TW457237B - Method to produce and purify cyclic esters - Google Patents
Method to produce and purify cyclic esters Download PDFInfo
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- TW457237B TW457237B TW84112588A TW84112588A TW457237B TW 457237 B TW457237 B TW 457237B TW 84112588 A TW84112588 A TW 84112588A TW 84112588 A TW84112588 A TW 84112588A TW 457237 B TW457237 B TW 457237B
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經濟部中央標準局員工消費合作社印製 457237 Α7 Β7 五、發明説明(1 ) 本申請案是1993年9月29日申請的美國專利申請条列 08/128,797號之延續部分,而後者又是1992年3月19日申 請的美國專利申請糸列07/854,559號,現為美國專利 5,319, 107號之延續,在此編入其掲露Μ供完整的參考。 本發明係有關於環酯和環酯組成物之製造、回收和純 化的方法。在一特定的實髏,本發明係有闘於丙交酯和丙 交酯組成物之製造、回收和純化。 環酯適用於多種應用中。例如,以羥基羧酸衍生之環 酯適用於製備環境生物降解塑膠树料,而對於塑膦材料, 當在醫學上應用時會再吸收。特別有用的聚合物是那些從 α -羥基羧酸,諸如乳酸,衍生的,因爲它們在大多數環 境條件下能隨時間藉水解而降解。結果的羥基酸單位(例 ,乳酸)或從其而來的低聚物能容易地被環境中之微生物 吸收並需氧地轉化成二氧化硪和水,或厭氧地轉化成二氧 化碳和甲烷。 環酯,諸如羥基羧酸之環酯可經一些機理製成;然而 ,這樣的環酯產物典型地含有多樣不良的雜質。這類雜質 能降解產品中之環酯,結果造成製得的環酯是短擱置壽命 的。例如,在環酯組成物内之游離酸和水能增長環酯鍵之 水解,使環酯降解回到羥基羧酸或其它降解產物。另外, 在環酯組成物中的雜質會千擾環酯聚合反應速率和分子量 ,因而阻止了合窻的較高分子量聚合產物之生成。因此, 為了需要獲得基本上純的環酯,它基本上不含會降解化合 物或干擾後續之化學反應,諸如環酯聚合反應成高分子量 (請先間讀背面之注意事項再填寫本頁) 訂 h· 本紙張尺度適用中國國家標準(CNS ) A4規格(2丨ΰΧ297公釐) 一 4 一 4 經濟部中央標準局員工消費合作社印製 457237 A7 _____ B7 五、發明説明(2 ) 聚合物,的雜質。 已知有純化合成的環酯組成物之一些方法。這類方法 包括溶劑結晶、溶劑洗滌、溶劑萃取、蒸餾、熔化結晶和 昇華。雖然在控制的實驗室條件下能獲得滿意的結果,但 許多方法難Μ按工業童操件,因為它們是複雜的或有不實 際的操作參數。另外,這類方法可能需要昂貴的能量、高 價的設備或價昂之試劑。更者,可能尚未有機械能以工業 量來實施這些方法。 另外一些方法是工業上不能被接納的,因為進行環酯 純化時,由於方法中的停留時間或溫度限制,環酯可能降 解而導至低純度。更者,許多方法提供的是低產率Μ致不 合經濟原則。 為此,需要不昂貴的可靠的方法來純化環酯。特別是 需要一些方法來獲得有足夠純度之環酯能用於生產高分子 量之聚合物。更者,需要能回收所有環酯異構體的一些純 化環酯的方法。 依照本發明,提供了製造,回收和純化荏環酯組成物 中環酯的一些方法。 本發明的一値方面是製造環酯的一方法,它包括提供 一進料流,其中包括直鍵分子的一羥基羧酸或它的酯、鹽 或醢胺,並從進料中除去水來生產一環酯組成物,並將環 酯與一吸附劑接觸,以除去環酯組成物中至少一種雜質, 進料流中能含有,例如,ΧΑ,其中一 ΧΑ包含選自下列組群 中之化合物,組群包括一單羥基羧酸或其酯、鹽或酿胺 本紙張尺度逍用中國國家摞準(CNS ) Α4規格(2!0X297公釐) (請先閲讀背面之注意事頃再填窝本頁) 、Tr 457237 Μ _ n? 五、發明说明(3 ) (X,ίΐ) ; X i 的一直鍵.一-元分+ ( X a .A〉; X i A的一直鰱三元分 子(XaA) ; Xi A的…直_四元分子A) ; A的…直鐽五元 分子(X s W ;和其況化物。理想地,製洱的埸酯組成物含 少於2ϋ9ϊ5 (¾¾)之Χ,Λ坟應显合物。能從環組成物中 除去之雜質包括那些逛亩包含游離酸(ΧΜ、水和其混合物 的組群。如此生產的項酯能被回收,諸如經溶劑或熔化結 晶、噴猱乾燥和成1珠,或能聚台成高分Τ里聚合物。 裝- 本發明的進-步方面是提供純化頊酯纽成物之乃法* 它包栝将含雜質之壊酯組成物與一咴附劑接觸1從環酷紐 成物屮除去雜質中至少…種。逭頚方法進一也包括將一環 fl旨組成物與一榷或多a吸附劑接觸> Η菝阵性地從琮酯紐 成物中除去一.槿或多棰雜1。理想地,在本發明中m ffl吸 附劑不會降解琨艏組成物中的環賄:> 在太發明屮恃別有用 的吸附劑是能除去雜質的,諸如ΧΛ,離子交換榥,和分 子篩,它能從環酯組成物中除去水。另外,理想的圾附剤 是能再生*可用於多車吸附循頃中。 經濟邱中央-攻:卑局封工消费合作社印災 本發明也塲尙纯化環酯組成物,fci括镂苒錢本發明方 法所推得的組成物。這頦環酯組成物乜括那些含有琮脂和 少Si約2 0 p b水的Μ成物。本發明的環臨組成掏進一步控· 括那些含荇環酯和其虽少於約為ΰ 0丨毫萏贵/仟克瓌脂的 游瞄酸= 也在本發明軺嘀的是頃酯產品,它含少於約200 _)ρΒ 水和少於约I 〇窀當量游雛酸/仟克環酯包裝在—水秘'氣 透過率芘ϊ 〇tTP和9ϋ%相對源度下為小於约〇. 1克/ 1 〇〇平 本紙張尺及迪用中囝剷雾梂毕K:vs Μ视格ί加人加公势) 4 5 7 2 3 7 A7 B7 五、發明説明( 方吋(24小時)的包裝材料中。在一理想實鹾中,這類包裝 材料包括與低密度聚乙烯膜層壓的箔。 按照本發明,進一步提供藉聚合環酯製成的聚合物並 依照本發明的方法來純化它的過程。這類過程包括在溫度 高於150TC在少於約30小時聚合環酯,製得的聚合物之平 均聚合度約大於1700。理想地,聚合的環酯是丙交酯,所 製得聚合物之最後分子量(Μω)約大於400,000。 第1圖是總的環酯生產和純化過程之一實體的流程圖Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 457237 Α7 Β7 V. Description of the Invention (1) This application is a continuation of US Patent Application No. 08 / 128,797, which was filed on September 29, 1993, and the latter is 1992 US Patent Application No. 07 / 854,559, filed on March 19, 2014, is now a continuation of US Patent No. 5,319, 107, which is incorporated herein by reference for complete reference. The present invention relates to a method for producing, recovering, and purifying cyclic esters and cyclic ester compositions. In a particular embodiment, the present invention relates to the manufacture, recovery and purification of lactide and lactide compositions. Cyclic esters are suitable for a variety of applications. For example, cyclic esters derived from hydroxycarboxylic acids are suitable for the preparation of environmentally biodegradable plastic tree materials, and for plastic phosphine materials, they are reabsorbed when used in medical applications. Particularly useful polymers are those derived from alpha-hydroxycarboxylic acids, such as lactic acid, because they can be degraded by hydrolysis over time under most environmental conditions. The resulting hydroxy acid units (eg, lactic acid) or the oligomers derived therefrom can be easily absorbed by the microorganisms in the environment and converted aerobically to thorium dioxide and water, or anaerobic to carbon dioxide and methane. Cyclic esters, such as cyclic esters of hydroxycarboxylic acids, can be made by a number of mechanisms; however, such cyclic ester products typically contain a variety of undesirable impurities. Such impurities can degrade the cyclic esters in the product, resulting in the resulting cyclic esters having a short shelf life. For example, the free acid and water in the cyclic ester composition can increase the hydrolysis of the cyclic ester bond, degrading the cyclic ester back to the hydroxycarboxylic acid or other degradation products. In addition, impurities in the cyclic ester composition can interfere with the cyclic ester polymerization reaction rate and molecular weight, thereby preventing the formation of a higher molecular weight polymerization product. Therefore, in order to obtain a substantially pure cyclic ester, it is basically free of compounds that would degrade or interfere with subsequent chemical reactions, such as the polymerization of cyclic esters to high molecular weight (please read the precautions on the back before filling this page). h · This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 × 297mm) 1-4 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 457237 A7 _____ B7 V. Description of the invention (2) Polymer, Impurities. Some methods are known for purifying synthetic cyclic ester compositions. Such methods include solvent crystallization, solvent washing, solvent extraction, distillation, melt crystallization, and sublimation. Although satisfactory results can be obtained under controlled laboratory conditions, many methods are difficult to apply to industrial childcare components because they are complex or have unrealistic operating parameters. In addition, such methods may require expensive energy, expensive equipment, or expensive reagents. Furthermore, there may not be mechanical energy to implement these methods on an industrial scale. Other methods are not acceptable industrially because cyclic esters may be degraded to low purity due to dwell time or temperature limitations in the method when performing cyclic ester purification. Furthermore, many methods provide low yields M which are uneconomical. For this reason, inexpensive and reliable methods are needed to purify cyclic esters. In particular, methods are needed to obtain cyclic esters of sufficient purity that can be used to produce high molecular weight polymers. Furthermore, there is a need for a method for purifying some cyclic esters which is capable of recovering all cyclic ester isomers. According to the present invention, there are provided methods for producing, recovering, and purifying cyclic esters in a fluorene ester composition. One aspect of the present invention is a method for making a cyclic ester, which includes providing a feed stream including a linear molecule of a monohydroxycarboxylic acid or its ester, salt, or amidine, and removing water from the feed. A cyclic ester composition is produced and the cyclic ester is contacted with an adsorbent to remove at least one impurity in the cyclic ester composition. The feed stream can contain, for example, XA, where XA contains a compound selected from the group The group includes a monohydroxycarboxylic acid or its ester, salt or amine. The paper size is in accordance with China National Standards (CNS) A4 specification (2! 0X297 mm) (Please read the notes on the back before filling the nest. (This page), Tr 457237 Μ_n? V. Description of the invention (3) (X, ίΐ); a constant bond of X i. One-element + + (X a. A>; a constant ternary molecule of X i A (XaA); Xi A ... Straight_quaternary molecule A); A's ... Straight quaternary molecule (X s W; and its compounds. Ideally, the fluorene ester composition contains less than 2 少于 9ϊ5 (¾¾ ), X, Λ grave should show compounds. Impurities that can be removed from the ring composition include those groups that contain free acid (XM, water and mixtures thereof) The so-produced esters can be recovered, such as by solvent or melt crystallization, spray-dried and beaded, or can be aggregated to form high-resolution polymers. Packing-A further aspect of the present invention is to provide purification. The method of forming an ester compound is to include: contacting an ester composition containing impurities with an adhering agent 1 to remove at least one of the impurities from the cyclone compound. The method also includes the following steps: The composition is in contact with one or more a sorbents > 槿 is removed from the phosphonium ester complex in a matrix. 1. Hibiscus or multi-hybrid 1. Ideally, m ffl sorbents will not degrade 琨 in the present invention Cyclic bridging in the rhenium composition: > The adsorbents useful in the invention are those capable of removing impurities, such as χΛ, ion exchange rhenium, and molecular sieves, which can remove water from the cyclic ester composition. In addition, ideally The rubbish attached can be regenerated * and can be used in multi-vehicle adsorption cycle. Economic Qiu Zhongzhong-Offensive: Sealed off the consumer co-operatives in the humble bureau The invention also purifies the cyclic ester composition, fci includes the method of the invention The derived composition. This cyclic ester composition includes those containing phospholipid and less Si about 2 0 The M product of pb water. The composition of the present invention of the present invention is further controlled, including those containing cyclic esters and thio acids that are less than about 丨 0 丨 mmol / g of fat, but also in the present invention.轺 嘀 is an ester product, which contains less than about 200 _) ρΒ water and less than about 1 〇 窀 equivalent of free acid / 仟 cyclic ester is packaged in-water secret 'gas permeability 芘 ϊ 〇tTP and 9ϋ% Under relative source, it is less than about 0.1 g / 1. 00 paper ruler and medium-sized shovel with fog (K: vs Μ 格格加加加 加) 4 5 7 2 3 7 A7 B7 5 2. Description of the invention (in square inches (24 hours). In an ideal embodiment, such packaging materials include foils laminated with a low density polyethylene film. According to the present invention, there is further provided a process for polymerizing a polymer made by polymerizing a cyclic ester and purifying it according to the method of the present invention. Such processes include polymerizing cyclic esters at temperatures above 150 ° C in less than about 30 hours, and the average degree of polymerization of the resulting polymer is greater than about 1,700. Ideally, the polymerized cyclic ester is lactide, and the final molecular weight (Mω) of the resulting polymer is greater than about 400,000. Figure 1 is a flowchart of one entity of the total cyclic ester production and purification process
(請先聞讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本發於生產和純化聚酯。這類化合物適用於 製造聚合物如,諸如丙交酯的一環酯適用於生產聚乳 酸。本發明特別是有關於製造和純化基本上不含雜質之環 酯,雜質會降解環酯或干擾聚酯聚合成高分子量聚合物。 本發明之方法包括製造和純化從羥基羧酸、羥基羧酸 酯、羥基羧酸鹽、或羥基羧酸醯胺衍生而得之環酯。術語 ‘‘從....衍生”是指製造環酯的反應中,這些組分或這些 組分之產物是反應物。將從任何二個羥基羧酸、其酯、其 鹽或其醯胺所生成的酯轉變成一環二酯來生成環酯。環酯 亦可以是分子内酯或一環單酯,諸如丙酯。本文之環酯乃 M XD表之。XiA指-羥基羧酸、羥基羧酸酯、羥基羧酸鹽、 或羥基羧酸酿胺。X*A指一 XiA分子之線形二聚合分子。X3A 指一 ΧιΑ分子之線柩二聚合分子、而XnA指π個Χ〇· A分子之線 形η-聚合分子。沒有寫於下邊數字的XA表示一個或多値)UA 、XaA、X3A、和)UA或含這些物種之溶液。必須明白當X被 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 7 經濟部中央標準局員工消費合作社印製 457237 A7 _B7 五、發明説明(5 ) L取代時,意指它是基於乳酸所對應的化合物。例如,LA 指以乳酸為基礎之混合物,包括UA、UA、UA和UA,而 LD指乳酸之環二聚體 > 例丙交酯。 本發明之環酯包括上逑之那些化合物。製造環酯之理 想XM物種包括,但不限於,下列之酸和對應之酯、鹽、 或其醯胺:乳酸、乙醇酸、酒石酸、扁桃酸、蘋果酸、1-羥基1-環己烷狻酸、2-羥基-2-(2-四氫呋喃基)乙醇酸、 2-羥基-2-(2-呋喃基)乙醇酸、2-羥基-2苯丙酸、2-羥基-2-甲基丙酸、2-羥基-2-甲基丁酸、2-羥基丁酸、2-羥基 戊酸、2-羥基己酸、2-羥基辛酸、和其混合物。 本發明特定的環酯生產過程詳述於下。然而,這類生 產過程可以是是從一 A物種直接形成環酯的環酯生產方 法,諸如在美國專利5,319, 107號所述。另外,也能用其 它己知方法來生產環酯,諸如較低分子量的線形酯之解聚 合或由狻酸的α-鹵鹽反應來合成。 環酯之純化--吸附處理 本發明包括從含環酯的進料中除去雜質。這類雜質包 括,例如:水、ΧΑ (例,游離酸)、金靥離子、礦物酸、 環酯合成催化劑和相關的催化降解產品,和典型的發酵酸 和醇,諸如甲酸、·乙酸、丙酸、丁酸、乙醇和丁醇,所有 這些都能有份於環酯的降解或干擾Μ後環酯之聚合成有用 的高分子量聚合物。 進料也能包括一溶劑*環酯在其中有良好溶解度,但 它不會降解環酯,諸如與環酯起作用。這類溶劑包括那些 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) 8 (請先聞讀背面之注意事項再填寫本頁) .'裝- 訂 457237 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(6 ) 用於製造和回收環酯之溶劑,如下述。這類溶劑之例包括 ,但不限制於,二甲苯、甲苯、苯、苯甲醚、甲異丁酮 (MIBK>、異丙醚和其混合物,一理想的溶劑包括二甲苯。 不理想的溶劑乃因會與環酯作用,包括醇類、有機酸類、 酯類和含醇、過氧化物和/或酸雜質之醚、酮類、有一穩 定烯醇式的醛類和胺類。 在本發明的純化方法中*進料經受一吸附步驟,在此 步驟中,進料中至少一種雜質被一吸附劑從進料中被吸附 ,因而將進料中的環酯紐分濃縮並純化。術語“吸附w指 在進料流中的一雑質與一吸附劑之間的吸引或相互作用。 理想地,一雜質與一吸附劑之間的這種吸引或相互作用是 一非共價吸引力*它是可逆的。這類吸引,例如,是吸附 劑和雜質間基於電荷之不同或電荷分佈之不同,諸如在一 離子交換樹脂捕獲一分子物種。包括在這定義中的是離子 交換的觀念,其中帶電物種在吸附劑表面或其結構内部有 可逆的交換。如Μ下更詳細之討論,本發明的方法中,結 果純化之溶液中含純化的環酯,然後Μ—後吸附處理,諸 如回收環酯的固體形態或諸如藉聚合反應直接應用環酯。 適用於本發明的吸附劑包括離子交換試劑、分子篩、 礬土、矽石凝膠、活性碳、黏土和技術已知的其它吸附劑 。理想的吸附劑是離子交換樹脂、分子篩、矽石凝膠、活 性碳和黏土,特別理想的吸附劑包括離子交換樹脂和分子 筛0 對一特定方法,選擇一特定的吸附劑決定於要從進料 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS )八4规格(2丨0X297公釐) 457237 Α7 Β7 王、發明説明( 中附去的雜質類型。例如,若雑質是一 XA酸,通常要從進 料中除去雑質是將它與一弱的或一強的陰離子交換樹脂接 觸。然而,理想地要從進料中除去諸如XA的酸雜質,希望 用弱陰離子交換樹脂。弱陰離子交換樹脂能獲得可接受的 除雜質速率,然而仍能容許樹脂相當容易地再生。適用的 工業上已有的弱陰離子交換樹脂之例有Re illy Industries, Inc., Indianapolis, Indiana 出售的產品商名爲 REILLEX® 425和Rohm and Haas, Philadelphia, Pennsylvania的產 品商名為 AMBERLYST® A-21°REILLEX® 425 是聚-4-乙烯 吡啶交鏈的巨網狀珠粒形式。AMBERLYST® A-21是有三级 胺官能圍之二乙烯苯-苯乙烯為基礎之樹脂。 要從進料中除去水^雜質,進料可與一吸附劑接觸,吸 黨 經濟部中央標準局員工消費合作社印製 附劑選自包括分子篩、‘和矽石凝膠之組群,最理想的是 分子篩。本文中所用術語w分子篩”指一吸附劑,其結構 之特性能促進雜質的吸附,它包括吸附環酯。 要除去雜質〇酿胺,通常希望使用錯合樹脂。要除去 鹽,通常希望使用一強陰離子交換樹脂。 '要除去雜質醇類,通常希望使用分子篩或離子交換樹 脂。因爲這類吸附劑對於在進料中較高極性雜質,諸如XA 和水有較強的親合力,通常希望在進料中作醇吸附處理Μ 前先除去這些較強極性的雜質。除去這些較強極性雜質使 得較低親合力的醇類能吸附在這些材料上,不至需與在進 料中有較強極性高親合力雜質去競爭,因此增加這些醇吸 附劑之容量。(Please read the notes on the back before filling out this page.) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. Produced and purified polyester. Such compounds are suitable for use in the manufacture of polymers such as monocyclic esters such as lactide and are suitable for use in the production of polylactic acid. In particular, the present invention relates to the manufacture and purification of cyclic esters that are substantially free of impurities that can degrade the cyclic esters or interfere with the polymerization of polyesters into high molecular weight polymers. The method of the present invention includes manufacturing and purifying a cyclic ester derived from a hydroxycarboxylic acid, a hydroxycarboxylic acid ester, a hydroxycarboxylic acid salt, or ammonium hydroxycarboxylic acid. The term `` derived from '' means that in the reaction for making cyclic esters, these components or products of these components are reactants. They will be derived from any two hydroxycarboxylic acids, their esters, their salts or their amines. The resulting ester is converted into a cyclic diester to form a cyclic ester. The cyclic ester may also be a molecular lactone or a cyclic monoester such as propyl ester. The cyclic ester herein is represented by M XD. XiA means -hydroxycarboxylic acid, hydroxycarboxylic acid Acid ester, hydroxycarboxylic acid salt, or hydroxycarboxylic acid amine. X * A refers to a linear dimer molecule of one XiA molecule. X3A refers to a linear dimer molecule of one XA molecule, and XnA refers to π X0 · A molecules Linear η-polymeric molecules. XA without the numbers below indicates one or more) UA, XaA, X3A, and) UA or a solution containing these species. It must be understood that when X is covered by this paper, the Chinese National Standard (CNS) ) A4 size (210X297 mm) 7 Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 457237 A7 _B7 V. Description of the invention (5) When L is substituted, it means that it is a compound based on lactic acid. For example, LA refers to lactic acid Based mixtures, including UA, UA, UA and UA, and LD means Acid ring dimers> Examples of lactide. The cyclic esters of the present invention include those compounds listed above. Ideal XM species for making cyclic esters include, but are not limited to, the following acids and corresponding esters, salts, or Ammonium: lactic acid, glycolic acid, tartaric acid, mandelic acid, malic acid, 1-hydroxyl-cyclohexane acetic acid, 2-hydroxy-2- (2-tetrahydrofuryl) glycolic acid, 2-hydroxy-2- (2 -Furyl) glycolic acid, 2-hydroxy-2 phenylpropanoic acid, 2-hydroxy-2-methylpropionic acid, 2-hydroxy-2-methylbutanoic acid, 2-hydroxybutanoic acid, 2-hydroxyvaleric acid, 2-hydroxyhexanoic acid, 2-hydroxyoctanoic acid, and mixtures thereof. The specific cyclic ester production process of the present invention is described in detail below. However, this type of production process may be a cyclic ester production method in which a cyclic ester is directly formed from a species A Such as described in U.S. Patent No. 5,319, 107. In addition, other known methods can be used to produce cyclic esters, such as the depolymerization of lower molecular weight linear esters or synthesis by the reaction of alpha-halide salts of osmic acid. Purification of esters-adsorption treatment The present invention includes the removal of impurities from a cyclic ester-containing feed. Such impurities include, for example, water, XA (eg, Acid), gold ions, mineral acids, cyclic ester synthesis catalysts and related catalytic degradation products, and typical fermentation acids and alcohols such as formic acid, acetic acid, propionic acid, butyric acid, ethanol and butanol, all of which are Can contribute to the degradation of cyclic esters or interfere with the polymerization of cyclic esters after M to useful high molecular weight polymers. The feed can also include a solvent * cyclic esters have good solubility in it, but it will not degrade cyclic esters, such as with Cyclic esters work. Such solvents include those that are sized to the Chinese National Standard (CNS) A4 (210 × 297 mm) for this paper size 8 (Please read the precautions on the back before filling out this page). 'Packing-Order 457237 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (6) Solvents used in the manufacture and recovery of cyclic esters are as follows. Examples of such solvents include, but are not limited to, xylene, toluene, benzene, anisole, methyl isobutyl ketone (MIBK >, isopropyl ether, and mixtures thereof). A desirable solvent includes xylene. Undesirable solvents Because it interacts with cyclic esters, it includes alcohols, organic acids, esters and ethers containing alcohols, peroxides and / or acid impurities, ketones, aldehydes and amines having a stable enol form. In the present invention In the purification method of *, the feed is subjected to an adsorption step, in which at least one impurity in the feed is adsorbed from the feed by an adsorbent, thereby condensing and purifying the cyclic ester bonds in the feed. The term " Adsorption w refers to the attraction or interaction between a substance and an adsorbent in the feed stream. Ideally, this attraction or interaction between an impurity and an adsorbent is a non-covalent attraction * It is reversible. This type of attraction, for example, is based on the difference in charge or difference in charge distribution between the adsorbent and the impurity, such as the capture of a molecular species in an ion exchange resin. Included in this definition is the concept of ion exchange, Where charged species are adsorbed There is a reversible exchange on the surface or inside the structure. As discussed in more detail below, in the method of the present invention, the resulting purified solution contains a purified cyclic ester, and then M-post-adsorption treatment, such as recovering the solid form of the cyclic ester or Such as the direct application of cyclic esters by polymerization. Adsorbents suitable for the present invention include ion exchange reagents, molecular sieves, alumina, silica gel, activated carbon, clay, and other adsorbents known in the art. The ideal adsorbent is ions Exchange resins, molecular sieves, silica gels, activated carbon and clays. Particularly ideal sorbents include ion exchange resins and molecular sieves. For a specific method, the choice of a specific sorbent depends on the feed (please read the Note: Please fill in this page again.) This paper size is in accordance with Chinese National Standard (CNS) 8-4 specification (2 丨 0X297 mm) 457237 Α7 Β7 Wang, invention description (the type of impurities attached to the paper. For example, if the quality is a XA Acid is usually removed from the feed by contacting it with a weak or strong anion exchange resin. However, it is desirable to remove, for example, X from the feed For the acid impurity of A, it is desirable to use a weak anion exchange resin. The weak anion exchange resin can obtain an acceptable impurity removal rate, but still allow the resin to be relatively easily regenerated. Examples of suitable industrially existing weak anion exchange resins include Re illy Industries, Inc., Indianapolis, Indiana sells products under the trade names REILLEX® 425 and Rohm and Haas, Philadelphia, Pennsylvania under the trade names AMBERLYST® A-21 ° REILLEX® 425 is poly-4-vinylpyridine cross-linked Macroreticular beads. AMBERLYST® A-21 is a divinylbenzene-styrene based resin with tertiary amine functionality. To remove water and impurities from the feed, the feed can be contacted with an adsorbent. The additive printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is selected from the group consisting of molecular sieves, silica gel, and silica gel. It is molecular sieve. The term "w molecular sieve" as used herein refers to an adsorbent whose structural properties promote the adsorption of impurities, including adsorption of cyclic esters. To remove impurities, amines, it is usually desirable to use a complex resin. To remove salts, it is generally desirable to use a Strong anion exchange resin. 'To remove impurity alcohols, it is usually desirable to use molecular sieves or ion exchange resins. Because this type of adsorbent has a strong affinity for higher polar impurities in the feed, such as XA and water, it is usually desirable to Remove these more polar impurities before the alcohol adsorption treatment in the feed. Removing these more polar impurities allows lower affinity alcohols to be adsorbed on these materials, which does not need to be stronger than in the feed. The polar high-affinity impurities compete to increase the capacity of these alcohol adsorbents.
5 (請先閲讀背面之注意事項再填寫本頁)5 (Please read the notes on the back before filling this page)
本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) 10 457237 A7 B7 經濟部中央樣準局員工消費合作社印製 五、發明説明(8 ) 將進料流與一吸附劑接觸的步驟能在有可被接納的吸 附發生速率的任何適當之溫度中進行。理想地,進料流之 溫度在約為0¾和約爲loot:之間,更理想的是約在25X3和 約45=0之間。 在本發明的吸附過程之一理想實體中,進料經受第一 次吸附Μ除去第一雜質,然後經受第二次吸附Μ除去第二 雜質。具選擇性,可進行更多的吸附步驟。然後純化的含 環酯之進料能經受後吸附處理Μ回收環酯,如下述。使用 這類多重步驟吸附過程在本發明中特別有用,因為它們提 供了從進料中除去多重之雜質。例如進行第一次吸附能從 進料中除去諸如ΧΑ的雜質,而進行第二次吸附能從進料中 除去水,或反之。可具選擇性進行第三次吸附,例如,除 在的醇類。可具選擇性進一步進行第四次吸附,例 如,Μ—顔色過濾除去若存在的顔色物體。在多重步驟吸 附中,各步驟能Κ任何所希望的次序進行。 在一理想實體中,本發明所用的適當吸附劑是在溫度 高於lOOt:時是熱穩定的,更理想是高於約130¾。術語“ 熱穩定”是指吸附劑在經受高溫度時仍能保存它的吸附容 量之能力,當吸附劑恢復正常吸附超作溫度時仍能吸附雜 質。例如,雖然REILLEX® 425樹脂在溫度低於約100¾時 能用作吸附雜質,當溫度高達26〇υ時,它仍是熱穩定的 。因此,這類樹脂特別適用於一純化過程中*其中樹腊在 正常操作溫度中吸附後,它能藉升高溫度來再生。 , ---s · 本發明的理想吸附劑是包括使進料中之環酯降解 .' ... (諳先聞讀背面之注$項再填寫本頁) 裝· -訂_ 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 11 457237 經濟部中央操準局員工消費合作社印製 A7 __B7五、發明説明(9 ) 的吸附劑。例如,本發明的方法是以吸附劑來進行的,條 件是理想地只有少於約25%重量之環酯是因與吸附劑接觸 而降解的,更理想是少於約10%重量 '最理想是少於約5% 重量。在使環酯降解方面,諸如離子交換樹脂的吸附劑是 比諸如礬土的吸附劑較為理想。 本發明的吸附步驟可用多種儀器來完成,諸如用填充 柱或床的固定吸附劑,這些在技術上都為已知。這些類型 體条的一些例有:移動床、模擬的移動床、二柱安排和三 柱安排,另外,也可Μ用在進料中鬆馳的吸附劑,諸如從 吸附材料和進料形成一淤漿。 本發明純化過程的吸附操作之進行可以是整枇或是連 續的模式。然而,這箜吸附方法理想的是連纊操作。 在本發明進一步一實體中,吸附處理能包括吸附處理 一蒸發的溶劑流,它是在一主要結晶純化過程前藉蒸發產 生的。例如,己知環酯能藉多種結晶方法來純化,包括溶 劑結晶。在一習用的溶劑結晶過程前,一含環酯的產品流 中可附加包括雜質和溶劑,可藉蒸發除去一部分溶劑來濃 縮。在此情況中,所產生的蒸發溶劑因而包括少量的環酯 和雜質。因此在本文中泛逑,蒸發的溶劑流能藉吸附處理 來純化,然後蒸發的溶劑流可再用於其它單元之操作。例 如,蒸發的溶劑流能經受一個或多値吸附步驟,諸如一酸 吸附步驟和一水吸附步驟來除去酸和水雜質。結果之溶劑 流包括溶劑和剩餘的環酯,它們沒有在吸附步驟中被除去 。然後這樣的流可用於整體囬收過程中之其它操作中。例 (請先閲讀背面之注意事項再填寫本頁). 裝· 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) 457237 Α7 Β7 五、發明説明(10 ) 如,這樣的溶劑澝可用於從最開始溶劑蒸發後結果之濃縮 環酯組成物的溶劑結晶過程中之溶劑。這樣的結晶可Μ是 多重階段之再結晶過程。 從溶劑結晶結.果之溶劑能進一步再循環至環酯整體回 收和純化中的其它地方。例如,這樣的溶劑流中包括有雜 質和環酯,能在濃编含環酯的產品流之前再循環至一液一 液相分離步驟中。 後趿附虑理 如上所提到的,繼吸附純化後,能用多種後吸附處理 來回收環酯成固態或直接聚合環酯。回收過程除了在技術 上已知的過程,尚包括濃縮過程、乾燥過程和進一步純化。 在回收的一實髏中,可藉噴霧乾燥純化的進料來回收 環酯,為了 Μ粉末形狀回收環酯。噴霧乾燥包括在一乾燥 的氣體,理想地是乾燥並惰性的相反對滾中露化純化的進 料,從純化的進料中驅除溶劑。典型地,在升溫中進行噴 霧乾燥。噴霧乾燥結果產生一粉末是能包裝並出售,且適 用於諸如生產聚合的材料。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 在另一後吸附處理中,純化的進料能濃縮,諸如通過 使用一蒸發器。例如,純化的進料首先經過一蒸發器單元 ,在其中驅除溶劑。在理想實體中,驅除足量之溶劑,因 此剩餘的環酯混合物中有在約1%和約80%重量之間的溶 劑,更理想是約5%和約50%之間的溶劑,甚至更理想是 約15%和約30%之間的溶劑。必須注意在濃縮中除去的溶 劑能再循環,例如回到整體過程中的其它階段,包括,例 本紙張尺皮適用中國國家標準(CNS ) Α4規格(210X297公釐) 13 斗57237 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明(11) 如在環酯生產前回收Xi A,為酸吸收單元的再生流體,或 直接回到環酯生產的操作中,以下有更詳述。這類溶劑也 能向前帶到用於Μ後的回收或純化操作中*諸如溶劑結晶 中。在離開蒸發器單元後,在進一步回收或純化操作前, 含環酯之流能冷卻。 猥縮後,濃縮的、純化的進料能直接聚合或乾燥成最 後產物。在乾燥濃縮的環酯料的實體中,濃縮的進料在乾 燥前能具選擇性地進一步純化。可有許多方法來完成乾燥 *諸如,如上述將濃縮的純化的進料噴霧乾燥。進而,濃 縮的環酯能製成小九。製成小九是指將一固髏材料九化的 過程》包括將材料熔化,將熔化的材料噴霧,於是滴狀材 料固化。製成小丸包括將基本上不含溶劑,熔化純化的進 料在一冷郤的,理想爲乾燥並惰性的相反流動氣體中霧化 ,並固化純化的進料。典型地,在接近室溫時來進行製造 小丸。製成小九之結果是產生珠粒,它能包裝並出售,且 適用於諸如聚合的材料之生產中。 如注意的,回牧的環酯之進一步純化可在乾燥前進行 ,諸如藉溶劑冷卻結晶、溶劑蒸發結晶、熔化結晶、蒸餾 、或其組合。所有這瞾方法被列為是積極的纯化步驟,因 為期望的環酯物種理想地進行相改變並從不純的進料中除 去。相反地*上面討論Μ吸附為基礎之純化則列為扣除的 純化步驟*因為它們從不純進料中除去特定的雜質。雖然 扣除的純化步驟能使雜質之量,諸如酸、水和醇,降至十 分低的程度》但若不用一正面的純化步驟,也可能通過吸 (請先閲讀背面之注#1^項再嗔寫本頁) 裝. '訂 本紙張尺度適用中國國家標隼(CNS ) Α4規I ( 2〖〇X 297公釐) 14 37237 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明(l2 ) 收步驟在結果環酯產物中引人其它不希望有的物種。例如 ,在工桊級溶劑諸如二甲苯中通常發現有蟠狀殘留物,它 們不能Μ吸附處理除去。若後吸收處理只包括蒸發和噴锈 乾燥或成九,這些蟠狀殘留物至終會在用於聚合反應之環 酯產物中。雖然此特定污染物不一定會影響聚合反應速率 和結果之分子量,它可能負面影饗檢定值和環酯產品之外 觀*二者對商品皆為重要的。作為另一例,從Μ發酵為基 礎的方法所得之)(Α通常含低量的無法定義之污穢物,它們 也能透過吸附純化步驟。為此緣故,常希望在後吸附處理 過程中能包括這些正面的純化步驟之一。 在後吸附純化處理步驟前,使用吸附步驟有數値優點 。例如,在後吸附結晶的情況中,能產生較大的晶體,因 為當結晶茌低雜質量之溶液中進行時,通常晶體大小會增 加。大晶體易於處理,有較低的表面積對體稹比例,且通 常更取悅於環酯產品的可能顧客。作爲另例,在正面的純 化步驟前Μ吸附除去ΧΑ和水,在後吸附處理中可使用較高 溫的方法不致顯著地降解環酯產品。因此,例如,可用像 製九和蒸餾的高溫處理步驟比若有顯箸地ΧΑ和水存在時有 較低的降解。下述對正面純化型後吸附處理步驟Μ高溫處 理增加的程度來評定。 在一實髖中,濃縮的進料能Κ溶劑結晶來獲得一純化 的餅,然後進一步乾燥除去殘留溶劑。有許多形式的設備 能用於溶劑冷郤和溶劑蒸發結晶。熟悉技術者能針對特定 的應用選出一適宜之形式。 本紙張又度適用中國國家標準(CNS ) Α4规格(2Ι0Χ297公釐) (請先閲讀背面之注意事項再填寫本頁)This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) 10 457237 A7 B7 Printed by the Consumer Cooperatives of the Central Sample Bureau of the Ministry of Economic Affairs 5. Description of the invention (8) Steps of contacting the feed stream with an adsorbent It can be carried out at any suitable temperature that has an acceptable rate of adsorption occurrence. Ideally, the temperature of the feed stream is between about 0¾ and about loo :, more preferably between about 25X3 and about 45 = 0. In an ideal entity of the adsorption process of the present invention, the feed is subjected to a first adsorption M to remove a first impurity, and then subjected to a second adsorption M to remove a second impurity. Selective, allowing for more adsorption steps. The purified cyclic ester-containing feed can then be subjected to a post-adsorption treatment to recover the cyclic ester, as described below. The use of such multiple step adsorption processes is particularly useful in the present invention because they provide the removal of multiple impurities from the feed. For example, performing a first adsorption can remove impurities such as XA from the feed, and a second adsorption can remove water from the feed, or vice versa. A third adsorption can be performed selectively, for example, by removing alcohols. A further fourth adsorption may be performed selectively, for example, M-color filtering to remove color objects if present. In multiple step adsorption, each step can be performed in any desired order. In an ideal entity, a suitable adsorbent for use in the present invention is thermally stable at temperatures above 100 t :, more preferably above about 130 °. The term "thermally stable" refers to the ability of an adsorbent to retain its adsorption capacity when subjected to high temperatures, and to retain impurities when the adsorbent resumes normal adsorption over-temperature. For example, although REILLEX® 425 resin can be used to adsorb impurities at temperatures below about 100¾, it is still thermally stable at temperatures up to 26 °. Therefore, this type of resin is particularly suitable for use in a purification process * where the wax is adsorbed at normal operating temperatures and it can be regenerated by increasing the temperature. , --- s · The ideal adsorbent of the present invention includes the degradation of cyclic esters in the feed. ... (谙 read the note $ on the back before filling this page) Applicable to China National Standard (CNS) A4 specification (210X297 mm) 11 457237 A7 __B7 printed by the Consumer Cooperatives of the Central Office of the Ministry of Economic Affairs of the