201144274 六、發明說明： 【發明所屬之技術領域】 本發明係關於使用含有乙烯醚之醇製造（甲基）丙@ 酸羥基烷基酯之方法。 【先前技術】 (甲基）丙烯酸羥基烷基酯之製造方法—般係以藉由 酯化反應，自烷二醇獲得二醇、單酯'二酯混合物後，僅 萃取分離單酯體之方法爲主流。具體而言，已報告有在強 酸存在下使（甲基）丙烯酸與院二醇反應之方法（參照例 如專利文獻1 )，但因強酸而產生副產物，而有收率降低 等之缺點。解決該問題之方法針對烷二醇與（甲基）丙烯 酸酯之酯交換反應已有各種報告（參照例如專利文獻2~4 )。另外，關於（甲基）丙烯酸4_羥基丁酯，亦提出有效 率萃取及純化之方法（參照例如專利文獻5〜6 )等。然而 ，自該等烷二醇之酯化反應獲得之產物由於爲二醇、單酯 、二酯之混合物，故需要過量的萃取溶劑及多階段之作業 步驟以僅分離出單酯，而無效率。 以兩階段獲得（甲基）丙烯酸羥基烷基酯之方法已報 告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（參照例如專利文獻7 )。然而，該 方法在脫乙烯化反應時由於會產生例如乙二醇甲基乙縮醛 等副產物，故有必要將其去除，但反應時過量使用之醇必 須利用水洗去除而丟棄，並無效率。 201144274 [先前技術文獻] [專利文獻] [專利文獻1]德國專利第1 5 1 1 8 5 72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8-53 392號公報 [專利文獻6]特開2005-194201號公報 [專利文獻7]特開平1 0- 1 825 55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複雜之純化步驟即 可有效率地製造髙純度之（甲基）丙烯酸羥基烷基酯之方 法。 [解決課題之手段] 本發明人等進行各種檢討之結果，發現使含有乙烯基 醚之醇經（甲基）丙烯酸酯化成爲含有乙烯基醚之（甲基 )丙烯酸酯後，在酸觸媒存在下，藉由使水共存進行之脫 乙烯化法，可有效率地獲得（甲基）丙烯酸羥基烷基酯。 另外’發現脫乙烯化反應時會以副產物產生乙縮醛二聚物 之化合物（二酯），但乙縮醛二聚物經脫乙烯化反應後藉 -6- 201144274 由加水而分解，可獲得高純度之（甲基）丙烯酸羥基烷基 酯。 亦即，本發明如下述。 (1) 一種（甲基）丙烯酸羥基烷基酯之製造方法， 其特徵爲含有利用酯交換法使含有乙烯基醚之醇經（甲基 )丙烯酸酯化成爲含有乙烯基醚之（甲基）丙烯酸酯，且 在酸觸媒及水的存在下，進行脫乙烯化反應後，再添加水 進行脫縮醛化反應之步驟。 (2) 如前述（1)所述之（甲基）丙烯酸羥基烷基酯 之製造方法，其係在使反應系統內之壓力成爲2〇〜40kPa以 進行脫乙烯化反應後，在10kPa以下進行脫縮醛化反應。 (3) 如前述（1)或（2)所述之（甲基）丙烯酸羥 基烷基酯之製造方法，其中含有乙烯基醚之醇係以下述通 式（I)或（Π)表示·· 【化1】201144274 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing a (meth)propionic acid hydroxyalkyl ester using an alcohol containing a vinyl ether. [Previous Art] A method for producing a hydroxyalkyl (meth) acrylate is generally a method for extracting and separating a monoester by obtaining an diol, a monoester 'diester mixture from an alkanediol by an esterification reaction. For the mainstream. Specifically, a method of reacting (meth)acrylic acid with a diol in the presence of a strong acid (see, for example, Patent Document 1) has been reported, but by-products are generated by strong acid, and there are disadvantages such as a decrease in yield. A method for solving this problem has been reported for the transesterification reaction of an alkanediol with a (meth) acrylate (see, for example, Patent Documents 2 to 4). Further, regarding 4-hydroxybutyl (meth)acrylate, a method of efficient extraction and purification (see, for example, Patent Documents 5 to 6) has been proposed. However, since the product obtained from the esterification reaction of the alkanediols is a mixture of diols, monoesters and diesters, an excessive extraction solvent and a multi-stage working procedure are required to separate only the monoester, and the inefficiency . A method of obtaining a hydroxyalkyl (meth) acrylate in two stages has been reported as a method of devinylating an alcohol having a vinyl ether after transesterification in the presence of an acid catalyst and an alcohol (see, for example, Patent Document 7). ). However, in this method, since a by-product such as ethylene glycol methyl acetal is generated during the de-ethylation reaction, it is necessary to remove it, but the alcohol used in excess during the reaction must be removed by washing with water and discarded. . [Patent Document 1] [Patent Document 1] German Patent No. 1 5 1 1 8 5 72 [Patent Document 2] JP-A-10-298143 [Patent Document 3] Japanese Patent Laid-Open No. Hei 1 1 - 43466 [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. OBJECTIVE OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a method for efficiently producing a hydroxyalkyl (meth) acrylate having a purity of ruthenium without requiring a complicated purification step. [Means for Solving the Problem] As a result of various reviews, the inventors of the present invention found that the vinyl ether-containing alcohol is (meth) acrylated to a vinyl ether-containing (meth) acrylate, and the acid catalyst is used. In the presence of the deethylation process by coexistence of water, a hydroxyalkyl (meth)acrylate can be obtained efficiently. In addition, it is found that the deacetalization reaction produces a compound (diester) of an acetal dimer as a by-product, but the acetal dimer is decomposed by de-ethylation reaction and then decomposed by adding water to -6-201144274. A high purity hydroxyalkyl (meth) acrylate is obtained. That is, the present invention is as follows. (1) A method for producing a hydroxyalkyl (meth) acrylate, which comprises esterifying a vinyl ether-containing alcohol to a vinyl ether-containing (meth) by a transesterification method The step of de-alloying the acrylate, and de-alloying the reaction in the presence of an acid catalyst and water, and then adding water. (2) The method for producing a hydroxyalkyl (meth) acrylate according to the above (1), wherein the pressure in the reaction system is 2 Torr to 40 kPa to carry out a de-alloyation reaction, and then the reaction is carried out at 10 kPa or less. Deacetalization reaction. (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 (Π). 【化1】
