201209035 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之羥基烷基（甲基 )丙烯酸酯之製造方法。 【先前技術】 羥基烷基（甲基）丙烯酸酯之製造方法，一般主流爲 藉由酯化反應，自烷二醇獲得二元醇、單酯、二酯混合物 後，僅萃取分離單酯體之方法。具體而言，雖報導有在強 酸存在下使（甲基）丙烯酸與烷二醇反應之方法（參照例 如專利文獻1 )，但因強酸產生副產物，而有收率下降等 之缺點。作爲解決該問題之方法，有關烷二醇與（甲基） 丙烯酸酯之酯交換反應有各種報告（參照例如專利文獻 2〜4)。另外，有關於（甲基）丙烯酸4-羥基丁酯，亦已 報導有效地萃取及純化之方法（參照例如專利文獻5〜6 ) 等。然而，由該等烷二醇之酯化反應中，由於所得產物爲 二元醇、單酯、二酯之混合物，故僅分離出單酯需要過量 之萃取溶劑及多段之作業步驟，並無效率。 以兩階段獲得羥基烷基（甲基）丙烯酸酯之方法已報 導有使含有乙烯醚之醇進行酯交換後，在酸觸媒及醇存在 下脫乙烯化之方法（參照例如專利文獻7)。然而，該方 法被新判定出有反應系統內容易凝膠化之傾向。 [先前技術文獻] -5- 201209035 [專利文獻] [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1 0-298 1 43號公報 [專利文獻3]特開平11_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2005-1 942〇1號公報 [專利文獻7]特開平1 0- 1 82555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有效率地製造高純度之羥 基烷基（甲基）丙烯酸酯之製造方法。 [用以解決課題之手段] 本發明人等經各種檢討之結果，發現使含有乙烯醚之 醇經（甲基）丙烯酸化而成爲含有乙烯醚之（甲基）丙烯 酸酯後，在酸觸媒存在下，藉由使二醇共存之脫乙烯化法 中，藉由二醇之添加使反應時產生之乙縮醛二聚物之化合 物（二酯）分解，獲得高純度之羥基烷基（甲基）丙烯酸 酯。 亦即，本發明如下所述。 (1) 一種羥基烷基（甲基）丙烯酸酯之製造方法， 其特徵爲利用酯交換法使含有乙烯醚之醇經（甲基）丙烯 -6- 201209035 酸化而成爲含有乙烯醚之（甲基）丙烯酸酯，且 及二醇存在下，進行脫乙烯化反應後，再添加二 乙縮醛化反應。 (2)如前述（1)所述之羥基烷基（甲基） 之製造方法，其係使反應系統內之壓力成爲20〜 行脫乙烯化反應後，在1 OkP a以下進行脫乙縮醛 [發明效果] 依據本發明，可提供不需經歷蒸餾等複雜之 ’而有效率地獲得高純度羥基烷基（甲基）丙烯 造方法。 【實施方式】 針對本發明之羥基烷基（甲基）丙烯酸酯之 之實施形態加以詳細說明。 本發明之羥基烷基（甲基）丙烯酸酯之製造 徵爲利用酯交換法使含有乙烯醚之醇經（甲基） 而成爲含有乙烯醚之（甲基）丙烯酸酯後，在酸 下’進行脫乙烯化反應之過程中共存有二醇。 本發明係最先使含有乙烯醚之醇之羥基酯化 #乙烯醚之（甲基）丙烯酸酯。酯化方法主要列 (甲基）丙烯酸之脫水酯化法、使用低級（甲基 醋之酯交換法、使用（甲基）丙烯醯氯之醯鹵法 ’脫水酯化法由於使用酸觸媒，會同時引起脫乙 在酸觸媒 醇進行脫 丙烯酸酯 40kPa 進 化反應。 純化步驟 酸酯之製 製造方法 方法之特 丙烯酸化 觸媒存在 ，獲得含 舉爲使用 )丙烯酸 ，但其中 烧化而不 201209035 適用。另外，醯鹵法由於因反應使鹵素脫離並殘留在系統 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不需要純化作業，故本發明中採用酯 交換法。 本發明中使用之含有乙烯醚之醇列舉爲例如4-羥基 丁基乙烯醚、6-羥基己基乙烯醚、9-羥基壬基乙烯醚、 10-羥基癸基乙烯醚、12-羥基十二烷基乙烯醚等以下述通 式（I)表示之化合物；環己烷二甲醇單乙烯醚等以下述 通式（II)表示之化合物；苯基二甲醇單乙烯醚等。 【化1】 通式⑴ (通式（I)中，η表示3〜11之整數）。 【化2】201209035 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a hydroxyalkyl (meth) acrylate using an alcohol containing a vinyl ether. [Prior Art] A method for producing a hydroxyalkyl (meth) acrylate is generally carried out by extracting a diol, a monoester or a diester mixture from an alkane diol by an esterification reaction, and extracting and separating only the monoester body. method. Specifically, a method of reacting (meth)acrylic acid with an alkanediol in the presence of a strong acid (see, for example, Patent Document 1) has been reported, but a by-product is produced by a strong acid, and there is a disadvantage that the yield is lowered. As a method for solving this problem, various transesterification reactions of an alkanediol and a (meth) acrylate have been reported (see, for example, Patent Documents 2 to 4). Further, regarding 4-hydroxybutyl (meth)acrylate, a method of efficiently extracting and purifying has been reported (see, for example, Patent Documents 5 to 6). However, in the esterification reaction of the alkanediols, since the