201029969 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用含有乙烯基醚之醇類之（甲基 )丙烯酸羥烷酯之製造方法。 【先前技術】 (甲基）丙烯酸羥烷酯之製造方法之主流通常係由烷 φ 二醇經酯化反應獲得二醇、單酯、二酯混合物後，萃取分 離出僅單酯物之方法。具體而言，已經提出在強酸存在下 使丙烯酸與烷二醇反應之方法（例如，參照專利文獻1 ) ，但會有由於強酸而產生副產物，且產率下降等缺點。解 決該問題之方法已有針對烷二醇與（甲基）丙烯酸酯之酯 交換反應之各種報告（例如，參照專利文獻2〜4 )。又， 亦報導有關於（甲基）丙烯酸4-羥基丁酯之有效率地萃取 及純化之方法（例如，參照專利文獻5〜6 )。然而自烷二 醇之酯交換法由於所得產物爲混合物，因此需要過量之萃 取溶液以僅分離出單酯，不具效率。 分二階段獲得（甲基）丙烯酸羥烷酯之方法已報導有 使含有乙烯基醚之醇經酯交換後，在酸觸媒與醇存在下脫 • 乙烯基化之方法（例如，參照專利文獻7)。然而，該方 法在脫乙烯基化反應之際，由於產生醛化合物而有必要去 除醛化合物，但去除反應中之醛化合物之作業並不容易。 另外，該反應時過量使用之醇必須藉由水洗去除並丟棄， 而不具效率。 -5- 201029969 專利文獻1 :德國專利第1 5 1 1 8 5 7 2號公報 專利文獻2:特開平10-298143號公報 專利文獻3 :特開平1 1 -43466號公報 專利文獻4 :特開2000-159727號公報 專利文獻5:特開平8-53392號公報 - 專利文獻6:特開2005-194201號公報 專利文獻7:特開平1〇-182555號公報 【發明內容】 [發明欲解決之課題] 本發明之課題爲提供一種可不需要繁雜之純化步驟而 有效率地製造（甲基）丙烯酸羥烷酯之製造方法。 [解決課題之手段] 本發明人等經各種檢討之結果，發現藉由使含有乙嫌 基醚之醇經（甲基）丙烯酸化成爲含有乙烯基醚之（甲基 〇 )丙烯酸酯之後’在酸觸媒存在下，與水共存之脫乙烯化 法’可以高產率獲得高純度之（甲基）丙烯酸羥烷酯，且 脫乙烯化後分離回收之水層可被再利用。 換言之，本發明係如下： - (1) 一種（甲基）丙烯酸羥烷酯之製造方法，其特 徵爲藉由酯交換法，使含有乙烯基醚之醇經（甲基）丙烯 酸化成爲含有乙烯基醚之（甲基）丙烯酸酯之後，在酸觸 媒存在下，進行脫乙烯基化反應之際，使水共存。 -6- 201029969 (2) 如前述（i)所述之（甲基）丙烯酸羥烷酯之製 造方法，其中脫乙烯基化反應時之反應溫度爲60°C以下。 (3) 如前述（1)或（2)所述之（甲基）丙烯酸羥 烷酯之製造方法，其中含有乙烯基醚之醇係以下述通式（ I)或（II)表示： [化1] 通式ω (通式（I)中，η表示3〜11之整數） [化2] 八Α八ΟΗ 通式(Π) (通式（II)中，A表示伸環戊基或伸環己基）。 本申請案同時基於本申請人之先前日本專利申請案， 亦即特願2008-306256 (申請日2008年12月1日）主張 優先權，該等說明書倂入本文中供參考。 [發明效果] 依據本發明，由於可在不經歷蒸餾等繁雜之純化步驟 -7- 201029969 而有效率地獲得（甲基）丙烯酸羥烷酯，進而於脫乙烯基 化步驟中使用之水可再利用，因此可提供步驟短且經濟地 製造（甲基）丙烯酸羥烷酯之方法。 【實施方式】 針對本發明之（甲基）丙烯酸羥烷酯之製造方法之實 施方式加以詳細說明。 本發明之（甲基）丙烯酸羥烷酯之製造方法之特徵爲 @ 藉由酯交換法使含有乙烯基醚之醇經（甲基）丙烯酸化成 爲含有乙烯基醚之（甲基）丙烯酸酯後，在酸觸媒存在下 進行脫乙烯基化之際與水共存。 於本發明，首先，使含有乙烯基醚之醇之羥基酯化， 獲得含有乙烯基醚之（甲基）丙烯酸酯。酯化之方法主要 爲使用（甲基）丙烯酸之脫水酯化法，使用低級（甲基） 丙烯酸酯之酯交換法，使用（甲基）丙烯醯鹵化物之醯鹵 法，其中由於脫水酯化法使用酸觸媒，無法適用於同時引 @ 起脫乙烯基化。另外，醯鹵法由於利用反應使鹵素脫離而 殘留在系統內，故需要水洗、吸附或蒸餾等純化處理。另 一方面，酯交換法由於雜質少亦無純化作業之必要，因此 本發明採用酯交換法。 本發明中使用之含有乙烯基醚之醇舉例爲例如4-羥基 丁基乙烯基醚、6-羥基己基乙烯基醚、9-羥基壬基乙烯基 醚、10-羥基癸基乙烯基醚、12-羥基十二烷基乙烯基醚等 之以下列通式（I)表示之化合物；環己烷二甲醇單乙烯 -8 - 201029969 基醚等之以下列通式（11)表示之化合物；苯 乙烯基醚等。 [化3] ^〇^〇Η 通式① (通式（I)中’ 11表不3〜11之整數） [化4] #0 八Α^ΟΗ 通式(Π) (通式（Π)中’ Α表示伸環戊基或伸環ξ 酯交換法所使用之低級（甲基）丙烯酸酯 例爲（甲基）丙烯酸甲酯、（甲基）丙烯酸乙 )丙烯酸丙酯、（甲基）丙烯酸丁酯等。亦即 中所謂的低級（甲基）丙烯酸酯爲具有碳數4 作爲酯交換基者。 酯交換反應之際，就反應時間短、高酯轉 後之後處理之觀點而言，對於含有乙烯基醚之 等量至過量使用低級（甲基）丙烯酸酯較佳。 通常相對於含有乙烯基醚之醇化合物所具有之 基二甲醇單 3基）。 之具體例舉 酯、（甲基 ，本說明書 以下之烷基 換率、反應 醇化合物以 具體而言， 羥基1莫耳 -9- 201029969 ，以1.0~20莫耳範圍使用丙烯酸酯較佳。低級（甲基） 丙烯酸酯之使用量相對於含有乙烯基醚之醇化合物之羥基 1莫耳，若未達1.0莫耳則反應無法充分進行，又若超過 20莫耳則反應後之濃縮步驟所需時間長，使生產性變差。 酯交換法所使用之觸媒舉例爲氫氧化鋰、氫氧化鈉、 氫氧化鉀等鹼金屬氫氧化物；碳酸鋰、碳酸鈉、碳酸鉀等 驗金屬碳酸化物；甲氧化鋰（lithium methoxide)、甲氧化 鈉、乙氧化鈉、第三丁氧化鉀等鹼金屬烷氧化物；醯胺鋰 @ 、醯胺鈉、醯胺鉀等鹼金屬醯胺；原鈦酸四甲酯、原鈦酸 四乙酯、原鈦酸四丙酯、原鈦酸四異丙酯、原鈦酸四丁酯 等之烷氧化鈦；其他烷氧化鋁；烷氧化錫等。其中就副反 應被極力的抑制，可於反應結束後藉添加水輕易去除之觀 點而言，以烷氧化鈦或烷氧化鋁較佳。 又，觸媒之使用量相對於低級（甲基）丙烯酸酯與含 有乙烯基醚之醇化合物之合計量，通常較好爲0.01〜5.0質 量％之範圍。觸媒量即使超過所需量以上亦幾乎不會影響 〇 反應速度，反而在去除觸媒時需要大量的水等，而不經濟 〇 本發明中之酯交換反應中，可添加、倂用習知之聚合 抑制劑。聚合抑制劑舉例爲例如氫醌、氫醌單甲基醚（亦 稱爲「甲氧苯酚」）等酚類；吩噻啶、伸乙基硫脲（ Ethylenethiourea)等硫化合物；二丁基二硫代胺基甲酸銅 等銅鹽；乙酸錳等錳鹽；硝基化合物、亞硝基化合物、4-羥基-2,2,6,6-四甲基哌啶氧基等之N-氧基化合物等。聚合 -10- 201029969 抑制劑之添加量相對於生成之酯以0.1質量％以下較佳。 超過〇· 1質量％時會有因添加劑造成著色之情況。 酯交換反應之際，較好吹入少量之分子狀氧以防止反 應中反應液聚合。分子狀氧較好以經稀釋之狀態使用，且 以使用空氣較適宜。另外，吹入分子狀氧亦較好以蒸發之 — 蒸氣存在，以抑制凝縮在上部之反應釜壁面等之（甲基） 丙烯酸酯類之聚合。 φ 所謂分子狀氧意指由兩個氧原子形成之基底態之三重 態氧分子（〇2) ’且意指以此狀態與反應直接相關，或藉由 觸媒與反應試劑之相互作用，轉變成單重態氧（Singlet oxygen)分子或氧原子、超氧化物、過氧化物等狀態後， 可與反應相關之氧分子。 分子狀氧之導入量亦受到反應機之形狀或攪拌動力之 影響，但相對於原料之含有乙烯基醚之醇1莫耳較好以 5~50〇1111/分（空氣爲2 5~2 5 0〇1111/分）之速度吹入較佳。分 φ 子狀氧之導入量未達5ml/分時，聚合抑制之效果不足，超 過5 00ml/分時，會使低級（甲基）丙烯酸酯押出於系統外 之不佳效果變強，導致作爲原料之低級（甲基）丙烯酸酯 之損失。 - 本發明中之酯交換反應較好在常壓或減壓下，於 60〜120°C下進行。溫度未達60°C時，反應速度極慢，又超 過120°C時，容易引起藉酯交換反應獲得之含有乙烯基醚 之（甲基）丙烯酸酯之聚合，且亦容易引起著色。 酯交換反應之形態可以熟悉本技藝者一般習知之製造 -11 - 201029969 (甲基）丙烯酸酯之方法進行。酯交換反應時，需要以低 級（甲基）丙烯酸酯及/或溶劑共沸餾除副生成之低級醇 。因此，使用例如加裝精餾塔之回流式反應槽作爲反應裝 置。 酯交換反應結束後，利用水使觸媒失活，且以濃縮裝 置餾除過剩之低沸點成份。以低沸點成份之濃縮裝置餾除 較好在常壓或減壓下，使液溫維持在9 0 °C以下進行，更好 在50〜70°C之範圍內進行。液溫超過90°C時，引起含有乙 @ 烯基醚之（甲基）丙烯酸酯之著色或聚合之可能性提高。 低沸點成份之餾除完成後之含有乙烯基醚之（甲基） 丙烯酸酯可藉由進行過濾去除掉殘留之失活觸媒等不溶份 。過濾時較好使用矽藻土等過濾助劑以有效去除不溶份。 接著，針對進行含有乙烯基醚之（甲基）丙烯酸酯之 脫乙烯基化反應，獲得（甲基）丙烯酸羥烷酯之方法加以 說明。 本發明係在酸觸媒存在下進行脫乙烯基化反應，可使 G 用之酸觸媒通常舉例爲硫酸、硫酸氫鈉、對甲苯磺酸、苯 擴酸、甲垸擴酸、固體酸（沸石、Amberlite、Amberlyst 、Nafion等）。又，使用之觸媒量相對於反應之含有乙烯 基醚之（甲基）丙烯酸酯較好爲〇.〇1質量％~1〇質量％， 更好爲0.1質量％〜5質量％。使用之觸媒量未達0.01質量 %時’反應性顯著下降，而有脫乙烯化反應極慢之情況。 又’超過10質量％時，除對反應速度幾乎不影響外，亦會 有產生雜質之顧慮。 -12- 201029969 本發明之脫乙烯基化反應之特徵爲在與水共存之下進 行。藉由與水共存之下進行，可容易地去除脫乙烯基化反 應時副生成之醛類。水之使用量以含有乙烯基醚之（甲基 )丙烯酸酯作爲基準，只要在等莫耳以上即無特別限制， 但較好以含有乙烯基醚之（甲基）丙烯酸酯作爲基準，使 ' 用兩倍莫耳以上以使反應加速進行。水以少於等莫耳之比 例下使用時，反應會在中途停止。 φ 本發明之脫乙烯基化反應爲放熱反應。此時，將反應 溫度控制在60°C以下，較好控制在〇°C〜40°C下，可獲得高 純度之（甲基）丙烯酸羥烷酯。控制反應溫度之方法舉例 爲使反應器冷卻之方法，或者將含有乙烯基醚之（甲基） 丙烯酸酯緩慢添加於觸媒水溶液中之方法。又，反應時雖 副生成乙醛，但藉由使系統內減壓可加速去除乙醛，可促 進反應進行。 脫乙烯基化反應結束後，自反應殘留液體分離去除水 Φ 層。此時，可例如單獨使用甲苯或二甲苯等溶劑或組合兩 種以上使用，以提高分離能。分離去除所獲得之水層之水 可做爲下次製造中之脫乙烯化反應共存之水再利用。 分離之有機層由於含有觸媒，因此可利用鹼中和分離 去除。鹼之例舉例爲例如氫氧化鉀、氫氧化鈉、碳酸鉀、 碳酸鈉、碳酸氫鉀、碳酸氫鈉等鹼金屬、鹼土類金屬之氫 氧化物或鹽。該等較好以水溶液使用，且於中和後分離去 除後使用之方法。 中和後，以水或中性鹽水溶液洗淨去除過量之鹼後， -13- 201029969 藉濃縮使過量之水分餾除或在使用溶劑之情況下使溶劑餾 除。濃縮較好在常壓或減壓下，使液溫維持在9 0 °C以下進 行，更好在50°C~80°C之範圍內進行。液溫超過90°C時， 引起（甲基）丙烯酸羥烷酯之著色或聚合之可能性變高。 濃縮後可藉由進行過濾去除殘留之中和鹽等不溶份。 過濾時較好使用矽藻土等過濾助劑以有效地去除不溶份。 本發明之（甲基）丙烯酸羥烷酯之製造方法由於在脫 乙烯基化反應之際使用水，由於可獲得高純度之（甲基） © 丙烯酸羥烷酯，因此不需要蒸餾等純化步驟。 實施例 以下列舉實施例更具體說明本發明，但本發明並不受 該等之限制。 [實施例1] (甲基丙烯酸乙烯基氧基丁酯之合成） 將1000克之4-羥基丁基乙烯基醚（九善石油化學製 造之HBVE) 、3000克之甲基丙烯酸甲酯、0.65克之甲氧 苯酚饋入4升之四頸圓底分離燒瓶中，且設置精餾塔（15 段）、攪拌機、空氣導入管、溫度計。在攪拌下一邊以 100ml/分導入乾燥空氣一邊開始加熱，使回流時燒瓶內之 液溫維持在751之方式，且將壓力調整成40kPa左右，去 除系統內之水分。