通式（丨） (通式（I)中，η表示3~11之整數）’ 【化2】 通式（II) 201144274 (通式（II)中，A表示伸環戊基或伸環己基）。 [發明效果] 依據本發明，可提供一種不需經蒸餾等複雜之純化步 驟有效率地獲得高純度之（甲基）丙烯酸羥基烷基酯之製 造方法。 【實施方式】 針對本發明之（甲基）丙烯酸羥基烷基酯之製造方法 之實施形態加以詳細說明。 本發明之（甲基）丙烯酸羥基烷基酯之製造方法之特 徵爲包含利用酯交換法使含有乙烯基醚之醇經（甲基）丙 烯酸酯化成爲含有乙烯基醚之（甲基）丙烯酸酯，且在酸 觸媒及水之存在下，進行脫乙烯化反應後，再添加水進行 脫縮醛化反應之步驟。 本發明首先係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。酯化方法主要列舉爲 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）丙烯醯氯之醯鹵法，但 其中，脫水酯化法由於使用酸觸媒，會同時引起脫乙烯化 而不適用。又，醯鹵法因反應使鹵素脫離而殘留於系統內 ，故需要水洗、吸附或蒸餾等純化處理。另一方面，酯交 換法由於雜質少亦不需要純化作業，故本發明採用酯交換 法。 -8 - 201144274 本發明中使用之含有乙烯基醚之醇列舉爲例 丁基乙烯基醚、6-羥基己基乙烯基醚、9-羥基壬 醚、10-羥基癸基乙烯基醚、12-羥基十二烷基乙 之以下述通式（I)表示之化合物；環己烷二甲 基醚等之以下述通式（II)表示之化合物；苯基 乙烯基醚等。 【化3】 η 通式（丨） (通式（I)中，η表示3〜11之整數）， 【化4】 〆0八αΑ〇η 通式（丨丨） (通式（Π)中，Α表示伸環戊基或伸環己基）。 酯交換法中使用之低級（甲基）丙烯酸酯之 舉爲（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯 )丙烯酸丙酯、（甲基）丙烯酸丁酯等。亦即， 所稱之低級（甲基）丙烯酸酯意指具有碳數4以 者。 酯交換反應時，就短時間反應、高酯轉換率 之後處理之觀點而言，較好相對於含有乙烯基醚 物以等量至過量使用低級（甲基）丙烯酸酯。具 如4-羥基 基乙烯基 烯基醚等 醇單乙烯 二甲醇單 具體例列 、（甲基 本申請案 下之烷基 、反應後 之醇化合 體而言， -9 - 201144274 通常相對於含有乙烯基醚之醇化合物所具有之羥基1莫耳 ’較好以1.0〜20莫耳之範圍使用低級（甲基）丙烯酸酯。 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莫耳未達1.0莫耳時，反應無法充分進行， 又超過20莫耳時，反應後之濃縮步驟需要長時間而使生產 性惡化。 酯交換法使用之觸媒列舉爲氫氧化鋰、氫氧化鈉、氫 氧化鉀等鹼金屬氫氧化物；碳酸鋰、碳酸鈉、碳酸鉀等鹼 金屬碳酸化物；甲氧化鋰、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、原鈦酸四丁酯等烷氧化鈦；其他烷氧 化鋁；烷氧化錫等》就盡量抑制該副反應，於反應結束後 添加水即可輕易的去除觸媒而言，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，通常以0.01〜5.0質量％ 之範圍較佳。觸媒量超過5.0質量％時，對反應速度幾乎沒 有影響，相反地去除觸媒時需大量的水等，僅是不經濟。 本發明之酯交換反應中，可添加、倂用習知之聚合抑 制劑。聚合抑制劑列舉爲例如氫醌、氫醌單甲基醚（亦稱 爲「甲醌j )等酚類；吩噻嗪、乙烯硫脲等硫化合物；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基氧基等 -10- 201144274 N-氧基化合物等。聚合抑制劑之添加量相對於生成之酯較 好爲〇.1質量％以下。超過0.1質量％時，會有起因於添加劑 而產生著色之情況。 酯交換反應時，較好吹入少量之分子狀氧以防止反應 中反應液之聚合。分子狀氧較好以稀釋狀態使用，更好使 用空氣。又，分子狀氧之吹入由於經蒸發而以蒸氣存在， 可防止凝縮於上部釜壁面等上之（甲基）丙烯酸酯類之聚 合故亦較佳。 所謂分子狀氧意指藉由兩個氧原子形成之基底狀態之 三重態氧分子（〇2 )，反應雖亦可就此狀態直接參與，但 亦意指藉由與觸媒或反應試劑之相互作用，轉換成一重態 分子或氧原子、超氧化物、過氧化物等狀態後參與反應之 氧分子。 分子狀氧之導入量儘管亦受到反應機之形狀或攪拌動 力之影響，但相對於原料含有乙烯基醚之醇1莫耳，以 5〜500ml/分鐘（作爲空氣爲25〜2500ml/分鐘）之速度吹送 即可。分子狀氧之導入量未達5ml/分鐘時，聚合抑制之效 果不足，超過5〇〇ml/分鐘時，使低級（甲基）丙烯酸醋擠 出到系統外之效果變強，而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〜 l2〇°C進行。溫度未達60°C時，反應速度造成反應極度緩慢 ，另外超過120°C時，容易引起以酯交換反應獲得之含有 乙烯基醚之（甲基）丙烯酸酯之聚合，且容易引起著色。 -11 - 201144274 酯交換反應之形態可藉熟悉製造（甲 本技藝者一般習知之方法進行。酯交換反 級（甲基）丙烯酸酯及/或溶劑共沸餾除 因此，作爲反應裝置係使用例如安裝有精 應槽。 酯交換反應結束後，以水使觸媒失活 除過量之低沸點成份。以濃縮裝置餾除低 常壓或減壓下，邊將液溫保持在90°C以下 50〜70°C之範圍內。液溫超過90°C時，引起 (甲基）丙烯酸酯之著色或聚合的可能性 完成餾除低沸點成份之含有乙烯基醚 酸酯可藉由進行過濾去除殘留之失活觸媒 時爲了效率良好地去除不溶份，較好使用 助劑。 接著，對進行含有乙烯基醚之（甲基 乙烯化反應，獲得（甲基）丙烯酸羥基烷 說明。 本發明之脫乙烯化反應係在酸觸媒存 而進行。脫乙烯化反應時生成之乙醛可藉 部減壓而去除，但乙醛之一部分進入水中 化反應生成之（甲基）丙烯酸羥基烷基酯 基）丙烯酸羥基烷基酯甲基乙縮醛（乙縮 留乙縮醛二聚物時，在聚合時因交聯反應 或凝膠化等之缺陷。然而，乙縮醛二聚物 基）丙烯酸酯該 應時有必要以低 副生之低級醇。 餾塔之回流式反 ，以濃縮裝置餾 沸點成份較好在 而進行，更好在 含有乙烯基醚之 變高。 之（甲基）丙烯 等不溶份。過濾 矽藻土等之過濾 )丙烯酸酯之脫 基酯之方法加以 在下，使水共存 由使反應系統內 ，與藉由脫乙烯 反應，形成（甲 醛二聚物）。殘 而產生高黏度化 化反應爲可逆反 -12- 201144274 應，在酸觸媒下容易脫縮醛化，故本發明中，於 反應後，藉由進行後述之脫縮醛化反應，使生成 二聚物分解。 本發明之脫乙烯化反應時可使用之酸觸媒列 硫酸、硫酸氫鈉、對甲苯磺酸、苯磺酸、甲烷磺 酸（沸石、Amberlite、Amberlyst、Nafion 等） 用之觸媒量相對於反應之含有乙烯基醚之（甲基 酯較好爲0.1〜10質量％，更好爲0.5〜3質量％。使 量未達〇. 1質量％時，脫乙烯化反應顯著降低，反 慢。且，多於1 0質量％時，會有大量生成乙縮醛 副產物之傾向。 本發明之脫乙烯化反應時之水使用量只要相 乙烯基酸之（甲基）丙烯酸酯爲等莫耳以上即無 ，但較好，相對於含有乙烯基醚之（甲基）丙烯 20〜40質量％，藉此加速脫乙烯化反應之進行，且 縮醛二聚物之生成量。水之使用量相對於含有乙 (甲基）丙烯酸酯未達20質量％時，乙縮醛二聚 變多，超過40質量％時，脫乙烯化反應變慢。再 等莫耳時脫乙烯化反應之進行會在中途停止。 本發明之脫乙烯化反應爲發熱反應，因反應 乙醛有必要藉由使系統內減壓而去除。反應溫 60°C以下，藉由控制在20t〜40°C可獲得高純度之 丙烯酸羥基烷基酯。控制反應溫度之方法列舉有 冷卻，或將含有乙烯基醚之（甲基）丙烯酸酯緩 脫乙烯化 之乙縮醛 舉通常爲 酸、固體 。又，使 )丙烯酸 用之觸媒 應極度變 二聚物等 對於含有 特別限制 酸酯使用 可抑制乙 烯基醚之 物之產量 者’未達 而生成之 度較好爲 (甲基） 使反應器 慢添加於 -13- 201144274 觸媒水溶液中之方法。又，發熱結束後，可以溫浴等加溫 以保持溫度。反應溫度若在20°C~40°C，則系統內壓力在 2 0〜4 Ok Pa左右可效率良好地去除乙醛。 本發明之特徵爲在進行脫乙烯化反應後，再添加水進 行脫縮醛化反應。水之添加量並無特別限制，但以含有乙 烯基醚之（甲基）丙烯酸酯作爲基準較好爲3〜30質量％。 水之使用量在該範圍外時，無法效率良好地進行脫縮醛化 反應。又，水之添加方法可爲緩慢滴加之方法，亦可一次 添加之方法。且，脫縮醛化時爲了有效去除乙醛，更好使 系統內之壓力成爲10kPa以下。 本發明之脫乙烯化反應及脫縮醛化反應時，爲了防止 反應中反應液聚合，較好與酯交換反應時同樣地吹入少量 之分子狀氧。 脫縮醛化反應結束後，有必要以鹼中和酸觸媒並分離 去除。鹼列舉爲例如氫氧化鉀、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。又，中和後分離去除水層時，爲了提髙分離能， 可例如單獨或組合兩種以上使用甲苯或二甲苯，或可使用 藉由添加氯化鈉等提高水層比重之方法。 中和後，藉由濃縮餾除過量之水分或使用溶劑時餾除 溶劑。濃縮較好在常壓或減壓下，將液溫維持在9(TC以下 進行，更好在65〜85°C之範圍內。液溫超過90°C時，造成（ 甲基）丙烯酸羥基烷基酯之著色或聚合的可能性變高。 濃縮後，可藉由過濾去除殘留之中和鹽等不溶份。過 -14- 201144274 濾時爲了效率良好地去除不溶份，較好使用矽藻土等過濾 助劑。 本發明之（甲基）丙烯酸羥基烷基酯之製造方法由於 可藉由使用水進行脫乙烯化反應及脫縮醛化反應，獲得高 純度之（甲基）丙烯酸羥基烷酯，故不需要過濾以外之生 成步驟，但可視情況進行蒸餾等一般之純化方法。 [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） 於4L之四頸圓底分離燒瓶中注入4-羥基丁基乙烯基醚 (九善石油化學製造 HBVE) l〇〇〇g、甲基丙烯酸甲酯 3000g、甲醌0_65g，且設置精餾塔（15段）、攪拌機、空 氣導入管、溫度計。在攪拌下邊以l〇〇ml/分鐘導入乾燥空 氣邊開始加熱，以使回流時燒瓶內之液溫成爲75 °C之方式 將壓力調整至40kPa左右，去除系統內之水分。確認系統 內之水份爲3 00ppm以下之後，注入作爲觸媒之四異丙氧化 鈦8.6g，以使反應溫度成爲95±5°C之方式將燒瓶內之壓力 控制至60kPa左右。監控加熱回流時精餾塔上部之溫度（ 塔頂溫度），由於接近生成之甲醇與甲基丙烯酸甲酯之共 沸溫度，故以使塔頂溫度成爲6〇°C左右之方式調節回流比 -15- 201144274 ，使甲醇作爲與甲基丙烯酸甲酯之共沸物而餾除邊進行反 應。經過4小時反應後塔頂溫度開始上升，故緩慢加大回 流比繼續反應。以氣相層析分析反應第5小時之反應液後 ，酯轉換率爲99.2%，故終止反應。將反應液冷卻，使液 溫成爲75°C下添加17質量％食鹽水250g使觸媒水解。靜置 15分鐘後，藉由傾析將有機層倒入梨型燒瓶中，使用旋轉 蒸發器，減壓下餾除過量之甲基丙烯酸甲酯，以抽氣過濾 而過濾梨型燒瓶內之液體，獲得15 22 g之標的甲基丙烯酸 乙烯基氧基丁酯。 (甲基丙烯酸4-羥基丁酯之合成） 將對甲苯磺酸2.5g、純水150g饋入1L之四頸分離燒瓶 中，且設置攪拌機、溫度計、空氣導入管、附冷凝阱之真 空泵。邊攪拌邊調節液溫使維持在40°C將上述合成之甲基 丙烯酸乙烯基氧基丁酯5 00g緩慢添加於燒瓶中。添加結束 後，減壓至30kPa，以l〇〇ml/分鐘導入乾燥空氣，繼續攪 拌1小時，且以氣相層析分析反應液後，未發現有甲基丙 烯酸乙烯基氧基丁酯之峰。然而，藉由液體層析之分析發 現生成19.8%之乙縮醛二聚物，故添加純水25g，使壓力成 爲5kPa進行脫縮醛化反應。反應1小時後分析乙縮醛二聚 物之峰幾乎消失，故結束反應。於反應結束之液體中注入 碳酸氫鈉3.8 g進行中和後，混合17%食鹽水88g，靜置10分 鐘直至油水完全分離爲止。藉由傾析將有機層倒入梨型燒 瓶中，使用旋轉蒸發器，減壓下餾除水分後，以抽氣過濾 -16- 201144274 而過濾梨型燒瓶內之液體，以收率90%獲得標的物質3 86g [比較例1 ] 將對甲苯磺酸2.5g、純水150g饋入1L之四頸分離燒瓶 中，且設置攪拌機、溫度計、空氣導入管、安裝冷卻阱之 真空泵。邊攪拌邊調節液溫使維持在40°C將上述合成之甲 基丙烯酸乙烯基氧基丁酯5 00g緩慢添加於燒瓶中。添加結 束後，減壓至30kPa，以100ml/分鐘導入乾燥空氣，繼續 攪拌1小時，且以氣相層析分析反應液後，由於未發現有 甲基丙烯酸乙烯基氧基丁酯之峰，故終止反應。於反應結 束之液體中注入碳酸氫鈉3.8 g進行中和後，混合17%之食 鹽水88g，且靜置10分鐘直至油水完全分離爲止。藉由傾 析將有機層倒入梨型燒瓶中，使用旋轉蒸發器，減壓下餾 除水分後，以抽氣過濾而過瀘梨型燒瓶內之液體，以收率 93%獲得標的物質398层》 [比較例2] 將對甲苯磺酸2.5g、純水175 g饋入（亦即，饋入以實 施例1中之後添加之水合起來之量）於1L之四頸分離燒瓶 中，設置攪拌機、溫度計、空氣導入管、安裝冷卻阱之真 空栗。邊攪拌邊調節液溫使維持在40°C將上述合成之甲基 丙烯酸乙烯基氧基丁酯5 00g緩慢添加於燒瓶中。添加結束 後，減壓至3〇kPa，以100ml/分鐘導入乾燥空氣，繼續攪 -17- 201144274 拌2小時，以氣相層析分析反應液後，未發現有甲基丙烯 酸乙烯基氧基丁酯之峰，故結束反應。於反應結束之液體 中注入碳酸氫鈉3.8g予以中和後，混合17%食鹽水88g，靜 置10分鐘直至油水完全分離爲止。藉由傾析將有機層倒入 梨型燒瓶中，使用旋轉蒸發器，減壓下餾除水分後，以抽 氣過濾而過濾梨型燒瓶內之液體，以收率88%獲得標的物 質 3 7 7g。 [實施例2] (丙烯酸乙烯基氧基丁酯之合成） 於4L之四頸圓底分離燒瓶中注入4_羥基丁基乙烯基醚 (九善石油化學製造 HBVE) 1000g、丙烯酸乙酯3000g、 甲醌（K65g，且設置精餾塔（15段）、攪拌機、空氣導入 管、溫度計。在攪拌下邊以100ml/分鐘導入乾燥空氣邊開 始加熱，以使回流時燒瓶內之液溫成爲75 °C之方式將壓力 調整至40kPa左右，去除系統內之水分。確認系統內之水 分爲3 00ppm以下之後，注入作爲觸媒之四異丙氧化鈦8.6g ，以使反應溫度成爲95±5t之方式將燒瓶內之壓力控制在 6 0kPa左右。監控加熱回流時精餾塔上部之溫度（塔頂溫 度），由於生成之乙醇與丙烯酸乙酯之共沸溫度相近，故 以使塔頂溫度成爲7〇 t：左右之方式調節回流比，將乙醇以 作爲與丙烯酸甲酯之共沸物邊餾除邊進行反應。經過4小 時反應後塔頂溫度開始上升，故緩慢加大回流比繼續反應 。