solution; the obtained BPA-NaOH solution at 40 ^ / hr 'concentration and 25% by weight p-tert-butyl-21-200528488 (19) phenol (P TB P; molecular weight regulator)-dichloromethane solution at 0.3 w / hr, One of the solvents, methyl chloride, was introduced at a flow rate of 8 · / hr into a tube-type reactor with an inner diameter of 6 mm and a length of 3011 immersed in a cooling bath of 200 ° F; and was blown in at a flow rate of 3.8 kg / hr. Phosgene; the reaction mixture discharged from the reaction is introduced into a separation tank to separate the aqueous phase, and an organic phase formed by a dichloromethane solution of a polycarbonate oligomer is obtained. The properties of the obtained polycarbonate oligomer were analyzed as follows. Average molecular weight: 8 60 (determined by vapor pressure osmometer (vp0) Number average molecular weight] Chloroform ester group concentration: 0.68 mol / liter (as an organic solvent solution of an oligomer) (2) Production of polycarbonate:

The dichloromethane solution of the polycarbonate oligomer obtained in (1) was prepared at 20 < / 1 ^, and the concentration of 14.5% by weight in the above-mentioned (1) 3? Human- ^ 〇11 solution was prepared by 1 1.5 < / hr, 4% by weight triethylamine (TEA: catalyst) aqueous solution at 0.04 i / hr, 25% by weight aqueous NaOH solution at 0.8 < / hr, and solvent methylene chloride at a flow rate of 13 < / hr, The reaction was introduced into a tower-type reactor; the residence time was 1 hour; thereafter, a polycarbonate-containing reaction mixture was obtained from the overflow. [Example 11 In the reaction mixture containing polycarbonate obtained in the above Production Example 1, -22-200528488 (20) was added with dichloromethane to prepare a polycarbonate solution having an organic phase side polycarbonate concentration of 1 2 % By weight, while standing still for 1 hour, separated into a dichloromethane solution (organic phase) containing polycarbonate and water phase; the result of measuring the water content in this separated organic phase was 7500 weight ppm; The crude polycarbonate before the addition of dichloromethane was measured for the viscosity average molecular weight of the other polymer. The result was Mv = 28700. In the aqueous phase analysis, the BPA was dissolved at a concentration of 21 gM and the concentration of NaOH was 0.22 mol / <. The thus obtained polycarbonate-containing dichloromethane solution (organic phase) was introduced into a line mixer at 600 < / hr and a sodium hydroxide aqueous solution of pH = 13 prepared with additional NaOH at 60 < / hr. Mixing at 2600 rpm in a pipeline homogenizer (manufactured by Special Mechanization and Chemical Industry Co., Ltd.) and washing; confirm that the phase state of the emulsion at the outlet is water-in-oil type; and that the stirring power given to the fluid at this time is 0.53 kw / m3 / hr; furthermore, a condenser (a condenser manufactured by Hexing Industrial Co., Ltd., a component of a size gauge: 180 mm in diameter, an internal volume of 70 (W, the material of the component: carbon fiber) ) Continuous flow of liquid; soon, a transparent polymer solution can be obtained from the outlet below the condenser, and an aqueous