People's Republic of China 5. Adsorbent for description of invention (9). For example, the method of the present invention is performed with an adsorbent, provided that ideally less than about 25% by weight of the cyclic ester is degraded by contact with the adsorbent, and more preferably less than about 10% by weight. Is less than about 5% by weight. In terms of cyclic ester degradation, an adsorbent such as an ion exchange resin is more preferable than an adsorbent such as alumina. The adsorption step of the present invention can be performed by a variety of instruments, such as fixed adsorbents using packed columns or beds, which are known in the art. Some examples of these types of slats are: moving beds, simulated moving beds, two-column arrangements, and three-column arrangements. In addition, adsorbents that can relax in the feed can also be used, such as forming an adsorbent from the adsorbent material and the feed. Slurry. The adsorption operation of the purification process of the present invention can be carried out in a tidy or continuous mode. However, this plutonium adsorption method is ideal for flail operation. In a further aspect of the invention, the adsorption treatment can include an adsorption treatment-an evaporated solvent stream, which is produced by evaporation before a main crystallization purification process. For example, cyclic esters are known to be purified by a variety of crystallization methods, including solvent crystallization. Prior to a conventional solvent crystallization process, a cyclic ester-containing product stream can additionally include impurities and solvents, which can be concentrated by removing a portion of the solvent by evaporation. In this case, the generated evaporated solvent thus includes a small amount of cyclic esters and impurities. Therefore, in this paper, the evaporated solvent stream can be purified by adsorption treatment, and then the evaporated solvent stream can be reused for other unit operations. For example, the evaporated solvent stream can be subjected to one or more hydrazone adsorption steps, such as an acid adsorption step and a water adsorption step to remove acid and water impurities. The resulting solvent stream includes solvents and residual cyclic esters, which were not removed during the adsorption step. Such a stream can then be used in other operations in the overall recovery process. Example (please read the precautions on the back before filling this page). The size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 457237 Α7 Β7 5. Description of the invention (10) For example, such a solvent 澝It can be used as a solvent in the solvent crystallization process of the concentrated cyclic ester composition resulting from the initial evaporation of the solvent. Such crystallization can be a multi-stage recrystallization process. The solvent crystallizes from the solvent. The solvent can be further recycled to other places in the overall recovery and purification of the cyclic ester. For example, such a solvent stream includes impurities and cyclic esters that can be recycled to a one-liquid-liquid phase separation step before the cyclic ester-containing product stream is concentrated. After-effect considerations As mentioned above, after adsorption purification, a variety of post-adsorption treatments can be used to recover cyclic esters into solid or directly polymerized cyclic esters. The recovery process includes, in addition to processes known in the art, a concentration process, a drying process, and further purification. In the recovered solid, the cyclic ester can be recovered by spray-drying the purified feed, and the cyclic ester can be recovered for the M powder shape. Spray drying involves exposing the purified feed in a dry gas, ideally a dry and inert opposite pair of rolls, to drive off the solvent from the purified feed. Typically, spray drying is carried out at elevated temperatures. Spray drying results in a powder that can be packaged and sold and is suitable for applications such as the production of polymeric materials. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). In another post-adsorption process, the purified feed can be concentrated, such as by using an evaporator. For example, the purified feed first passes through an evaporator unit where the solvent is driven off. In an ideal entity, a sufficient amount of solvent is driven off, so the remaining cyclic ester mixture contains between about 1% and about 80% by weight of the solvent, more preferably between about 5% and about 50%, and even more Ideally, it is a solvent between about 15% and about 30%. It must be noted that the solvent removed during concentration can be recycled, for example, to return to other stages in the overall process, including, for example, the paper ruler applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) 13 bucket 57237 Α7 Β7 Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 5. Description of the invention (11) If Xi A is recovered before the production of cyclic esters, it is the regeneration fluid of the acid absorption unit, or it is directly returned to the operation of cyclic ester production, as described in more detail below. Such solvents can also be carried forward for use in post-M recovery or purification operations * such as solvent crystallization. After leaving the evaporator unit, the cyclic ester-containing stream can be cooled before further recovery or purification operations. After shrinking, the concentrated, purified feed can be polymerized directly or dried to the final product. In the entity of the dried concentrated cyclic ester material, the concentrated feed can be selectively further purified before drying. There are many ways to accomplish the drying * such as spray drying the concentrated purified feed as described above. Furthermore, the concentrated cyclic ester can be made into small nine. Making small nine refers to the process of a nine-piece solid material. It includes melting the material, spraying the molten material, and then the drop-shaped material is solidified. Making pellets includes atomizing a melt-purified feed that is substantially solvent-free in a cooled, ideally dry and inert, counter-flowing gas, and solidifies the purified feed. Pellets are typically produced near room temperature. The result of making small nine is to produce beads, which can be packaged and sold, and are suitable for use in the production of materials such as polymers. As noted, further purification of the cyclic esters of Huimu can be performed before drying, such as cooling by solvent crystallization, solvent evaporation crystallization, melting crystallization, distillation, or a combination thereof. All of these processes are listed as active purification steps because the desired cyclic ester species ideally undergoes a phase change and is removed from the impure feed. Conversely * M adsorption-based purifications discussed above are listed as subtractive purification steps * because they remove specific impurities from the impure feed. Although the deducted purification step can reduce the amount of impurities, such as acid, water and alcohol, to a very low level ", but if a positive purification step is not used, it may also be absorbed (please read the note # 1 ^ on the back side first) (This page is written on the page) Binding. 'The paper size of the book is applicable to China National Standards (CNS) Α4 Regulation I (2 〖〇X 297mm) 14 37237 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the Invention (L2) This step attracts other undesired species in the resulting cyclic ester product. For example, amidine residues are commonly found in industrial grade solvents such as xylene, and they cannot be removed by M adsorption treatment. If post-absorption treatments only include evaporation and rust-drying or drying, these scum-like residues will eventually be in the cyclic ester product used for the polymerization reaction. Although this particular contaminant does not necessarily affect the polymerization rate and molecular weight of the results, it may negatively affect the test value and the appearance of the cyclic ester product. Both are important to the product. As another example, obtained from M fermentation-based methods) (A usually contains low levels of undefined contamination, which can also pass through the adsorption purification step. For this reason, it is often desirable to include these in the post-adsorption treatment process. One of the positive purification steps. Before the post-adsorption purification treatment step, there are several advantages to using the adsorption step. For example, in the case of post-adsorption crystallization, larger crystals can be generated because when crystallized in a low impurity solution Crystals usually increase in size. Large crystals are easy to handle, have a lower surface area to body ratio, and are generally more pleasing to potential customers of cyclic ester products. As another example, M adsorption removes XA and X before the positive purification step. Water can be used in post-adsorption treatments at higher temperatures without significantly degrading the cyclic ester product. Therefore, for example, high-temperature treatment steps such as the production of nine and distillation can be used to lower the temperature than in the presence of significant XA and water. Degradation. The degree of increase in high temperature treatment of the front purification type post-adsorption treatment step M is evaluated as follows. In a solid hip, the concentrated feed can solvate Crystal to obtain a purified cake, and then further drying to remove residual solvent. There are many forms of equipment that can be used for solvent cooling and solvent evaporation crystallization. Those skilled in the art can choose a suitable form for specific applications. This paper is also suitable for use Chinese National Standard (CNS) Α4 specification (2Ι0 × 297 mm) (Please read the precautions on the back before filling this page)
457237 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明(l3 ) 在結晶過程中*用於進行溶劑結晶之溶劑有一些作用 。藉使用一溶劑來進行結晶,比在無溶劑時可用較低溫度 。另外,溶劑之存在能降低體糸之黏度,因而對材料之處 理和泵送較易並改善了熱傳導。更者,溶劑之存在能產生 較純的結晶過程,當結晶過程中提供一含有諸如14和\1 A 之低聚物雜質的媒介。因此,後來從結晶混合物中分離晶 體時,諸如乂1纟和\1纟低聚物之雜質更容易與液流分離而不 是黏附在晶體上。 從環酯晶體分離的結果之液流能進一步處理,可從液 流中再回收環酯。另外,液流加Μ處理,將在液體中之hA 和XM之低聚物再循環。 在另一實體中,環酯可藉熔化結晶作進一步純化。在 一熔化結晶過程中*環酯材料經受溫度足Μ熔化環酯而不 需有顯箸童的溶劑存在。然後將熔化材料冷卻,使一部分 材料結晶。在數種形式的設備可用於熔化結晶。熟悉技術 的人士能針對某一應用選擇適用之形式。 必須注意熔化結晶比溶劑結晶過程有一些特別的優點 。例如,因彘要處理的材料體積在無溶劑下是明顯地減小 ,只需較小的設備就可獲得相同的產量。另也發現藉 熔化結晶可獲得較大的晶體。由於較高的面比率, 通常較大的晶體比較小晶體更純,因此降低ϋ附雑質的 表面積。 本發明的進一步實體是當後吸附處理包括一附加的純 化步驟諸如結晶,是從包括多於一種環酯的異構物撞中選 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 16 m- al^i ^1^1- n^i t--- i l^n I - -«—^1 ! 一eJ (請先聞讀背面之注意事項再填寫本頁) 4 572 37 經濟部中央標準局貝工消費合作社印裝 A7 B7 五、發明説明(l4 ) 擇回牧環酯。此方法包括選擇結晶環酯的一種異構物種, 並回收那異構物種。此回收方法適用於當)(4是一手形分 子,因此有^的形式。例如,乳酸是XiA的一種手形物 種。乳酸光學異構體,L-乳酸和D-乳酸。結果丙交 酯就可能是L-LY (從二値L-乳酸分子形成的一丙交酯分子 )、D-LD (從二個D-乳酸分子所形成的一丙交酯分子)、 內消-LD (例,M-丙交酯,從一値卜乳酸分子和一個D-乳 酸分子所生成的一丙交酯分子)、或D,L-LD ( —分子間物 種,包括一個L-LD分子和一値D-LD分子)。不同物種之丙 交酯有不同的熔點。内消一LD之熔點最低,是52.8¾,異 構的純〇-1^和1-1^二者之熔點為98.7^,而純0,卜1^之熔 點最高,為128¾。 例如,一給定〇分子的異構物種比其它異構物種之熔 點較高時能在熔化結晶過程中作選擇性結晶。使全部環酯 混合物形成一熔化體,在高於較低熔點環酯物種之溫度結 晶較高熔點之物種,就能選擇結晶較高熔點的物種。另外 ,一給定XD分子之異構物種比其它異構物種有較高熔點, 通常在任何给定溶劑中的溶解較少。在高於有較低熔點的 環酯物種之溶解為極限的溫度中進行溶劑結晶,較高熔點 物種能選擇性地結晶。 繼而,在回收晶髖時,例如藉離心法 > 結果的固體是 有較高熔點的異構物棰,加殘留置的較低熔點之異構物種 。從此結晶的餅有可能用作二锢XD進料中之一來進行XD聚 合反應步驟。XD聚合反應步驟之另一進料能藉使用各種不 本紙張尺度適用中國國家標準(CNS ) A4规格(2ί〇Χ297公釐) 17 (請先聞讀背面之注意事項再填寫本頁) -澤 -9457237 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (l3) During the crystallization process * the solvent used for solvent crystallization has some functions. By using a solvent for crystallization, a lower temperature can be used than in the absence of a solvent. In addition, the presence of a solvent can reduce the viscosity of the body, thus making it easier to handle and pump the material and improving heat transfer. Furthermore, the presence of a solvent can produce a relatively pure crystallization process, and when the crystallization process provides a medium containing oligomer impurities such as 14 and \ 1 A. Therefore, when the crystal is later separated from the crystalline mixture, impurities such as 乂 1 纟 and \ 1 纟 oligomers are more likely to be separated from the liquid stream rather than sticking to the crystal. The liquid stream resulting from the separation of the cyclic ester crystals can be further processed, and the cyclic ester can be recovered from the liquid stream. In addition, the liquid stream is treated with M to recycle the oligomers of hA and XM in the liquid. In another entity, the cyclic ester can be further purified by melting crystals. The cyclic ester material is subjected to a temperature sufficient to melt the cyclic ester during a melt crystallization process without the need for a solvent that is substantially transparent. The molten material is then cooled to crystallize a portion of the material. Equipment in several forms is available for melt crystallization. Those skilled in the art can choose the appropriate form for an application. It must be noted that melt crystallization has some special advantages over solvent crystallization processes. For example, because the volume of the material to be processed is significantly reduced in the absence of solvents, the same throughput can be achieved with smaller equipment. It has also been found that larger crystals can be obtained by melting crystals. Due to the higher aspect ratio, larger crystals are usually purer than smaller crystals, thus reducing the surface area of the adhering substance. A further entity of the present invention is when the post-adsorption treatment includes an additional purification step such as crystallization, which is selected from isomers including more than one cyclic ester. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm). ) 16 m- al ^ i ^ 1 ^ 1- n ^ i t --- il ^ n I--«— ^ 1! One eJ (Please read the notes on the back before filling out this page) 4 572 37 Economy Printed by the Central Standards Bureau, Shellfish Consumer Cooperative, A7 B7 V. Description of the Invention (l4) Selective cyclamate. This method involves selecting one isomeric species of the crystalline cyclic ester and recovering that isomeric species. This recovery method is applicable when) (4 is a hand-shaped molecule, so it has the form of ^. For example, lactic acid is a hand-shaped species of XiA. Optical isomers of lactic acid, L-lactic acid and D-lactic acid. As a result, lactide is possible L-LY (a monolactide molecule formed from di-L-lactic acid molecules), D-LD (a monolactide molecule formed from two D-lactic acid molecules), endo-LD (eg, M -Lactide, a lactide molecule produced from a lactic acid molecule and a D-lactic acid molecule), or D, L-LD (— an intermolecular species, including an L-LD molecule and a D- LD molecule). Different species of lactide have different melting points. Endo-LD has the lowest melting point, which is 52.8¾, the melting point of both isomeric pure 0-1 ^ and 1-1 ^ is 98.7 ^, and pure 0, Bu 1 ^ has the highest melting point, which is 128¾. For example, a given 0 molecule of an isomeric species has a higher melting point than other isomeric species can be selectively crystallized during the melting and crystallization process. All cyclic ester mixtures are formed As soon as the melt crystallizes the higher melting species at a temperature higher than the lower melting cyclic ester species, the higher crystalline species can be selected. An isomeric species of a given XD molecule has a higher melting point than other isomeric species, and generally has less solubility in any given solvent. At temperatures above the limit where the dissolution of cyclic ester species with lower melting points is the limit Solvent crystallization can selectively crystallize higher melting point species. Then, when recovering the crystalline hips, for example, by centrifugation, the solid is a high-melting isomer, and the remaining lower melting point is added. Heterogeneous species. The cake crystallized from this may be used as one of the two XD polymerization feeds for the XD polymerization step. The other feed of the XD polymerization step can use various paper sizes to apply Chinese national standards (CNS ) A4 size (2ί297 × 297 mm) 17 (Please read the precautions on the back before filling out this page)-Ze-9