以氣相層析分析反應第5小時之反應液後，酯轉換率爲 -18- 201144274 9 9 ·〇%’故終止反應。將反應液冷卻，使液溫成爲75 °C後 添加17質量％食鹽水250g使觸媒水解。靜置15分鐘後，藉 由傾析將有機層倒入梨型燒瓶中，使用旋轉蒸發器，減壓 下餾除過量之丙烯酸乙酯，以抽氣過濾而過濾梨型燒瓶內 之液體’獲得1376g之標的丙烯酸乙烯基氧基丁酯。 (丙烯酸4-羥基丁酯之合成） 將對甲苯磺酸2.5g '純水150g饋入1L之四頸分離燒瓶 中，且設置攪拌機、溫度計、空氣導入管、安裝冷卻阱之 真空泵。邊攪拌邊調節液溫使維持在40°C將上述合成之丙 烯酸乙烯基氧基丁酯5 00g緩慢添加於燒瓶中。添加結束後 ，減壓至30kPa，以100ml/分鐘導入乾燥空氣，繼續攪拌1 小時，以氣相層析分析反應液後，未發現有丙烯酸乙烯基 氧基丁酯之峰。然而，藉由液體層析分析由於生成2 0.5% 之乙縮醛二聚物，故添加純水25g，使壓力成爲5kPa進行 脫縮醛化反應。反應1小時後分析乙縮醛二聚物之峰幾乎 消失，故結束反應。於反應結束之液體中注入碳酸氫鈉 3.8g予以中和後，混合17%食鹽水86g，靜置10分鐘直至油 水完全分離爲止。藉由傾析將有機層倒入梨型燒瓶中，使 用旋轉蒸發器’減壓下餾除水分，以抽氣過濾而過濾梨型 燒瓶內之液體，以收率9 1 %獲得標的之丙烯酸4-羥基丁酯 3 8 5 g ° [比較例3 ] -19- 201144274 將對甲苯磺酸2.5g、純水I50g饋入1L之四頸分離燒瓶 中，且設置攪拌機、溫度計、空氣導入管、安裝冷卻阱之 真空泵。邊攪拌邊調節液溫使維持在4(TC將上述合成之丙 烯酸乙烯基氧基丁酯5 00g緩慢添加於燒瓶中。添加結束後 ，減壓至30kPa，以100ml/分鐘導入乾燥空氣，繼續攪拌1 小時，以氣相層析分析反應液後，由於未發現有丙烯酸乙 烯基氧基丁酯之峰，故終止反應。於反應結束之液體中注 入碳酸氫鈉3.8g予以中和後，混合17%食鹽水86g，靜置10 分鐘直至油水完全分離爲止。藉由傾析將有機層倒入梨型 燒瓶中，使用旋轉蒸發器，減壓下餾除水分，以抽氣過濾 而過濾梨型燒瓶內之液體，以收率88 %獲得標的之丙烯酸 4-羥基丁酯3 72g。 [實施例3] (環己烷二甲醇乙烯基醚丙烯酸酯之合成） 於1L之四頸圓底分離燒瓶中注入環己烷二甲醇單乙烯 基醚（九善石油化學製造 CHMVE ) 3 00g、丙烯酸乙酯 600g、甲醌0.20g，且設置精餾塔（15段）、攪拌機、空 氣導入管、溫度計。在攪拌下邊以l〇〇ml/分鐘導入乾燥空 氣邊開始加熱，以使回流時燒瓶內之液溫成爲7 5 °C之方式 將壓力調整至4 OkP a左右，去除系統內之水分。確認系統 內之水分爲300 ppm以下之後’注入作爲觸媒之四異丙氧 化鈦2.6g，以使反應溫度成爲95±5°C之方式將燒瓶內之壓 力控制在60kPa左右。監控加熱回流時精餾塔上部之溫度 -20- 201144274 (塔頂溫度），由於接近生成之乙醇與丙烯酸乙酯之共沸 溫度，故以使塔頂溫度成爲70°c左右之方式調節回流比’ 乙醇以作爲與丙烯酸乙酯之共沸物邊餾除邊進行反應。經 過2小時反應後塔頂溫度開始上升’故緩慢加大回流比繼 續反應。以氣相層析分析反應第3小時之反應液後’酯轉 換率爲99.4%，故終止反應。將反應液冷卻，使液溫成爲 7 5 °C後添加1 7質量％食鹽水1 〇 〇 g使觸媒水解。靜置1 5分鐘 後，藉由傾析將有機層倒入梨型燒瓶中’使用旋轉蒸發器 ，減壓下餾除過量之丙烯酸乙酯後’以抽氣過濾而過濾梨 型燒瓶內之液體，獲得385g之標的環己烷二甲醇乙烯基醚 丙烯酸酯。 (環己烷二甲醇單丙烯酸酯之合成） 將對甲苯磺酸l.Og、純水60g饋入500mL之四頸分離燒 瓶中，且設置攪拌機、溫度計、空氣導入管、安裝冷凝阱 之真空泵。邊攪拌邊調節液溫使維持在40 °C將製造例3合 成之環己烷二甲醇乙烯基醚丙烯酸酯2〇〇 g緩慢添加於燒瓶 中。添加結束後，減壓至3〇kPa ’以100ml/分鐘導入乾燥 空氣，繼續攪拌1小時，以氣相層析分析反應液後’未發 現有丙烯酸乙烯基氧基丁酯之峰。然而’藉由液體層析分 析由於生成13.6%之乙縮醛二聚物’故添加純水l〇g ’使壓 力成爲5kPa進行脫縮醛化反應。反應1小時後分析乙縮醛 二聚物之峰消失，故結束反應。反應結束後注入碳酸氫鈉 1.5g予以中和後，混合17%食鹽水35g，靜置10分鐘直至油 -21 - 201144274 水完全分離爲止。藉由傾析將有機層倒入梨型燒瓶中，使 用旋轉蒸發器，減壓下餾除水分，以抽氣過濾而過濾梨型 燒瓶內之液體，以收率93%獲得標的之環己烷二甲醇單丙 烯酸酯1 66g » [比較例4] 將對甲苯磺酸l.Og、純水60g饋入500mL之四頸分離燒 瓶中，且設置攪拌機、溫度計、空氣導入管、安裝冷卻阱 之真空泵。邊攪拌邊調節液溫使維持在40t將製造例3合 成之環己烷二甲醇乙烯基醚丙烯酸酯2 00g緩慢添加於燒瓶 中。添加結束後，減壓至30kPa，以1 〇〇ml/分鐘導入乾燥 空氣’繼續攪拌1小時，以氣相層析分析反應液後，由於 未發現有丙烯酸乙烯基氧基丁酯之峰，故終止反應。反應 結束後注入碳酸氫鈉1 .5g予以中和後，混合1 7%食鹽水35g ，靜置10分鐘直至油水完全分離爲止。藉由傾析將有機層 倒入梨型燒瓶中’使用旋轉蒸發器，減壓下餾除水分後， 以抽氣過濾而過濾梨型燒瓶內之液體，以收率9 5 %獲得標 的之環己烷二甲醇單丙烯酸酯169g。 -22- 201144274 [表i] 項目 實施例1 比較例1 比較例2 實施例2 比較例3 實施例3 比較例4 標的物質 4HBMA 4HBMA 4HBMA 4HBA 4HBA CHDM-MA CHDM-MA 脫乙烯化率 [%1 100 100 100 100 100 100 100 乙縮醛二聚 物[%] 0.09 27.7 18.2 0.11 35.5 0.1 32.8 4HBMA :甲基丙烯酸4-羥基丁酯 4HBA :丙烯酸4-羥基丁酯 CHDM-MA :環己烷二甲醇單丙烯酸酯 由上述表1可了解，脫乙烯化反應後進而添加水進行 脫縮醛化之實施例1 ~3，乙縮醛二聚物大幅減少，且，比 較例2中，合倂實施例1初期使用之水量與後添加時之水量 於初期使用，仍存在乙縮醛二聚物。 -23-General formula (丨) (in the general formula (I), η represents an integer of 3 to 11) 'Chemical 2' Formula (II) 201144274 (In the formula (II), A represents a cyclopentylene group or a cyclohexylene group. ). [Effect of the Invention] According to the present invention, it is possible to provide a process for producing a high-purity hydroxyalkyl (meth) acrylate without requiring a complicated purification step such as distillation. [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 by comprising (meth)acrylating an alcohol containing a vinyl ether to a (meth) acrylate containing a vinyl ether by a transesterification method. And, in the presence of an acid catalyst and water, a de-alloyation reaction is carried out, and then water is added to carry out a step of deacetalization reaction. The present invention first esterifies a hydroxyl group of a vinyl ether-containing alcohol to obtain a vinyl ether-containing (meth) acrylate. The esterification method is mainly exemplified by a dehydration esterification method using (meth)acrylic acid, a transesterification method using a lower (meth) acrylate, and a hydrazine halogen method using (meth) propylene ruthenium chloride, but among them, dehydration esterification Because of the use of an acid catalyst, the method causes de-ethylation at the same time and is not suitable. Further, the hydrazine halogen method leaves the halogen in the reaction due to the reaction, and therefore requires purification treatment such as water washing, adsorption, or distillation. On the other hand, since the ester exchange method requires little purification and does not require a purification operation, the present invention employs a transesterification method. -8 - 201144274 The vinyl ether-containing alcohol used in the present invention is exemplified by butyl vinyl ether, 6-hydroxyhexyl vinyl ether, 9-hydroxy anthracene ether, 10-hydroxydecyl vinyl ether, 12-hydroxyl group. The dodecyl group is a compound represented by the following formula (I); a compound represented by the following formula (II) such as cyclohexane dimethyl ether; a phenyl vinyl ether or the like. η General formula (丨) (In the general formula (I), η represents an integer of 3 to 11), [Chemical 4] 〆08αΑ〇η General formula (丨丨) (Formula (Π) , Α means stretching cyclopentyl or stretching cyclohexyl). The lower (meth) acrylate used in the transesterification method is methyl (meth)acrylate, ethyl (meth)acrylate) propyl acrylate or butyl (meth)acrylate. That is, the so-called lower (meth) acrylate means having a carbon number of 4. In the transesterification reaction, it is preferred to use a lower (meth) acrylate in an equivalent amount to an excess amount with respect to the vinyl ether-containing compound from the viewpoint of a short-time reaction and a high ester conversion ratio. Specific examples of alcohols such as 4-hydroxyvinyl alkenyl ether, monovinyl dimethanol, (methyl group in the present