TW200528488A - A method of producing organic solution of refined polycarbonicester and high purity polycarbonic ester - Google Patents
A method of producing organic solution of refined polycarbonicester and high purity polycarbonic ester Download PDFInfo
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200528488 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關,將以界面縮聚法所得之含有水溶性雜 質的粗製聚碳酸酯有機溶液,使用水性洗淨液洗淨,以製 造精製聚碳酸酯有機溶液之方法,及使用該精製聚碳酸酯 有機溶液製造高純度聚碳酸酯之方法者;更詳細的說,本 發明係有關,將以界面縮聚法所得之含有水溶性雜質的粗 製聚碳酸酯有機溶液,與水性洗淨液混合而乳化;在使用 I 凝結器將乳濁液分離爲有機相與含有雜質之水相,製造精 製聚碳酸酯有機溶液之際,藉由使該凝結器於特定之操作 條件下運轉,在凝結器內之至少元件部,能防止中間比重 之雜質的黏附與聚集,可穩定進行分離操作;同時能有效 的製造精製聚碳酸酯有機溶液之方法,及使用該精製聚碳 酸酯有機溶液製造高純度聚碳酸酯之方法者。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.
聚碳酸酯之製造方法,係使用二氯甲烷等鹵素系有機 溶劑之界面縮聚法;以該界面縮聚法製造聚碳酸酯時,於 縮聚反應完成後,獲得含聚碳酸酯之有機溶液與水溶液之 混合物;含聚碳酸酯之有機溶液,通常爲乳濁液狀態之故 ,必要將乳濁液分離爲聚碳酸酯之有機溶液、與含雜質之 水溶液的操作。 又,反應完成後之聚碳酸酯有機溶液中,殘留有影響 品質之鈉、未反應單體、催化劑等雜質之故,一般施行在 -4- 200528488 (2) 聚碳酸酯有機溶液中,加入鹼性水溶液、酸性水溶液、純 水等,攪拌洗淨之方法去除;進而,爲提高洗淨效率之目 的,將粗製聚碳酸酯有機溶液與洗淨液之混合物強力攪拌 ,進行乳化。 已往,將如此而得之乳濁液再分離的方法,有液一液 離心分離法、靜置分離法、或凝聚份離法等;不過,離心 分離法不僅設備費及維修費高,旋轉部份之故障及磨損, 由於反應溶劑之二氯甲烷的飛散等使累積之樹脂燒結,屢 次引起分離機之停止等的故障之故,必要準備預備機;又 ,靜置分離法亦因沉降速度緩慢之故,有必要大型之靜置 分離槽的缺點。 因此,進行開發解決此等之方法的凝聚分離法;例如 有使聚碳酸酯樹脂液通過與水之接觸角爲40 °C以下的過濾 而分離之方法的揭示(例如參照特公昭46 - 4 1 622號公報 );不過,此方法中,較難去除微細的水滴之故,必要重 覆通過過濾層;又,分離後,亦有由濾材層混入污染之情 況;進而,自通過濾材至分離需要較長之時間,必要較大 的靜置分離槽。 有使用pH2〜14之範圍的水性相,使聚碳酸酯有機溶液 乳化,以0.01〜2cm/秒之空間速度通過10〜5 00mm之厚度, 0.2〜0.7g/m£之表觀密度的纖維層,使二相分離之方法的揭 示(例如參照特開昭5 5 - 1 043 1 6號公報);不過,此方法 中,濾材層之厚度太厚,有因塡充物產生壓力損失等之問 題0 -5- 200528488 (3) 又’有將聚碳酸酯溶液與水性洗淨液以混合器混合, 成爲水中油型乳化狀態之混合溶液後,藉由通過濾材層, 分離爲聚碳酸酯溶液相與水性洗淨液相之聚碳酸酯溶液的 洗淨方法之揭示(例如參照特開平7 - 3 0 9 9 4 0號公報); 不過’此方法由於使用多量之水性洗淨液相,其排水處理 會增加成本,並非適合者。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.
進而’有以金屬濾材將油中水型乳濁液分離之方法的 揭示(例如參照特開2 0 0 1 — 3 1 7 5 5號公報);不過,從水 份量而言,其分離性能不充分。 有以界面縮聚法製造聚碳酸酯樹脂之方法中,使用水 性洗淨液將含聚碳酸酯之溶液洗淨,在將此洗淨液由含聚 碳酸酯溶液分離之際,於含親水性之塡充材料的凝結器中 使進行第一階段洗淨之含聚碳酸酯有機溶液與洗淨液互相分 離的方法之揭示(例如參照特表2002 — 528580號公報。)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).