系統內之水分確認爲300ppm以下後， 加入8.6克之四異丙氧化鈦作爲觸媒，使反應溫度成爲95 -14- 201029969 ±5°C，且將燒瓶內壓力控制在60kPa左右。監控加熱回流 時精餾塔上部之溫度（塔頂溫度）時，由於與生成之甲醇 與甲基丙烯酸甲酯之共沸溫度相近，因此調節回流比使塔 頂溫度成爲60°C左右，使甲醇作爲與甲基丙烯酸甲酯之共 沸物餾除進行反應。 反應經過4小時後由於塔頂溫度開始上升，因此緩慢 的提高回流比使反應繼續進行。以氣體層析分析反應5小 φ 時之反應液體後，由於酯轉換率爲99.2%，因而結束反應 。使反應液體冷卻，使液溫成爲75 °C後添加250克之17 質量％食鹽水使觸媒水解。靜置1 5分鐘後，藉由傾析將有 機層取入梨型燒瓶中，使用旋轉蒸發器減壓餾除過量之甲 基丙烯酸甲酯，以抽氣過濾使梨型燒瓶內之液體過濾，獲 得1522克標的之甲基丙烯酸乙烯基氧基丁酯。 (甲基丙烯酸4-羥基丁酯之合成） φ 將16克之對甲苯磺酸、2 00克之純水饋入1升之四頸 分離燒瓶中，且設置攪拌機、溫度計、空氣導入管、附冷 卻阱之真空泵。將500克如上述般合成之甲基丙烯酸乙烯 基氧基丁酯緩慢添加於該燒瓶中。使系統內壓力成爲 20kPa，在攪拌下一邊自系統內去除生成之乙醛一邊使反 應進行。此時，一邊以冰水冷卻燒瓶一邊使反應溫度維持 在1 5~3 0°C。反應3小時後，以氣體層析儀分析之反應轉 換率幾乎爲100%，因此結束反應。於反應完成之液體中 注入1〇〇克甲苯、50克17質量％之食鹽水進行油水分離 201029969 ，且僅取出有機層（水層在實施例4中使用）。使用分液 漏斗，以70克之5質量％碳酸氫鈉水溶液洗淨有機層後， 以70克之1 7質量％食鹽水洗淨。將有機層傾析至梨型燒 瓶中，使用旋轉蒸發器減壓餾除過量之甲苯，且以抽氣過 濾進行過瀘，獲得3 95克標的之甲基丙烯酸4-羥基丁酯（ 產率 9 2.2 %，純度 9 9.1 % )。 [實施例2] φ (丙烯酸乙烯基氧基丁酯之合成） 將1000克之4-羥基丁基乙烯基醚（九善石油化學製 造之HBVE) 、3 00 0克之丙烯酸乙酯、0.65克之甲氧苯酚 饋入4升之四頸圓底分離燒瓶中，且設置精餾塔（15段） 、攪拌機、空氣導入管、溫度計。在攪拌下一邊以l〇〇ml/ 分導入乾燥空氣一邊開始加熱，使回流時燒瓶內之液溫維 持在75 °C之方式將壓力調整至4 0kP a左右，去除系統內之 水分。系統內之水份確認爲 300ppm以下之後，加入 8.6 ❹ 克之四異丙氧化鈦作爲觸媒，使反應溫度成爲95±5°C ’且 將燒瓶內壓力控制在60kPa左右。監控加熱回流時精餾塔 上部之溫度（塔頂溫度）時，由於與生成之甲醇與丙烯酸 乙酯之共沸溫度相近，因此調節回流比使塔頂溫度成爲 70 °C左右，使甲醇作爲與甲基丙烯酸甲酯之共沸物餾除而 進行反應。 反應經過4小時後由於塔頂溫度開始上升’因此緩慢 的提高回流比使反應繼續進行。以氣體層析分析反應5小 -16 - 201029969 時之反應液體，由於酯轉換率爲99·0%，因而結束反應。 使反應液體冷卻，使液溫成爲75°c後添加250克之17質 量％食鹽水使觸媒水解。靜置1 5分鐘後，將有機層傾析至 梨型燒瓶中，且使用旋轉蒸發器減壓飽除過量之丙稀酸乙 酯，且以抽氣過濾使梨型燒瓶內之液體過濾’獲得1376 ' 克標的之丙烯酸乙烯基氧基丁酯。 _ (丙烯酸4-羥基丁酯之合成） 將16克之對甲苯磺酸、200克之純水饋入1升之四頸 分離燒瓶中，且設置攪拌機、溫度計、空氣導入管、附冷 卻阱之真空栗。將500克如上述合成之丙烯酸乙烯基氧基 丁酯緩慢添加於該燒瓶中。使系統內壓力成爲2 0kPa，在 攪拌下一邊自系統內去除生成之乙醛一邊進行反應。此時 ，一邊以冰水冷卻燒瓶一邊使反應溫度維持在15〜30 °C。 反應3小時後，以氣體層析儀分析之反應轉換率幾乎爲 φ 99·9%，因此結束反應。於反應完成之液體中注入200克 甲苯、50克17質量％之食鹽水進行油水分離，且僅取出 有機層。使用分液漏斗，以70克之5質量％碳酸氫鈉水溶 液洗淨有機層後，以70克之17質量％食鹽水洗淨。將有 - 機層傾析至梨型燒瓶中，且使用旋轉蒸發器減壓餾除過量 之甲苯，且以抽氣過濾進行過濾，獲得3 89克標的之丙烯 酸4-羥基丁酯（產率92.0%，純度99.0%)。 [實施例3] -17- 201029969 (環己烷二甲醇乙烯基醚甲基丙烯酸酯之合成） 將3 00克之環己烷二甲醇單乙烯基醚（九善石油化學 製造之CHMVE) 、600克之甲基丙烯酸甲酯、0.20克之 甲氧苯酚饋入1升之四頸圓底燒瓶中，且設置精餾塔（15 段）、攪拌機、空氣導入管、溫度計。在攪拌下一邊以 100ml/分導入乾燥空氣一邊開始加熱，使回流時燒瓶內之 液溫維持在75 °C之方式，將壓力調整成4 0kP a左右，去除 系統內之水分。系統內之水分確認爲300ppm以下後，加 ❹ 入2.6克之四異丙氧化鈦作爲觸媒，使反應溫度成爲95± 5°C之方式，將燒瓶內壓力控制在60kPa左右。監控加熱 回流時精餾塔上部之溫度（塔頂溫度）時，由於與生成之 甲醇與甲基丙烯酸甲酯之共沸溫度相近，因此調節回流比 使塔頂溫度成爲60°C左右，使甲醇作爲與甲基丙烯酸甲酯 之共沸物餾除並進行反應。 反應經過2小時後由於塔頂溫度開始上升，因此緩慢 的提高回流比並繼續進行反應。以氣體層析分析反應3小 〇 時之反應液體，由於酯轉換率爲99.4% ’因而結束反應。 使反應液體冷卻，使液溫成爲75 °C後添加1〇〇克之17質 量％食鹽水使觸媒水解。靜置1 5分鐘後，將有機層傾析至 梨型燒瓶中，且使用旋轉蒸發器減壓餾除過量之甲基丙烯. 酸甲酯，且以抽氣過濾使梨型燒瓶內之液體過濾，獲得 385克標的之環己烷二甲醇乙烯基醚甲基丙烯酸酯。 (環己烷二甲醇單甲基丙烯酸酯之合成） -18- 201029969 將6.4克之對甲苯磺酸、80克之純水饋入500毫升之 四頸分離燒瓶中，且設置攪拌機、溫度計、空氣導入管、 附冷卻阱之真空泵。將200克如上述般合成之環己烷二甲 醇乙烯基醚甲基丙烯酸酯緩慢添加於該燒瓶中。使系統內 壓力成爲20kPa，在攪拌下一邊自系統內去除生成之乙醛 ' 一邊進行反應。此時，一邊以冰水冷卻燒瓶一邊使反應溫 度維持在15〜3 (TC。反應2小時後，以氣體層析儀分析之 ❹ 反應轉換率幾乎爲99.9%，因此結束反應。於反應完成之 液體中注入8 0克甲苯、3 0克1 7質量％之食鹽水進行油水 分離，且僅取出有機層。使用分液漏斗，以20克之5質 量％碳酸氫鈉水溶液洗淨有機層後，以3 0克之1 7質量％ 食鹽水洗淨。將有機層倒入梨型燒瓶中，且使用旋轉蒸發 器減壓餾除過量之甲苯，且以抽氣過濾進行過濾，獲得 163克標的之環己烷二甲醇單甲基丙烯酸酯（產率91.5% ，純度 99.4% )。 ❹ [實施例4] (藉由水再利用製造甲基丙烯酸4-羥基丁酯之方法） 將實施例1中反應後分離之水層（全量）饋入1升四 • 頸分液燒瓶中，且設置攪拌機、溫度計、空氣導入管、附201029969 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a process for producing a hydroxyalkyl (meth)acrylate using an alcohol containing a vinyl ether. [Prior Art] The main method for producing a hydroxyalkyl (meth) acrylate is usually a method in which a diol, a monoester or a diester mixture is obtained by esterification of an alkane diol to extract a monoester. Specifically, a method of reacting acrylic acid with an alkanediol in the presence of a strong acid has been proposed (for example, refer to Patent Document 1), but there are disadvantages such as generation of by-products due to strong acid and a decrease in yield. A method for solving this problem has been reported for the transesterification reaction of an alkanediol with a (meth) acrylate (for example, refer to Patent Documents 2 to 4). Further, a method of efficiently extracting and purifying 4-hydroxybutyl (meth)acrylate has been reported (for example, refer to Patent Documents 5 to 6). However, since the transesterification method from the alkanediol is a mixture because of the obtained product, an excessive extraction solution is required to separate only the monoester, which is not efficient. A method for obtaining a hydroxyalkyl (meth) acrylate in two stages has been reported to have a method of devinylation of an alcohol containing a vinyl ether in the presence of an acid catalyst and an alcohol (for example, refer to the patent document). 7). However, in the devinylation reaction, it is necessary to remove the aldehyde compound due to the generation of the aldehyde compound, but the operation of removing the aldehyde compound in the reaction is not easy. In addition, the alcohol used in excess during the reaction must be removed by water washing and discarded without being efficient. -5 - 201029969 Patent Document 1: German Patent No. 1 5 1 1 8 5 7 2 2 Patent Document 2: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. [Patent Document 6: JP-A-2005-194201] [Patent Document 6: JP-A-2005-194201] [Patent Document 7] [Problems to be Solved by the Invention] An object of the present invention is to provide a process for producing a hydroxyalkyl (meth)acrylate which can efficiently produce a complicated purification step. [Means for Solving the Problem] As a result of