application, alcoholic group after reaction, -9 - 201144274 usually relative to vinyl containing The hydroxyl group 1 of the ether alcohol compound preferably uses a lower (meth) acrylate in the range of 1.0 to 20 moles. The amount of the lower (meth) acrylate is relative to the alcohol compound containing a vinyl ether. When the hydroxyl group 1 mole is less than 1.0 mol, the reaction does not proceed sufficiently, and when it exceeds 20 mol, the concentration step after the reaction takes a long time to deteriorate the productivity. The catalyst used in the transesterification method is exemplified by lithium hydroxide. Alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate; alkali metal alkane such as lithium pentoxide, sodium methoxide, sodium ethoxide or potassium third potassium hydride Oxide; alkali metal amide such as lithium amide, sodium amide, potassium amide; tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetraisopropyl orthotitanate Alkyl titanium oxide such as tetrabutyl titanate; The alkane-alumina, the alkoxy tin oxide, etc., try to suppress the side reaction, and it is preferable to add the water after the reaction to remove the catalyst, and it is preferable to use a titanium alkoxide or an alkane oxide. The amount is usually in the range of 0.01 to 5.0% by mass based on the total amount of the lower (meth) acrylate and the vinyl ether-containing alcohol compound. When the amount of the catalyst exceeds 5.0% by mass, the reaction rate is hardly affected. On the contrary, a large amount of water or the like is required to remove the catalyst, which is only uneconomical. In the transesterification reaction of the present invention, a conventional polymerization inhibitor may be added or used. The polymerization inhibitor is exemplified by, for example, hydroquinone or hydroquinone monomethyl. Phenols such as ether (also known as "JiJ"); sulfur compounds such as phenothiazine and ethylene thiourea; copper salts such as copper dibutyldithiocarbamate; manganese salts such as manganese acetate: nitro compounds, sub- Nitro compound, 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy group, etc.-10-201144274 N-oxyl compound, etc. The amount of the polymerization inhibitor added is preferably relative to the ester formed. 〇.1% by mass or less. When it exceeds 0.1% by mass, there may be a result of adding When the transesterification reaction is carried out, it is preferred to blow a small amount of molecular oxygen to prevent the polymerization of the reaction liquid in the reaction. The molecular oxygen is preferably used in a diluted state, and the air is better used. It is also preferred that the blowing is carried out by vaporization to prevent condensation of (meth) acrylates on the upper wall surface of the upper wall, etc. The molecular oxygen means a substrate formed by two oxygen atoms. The state of the triplet oxygen molecule (〇2), although the reaction can directly participate in this state, but also means to convert into a heavy molecule or oxygen atom, superoxide, peroxidation by interaction with a catalyst or a reagent. The oxygen molecule participating in the reaction after the state of the substance. Although the molecular oxygen introduction amount is affected by the shape of the reactor or the stirring power, it is 5 to 500 ml/min with respect to the alcohol containing alcohol ether 1 mol. It can be blown at a speed of 25 to 2500 ml/min. When the introduction amount of molecular oxygen is less than 5 ml/min, the effect of suppressing polymerization is insufficient, and when it exceeds 5 〇〇ml/min, the effect of extruding the lower (meth)acrylic acid vinegar outside the system becomes strong, resulting in a raw material. Loss of lower (meth) acrylate. The transesterification reaction in the present invention is preferably carried out at 60 to 12 ° C under normal pressure or reduced pressure. When the temperature is less than 60 °C, the reaction rate causes the reaction to be extremely slow. When the temperature exceeds 120 °C, polymerization of the vinyl ether-containing (meth) acrylate obtained by the transesterification reaction is likely to occur, and coloring is likely to occur. -11 - 201144274 The form of the transesterification reaction can be carried out by a familiar method (a method generally known to those skilled in the art). The transesterification of the reverse (meth) acrylate and/or solvent is azeotropically distilled. Therefore, for example, a reaction apparatus is used. The finishing tank is installed. After the transesterification reaction, the catalyst is deactivated by water to remove excess low-boiling components. The liquid is kept at a temperature below 90 °C by distilling off the low normal pressure or reduced pressure with a concentrating device. In the range of ~70 ° C. When the liquid temperature exceeds 90 ° C, the possibility of coloring or polymerization of (meth) acrylate is caused. Complete distillation of the low-boiling component containing vinyl ether ester can be carried out by filtration to remove the residue. In order to inefficiently remove the insoluble matter in the case of inactivating the catalyst, it is preferred to use an auxiliary agent. Next, the vinyl etherification reaction is carried out to obtain a (meth)acrylic acid hydroxy alkane. The vinylation reaction is carried out in the presence of an acid catalyst. The acetaldehyde formed during the de-ethylation reaction can be removed by decompression, but one part of the acetaldehyde enters the hydroxyalkyl (meth) acrylate formed by the hydration reaction. Alkyl hydroxyalkyl