201223940 六、發明說明： ' 【發明所屬之技術領域】 本發明係關於一種用於製備（甲基）丙稀酸燒醋的方法 種 用於製備以（曱基）丙烯酸酯為基質的聚合物的方法以及乂可 由本方法獲得之以（甲基）丙烯酸酯為基質的聚合物。 【先前技術】 (甲基）丙烯酸的烷酯係為人所熟知，且在如製造含水聚入物 分散體（尤其用作黏著劑）的起始單體時具有其重要性^在本文 中’丙烯酸正丁酯尤其係工業上特別重要的單體。 在高溫與供應質子之催化劑的存在下，藉由在岣勻液相中反應 (甲基）丙稀酸與具有i至5個碳原子的單元醇（_。_二 alcohol)而製備（甲基）丙烯酸烷酯的方法係為已知，並描述於 如 DE-A-14 的 932、DE_A_22 % 829 及 DE_A_22 52 别等中。此 等反應係典型的平衡反應，其中（甲基）丙稀酸與各別之烧基醇 轉化成對應_程度係明顯受到平衡常數的限制。為了使平 向反應產物（即（甲基）丙烯酸醋）側，因此利用蒸顧法，將水 自反應混合物於頂部（。油ad)與未反應㈣以㈣物的形式移 徐。此一方法係特別描述於DE_A_25 52 987中。 以此方式自頂部離開的存在於該含 一八她mi 3水相中之至少部分該醇係於 刀離器中自此相分離，並再循環進入蒸餘塔。包含（甲基 稀酸朗與未反應之（甲基底部產物首先藉助水洗膝 (咖讀b)去除仍存在的S旨化催化劑，之後進行驗性反應萃取 以將特別係未反應之（甲基）丙烯酸以驗金屬鹽的形式分離，且 201223940 此中和反應所獲得之產物係以小流量的水沖洗。此一製備（甲基） 丙烯酸酯的方法係描述於如DE-A-196 04 253 A1中。 然而，此先前技術已知的方法係有其缺點，即由於此驗性洗滌 之故，聚合物之形成頻繁發生，結果導致下游蒸餾塔或位於蒸餾 塔上游之熱交換器的堵塞，因而為了清潔目的故需將該設備之對 應元件關機。除了因此等聚合物沉積物造成設備元件的堵塞，此 等聚合物的形成亦與（甲基）丙烯酸烷酯之損失有關。 【發明内容】 本發明的之一目的係克服先前技術關於製備（曱基）丙烯酸烷 酯的缺點。 特定言之，本發明的之一目的係提供一種製備（曱基）丙烯酸 烷酯的方法，其可操作得到非常高產率的（甲基）丙烯酸烷酯。 與先前技術所知的方法相比，本方法亦應得到較低程度之由於形 成聚合物所導致的沉積物，並因此減少設備個別元件的停機時間。 前述目的之解決係歸功於一種藉由反應一醇相與一（曱基）丙 烯酸相而製備（甲基）丙烯酸酯的方法，其係包含以下方法步驟： 使一包含該（曱基）丙烯酸醋與未反應之（甲基）丙'烯酸的液 相與一鹼接觸，並以該鹼至少部分中和該未反應之（甲基）丙烯 酸， 其中係滿足以下條件之至少一者，較佳二者： i) 與該鹼接觸後之該液相較佳於2 0 ° C所測得之p Η值係不大 於10.5，較佳不大於10.0，且最佳不大於9.5，而pH值較 5 201223940 佳係不小於7.0，尤佳8.0且最佳8.5 ; ii) 該鹼之用量係該鹼可釋放之氫氧根離子與（甲基）丙烯酸 的莫耳數比（〇H_ :(甲基）丙烯酸）為不大於1.10 : 1，尤 佳不大於1.02 : 1，且最佳不大於1.00 : 1，該莫耳數比較 佳係不小於0.95 : 1，尤佳0.99 : 1且最佳0.995 : 1。 令人驚訝但有利的是，目前已發現經鹼性反應萃取後聚合物非 所欲的生成係可歸因於該（曱基）丙烯酸酯部分水解形成該醇與 該（曱基）丙烯酸。所生成之（曱基）丙烯酸的鹼金屬鹽具有進 行聚合反應的強烈傾向。因此，本發明方法係提供一種對策，使 用理想化學計量之鹼且較佳亦於非常均勻的條件下，進行該等酸 之中和。此容許在液相中具高濃度的方法條件。這些措施例如可 藉由一離子交換劑取代引入一含水驗溶液來進行中和反應而實 現，或於一混合器-沉降器設備中進行該中和反應，該設備係包含 一循環的含水流，該中和反應所需的鹼用量係於pH調節下引入該 流中，且僅接著在混合器中與該含酸之產物流結合。 於本發明方法之一較佳具體實施態樣中，該液相與該鹼的接觸 係於一接觸區中進行，且在該液相與鹼接觸後，在歷時至少1秒， 較佳至少5秒且最佳至少10秒之時間後，該液相較佳在20°C下 所測得之pH值於接觸區中係不大於13.0，較佳不大於12.0，最佳 不大於11.0。 於本發明方法之一特定具體實施態樣中，係滿足條件i);於本 發明方法之另一具體實施態樣中，係滿足條件ii);而於本發明方 法之再一具體實施態樣中，係滿足條件i)及條件ii)。 201223940 '於本發明方法之一較佳具體實施態樣中，該方法係包含以下方 法步驟： l) 於一酯化催化劑存在下，反應一醇相與一（甲基）丙烯酸 相而得到一（曱基）丙烯酸烷酯相， H)以蒸餾法移除存在於該（甲基）丙烯酸酯相中的至少部分 水而付到一包含該（甲基）丙稀酸醋與少量水之（甲基） 丙稀日相’以及一含水頂部產物（〇verheacj pr〇duct)， m) 首先以水第-次萃取包含該（甲基）丙烯酸酯與少量水之 該（甲基）丙浠酸酯相以得到一液相的第一萃取物，包含 該（甲基）丙稀酸酯及未反應之（甲基）丙稀酸， ϊν)藉由使該第一萃取物與一鹼接觸以第二次萃取該第一萃取 物’並以驗至少部分中和該未反應之（甲基）丙婦酸以得 到一第二萃取物， V)去除該第二萃取物中的其它副產物以得到一高純度的（甲 基）丙烯酸酯相， 其中係滿足以下條件之至少一者，較佳二者： G與該驗接觸後之該第一萃取物較佳於20oc所測得之阳值 係不大於10.5,較佳不大於1〇 〇,且最佳不大於9 5，而 值較佳係不小於7·〇 ’尤佳8.0且最佳8 5， ⑴在方法步驟IV)中使用之該驗之用量係該驗可釋放之氣氧 根離子與（甲基）丙稀酸的莫耳數比（〇H_:(曱基）丙歸 ' 酸）為不切佳不大於1祀，且最佳不大於 201223940 100:1，而莫耳數昆較佳係不小於〇 95:1，尤佳〇 99:1且最 佳 0.995:1。 此處亦同，於一接觸區中進行該液相與該鹼的接觸係有利的， 且該液相與該鹼接觸後，在歷時至少丨秒’較佳至少5秒且最佳 至少10秒之時間後，於該接觸區中任何一點該液相較佳在2〇〇c 下測得之pH值係不大於13·〇,較佳不大於12 〇且最佳不大於n 〇。 於本發明方法之方法步驟〗）中，一醇相係於酯化催化劑存在下 先與（曱基）丙烯酸相反應而得到一（甲基）丙烯酸酯相，尤佳 係包含正丁醇之該醇相與包含丙烯酸之該（甲基）丙烯酸相（因 此所形成之該（曱基）丙烯酸酯較佳係丙浠酸正丁酯然而亦可 使用其它醇類取代正丁醇，如單元醇（如甲醇、乙醇、丨_丙醇、 2-丙醇、異丙醇或三級丁醇）或多元醇（如丙三醇、丨，2_丙二醇或 新戊四醇（pentaerythHtol))。此等醇可與丙烯酸或曱基丙烯酸反 應而形成對應之酯。多元醇之使用在製備用於表面塗覆之中間產 物時特別有用。 於方法步驟II)中，係以蒸餾法分離存在於（甲基）丙烯酸酯相 中的至少部分水（以及存在於（甲基）丙烯酸酯中的至少部分未 反應之醇）而得到一包含（甲基）丙烯酸酯和少量水的（甲基） 丙烯酸酯相，以及一含水頂部餾出產物。 較佳係藉由在包含一或多個反應區之一反應區域中進行的酯化 反應實現此二方法步驟I)和II)，且一或多個分餾單元（rectificati〇n unit)係疊置於該一或多個反應區之上，其中存在於（甲基）丙埽 酸酯相的至少部分水以及存在於（甲基）丙烯酸酯相的至少部分 201223940 未反應之醇係於該分德單元頂部分離出。此等方、式係描述於如 DE-A-196 04 252中，該文件係揭露關於酯化反應之分離以及藉由 蒸餾該（甲基）丙烯酸酯的隔離（丨s〇lation ) ’併於此處供參考。 為了本發明之目的’「分顧單元」一詞較佳係指一設備，其中一 氣相係藉由加熱存在於該分餾單元中之至少部分之液相而製造， 且此氣相係於該分餾單元内上升並與下降之液相接觸。因此「分 餾單元」一詞亦包括簡單之蒸餾塔。然而，所論單元一般係一分 餾塔，其中内部設計製造出液相與氣相之間的密集接觸。此等内 部設計係板，如泡罩板（bubble cap tray )、多孔板（perforated tray ) ’ 尤其係雙流板（dual-flow tray )、床（bed )、有序填料（ordered packing)等。 根據本發明，於方法步驟I)中，各情況下以該醇相之總重量計， 該醇相尤佳係以至少75重量％，再更佳至少90重量％，更佳至少 95重量％且最佳至少99重量％程度之前述單元醇或多元醇之一者 為基質，較佳係正丁醇；而各情況下以該（甲基）丙烯酸相之總 重量計，（甲基）丙烯酸相較佳係以大於75重量％，再更佳大於 90重量。/〇,更佳大於95重量％，再更佳大於99重量。/❶且最佳大於 99.5重量％程度之丙烯酸為基質。 於方法步驟I)中該醇相與該（甲基）丙烯酸相之反應係發生於 一反應區域中，該反應區域可視需要包含複數個反應區；在此情 況中，串接（cascade )此等二或多個反應區係可為有利的。一反 應區之液體輸出流（output stream)接著係形成後續反應區之進 料’此可以藉助一溢流（overflow)進行。較佳舞串接2、3或4 201223940 個反應區，極佳係4個反應區。若於同一反應器中建立多於一個 反應區（即使用分隔板）’反應區數目亦可大於4。於多個反應區 的情況中’來自該反應區的蒸氣係進料至一聯合分顧單元（j 〇int rectification unit)’如一聯合分餾塔，其液體輸出係有利地進入第 一反應區。 在方法步驟I)中酯化反應的分離與在方法步驟H)中藉由蒸餾 (甲基）丙烯酸之烧酯的隔離係容許較溫和之反應條件。於所有 反應區中之反應係可於100毫巴至大氣壓力，較佳200至700毫 巴，尤佳300至450毫巴之壓力下，於（分餾塔之）頂部且90°C 至115°C之溫度下操作。所有反應區中之壓力可皆相同，但於個 別反應區中在不同之壓力條件下進行該酯化反應，且於單一的疊 加式分餾單元的情況中，將蒸氣自反應區以不同高度進料至分镏 單元中亦係有利的。 在方法步驟I)中之酯化催化劑，係可使用本領域之技術人士所 知且催化（曱基）丙烯酸與醇的反應，尤其係丙烯酸與正丁醇之 反應的所有催化劑，尤佳使用具催化活性的酸，更佳使用磺酸 (sulphonic acid)或硫酸（sulphuric acid)，而最佳使用對曱苯績 酸。根據本發明，於本文中，較佳地，以此處所述之反應混合物 計’具催化活性的酸（最佳係對甲苯磺酸）之含量係在0.1至10 重量％，較佳在〇·1至6重量％範圍。在反應區域内反應物的總滯 留時間（residence time ) —般係0.25至15小時，較佳1至7小時’ 尤佳2至5小時。較佳地，於後續區域中的滞留時間降低。 在本發明方法之方法步驟III)中，包含該甲基丙烯酸酯及少量水 201223940 之該（甲基）丙烯酸酯相係使用水進行第一次萃取，以分離出仍 存在於此相中之至少部分催化劑。為此目的，包含該曱基丙烯酸 酯及少量水之該（甲基）丙烯酸酯相係自該反應區域排出並進料 至一萃取單元（以下係指萃取單元A)之下方區域，較佳至下方 三分之一處，更佳至下方四分之一處，進入上方區域，水較佳係 由上方區域之上方三分之一處，更佳上方四分之一處引入，使得 水洗滌此萃取單元A内逆流上升之該有機液相，較佳係確保水係 以液滴形式向下流經該連續有機相。 以此方式，係於萃取單元A之頂部得到作為第一萃取物之包含 該（甲基）丙烯酸酯與少量水及催化劑之（甲基）丙烯酸酯相， 該相接著於方法步驟IV)中進行鹼性反應萃取。萃取單元A中之 催化劑係以水洗滌而分離出，且較佳係於大氣壓力及在30°C至 60°C範圍的溫度下操作。於此萃取單元A之下方部分得到之該含 水相，其係包含大量之催化劑，較佳係再循環至反應區（若反應 區包含複數個反應區，較佳係再循環至亦進料該醇相與該（甲基） 丙稀酸相之反應區）。 在本文中，根據本發明，較佳地，自萃取單元A頂部得到的第 一萃取物係包含： (αΐ)至少70重量％、尤佳至少75重量％且最佳至少80重量％ 的（甲基）丙烯酸烷酯， (α2) 5至20重量％，尤佳6.5至15重量％且最佳8至10重量％ 的未反應之醇， 201223940 (cx3) 0.1至5重量％，尤金0.5至2重量％且最佳0.75至1.25重 量％的未反應之（曱基）丙烯酸， (α4) 0.1至10重量％，尤佳1至8重量％且最佳2至5重量％的 水，以及 (α5) 1至10重量％，尤佳2至8重量％且最佳4至6重量％的不 同於成分〇1)至（α4)之雜質。 其中成分（αΐ)至（α5)之總和為100重量％。於製造丙烯酸正丁酯 之情況中，該不同於成分(αΐ)至（α4)之雜質係特別包含丙酸β-丁氧 基丁酯、丙酸丙烯醯氧基丁酯、二丁基醚、以及對甲苯磺酸（使 用對曱苯磺酸作為催化劑時）。 萃取單元Α頂部得到的第一萃取物接著於方法步驟IV)中進行 一第二次萃取，其中該第一萃取物與鹼接觸，且滿足條件i)及ii) 中至少一者。此第一萃取物與鹼之接觸較佳係15至60°C，尤佳在 20至40°C且最佳在25至35°C範圍的溫度下進行。 利用水洗滌以分離出催化劑之萃取單元A係於大氣壓力及在15 至60°C，尤佳在20至40°C且最佳在25至35°C範圍的溫度下操 作。 於本發明方法中，與包含該（曱基）丙烯酸酯與未反應之（曱 基）丙烯酸之液相（因此較佳係與第一萃取物）接觸之鹼，較佳 係一氫氧化納水溶液。 