不過,於凝結器之分離操作係在如何的操作條件下進 行並無揭示,因而本發明未記載。 【發明內容】 [發明之揭示] 本發明在此狀況下,以提供將採用界面縮聚法所得之 含有水溶性雜質的粗製聚碳酸酯有機溶液、與水性洗淨、液 混合而乳化;使用凝結器將該乳濁液分離爲有機相與水相 ;在製造精製聚碳酸酯有機溶液之際,藉由使該凝結器於 特定之操作條件下運轉,在凝結器內之至少元件部,能防 -6- 200528488 (4) 止中間比重之雜質的黏附與聚集,可穩定進行分離操作; 同時能有效的製造精製聚碳酸酯有機溶液之方法,及使用 該精製聚碳酸酯有機溶液製造高純度聚碳酸酯之方法爲目 的。 本發明之工作同仁,爲解決上述之課題,經深入探討 ,不斷硏究之結果發現,藉由於凝結器內之至少元件部, 使聚碳酸酯有機溶液與水性洗淨液分離爲有機相及水相之 二相,可實質上不形成界面,爲該凝結器之操作條件,能 達成上述之目的,以此發現爲基準完成本發明。 本發明係由下述構成者。 (1) 一種精製聚碳酸酯有機溶液之製造方法,其特 徵爲,在將以界面縮聚法進行縮聚反應完成之粗製聚碳酸 酯有機溶液、與水性洗淨液混合而乳化;將所得乳濁液導 入凝結器,藉由去除水份而得精製聚碳酸酯有機溶液之方 法中,藉由控制自凝結器排出之去除水份的聚碳酸酯有機 溶液之排出量、及由凝結器頂部排出之含有含聚碳酸酯有 機溶液的一部份之雜質的水溶液之排出量,使於凝結器內 之至少元件部,聚碳酸酯有機溶液與水性洗淨液分離爲有 機相與水相之二相,可實質上不形成界面;即得去除水份 之聚碳酸酯有機溶液。 (2) 如上述(1)記載之精製聚碳酸酯有機溶液之製 造方法,其中將由凝結器頂部排出之含有含聚碳酸酯有機 溶液的一部份之雜質的水溶液之排出量,控制於供給之水 性洗淨液量的1〜1 . 5倍之量。 200528488 (5) (3 ) —種精製聚碳酸酯有機溶液之製造方法,其特 徵爲,在將以界面縮聚法進行縮聚反應完成之粗製聚碳酸 酯有機溶液、與水性洗淨液混合爲乳濁液;將所得乳濁液 導入凝結器,藉由去除水份而得精製聚碳酸酯有機溶液之 方法中;將供給至凝結器內之粗製聚碳酸酯的有機溶液之 量、與供給的水性洗淨液之量的合計量,由凝結器內排至 設置於下游之靜置分離槽,自該靜置分離槽將聚碳酸酯有 機溶液層排出,使於該凝結器內之至少元件部,聚碳酸酯 有機溶液與水性洗淨液分離爲有機相與水相之二相,可實 質上不形成界面。 (4 )如上述(1 )〜(3 )項中任一項記載之精製聚碳 酸酯有機溶液之製造方法,其中粗製聚碳酸酯有機溶液與 水性洗淨液之混合方法,係採用聯機混合器、靜態混合器 、或銳孔板混合器者。 (5 )如上述(1 )〜(4 )項中任一項記載之精製聚碳 酸酯有機溶液之製造方法,其中凝結器內之元件的材質, 爲玻璃纖維、碳纖維、金屬纖維、聚四氟乙烯纖維、聚丙 烯纖維、聚乙烯纖維、紙漿纖維、或木棉纖維者。 (6 )如上述(1 )〜(5 )項中任一項記載之精製聚碳 酸酯有機溶液之製造方法,其中凝結器內之元件的形狀, 爲平板狀、圓筒狀、或折疊狀者。 (7 )如上述(1 )〜(6 )項中任一項記載之精製聚碳 酸酯有機溶液之製造方法,其中凝結器內之元件的結構, 係於圓筒箱體內安裝纖維層者。 200528488 (6) (8 ) —種高純度聚碳酸醋之製造方法,其特徵爲,使 用以上述(1 )〜(7 )項中任一項記載之製造方法所得的精 製聚碳酸酯有機溶液。 [用以實施發明之最佳型態]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]
本發明係,將以界面縮聚法所得之含有水溶性雜質的 粗製聚碳酸酯有機溶液、與水性洗淨液混合而乳化;使用 凝結器將乳濁液分離爲有機相與水相;在製造精製聚碳酸 酯有機溶液之際,藉由使該凝結器於特定之操作條件下運 轉’在凝結器內之至少元件部,能防止中間比重之雜質的 黏附與聚集,可穩定進行分離操作;同時能有效的製造精 製聚碳酸酯有機溶液之方法,及使用該精製聚碳酸酯有機 溶液製造高純度聚碳酸酯之方法者。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.
該界面縮聚法係以二價苯酚爲主成份,加入爲溶解少 量之末端終止制(亦稱爲分子量調節劑)與二價苯酹之苛 性鹼、及因應需求之支化劑’藉由與光氣或光氣衍生物在 有機溶劑中反應而製造;所得粗製聚碳酸酯有機溶液與水性 洗淨液混合攪拌’將水溶性之雜質洗淨;接著經離析、回 收步驟,製造聚碳酸酯者。 該界面縮聚法中,做爲聚碳酸酯之原料使用的二價苯 酚,有例如以一般式(I )表示之化合物等。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) 上述一般式(I )中,X1及X2分別爲碳數1〜6之直鏈狀 、支鏈狀或環狀之烷基;具體例有,甲基、乙基、正丙基 、異丙基、正丁基、異丁基、叔丁基、正戊基、異戊基、 正己基、異己基、環戊基、環己基等;此X1及X2互爲相同 或相異均可;a及b分別爲X1及X2之取代數,〇〜4之整數; χΐ爲複數時,複數之X1互爲相同或相異均可,X2爲複數時 ’複數之X2互爲相同或相異均可。 