various reviews, the present inventors have found that by (meth)acrylating an alcohol containing an ethyl ether ether into a (methyl anthracene) acrylate containing a vinyl ether In the presence of an acid catalyst, the de-ethylation method coexisting with water can obtain a high-purity hydroxyalkyl (meth) acrylate in a high yield, and the aqueous layer separated and recovered after de-ethylation can be reused. In other words, the present invention is as follows: - (1) A method for producing a hydroxyalkyl (meth) acrylate, characterized in that a vinyl ether-containing alcohol is (meth) acrylated to contain ethylene by a transesterification method After the (meth) acrylate of the ether group, water is allowed to coexist when the devinylation reaction is carried out in the presence of an acid catalyst. -6-201029969 (2) A method for producing a hydroxyalkyl (meth) acrylate according to the above (i), wherein the reaction temperature in the devinylation reaction is 60 ° C or lower. (3) The method for producing a hydroxyalkyl (meth) acrylate according to the above (1) or (2), wherein the vinyl ether-containing alcohol is represented by the following formula (I) or (II): 1] General formula ω (in the general formula (I), η represents an integer of 3 to 11) [Chemical 2] octagonal octagonal Formula (Π) (In the formula (II), A represents a cyclopentyl group or a stretch Cyclohexyl). The present application claims priority based on the prior Japanese Patent Application of the Applicant, which is hereby incorporated by reference in its entirety, the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire all all all all all all [Effect of the Invention] According to the present invention, since the hydroxyalkyl (meth) acrylate can be efficiently obtained without undergoing a complicated purification step -7 to 201029969 such as distillation, the water used in the devinylation step can be further used. Utilizing, it is therefore possible to provide a method for producing a hydroxyalkyl (meth) acrylate in a short and economical manner. [Embodiment] An embodiment of a method for producing a hydroxyalkyl (meth) acrylate of the present invention will be described in detail. The method for producing a hydroxyalkyl (meth) acrylate of the present invention is characterized in that: after the (meth) acrylate of a vinyl ether-containing alcohol is converted into a vinyl ether-containing (meth) acrylate by a transesterification method It coexists with water at the time of devinylation in the presence of an acid catalyst. In the present invention, first, a hydroxyl group-containing alcohol hydroxy group is esterified to obtain a vinyl ether-containing (meth) acrylate. The esterification method is mainly a dehydration esterification method using (meth)acrylic acid, a transesterification method using a lower (meth) acrylate, and a hydrazine halogen method using a (meth) propylene hydride halide, wherein dehydration esterification is used. The method uses an acid catalyst and cannot be applied to the simultaneous introduction of vinyl. Further, since the hydrazine halogen method is left in the system by detaching the halogen by the reaction, purification treatment such as water washing, adsorption, or distillation is required. On the other hand, since the transesterification method requires little impurities and no purification operation, the present invention employs a transesterification method. The vinyl ether-containing alcohol used in the present invention is exemplified by, for example, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 9-hydroxydecyl vinyl ether, 10-hydroxydecyl vinyl ether, 12 a compound represented by the following formula (I): a compound represented by the following formula (I); a compound represented by the following formula (11): cyclohexanedimethanol monovinyl-8 - 201029969 alkyl ether; Ether and the like. [Chemical Formula 3] ^〇^〇Η Formula 1 (In the formula (I), '11 is not an integer from 3 to 11) [Chemical 4] #0 八Α^ΟΗ Formula (Π) (Formula (Π) Wherein 'Α denotes a cyclopentyl or exocyclic oxime. The lower (meth) acrylate used in the transesterification process is methyl (meth) acrylate, propyl (meth) acrylate acrylate, (methyl) Butyl acrylate and the like. That is, the so-called lower (meth) acrylate is a one having a carbon number of 4 as a transesterification group. In the case of the transesterification reaction, it is preferred to use the lower (meth) acrylate in an equivalent amount to the excess of the vinyl ether from the viewpoint of a short reaction time and a high post-ester conversion treatment. It is usually based on the bis-methanol monomethyl group of the vinyl ether-containing alcohol compound. Specific examples thereof include esters, (methyl groups, alkyl group conversion ratios below the specification, and reactive alcohol compounds, specifically, hydroxyl group 1 - 9 - 19929969, preferably acrylates in the range of 1.0 to 20 moles. The amount of (meth) acrylate used is 1 mol relative to the hydroxyl group of the vinyl ether-containing alcohol compound. If it is less than 1.0 mol, the reaction cannot be sufficiently carried out. If it exceeds 20 mol, the concentration step after the reaction is