然而，根據本發明，較佳係包含該（甲基）丙烯酸酯與未反應 之（曱基）丙稀酸之液相僅與一定義量之驗（尤其係氫氧化納水 12 201223940 溶液）接觸。為了避免聚合物沉積物的形成，應謹慎看顧以確保 未使用超過待中和之（曱基）丙烯酸量之用量的鹼。可使用數種 方式以適當地計量所加入之驗量。 於本發明之一特定具體實施態樣中，包含該（甲基）丙烯酸酯 與未反應之（曱基）丙烯酸之該液相與該鹼之接觸，以及藉由該 鹼至少部分中和該未反應之（曱基）丙烯酸（或根據方法步驟IV) 之第二次萃取），係於以液體流通方式（fluid-conducting manner ) 與分離單元連接的混合單元中進行。此等設備亦稱作「混合-沉降 萃取器」，在此情況中，較佳係使用驗性水溶液，尤佳氫氧化納水 溶液，作為驗。 在此一「混合-沉降萃取器」中，pH值落在條件i)定義内之中和 反應、或莫耳數比落在條件ii)定義内之中和反應所需之鹼（氳氧 化鈉水溶液）的用量首先係計量加入一混合單元内。此處若遵守 條件i)，則可配備一用於測量pH值之裝置在該混合單元中，使得 該鹼係經引入直至達到所需之pH值。若遵守條件ii)，則可配備 一藉助於測定該液相中之未反應酸之含量的分析設備在該混合單 元中或在包含該（甲基）丙烯酸酯與未反應之（甲基）丙烯酸之 該液相的進料線中，使得該鹼經引入的量達到所需之莫耳數比。 鹼與包含該（曱基）丙烯酸酯與未反應之（甲基）丙烯酸之該液 相所得之混合物接著係自此混合單元進入一與該混合單元相連之 分離單元，其中該有機相（即第二萃取物）係與該含水相分離。 該含水相接著可至少部分地回到該混合單元中。 當使用「混合-沉降萃取器」時，尤佳係於水存在下萃取包含該 13 201223940 ^甲基）丙稀酸醋與未反應之（甲基）丙烯酸之該液相 量係水：有機相之重量比較佳在G」：i至i:卜 ’水的用201223940 VI. Description of the invention: 'Technical field to which the invention pertains» The present invention relates to a method for preparing (meth)acrylic acid vinegar for preparing a polymer based on (mercapto) acrylate The method and the (meth) acrylate-based polymer obtainable by the process. [Prior Art] Alkyl esters of (meth)acrylic acid are well known and are of importance in the production of starting monomers such as aqueous dispersions (especially as an adhesive). N-butyl acrylate is especially an industrially important monomer. Prepared by reacting (meth)acrylic acid with a unit alcohol having from 1 to 5 carbon atoms (_.-di-alcohol) in the presence of a high temperature catalyst for the supply of protons. The method of alkyl acrylate is known and described in, for example, 932, DE_A_22% 829 and DE_A_22 52 of DE-A-14. These reactions are typical equilibrium reactions in which the conversion of (meth)acrylic acid to the respective alkyl alcohol is clearly limited by the equilibrium constant. In order to bring the reaction product (i.e., (meth)acrylic acid vinegar) side, the water is reacted from the reaction mixture at the top (. oil ad) and unreacted (d) in the form of (iv) by a steaming method. This method is described in particular in DE_A_25 52 987. At least a portion of the alcohol present in the aqueous phase containing the amino acid in this manner is separated from the separator in this manner and recycled to the distillation column. Containing (methyl dilute and unreacted (methyl bottom product first by means of water washing knees (coffee reading b) to remove the still existing S catalyst, followed by an inertial reaction extraction to remove the special unreacted (methyl Acrylic acid is isolated in the form of a metal salt, and 201223940 The product obtained by this neutralization reaction is washed with a small flow of water. This method for preparing (meth) acrylate is described, for example, in DE-A-196 04 253 In A1. However, the method known from the prior art has the disadvantage that the formation of the polymer frequently occurs due to this accommodative washing, resulting in clogging of the downstream distillation column or the heat exchanger located upstream of the distillation column. Therefore, it is necessary to shut down the corresponding components of the device for cleaning purposes. In addition to the clogging of the device components caused by polymer deposits, the formation of such polymers is also related to the loss of alkyl (meth)acrylate. One of the objects of the present invention is to overcome the disadvantages of the prior art with regard to the preparation of alkyl (meth) acrylates. In particular, it is an object of the present invention to provide a preparation a process for alkyl acrylates which is operable to give very high yields of alkyl (meth)acrylates. Compared to processes known in the prior art, the process should also result in a lower degree of deposition due to polymer formation. And thus reduce the downtime of individual components of the device. The foregoing object is solved by a method for preparing a (meth) acrylate by reacting a monohydric alcohol phase with a (mercapto)acrylic acid phase, which comprises the following method Step: contacting a liquid phase comprising the (mercapto)acrylic acid vinegar with unreacted (meth)propionic acid with a base, and at least partially neutralizing the unreacted (meth)acrylic acid with the base, Wherein at least one of the following conditions is satisfied, preferably both: i) the liquid phase after contact with the base is preferably at 20 ° C. The p Η value measured is not more than 10.5, preferably not more than 10.0. And the optimum is not more than 9.5, and the pH value is not less than 7.0, especially preferably 8.0 and the best 8.5 is better than 5 201223940; ii) the amount of the base is the hydroxide ion and (meth)acrylic acid which can be released from the base Mohr ratio (〇H_ :(methyl)-propyl The acid) is not more than 1.10: 1, especially preferably not more than 1.02: 1, and the best is not more than 1.00: 1, the molar number is preferably not less than 0.95: 1, especially preferably 0.99: 1 and the best 0.995: 1 . Surprisingly, it has been found that it has now been found that undesired formation of the polymer after alkaline reaction extraction can be attributed to partial hydrolysis of the (mercapto) acrylate to form the alcohol with the (mercapto) acrylic acid. The alkali metal salt of the (indenyl)acrylic acid formed has a strong tendency to undergo polymerization. Accordingly, the process of the present invention provides a countermeasure for neutralizing the acid using a stoichiometric base and preferably also under very uniform conditions. This allows for a high concentration of process conditions in the liquid