457237 A7 B7 五、發明説明(15 ) 同技術在選擇結晶步驟中從產生的液態殘留物中回收,各 技術有諸如噴霧乾燥、製九、結晶、蒸餾、蒸發,或其組 合。 必須注意,如上討論的,選擇性結晶不能達到100% 的選擇性。因此,在Μ上討論的例中,第一次結晶的部分 可能含有殘留fi之較低熔點物種。同樣第二次回收的部分 可能含有顯著量之較高熔點物種。然而,只要對於聚合反 應操作的光學異構物之預期tb例是在二掴XD產品的異構體 含量之間,可用一簡單的摻合操作來調整對聚合反應操作 在XD進料中之光學異構體之真正比例。這是顯然的 > 因它 是控制M XD為基礎的聚合物之光學異構體含童的一個可能 方法,它控制了許多KXD為基礎的聚合物之物理和降解性 質。 在後吸附方法的另一實體中,藉蒸餾可進一步純化環 酯。典型地,在一整批蒸讅方法中取中間部份作爲產物。 另法是在一連續蒸餾糸統中用一標準兩柱法來產生中間份 或在一柱法中用一側流抽取產品流來產生中間份。 經濟部中央標準局員工消費合作社印製 蒸餾方法的產品可直接用於XD聚合反應。另外,產品 也能噴霧乾燥或製丸,然後貯存供Μ後使用。 當後吸附處理包栝一附加的蒸餾純化步驟時*本發明 的一進一步實體環酯的選揮異構體之回收。例如,L-LD、 D-LD和D,L-LD之沸點皆十分接近,故不能用蒸餾來分離這 些物棰。然而,M-LD之沸點比其它異構體之沸點明顯地較 低,因此可設計一蒸餾条統來製得有顯著不同異構物含量 18 (請先鬩讀背面之注意事頃再填寫本頁) 本紙張尺度適用中國國家標隼(CNS ) A4規格(210 X 297公釐) 4 57 Α7 Β7 經濟部中央標準局員工消費合作社印製 發明説明(is 的兩種產品份。這代表了控制〇聚合反應單元進料中異構 物含量,因此控制了在XD為基礎聚合物的異構物含量。 從前面的討論,可清楚在環酯回收過程中一橱主要間 題是如何控制用於聚合反應的環酯產品中之異構體含量。 吸附處理的一値主要優點是它們是非立體特定的純化作用 ,因此吸附處理步驟之產品的異構體含量是與趿附處理步 驟進料中異構體含量是相同的。在此討論的所有Μ非純化 為基礎的後吸附處理步驟也都是非立體特定的處理步驟。 因此舉例來說,若用濃縮接著噴霧乾燥作為後吸附處理步 驟,環酯產物的異構體含量決定於吸附純化步驟進料的異 構體含量。此結果是重要的,因爲藉控制向合成反應器ΧΑ 進料之異構物比例,或藉控制在XD合成反臛器中所發生的 外消旋化作用之程度,包括改變溫度、停留時間、加於反 應器的消旋化劑之程度等,或藉ΧΑ進料異構物控制和XD合 成反應器條件之組合,可Κ容易地進行異構物之控制。 在此討論的Μ純化為基礎的後吸附處理步驟有不同程 度之立體特定性。Μ結晶為基礎的方法通常產生純化的產 品中只含一種或二種環酯的立體異構體。如前面所述,其 它異構物可從結晶步驟的液態殘留物中回收。另外,也能 在Μ結晶彘基礎的方法中用一阻斷操作模式,其中XD合成 和回收的全部操作是在產生環酯產品的各棰預期真構體間 作時間分配。Μ蒸餾為基礎的方法通常不如結晶法那麼立 體特定的。例如,M-LD之沸點與其它異構體是十分接近, 就能設計要一種或二種產品的體糸。一種產品體条之異構 各紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) 19 I.— i---L---裝------訂------J (請先閲讀背面之注意事項再填寫本頁) 457237 經濟部中央標準局員工消費合作社印製 A7 B7 五 '發明説明(17 ) — 體含量基本上與進入吸附單元的異構體含量相同。前面所 述的二種產品蒸餾體糸則可平行地各別控制多重聚合反應 線操作之異構體含量。 防附割之再牛 本發明的純化過程也能包括消耗的吸附劑之再生,其 中處理已用的吸附劑為了除去或“脫附”至少一部分吸附 的雑質,繼而再使用再生的吸附劑來吸附。適用的再生技 術有許多,依賴於所使用的吸附劑類型。通常再生是需要 將吸附劑與一流體(氣體、液體、或超臨界的)在能使吸 附的雜質從吸附劑止脫附進入流髏中的條件下發生接觸。 在要從一吸附劑上脫附的雜質是水的情況中,例如, 要從一分子篩上脫附,脫附的步驟是一乾燥過程。這類乾 燥過程之完成是用已知技術來乾燥吸附劑。例如,典型乾 燥過程包括將吸附劑與一熱的,理想地是一惰性氣體,來 除去吸陷的水。可在任何適合之溫度來進行乾燥,進行的 理想溫度在約175¾和約300¾之間,決定於所用的分子飾 類型。乾燥也可具選擇性地在一降壓環境中進行來加速水 的釋出。 在要從一吸附劑上脫附的雜質是包括一 XA物種和/或 XA低聚物的情況中,脫附流體可為一有機溶劑、一水性溶 液或一熱情性氣體。例如,能用一溶劑是原來就在進料中 的溶劑來從樹脂上脫附雜質。另外,可溶解雑質的其它溶 劑也可被接受用作脫附,包括,但不限制於,那些在上述 討論上所定規的有關吸附處理的。理想的脫附溶劑是二甲 本紙張尺度適用中國國家標隼(CNS ) A4规格(210X297公釐) 20 II ^---—---Ο 裝------訂------^J (請先閲讀背面之注意事項再填寫本頁) 457237 經濟部中央檩率局員工消賢合作祍印製 Α7 Β7 五'、發明説明(IS ) 苯。 在一具選擇性的實體中,在吸附劑接觸前,脫附流髏 能先加熱來改善其效果。將加熱的脫附流體與吸附劑接觸 能導至吸附劑溫度之升高。反過來導至吸附平衡之降低, 所Μ —部分吸附的XA物種會從吸附劑上脫附。藉加熱脫附 的ΧΑ之量決定於吸附劑溫度上升的量和對一給定的吸附劑 和溶液組合的吸附平衡之溫度敏感度。典型地,對弱吸附 劑諸如弱陰離子交換樹脂之吸附平衡舆強吸附劑比較,前 者較敏感於溫度之改變。 其它可用的方法是加熱吸附劑。例如,若吸附劑是裝 在有外殼的管中,並有管熱交換器,可向外殼施Μ蒸汽或 其它熱交換介質來加熱吸附劑。在此形式中,仍然需要一 脫附流體將ΧΑ物種從樹脂中帶走,然而所需的脫附流體量 通常比前段所逑的絕熱加熱循環為少。 再生吸附劑之溫度通常範圍是約100^至約260Τ。可 選擇適合之溫度,使獲得可接鈉的脫附速率而不致有實質 上的降解或損失吸附容量。在脫附溫度超過脫附潦體之沸 點的情況中,可在加壓下進行脫附。 熱再生方法之主要優點是不生成廢物,除了在所選擇 的溶劑中的ΧΑ物種。因此再生釋出流可輕省地再循環及環 酯合成過程中的數處,只需少量或不需外加的處理。然而 熱再生法是相當溫和,不能使吸附的物棰從樹脂上強烈脫 附。這些強烈吸收的物種典型地包括金屬離子、擴物酸、 和催化劑降解產品,諸如磺化的二甲苯。經過一段時間, 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐〉 -91- ------,,---------訂------J (請先閱讀背面之注意事項再填寫本頁) ‘ 45.72 37 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明(19) 這些強烈吸附的物種可能減少樹脂的XA容量至某點需要更 有力的脫附技術。 4 也能用化學再生法脂上脱附XA物種。與熱方法比 較,這些方法使用更有力的脫附劑。在化學再生中,用一 苛性鹼溶液從樹脂上脫附XA和其它強力吸附的物種。苛性 鹸溶液可Μ是水性鹼溶液或者是能溶於極性有機溶劑,諸 姐甲醇,的苛性鹼。雖然化學方法是更有力,使用它們會 、些外加的困難。首先,在脫附循環之結尾 >,樹脂會 ''W 含有苛性鹼溶液,在下一次吸附循環前必須先從樹脂除去 。因為這些溶液含有苛性鹼、水、和/或醇類,所有這些 在環酯回收或聚合過程中都是有害的,需要相當嚴格的除 去這些物種。其次,從苛性鹼再生的滾出液通常含鹽,在 再循環或索置前必須經過處理。此處理設備可Μ是位於XD 生產和純化單元之内的另一組分開的設備。或者*若送至 合成反應器的ΧΑ進料是衍生自發酵液之酸化,再生的流出 液能送至酸化步驟的發酵回收中,供應ΧΑ和ΧΕ)的綜合生產 0 能結合使用熱和化學的再生方法。例如,在許多再生 循環中使用熱再生,直至樹脂的吸附容量降至預期的最低 值以下。然後》用一種或數種Κ化合物為基礎之再生循環 來回復樹脂的容量。然後,再可Μ用熱再生循環,直至吸 附容量降至預期功能以下。 本發明的另一方面,在可Μ熱再生ΧΑ吸附單元的上游 使用多種保護柱的形態。保護柱的目的是從進料中作選擇 ---------1---3 裝-- (請先閲讀背面之注意事項再填客本頁) 訂 J_ 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 22 457237 A7 B7 五、發明説明(2〇 ) (請先閲讀背面之注意事項再填寫本頁) 性吸附能強烈吸附的物種,並使XA物種通過到可熱可再生 XA的吸附柱上。如此使XA吸附柱要使用化合物再生方法的 頻率大大減少。本法的另一優點是,因為無論如何保護柱 乃要用化學法再生,用在保護柱中樹脂的熱穩定性就不是 一重要事件了。因此,在保護柱中可用價廉的、高容量的 、低熱'穩定性之樹脂。保護柱樹脂的一良好候選之例是前 述的AMBERLYST® A~21樹脂;它是價廉的,其容量是REILLEX® 425之六倍,但其高溫穩定極限只有約75°C。反之,REILLEX® 425是更貴,有較低容量,但可以在高至260TC的溫度中熱 再生,因此使此樹脂成為一合理的選擇,用於XA吸附之應 用中。 經濟部中央標準局員工消費合作社印製 含脫附之雜質的脫附流體能再循環用於環酯生產和回 收整個過程的其它階段中。這類再循環流之目的地決定於 脫附流體和在其中雑質之本質。例如,若脫附流髏是一有 機溶劑,諸如二甲苯,而雖質是XA物種,在再循環過程中 可產生小量的環酯。因此*再循環流能在吸附前引至一後 環酯生產階段。例如,以下有更詳細之敘述,環酯生產過 程能包括在環酯生產後但在吸附前的一相分配或萃取步驟 。藉將再循環一再生流至這樣的相分配/萃取步驟,U) 在吸附純化中能®收產生的環酯,和(2)低聚物和XA酸物 種能分離,和例如在環酯生產過程前送至一水解單元。 在脫附流體為水的情況中,例如,在環酯生產過程前 ,脫附再循環流能直接再循環至一水解單元。在此情況中 ,在再循環流中之低聚物水解能藉水開始,因而降低了水. 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X297公釐) 457237 A7 B7 五、發明説明(21 ) 解單元所需的體積〇 在連續過程中,它包含吸附劑之再生,能使用二條或 多條吸附柱或床,為了能交替使用令過程能連續操作。當 一條吸附柱或床達到其容量時,此柱或床從操作線上取下 ,轉移至一新的再生柱或床來執行吸附工作。 姊仆.的撐酷细成物 本發明的進一步方面包括高純度之環酯組成物。這類 組成物能藉本發明的方法製造。諸如丙交酯的環酯組成物 在水和酸存在下是不穩定的。在水存在下,丙交酯能水解 * 成UA,而它又能水解成U A。更者,游離酸能催化水解反 應。因此按照本發明的環酯組成物是只有低置的水和游離 酸,因而造成結果之穩定性,當蓮輸和貯存和延長的擱置 壽命上是其高度的優點。 轾濟部中央撮率局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 在一丙交酯產品中,因水解反應,每消耗10 PPn水會 導至增加0.56毫當量游離酸/公斤LD。工業上丙交酯之典 型特定説明是最多有200 ppb水和最多1 neq游離酸/kg LD 。因此,即使在起初能符合產品說明之丙交酯產品,已存 在過量的水,在以後的貯存和處理中會產生游離酸Μ致高 於可接納的程度。因此,必須淸楚目前的工業產品因有這 樣高童的水,其擱置壽命不會長久,因水解反應會導致游 離酸之量在相當短時間内會升至其說明量之上。 依照本發明所提供的環酯組成物每百萬分中水含量是 低於200分(ppm),更理想是低於約60 ppm,而最理想是低 於約20 PPm。更者,依照本發明所提供的環酯組成物,在 紙張尺度適用中國國家標準(CNS ) M規格(2丨0 X 297公釐) -2 4 - 457237 Α7 Β7 經濟部中央梯準^J員工消費合作社印製 五、發明説明(22) 每仟克環酯中游離酸含量是少於1毫當童Ueq/kg>,更理 想是少於約0.10 meq/kg,而最理想是少於約0.04 meq/kg 。如上所提,在環酯組成物中水和游離酸相互作用降解了 環酯。因此本發明所包括的環酯組成物是既有低水量又有 低酸垦,如上所鑑定的。 本發明的環酯組成物之一進一步方面包括一包裝的瓌 酯產品,因為所含環酯產品對水極端敏感,故此產品是高 度不滲透水的。這類產品是低水和酸含量的》並包裝在防 止能有顯著量之水透過進入含環酯組成物包裝內部的包裝 體中。特別是,本發明之瓌酯組成物是包裝在包裝體中, 其水蒸氣透過率在100°F和90%相對玀度是低於約0.1克/ (100时*)(24小時),更理想者低於約O.OlgAlOO in”(24 小時),而最理想者是低於約O.OOUMIOO 1)^)(24小時) 〇 對熟悉技術人士,能符合上逑要求的適合包裝和包裝 技術乃為己知。例如,高質量的LDPE箔層壓體在100°F和 90%相對濕度中水蒸汽透過率可低至0.006 g/(100 inM (24小時)。金屬化膜也已知具低水蒸汽透過率。可Μ用其 間置一乾燥劑的雙層袋之包裝条統,或甚至可以用更高水 蒸汽阻隔包裝體条,諸如金匦容器或玻璃容器。另外,貯 存技術,諸如降低包裝體所曝露的外界空氣之相對濕度, 和/或降低貯存溫度*都能進一步減少環酯產品之降解。 聚合物细戒物 本發明的進一步方面包括在可被接納的聚合條件下從 (諳先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準(CNS ) Α4規格(210 X 297公釐) -2 5 - 457237 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(23 ) 環酯來製造高分子量聚合物。已知在低聚合溫度和長聚合 時間的極端條件下*可獲得髙分子量的環酯聚合物,諸如 聚乳酸。然而在高溫較短時間範圍内的聚合反應嘗試產生 了較低分子量的聚合物。必須承認¥酯原始材料中之雜 質,對工業上預期的聚合條件中,限制分子量之問 題。也要承認,在環酯原始材料中之^降低了聚合反應 速率因而増加了需要逹到給定轉化率之反應時間。更者, 也必須承認在聚合過程中所發生的混合程度對反應速率有 戲劇性之影響,較高程度之混合使聚合反應有顯著加快的 速率。已測定用例如,本發明的純度高的環酯組成物,可 製得符合工業上被接受的條件之高分子量聚合物。 鑑於上述,本發明一進一步方面包括製造聚合物的一 方法,其它括在溫度高於約150它,在少於約30小時 合環酯,其中結果聚合的組成物之聚合度大於約1, 中XD是定義聚合度的單體基礎。本法之進一步賁體中*溫 度能高於約160Ό,最理想是大於約170Ϊ:。更進一步的實 體中,聚合反應時間是少於約15小時,理想者少於約5小 時,而最理想的是少於15分鐘。本發明尚有更進一步的實 體,結果聚合的組成物之聚合度是大於約2, 100,更理想 者大於約2,800。 在本發明聚合方法的理想實體中,進行聚合的環酯包 括上述的環酯組成物,它們能藉本文敘述之純化方法來製 造。 可用本發明之聚合方法來製備高分子量聚合物。例如 本紙張尺度適用中國國家標準(CNS ) A4规格(21 〇 X 297公釐) (請先閱讀背面之注意事項再填寫本覓) -裝-457237 A7 B7 V. Description of the invention (15) The same technology is recovered from the liquid residue generated in the selective crystallization step. Each technology includes, for example, spray drying, nine production, crystallization, distillation, evaporation, or a combination thereof. It must be noted that, as discussed above, selective crystallization cannot achieve 100% selectivity. Therefore, in the example discussed on M, the first crystallized portion may contain lower melting species of residual fi. Also the second recovered portion may contain significant amounts of higher melting species. However, as long as the expected tb for the optical isomers of the polymerization operation is between the isomer content of the difluoride XD product, a simple blending operation can be used to adjust the optical properties of the polymerization operation in the XD feed. The true ratio of isomers. This is obvious > because it is a possible method to control the optical isomers of M XD-based polymers, which controls the physical and degrading properties of many KXD-based polymers. In another entity of the post-adsorption process, cyclic esters can be further purified by distillation. Typically, the middle portion is taken as the product in a full batch steamed process. Another method is to use a standard two-column method to produce the middle portion in a continuous distillation system or to extract the product stream by using a side stream in a one-column method to generate the middle portion. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The products of the distillation method can be directly used for XD polymerization. Alternatively, the product can be spray-dried or pelletized and then stored for later use. When the post-adsorption treatment involves an additional distillation purification step * recovery of the volatile isomers of a further solid cyclic ester of the present invention. For example, the boiling points of L-LD, D-LD and D, L-LD are all very close, so distillation cannot be used to separate these substances. However, the boiling point of M-LD is significantly lower than the boiling points of other isomers, so a distillation system can be designed to produce significantly different isomer content18 (please read the notes on the back before filling out this (Page) This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 4 57 Α7 Β7 Printed Invention Notes (is two product copies.) Of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. This represents control 〇Isomer content in the feed of the polymerization unit, so the isomer content in the XD-based polymer is controlled. From the previous discussion, it is clear how to control the main problem in the recovery of cyclic esters. Isomeric content in cyclic ester products of polymerization. One of the main advantages of adsorption treatment is that they are non-stereospecific purification, so the isomer content of the product in the adsorption treatment step is different from that in the feed of the adsorption treatment step. The structure content is the same. All M non-purification-based post-adsorption treatment steps discussed here are also non-stereospecific treatment steps. So, for example, if concentration followed by spray drying As a post-adsorption treatment step, the isomer content of the cyclic ester product is determined by the isomer content of the feed to the adsorption purification step. This result is important because by controlling the proportion of isomers fed to the synthesis reactor XA, or By controlling the degree of racemization in the XD synthesis reactor, including changing the temperature, residence time, the degree of racemization agent added to the reactor, etc., or by controlling the XA feed isomers and The combination of XD synthesis reactor conditions makes it easy to control isomers. The M-purification-based post-adsorption treatment steps discussed here have varying degrees of stereospecificity. M-crystallization-based methods often produce purified The product contains only one or two stereoisomers of cyclic esters. As mentioned earlier, other isomers can be recovered from the liquid residue in the crystallization step. In addition, it can also be used in M crystallography based methods. Blocking mode of operation, in which the entire operation of XD synthesis and recovery is time-sharing among the expected true conformers of the cyclic ester product. M distillation-based methods are generally not as robust as crystallization Specific. For example, the boiling point of M-LD is very close to other isomers, it is possible to design the body of one or two products. The isomerism of a product body is applicable to Chinese national standards (CNS) A4. Specifications (210X297mm) 19 I.