required. The long time is, and the productivity is deteriorated. The catalyst used in the transesterification method is an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; and a metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate. ; alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, potassium butoxide; alkali metal amides such as lithium guanidinium, sodium amide, potassium amide; Alkyl titanium oxide such as tetramethyl ester, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetraisopropyl orthotitanate, tetrabutyl orthotitanate; other alkane alumina; alkoxy tin oxide, etc. The side reaction is suppressed to the utmost, after the reaction is over. From the viewpoint of easily removing water, it is preferred to use a titanium alkoxide or an alkane oxide. Further, the amount of the catalyst used is generally higher than the total amount of the lower (meth) acrylate and the vinyl ether-containing alcohol compound. It is preferably in the range of 0.01 to 5.0% by mass. Even if the amount of the catalyst exceeds the required amount, the reaction rate is hardly affected, and a large amount of water or the like is required in the removal of the catalyst, and the transesterification in the present invention is uneconomical. In the reaction, a conventional polymerization inhibitor may be added or used. Examples of the polymerization inhibitor are phenols such as hydroquinone or hydroquinone monomethyl ether (also referred to as "methoxyphenol"); phenothiazine and ethylidene a sulfur compound such as thiourea (Ethylenethiourea); a copper salt such as copper dibutyldithiocarbamate; a manganese salt such as manganese acetate; a nitro compound, a nitroso compound, 4-hydroxy-2,2,6,6- N-oxyl compound such as tetramethylpiperidinyloxy group, etc. Polymerization-10-201029969 The amount of the inhibitor added is preferably 0.1% by mass or less based on the ester to be produced. Cause the coloring. At the time of the transesterification reaction, It is good to blow a small amount of molecular oxygen to prevent the reaction liquid from polymerizing in the reaction. Molecular oxygen is preferably used in a diluted state, and it is preferable to use air. In addition, molecular oxygen is preferably blown off by evaporation - vapor There is a polymerization to inhibit the condensation of (meth) acrylates on the wall surface of the reactor wall, etc. φ. Molecular oxygen means a triplet oxygen molecule (〇2) in a ground state formed by two oxygen atoms. It means that the state is directly related to the reaction, or by the interaction of the catalyst and the reaction reagent, it is converted into a singlet oxygen molecule, an oxygen atom, a superoxide, a peroxide, etc. Related oxygen molecules. The amount of molecular oxygen introduced is also affected by the shape of the reactor or the stirring power, but the alcohol containing alcohol ether is preferably 5 to 50 〇 1111 / min relative to the raw material (air is The speed of 2 5~2 5 0〇1111/min) is better. When the amount of introduction of φ sub-form oxygen is less than 5 ml/min, the effect of polymerization inhibition is insufficient, and when it exceeds 500 ml/min, the effect of lowering the (meth) acrylate to the outside of the system becomes stronger, resulting in Loss of the lower (meth) acrylate of the raw material. - The transesterification reaction in the present invention is preferably carried out at 60 to 120 ° C under normal pressure or reduced pressure. When the temperature is less than 60 ° C, the reaction rate is extremely slow, and when it exceeds 120 ° C, polymerization of a vinyl ether-containing (meth) acrylate obtained by a transesterification reaction is liable to occur, and coloring is also likely to occur. The morphology of the transesterification reaction can be carried out by a method known in the art for the manufacture of -11 - 201029969 (meth) acrylate. In the transesterification reaction, it is necessary to azeotropically distill off the by-produced lower alcohol with a lower (meth) acrylate and/or a solvent. Therefore, for example, a reflux type reaction tank to which a rectification column is installed is used as a reaction device. After the end of the transesterification reaction, the catalyst is deactivated by water, and the excess low boiling point component is distilled off by a concentration apparatus. The distillation is carried out by a concentrating device having a low boiling point component, preferably at a normal pressure or a reduced pressure, and the liquid temperature is maintained at 90 ° C or lower, more preferably in the range of 50 to 70 ° C. When the liquid temperature exceeds 90 ° C, the possibility of coloring or polymerization of the (meth) acrylate containing ethyl b-alkenyl ether is increased. The vinyl ether-containing (meth) acrylate after completion of the distillation of the low-boiling component can be removed by filtration to remove residual insoluble catalyst or the like. When filtering, it is preferred to use a filter aid such as diatomaceous earth to effectively remove insoluble matters. Next, a method of obtaining a hydroxyalkyl (meth) acrylate by performing a devinylation reaction of a vinyl ether-containing (meth) acrylate will be described. In the present invention, the devinylation reaction is carried out in the presence of an acid catalyst, and the acid catalyst for G can be generally exemplified by sulfuric acid, sodium hydrogen sulfate, p-toluenesulfonic acid, benzene acid expansion, formazan acid expansion, solid acid ( Zeolite, Amberlite, Amberlyst, Nafion, etc.). Further, the amount of the catalyst to be used is preferably from 质量1% by mass to 1% by mass, more preferably from 0.1% by mass to 5% by mass based on the (meth) acrylate containing the vinyl ether. When the amount of the catalyst used is less than 0.01% by mass, the reactivity is remarkably lowered, and the de-vinylation reaction is extremely slow. Further, when it exceeds 10% by mass, there is a concern that impurities are generated, and there is little influence on the reaction rate. -12- 201029969 The devinylation reaction of the present invention is characterized by being carried out in the presence of water. The aldehyde formed by the devinylation reaction can be easily removed by coexistence with water. The amount of water used is based on a (meth) acrylate containing a vinyl ether, and is not particularly limited as long as it is equal to or higher than the molar amount, but it is preferably based on a (meth) acrylate containing a vinyl ether. Use twice the molar amount to accelerate the reaction. When the water is used in a ratio of less than the molar ratio, the reaction will stop in the middle. φ The devinylation reaction of the present invention is an exothermic reaction. At this time, the reaction temperature is controlled to be 60 ° C or lower, preferably controlled at 〇 ° C to 40 ° C to obtain a highly pure hydroxyalkyl (meth) acrylate. The method of controlling the reaction temperature is exemplified by a method of cooling the reactor or a method of slowly adding a vinyl ether-containing (meth) acrylate to an aqueous solution of a catalyst. Further, although acetaldehyde is produced by-product during the reaction, the reaction can be accelerated by accelerating the removal of acetaldehyde by decompression in the system. After the devinylation reaction is completed, the water Φ layer is separated from the residual liquid of the reaction. In this case, for example, a solvent such as toluene or xylene or a combination of two or more kinds may be used alone to improve the separation energy. Separating and removing the water of the obtained aqueous layer can be reused as water coexisting in the de-ethyleneation reaction in the next production. The separated organic layer contains a catalyst and can be removed by neutralization and separation. Examples of the base are, for example, an alkali metal such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate or sodium hydrogencarbonate, or a hydroxide or salt of an alkaline earth metal. These are preferably used in the form of an aqueous solution and are used after separation after neutralization. After neutralization, after washing with water or a neutral saline solution to remove excess alkali, -13-201029969 distills off excess water or distills off the solvent using a solvent. The concentration is preferably carried out under normal pressure or reduced pressure to maintain the liquid temperature below 90 °C, more preferably in the range of 50 °C to 80 °C. When the liquid temperature exceeds 90 ° C, the possibility of coloring or polymerization of the hydroxyalkyl (meth) acrylate is increased. After concentration, the residue and the insoluble matter such as salt can be removed by filtration. When filtering, it is preferred to use a filter aid such as diatomaceous earth to effectively remove insoluble matters. In the method for producing a hydroxyalkyl (meth) acrylate of the present invention, since water is used in the devinylation reaction, since a high-purity (meth) hydroxyalkyl acrylate can be obtained, a purification step such as distillation is not required. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. [Example 1] (Synthesis of vinyloxybutyl methacrylate) 1000 g of 4-hydroxybutyl vinyl ether (HBVE manufactured by Jiushan Petrochemical Co., Ltd.), 3000 g of methyl methacrylate, and 0.65 g of a Oxyphenol was fed into a 4-liter four-neck round bottom separation flask, and a rectification column (15 stages), a stirrer, an air introduction tube, and a thermometer were placed. Heating was started while introducing dry air at 100 ml/min with stirring, and the liquid temperature in the flask was maintained at 751 during the reflux, and the pressure was adjusted to about 40 kPa to remove moisture in the system. After the moisture in the system was confirmed to be 300 ppm or less, 8.6 g of tetraisopropoxide was added as a catalyst to adjust the reaction temperature to 95 -14 to 201029969 ±5 ° C, and the pressure in the flask was controlled to about 60 kPa. When the temperature at the top of the rectification column (top temperature) during heating and reflux is monitored, since the azeotropic temperature of the produced methanol and methyl methacrylate is similar, the reflux ratio is adjusted so that the temperature at the top of the column becomes about 60 ° C to make methanol. The reaction is