phase. These measures can be carried out, for example, by introducing an ion exchanger instead of introducing an aqueous test solution for neutralization, or performing the neutralization reaction in a mixer-settler apparatus comprising a circulating aqueous stream, The amount of base required for the neutralization reaction is introduced into the stream under pH adjustment and is then only combined with the acid-containing product stream in a mixer. In a preferred embodiment of the method of the present invention, the contact of the liquid phase with the base is carried out in a contact zone, and after the liquid phase is contacted with the base, for at least 1 second, preferably at least 5 Preferably, after a period of at least 10 seconds, preferably, the pH of the liquid phase at 20 ° C is no greater than 13.0, preferably no greater than 12.0, and most preferably greater than 11.0 in the contact zone. In a specific embodiment of the method of the present invention, the condition i) is satisfied; in another embodiment of the method of the present invention, the condition ii) is satisfied; and in another embodiment of the method of the present invention In the case, the condition i) and the condition ii) are satisfied. 201223940 'In a preferred embodiment of the method of the present invention, the method comprises the following method steps: l) reacting a monol phase with a (meth)acrylic acid in the presence of an esterification catalyst to obtain one ( a mercapto alkyl acrylate phase, H) removing at least a portion of the water present in the (meth) acrylate phase by distillation and paying a solution comprising the (meth) acrylate vinegar and a small amount of water a propylene phase and an aqueous top product (〇verheacj pr〇duct), m) first extracting the (meth) acrylate containing the (meth) acrylate and a small amount of water with water And obtaining a first extract of a liquid phase comprising the (meth) acrylate and unreacted (meth) acrylate, ϊ ν) by contacting the first extract with a base Secondary extraction of the first extract' and at least partially neutralizing the unreacted (meth)propanic acid to obtain a second extract, V) removing other by-products from the second extract to obtain a high purity (meth) acrylate phase, wherein at least the following conditions are met In one case, it is preferable that the first extract obtained by contacting G with the test preferably has a positive value of not more than 10.5, preferably not more than 1〇〇, and preferably not more than 9 5 as measured by 20oc. And the value is preferably not less than 7 · 〇 ' 佳 8.0 and the best 8.5, (1) the amount of the test used in the method step IV) is the test releaseable oxygen ion and (meth) propyl The molar ratio of dilute acid (〇H_:(曱)) is not more than 1祀, and the best is not more than 201223940 100:1, and the molar number is not less than 〇 95:1, especially good 99:1 and the best 0.995:1. Here too, it is advantageous to carry out the contact of the liquid phase with the base in a contact zone, and the liquid phase is contacted with the base for at least 丨 seconds, preferably at least 5 seconds and preferably at least 10 seconds. After the time, the pH of the liquid phase measured at 2 〇〇c at any point in the contact zone is not more than 13 〇, preferably not more than 12 〇 and most preferably not more than n 〇. In the method step 〖) of the process of the invention, an alcohol phase is first reacted with a (mercapto)acrylic acid in the presence of an esterification catalyst to obtain a (meth) acrylate phase, particularly preferably comprising n-butanol. The alcohol phase and the (meth)acrylic acid phase comprising acrylic acid (so the (mercapto) acrylate formed is preferably n-butyl acrylate. However, other alcohols may be used instead of n-butanol, such as a unit alcohol ( Such as methanol, ethanol, 丨-propanol, 2-propanol, isopropanol or tertiary butanol) or polyols (such as glycerol, hydrazine, 2-propylene glycol or pentaerythrthol (topenterthHtol). The alcohol can be reacted with acrylic acid or methacrylic acid to form the corresponding ester. The use of the polyol is particularly useful in the preparation of intermediate products for surface coating. In process step II), it is isolated by distillation in the presence of (methyl) At least a portion of the water in the acrylate phase (and at least a portion of the unreacted alcohol present in the (meth) acrylate) to provide a (meth) acrylate phase comprising (meth) acrylate and a minor amount of water, And an aqueous top distillate . Preferably, the two process steps I) and II) are carried out by an esterification reaction carried out in a reaction zone comprising one or more reaction zones, and one or more fractionation units are stacked Above the one or more reaction zones, wherein at least a portion of the water present in the (meth)propionate phase and at least a portion of the unreacted alcohol present in the (meth)acrylate phase are in the The top of the unit is separated. Such methods are described, for example, in DE-A-196 04 252, which discloses the separation of the esterification reaction and the separation of the (meth) acrylate by distillation [并s〇lation] For reference here. For the purposes of the present invention, the term "dividing unit" preferably refers to a device in which a gas phase is produced by heating at least a portion of the liquid phase present in the fractionation unit, and the gas phase is in the fractionation. The cell rises and contacts the falling liquid phase. Therefore, the term "fraction unit" also includes a simple distillation