Υ爲單鍵、碳數1〜8之烯基(例如亞甲基、乙烯基、 丙條基、丁稀基、戊稀基、己嫌基等)、碳數2〜8之亞院 基(例如亞乙基、亞異丙基等)、碳數5〜1 5之環烯基(例 如環戊烯基、環己烯基等)、碳數5〜1 5之環亞烷基(例如 環亞戊基、環亞己基等)、一 s -、_SO-、— S02—、 〜〇一、一 c〇 -鍵或式(Π - 1)或式(II 一 2)所示之鍵• 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) 於此,上述一般式(I)所示之二價苯酚’有各式各 樣考,以2,2 -雙(4 一羥基苯基)丙烷(通稱雙酚A ) 最爲適合;雙酚A以外之二價苯酚有,例如雙(4 -羥基苯 -10- 200528488 (8) 基)甲烷;雙(4 一羥基苯基)苯基甲烷;雙(4 一羥基苯 基)萘基甲烷;雙(4 一羥基苯基)一 (4 一異丙基苯基) 甲烷;雙(3,5 —二氯一 4 —羥基苯基)甲烷;雙(3,5 一二甲基一 4 —羥基苯基)甲烷;1,1 一雙(4 一羥基苯基 )乙烷;1 —萘基—i,1 一雙(4 —羥基苯基)乙烷;1 — 苯基一 1,1 一雙(4 —羥基苯基)乙烷;1,2-雙(4 —羥 基苯基)乙烷;2 —甲基—1,1 一雙(4 一羥基苯基)丙烷 ;2,2 —雙(3,5 —二甲基—4一羥基苯基)丙烷;1—乙 基一 1,1—雙(4 一羥基苯基)丙烷;2,2 —雙(3,5_ 二氯—4 —經基苯基)丙院;2,2 —雙(3,5 —二溴—4 — 羥基苯基)丙烷;2,2-雙(3 -氯一 4一羥基苯基)丙烷 ;2,2 —雙(3 -甲基—4一羥基苯基)丙烷;2,2 —雙( 3 -氟一 4 —羥基苯基)丙烷;1,1 一雙(4 一羥基苯基) 丁烷;2,2 -雙(4 —羥基苯基)丁烷;1,4 一雙(4 一羥 基苯基)丁烷;2,2 —雙(4 —羥基苯基)戊烷;4 —甲基 一 2,2—雙(4 —羥基苯基)戊烷;2,2 —雙(4 一羥基苯 基)己烷;4,4 —雙(4 —羥基苯基)庚烷;2,2-雙(4 —羥基苯基)壬烷;1,1 〇 —雙(4 一羥基苯基)癸烷;1 ,1—雙(4 —羥基苯基)—3,3,5-三甲基環己烷;2, 2-雙(4 一羥基苯基)一 1,1,1,3,3,3 —六氟丙烷等 二羥基二芳基烷類、1,1 一雙(4 一羥基苯基)環己烷;1 ,1 一雙(3,5-二氯—4_羥基苯基)環己烷;1,1 一雙 (4 一羥基苯基)環癸烷等二羥基二芳基環烷類、雙(4一 羥基苯基)硕;雙(3,5 -二甲基一 4一羥基苯基)砸; -11 - 200528488 (9) 雙(3 —氯—4 一羥基苯基)硕等二羥基二芳基硕類、雙(4 一羥基苯基)醚;雙(3,5-二甲基一 4一羥基苯基)醚等 二羥基二芳基醚類、4,4· 一二羥基二苯甲酮;3,3',5,5' 一四甲基一 4,4’一二羥基二苯甲酮等二羥基二芳基酮類、 雙(4 一羥基苯基)硫化物;雙(3 -甲基一 4一羥基苯基 )硫化物;雙(3,5 —二甲基一 4 一羥基苯基)硫化物等 二羥基二芳基硫化物類、雙(4 一羥基苯基)亞硕等二羥 基二芳基亞硕類、4,^一二羥基二苯基等二羥基二苯基類 、9,9一雙(4一羥基苯基)芴等二羥二芳基芴類等等;又 ,該一般式(I )所示之二價苯酚類以外,尙有對苯二酚、 間苯二酚、甲基對苯二酚等二羥基苯類、1,5 —二羥基萘; 2,6 —二羥基萘等二羥基萘類等等;此等二價苯酚可分別單 獨使用,亦可兩種以上組合使用。 分子量調節劑,只要爲通常聚碳酸酯之聚合所使用者 ,各種均可使用;具體的,一價苯酚有,例如苯酚、對-甲酚、對-叔丁基苯酚、對-叔辛基苯酚、對異丙苯基苯酚 、溴苯酚、三溴苯酚、壬基苯酚等等;其中,從經濟性, 取得之容易度等的觀點而言,以對-叔丁基苯酚及苯酚較 爲適合。 本發明中,上述二價苯酚可與適當之支化劑同時使用 ,·此支化劑爲三價以上之多價苯酚;具體的有,1,1,1 一 三(4 一羥基苯基)乙烷、α,α·,α” —三(4 一羥基苯基 )一 1,3,5 —三異丙基苯、1— [α〜甲基一 α (41—羥基 苯基)乙基]一 4一 [α,,α’一 (雙(41,—羥基苯基)乙基] -12- 200528488 (10) 苯、均苯三酚、靛紅雙(鄰-甲酚)等等;此等支化劑之 使用量,隨目標之支化度而異,通常對二價苯酚爲0.05〜2莫 耳%之程度。 以界面縮聚法製造聚碳酸酯時,生成聚碳酸酯主鏈中 之碳酸酯鍵的化合物有,例如光氣、三光氣、溴光氣、雙 (2,4,6 —三氯苯基)碳酸酯、雙(2,4 一二氯苯基)碳 酸酯、雙(2—氰基苯基)碳酸酯、氯甲酸三氯甲基酯等可 使用。 界面縮聚法中,聚碳酸酯之製造步驟,沒有特別的限 制,可使用已往以界面縮聚法製造聚碳酸酯所慣用之步驟 ;例如藉由施行(A )二價苯酚聚碳酸酯低聚物之調製步驟 、(B )上述低聚物之聚合步驟、(C )洗淨步驟、及(D )聚碳酸酯之離析•回收步驟,可有效製造目標之聚碳酸 酯。 還有,本發明中,不將上述(A)步驟與(B)步驟 分離,直接以聚合物進行聚合亦可;又,聚碳酸酯之製造 形式,爲分批式或連續式之任一種均可,但以連續式較適 合;採用此連續式時,將上述(A )步驟及(b )步驟連 結進行較爲有利。 其次,將各步驟簡單說明如下。 (A )步驟: 此(A )步驟,係將二價苯酚與光氣或光氣衍生物進 行界面縮聚,以調製二價苯酣聚碳酸醋低聚物之步驟。 -13- 200528488 (11) 此二價苯酚聚碳酸酯低聚物之調製方法,沒 限制,例如可使用下述之適合的方法。 首先,調製含有原料之上述二價苯酚的鹼水 其與惰性有機溶劑混合,攪拌,同時藉由在含有 之鹼水溶液與惰性有機溶劑的共存下,將光氣或 物反應,即得二價苯酚聚碳酸酯低聚物。 此時,鹼水溶液之濃度,通常以使用1〜1 5重 爲適合;又,鹼水溶液中之二價苯酚的含量 0.5〜20重量%之範圍選擇;進而,惰性有機劑之 以選定使有機相與水相之容量比可達5/1〜1/7較 可達2/1〜1/4更佳;反應溫度通常爲〇〜50°C,以 之範圍選擇爲佳。 