carried out as an azeotrope distillation with methyl methacrylate. After the reaction for 4 hours, since the temperature at the top of the column began to rise, the reflux ratio was slowly increased to allow the reaction to proceed. After the reaction liquid at a reaction time of 5 φ was analyzed by gas chromatography, the reaction was terminated because the ester conversion rate was 99.2%. The reaction liquid was allowed to cool, and the liquid temperature was changed to 75 ° C, and then 250 g of 17 mass% saline was added to hydrolyze the catalyst. After standing for 15 minutes, the organic layer was taken into a pear-shaped flask by decantation, excess methyl methacrylate was distilled off under reduced pressure using a rotary evaporator, and the liquid in the pear-shaped flask was filtered by suction filtration. 1522 g of the standard vinyl butyl methacrylate was obtained. (Synthesis of 4-hydroxybutyl methacrylate) φ 16 g of p-toluenesulfonic acid and 200 g of pure water were fed into a 1-liter four-necked separation flask, and a stirrer, a thermometer, an air introduction tube, and a cooling trap were provided. Vacuum pump. 500 g of vinyl butyl methacrylate synthesized as described above was slowly added to the flask. The pressure in the system was changed to 20 kPa, and the reaction was carried out while removing the generated acetaldehyde from the system while stirring. At this time, the reaction temperature was maintained at 15 to 30 ° C while cooling the flask with ice water. After the reaction for 3 hours, the reaction conversion rate analyzed by a gas chromatograph was almost 100%, so the reaction was terminated. To the liquid in which the reaction was completed, 1 g of toluene and 50 g of 17 mass% of saline were injected for oil-water separation 201029969, and only the organic layer was taken out (the aqueous layer was used in Example 4). The organic layer was washed with 70 g of a 5 mass% sodium hydrogencarbonate aqueous solution using a separatory funnel, and then washed with 70 g of a 7 mass% saline solution. The organic layer was decanted into a pear-shaped flask, and excess toluene was distilled off under reduced pressure using a rotary evaporator, and filtered under suction to obtain 3 95 g of 4-hydroxybutyl methacrylate (yield 9). 2.2%, purity 9 9.1 %). [Example 2] φ (synthesis of vinyl butyl acrylate) 1000 g of 4-hydroxybutyl vinyl ether (HBVE manufactured by Jiushan Petrochemical Co., Ltd.), 300 g of ethyl acrylate, and 0.65 g of methoxy Phenol was fed into a 4-liter four-neck round bottom separation flask, and a rectification column (15 stages), a stirrer, an air introduction tube, and a thermometer were placed. Heating was started while introducing dry air at l〇〇ml/min with stirring, and the pressure in the flask was maintained at 75 °C while refluxing, and the pressure was adjusted to about 40 kPa, and the moisture in the system was removed. After the water content in the system was confirmed to be 300 ppm or less, 8.6 g of tetraisopropoxide as a catalyst was added to make the reaction temperature 95 ± 5 ° C ' and the pressure in the flask was controlled to about 60 kPa. When monitoring the temperature at the top of the rectification column (top temperature) during heating and reflux, the azeotropic temperature of methanol and ethyl acrylate is similar, so the reflux ratio is adjusted to about 70 °C, so that methanol acts as The reaction is carried out by distilling off the azeotrope of methyl methacrylate. After the reaction was carried out for 4 hours, the temperature at the top of the column began to rise. Therefore, the reflux ratio was slowly increased to allow the reaction to proceed. The reaction liquid at a reaction time of 5 -16 - 201029969 was analyzed by gas chromatography, and the reaction was terminated because the ester conversion rate was 99. 0%. The reaction liquid was allowed to cool, and the liquid temperature was changed to 75 ° C, and then 250 g of 17 mass% saline was added to hydrolyze the catalyst. After standing for 15 minutes, the organic layer was decanted into a pear-shaped flask, and excess ethyl acrylate was saturated under reduced pressure using a rotary evaporator, and the liquid in the pear-shaped flask was filtered by suction filtration to obtain 1376' gram of vinyl butyl acrylate. _ (Synthesis of 4-hydroxybutyl acrylate) 16 g of p-toluenesulfonic acid and 200 g of pure water were fed into a 1-liter four-necked separation flask, and a mixer, a thermometer, an air introduction tube, and a vacuum pump with a cooling trap were placed. . 500 g of vinyl butyl acrylate synthesized as described above was slowly added to the flask. The pressure in the system was changed to 20 kPa, and the reaction was carried out while removing the generated acetaldehyde from the system while stirring. At this time, the reaction temperature was maintained at 15 to 30 ° C while cooling the flask with ice water. After the reaction for 3 hours, the reaction conversion rate analyzed by a gas chromatograph was almost φ 99.9%, and thus the reaction was terminated. 