column. However, the unit in question is typically a fractionation column in which the internal design creates a dense contact between the liquid phase and the gas phase. Such internal design panels, such as bubble cap trays, perforated trays, are particularly dual-flow trays, beds, ordered packings, and the like. According to the invention, in process step I), the alcohol phase is in each case at least 75% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight, based on the total weight of the alcohol phase. Preferably, at least 99% by weight of one of the aforementioned unit alcohols or polyols is a substrate, preferably n-butanol; and in each case, the (meth)acrylic acid phase is based on the total weight of the (meth)acrylic acid phase. It is preferably greater than 75% by weight, and even more preferably greater than 90% by weight. More preferably, it is more than 95% by weight, and even more preferably more than 99% by weight. Preferably, acrylic acid is used as a substrate in an amount greater than 99.5% by weight. The reaction of the alcohol phase with the (meth)acrylic acid phase in process step I) takes place in a reaction zone which optionally contains a plurality of reaction zones; in this case, cascades such Two or more reaction zones may be advantageous. The liquid output stream of a reaction zone is followed by the formation of a feed to the subsequent reaction zone. This can be done by means of an overflow. The preferred dance is connected to 2, 3 or 4 201223940 reaction zones, which are excellent for 4 reaction zones. If more than one reaction zone is established in the same reactor (i.e., using a separator), the number of reaction zones can also be greater than four. In the case of a plurality of reaction zones, the vapor from the reaction zone is fed to a combined rectification unit, such as a combined fractionation column, the liquid output of which advantageously enters the first reaction zone. The separation of the esterification reaction in process step I) and the isolation of the ester of (meth)acrylic acid in process step H) allow for milder reaction conditions. The reaction in all reaction zones can be at a pressure of 100 mbar to atmospheric pressure, preferably 200 to 700 mbar, particularly preferably 300 to 450 mbar, at the top of the fractionation column and at 90 ° C to 115 ° Operating at the temperature of C. The pressures in all reaction zones may be the same, but the esterification reaction is carried out under different pressure conditions in individual reaction zones, and in the case of a single superposition fractionation unit, the vapor is fed from the reaction zone at different heights. It is also advantageous to the branching unit. The esterification catalysts in process step I) are those known to those skilled in the art and which catalyze the reaction of (indenyl)acrylic acid with an alcohol, in particular all of the catalysts of the reaction of acrylic acid with n-butanol, particularly preferably The catalytically active acid is more preferably sulphonic acid or sulphuric acid, and the most preferred is phthalic acid. According to the present invention, preferably, the content of the catalytically active acid (optimal p-toluenesulfonic acid) is from 0.1 to 10% by weight, preferably in the case of the reaction mixture described herein. • A range of 1 to 6 wt%. The total residence time of the reactants in the reaction zone is generally from 0.25 to 15 hours, preferably from 1 to 7 hours', particularly preferably from 2 to 5 hours. Preferably, the residence time in the subsequent regions is reduced. In the method step III) of the process according to the invention, the (meth) acrylate phase comprising the methacrylate and a small amount of water 201223940 is first extracted with water to isolate at least the still present phase. Part of the catalyst. For this purpose, the (meth) acrylate phase comprising the mercapto acrylate and a small amount of water is discharged from the reaction zone and fed to a lower region of an extraction unit (hereinafter referred to as extraction unit A), preferably to the lower portion. One third, preferably to the lower quarter, into the upper area, the water is preferably introduced from the upper third of the upper area, preferably above the upper quarter, so that the water washes the extract The organic liquid phase which rises countercurrently in unit A preferably ensures that the water system flows downwardly through the continuous organic phase in the form of droplets. In this way, a (meth) acrylate phase comprising the (meth) acrylate with a small amount of water and a catalyst is obtained as a first extract at the top of the extraction unit A, which phase is subsequently carried out in method step IV) Alkaline reaction extraction. The catalyst in the extraction unit A is separated by washing with water, and is preferably operated at atmospheric pressure and at a temperature ranging from 30 ° C to 60 ° C. The aqueous phase obtained in the lower part of the extraction unit A, which comprises a large amount of catalyst, is preferably recycled to the reaction zone (if the reaction zone comprises a plurality of reaction zones, preferably recycled to also feed the alcohol The reaction zone of the phase with the (meth)acrylic acid phase). Herein, according to the present invention, preferably, the first extract obtained from the top of the extraction unit A comprises: (αΐ) at least 70% by weight, particularly preferably at least 75% by weight and optimally at least 80% by weight (A) Alkyl acrylate, (α2) 5 to 20% by weight, particularly