此反應中,於將光氣或光氣衍生物反應之後 含有二價苯酚之鹼水溶液、末端終止劑之一部份 望之催化劑,能使反應順利進行。 調製上述含有二價苯酚之鹼水溶液所使用的 如氫氧化鈉、氫氧化鉀、氫氧化鋰、氫氧化鉋等 氫氧化鈉及氫氧化鉀較適合,以氫氧化鈉更佳; ,惰性有機溶劑有各式各樣者;例如,二氯甲烷 烷、四氯化碳、1,1 一二氯乙烷、1,2-二氯乙 ,1 —三氯乙烷、1,1,2 —三氯乙烷、1,1,1, 乙烷、1,1,2,2—四氯乙烷、五氯乙烷、氯苯 ;甲苯、苯乙酮等;此等有機溶劑可分別單獨使 二種以上組合使用;其中以二氯甲烷最適合。 有特別的 溶液,將 二價苯酚 光氣衍生 :量%者較 ,通常於 使用量, 適合,以 於5〜40V ,更加入 、及所期 鹼有,例 ;其中以 另一方面 、三氯甲 垸、1,1 2 —四氯 等氯化烴 用,亦可 -14- 200528488 (12) 催化劑爲相間移動催化劑,例如可使用適合之叔胺或 其鹽、季銨鹽、季鳞鹽等等。 叔胺有,例如三乙胺、三丁胺、N,N —二甲基環己 基胺、吡啶、二甲基苯胺、N -甲基哌啶等;又,叔胺鹽 有,例如此等叔胺之鹽酸鹽、溴酸鹽等;季銨鹽有,例如 三甲基苄基銨氯化物、三乙基苄基銨氯化物、三丁基苄基 銨氯化物、三辛基甲基銨氯化物、四丁基銨氯化物、四丁 基銨溴化物等;季鱗鹽有,例如,四丁基鱗氯化物、四丁 基鳞溴化物等等;此等催化劑可分別單獨使用,亦可兩種 以上組合使用;上述催化劑中,以叔胺較適合,尤其以三 乙胺更適合。 反應後,以靜置或離心分離等操作,分離爲水相與含 聚碳酸酯低聚物之有機相;有機相可不將聚碳酸酯低聚物 離析,使用於下一步驟。 (B )步驟 係上述(A )步驟所得之聚碳酸酯低聚物的聚合步驟 ;在剩餘之末端終止劑、與所期望使用之催化劑、鹼水溶 液、及惰性有機溶劑的存在下,將該聚碳酸酯低聚物與二 價苯酚進行界面縮聚。 具體的說,將上述(A )步驟所得之聚碳酸酯低聚物 溶液、與剩餘之末端終止劑、所期望使用之催化劑、惰性 有機溶劑、鹼水溶液、及二價苯酚之鹼水溶液’混合後’ 通常於0〜5 (TC進行界面縮聚,以於5〜40°C之範圍更適合。 -15- 200528488 (13) 此時所使用之鹼、惰性有機溶劑、及催化劑,可爲與 上述(A )步驟中之說明相同者;又,此界面縮聚中,有 機相與水相之容量比,與上述(A )步驟之情況相同。 還有,此聚合步驟可劃分爲預備聚合(前聚合)及本 聚合(後聚合)進行聚合;即,首先將上述(A )步驟所 得之聚碳酸酯低聚物溶液、與剩餘之末端終止劑、所期望 使用之催化劑、惰性有機溶劑、及鹼水溶液混合、於較低(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
之溫度(例如低於2 0 C之溫度)進行預備聚合(前聚合) ;接著,於其中加入二價苯酚之鹼水溶液,於較高之溫度 (例如20〜40°C )進行本聚合(後聚合)。 反應後,以惰性有機溶劑適當稀釋之後,經靜置或離 心分離等操作,分離爲水相與含聚碳酸酯之有機相。 (C )步驟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
此(C )步驟,係以上述(b )步驟分離之粗製聚碳 酸酯有機溶液的洗淨步驟·,將雜質之殘留單體、催化劑、 驗物質等自該聚碳酸酯有機溶液去除,以獲得高純度之聚 碳酸醋有機溶液的方法,係藉由於該聚碳酸酯有棧溶液中 ’加入驗性水溶液、酸性水溶液、純水等洗淨水攪拌混合 ’將水相側之雜質萃取而施行;此洗淨,僅施行此等洗淨 操作之任一種亦可’將2種或3種以上之洗淨方法組合亦可 :又’因應需求’此等洗淨操作之次數,亦可隨意設定。 粗製聚碳酸酯有機溶液與水性洗淨液之混合方法,以 液/液混合爲目的之市售的任何機器均可使用,爲獲得所 -16- 200528488 (14) 期望之攪拌效率,例如以聯機混合器、靜態混合器、銳孔 板混合器較爲適合;此等混合器之攪拌動力,與後述之凝 結器內的元件材質亦有關係,通常爲0.1kw/m3/hi*以上, 以0.2kw/m3/hr以上較適合,以0.5kw/m3/hr以上更佳;攪 拌強度薄弱時,不僅不能充分洗淨,使分離後之聚碳酸酯 有機溶液中的水份增多,結果導致所得聚碳酸酯之品質降 低;此較多之品質上不適合的物質,並非在有機相側,而 是顯示存在於水相側。 粗製聚碳酸酯有機溶液與水性洗淨液混合時之水性洗 淨液的水相量,通常爲50容積%以下,以30〜3容積%較適 合,以20〜5容積%更佳;水性洗淨液多量使用時,需要更 多之排水處理的費用,極不經濟。 本發明之洗淨中,構成乳濁液之有機相(油相)與水 相的關係,爲油中水滴分散型、水中油滴分散型之任一種 均可使用,以油中水滴分散型更爲適合。 