— i --- L --- installation ------ order ------ J (Please read the precautions on the back before filling this page) 457237 Central Ministry of Economic Affairs Printed by the Bureau of Consumers of the Standards Bureau A7 B7 Five 'Invention Description (17)-The volume content is basically the same as the content of the isomers entering the adsorption unit. The two product distillates described above can be controlled separately in parallel. Isomeric content of the polymerization reaction line operation. Anti-adhesive repurification of the invention The purification process of the present invention can also include regeneration of the consumed adsorbent, wherein the used adsorbent is treated in order to remove or "desorb" at least a portion of the adsorbed tritium And then use a regenerated adsorbent for adsorption. There are many suitable regeneration technologies, depending on the type of adsorbent used. Regeneration usually involves contacting the sorbent with a fluid (gas, liquid, or supercritical) under conditions that allow the adsorbed impurities to be desorbed from the sorbent into the crossbones. In the case where the impurity to be desorbed from an adsorbent is water, for example, to desorb from a molecular sieve, the step of desorption is a drying process. This type of drying process is accomplished by drying the adsorbent using known techniques. For example, a typical drying process involves removing the adsorbed water with a sorbent and a hot, ideally, an inert gas. Drying can be performed at any suitable temperature. The ideal temperature is between about 175¾ and about 300¾, depending on the type of molecular trim used. Drying can also be selectively performed in a reduced pressure environment to accelerate water release. In the case where the impurity to be desorbed from an adsorbent includes an XA species and / or an XA oligomer, the desorption fluid may be an organic solvent, an aqueous solution, or a warm gas. For example, impurities can be desorbed from the resin using a solvent that is already in the feed. In addition, other solvents that can dissolve luteolin can also be accepted for desorption, including, but not limited to, those related to adsorption treatment as specified in the discussion above. The ideal desorption solvent is Dijia paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 20 II ^ ------------------------------ Order -^ J (Please read the notes on the back before filling out this page) 457237 Employees of the Central Government Bureau of the Ministry of Economic Affairs have cooperated with each other to print A7, B7, and F5, Invention Description (IS) benzene. In a selective entity, the desorption stream can be heated to improve its effect before the adsorbent is contacted. Contacting the heated desorption fluid with the adsorbent can lead to an increase in the temperature of the adsorbent. This in turn leads to a decrease in the adsorption equilibrium, so that M-partially adsorbed XA species will be desorbed from the adsorbent. The amount of XA desorbed by heating is determined by the amount of temperature rise of the adsorbent and the temperature sensitivity of the adsorption equilibrium for a given combination of adsorbent and solution. Typically, a weak adsorbent, such as a weak anion exchange resin, is more sensitive to temperature changes than a strong adsorbent. Other available methods are heating the sorbent. For example, if the adsorbent is contained in a tube with a shell and a tube heat exchanger, the shell may be heated by applying M steam or other heat exchange medium. In this form, a desorption fluid is still required to remove the XA species from the resin, but the amount of desorption fluid required is usually less than the adiabatic heating cycle described in the previous paragraph. The temperature of the regenerated adsorbent typically ranges from about 100 ° C to about 260T. A suitable temperature can be selected so that a desorption rate of accessible sodium is obtained without substantial degradation or loss of adsorption capacity. In the case where the desorption temperature exceeds the boiling point of the desorption carcass, desorption can be performed under pressure. The main advantage of the thermal regeneration method is that no waste is generated, except for the XA species in the solvent of choice. Therefore, the regenerating release stream can be recycled and saved in several places in the cyclic ester synthesis process with little or no additional treatment. However, the thermal regeneration method is quite mild and cannot strongly adsorb the adsorbed species from the resin. These strongly absorbed species typically include metal ions, extender acids, and catalyst degradation products such as sulfonated xylene. After a period of time, the size of this paper applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -91- ------ ,, --------- order ------ J ( Please read the precautions on the back before filling this page) '45.72 37 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (19) These strongly adsorbed species may reduce the XA capacity of the resin to a certain point. Powerful desorption technology. 4 XA species can also be desorbed by chemical regeneration. These methods use more powerful desorption agents than thermal methods. In chemical regeneration, a caustic solution is used to desorb the resin. XA and other strongly adsorbed species. Caustic soda solution can be aqueous alkali solution or caustic alkali that can be dissolved in polar organic solvents, sisters methanol, although chemical methods are more powerful, using them will have some additional difficulties. First, at the end of the desorption cycle > the resin will contain caustic solutions, which must be removed from the resin before the next adsorption cycle. Because these solutions contain caustic, water, and / or alcohols, all these Cyclic ester recovery or poly The process is harmful and requires fairly stringent removal of these species. Secondly, the effluent regenerated from caustic is usually salty and must be treated before being recycled or placed. This processing equipment can be located in XD production and Equipment opened by another component in the purification unit. Or * If the XA feed to the synthesis reactor is derived from the acidification of the fermentation broth, the regenerated effluent can be sent to the fermentation recovery of the acidification step to supply XA and XE ) Integrated production 0 A combination of thermal and chemical regeneration methods can be used. For example, thermal regeneration is used in many regeneration cycles until the adsorption capacity of the resin falls below the expected minimum. Then, the regeneration capacity of the resin is restored by using one or several K-based regeneration cycles. Then, the heat regeneration cycle can be used again until the adsorption capacity drops below the expected function. In another aspect of the present invention, a plurality of guard columns are used in the form of an upstream of the heat-recoverable XA adsorption unit. The purpose of the protective column is to choose from the feed --------- 1 --- 3 Packing-(Please read the precautions on the back before filling this page) Order J_ This paper size is applicable to China Standard (CNS) A4 specification (210X297 mm) 22 457237 A7 B7 V. Description of the invention (20) (Please read the notes on the back before filling this page) The species with strong adsorptive capacity can be absorbed by XA species, Thermally renewable XA adsorption column. This reduces the frequency with which XA columns need to be regenerated using compounds. Another advantage of this method is that because the guard column is chemically regenerated anyway, the thermal stability of the resin used in the guard column is not an important event. Therefore, inexpensive, high-capacity, low-thermal 'stability resins can be used in guard columns. A good candidate for a guard column resin is the aforementioned AMBERLYST® A ~ 21 resin; it is inexpensive and has a capacity six times that of REILLEX® 425, but its high temperature stability limit is only about 75 ° C. In contrast, REILLEX® 425 is more expensive and has a lower capacity, but can be thermally regenerated at temperatures up to 260TC, making this resin a reasonable choice for XA adsorption applications. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The desorption fluid containing desorbed impurities can be recycled for use in other stages of the cyclic ester production and recovery process. The destination of this type of recirculation stream depends on the nature of the desorbed fluid and the mass in it. For example, if the desorbed crossbones is an organic solvent, such as xylene, and although it is an XA species, a small amount of cyclic esters can be produced during the recycling process. Therefore the * recirculation stream can be directed to a cyclic ester production stage before adsorption. For example, as described in more detail below, the cyclic ester production process can include a phase distribution or extraction step after cyclic ester production but before adsorption. By recycling a regenerating stream to such a phase distribution / extraction step, U) the cyclic esters that can be produced in the adsorption purification, and (2) the oligomers and XA acid species can be separated, and for example in the cyclic ester production It is sent to a hydrolysis unit before the process. In the case where the desorption fluid is water, for example, before the cyclic ester production process, the desorption recycle stream can be directly recycled to a hydrolysis unit. In this case, the hydrolysis of the oligomer in the recycle stream can start with water, thus reducing the water. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X297 mm) 457237 A7 B7 V. Description of the invention (21) The volume required for the decomposition unit. In a continuous process, it includes regeneration of the adsorbent. Two or more adsorption columns or beds can be used. In order to be used alternately, the process can be continuously operated. When an adsorption column or bed reaches its capacity, the column or bed is removed from the operation line and transferred to a new regeneration column or bed to perform the adsorption work. The finely-formed products of the present invention A further aspect of the present invention includes a high-purity cyclic ester composition. Such a composition can be manufactured by the method of the present invention. Cyclic ester compositions such as lactide are unstable in the presence of water and acids. In the presence of water, lactide can hydrolyze * to UA, which in turn can hydrolyze to U A. Furthermore, the free acid can catalyze the hydrolysis reaction. Therefore, the cyclic ester composition according to the present invention has only low water and free acid, and thus results in stability of the result, which is highly advantageous when it is transported and stored and extended shelf life. Printed by the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) In a lactide product, due to the hydrolysis reaction, every 10 PPn of water consumed will lead to an increase of 0.56 milliequivalents of free Acid / kg LD. Typical specifications for industrial lactide are up to 200 ppb water and up to 1 neq free acid / kg LD. Therefore, even in the case of lactide products that initially meet the product specifications, excess water will be present and free acids M will be produced to a higher than acceptable level during subsequent storage and handling. Therefore, it must be known that the current industrial products will not have a long shelf life due to such high-grade water, and the amount of free acid will rise above their stated amount in a relatively short time due to the hydrolysis reaction. The cyclic ester composition provided according to the present invention has a water content of less than 200 parts per million (ppm), more preferably less than about 60 ppm, and most preferably less than about 20 PPm. Furthermore, according to the cyclic ester composition provided by the present invention, the Chinese National Standard (CNS) M specification (2 丨 0 X 297 mm) is applied at the paper scale. -2 4-457237 Α7 Β7 Printed by the Consumer Cooperative. V. Description of the invention (22) The free acid content per gram of cyclic ester is less than 1 milligram Ueq / kg >, more preferably less than about 0.10 meq / kg, and most preferably less than about 0.04 meq / kg. As mentioned above, water and free acids interact in the cyclic ester composition to degrade the cyclic ester. Therefore, the cyclic ester composition included in the present invention has both low water content and low acidity, as identified above. A further aspect of the cyclic ester composition of the present invention includes a packaged fluorene ester product. Since the cyclic ester product contained is extremely sensitive to water, the product is highly impermeable to water. These products are low in water and acid content and are packaged in packages that prevent significant amounts of water from penetrating into the interior of the cyclic ester-containing composition package. In particular, the ethyl ester composition of the present invention is packaged in a package, and its water vapor transmission rate at 100 ° F and 90% relative humidity is less than about 0.1 g / (100 hours *) (24 hours), and more Ideal is less than about O.OlgAlOO in "(24 hours), and the most ideal is less than about O.OOUMIOO 1) ^) (24 hours) 〇 Suitable packaging and packaging for those skilled in the art, can meet the requirements Technology is known. For example, high-quality LDPE foil laminates can have water vapor transmission rates as low as 0.006 g / (100 inM (24 hours) at 100 ° F and 90% relative humidity. Metallized films are also known It has a low water vapor transmission rate. It can be packed with a double-layer bag with a desiccant in between, or it can even be blocked with a higher water vapor, such as a gold container or a glass container. In addition, storage technology, Such as reducing the relative humidity of the outside air exposed to the package, and / or lowering the storage temperature * can further reduce the degradation of the cyclic ester product. Polymer fines further aspects of the present invention include from acceptable polymerization conditions from (谙 Please read the notes on the back before filling this page) Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) -2 5-457237 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (23) Cyclic esters to produce high molecular weight polymers. It is known that under extreme conditions of low polymerization temperature and long polymerization time, cyclic molecular polymers of fluorene molecular weight, such as polylactic acid, can be obtained. However, polymerization reactions within a short period of time at high temperatures have attempted to produce lower molecular weight polymers. It must be acknowledged that impurities in the ester raw material limit the problem of molecular weight in the polymerization conditions expected in the industry. It must also be acknowledged that the cyclic ester raw material reduces the polymerization reaction rate and therefore increases the need for a given conversion. The reaction time of the rate. Furthermore, it must be acknowledged that the degree of mixing that occurs during the polymerization process has a dramatic effect on the reaction rate, and a higher degree of mixing results in a significantly accelerated rate of the polymerization reaction. The cyclic ester composition with high purity can prepare a high molecular weight polymer that meets industrially accepted conditions. In view of the above, the present invention A further aspect includes a method of making a polymer. Others include cyclizing esters at temperatures above about 150 and less than about 30 hours, where the degree of polymerization of the resulting polymerized composition is greater than about 1, where XD is the defined degree of polymerization. Monomer temperature. The temperature in the further carcass of this method can be higher than about 160 ° C, most preferably greater than about 170 ° C: In further entities, the polymerization reaction time is less than about 15 hours, ideally less than about 5 hours, The most ideal time is less than 15 minutes. There are still further entities in the present invention. As a result, the polymerization degree of the polymerized composition is greater than about 2,100, and more preferably greater than about 2,800. In the ideal entity of the polymerization method of the present invention, The cyclic esters to be polymerized include the cyclic ester compositions described above, which can be produced by the purification methods described herein. The polymerization method of the present invention can be used to prepare high molecular weight polymers. For example, this paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the precautions on the back before filling in this guide)