preferably 6.5 to 15% by weight and most preferably 8 to 10% by weight of unreacted alcohol, 201223940 (cx3) 0.1 to 5% by weight, Eugene 0.5 to 2% by weight and most preferably 0.75 to 1.25% by weight of unreacted (mercapto)acrylic acid, (α4) 0.1 to 10% by weight, particularly preferably 1 to 8% by weight and most preferably 2 to 5% by weight of water, and Α5) 1 to 10% by weight, particularly preferably 2 to 8% by weight and most preferably 4 to 6% by weight of impurities different from the components 〇1) to (α4). The sum of the components (αΐ) to (α5) was 100% by weight. In the case of producing n-butyl acrylate, the impurities different from the components (αΐ) to (α4) specifically include β-butoxybutyl propionate, butyl butyl acrylate, dibutyl ether, And p-toluenesulfonic acid (when p-toluenesulfonic acid is used as a catalyst). The first extract obtained at the top of the extraction unit is then subjected to a second extraction in method step IV) wherein the first extract is contacted with a base and at least one of conditions i) and ii) is satisfied. The contact of the first extract with the base is preferably carried out at a temperature of from 15 to 60 ° C, particularly preferably from 20 to 40 ° C and most preferably from 25 to 35 ° C. The extraction unit A which is washed with water to separate the catalyst is operated at atmospheric pressure and at a temperature of from 15 to 60 ° C, particularly preferably from 20 to 40 ° C and most preferably from 25 to 35 ° C. In the process of the present invention, the base which is in contact with the liquid phase (and thus preferably the first extract) comprising the (indenyl) acrylate and unreacted (hydrazino)acrylic acid is preferably an aqueous solution of sodium hydroxide. . However, in accordance with the present invention, it is preferred to include the liquid phase of the (meth) acrylate and unreacted (mercapto) acrylic acid in contact with only a defined amount of the test (especially sodium hydroxide water 12 201223940 solution). . In order to avoid the formation of polymer deposits, care should be taken to ensure that no base is used in excess of the amount of (fluorenyl)acrylic acid to be neutralized. Several ways can be used to properly meter the added test. In a specific embodiment of the present invention, the liquid phase comprising the (meth) acrylate and unreacted (hydrazino) acrylic acid is contacted with the base, and the base is at least partially neutralized by the base. The reaction (mercapto)acrylic acid (or the second extraction according to method step IV) is carried out in a mixing unit connected to the separation unit in a fluid-conducting manner. These devices are also referred to as "mixing-settling extractors". In this case, it is preferred to use an aqueous test solution, preferably a sodium hydroxide aqueous solution. In this "mixing-settlement extractor", the pH falls within the definition of condition i) and the reaction, or the molar ratio falls within the definition of condition ii) and the base required for the reaction (sodium niobium oxide) The amount of aqueous solution used is first metered into a mixing unit. If condition i) is followed here, a means for measuring the pH can be provided in the mixing unit such that the base is introduced until the desired pH is reached. If condition ii) is followed, an analytical device for determining the amount of unreacted acid in the liquid phase may be provided in the mixing unit or in the presence of the (meth) acrylate and unreacted (meth)acrylic acid. In the feed line of the liquid phase, the base is introduced in an amount to achieve the desired molar ratio. a mixture of a base and the liquid phase comprising the (indenyl) acrylate and unreacted (meth)acrylic acid is then fed from the mixing unit into a separation unit connected to the mixing unit, wherein the organic phase (ie, The two extracts are separated from the aqueous phase. The aqueous phase can then be at least partially returned to the mixing unit. When a "mixing-settlement extractor" is used, it is preferred to extract the liquid phase containing the 13 201223940 ^methyl) acrylate vinegar and unreacted (meth) acrylic acid in the presence of water: organic phase The weight is better at G": i to i: the use of water
氫氧化鈉水溶液在接觸包含該（甲基）丙烯_與未反應之（甲 基）丙缔酸之該液相前係經此額外加入之水或再循環之含水相稀 釋。在此情況巾，該濃驗麵（較佳錢氧化鈉水溶液）之濃唐，The aqueous sodium hydroxide solution is diluted with the additionally added water or recycled aqueous phase before contacting the liquid phase containing the (meth) propylene _ and unreacted (methyl) propionic acid. In this case, the thick face, which is better than the sodium hydroxide solution,
醋與未反應之（甲基）丙烯酸之該液相接觸時，其濃度較佳係在 0.5至10重量％，尤佳在丨5至6重量％且最佳在2至 4重量％範 此外，當此經稀釋之鹼性水溶液（較佳係此經稀釋之氩氡化鈉 水溶液）與包含該（曱基）丙烯酸酯與未反應之（甲基）丙烯酸 之該液相於「混合-沉降萃取器」之混合單元中接觸時，此二相較 佳係以該含水相形成分散於有機相中的液滴的方式彼此混合。因 此該混合單元中形成一液態多相系統，該系統亦可以一乳液呈現。 「混合-沉降萃取器」之操作模式及其精確建造方式係描述於如 Α. 於 1997 年之 r c〇pper SX/EW Seminar:肋咖的加化此, 201223940 j/iemaiz.ves, 尸/awi ；M. L. Jansen 與 A. Taylor 於 1997 年之 ▽ Solvent Extraction Mixer-Settlers and Contactor's: Developments irnd （ALTA 於 1997 年之 Copper Hydrometallurgy ForumWhen the vinegar is contacted with the liquid phase of unreacted (meth)acrylic acid, the concentration thereof is preferably from 0.5 to 10% by weight, particularly preferably from 5 to 6% by weight and most preferably from 2 to 4% by weight. When the diluted alkaline aqueous solution (preferably, the diluted aqueous solution of sodium arsenide) is mixed with the liquid phase containing the (mercapto) acrylate and unreacted (meth) acrylic acid in the "mixing-settlement extraction" When contacting in a mixing unit of the apparatus, the two phases are preferably mixed with each other in such a manner that the aqueous phase forms droplets dispersed in the organic phase. Therefore, a liquid multiphase system is formed in the mixing unit, and the system can also be presented as an emulsion. The operation mode of the "mixing-settlement extractor" and its precise construction method are described in Rugao. In rc〇pper SX/EW Seminar in 1997: Adding Ribs, 201223940 j/iemaiz.ves, corpse/awi ;ML Jansen and A. Taylor after 1997 Solvent Extraction Mixer-Settlers and Contactor's: Developments irnd (ALTA in 1997 at the Copper Hydrometallurgy Forum