本發明中,於聚合步驟與水相分離之粗製聚碳酸酯有 機溶液,與水性洗淨液混合,進行乳化;使用凝結器將其 分離爲有機相與水相;凝結器能促進乳濁液中之水滴等凝 聚,流通溶液時引起有機相與水相之分離,通常於凝結器 殼體內進行分離;此時,在殼體內或殼體內之元件部實質 上存在有機相與水相之二相的界面之狀態下施行分離操作 時,雜質之中間比重物質,例如金屬氯化物、金屬氫氧化 物、劣化單體及聚合物等聚集於該殻體內,此爲凝結器內 之元件縮短壽命的主要原因,不僅不能穩定的進行分離操 -17- 200528488 (15) 作,且精製之精確度下降,更不能獲得高純度之精製聚碳 酸酯有機溶液;還有,於此所謂殼體內之元件部,係指分 別包含元件之上端面及下端面的殻體內兩水平面之間的領 域;因此,通過凝結器之有機相與水相的分離,係在另外 之分離槽施行;由凝結器頂部排出之含有含聚聚碳酸酯有 機溶液的一部份之雜質的水溶液之排出量,必要使於凝結 器之殻體內的至少元件部,有機相與水相之二相可實質上 不形成界面;藉此,實質上於凝結器之殼體內的至少元件 部,形成有機相與水相之二相的界面不存在;此時,於前 段之步驟設置分離槽,利用其分離亦可(例如參照圖1,圖 3),於凝結器之下游側設置分離槽亦可(例如參照圖2 ) ;又,含有含聚碳酸酯有機溶液之一部份的雜質之水溶液 的排出量,沒有特別的限制,控制在供給水性洗淨液之量 的1〜1.5倍之量即足夠;進而,藉由採用以供給至凝結器內 的聚碳酸酯有機溶液之量,與供給水性洗淨液之量的合計 量,由凝結器排至設置於下游之靜置分離槽的方法,使於 凝結器之殼體內的至少元件部,有機相與水相之二相實質 上形成之界面不存在亦可(例如參照圖4 )。 所使用之凝結器,通常可使用市售之任一形式者,例 如可使用和興產業股份有限公司、日本波魯股份有限公司、 富士過濾器股份有限公司、旭化成纖維股份有限公司等之產 品。 凝結器內實際上裝配有具促進凝聚之功能的元件;該元 件之材質沒有特別的限制,可使用早已知悉之玻璃纖維、 -18- 200528488 (16) 碳纖維、金屬纖維、聚四氟乙烯(PTFE )、聚丙烯(PP ) 、或聚乙烯(PE )等合成纖維、紙漿、木棉等有機纖維, 多孔性石墨等多孔性材料;其中尤其以碳纖維或玻璃纖維 ,較適合於聚碳酸酯有機溶液之洗淨後的分離。 元件之形狀,從處理、設置之容易度、成本之觀而言 ,選定最適當者即可;可使用平板狀、圓筒狀、折疊狀者 ,從處理之點而言以圓筒狀者較適合;又,元件之結構, 僅爲纖維層亦可;爲具備強度,護圈等之結構物亦可;爲 性能上及將流體中之雜質去除,雙層或其以上之多層結構 亦可;其中尤其以結構上,在圓筒箱體內安裝纖維層者爲 佳;構成元件之纖維層的厚度亦可隨性能自由設定,例如 可由纖維層之厚度、與壓力差△ P及分離性能最適化。 又,該元件之設置,爲縱方向、橫方向均可。 其次,以圖式爲基準說明使用凝結器之本發明的分離 操作之實施型態例如下。 圖1爲,將來自聚合步驟之含聚碳酸酯的反應液,導 入前段之靜置分離槽,以泵等將比重較大之下層的粗製聚 碳酸酯有機溶液排出,於中途加入水性洗淨液,以管路混 合器攪拌混合而乳化;使該乳濁液通過凝結器,分離爲有 機相與水相;同時,於凝結器內之至少元件部,使有機相 與水相實質上不形成二相;將水相由頂部以含一部份有機 相之型態排出,循環於上述之靜置分離槽;由凝結器之側 部將精製的有機相排出,輸送至下一步驟之表示本發明的 實施型態之一例者。 -19- 200528488 (17) 此時,由頂部排出之含一部份有機相的水相之量’沒 有特別的限制;如上所述’控制在供給水性洗淨液之量的 i〜i . 5倍即足夠;靜置分離槽中之水相部,以另外之方法 排出,輸送至排水處理步驟。 圖2爲,在將乳濁液導入凝結器分離爲有機相與水相 後;於凝結器內之至少元件部’使有機相與水相不形成二 相;將水相由頂部以含有一部份有機相之型態排出’導入 設置於下游側之靜置分離槽’於後段一部份分離’同時由 凝結器之側部將精製有機相排出的型態表示者;由頂部排 出之含一部份有機相的水相之量’亦與上述相同即足夠; 設置於下游之靜置分離槽中的水相部’以另外之方法排出 ,輸送至排水處理步驟。 圖3爲,表示使用將鹼洗淨、酸洗淨;及水洗淨串聯 設置之凝結器的實施之例者;此情況,靜置分離槽中之水 相部,亦以另法排出,輸送至排水處理步驟。 圖4爲,表示將供給至凝結器內的聚碳酸酯有機溶液 之量、與供給水性洗淨液之量的合計量,由凝結器內輸送 至設置於下游之靜置分離槽而排出,在凝結器內之至少元 件部’使聚碳酸酯有機溶液與水性洗淨液分離爲有機相與 水相之二相,實質上不形成界面,於該靜置分離槽進行分 離操作之本發明的實施型態者;此情況,靜置分離槽中之 水相部,亦以另法排出,輸送至排水處理步驟。 (D )步驟: -20- 200528488 (18) 此(D )步驟,係聚碳酸酯之離析、回收步驟;具體的 說,例如將上述(C )步驟所得之經洗淨處理的精製聚碳酸 酯有機溶液濃縮之後,經粉碎處理,藉由將所得薄片施行 真空乾燥等乾燥處理,即得產品之高純度聚碳酸酯;進而 ,將該聚碳酸酯以擠壓機等熔融混煉,藉由擠壓而顆粒化 ,可得顆粒狀之型態。 聚碳酸酯,從機械強度及成型性之觀點而言,黏度平 均分子量(Mv )以10000〜100000之範圍較爲適合,以 1 2000〜40000更佳,以1 3000〜30000之範圍最適合;還有,該 黏度平均分子量(Mv ),係使用烏伯勞德型黏度計,測定 於20 °C二氯甲烷溶液之黏度,由其求出特性黏度[7?],依[ 77 ] = 1.23χ 10·5Μν 0.83 之式算出之値。 【實施方式】 [實施例] 其次,以實施例詳細說明本發明如下;本發明之範圍 並非限定於此等實施例;聚碳酸酯有機溶液(聚合物溶液 )中之水份量的測定,係採用卡爾費歇法。 [製造例1] (1 )聚碳酸酯低聚物之製造 將雙酚A ( B P A )溶解於濃度6重量%之氫氧化鈉水溶 液中,即得濃度14.5重量%之BPA — NaOH溶液;將所得 BPA — NaOH溶液以40^ /hr’濃度25重量%之對—叔丁基 -21 - 200528488 (19) 苯酚(P TB P ;分子量調節劑)—二氯甲烷溶液以〇 · 3 w /h r、溶劑之一氯甲烷以丨8 · /h r之流量,導入浸於2 〇艽 之冷卻槽的內徑6mm、長3〇111之管型反應器;於其中以 3· 8kg/hr之流量吹入光氣;將由反應排出之反應混合物導 入分離槽’使水相分離,即得由聚碳酸酯低聚物之二氯甲 烷溶液所成的有機相。 將所得聚碳酸酯低聚物之性狀分析的結果如下。 平均分子量:8 60 (以蒸氣壓滲透壓計(vp〇 )測定 數平均分子量] 氯仿酯基濃度:0.68莫耳/公升(爲低聚物之有機溶劑 溶液) (2 ) 聚碳酸酯之製造: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:
將(1 )所得之聚碳酸酯低聚物的二氯甲烷溶液以20 < /1^、上述(1)調製之濃度14.5重量%的3?人—^〇11溶液以 1 1.5 < /hr、濃度4重量%之三乙胺(TEA :催化劑)水溶液 以0.04 i /hr、濃度25重量%之NaOH水溶液以0.8 < /hr、溶 劑之二氯甲烷以13 < /hr之流量,導入塔型反應器反應;停 留時間爲1小時;其後,即得由溢流而出之含有聚碳酸酯的 反應混合物。 [實施例11 於上述製造例1所得之含有聚碳酸酯的反應混合物中, -22- 200528488 (20) 加入二氯甲烷,調製成有機相側之聚碳酸酯溶液的聚碳酸 酯濃度爲1 2重量%,同時進行1小時靜置分離,分離爲含聚 碳酸酯之二氯甲烷溶液(有機相)與水相;測定此分離之 有機相中的水份之結果,爲7500重量ppm ;還有,加入二氯 甲烷之前的粗製聚碳酸酯,測定另外之聚合物的黏度平均 分子量之結果爲Mv = 28700;就水相側分析時,BPA以21gM 之濃度溶解,NaOH之濃度爲0.22莫耳/<。 將如此而得之含聚碳酸酯的二氯甲烷溶液(有機相) 以600 < /hr、以另外NaOH調製之pH=13的氫氧化鈉水溶液 以60< /hr,導入管路混合器(特殊機化工業公司製,管 路勻化器)中,以2600rpm混合,施行洗淨;確認出口 之乳濁液的相狀態爲油中水型;又,此時賦予流體之攪拌 動力爲0.53 kw/m3/hr ;進而,於安裝檢測此乳濁液界面用 之液位計的凝結器(和興產業公司製之凝結器,元件尺寸 :直徑180mm、內容積70(W ,元件之材質:碳纖維)連 續流通液體;不久,由凝結器之下方出口,可得透明感之 聚合物溶液,由頂部出口可得含聚合物溶液之一部份的水 溶液;頂部之水溶液流量,由設置之流量計可知,以8 0 < / h r連續排出’施行約1小時之連續操作;藉由液位計確認 有機相與水相不產生界面;出口之聚合物溶液的溫度爲3 2 °C ;測定出口之聚合物溶液的水份約爲2〇〇〇重量ppm ’判 定於凝結器流通溶液,能使水份充分分離;又,以此方法 ,施行30天之連續操作後,開放凝結器本體,以目視觀察 本體內部及元件,確認並無與開始操作前不同之污染及雜 -23- 200528488 (21) 質聚集;其結果如表1所示。 [實施例2〜11] 除聚合物溶液流量、水性洗淨液供給量、攪拌動力 凝結器內之元件材質,如表1之記載改變以外,依實施例 進行;其結果如表1所示。 -24- 200528488 (22) 聚合物溶液水份量 (*1 Μ重量ppm) 2000 2100 2000 2400 2000 2100 2200 2300 2600 2400 2200 3700 δ800 13000 2200 2000 2300 2000 2100 3400 凝結器內元件之材質 碳纖維 (* 2) δ δ 不銹鋼SUS 316(* 2) 碳纖維 (* 2) 聚丙烯(*3) PTFE製(*4) 玻璃纖維 (* 2) 5: 5: 碳纖維 (* 2) 混合器攪拌動力 (kw/m3/hr) 0.53 0.62 0.49 0.45 s ο 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 水相比 (容積%) oq 14.3 25.0 τ— 11.2 s 10.3 卜 CO T~ 5 CO 〇〇 10.4 12.5 寸 〇 10.5 13.0 13.0 水性洗淨液 (1/hr) g S 〇 o ο 04 S S *τ~ s s S S g s Ο 〇 〇 S 〇 S S S _ Μ 紫:g 键£ <Π m ο <〇 O S o CO Ο CO ο ο 950 ο g o <〇 o to O o o ο CO ο 〇 600 350 〇 2 S 〇 〇〇 〇 〇〇 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 ! 實施例11 實施例11 一1 實施例11 一2 實施例11 一3 實施例1 2 實施例1 3 實施例1 4 實施例1 5 實施例1 6 實施例16 — 2 ϋ—Λ ^ ^ * 2:813>骓||^骓^頰^螂_鉍陌<<[(袈)骓鹪«§^鲫:00* 蹿ig骧昍蹿賴#ΘΤΙΪ?<<(^)纖酬«g: s * 码 H 班繇«—Μ+Κ1:τ* -25- 200528488 (23) [實施例π - 1〜11 — 3 ] 除聚合物溶液流量、洗淨液供給量、攪拌動力、凝結 器內之元件材質,如表1之記載改變以外,依實施例1進行 ;其結果如表1所示。 [實施例12〜13] 使用實施例1所得,於鹼大氣下完成洗淨之聚合物溶 液,施行酸洗淨;除使用以鹽酸調整爲ΡΗ= 1之水爲水性洗 淨液以外,依實施例1施行酸洗淨;其結果如表1所示。 [實施例14〜16— 2] 使用實施例1 2〜1 3所得,於酸大氣下完成洗淨之聚合 物溶液,施行其次之水洗淨;除使用純水爲水性洗淨液以 外,依實施例1施行水洗淨;其結果如表1所示。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.