methacrylate methyl acetal (dehydration of acetal dimer, due to defects such as crosslinking reaction or gelation during polymerization. However, acetal dimer based) acrylic acid It is necessary for the ester to have a low by-product lower alcohol. The reflux of the distillation column is preferably carried out by distilling the boiling point component of the distillation unit, and more preferably, the vinyl ether is high. The method of filtering the diatomaceous earth or the like by filtering the decyl ester of the acrylate is carried out by allowing the water to coexist in the reaction system to form a (formaldehyde dimer) by reacting with ethylene. Residual and high-viscosity reaction is reversible inverse -12-201144274. It is easy to deacetalize under acid catalyst. Therefore, in the present invention, after the reaction, the deacetalization reaction described later is carried out to generate Dimer decomposition. The amount of catalyst used for the acid catalyst, sulfuric acid, sodium hydrogen sulfate, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid (zeolite, Amberlite, Amberlyst, Nafion, etc.) which can be used in the deethylation reaction of the present invention is relative to The reaction contains a vinyl ether (the methyl ester is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 3% by mass. When the amount is less than 0.1% by mass, the de-ethylation reaction is remarkably lowered, and the reaction is slow. Further, when it is more than 10% by mass, a large amount of acetal by-products tend to be formed. The amount of water used in the de-ethylation reaction of the present invention is as long as the (meth) acrylate of the phase vinyl acid is equimolar. The above is not, but it is preferably 20 to 40% by mass based on the (meth) propylene containing a vinyl ether, thereby accelerating the progress of the devinylation reaction and the amount of acetal dimer formed. When the amount of ethylene (meth) acrylate is less than 20% by mass, the acetal dimerization becomes large, and when it exceeds 40% by mass, the devinylation reaction becomes slow. When the molar reaction is carried out, the deethylation reaction proceeds. Stopping halfway. The deethylation reaction of the present invention is a fever reaction Since the reaction of acetaldehyde is necessary to remove the pressure in the system, the reaction temperature is 60 ° C or lower, and a high-purity hydroxyalkyl acrylate can be obtained by controlling at 20 t to 40 ° C. The method for controlling the reaction temperature is exemplified. The acetal which is cooled or slowly de-ethylated with a vinyl ether-containing (meth) acrylate is usually an acid or a solid. Further, the catalyst for acrylic acid should be extremely dimerized, etc. The use of a limiting acid ester to inhibit the yield of a vinyl ether is not achieved. The degree of formation is preferably (meth). The reactor is slowly added to the aqueous solution of the catalyst of -13,044,044,274. Further, after the end of the heat generation, the temperature can be maintained by warming in a warm bath or the like. When the reaction temperature is between 20 ° C and 40 ° C, the pressure in the system is about 20 to 4 Ok Pa to efficiently remove acetaldehyde. The present invention is characterized in that after the devinylation reaction, water is further added to carry out the deacetalization reaction. The amount of water added is not particularly limited, but is preferably from 3 to 30% by mass based on the (meth) acrylate containing a vinyl ether. When the amount of water used is outside this range, the deacetalization reaction cannot be carried out efficiently. Further, the method of adding water may be a method of slowly adding dropwise, or a method of adding one at a time. Further, in order to effectively remove acetaldehyde during deacetalization, the pressure in the system is preferably 10 kPa or less. In the devinylation reaction and the deacetalization reaction of the present invention, in order to prevent polymerization of the reaction liquid during the reaction, it is preferred to blow a small amount of molecular oxygen in the same manner as in the transesterification reaction. After the completion of the deacetalization reaction, it is necessary to neutralize the acid catalyst with a base and separate and remove it. The base is exemplified by 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. Further, when the water layer is separated and removed after the neutralization, for example, toluene or xylene may be used singly or in combination of two or more kinds, or a method of increasing the specific gravity of the water layer by adding sodium chloride or the like may be used. After the neutralization, the solvent is distilled off by distilling off excess water or using a solvent. Concentration is preferably carried out under normal pressure or reduced pressure, maintaining the liquid temperature at 9 (below TC, more preferably in the range of 65 to 85 ° C. When the liquid temperature exceeds 90 ° C, causing (meth)acrylic acid hydroxyalkane The coloring or the possibility of polymerization of the base ester becomes high. After concentration, the insoluble matter such as the residual salt and the salt can be removed by filtration. Over-14- 201144274 In order to efficiently remove the insoluble matter during filtration, it is preferred to use the diatomaceous earth. The method for producing a hydroxyalkyl (meth) acrylate according to the present invention can obtain a high-purity hydroxyalkyl (meth) acrylate by de-ethylation reaction and de-acetalization reaction using