Proceedings );M. A. Giralico、T.A. Post、M. C. Greaves、E. Stevenson 於 1998 年之「Introducing LIGHTNIN’s Integrated SW/EW （ALTA 於 1998 年之 Copper Hydrometallurgy Forum Proceedings) ; W. R. Hopkins 於 1996 年之「inverse Mixer •Seii/er·?/ ALTA 於 1996 年之 Copper Hydrometallurgy Forum Proceedings ) ; B. Nyman 等人於 1998 年之「777e OwioArwmpw Copper Solvent Extraction Process — An Approach Based on Interactions Between Running Parameters and Mixer-Settler Design Introduced at Radomiro Tomic VSF SX Plant in Chile Ji ALTA 於 199% 年之 CoTpper Hydrometallurgy Forum Proceedings) ; R. L. Williams 與 A. A. Sonntag 於 1995 年之1So/veni Exiraciz’ow j( ALTA 於 1995 年之 Copper Hydrometallurgy Forum Proceedings) ; E. M. Buchalter 與 R. Kleinberger 於 1998 年之「Copper <So/ve«i im’wg· aProceedings); MA Giralico, TA Post, MC Greaves, E. Stevenson, 1998, "Introducing LIGHT NIN's Integrated SW/EW (ALTA, 1998, Copper Hydrometallurgy Forum Proceedings); WR Hopkins, 1996, "inverse Mixer • Seii/ Er·?/ ALTA in 1996, Copper Hydrometallurgy Forum Proceedings); B. Nyman et al., 1998, “777e OwioArwmpw Copper Solvent Extraction Process — An Approach Based on Interactions Between Running Parameters and Mixer-Settler Design Introduced at Radomiro Tomic VSF SX Plant in Chile Ji ALTA in 19% of CoTpper Hydrometallurgy Forum Proceedings); RL Williams and AA Sonntag in 1995 1 So/veni Exiraciz'ow j (ALTA in 1995, Copper Hydrometallurgy Forum Proceedings); EM Buchalter and R. Kleinberger, 1998, "Copper <So/ve«i im'wg·a
Bateman Pulse Column { ALTA 於 1998 年之 Copper Hydrometallurgy Forum Proceedings) o 該混合-沉降萃取器中之萃取作用視情況亦可裝配成串聯式多 段萃取（multistage extraction cascade )，其中係以串聯方式連接複 數個混合器-沉降器對，描述於如Wilhelm R. A. Vauck與Hermann A.所箸之F Grundoperationen Chemischer Verfahrenstechnik j (第11版，Wiley-VCH-Verlag，第797頁）。該鹼係可以鹼性水溶 液的形式（較佳係氫氧化鈉水溶液）依一針對方式（targeted 15 201223940 manner )引入各混合單元，莫用量係滿足條件i)、ii)或i)及ii)。 於本發明方法之另一特定具體實施態樣中，並非藉助鹼性水溶 液進行至少部分中和反應，而係以包含該（甲基）丙烯酸酯與未 反應之（曱基）丙烯酸之該液相與一離子交換劑，較佳係鹼性離 子交換劑接觸而進行。該液相與該離子交換劑之接觸可以藉由如 該液相流經管柱（column )中之離子交換劑床而實施。較佳係使 用鹼性離子交換劑，尤其係pKa值在8至11，尤佳在8.5至9.5 範圍的鹼性離子交換劑。作為合適離子交換劑之特定例子，可以 Amberlyst®A21或Amberlyst®A24 (羅門哈斯公司，美國費城）、 DOWEX 66、DOWEX MONOSPHERE 66、DOWEX MONOSPHERE 77、DOWEX MARA-THON WBA、DOWEX MARA-THON WBA-2、 DOWEX UPCORE Mono WB-500、XUS 43594.00、DOW-EX M-43 或DOWEX M4195 (陶式化學公司，美國密德蘭）、ZGA 451 (蘇 州博杰樹脂科技有限公司，中國蘇州市）以及SA 400 (西安藍曉 科技有限公司，中國陝西西安市）達成。 作為第二萃取物之一有機相係自「混合-沉降萃取器」之分離器 中得到、或在包含該（甲基）丙稀酸酯與未反應之（曱基）丙烯 酸之.液相與該離子交換劑接觸後得到，且此有機相係於方法步驟 V)中去除其它副產物以得到一高純度之（甲基）丙烯酸烷酯相。 首先，將此第二萃取物先進料至一另外之萃取單元（以下係指 萃取單元B)係有利的，水係進料至該另外之萃取單元的上方區， 較佳係其上方三分之一處，更佳係其上方四分之一處，使得水洗 滌萃取單元B中逆流上升之有機液相；此處亦同，較佳係確保該 201223940 有機相以液滴形式通過該連續含水相，而另外之鹼，、較佳以一鹼 性水溶液形式，尤其係以氫氧化鈉水溶液之形式，亦可視需要加 入此萃取單元B。各情況以經純化之（曱基）丙烯酸g旨相之總重 里计，以此方式彳于到之該第三萃取物較佳係包含至少5重量％， 尤佳至少80重量％且最佳至少84.7重量％之該（甲基）丙稀酸醋。 可接著去除其它副產物（低沸物與高沸物，即沸點低於或高於 該（甲基）丙稀酸醋之彿點的化合物）而得到一高純度（甲基） 丙稀酸醋相’而此進-步之純化較佳係以__或多次另外之蒸館步 驟’較佳於-或多個另外之分顧單^中進行。各情況中以該高純 度（甲基）丙稀酸醋相之總重量計，以此方式得到之該高純度（甲 基）丙烯酸酯相較佳係以至少90重量％、尤佳至少％重量％且最 佳至少99.7重量％程度之該（曱基）丙烯酸酯為基質。 開頭所述目標之達成亦係藉由可以前述方法得到之（甲基）丙 稀酸醋，尤佳丙烯酸正丁酯所貢獻。 開頭所述目標之達成亦係藉由製備以（甲基）丙_醋（尤佳 係丙稀酸iLTS旨）為基質之聚合物之方法所貢獻，該方法包含以 下方法步驟： ()藉由上述方法之製備一（甲基）丙烯酸酯，尤佳丙烯酸正 丁酯； ()進行該（曱基）丙烯酸酯，尤佳丙烯酸正丁酯之自由基聚 合反應。 開頭所述目標之達成亦係藉由以（甲基）丙稀酸醋，尤其係丙 17 201223940 烯酸正丁酯為基質，且可以上述方法得到之聚合物所貢獻。 【實施方式】 本發明將借助非限制性之圖式與實施例進行說明。 根據第1圖，在製備（曱基）丙烯酸酯的傳統方法中，於一反 應區域（例如包含二反應區1及2)中反應正丁醇（BuOH)與丙 烯酸（AA)以形成丙烯酸正丁酯。所用之丙烯酸較佳具有至少75 重量％、更佳至少90重量％、再更佳至少95%且最佳至少99重量 %的純度。該來自反應區1之液態輸出流係形成該後續反應區2 之進料，且係以溢流方式進入反應區2。分餾單元3係疊於該反應 區域之上，而來自反應區1及2之蒸氣係進料至分餾單元3。在此 分餾單元中，一包含水與尤其係正丁醇之含水產物係自頂部離開 並於一分離器3中冷凝。此即形成一基本上由正丁醇所組成之有 機相，及一基本上由水所組成之作業廢水相。該基本上由正丁醇 所組成之有機相係再循環至分餾單元3,而作業廢水相則係引入收 集槽5。 保留於該反應區域中之該包含丙烯酸正丁酯之反應混合物（①） 首先係進料至一第一萃取單元7(即先前所述之萃取單元A)之水 洗滌液中以分離出尤其係催化劑（對曱苯磺酸）。該來自此萃取單 元A、包含大量之對甲苯磺酸之底部產物（②），係再循環至反應 區1中。來自此萃取單元之頂部產物（主要包含丙烯酸正丁酯） 接著進料至一另外的萃取單元8之鹼性反應萃取，其中仍在之催 化劑、未反應之丙烯酸與另外之副產物係以其鹼金屬鹽之形式分 離。一包含驗金屬鹽之二次成分相（③）係由萃取單元8之底部得 201223940 到 '，且與於收集槽5中之作業廢水相結合。該來自萃取單元B的 包含烷基酯之頂部產物係進一步於另外之蒸餾步驟（未顯示）中 純化以得到高純度丙烯酸正丁酯。 仍存在於收集槽5得到之組合物中的正丁醇接著係以另外之分 餾單元6分離出（④），並同樣再循環至分餾單元3中。該保留作 為分餾單元6底部產物之含水相接著係通入一灰化單元 (incineration unit)。 在第2圖中顯示之本發明方法中，相對於第1圖，該鹼性反應 萃取作用係非藉由在另一分餾塔中以濃鹼溶液萃取來自萃取單元 A之頂部產物進行，而係根據在第2圖中顯示之本發明方法之特 定具體實施態樣，使用「混合-沉降萃取器」。於萃取單元7得到 之該頂部產物（主要包含丙烯酸正丁酯與未反應之丙烯酸）係引 入一「混合-沉降萃取器」之混合區9中，並於該處與一氫氧化鈉 水溶液混合以形成一乳液呈由含水相與有機相組成之液態多相系 統。此乳液接著係進入「混合-沉降萃取器」之分離器10，該含水 相與有機相係於其中進行分離。通常包含少於1重量％氩氧化鈉之 該含水相係再循環至混合區中，使用根據條件i)或ii)，較佳i)及 ii)之中和反應所需之驗的用量，以添加濃氫氧化納溶液適當地設 定。未再循環之含水相係可以如第1圖所示作為流②再循環至反應 區1。有機相係該於分離器10中分離出，其包含丙烯酸正丁酯， 且可使用水進行更新之萃取作用。隨後可以蒸餾方式進行進一步 的純化以得到純丙烯酸正丁酯。 實施例 19 201223940 實施例1:以氫氧化鈉溶液中扣混合物 正丁醇及1重量％丙稀酸（以丙烯酸正丁酯之重量計）之混合物 係與不同量之氫氧化鈉水溶液混合。觀察結果如下： 所用氫氧化鈉係超過存在於混合物中之丙烯酸的2倍： 八天後，因聚合物形成而造成嚴重的脫色現象 所用氫氧化鈉係超過存在於混合物中之丙烯酸的1.5倍： 八天後，因聚合物形成而造成嚴重的脫色現象 所用氫氧化鈉係與存在於混合物中之丙烯酸等量： 即使於八天後亦無脫色現象。 實施例2 :利用鹼性陰離子交換劑中和混合物 丙烯酸正丁酯及1重量％丙烯酸（以丙烯酸正丁酯的重量計）之 混合物係與 Amberlyst®A21( pKa = 9.0)或 Amberlyst®A26 OH( pKa =9.0)(皆為羅門哈斯公司，美國費城）。該陰離子交換劑係預先 以去離子水沖洗並使用5重量％強度之氫氧化鈉溶液調節。該混合 物隨後係進行分析以測定其組成。結果發現，特別是在使用陰離 子交換劑Amberlyst® A21時可有效去除丙稀酸而不會明顯裂解 (cleave )丙豨酸正丁醋。相較之下，使用陰離子交換劑 Amberlyst®A2 6 OH則造成丙稀酸正丁酯實質上被裂解 【圖式簡單說明】 第1圖係顯示用於製備（甲基）丙烯酸酯（丙烯酸正丁酯）之 傳統方法。 