solution containing a portion of the polymer solution can be obtained from the top outlet; the flow rate of the aqueous solution at the top can be known from the flow meter installed Continuous discharge at 80 < / hr 'for about 1 hour of continuous operation; confirm that the organic phase and the water phase do not generate an interface with a level gauge; the temperature of the polymer solution at the outlet is 3 2 ° C; Water content of polymer solution 2000 ppm by weight 'It is judged that the solution can be fully circulated in the condenser, so that the water can be sufficiently separated. In this method, after 30 days of continuous operation, the condenser body is opened, and the interior and components of the body are visually observed to confirm There were no contamination and impurities different from those before the operation. 23- 200528488 (21) Mass accumulation; the results are shown in Table 1. [Examples 2 to 11] Excluding the polymer solution flow rate, the amount of aqueous cleaning solution supply, and stirring The materials of the components in the power condenser are changed according to the examples except those described in Table 1. The results are shown in Table 1. -24- 200528488 (22) Water content of polymer solution (* 1 MW ppm) 2000 2100 2000 2400 2000 2100 2200 2300 2600 2400 2200 3700 δ800 13000 2200 2000 2300 2000 2100 3400 Material of condenser internal components Carbon fiber (* 2) δ δ Stainless steel SUS 316 (* 2) Carbon fiber (* 2) Polypropylene (* 3) PTFE (* 4) Glass fiber (* 2) 5: 5: Carbon fiber (* 2) Mixer stirring power (kw / m3 / hr) 0.53 0.62 0.49 0.45 s 0.61 0.30 0.15 ι_ 0.07 0.50 0.30 0.03 0.50 0.50 0.53 0.70 0.45 0.55 0.30 0.03 water phase (Volume%) oq 14.3 25.0 τ— 11.2 s 10.3 CO T ~ 5 CO 〇〇10.4 12.5 inch 〇10.5 13.0 13.0 aqueous cleaning solution (1 / hr) g S 〇o ο 04 SS * τ ~ ss SS gs 〇 〇〇S 〇SSS _ Violet: g key £ < Π m ο < 〇OS o CO Ο CO ο ο 950 ο go < 〇o to O oo ο CO ο 〇600 350 〇2 S 〇〇〇〇〇 〇 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10! Example 11 Example 11-1 Example 11 2 Example 11-1 3 Example 1 2 Example 1 3 Example 1 4 Example 1 5 Example 16 6 Example 16 — 2 ϋ — Λ ^ ^ * 2: 813 > 骓 || ^ 骓 ^ ^ ^ 螂 陌 _ Bi Mo Mo < < [(袈) 骓 鹪 «§ ^ 鲫: 00 * 蹿 ig 骧 昍 蹿 赖 # ΘΤΙΪ? < (^) Fiber pay« g: s * code H class 繇 «—Μ + Κ1: τ * -25- 200528488 (23) [Example π-1 ~ 11 — 3] Except for changes in polymer solution flow rate, cleaning solution supply amount, stirring power, and component materials in the condenser as described in Table 1, implementation Example 1 was performed; the results are shown in Table 1. [Examples 12 to 13] The polymer solution obtained in Example 1 and washed in an alkaline atmosphere was subjected to acid washing. Except for using an aqueous cleaning solution in which water adjusted to pH 1 with hydrochloric acid was used, implementation was performed in accordance with Example 1 was subjected to acid cleaning; the results are shown in Table 1. [Examples 14 to 16-2] The polymer solution obtained in Examples 1 to 2 and used in Example 1 to complete the washing under an acid atmosphere, followed by water washing; except using pure water as an aqueous washing solution, Example 1 was washed with water; the results are shown in Table 1.