200 g of toluene and 50 g of 17 mass% of saline were poured into the liquid in which the reaction was completed to carry out oil-water separation, and only the organic layer was taken out. The organic layer was washed with 70 g of a 5% by mass aqueous sodium hydrogencarbonate solution using a separatory funnel, and then washed with 70 g of 17 mass% saline. The organic layer was decanted into a pear-shaped flask, and excess toluene was distilled off under reduced pressure using a rotary evaporator, and filtered by suction filtration to obtain 3 89 g of 4-hydroxybutyl acrylate (yield 92.0). %, purity 99.0%). [Example 3] -17- 201029969 (Synthesis of cyclohexanedimethanol vinyl ether methacrylate) 300 g of cyclohexanedimethanol monovinyl ether (CHMVE manufactured by Jiushan Petrochemical Co., Ltd.), 600 g Methyl methacrylate and 0.20 g of methoxyphenol were fed into a 1-liter four-necked round bottom flask, and a rectification column (15 stages), a stirrer, an air introduction tube, and a thermometer were placed. Heating was started while introducing dry air at 100 ml/min with stirring, and the liquid temperature in the flask was maintained at 75 °C during the reflux, and the pressure was adjusted to about 40 kPa to remove moisture in the system. After the water content in the system was confirmed to be 300 ppm or less, 2.6 g of tetraisopropoxide was added as a catalyst, and the reaction temperature was changed to 95 ± 5 ° C, and the pressure in the flask was controlled to about 60 kPa. When the temperature at the top of the rectification column (top temperature) during heating and reflux is monitored, since the azeotropic temperature of the produced methanol and methyl methacrylate is similar, the reflux ratio is adjusted so that the temperature at the top of the column becomes about 60 ° C to make methanol. It is distilled off as an azeotrope with methyl methacrylate and reacted. After the reaction was carried out for 2 hours, since the temperature at the top of the column began to rise, the reflux ratio was slowly increased and the reaction was continued. The reaction liquid at the time of reaction of 3 hours was analyzed by gas chromatography, and the reaction was terminated because the ester conversion rate was 99.4%. The reaction liquid was allowed to cool, and the liquid temperature was changed to 75 ° C, and then 1 gram of 17 mass% saline was added to hydrolyze the catalyst. After standing for 15 minutes, the organic layer was decanted into a pear-shaped flask, and excess methyl methacrylate was distilled off under reduced pressure using a rotary evaporator, and the liquid in the pear-shaped flask was filtered by suction filtration. 385 g of the title cyclohexane dimethanol vinyl ether methacrylate was obtained. (Synthesis of cyclohexanedimethanol monomethacrylate) -18- 201029969 6.4 g of p-toluenesulfonic acid and 80 g of pure water were fed into a 500 ml four-necked separation flask, and a stirrer, a thermometer, and an air introduction tube were set. , a vacuum pump with a cooling trap. 200 g of cyclohexanedimethylol vinyl ether methacrylate synthesized as described above was slowly added to the flask. The pressure in the system was changed to 20 kPa, and the reaction was carried out while removing the generated acetaldehyde from the system while stirring. At this time, the reaction temperature was maintained at 15 to 3 (TC after cooling the flask with ice water. After the reaction for 2 hours, the reaction conversion rate was almost 99.9% after analysis by a gas chromatograph, and the reaction was terminated. 80 g of toluene and 30 g of 17% by mass of saline were poured into the liquid to separate the oil and water, and only the organic layer was taken out. After washing the organic layer with 20 g of a 5 mass% sodium hydrogencarbonate aqueous solution using a separatory funnel, 30 g of 1 7 mass% was washed with saline. The organic layer was poured into a pear-shaped flask, and excess toluene was distilled off under reduced pressure using a rotary evaporator, and filtered by suction filtration to obtain 163 g of the target ring. Alkanediethanol monomethacrylate (yield 91.5%, purity 99.4%). 实施 [Example 4] (Method for producing 4-hydroxybutyl methacrylate by water reuse) After the reaction in Example 1 The separated aqueous layer (full amount) is fed into a 1 liter four-necked liquid separation flask, and a mixer, thermometer, air introduction tube, and attached
• 冷卻阱之真空泵。將500克實施例1中合成之甲基丙烯酸 乙烯基氧基丁酯緩慢添加於該燒瓶中。使系統內壓力成爲 2 OkP a，在攪拌下一邊自系統內去除生成之乙醛一邊進行 反應。此時’以冰水冷卻燒瓶使反應溫度維持在15~ 3 (TC -19 - 201029969 。反應3小時後’以氣體層析儀分析之反應轉換率幾乎爲 99.9%，因此結束反應。於反應完成之液體中注入1 〇〇克 甲苯進行油水分離’且僅取出有機層。使用分液漏斗，以 70克之5質量％碳酸氫鈉水溶液洗淨有機層後’以70克 之17質量％食鹽水洗淨。將有機層倒入梨型燒瓶中，使用 旋轉蒸發器減壓餾除過量之甲苯’且以抽氣過濾進行過濾 ，獲得398克標的之甲基丙烯酸4 -羥基丁酯（產率92.8% ，純度 9 9.2 % )。 [實施例5] (反應溫度60t以上之情況製造甲基丙烯酸4-羥基丁酯之 方法） 將16克之對甲苯磺酸、200克之純水饋入1升之四頸 分離燒瓶中，且設置攪拌機、溫度計、空氣導入管、附冷 卻阱之真空泵。將500克實施例1中合成之甲基丙烯酸乙 烯基氧基丁酯一次添加於該燒瓶中後，立即使系統內之壓 @ 力成爲20kPa，在攪拌下一邊自系統內去除生成之乙醛一 邊進行反應。此時，燒瓶未經冷卻靜置後，反應溫度上升 至。反應3小時後，以氣體層析儀分析之反應轉換率 幾乎爲100%，因此結束反應。於反應完成之液體中注入 100克甲苯、50克之17質量％之食鹽水進行油水分離，且 · 僅取出有機層。使用分液漏斗，以70克之5質量％碳酸氫 鈉水溶液洗淨有機層後，以7 0克之1 7質量％食鹽水洗淨 。將有機層倒入梨型燒瓶中，使用旋轉蒸發器減壓餾除過 -20- 201029969 量之甲苯，且以抽氣過濾進行過瀘，獲得385克標的之甲 基丙烯酸羥基丁酯（產率89.9%，純度97.0%)。 據此，可了解反應溫度超過6(TC時，與實施例1相較 產率梢微下降。 * [比較例1] (在二醇共存下製造甲基丙烯酸4-羥基丁酯之方法） φ 將16克之對甲苯磺酸、2 00克之乙二醇饋入1升之四 頸分離燒瓶中，且設置攪拌機、溫度計、空氣導入管、附 冷卻阱之真空泵。