第2圖係顯示用於製備（曱基）丙烯酸酯（丙婦酸正丁酯）之 20 201223940 本發明方法。 【主要元件符號說明】 1、2 :反應區域之串聯式反應區 3 ： 分餾塔 4: 分離器 5 ： 收集槽 6: 用於分離出正丁醇之分餾塔Bateman Pulse Column { ALTA, 1998, Copper Hydrometallurgy Forum Proceedings) o The extraction in the mixing-sedimentation extractor can also be assembled into a multistage extraction cascade, where a plurality of mixtures are connected in series. The pair of settler pairs is described, for example, by Wilhelm RA Vauck and Hermann A., F Grundoperationen Chemischer Verfahrenstechnik j (11th edition, Wiley-VCH-Verlag, page 797). The base may be introduced into each mixing unit in the form of an alkaline aqueous solution (preferably aqueous sodium hydroxide solution) in a targeted manner (targeted 15 201223940 manner), and the molar amount satisfies the conditions i), ii) or i) and ii). In another specific embodiment of the method of the present invention, the at least partial neutralization reaction is not carried out by means of an aqueous alkaline solution, but the liquid phase comprising the (meth) acrylate and unreacted (hydrazino) acrylic acid is used. It is carried out in contact with an ion exchanger, preferably a basic ion exchanger. Contact of the liquid phase with the ion exchanger can be carried out by flowing the liquid phase through an ion exchanger bed in a column. It is preferred to use a basic ion exchanger, especially a basic ion exchanger having a pKa value of from 8 to 11, particularly preferably from 8.5 to 9.5. As a specific example of a suitable ion exchanger, Amberlyst® A21 or Amberlyst® A24 (Rohm and Haas Company, Philadelphia, USA), DOWEX 66, DOWEX MONOSPHERE 66, DOWEX MONOSPHERE 77, DOWEX MARA-THON WBA, DOWEX MARA-THON WBA- 2. DOWEX UPCORE Mono WB-500, XUS 43594.00, DOW-EX M-43 or DOWEX M4195 (Tao Chemical Company, Midland, USA), ZGA 451 (Suzhou Bojie Resin Technology Co., Ltd., Suzhou, China) and SA 400 (Xi'an Lanxiao Technology Co., Ltd., Xi'an, Shaanxi, China) was reached. As one of the second extracts, the organic phase is obtained from a separator of a "mixing-settlement extractor" or in a liquid phase comprising the (meth) acrylate and unreacted (fluorenyl) acrylic acid. The ion exchanger is obtained after contact, and the organic phase is removed in process step V) to remove other by-products to obtain a high purity alkyl (meth)acrylate phase. First, it is advantageous to feed the second extract to a further extraction unit (hereinafter referred to as extraction unit B), and the aqueous system feeds to the upper zone of the additional extraction unit, preferably above the third of the extraction unit. In one place, more preferably in the upper quarter thereof, the water washes the countercurrent rising organic liquid phase in the extraction unit B; here again, it is preferred to ensure that the 201223940 organic phase passes through the continuous aqueous phase in the form of droplets. Further, the base, preferably in the form of an aqueous alkaline solution, especially in the form of an aqueous solution of sodium hydroxide, may be added to the extraction unit B as needed. In each case, based on the total weight of the purified (mercapto)acrylic acid g phase, the third extract preferably comprises at least 5% by weight, particularly preferably at least 80% by weight and most preferably at least 84.7% by weight of the (meth) acrylate vinegar. Other by-products (low boilers and high boilers, ie, compounds having a boiling point lower or higher than the point of the (meth) acrylate vinegar) can be removed to obtain a high purity (meth) acrylate vinegar. The purification of the phase is preferably carried out in __ or in a plurality of additional steaming steps, preferably in one or more separate partitions. In each case, the high purity (meth) acrylate phase obtained in this manner is preferably at least 90% by weight, particularly preferably at least % by weight, based on the total weight of the high purity (meth) acrylate vinegar phase. % (and preferably at least 99.7 wt%) of the (indenyl) acrylate is the matrix. The achievement of the above-mentioned objectives is also contributed by (meth)acrylic acid vinegar, especially n-butyl acrylate, which can be obtained by the aforementioned method. The achievement of the above-mentioned object is also achieved by a method for preparing a polymer based on (meth) propyl vinegar (preferably acrylic acid iLTS), which comprises the following method steps: The above method produces a (meth) acrylate, especially n-butyl acrylate; () a free radical polymerization of the (fluorenyl) acrylate, especially n-butyl acrylate. The achievement of the objectives mentioned at the outset is also achieved by the use of (meth)acrylic acid vinegar, in particular C, 17 201223940 n-butyl acrylate, and which can be obtained by the polymers obtained by the above process. [Embodiment] The present invention will be described by way of non-limiting illustrations and embodiments. According to Fig. 1, in a conventional method for preparing a (mercapto) acrylate, n-butanol (BuOH) and acrylic acid (AA) are reacted in a reaction zone (for example, including two reaction zones 1 and 2) to form n-butyl acrylate. ester. The acrylic acid used preferably has a purity of at least 75% by weight, more preferably at least 90% by weight, still more preferably at least 95% and most preferably at least 99% by weight. The liquid output stream from reaction zone 1 forms the feed to the subsequent reaction zone 2 and enters reaction zone 2 in an overflow manner. The fractionation unit 3 is superposed on the reaction zone, and the vapors from the reaction