' .-IT 4 5 7 2 3 7 A7 B7 經濟部中央標準局負工消費合作社印袋 五、發明説明(24 ) ,在XD是丙交酯的情況中,可製得聚合物之分子量超過^ =250,000 ,更理想的分子量是超過Mw = 300,0〇0,而最理想 的分子量是超過1 = 400,000。在XD是四甲基乙交酯的情況 中,可製得聚合物分子量是超過^=300,000,更理想的分 子量是超過Mw = 360,000 ,而最理想的分子量是超過Mu = 480,000。 瑗酯之製诘 上述環酯純化方法適用於含環酯的任何紐成物之純化 。雖然方法的主要用途是為了從環酯的製造過程中純化含 環酯的組成物,純化方法也可用於從工業來源的含環酯組 成物之純化。 適當的環酯製造方法已有揭露*例如,在美國專利第 5,319,107號和在待決之美國糸列08/128,797號,這砦掲. 露編入本文中以供參考。這些揭露提供一般性的環酯製造 。一橱理想的實髏包括藉提供含XA的一進料流*並處理進 料流從XA中的組分X2 A直接形成環酯來製造環酯。在另一 理想實體中,環酯製造過程包括(1>提供組分XA在一溶劑 中的進料流,和(2〉從進料流中除去水來生成一含有該環 酯的產品流,其中在產品流中之X»A和較高低聚物之濃度 在過程中是低於反應混合物之約20% (重量)。進一步理 想的製造環酯之方法包括U)提供含有稀釋於一有機溶劑 中XA的進料流;和(b)從該進料流中除去水,從)UA直接生 成該聚酯。 各種環酯生產方法也能包括在如上逑的吸附純化前的 ---------^)裝------訂-------J (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度逍用中國國家榇準(CNS ) A4規格(210X297公釐) 27 457237 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明(25) 一値或多痼起始純化步驟。一第一値這類起始純化步驟能 包括在這樣的狀態中進行環酯的生產過程,卽在製得反應 混合物後形成二β平衡的液相,可基本上將〇從雜質中分 離。一値這樣的相主要含XiA和父“的低聚物。方法包括提 供環酯製造混合物之回收溶劑,而回收溶劑能是用於製造 環酯的溶劑。必須注意第二相可K是包括一第二相的瑢劑 ,或是主要包含)(4的。然後環酯Μ上逑的吸附處理從第 一相回收。環酯生產混合物能進一步包括可溶的酯化反應 催化劑,諸如硫酸,它理想地分配入第二相中。在此情況 中,催化劑很容易從環酯中分離。 具有按照上述回收溶劑的功能參數之適當特性的任何 溶劑都能適用於本發明的方法。更特定的是,適用之回收 溶剤包括二甲苯、甲苯、苯甲醚、苯、ΜΙΒΚ、和異丙醚, 更理想的回收溶劑包括二甲苯和甲苯,而二甲苯更為理想 Ο 使環酯生產混合物分成第一和第二相的相分離步驄典 型地是使混合物在停止任何混合或其它攪動下冷卻就能簡 單地完成。另外可Μ使用利用多孔性介質或電場的特殊設 備使之聚結。這些方法可Μ整批進行或用已知於技術人士 的標準相分離設備連續進行。 在用相分離法從“△和“八之低聚物中分離出環酯和溶 劑的方法Μ外,另一實體中是進行對第二相的附加溶劑萃 取步驟,第二相中是富於ΧιΑ和;ίΜ之低聚物的。進行此溶 劑萃取步驟乃為回收殘留於第二相中之環酯和溶劑。例如 I—.------oi— (請先閱讀背面之注意事項再填寫本頁) 訂 i" 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 28 爲57237 A7 B7 經濟部中央標率局員工消費合作社印製 五、發明説明(26 ) ,溶劑是典型的回收溶劑,而將第二相引入一萃取單元中 來回收在第二相中殘留的環酯和溶劑。 其它的環酯生產方法為己知,並能適用於本發明的環 酯之製造。例如,製造一環酯的另外方法包括將含有XA的 進料流之一部分蒸發,並在一反應區域中使已蒸發一部分 的進料流起作用,反應區保持的壓力和溫度條件是足K保 持蒸發的部分在一蒸發狀態且生成環酯。環配之製造也可 透過使用α-囱代鹽之去聚作用和縮合反應。例如,一含 聚乳酸之組成物能透過用「回晈」機理的去聚合而獲得環 酯。在一 α-鹵代鹽反應中,藉α-鹵代鹽分子之作用可製 得環酯。 總璟酯魁诰和鋪仆 本發明進一步包括製造環醋的一總方法和藉如上廣述 之吸附處理來純化。多種這類環酯製造方法也述於上。在 一理想實體中,這類總方法包括(1)提供在一溶劑中含有ΧΑ 的進料流,(2>從進料流中除去水來生成一產品流,它包 括環酯,在產品流中Α和較高低聚物之濃度是少於在過 程中反應混合物之約20% (重量);和(3)使產物流與一 第一吸附劑接觸,從產品流中除去至少一種雜質,選自游 離酸、水和其混合物,能得一純化的產品流。 現參照第1圖*本發明一實體的一流程圖,圖示本發 明的環酯丙交酯的一總生產和純化過程。在第1圖中,乳 睃100送入一水解單元102中,並與水104和一異構體控制 劑106接觸,它們也是送入水解單元中的。乳酸ML3 A表之 (請先閲讀背面之注意事項再填寫本頁) •裝· 本紙張尺度適用中國國家標準(CNS ) A4规格(210X297公旋) 29 - 29 5 7237 A7 B7 五、發明説明(27 ) 經濟部中央標準局員工消費合作社印製 ,較高级的低聚物在水解單,元102中水解爲了能產生主要 的UA和LSA進料i〇8至LD反應器110中。從水解單元102用 過的水U2從条統中沖洗出來。在乳酸進料1〇8中的乳酸進 入LD反應器110,與一溶劑114和,如有需要,一催化劑116 結合,後二者也是送入LD反應器110的。在LD反應器110中 藉前述之技術製得丙交酯。在丙交酯製造反應中除去的水 可Μ再循環並用作如前述的元102中之水104。然後 在LD反應器11〇中所製得的丙^^^_質、和溶劑混合物11δ 可送人一柑分配或萃取過程12〇ί<為開姶從丙交酯和溶 劑混合物中除去雜質,(例如XA和XA低聚物)。從丙交酯 、雜質和溶劑混合物中除去的XA雜質112能再循環回至水 解單元102中。純化的丙交酯和溶劑混合物124能經受一第 一吸附216為除去至少一部分的XA雜質,包括酸雜質,諸 如通過使用一陰離子交換樹脂的。從第一吸附純化的丙交 酯和溶劑混合物128然後送入一第二吸附130中Μ除去可能 仍存在於純化的丙交酯和溶劑混合物128中的水。從第二 吸附的純化之丙交酯和溶液混合物132然後能濃縮,諸如 透遇使用一蒸發單元134,在其中驅除溶劑136,它能再循 環或與附加的溶劑結合成為溶劑流114送入丙交酯反應器 110中。從蒸發單元134所得的濃縮的、純化的丙交酯和溶 劑溶液140能如上述進一步純化,或能用作丙交酯之聚合 成為聚乳酸。 如第1圖所述之實體也顯示在第一吸附126和第二吸 附130中吸附劑的再生。溶劑142,諸如用作LD反應器110 (請先聞讀背面之注意事項再填寫本頁) .裝. 訂_'.-IT 4 5 7 2 3 7 A7 B7 Printing bags of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (24) In the case where XD is lactide, the molecular weight of the polymer obtained can exceed ^ = 250,000, the more ideal molecular weight is more than Mw = 300,00, and the most ideal molecular weight is more than 1 = 400,000. In the case where XD is tetramethylglycolide, the polymer can be obtained with a molecular weight of more than ^ = 300,000, a more desirable molecular weight is more than Mw = 360,000, and an optimal molecular weight is more than Mu = 480,000. Preparation of phospholipids The above cyclic ester purification method is applicable to the purification of any cyclic ester-containing compounds. Although the main purpose of the method is to purify the cyclic ester-containing composition from the manufacturing process of the cyclic ester, the purification method can also be used to purify the cyclic ester-containing composition from industrial sources. Appropriate cyclic ester manufacturing methods have been disclosed *, for example, in U.S. Patent No. 5,319,107 and pending U.S. queue No. 08 / 128,797, which are incorporated herein by reference. These disclosures provide general cyclic ester manufacturing. An ideal solid skeleton includes making a cyclic ester by providing an XA-containing feed stream * and processing the feed stream to form a cyclic ester directly from component X2 A in XA. In another ideal entity, the cyclic ester manufacturing process includes (1> a feed stream providing component XA in a solvent, and (2> removing water from the feed stream to produce a product stream containing the cyclic ester, Wherein the concentration of X »A and higher oligomers in the product stream is less than about 20% by weight of the reaction mixture in the process. Further desirable methods of making cyclic esters include U) providing a solution containing dilute in an organic solvent The XA feed stream; and (b) removing water from the feed stream, the polyester is produced directly from the) UA. Various cyclic ester production methods can also be included before the adsorption and purification of the above ------------ ^) equipment -------- order ------ J (Please read the note on the back first Please fill in this page for more details.) This paper size is in accordance with China National Standards (CNS) A4 specifications (210X297 mm) 27 457237 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (25) One or more痼 Start the purification step. A first such initial purification step can include the production of a cyclic ester in such a state that, after the reaction mixture is prepared, a two-beta equilibrium liquid phase is formed, which essentially separates 0 from the impurities. One such phase mainly contains XiA and the parent "oligomer. The method includes providing a recovered solvent for the cyclic ester manufacturing mixture, and the recovered solvent can be a solvent used to make the cyclic ester. It must be noted that the second phase may include a The elixir of the second phase, or mainly contains) (4. Then, the adsorption treatment of the cyclic ester M on rhenium is recovered from the first phase. The cyclic ester production mixture can further include a soluble esterification reaction catalyst such as sulfuric acid, which Ideally partitioned into the second phase. In this case, the catalyst is easily separated from the cyclic ester. Any solvent having suitable characteristics according to the functional parameters of the recovered solvent described above can be used in the process of the present invention. More specifically, Applicable recovery solvents include xylene, toluene, anisole, benzene, MIBK, and isopropyl ether. More ideal recovery solvents include xylene and toluene, and xylene is more desirable. O The cyclic ester production mixture is divided into the first The phase separation step from the second phase is typically accomplished simply by cooling the mixture without stopping any mixing or other agitation. In addition, it is possible to use a porous medium or electricity Special equipment to make them agglomerate. These methods can be performed in batches or continuously using standard phase separation equipment known to the skilled person. Phase separation is used to separate the cyclic esters from the "△" and "eight of the oligomers" In addition to the method M of solvent, in another entity, an additional solvent extraction step for the second phase is performed, and the second phase is rich in oligomers of ΑΑ and ίΜ. This solvent extraction step is performed to recover the residual Cyclic esters and solvents in the second phase. For example, I —.------ oi— (Please read the notes on the back before filling out this page) Order i " This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 28 Printed by 57237 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Description (26) The solvent is a typical recovery solvent, and the second phase is introduced into an extraction unit to be recovered in the first Residual cyclic esters and solvents in the two phases. Other cyclic ester production methods are known and can be applied to the production of the cyclic esters of the present invention. For example, an additional method for making a cyclic ester includes including a portion of a feed stream containing XA Evaporate and reverse In the zone, a part of the feed stream that has been evaporated is activated, and the pressure and temperature conditions maintained in the reaction zone are sufficient to keep the evaporated part in an evaporating state and generate cyclic esters. The manufacture of cyclic compounds can also be achieved through the use of α-methane salts Depolymerization and condensation reaction. For example, a polylactic acid-containing composition can be obtained by depolymerization using the "back loop" mechanism. In an α-halogenated salt reaction, an α-halogenated salt molecule is used. The present invention further includes a general method for the production of cyclic vinegar and purification by adsorption treatment as broadly described above. A variety of methods for making such cyclic esters are also described above. In an ideal entity, this type of overall process includes (1) providing a feed stream containing XA in a solvent, (2) removing water from the feed stream to produce a product stream that includes cyclic esters, and The concentration of medium A and the higher oligomer is less than about 20% by weight of the reaction mixture in the process; and (3) contacting the product stream with a first adsorbent to remove at least one impurity from the product stream, and selecting From free acid, water and mixtures A purified product stream. Referring now to Figure 1 *, a flow chart of an entity of the present invention illustrates a total production and purification process of the cyclic ester lactide of the present invention. In Figure 1, lactone 100 is sent to a hydrolysis unit 102 and is contacted with water 104 and an isomer control agent 106, which are also sent to the hydrolysis unit. Lactic acid ML3 Form A (please read the precautions on the back before filling this page) • Loading · This paper size is applicable to China National Standard (CNS) A4 specification (210X297 revolution) 29-29 5 7237 A7 B7 V. Description of the invention ( 27) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, the higher oligomers are hydrolyzed in the hydrolysis unit, Yuan 102, to produce the main UA and LSA feed i08 into the LD reactor 110. The water U2 used from the hydrolysis unit 102 is rinsed out of the system. The lactic acid in the lactic acid feed 108 is fed to the LD reactor 110, combined with a solvent 114 and, if necessary, a catalyst 116, and the latter two are also sent to the LD reactor 110. In the LD reactor 110, lactide is produced by the aforementioned technique. The water removed in the lactide manufacturing reaction can be recycled and used as the water 104 in the element 102 as previously described. Then the propyl alcohol and solvent mixture 11δ prepared in the LD reactor 11 can be sent to a mandarin distribution or extraction process 12〇 < Removal of impurities from the lactide and solvent mixture for Kailuan, (Eg XA and XA oligomers). The XA impurities 112 removed from the lactide, impurities, and solvent mixture can be recycled back to the hydrolysis unit 102. The purified lactide and solvent mixture 124 can withstand a first adsorption 216 to remove at least a portion of XA impurities, including acid impurities, such as by using an anion exchange resin. The lactide and solvent mixture 128 purified from the first adsorption is then passed to a second adsorption 130 to remove water that may still be present in the purified lactide and solvent mixture 128. The purified lactide and solution mixture 132 from the second adsorption can then be concentrated, such as through the use of an evaporation unit 134, in which the solvent 136 is driven off, which can be recycled or combined with additional solvents to form a solvent stream 114 and sent to the propylene. Lactide reactor 110. The concentrated, purified lactide and solvent solution 140 obtained from the evaporation unit 134 can be further purified as described above, or can be used for polymerization of lactide to polylactic acid. The entity as shown in Fig. 1 also shows the regeneration of the adsorbent in the first adsorption 126 and the second adsorption 130. Solvent 142, such as used as LD reactor 110 (Please read the notes on the back before filling this page).