WW
[比較例1] 實施例1中,凝結器之操作方法爲,在本體設置檢測 界面用之液位計,調整水側之排出量,進行使凝結器內形 成分離界面之操作(參照圖5 );施行如此之連續操作1 20 天;定期確認聚合物溶液中之水份的結果,判定初期爲水 份2000重量ppm、120天後上升至2 60 0重量;又,確認凝結 器前後之壓力差,確認初期△ P = 9.8kPa、上升至26.46kPa ; 操作完成後,排出溶液確認內部之結果,在凝結器本體內 -26- 200528488 (24) ,對設定界面之位置確認於水平線有茶褐色之具黏性的附 著物;此附著物進行金屬分析之結果確認爲Fe、Cr、Ni ;此 料必爲前步驟所使用之不銹鋼材料的一部份洗提,於界面 附近聚集者;又,於同一位置,在凝結器之筒部亦有附著 ;此推定爲壓力上升及水份上升之起因。 [參考例1] 以實施例1記載之方法,調製粗製聚碳酸酯溶液,靜 φ 置分離後,以pH=13之洗淨水使用管路混合器混合,至此 同樣的施行;以1〇〇〇 J之量筒採取所得之乳濁液,進行靜 置分離,確認其分離速度及分離後之聚合物溶液的水份量 ;其結果,於1小時之靜置分離後,聚合物溶液中水份量 爲5重量%、2小時靜置分離後爲2重量%。 [實施例1 7](依界面縮聚法施行全洗淨步驟) 確認將以實施例所得之粗製聚碳酸酯有機溶液,如圖 y 3所示,連續處理而得澄淸的聚碳酸酯有機溶液之方法; 聚碳酸酯有機溶液之洗淨,係最初鹼洗淨,其次酸洗淨, 進行純水洗淨,如此分別施行二次;聚合物溶液使用600 < /hr,於全部之洗淨步驟,水相比調製爲1 2容積% ;又, 混合器,攪拌動力調整爲Pv = 〇.5kw/m3/hr ;就所得澄淸的 聚碳酸酯有機溶液,測定代表性之雜質的結果,Na離子爲 〇·1重量ppm以下、Fe離子爲0.1重量ppm以下、殘留BPA爲3.2 重量ppm,確認爲效率優異,且獲得澄淸的聚碳酸酯有機溶 •27- 200528488 (25) 液。 其次,將實施例1〜1 7所得之精製聚碳酸酯溶液,分別 濃縮後,經粉碎處理;將所得薄片施行真空乾燥處理,即 得高純度聚碳酸酯;進而,以擠壓機等將該聚碳酸酯熔融 混煉,藉由擠壓顆粒化,即得高純度聚碳酸酯之顆粒。 [產業上利用性] 依本發明能提供,將以界面縮聚法所得之含有水溶性 φ 雜質的粗製聚碳酸酯有機溶液、與水性洗淨液混合而乳化 ;在使用凝結器將乳濁液分離爲有機相與水相,製造精製 聚碳酸酯有機溶液之際,藉由在該凝結器內之至少元件部 ,使聚碳酸酯有機溶液與水性洗淨液分離爲有機相與水相 之二相,實質上不形成界面的操作條件下,運轉凝結器; 在凝結器內之至少元件部,能防止中間比重之雜質的黏附 與聚集,可穩定進行分離操作;同時能有效的製造精製聚 碳酸酯有機溶液的方法,及使用該精製聚碳酸酯有機溶液 _ 製造高純度聚碳酸酯之方法。 【圖式簡單說明】 圖1爲表示在凝結器內之至少元件部,使有機相與水 相不形成二相;將水相由頂部以含有一部份有機相之型態 排出’循環於設置在前段之靜置分離槽;將精製之有機相 由凝結器的側部排出,輸出至下一步驟之本發明的實施型 態之一例。 -28- 200528488 (26) 圖2爲表示在凝結器內之至少元件部,使有機相與水相 不形成二相;將水相由頂部以含有一部份有機相之型態排出 ,導入設置於下游側之靜置分離槽,於後段一部份分離, 同時亦由側部將精製有機相排出之本發明的實施型態。 圖3爲表示使用將鹼洗淨、酸洗淨、及水洗淨之洗淨操 作串聯設置之凝結器依序施行的本發明之實施型態。 圖4爲表示在凝結器內之至少元件部,使聚碳酸酯有機 溶液與水性洗淨液分離爲有機相與水相之二相,實質上不 馨 形成界面;將供給至凝結器內的粗製聚碳酸酯有機溶液之量 、與供給的水性洗淨液之量的合計量’由凝結器內輸送至 設置於下游之靜置分離槽而排出,於該靜置分離槽總括分 離之本發明的實施型態。 圖5爲表示以比較例實施之設置的模示圖。[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.
-29--29-
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JP2004018276A JP4567981B2 (en) | 2004-01-27 | 2004-01-27 | Purified polycarbonate organic solution and method for producing high-purity polycarbonate |
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TW200528488A true TW200528488A (en) | 2005-09-01 |
TWI367225B TWI367225B (en) | 2012-07-01 |
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CN102604068B (en) * | 2012-02-24 | 2013-06-26 | 青岛科技大学 | Washing and purifying method for polycarbonate adhesive solution |