將500克合成例1中合成之甲基丙烯酸 乙烯基氧基丁酯緩慢添加於該燒瓶中。使系統內之壓力成 爲20kPa，且在攪拌下一邊自系統內去除生成之乙縮醛， 一邊進行反應。此時，一邊以冰水使燒瓶冷卻一邊使反應 溫度維持在1 5〜3 0 °C。反應3小時後，以氣體層析儀分析 之反應轉換率爲78%。又，由於利用分析發現反應系統內 ❹ 殘留乙縮醛化合物，因此加熱至50°C繼續反應。由於開始 加熱1小時後之反應轉換率爲98.4%，因此結束反應。於 反應完成之液體中注入200克甲苯、150克之5質量％之 食鹽水進行油水分離，且僅取出有機層。使用分液漏斗， . 以70克之5質量％碳酸氫鈉水溶液洗淨有機層後，以70 * 克之17質量％食鹽水洗淨。將有機層倒入梨型燒瓶中，使 用旋轉蒸發器減壓餾除過量之甲苯，且以抽氣過濾進行過 濾，獲得3 95克標的之甲基丙烯酸4-羥基丁酯（產率 87.6%，純度 92.3% )。 -21 - 201029969 由以上之結果，在用以獲得（甲基） 脫乙烯基化反應之際，藉由共存水，可以高產率獲得局純 度的（甲基）丙烯酸羥烷酯。又，由實施例4可知脫乙稀 基化後分離回收之水層可在下次之製造中再利用於脫乙烯 基化反應。• Vacuum pump for cooling traps. 500 g of the vinyl butyl methacrylate synthesized in Example 1 was slowly added to the flask. The pressure in the system was changed to 2 OkPa, and the reaction was carried out while removing the generated acetaldehyde from the system while stirring. At this time, the flask was cooled with ice water to maintain the reaction temperature at 15~3 (TC -19 - 201029969. After 3 hours of reaction, the reaction conversion rate by gas chromatograph was almost 99.9%, so the reaction was terminated. Injecting 1 g of toluene into the liquid for oil-water separation' and taking out only the organic layer. Using a separatory funnel, washing the organic layer with 70 g of a 5 mass% sodium hydrogencarbonate aqueous solution, and then washing with 70 g of 17 mass% saline solution. The organic layer was poured into a pear-shaped flask, and excess toluene was distilled off under reduced pressure using a rotary evaporator, and filtered by suction filtration to obtain 398 g of 4-hydroxybutyl methacrylate (yield 92.8%). Purity: 9 9.2 %) [Example 5] (Method for producing 4-hydroxybutyl methacrylate at a reaction temperature of 60 t or more) 16 g of p-toluenesulfonic acid and 200 g of pure water were fed into a four-neck separation of 1 liter. A flask, a thermometer, an air introduction tube, and a vacuum pump with a cooling trap were placed in the flask. After 500 g of the vinyl butyl methacrylate synthesized in Example 1 was added to the flask at a time, immediately in the system. Pressure @ The reaction was carried out while removing 20 g of acetaldehyde from the system while stirring. At this time, the reaction temperature was raised until the flask was left uncooled. After 3 hours of reaction, the reaction conversion rate was analyzed by a gas chromatograph. It was almost 100%, so the reaction was terminated. 100 g of toluene and 50 g of 17 mass% of saline were poured into the liquid in the reaction to carry out oil-water separation, and only the organic layer was taken out. Using a separatory funnel, 70 g of 7% by mass After washing the organic layer with an aqueous solution of sodium hydrogencarbonate, it was washed with 70 g of a 7 mass% saline solution. The organic layer was poured into a pear-shaped flask, and toluene of -20-201029969 was distilled off under reduced pressure using a rotary evaporator. The mixture was filtered through suction to obtain 385 g of hydroxybutyl methacrylate (yield 89.9%, purity: 97.0%). Accordingly, it can be understood that the reaction temperature exceeds 6 (TC, compared with Example 1). The yield was slightly decreased. * [Comparative Example 1] (Method for producing 4-hydroxybutyl methacrylate in the presence of a diol) φ 16 g of p-toluenesulfonic acid and 200 g of ethylene glycol were fed into 1 liter. Four-neck separation flask with stirring Machine, thermometer, air introduction tube, vacuum pump with cooling trap. 500 g of vinyl butyl methacrylate synthesized in Synthesis Example 1 was slowly added to the flask. The pressure in the system was 20 kPa, and stirring was performed. The reaction was carried out while removing the produced acetal from the system. At this time, the reaction temperature was maintained at 15 to 30 ° C while cooling the flask with ice water. After 3 hours of reaction, the gas chromatograph was used. The reaction conversion rate of the analysis was 78%. Further, since the analysis revealed that the acetal compound remained in the reaction system, the reaction was continued by heating to 50 ° C. Since the reaction conversion rate after the start of heating for 1 hour was 98.4%, the end was completed. reaction. To the liquid in which the reaction was completed, 200 g of toluene and 150 g of 5% by mass of brine were poured to carry out oil-water separation, and only the organic layer was taken out. Using a separatory funnel, the organic layer was washed with 70 g of a 5 mass% sodium hydrogencarbonate aqueous solution, and then washed with 70 g of a 17 mass% saline solution. The organic layer was poured into a pear-shaped flask, and excess toluene was distilled off under reduced pressure using a rotary evaporator, and filtered by suction filtration to obtain 3 95 g of 4-hydroxybutyl methacrylate (yield 87.6%). The purity is 92.3%). -21 - 201029969 From the above results, in order to obtain a (meth) devinylation reaction, a local purity of hydroxyalkyl (meth)acrylate can be obtained in a high yield by coexisting water. Further, from Example 4, it is understood that the aqueous layer separated and recovered after de-ethylation can be reused in the de-vinylation reaction in the next production.
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