W

[Comparative Example 1] In Example 1, the operation method of the condenser is to set a level gauge for the detection interface on the body, adjust the discharge amount on the water side, and perform the operation of forming a separation interface in the condenser (refer to Figure 5) Perform this continuous operation for 1 to 20 days; periodically confirm the results of the water content in the polymer solution, determine that the initial content is 2000 ppm by weight, and rise to 2 60 0 weight after 120 days; and confirm the pressure difference before and after the condenser , Confirm the initial △ P = 9.8kPa, rise to 26.46kPa; after the operation is completed, discharge the solution to confirm the internal results, in the condenser body -26- 200528488 (24), confirm the position of the setting interface on the horizontal line with a brown tea Viscous attachment; the result of metal analysis of this attachment was confirmed to be Fe, Cr, Ni; this material must be a part of the stainless steel material used in the previous step to elute and gather near the interface; also, in the same Position, also attached to the barrel of the condenser; this is presumed to be the cause of pressure rise and moisture rise. [Reference Example 1] A crude polycarbonate solution was prepared by the method described in Example 1, and after standing at φ, the mixture was washed with water of pH = 13 using a pipeline mixer, and the same operation was performed until now. 〇J The graduated cylinder takes the obtained emulsion and performs static separation to confirm the separation speed and the amount of water in the polymer solution after separation. As a result, after standing for 1 hour, the amount of water in the polymer solution is 5% by weight, 2% by weight after standing for 2 hours. [Example 1 7] (Perform a full washing step according to the interfacial polycondensation method) It was confirmed that the crude polycarbonate organic solution obtained in the example was continuously processed as shown in FIG. 3 to obtain a clear polycarbonate organic solution. Method: Polycarbonate organic solution is washed firstly by alkali, followed by acidic washing, and then washed with pure water, so as to be carried out twice respectively. The polymer solution is washed with 600 < / hr In the step, the water ratio is adjusted to 12% by volume; and the mixer and the stirring power are adjusted to Pv = 0.5kw / m3 / hr; the representative organic impurities of the obtained polycarbonate organic solution are measured. Na ion was 0.1 ppm by weight or less, Fe ion was 0.1 weight ppm or less, and residual BPA was 3.2 weight ppm. It was confirmed to be excellent in efficiency, and a clear polycarbonate organic solvent was obtained. 27-200528488 (25) solution. Next, the purified polycarbonate solutions obtained in Examples 1 to 17 were separately concentrated and then subjected to a pulverization treatment; the obtained flakes were subjected to a vacuum drying treatment to obtain a high-purity polycarbonate; Polycarbonate is melt-kneaded and granulated by extrusion to obtain pellets of high-purity polycarbonate. [Industrial Applicability] According to the present invention, a crude polycarbonate organic solution containing a water-soluble φ impurity obtained by an interfacial polycondensation method can be mixed with an aqueous cleaning solution to emulsify; the emulsion can be separated using a condenser. For the organic phase and the water phase, when producing a refined polycarbonate organic solution, the polycarbonate organic solution and the aqueous cleaning solution are separated into two phases of an organic phase and an aqueous phase by at least an element portion in the condenser. Under the operating conditions where no interface is formed substantially, the condenser is operated; at least the element part in the condenser can prevent the adhesion and aggregation of impurities of intermediate specific gravity, and can stably perform the separation operation; meanwhile, it can effectively manufacture refined polycarbonate Method for organic solution, and method for producing high-purity polycarbonate by using the refined polycarbonate organic solution_. [Schematic description] Figure 1 shows at least the element part in the condenser, so that the organic phase and the water phase do not form a two-phase; the water phase is discharged from the top in a form containing a part of the organic phase. The separation tank was left at the previous stage; the refined organic phase was discharged from the side of the condenser and output to an example of the embodiment of the present invention in the next step. -28- 200528488 (26) Figure 2 shows at least the element part in the condenser, so that the organic phase and the water phase do not form a two-phase; the water phase is discharged from the top as a part containing the organic phase and introduced into the setting A stationary separation tank on the downstream side separates a part of the rear section, and at the same time, the embodiment of the present invention also discharges the refined organic phase from the side. Fig. 3 is a diagram showing an embodiment of the present invention performed sequentially by using a condenser provided in series with washing operations for alkali washing, acid washing, and water washing. FIG. 4 shows that at least the element portion in the condenser separates the polycarbonate organic solution and the aqueous cleaning solution into two phases, the organic phase and the water phase, and forms an interface that is substantially unpleasant; The sum of the amount of the polycarbonate organic solution and the amount of the supplied aqueous cleaning solution is conveyed from the condenser to a static separation tank provided downstream and discharged, and the static separation tank collectively separates the Implementation type. Fig. 5 is a schematic diagram showing an arrangement implemented as a comparative example.