zones 1 and 2 are fed to the fractionation unit 3. In this fractionation unit, an aqueous product comprising water and especially n-butanol exits from the top and is condensed in a separator 3. This results in an organic phase consisting essentially of n-butanol and a working wastewater phase consisting essentially of water. The organic phase consisting essentially of n-butanol is recycled to the fractionation unit 3, while the working wastewater phase is introduced into the collection tank 5. The reaction mixture (1) containing n-butyl acrylate remaining in the reaction zone is first fed to a water washing liquid of a first extraction unit 7 (ie, the extraction unit A previously described) to separate the especially Catalyst (p-toluenesulfonic acid). The bottom product (2) from this extraction unit A containing a large amount of p-toluenesulfonic acid is recycled to the reaction zone 1. The top product from this extraction unit (mainly comprising n-butyl acrylate) is then fed to an additional extraction unit 8 for alkaline reaction extraction, wherein the catalyst, unreacted acrylic acid and further by-products are bases. The form of the metal salt is separated. A secondary component phase (3) comprising a metal salt is obtained from the bottom of the extraction unit 8 201223940 to ' and is combined with the working wastewater in the collection tank 5. The overhead product comprising the alkyl ester from extraction unit B is further purified in a separate distillation step (not shown) to provide high purity n-butyl acrylate. The n-butanol still present in the composition obtained in the collection tank 5 is then separated (4) by another fractionation unit 6, and is likewise recycled to the fractionation unit 3. The retained aqueous phase, which is the bottom product of the fractionation unit 6, is passed to an incineration unit. In the method of the present invention shown in Fig. 2, the alkaline reaction extraction is carried out by extracting the top product from the extraction unit A with a concentrated alkali solution in another fractionation column, relative to Fig. 1, According to a specific embodiment of the method of the invention shown in Figure 2, a "mixing-settling extractor" is used. The top product (mainly comprising n-butyl acrylate and unreacted acrylic acid) obtained in the extraction unit 7 is introduced into a mixing zone 9 of a "mixing-settlement extractor" where it is mixed with an aqueous sodium hydroxide solution. A liquid multiphase system consisting of an aqueous phase and an organic phase is formed. This emulsion is then passed to a separator 10 of a "mixing-settlement extractor" in which the aqueous phase is separated from the organic phase. Typically, the aqueous phase comprising less than 1% by weight of sodium aroxide is recycled to the mixing zone using the amount required to neutralize the reaction according to conditions i) or ii), preferably i) and ii) The concentrated sodium hydroxide solution was added as appropriate. The unrecycled aqueous phase can be recycled to reaction zone 1 as stream 2 as shown in Figure 1. The organic phase is separated in a separator 10 which contains n-butyl acrylate and can be subjected to an updated extraction using water. Further purification can then be carried out by distillation to give pure n-butyl acrylate. Example 19 201223940 Example 1: Buckling mixture in sodium hydroxide solution A mixture of n-butanol and 1% by weight of acrylic acid (by weight of n-butyl acrylate) was mixed with different amounts of aqueous sodium hydroxide solution. The observations were as follows: The sodium hydroxide used was more than twice that of the acrylic acid present in the mixture: After eight days, the severe decolorization caused by the formation of the polymer used 1.5 times more sodium hydroxide than the acrylic acid present in the mixture: After eight days, the sodium hydroxide used for the severe decolorization due to the formation of the polymer was equivalent to the acrylic acid present in the mixture: no decolorization occurred even after eight days. Example 2: A mixture of a neutral anion exchanger neutralizing mixture of n-butyl acrylate and 1% by weight of acrylic acid (by weight of n-butyl acrylate) with Amberlyst® A21 (pKa = 9.0) or Amberlyst® A26 OH ( pKa = 9.0) (all are Rohm and Haas Company, Philadelphia, USA). The anion exchanger was previously rinsed with deionized water and adjusted with a 5 wt% strength sodium hydroxide solution. The mixture was then analyzed to determine its composition. As a result, it was found that the use of the anion exchanger Amberlyst® A21 was effective in removing acrylic acid without significantly cleaving n-butyl acrylate. In contrast, the use of the anion exchanger Amberlyst® A2 6 OH causes the n-butyl acrylate to be substantially cleaved [Simplified illustration] Figure 1 shows the preparation of (meth) acrylate (acrylic acid butyl acrylate) The traditional method of ester). Figure 2 shows the process of the invention for the preparation of (mercapto) acrylate (n-butyl p-butyrate) 2012 20123940. [Explanation of main component symbols] 1, 2: Tandem reaction zone of reaction zone 3 : Fractionation column 4: Separator 5 : Collection tank 6: Fractionation tower for separating n-butanol
7 ： 萃取單元A7 : Extraction unit A
8 ： 萃取單元B 9: 混合器 10: 分離器 ① ： 含有丙烯酸正丁酯之反應混合物 ② ： 萃取單元A之底部產物 ③ ： 二次成分相 ④ ： 分餾單元6得到之正丁醇 218 : Extraction unit B 9: Mixer 10: Separator 1 : Reaction mixture containing n-butyl acrylate 2 : Bottom product of extraction unit A 3 : Secondary component phase 4 : n-butanol obtained by fractionation unit 6