water. Therefore, a production step other than filtration is not required, but a general purification method such as distillation may be carried out as appropriate. [Examples] Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited thereto. ] (Synthesis of vinyl butyl methacrylate) 4-hydroxybutyl vinyl ether (HBVE manufactured by Jiushan Petrochemical Co., Ltd.) was injected into a 4 L four-neck round bottom separation flask. l〇〇〇g, methacrylic acid Methyl ester 3000g, formazan 0_65g, and The distillation column (15 stages), a stirrer, an air introduction tube, and a thermometer are placed, and the drying air is introduced while stirring at l〇〇ml/min to start heating so that the liquid temperature in the flask at reflux is 75 °C. The pressure was adjusted to about 40 kPa, and the moisture in the system was removed. After confirming that the water content in the system was 300 ppm or less, 8.6 g of titanium tetraisopropoxide as a catalyst was injected so that the reaction temperature became 95 ± 5 ° C. The pressure in the flask was controlled to about 60 kPa. The temperature at the top of the rectification column (the temperature at the top of the column) was monitored under heating and reflux, and the temperature at the top of the column was 6 由于 due to the azeotropic temperature of the methanol and methyl methacrylate. The reflux ratio was adjusted to about -15-201144274, and the methanol was distilled as an azeotrope with methyl methacrylate to carry out the reaction. After 4 hours of reaction, the temperature at the top of the column began to rise, so the reflux ratio was slowly increased. The reaction was continued. After the reaction liquid was analyzed by gas chromatography for 5 hours, the ester conversion rate was 99.2%, so the reaction was terminated. The reaction solution was cooled, and the liquid temperature was changed to 75 ° C, and 17 mass% saline was added. The catalyst was hydrolyzed. After standing for 15 minutes, the organic layer was poured into a pear-shaped flask by decantation, and excess methyl methacrylate was distilled off under reduced pressure using a rotary evaporator, and filtered by suction to filter the pear type. The liquid in the flask obtained 15 22 g of vinyl butyl methacrylate. (Synthesis of 4-hydroxybutyl methacrylate) 2.5 g of p-toluenesulfonic acid and 150 g of pure water were fed into the neck of 1 L. The flask was separated, and a stirrer, a thermometer, an air introduction tube, and a vacuum pump with a condensation trap were placed. The liquid temperature was adjusted while stirring to maintain the above-mentioned synthesized vinyl butyl methacrylate 500 g at 40 ° C. In the flask, after the addition was completed, the pressure was reduced to 30 kPa, and dry air was introduced at 10 μml/min, stirring was continued for 1 hour, and after the reaction liquid was analyzed by gas chromatography, no vinyloxy methacrylate was observed. The peak of ester. However, since analysis of liquid chromatography revealed that 19.8% of the acetal dimer was formed, 25 g of pure water was added, and the pressure was changed to 5 kPa to carry out a deacetalization reaction. After the reaction for 1 hour, the peak of the acetal dimer was almost disappeared, so the reaction was terminated. After neutralizing 3.8 g of sodium hydrogencarbonate in the liquid at the end of the reaction, 88 g of 17% saline was mixed and allowed to stand for 10 minutes until the oil and water were completely separated. The organic layer was poured into a pear-shaped flask by decantation, and the liquid in the pear-shaped flask was filtered by suction filtration using a rotary evaporator under reduced pressure, and filtered in a yield of 90%. Standard substance 3 86 g [Comparative Example 1] 2.5 g of p-toluenesulfonic acid and 150 g of pure water were fed into a 1 L four-necked separation flask, and a stirrer, a thermometer, an air introduction tube, and a vacuum pump to which a cooling trap was attached were provided. The liquid temperature was adjusted while stirring, and 500 kg of the above-mentioned synthesized vinyl butyl methacrylate was slowly added to the flask while maintaining the temperature at 40 °C. After the completion of the addition, the pressure was reduced to 30 kPa, and dry air was introduced at 100 ml/min, stirring was continued for 1 hour, and after analyzing the reaction liquid by gas chromatography, since no peak of vinyl butyl methacrylate was observed, Stop the reaction. After neutralizing 3.8 g of sodium hydrogencarbonate in the liquid at the end of the reaction, 88 g of 17% saline was mixed, and allowed to stand for 10 minutes until the oil and water were completely separated. The organic layer was poured into a pear-shaped flask by decantation, and the water was distilled off under reduced pressure using a rotary evaporator, and then filtered through suction to pass through a liquid in an avocado-type flask to obtain a target substance in a yield of 93%. [Comparative Example 2] 2.5 g of p-toluenesulfonic acid and 175 g of pure water were fed (that is, the amount of hydration added after the addition of Example 1) was placed in a 1 L four-necked separation flask, and set. Mixer, thermometer, air inlet tube, vacuum pump with cooling trap installed. The liquid temperature was adjusted while stirring, and 500 g of the above-mentioned synthesized vinyl butyl methacrylate was slowly added to the flask while maintaining the temperature at 40 °C. After the end of the addition, the pressure was reduced to 3 kPa, and the dry air was introduced at 100 ml/min, and the mixture was further stirred for -17-201144274 for 2 hours. After the reaction liquid was analyzed by gas chromatography, no vinyl methacrylate was found. The peak of the ester ends the reaction. After 3.8 g of sodium hydrogencarbonate was injected into the liquid in which the reaction was completed, the mixture was neutralized, and 88 g of 17% saline was mixed and allowed to stand for 10 minutes until the oil and water were completely separated. The organic layer was poured into a pear-shaped flask by decantation, and the water was distilled off under reduced pressure using a rotary evaporator, and the liquid in the pear-shaped flask was filtered by suction filtration to obtain the target substance in a yield of 88%. 