—W 本紙張尺度適用中國國家標隼(CNS ) Α4規格(210X297公釐) 30 457237 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明(28) 進料的,能在第一吸附器126中與吸附劑接觸爲了脫附在 吸附材料上的雜質。結果含有雜質之溶劑144能用於相分 配/萃取儀器120中作為丙交酯和溶劑混合物118之開始純 化。用於第二吸附130之吸附劑也能藉乾燥來再生吸附劑 ,得到水和溶劑之混合物146,它能如前述再循環回到水 解單元102中。 提供下列諸例和試驗結果,目的是為了閨明,並不意 圖限制本發明之範畴。 钏1 下例說明本發明為獲得純化的羥基羧酸之環酯的純化 方法一實體之有效性。 環酷夕鳃港 5克外消旋的2-羥基辛酸的試樣,0.22克Dowex-50酸 性形式的陽離子交換樹脂(作爲反應催化劑),和195毫 升甲苯,加入一三頸瓶中,並配Μ—加熱套、溫度計、磁 '攪拌器、Dean-Stark管、迴流冷凝管、和一橡膠隔板。混 合物加熱至迴流,溫度約爲116=0,並保持約4S小時。 整份部分的反應混合物Μ重氮甲烷衍生化,並Μ氣體 層折-質譜儀(GC-MS)分析。各峯之鑑定爲:2-羥基辛酸 ,從2分子的2-羥基辛酸生成的線形酯;2-羥基辛酸的環 二酯之内消旋異構體;2-羥基辛酸的環酯之D和L異構體; 和一較長滞留時間的未知化合物,一般認為是一種或多種 較高線形的酯化反應之產物。 璟醅之純化 (請先聞讀背面之注意事項再填寫本頁) -裝- -訂 本紙張尺度適用中國國家標隼(CNS ) Α4規格(210X297公釐) 31 457237 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(29 ) 用300毫升的AMBERLYST® A-21離子交換樹脂試樣作 為一吸附劑。樹脂先用丙嗣沖洗數次。將樹脂置入直徑為 1吋之一柱中,然後用1: 1的甲苯:丙酮混合物洗滌,為 了取代保留於樹脂中的任何起始的水。環酯反應混合物Μ 丙酮稀釋至一 1: i甲苯:丙嗣混合物,並通過前面所準備 的AMBERLYST® A-21離子交換樹脂床。收集流出液並蒸發 至乾。固髏產物K氣體層析術分析。發現了二個峯:2_羥 基辛酸的環二酯之内消旋異構髏,和2-羥基辛酸的環酯之 D和L異構體。因此,所得到的環酯純化是一非立體特定的 過程,藉K使得回收的環酯混合異構髏之數量符合於吸附 過程進步的異構體之組成。沒有發現酸和羥基羧酸的線形 酯化反應產物。獲得的固體產物之總量為0.6629克,按莫 爾基礎計算,分離產率爲理論產率之34%。 MJ2. 下例蘭明依照本發明一値賁體的環酯之製造與純化, 並繼而製造聚合物,也提供聚合反應中二種純化方法之比 較和嚐試。 瑾酯^製诰 製迨粗製的四甲基二交酯,從2-羥基-2-甲基丙酸直 接在液相中合成,用間二甲苯作為溶劑和對甲苯磺酸作為 催化劑。迴流混合物,以一Dean-Stark管除去水。 2.1瑗酯之純化和聚合 粗製之四甲基二交酯以碳酸鈉洗滌、中和、乾燥、然 後溶於丙酹中。將粗製的四甲基二交酯/丙酮溶液通過含 本紙張尺度適用中國國家標準(CNS ) A4规格(210 X 297公釐) -3 2 - ------------,裝— (請先閱讀背面之注§項再填寫本頁) -、?!- 457237 A7 B7 經濟部中央標準局員工消費合作社印製 五 '發明説明(3〇 ) 有AMBERLYST® A-21離子樹脂作為吸附劑的一柱以除 去酸雜質。從柱的流出液<_>乾。結果的固髏用石油醚 再結晶並乾燥。結杲的四甲基二交酯試樣Μ差示掃描熱量 計分析,並發現有一開始於80.9C的明顯熔點。 純化的四甲基二交酯用叔丁氧化鋰催化劑在約130t! 中聚合約8小時。結果之聚合物的分子量由膠透層析法測 定爲 Μω = 520,000和 M„ = 354,000。 2_,.2箆一 f:h較的擐B旨純介.和聚会g K 粗製的四甲基二交酯Μ碳酸鈉洗滌、中和、並乾燥。 用異丙醇作爲溶劑,將粗製四甲基二交酯溶解並再結晶。 再結晶材料之試樣以差示掃描熱量計分析,發現有一開姶 於70,0°C的寬熔點。 笫一次嘗試用辛酸錫作催化劑將純化的材料聚合失敗 了。沒有可測得的聚合反應發生,在反應長時間後固收未 反應的四甲基二交酯。 第二次嘗試將純化的材料聚合有部分成功。在130Ό $1¾氧化鋰作為催化劑來進行聚合。結果的聚合物之分 子量由膠透層析法測定為Mw = 17,200 , M„ = 14,525。只有42 %的原始單體轉化成聚合物。 此比較例的低分子量和差的轉化率表示溶劑再結晶的 四甲基二交酯的純度不足以製得高分子量的聚合物。相反 的,在例2.1中所述的基於吸附的純化法能製得高純度的 四甲基二交酯,是適於製造高分子量的聚合物。 2.3第二l:h齡的環酷姊朴.斑聚合砭應 (請先聞讀f面之注意事項再填寫本頁) 本紙張尺度適用中國國家標隼(CNS ) A4規格(2ίΟΧ297公釐) 33 457237 經濟部中央檩準局員x消費合作社印製—W This paper size is applicable to China National Standard (CNS) Α4 size (210X297 mm) 30 457237 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (28) It can be absorbed in the first The container 126 is brought into contact with the adsorbent in order to desorb the impurities on the adsorbent material. As a result, the solvent 144 containing impurities can be used in the phase separation / extraction apparatus 120 as the initial purification of the lactide and solvent mixture 118. The adsorbent used for the second adsorption 130 can also be regenerated by drying to obtain a mixture of water and solvent 146, which can be recycled back to the hydrolysis unit 102 as described above. The following examples and test results are provided for the sake of clarity and are not intended to limit the scope of the invention.钏 1 The following example illustrates the effectiveness of the purification method-entity of the present invention to obtain a purified cyclic ester of a hydroxycarboxylic acid. A sample of 5 g of racemic 2-hydroxyoctanoic acid in Gill Harbor, 0.22 g of Dowex-50 acid form cation exchange resin (as a reaction catalyst), and 195 ml of toluene were added to a three-necked flask and mixed with M—Heating jacket, thermometer, magnetic stirrer, Dean-Stark tube, reflux condenser, and a rubber partition. The mixture was heated to reflux, the temperature was about 116 = 0, and held for about 4S hours. An aliquot of the reaction mixture, M-diazomethane, was derivatized and analyzed by M-gas-layer-fold mass spectrometer (GC-MS). The peaks were identified as: 2-hydroxyoctanoic acid, a linear ester formed from 2 molecules of 2-hydroxyoctanoic acid; meso isomers of the cyclic diesters of 2-hydroxyoctanoic acid; D and L isomer; and an unknown compound with a longer residence time, generally considered to be the product of one or more higher linear esterification reactions. Purification of 璟 醅 (please read the precautions on the back before filling out this page) -Packing--The paper size of the book is applicable to China National Standard (CNS) Α4 size (210X297 mm) 31 457237 Employees of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 printed by the cooperative V. Description of the invention (29) A 300 ml sample of AMBERLYST® A-21 ion exchange resin was used as an adsorbent. The resin was rinsed with propane several times. The resin was placed in a 1-inch diameter column and then washed with a 1: 1 toluene: acetone mixture to replace any starting water remaining in the resin. The cyclic ester reaction mixture M was diluted with acetone to a 1: i toluene: propane mixture and passed through a previously prepared AMBERLYST® A-21 ion exchange resin bed. The effluent was collected and evaporated to dryness. K gas chromatography analysis of solid skull products. Two peaks were found: the meso isomer of the cyclic diester of 2-hydroxyoctanoic acid, and the D and L isomers of the cyclic ester of 2-hydroxyoctanoic acid. Therefore, the purification of the obtained cyclic ester is a non-stereospecific process, and the amount of the recovered cyclic ester mixed isomers conforms to the composition of the isomers that are improved in the adsorption process by K. No linear esterification reaction products of acid and hydroxycarboxylic acid were found. The total amount of solid product obtained was 0.6629 g. The isolated yield was 34% of the theoretical yield on a Moore basis. MJ2. The following example shows the manufacture and purification of a monocyclic cyclic ester in accordance with the present invention, followed by the manufacture of polymers. It also provides a comparison and attempt of two purification methods in polymerization. Glycolate is produced from crude tetramethyldilactide, which is synthesized from 2-hydroxy-2-methylpropionic acid directly in the liquid phase, using m-xylene as a solvent and p-toluenesulfonic acid as a catalyst. The mixture was refluxed and the water was removed in a Dean-Stark tube. 2.1 Purification and polymerization of ethyl ester The crude tetramethyl dilactide was washed with sodium carbonate, neutralized, dried, and then dissolved in propyl ethyl ester. Pass the crude tetramethyldilactide / acetone solution to the paper containing this paper and apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -3 2-------------, -(Please read the note § on the back before filling this page)-,?!-457237 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People ’s Republic of China (5) Invention Notes (30) AMBERLYST® A-21 Ion Resin A column as an adsorbent to remove acid impurities. The effluent from the column < _ > is dry. The resulting solid skull was recrystallized with petroleum ether and dried. A differential scanning calorimeter analysis of the scabbed tetramethyldilactide sample and found a clear melting point starting at 80.9C. The purified tetramethyldilactide was polymerized with a t-butyl lithium oxide catalyst in about 130t! For about 8 hours. The molecular weight of the resulting polymer was determined by permeation chromatography as Mω = 520,000 and M „= 354,000. 2 _ ,. 2 箆 a: f: h is more than 擐 B is purely pure; and 聚会 g K is a crude tetramethyl di The lactide M sodium carbonate was washed, neutralized, and dried. Using isopropanol as a solvent, the crude tetramethyldilactide was dissolved and recrystallized. A sample of the recrystallized material was analyzed by differential scanning calorimeter and it was found that an宽 A wide melting point of 70,0 ° C. 笫 A single attempt to polymerize the purified material using tin octoate as a catalyst failed. No measurable polymerization occurred, and unreacted tetramethyldi was collected after a long reaction time. Lactide. The second attempt to polymerize the purified material was partially successful. Polymerization was carried out at 130Ό $ 1¾ lithium oxide as a catalyst. The molecular weight of the resulting polymer was determined by permeation chromatography as Mw = 17,200, M „= 14,525 . Only 42% of the original monomer was converted into polymer. The low molecular weight and poor conversion of this comparative example indicate that the purity of the tetramethyldilactide recrystallized from the solvent was insufficient to obtain a polymer of high molecular weight. In contrast, the adsorption-based purification method described in Example 2.1 can produce high-purity tetramethyldilactide, and is suitable for producing high-molecular-weight polymers. 2.3 The second l: h age-old sister-in-law. The speckle aggregation application (please read the precautions on the f side before filling out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (2 〇 × 297 mm) 33 457237 Member of the Central Government Bureau of the Ministry of Economic Affairs x Printed by Consumer Cooperatives
A7 B7 五'發明説明(Μ ) 粗製的四甲基二交酯Μ碳酸鈉洗滌、中和、乾燥,然 後溶於丙酮中。粗製的四甲基二交酯/丙酮溶液通過含有 AMBERLYST® Α_21離子交換樹脂的一樹脂床以除去任何殘 留的酸物種。從柱的流出液蒸發至乾。結果的固體從異丙 醇再結晶並乾燥。此結果的四甲基二交酯之試樣Μ差示掃 描熱量計分析,發現有一開始於81.0¾的明顯熔點。 嘴試K叔丁氧化鋰作催化劑,在1301C來聚合純化的 西甲基二交酯失敗了。八小時後,幾乎沒有聚合反應之證 據。柑信在純化的四甲基二交S旨中之異丙醇殘留撤童是導 至聚合反應之失敗。當乾燥純化的四甲基二交酯除掉黏附 於晶體外部之溶劑,而沒有除去包藏在晶體內部陷入的溶 劑。因此,柑信在純化的材料中仍有徹量之醇。 此例之明顯熔點表示四甲基二交酯之純度可與例2.1 的四甲基二交酯之純度相比較。此例顯示甚至在以吸附為 基礎的方法後繼而用一正面的像溶劑結晶的純化步驟,使 用醇瑢劑來結晶會在環酯組成物中引入醇雜質而導致聚合 反應之失敗。 例3 下例關明發明的純化和回收方法之一實髏的回收 一混合的異構,酯產品。 將1025克混合的二甲苯試樣,50微升之硫酸,和一些 沸騰碎片置入一 2000毫升三頸瓶內,瓶子配以一Dean-Stark 管、冷凝管、和加熱套。內容物加熱至迴流,並加入5〇毫 本紙張尺度中國國家標準(CNS ) A4規格(210X297公釐) 34 - l·.—、---r---η,.ά------IT------^ (請先聞讀背面之注意事項再填寫本頁) 457237 Α7 Β7 經濟部中央標筚局舅工消費合作社印製 五'•發明説明(32 ) 升乳酸溶液。乳酸溶液由9份88% L-乳酸和1份88¾外消旋 乳酸組成,在原始材料中整體L: D比率為95: 5。反應混 合物在大氣壓力中加熱約4·5小時,在該時間内,在Dean-Stark管中收集了總共15毫升水。混合物冷卻至室溫並作 相分配。 蒱酯純化 將上層相中的977克試樣,它含有乳酸,加入一瓶中 ,瓶内含有214克以前共沸蒸餾的REIUEX® 425離子交換 樹脂作為酸吸附劑,144克3A分子篩作為水吸附劑,和50 克栝性磺作為顔色體之吸附劑。此混合物攪拌約4小時, 取出此溶液的一試樣,在作分析前通過一 0.45# m濾片來 過濾。 溶液之高操作液體層析術(HPLC)分析顯示無可偵測的 游離酸。在此應用中HPLC法之低偵測限度是2meq游離酸/ kg溶液。HPLC的結果也顯示材料的L: D: M[;b率沒有因吸 附處理而改變。Kar卜Fisher滴定顯示處理的溶液中含 16 _ 6 ppm水。 温合的里櫨物二夺酷商品:> 同帅 然後將處理過的溶液迴旋蒸發至乾燥來模擬噴霧乾燥 器之操作。殘留餅是一白色雪般的粉末。餅之分析顯示L :D : Μ異構物之比例潙96.70 : 1.04 : 2.26,表示當蒸發 時有一部分Μ-二交酯損失了。這並不意外,因Μ-二交酯比 其它異構體有較高的蒸氣壓。在工業設備中可Μ用一簡單 的汽提段來保留Μ-二交酯。粉末之高操作液體層析術顯示 本紙張尺度適用中國國家標準(CNS ) Α4规格(2丨ΟΧ29?公釐) 35 - (請先閲讀背面之注意事項再填寫本頁) -裝- 、1Τ 457237 A7 ----B7 -_ 五 '發明説明〇3 ) (請先閲讀背面之注意事項再填寫本頁) 沒有可偵測的游離酸。在本應用中HPLC法的低偵測限度鳥 9 aeq游離酸/kg二交酯。 m 4 下例闞明本發明吸附劑再生方法的一個實體。 一吸附儀器包括四條直徑Γ絕緣的不綉銅管,各約5 呎長,垂直架於一小車上並串建連接。在進料線上,各柱 間、和流出液線上安裝了試樣汽門。製備REILLEX® 425 藉與二甲苯共沸蒸餾Μ除去任何水。四條柱充裝了 311.6 克、356.4克、370.1克、和352.3克的濕樹脂,總床長度 約為16呎。向儀器泵人新鮮的二甲苯,使空氣從条統中流 出° 箆一趿附 趣濟部中央榡隼局員工消費合作杜印製 含二甲苯、乳酸、線形乳酸酯、和二交酯的室溫進料 溶液以約45 g/min的向上流方向泵過吸附儀器,使向上流 的表面速度為0 . 39呎/分鐘。每半小時在5値試樣汽門取 出試樣,並經受高操作液體層析術(HPLC)之分析。在起始 的二甲苯從条統移出後,第四柱流出液試樣中顯示沒有可 偵测的游離酸,直至柱的完成。第四柱之完成發生於在開 姶溶液進料後約270分鐘。本應用中HPLC法的低偵測極限 是2 tneq游離酸/ kg溶液。在完成前從第四柱取到的純化 流所保持的試樣有807克。向保留試樣中加入178克3A分子 篩試樣。然後攪拌保留的試樣並貯存為Μ後使用。 約270分鐘及Μ上,在第四柱完成的酸組分有相反的 分子量。此觀察指出當線形乳酸酯的鍵長增加時*樹脂容 36 1'紙張尺度適用中國國家標準(<3阳)八4规格(210'乂:297公釐) 457237 A7 B7 經濟部中央標準局貝工消費合作社印製 五、·發明説明_( 34 ) 量降低。在進料溶液開始後約480分鐘停止進料, 觀察到樹脂接近売全飽和。 瞄附·前:> 苒牛 從第一柱取出樹脂並置入一配以加熱套和一冷凝管的 三頸瓶中。加入足量之二甲苯Μ蓋住樹脂,加熱混合物直 至約在1331沸騰。約沸騰數分鐘後,趁熱過濾樹脂。在 相同情況下,在二甲苯中第二次沸騰樹脂,過濾*然後裝 回柱中。對第二、第三和第四柱重覆此熱再生過程。然後 將新鮮二甲苯泵人儀器中,並使空氣從糸統中流出。 筮二次昵附 用在第一次吸附循環中所用的相同二甲苯/乳酸/丙 交酯溶液在進行第二次室溫吸附循環。第二次吸附循環之 流速約爲47克/分鐘,使其向上表面速度為0.41呎/分鐘 。每半小時取一次試樣並作HPLC分析。當起始的二甲苯從 糸統中取代出來後,第四柱流出液的試樣中直至從柱中完 成流出時,顯示不含可偵測量之游離酸。第四柱的完成發 生於進料溶液開始後約240分鐘。如在第一次吸收循環中 ,在此應用中,HPLC分析的低偵測極限為2 meq游離酸/kg 溶液。在第四柱完成前,從它取得2580克純化流中的保留 試樣。在保留試樣中加入570克3A分子篩試樣。然後攆拌 試樣,並貯存作K後使用。 因爲(1)第一吸附循環之進行直至樹腊接近完全飽和 ,和(2>在第二吸附循環完成前的時間和第一次吸附循環 大約一樣長,視樹脂之熱再生為基本上完成了。A7 B7 Five 'invention description (M) The crude tetramethyldilactide M sodium carbonate was washed, neutralized, dried, and then dissolved in acetone. The crude tetramethyldilactide / acetone solution was passed through a resin bed containing AMBERLYST® A-21 ion exchange resin to remove any remaining acid species. The effluent from the column was evaporated to dryness. The resulting solid was recrystallized from isopropanol and dried. As a result of a differential scanning calorimeter analysis of a sample of tetramethyldilactide, a clear melting point starting at 81.0¾ was found. In the mouth test, K-tert-butyl lithium oxide was used as a catalyst, and the polymerization of purified dimethyl lactide at 1301C failed. After eight hours, there was little evidence of polymerization. Residual isopropanol removal in the purified tetramethyldisulfide was the cause of the polymerization failure. When the dried and purified tetramethyldilactide removed the solvent adhering to the outside of the crystal, it did not remove the solvent trapped inside the crystal. Therefore, Cixin still has a substantial amount of alcohol in the purified material. The apparent melting point of this example indicates that the purity of tetramethyldilactide is comparable to that of Example 2.1. This example shows that even in the adsorption-based method followed by a positive purification step like solvent crystallization, the use of alcohol elixirs for crystallization can introduce alcohol impurities into the cyclic ester composition and cause the polymerization reaction to fail. Example 3 The following example relates to the recovery of the real skull, one of the purification and recovery methods invented by the invention. A mixed isomerized, ester product. A 1025 g sample of mixed xylene, 50 microliters of sulfuric acid, and some boiling debris were placed in a 2000 ml three-necked bottle equipped with a Dean-Stark tube, a condenser tube, and a heating mantle. The contents are heated to reflux, and 50 millimeters of paper size Chinese National Standard (CNS) A4 specifications (210X297 mm) are added. 34-l · .—, --- r --- η, .ά ----- -IT ------ ^ (Please read the precautions on the back before filling out this page) 457237 Α7 Β7 Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Machining and Consumer Cooperatives, 5 '• Invention Note (32) liter of lactic acid solution. The lactic acid solution consists of 9 parts of 88% L-lactic acid and 1 part of 88¾ racemic lactic acid. The overall L: D ratio in the original material is 95: 5. The reaction mixture was heated at atmospheric pressure for about 4.5 hours, during which time a total of 15 ml of water was collected in a Dean-Stark tube. The mixture was cooled to room temperature and partitioned. Purification of ethyl esters: 977 grams of a sample in the upper phase containing lactic acid was added to a bottle containing 214 grams of previously azeotropically distilled REIUEX® 425 ion exchange resin as the acid adsorbent and 144 grams of 3A molecular sieve as the water adsorbent Agent, and 50 g of ammonium sulfonate as an adsorbent for the color body. The mixture was stirred for about 4 hours. A sample of the solution was taken out and filtered through a 0.45 #m filter before analysis. High operation liquid chromatography (HPLC) analysis of the solution showed no detectable free acid. The low detection limit of the HPLC method in this application is 2 meq free acid / kg solution. The HPLC results also showed that the L: D: M [; b ratio of the material did not change due to the adsorption treatment. Kar and Fisher titration showed that the treated solution contained 16 -6 ppm water. Warm linings won the second cool product: > Tongshuai Then the treated solution was convoluted and evaporated to dryness to simulate the operation of a spray dryer. The residual cake is a white snow-like powder. Analysis of the cake showed that the ratio of L: D: M isomers: 96.70: 1.04: 2.26, indicating that a portion of the M-dilactide was lost when evaporated. This is not surprising, as M-dilactide has a higher vapor pressure than other isomers. In industrial installations, a simple stripping section can be used to retain the M-dilactide. The high-performance liquid chromatography of the powder shows that the paper size is applicable to the Chinese National Standard (CNS) Α4 specification (2 丨 〇 × 29? Mm) 35-(Please read the precautions on the back before filling out this page)-Packing-1T 457237 A7 ---- B7 -_ Five 'invention description 〇3) (Please read the notes on the back before filling this page) There is no detectable free acid. In this application, the low detection limit of the HPLC method is 9 aeq free acid / kg of dilactide. m 4 The following example illustrates an entity of the adsorbent regeneration method of the present invention. An adsorption instrument consists of four non-embroidered copper tubes of Γ diameter, each about 5 feet long, which are vertically mounted on a trolley and connected in series. Sample valves are installed on the feed line, between the columns, and on the effluent line. REILLEX® 425 was prepared by azeotropic distillation with xylene to remove any water. The four columns were filled with 311.6 grams, 356.4 grams, 370.1 grams, and 352.3 grams of wet resin, with a total bed length of approximately 16 feet. Pump fresh xylene to the instrument to make the air flow out of the system The feed solution at room temperature was pumped through the adsorption apparatus in an upward flow direction of about 45 g / min so that the surface velocity of the upward flow was 0.39 feet / minute. Samples were taken every 5 hours at a 5 値 sample valve and subjected to high-performance liquid chromatography (HPLC) analysis. After the initial xylene was removed from the strip, the fourth column effluent sample showed no detectable free acid until completion of the column. The completion of the fourth column occurred about 270 minutes after the opening solution was fed. The low detection limit of the HPLC method in this application is 2 tneq free acid / kg solution. The purified stream taken from the fourth column before completion held a sample of 807 grams. To the retained sample was added 178 grams of a 3A molecular sieve sample. The remaining samples were then stirred and stored as M and used. At about 270 minutes and M, the acid components completed on the fourth column had opposite molecular weights. This observation indicates that when the bond length of the linear lactate is increased, the resin capacity 36 1 'paper size is applicable to the Chinese national standard (< 3 Yang) 8 4 specifications (210' 乂: 297 mm) 457237 A7 B7 Central Standard of the Ministry of Economic Affairs Printed by the local shellfish consumer cooperative V. Description of the invention_ (34) The amount is reduced. Feeding was stopped about 480 minutes after the start of the feeding solution, and it was observed that the resin was near full saturation. Sight and front: > Yak Take out the resin from the first column and place it in a three-necked flask equipped with a heating jacket and a condenser. Add sufficient xylene M to cover the resin and heat the mixture until it boils at about 1331. After about a few minutes of boiling, the resin was filtered while hot. In the same case, the resin was boiled a second time in xylene, filtered * and then loaded back into the column. This thermal regeneration process is repeated for the second, third and fourth columns. Fresh xylene was then pumped into the instrument and air was allowed to flow out of the system.筮 Secondary attachment A second room temperature adsorption cycle was performed using the same xylene / lactic acid / lactide solution used in the first adsorption cycle. The flow rate of the second adsorption cycle was about 47 g / min, which resulted in an upward surface velocity of 0.41 ft / min. Samples were taken every half hour and analyzed by HPLC. After the initial xylene was replaced from the system, the sample from the fourth column effluent until the effluent from the column was completed showed no detectable amount of free acid. Completion of the fourth column occurred about 240 minutes after the start of the feed solution. As in the first absorption cycle, the low detection limit for HPLC analysis in this application is 2 meq free acid / kg solution. Before completion of the fourth column, a retention sample of 2,580 grams of purified stream was taken from it. To the retained sample, 570 grams of a 3A molecular sieve sample was added. The samples were then mixed and stored for use after K. Because (1) the first adsorption cycle is carried out until the wax is nearly completely saturated, and (2) the time before the completion of the second adsorption cycle is about the same as the first adsorption cycle, depending on the thermal regeneration of the resin is basically completed .