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Claims (1)

200528488 (1) 10. Scope of patent application1. A method for producing a refined polycarbonate organic solution, which is characterized in that a crude poly carbonate organic solution which is subjected to a polycondensation reaction by an interfacial polycondensation method is mixed with an aqueous cleaning solution And emulsification; in the method of introducing the obtained emulsion into a condenser, and obtaining a purified polycarbonate organic solution by removing water, by controlling the discharge amount of the water-removing polycarbonate organic solution discharged from the condenser, And the discharge amount of the aqueous solution containing impurities containing a part of the polycarbonate organic solution discharged from the top of the condenser, so that at least the element portion of the g in the condenser, the polycarbonate organic solution and the aqueous cleaning solution are separated into The two phases of the organic phase and the water phase may not substantially form an interface; that is, a polycarbonate organic solution for removing water is obtained. 2. The method for producing a refined polycarbonate organic solution according to item 1 of the scope of the patent application, wherein the discharge amount of the aqueous solution containing impurities containing a part of the polycarbonate organic solution discharged from the top of the condenser is controlled to be supplied An amount of 1 to 1.5 times the amount of the aqueous cleaning solution. 3. A method for producing a refined polycarbonate organic solution, characterized in that a crude polycarbonate organic solution that has been subjected to a polycondensation reaction by an interfacial polycondensation method is mixed with an aqueous cleaning solution to form an emulsion; The method of introducing the turbid liquid into the condenser and removing the water to obtain a purified polycarbonate organic solution; the total amount of the crude polycarbonate organic solution supplied into the condenser and the amount of the aqueous cleaning solution supplied The amount is discharged from the inside of the condenser to a static separation tank provided downstream, and the polycarbonate organic solution layer is discharged from the static separation tank, so that at least the component part of the condenser, the polycarbonate organic solution and the water The washing liquid is separated into two phases of an organic phase and an aqueous phase, and substantially -30-200528488 (2) does not form an interface. 4. The method for manufacturing a refined polycarbonate organic solution according to item 1 or 2 of the patent application scope, wherein the mixing method of the crude polycarbonate organic solution and the aqueous cleaning solution is an in-line mixer, a static mixer, or a sharp Orifice mixer. 5 · The method for manufacturing a refined polycarbonate organic solution as described in item 3 of the scope of patent application, wherein the method of mixing the crude polycarbonate organic solution and the aqueous cleaning solution is an in-line mixer, a static mixer, or an orifice plate. Mixer. 6. The method for manufacturing a refined polycarbonate organic solution according to item 1 or 2 of the scope of patent application, wherein the material of the components in the condenser is glass fiber, carbon fiber, metal fiber, polytetrafluoroethylene fiber, polypropylene fiber, Polyethylene fibers, pulp fibers or kapok fibers. Ί As in the method of manufacturing a refined polycarbonate organic solution according to item 3 of the patent application, wherein the material of the components in the condenser is glass fiber, carbon fiber, metal fiber, polytetrafluoroethylene fiber, polypropylene fiber, polyethylene Fiber, pulp fiber or kapok fiber. 8. The method for manufacturing a refined polycarbonate organic solution as described in the scope of the patent application No. 1 or 2, wherein the shape of the components in the condenser is flat, cylindrical, or folded. 9. The method for manufacturing a refined polycarbonate organic solution according to item 3 of the scope of patent application, wherein the shape of the elements in the condenser is flat, cylindrical, or folded. 10. The method for manufacturing the refined polycarbonate organic solvent according to item 1 or 2 of the scope of patent application -31-200528488 (3) The manufacturing method of the liquid, wherein the structure of the components in the condenser is a fiber layer installed in the cylindrical box. 11. The method for manufacturing a refined polycarbonate organic solution according to the scope of application for patent No. 3, wherein the structure of the components in the condenser is a fiber layer installed in a cylindrical box. 1 2. A method for producing a high-purity polycarbonate, which is characterized by using a purified polycarbonate organic solution obtained by the production method according to any one of claims 1 to 11 of the scope of patent application. -32 ·