7g. [Example 2] (Synthesis of vinyl butyl acrylate) Into a 4 L four-necked round bottom separation flask, 4 g of hydroxybutyl vinyl ether (HBVE manufactured by Jiuzhen Petrochemical Co., Ltd.) and 1000 g of ethyl acrylate were injected. Formazan (K65g, and set up a distillation column (15 stages), a stirrer, an air introduction tube, a thermometer. Start heating with introduction of dry air at 100 ml/min while stirring, so that the liquid temperature in the flask at reflux is 75 °C. In this way, the pressure is adjusted to about 40 kPa, and the moisture in the system is removed. After confirming that the moisture in the system is 300 ppm or less, 8.6 g of titanium tetraisopropoxide as a catalyst is injected so that the reaction temperature becomes 95±5t. The pressure in the flask is controlled at about 60 kPa. The temperature at the top of the rectification column (the temperature at the top of the column) when the heating is refluxed is monitored. Since the azeotrope temperature of the produced ethanol and ethyl acrylate is similar, the temperature at the top of the column is 7 〇t. : The reflux ratio is adjusted in a left-right manner, and ethanol is reacted as azeotrope with methyl acrylate. After the reaction for 4 hours, the temperature at the top of the column starts to rise, so the reflux ratio is slowly increased. After analyzing the reaction liquid at the 5th hour of the reaction by gas chromatography, the ester conversion rate is -18-201144274 9 9 ·〇%', so the reaction is terminated. The reaction solution is cooled, and the liquid temperature is changed to 75 °C. The mass% saline 250 g was used to hydrolyze the catalyst. After standing for 15 minutes, the organic layer was poured into a pear-shaped flask by decantation, and excess ethyl acrylate was distilled off under reduced pressure using a rotary evaporator, and filtered by suction. The liquid in the pear-shaped flask was filtered to obtain 1376 g of the standard vinyl butyl acrylate. (Synthesis of 4-hydroxybutyl acrylate) 1.5 g of p-toluenesulfonic acid 2.5 g of pure water was fed into a 1 L four-neck separation flask. In addition, a mixer, a thermometer, an air introduction tube, and a vacuum pump to which a cooling trap is installed are provided, and the liquid temperature is adjusted while stirring, and 500 kg of the above-mentioned synthesized vinyl butyl acrylate is slowly added to the flask while maintaining the temperature at 40 ° C. After completion, the pressure was reduced to 30 kPa, and dry air was introduced at 100 ml/min, and stirring was continued for 1 hour. After analyzing the reaction liquid by gas chromatography, no peak of vinyl butyl acrylate was observed. However, by liquid layer Analysis of analysis 2 0.5% acetal dimer, 25 g of pure water was added, and the pressure was 5 kPa to carry out the deacetalization reaction. After 1 hour of reaction, the peak of the acetal dimer was almost disappeared, so the reaction was terminated. After filling 3.8 g of sodium hydrogencarbonate into the liquid to be neutralized, 86 g of 17% saline was mixed and allowed to stand for 10 minutes until the oil and water were completely separated. The organic layer was poured into a pear-shaped flask by decantation, and a rotary evaporator was used. The water was distilled off under reduced pressure, and the liquid in the pear-shaped flask was filtered by suction filtration to obtain the target 4-hydroxybutyl acrylate 3 8 5 g ° in a yield of 91% [Comparative Example 3] -19- 201144274 2.5 g of p-toluenesulfonic acid and 50 g of pure water were fed into a 1 L four-necked separation flask, and a stirrer, a thermometer, an air introduction tube, and a vacuum pump to which a cooling trap was attached were provided. The liquid temperature was adjusted while stirring, and the mixture was slowly added to the flask at 4 (TC). After the addition, the pressure was reduced to 30 kPa, and dry air was introduced at 100 ml/min to continue stirring. After 1 hour, the reaction liquid was analyzed by gas chromatography, and the reaction was terminated because no peak of vinyl butyl acrylate was observed. 