1'---ί----ο_ 裝-- (請先閲讀背面之注意事項再填寫本頁)1 '--- ί ---- ο_ Install-(Please read the notes on the back before filling this page)
本紙張尺度適用中國國家標隼(CNS ) A4規格(210X297公釐) 37 - 457237 A7 B7 經濟部中央橾準局員工消費合作社印製 五、發明説明(35 將從第一吸附和第二吸附循環的二次保留試樣結合, 在70T;和部分真空中* Μ迴旋蒸發此材料除去一部分二甲 苯。迴旋蒸發後,殘留物冷卻至室溫,在那時間中,在殘 留物瓶中生成白色針狀的L-丙交酯晶體。過濾晶體,Κ用 3Α分子篩乾燥過的新鮮二甲苯洗滌,然後在351:的真空烘 箱中乾燥。結晶狀產物之游離酸費低於甲氧碁鉀滴定法的 測貴極限*在此應用中是0.02 meg游離酸旨。 例5 下列比較例閫明用按照本發明的製備和純化方法的一 Μ實體所得的純化之環酯來製造高分子聚合物,並與用市 購的環酯所得的聚合掏之分子量作比較。 瞄附麵之魁備 在例4中所述的吸附儀器之頭兩支管子裝MBEILLEX © 425。事先Μ與二甲苯共沸蒸餾來製備REILLEX® 425。 第三和第四管則裝以3A分子篩珠粒。將二甲苯泵入条統中 ,使分子篩脫氣*並使空氣從柱中流出。 邋凰之lit 將85克L-丙交酯的試樣溶化4升二甲苯中。L-丙交酯 是商業级,相信是Μ去聚反應為基礎之反應製得的。製成 溶液前,將丙交酯長時期曝露於空氣中使它吸收水份並形 成游離酸。Μ甲氧基鉀滴定測得起始之丙交酯含91 meg游 離酸/kg丙交酯。MKarl Fisher滴定起始丙交酯、起始 二甲苯和丙交酯-二甲苯溶液,分別得260、78 ppm和84 ppm 之水。 本紙張尺度適用中國國家標準(CNS ) A4规格(2丨ox297公釐〉 38 -------^----0丫 裝·------訂------- (請先聞讀背面之注意事項再填寫本頁) 457237 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(36 ) 粗製的丙交酯-二甲苯溶液Μ速率46 g/min泵送經過 吸附儀器。當起始的二甲苯從条统中取代出來後,從第四 柱流出液中收集4升保留試樣。HPLC分析保留試樣顯示無 可測得的游離酸。在此應用中HPLC法的低偵測極限爲2 meg 游離酸/kg溶液。Karl Fisher滴定保留試樣顯示有7.7 ppm 水。 麵農回收 在65C和部分真空中以迴旋蒸發保留試樣從中除去一 部分二甲苯。迴旋蒸發後,殘留物冷卻主室溫 > 其時在殘 留物瓶中生成白色針狀晶體之L-內交酯。過濾晶體,以用 3A分子篩乾燥的新鮮二甲苯洗滌,然後在35t:真空烘箱中 乾燥。Μ甲氧基鉀滴定測得晶態產品之游離酸量為〇.〇4 aeg 游雜酸/kg丙交酯。KKarl Fisher滴定晶態產物顯示49 ppm水 〇 環酯之聚合反應 6支玻璃管各裝入10克或是吸附純化的丙交酯、一工 業丙交酯,或是起始的丙交醋材料。Μ甲氧基鉀 Karl Fjsher滴定測定,工業丙交酯含1·1 meg游離 丙交酵#59ρρπι水。各管中加入24wl的辛酸亞錫的10% ( 重量)知二甲基中的溶液,它對應的催化劑量是80叩^莫 耳或單體對催化劑比率為12500 :1。加熱玻璃管,使内容 物聚合。下列所示分子量是以膠透層析術分祈測定的: (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CMS ) A4規格(2Ι〇Χ 297公釐) 39 457237 A7 B7 五 '發明説明(37 ) 皆材 料 ΤίΠ) Li小 Bin 399,800 Ha 255,325 1 純化的丙交酯 167 4 2 工業的丙交酯 167 4 268,700 130,135 3 起姶的丙交酯 167 4 15,100 11,668 4 純化的丙交酯 145 44.5 441,100 179,600 5 工業的丙交酯 145 44.5 196,400 94,200 6 純化的丙交酯 145 44.5 30,200 29,900 經濟部中央標準局貝工消費合作社印製 因為從純化的丙交酯所衍_聚合物之分子量比從起 始材料所衍生的聚合物之分子#薄^^〇〇〇% .,純化過程是 成功的。從純化的丙交酯之聚合從工醋的聚合 物之分子量較髙50-125%。因為聚合條件是H相同的, 分子量之差異乃由於單體(丙交酯〉的純度。 例fi 下列閫明本發明純化方法之另一實體。 吸附劑之製備 將100 ml乾的AMBERLYST® A-21樹脂置入一直徑1吋 的玻璃柱內。以100 ral部分的丙酮沖洗2次,再K 100 ml 的50%水/ 50%丙酮沖洗一次。第一次丙酮冲洗液的PH為 9,且為黃色,表示在此處理時樹脂中有雜質除出。在柱 頂加入硫酸鎂(15克)和40 ml的3A分子篩。 雜質^瞄附 將10克L-丙交酯、5克無水乳酸、2克聚乳酸和約0.5 克蒸餾水與約20 ml丙酮混合,並加入含如上述製備的吸 附劑之柱中。製得的丙交酯從柱中洗提出來。從柱中洗提 的部分置入一迴轉蒸發器中,輕輕加熱除去溶劑。殘留丙 1.-------- , i-- (請先聞讀背面之注意事項再填寫本頁) 訂 i辣_ 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐了 40 4572 ^ 經濟部中央標準局舅工消費合作社印氯 Α7 Β7 五、發明説明(38 ) 酮之進一步蒸發是將這部分置人在五氧化磷的烘箱中。殘 留丙酮除去後,殘留的是十分白、輕片狀之物。得到的丙 交酯之產率約為93.5%。 m 7 下例闌明本發明的一包裝的環酯產品之改良擱置壽命 和穩定性。 將5 kg丙交酯試樣放入一 4 mil厚的低密度聚乙烯 (LDPE)袋中,其水蒸氣穿透率約為〇·39 g/(100in2· 24hr) ,另一5 kg丙交酯試樣則設入一LDPE—箔層製袋中,其水 蒸氣穿透率約為0.0006 g^lOOin* * 24hr>。兩袋之表面 積皆為418平方吋,然後將二袋丙交酯貯於100TF和約為90 炻相對濕度6個月。測定在4 mil厚LDPE袋的丙交酯之游 離酸童發現因水穿透過LDPE袋而上升至3332 meg游離酸/ kg丙交酯^皮,測定在LDPE—箔層製袋中丙交酯的游離 酸量發現因水ϋ穿透而上升只約為5.4 meg游離酸/kg 丙交酯 本發明的各種實體已經詳述,對技術人士而言對那些 實質可作改進及採用是顯然的。然而也是清楚明白的,這 類改進及採用乃在本發明範鏵之内,如在申請專利所提出 的。 本紙張尺度適用中國國家標隼(CNS ) Μ規格(2) 0 X 297公釐) ih^---裝------訂------^ (諳先閱讀背面之注意事項再填寫本頁) -41 -This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 37-457237 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (35 will be from the first adsorption and second adsorption cycle The secondary retention sample was combined at 70T; and in a partial vacuum, the material was swirled to remove a portion of the xylene. After the swirled evaporation, the residue was cooled to room temperature, during which time a white needle was formed in the residue bottle. L-lactide crystals. The crystals were filtered, K was washed with fresh xylene dried with 3A molecular sieve, and then dried in a 351: vacuum oven. The free acid cost of the crystalline product was lower than that of the potassium methoxide titration method. Test limit * In this application is 0.02 meg of free acid. Example 5 The following comparative example shows the use of a purified cyclic ester obtained from a 1M entity according to the preparation and purification method of the present invention to make a high molecular polymer, and The molecular weights obtained from the commercially available cyclic esters were used for comparison. The first two tubes of the adsorption apparatus described in Example 4 were equipped with MBEILLEX © 425. M was azeotropically distilled with xylene beforehand. Prepare REILLEX® 425. The third and fourth tubes are filled with 3A molecular sieve beads. Xylene is pumped into the system, the molecular sieve is degassed * and the air flows out of the column. A sample of lactide was dissolved in 4 liters of xylene. L-lactide is a commercial grade, which is believed to be prepared based on the M depolymerization reaction. Before making the solution, the lactide is exposed to the air for a long period of time Make it absorb water and form free acid. The initial lactide contains 91 meg free acid / kg lactide as measured by potassium methoxyl titration. Karl Fisher titrates initial lactide, initial xylene and Lactide-xylene solution, 260, 78 ppm, and 84 ppm of water were obtained. This paper size is applicable to China National Standard (CNS) A4 specifications (2 丨 ox297 mm> 38 ------- ^- --0 ya install ------- order ------- (please read the notes on the back before filling this page) 457237 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Note (36) The crude lactide-xylene solution at a rate of 46 g / min is pumped through the adsorption apparatus. When the original xylene is replaced from the system, the fourth A 4 liter retention sample was collected in the effluent. HPLC analysis of the retention sample showed no measurable free acid. In this application, the low detection limit of the HPLC method was 2 meg of free acid / kg solution. Karl Fisher titrated the retention sample 7.7 ppm of water was shown. Noodles were recovered at 65C and in a partial vacuum by rotary evaporation to retain a portion of the xylene removed from the sample. After the rotary evaporation, the residue was cooled to room temperature > white needles were then formed in the residue bottle L-lactone in crystals. The crystals were filtered, washed with fresh xylene dried with 3A molecular sieves, and then dried in a 35t: vacuum oven. The amount of free acid in the crystalline product was determined by potassium methoxide titration, which was 0.04 aeg, free-acid / kg lactide. The crystalline product of KKarl Fisher titration showed 49 ppm of water. Polymerization of cyclic esters. Six glass tubes were filled with 10 grams each of which was either adsorbed and purified lactide, industrial lactide, or the starting lactide material. Potassium methoxyl Karl Fjsher titration. Industrial lactide contains 1.1 meg of free lactase # 59ρρπι water. To each tube was added 24wl of a 10% (by weight) solution of stannous octoate in dimethyl ether, which corresponds to a catalyst amount of 80 叩 mol or a monomer to catalyst ratio of 12,500: 1. The glass tube is heated to polymerize the contents. The molecular weights shown below are determined by gel permeation chromatography: (Please read the precautions on the reverse side before filling out this page) This paper size is applicable to the Chinese National Standard (CMS) A4 (2Ι〇 × 297 mm) 39 457237 A7 B7 Five 'invention description (37) All materials ΤΠ) Li Xiao Bin 399,800 Ha 255,325 1 Purified lactide 167 4 2 Industrial lactide 167 4 268,700 130,135 3 Starting lactide 167 4 15,100 11,668 4 Purified lactide 145 44.5 441,100 179,600 5 Industrial lactide 145 44.5 196,400 94,200 6 Purified lactide 145 44.5 30,200 29,900 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs because it is derived from purified lactide_ The molecular weight of the polymer is thinner than that of the polymer derived from the starting material. The purification process was successful. The molecular weight of the polymer from purified lactide is from 50-125% compared to 髙. Because the polymerization conditions are the same for H, the difference in molecular weight is due to the purity of the monomer (lactide). Example fi The following illustrates another entity of the purification method of the present invention. Preparation of an adsorbent 100 ml of dry AMBERLYST® A- The 21 resin was placed in a 1-inch diameter glass column. Rinse twice with 100 ral portions of acetone, and then rinse once with K 100 ml of 50% water / 50% acetone. The pH of the first acetone rinse solution is 9, and A yellow color indicates that impurities were removed from the resin during this treatment. Magnesium sulfate (15 g) and 40 ml of 3A molecular sieve were added to the top of the column. Impurities ^ Attach 10 g of L-lactide, 5 g of anhydrous lactic acid, 2 grams of polylactic acid and about 0.5 grams of distilled water were mixed with about 20 ml of acetone and added to a column containing the adsorbent prepared as described above. The lactide produced was eluted from the column. The portion eluted from the column was placed Into a rotary evaporator, gently heat to remove the solvent. Residual propylene 1 .--------, i-- (Please read the precautions on the back before filling this page) Order i spicy_ This paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm 40 4572 Sheyin Chlorine A7 B7 V. Description of the invention (38) The further evaporation of the ketone is to place this part in an oven of phosphorus pentoxide. After the residual acetone is removed, the residue is a very white and light flake. The obtained acrylic The yield of lactide is about 93.5%. M 7 The following example shows the improved shelf life and stability of a packaged cyclic ester product of the present invention. A 5 kg lactide sample was placed in a 4 mil thick low density In a polyethylene (LDPE) bag, its water vapor transmission rate is about 0.39 g / (100in2 · 24hr), and another 5 kg lactide sample is placed in an LDPE-foil bag. The vapor transmission rate is approximately 0.0006 g ^ 100in * * 24hr >. The surface area of both bags is 418 square inches, and then two bags of lactide are stored at 100TF and a relative humidity of about 90 炻 for 6 months. Measured at 4 mil Thick LDPE bag of lactide free acid was found to rise to 3332 meg free acid per kg of lactide due to water passing through the LDPE bag, and the amount of lactide free acid in the LDPE-foil bag was found. The rise due to leech penetration is only about 5.4 meg free acid / kg lactide. The various entities of the present invention have been described in detail. It is obvious that these improvements can be made and adopted in substance. However, it is also clear that such improvements and uses are within the scope of the present invention, as proposed in the patent application. This paper standard applies to the Chinese National Standard (CNS) Μ specifications (2) 0 X 297 mm) ih ^ --- install -------- order ------ ^ (谙 Please read the precautions on the back before filling in this page) -41-
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