CN102775595B (en) * | 2012-03-12 | 2014-03-05 | 甘肃银光聚银化工有限公司 | Continuous purification method for polycarbonate emulsion |
CN102604067B (en) * | 2012-03-16 | 2013-10-30 | 甘肃银光聚银化工有限公司 | Method for separating and purifying polycarbonate glue solution |
KR102349078B1 (en) * | 2017-09-25 | 2022-01-07 | 주식회사 엘지화학 | Method for preparing polyalkylene carbonate resin |
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IT1110267B (en) * | 1979-02-05 | 1985-12-23 | Montedison Spa | PURIFICATION PROCESS OF POLYCARONATE SOLUTIONS |
JPH0317923Y2 (en) * | 1985-08-26 | 1991-04-16 | ||
JPH109940A (en) * | 1996-06-19 | 1998-01-16 | Mitsubishi Heavy Ind Ltd | Measuring apparatus for radiant power |
CN1233625A (en) * | 1998-04-30 | 1999-11-03 | 通用电气公司 | Method for recycling aromatic polycarbonates |
DE19849004A1 (en) * | 1998-10-24 | 2000-04-27 | Bayer Ag | High purity polycarbonate is produced using coalescer with hydrophilic packing to separate wash liquid from organic product solution after first washing step |
SG87068A1 (en) * | 1999-01-11 | 2002-03-19 | Mitsubishi Gas Chemical Co | Process for purifying polycarbonate resin solution |
JP4280881B2 (en) * | 1999-07-23 | 2009-06-17 | 三菱瓦斯化学株式会社 | Purification method of polycarbonate resin solution |
US6214892B1 (en) * | 1999-12-23 | 2001-04-10 | General Electric Company | Polycarbonate isolation through homogenization devolatization |
US6620906B1 (en) * | 2000-02-07 | 2003-09-16 | Bayer Aktiengesellschaft | Method for the production of highly pure polycarbonate and ultrapure polycarbonate |
KR100755285B1 (en) * | 2000-09-21 | 2007-09-05 | 제너럴 일렉트릭 캄파니 | Process for the purification of polycarbonate containing solutions by plate decantation |
JP2003038902A (en) * | 2001-07-27 | 2003-02-12 | Yamaha Motor Co Ltd | Oil-water separation apparatus |
-
2004
- 2004-01-27 JP JP2004018276A patent/JP4567981B2/en not_active Expired - Lifetime
- 2004-12-29 TW TW93141184A patent/TW200528488A/en unknown
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2005
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JP4567981B2 (en) | 2010-10-27 |
JP2005213284A (en) | 2005-08-11 |
CN100451048C (en) | 2009-01-14 |
TWI367225B (en) | 2012-07-01 |
CN1648153A (en) | 2005-08-03 |
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