3.8 g of sodium hydrogencarbonate was injected into the liquid at the end of the reaction to be neutralized, and then mixed. % of saline was placed in an amount of 86 g, and allowed to stand for 10 minutes until the oil and water were completely separated. The organic layer was poured into a pear-shaped flask by decantation, and the water was distilled off under reduced pressure using a rotary evaporator, and the pear-shaped flask was filtered by suction filtration. The liquid was obtained, and the target 4-hydroxybutyl acrylate 3 72 g was obtained in a yield of 88%. [Example 3] (Synthesis of cyclohexane dimethanol vinyl ether acrylate) In a 1 L four-neck round bottom separation flask Injection of cyclohexanedimethanol monovinyl ether (CHMVE manufactured by Jiushan Petrochemical Co., Ltd.) 300 g, ethyl acrylate 600 g, and formazan 0.20 g, and a rectification column (15 stages), a stirrer, an air introduction tube, and a thermometer were placed. Stir under the l〇 〇ml/min is introduced into the dry air to start heating, so that the liquid temperature in the flask at reflux is adjusted to 7 5 °C, the pressure is adjusted to about 4 OkPa, and the moisture in the system is removed. Confirm that the moisture in the system is 300 ppm. After that, 2.6 g of tetraisopropoxide as a catalyst was injected, and the pressure in the flask was controlled to about 60 kPa so that the reaction temperature became 95 ± 5 ° C. The temperature of the upper portion of the rectification column during heating and reflux was monitored -20 - 201144274 (top temperature), due to the azeotropic temperature of the produced ethanol and ethyl acrylate, the reflux ratio 'ethanol is adjusted as the azeotrope with ethyl acrylate in such a manner that the temperature at the top of the column becomes about 70 ° C. The reaction was carried out while distilling off. After the reaction for 2 hours, the temperature at the top of the column began to rise. Therefore, the reflux ratio was gradually increased to continue the reaction. After the reaction liquid of the third hour of the reaction was analyzed by gas chromatography, the ester conversion rate was 99.4%. The reaction solution was terminated, and the reaction liquid was cooled, and the liquid temperature was changed to 75 ° C, and then the catalyst was hydrolyzed by adding 1 g of salt water 1 〇〇g. After standing for 15 minutes, the organic layer was poured into pears by decantation. In the flask The evaporator was transferred to an evaporator, and excess ethyl acrylate was distilled off under reduced pressure. The liquid in the pear-shaped flask was filtered by suction filtration to obtain 385 g of the title cyclohexane dimethanol vinyl ether acrylate. (Cyclohexane dimethanol Synthesis of monoacrylate) 1.0 g of p-toluenesulfonic acid and 60 g of pure water were fed into a 500 mL four-necked separation flask, and a stirrer, a thermometer, an air introduction tube, and a vacuum pump equipped with a condensation trap were set. The liquid temperature was adjusted while stirring. 2 〇〇g of cyclohexane dimethanol vinyl ether acrylate synthesized in Production Example 3 was slowly added to the flask while maintaining the temperature at 40 ° C. After the addition, the pressure was reduced to 3 kPa kPa ', and dry air was introduced at 100 ml/min. Stirring was continued for 1 hour, and after analyzing the reaction liquid by gas chromatography, no peak of vinyl butyl acrylate was observed. However, by liquid chromatography, since 13.6% of the acetal dimer was formed, pure water l〇g ' was added to make the pressure 5 kPa to carry out the deacetalization reaction. After the reaction for 1 hour, the peak of the acetal dimer disappeared, and the reaction was terminated. After the completion of the reaction, 1.5 g of sodium hydrogencarbonate was added to neutralize, and then 35 g of 17% saline was mixed and allowed to stand for 10 minutes until the oil was completely separated from the oil - 21 - 201144274. The organic layer was poured into a pear-shaped flask by decantation, and the water was distilled off under reduced pressure using a rotary evaporator, and the liquid in the pear-shaped flask was filtered by suction filtration to obtain the target cyclohexane in a yield of 93%. Dimethanol monoacrylate 1 66g » [Comparative Example 4] 0.5 g of p-toluenesulfonic acid and 60 g of pure water were fed into a 500 mL four-necked separation flask, and a mixer, a thermometer, an air introduction tube, and a vacuum pump equipped with a cooling trap were installed. . The liquid temperature was adjusted while stirring, and 200 g of cyclohexanedimethanol vinyl ether acrylate synthesized in Production Example 3 was slowly added to the flask while maintaining the temperature at 40 t. After the completion of the addition, the pressure was reduced to 30 kPa, and dry air was introduced at 1 〇〇ml/min. 'Stirring was continued for 1 hour. After analyzing the reaction liquid by gas chromatography, no peak of vinyl butyl acrylate was observed. Stop the reaction. After the completion of the reaction, 1.5 g of sodium hydrogencarbonate was injected to neutralize, and 35 g of 1 7% saline was mixed and allowed to stand for 10 minutes until the oil and water were completely separated. The organic layer was poured into a pear-shaped flask by decantation. After distilling off the water under reduced pressure using a rotary evaporator, the liquid in the pear-shaped flask was filtered by suction filtration to obtain a target ring in a yield of 95%. Hexane dimethanol monoacrylate 169 g. -22- 201144274 [Table i] Item Example 1 Comparative Example 1 Comparative Example 2 Example 2 Comparative Example 3 Example 3 Comparative Example 4 Substance 4HBMA 4HBMA 4HBMA 4HBA 4HBA CHDM-MA CHDM-MA Deethylation rate [%1 100 100 100 100 100 100 100 Acetal dimer [%] 0.09 27.7 18.2 0.11 35.5 0.1 32.8 4HBMA : 4-hydroxybutyl methacrylate 4HBA : 4-hydroxybutyl acrylate CHDM-MA : cyclohexane dimethanol From the above Table 1, it can be understood that in Examples 1 to 3 in which dehydroformylation was further carried out by adding water to the de-alloyation reaction, the acetal dimer was greatly reduced, and in Comparative Example 2, the combined examples were 1 The amount of water used in the initial stage and the amount of water added at the time of initial addition are still used in the initial stage, and an acetal dimer still exists. -twenty three-