obtained product is a mixture of a glycol, a monoester, and a diester, only the separation of the monoester requires an excessive amount of the extraction solvent and a plurality of steps, which is inefficient. . In the method of obtaining a hydroxyalkyl (meth) acrylate in two stages, a method of deethylating in the presence of an acid catalyst and an alcohol after transesterification of an alcohol containing a vinyl ether has been reported (see, for example, Patent Document 7). However, this method has been newly judged to have a tendency to be easily gelled in the reaction system. [Prior Art Document] -5-201209035 [Patent Document 1] [Patent Document 1] German Patent No. 1 5 1 1 8 5 7 2 [Patent Document 2] Japanese Patent Publication No. Hei 1 0-298 1 43 [Patent Document 3 [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] An object of the present invention is to provide a method for producing a highly pure hydroxyalkyl (meth) acrylate which can be efficiently produced. [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 form a vinyl ether-containing (meth)acrylate, and then the acid catalyst. In the de-alloyation method in which a diol is coexisted, a compound (diester) of an acetal dimer produced during the reaction is decomposed by addition of a diol to obtain a high-purity hydroxyalkyl group (A) Base) acrylate. That is, the present invention is as follows. (1) A method for producing a hydroxyalkyl (meth) acrylate, characterized in that a vinyl ether-containing alcohol is acidified by (meth) propylene-6-201209035 by a transesterification method to form a vinyl ether-containing (methyl group) The acetalization reaction is carried out after the deethylation reaction is carried out in the presence of an acrylate and a diol. (2) A method for producing a hydroxyalkyl group (methyl) according to the above (1), wherein the pressure in the reaction system is 20 to dealkylation reaction, and then deacetal is carried out at 1 OkPa or less [Effect of the Invention] According to the present invention, it is possible to provide a method for efficiently obtaining a high-purity hydroxyalkyl (meth) propylene without undergoing a complicated process such as distillation. [Embodiment] An embodiment of the hydroxyalkyl (meth) acrylate of the present invention will be described in detail. The hydroxyalkyl (meth) acrylate of the present invention is produced by a transesterification method in which a vinyl ether-containing alcohol is subjected to a (meth) acrylate to a vinyl ether-containing (meth) acrylate. A diol is present in the process of the de-ethylation reaction. The present invention first esterifies a hydroxyl group of a vinyl ether-containing alcohol with a (meth) acrylate of #vinyl ether. The esterification method mainly comprises a dehydration esterification method of (meth)acrylic acid, a low-grade (ester exchange method of methyl vinegar, a hydrazine-halogen method using (meth) acrylonitrile, and a dehydration esterification method using an acid catalyst, At the same time, it will cause the 40 kPa evolutionary reaction of deacetylation in the acid-catalyzed alcohol. The purification step acid ester is produced by the method of manufacturing the special acrylate catalyst, which is obtained by using acrylic acid, but it is burned without 201209035. . Further, the hydrazine halogen method requires a purification treatment such as water washing, adsorption or distillation because the halogen is detached by the reaction and remains in the system. On the other hand, in the transesterification method, since the impurities are small and the purification operation is not required, the transesterification method is employed in the present invention. 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-hydroxydodecane. A compound represented by the following formula (I): a compound represented by the following formula (II) such as cyclohexanedimethanol monovinyl ether; a phenyldimethanol monovinyl ether or the like. In the formula (I), η represents an integer of from 3 to 11). [Chemical 2]
ΟΗ 通式(II) (通式（Π)中，Α表示伸環戊基或伸環己基）。 酯交換法所使用之低級（甲基）丙烯酸酯具體而言列 舉爲（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基 )丙烯酸丙酯、（甲基）丙烯酸丁酯等。亦即，本申請案 中所稱之低級（甲基）丙烯酸酯意指具有碳數4以下之烷 基者。 201209035 酯交換反應之過程中，就反應時間短、高的酯轉換率 、反應後之後處理之觀點而言，相對於含有乙烯醚之醇化 合物，較好等量至過量使用低級（甲基）丙烯酸酯。具體 而言，通常相對於含有乙烯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，且超過20莫耳時，反應後之濃縮步驟需要長時間 ，使生產性變差。 至於酯交換法所適用之觸媒，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。就極力抑制該等副反應，於 反應結束後可添加水輕易去除觸媒而言，更好爲烷氧化鈦 或烷氧化鋁。 又，觸媒之使用量相對於低級（甲基）丙烯酸酯與含 有乙烯醚之醇化合物之合計量，通常較好爲〇.〇1〜5.0質 量％之範圍。觸媒量即使多於必要以上之量亦幾乎不會影 響反應速度，相反地去除之際需要大量水等，僅是變得不 經濟而已。 本發明之酯交換反應中可添加、倂用習知之聚合抑制 -9- 201209035 劑。聚合抑制劑列舉爲例如氫醌、氫醌單甲基醚（亦稱爲 「對甲氧基苯酚」）等之酚類；吩噻嗪、伸乙基硫脲等之 硫化合物：二丁基二硫代胺基甲酸銅等之銅鹽；乙酸錳等 之錳鹽；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0.1質量％以下。超過0.1質量 %時會有因添加劑引起著色之情況。 於酯交換反應之際，較好吹入少量之分子狀氧以防止 反應中反應液之聚合。分子狀氧較好以稀釋狀態使用，且 以使用空氣較適當。另外，吹入分子狀氧亦可用以防止經 蒸發而以蒸汽存在並於上部釜壁面等上凝縮之（甲基）丙 烯酸酯類之聚合故而較佳。 所謂分子狀氧意指由兩個氧原子作成之基底狀態之三 重態氧分子（〇2 )，亦意指可直接以該狀態直接參與反應 ，但藉由與觸媒或反應試劑之相互作用，轉換成單重態氧 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。 至於分子狀氧之導入量亦受反應機形狀與攪拌動力之 影響，但相對於原料之含有乙烯醚之醇1莫耳，較好以 5~5 00 ml/分鐘（以空氣計爲25~2500 ml/分鐘）之速度吹 入。分子狀氧之導入量未達5 ml/分鐘時，聚合抑制效果 不足，超過500 ml/分鐘時，將低級（甲基）丙烯酸酯押 出系統外之效果變強，造成作爲原料之低級（甲基）丙烯 酸醋之耗損。 10- 201209035 本發明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6 (TC時反應速度使反應極度變慢，且超過 1 2 0°c時，容易引起酯交換反應中所得之含有乙烯醚之（ 甲基）丙烯酸酯之聚合，且容易引起著色。 至於酯交換反應之形態可以熟悉（甲基）丙烯酸酯製 造之該技藝者一般已知之方法進行。酯交換反應時必須使 副生之低級醇以低級（甲基）丙烯酸酯及/或溶劑共沸餾 除。因此，使用例如附加精餾塔之回分式反應槽作爲反應 裝置。 酯交換反應結束後，以水使觸媒失活，以濃縮裝置餾 除過量之低沸點成份。利用低沸點成份之濃縮裝置進行餾 除較好在常壓或減壓下，一面使液溫維持在9 0°C以下一面 進行，更好爲50〜70°C之範圍內。液溫超過90°C時，引起 含有乙烯醚之（甲基）丙烯酸酯之著色或聚合之可能性變 高。 完成低沸點成份餾除之含有乙烯醚之（甲基）丙烯酸 酯可藉由過濾去除殘留之失活觸媒等不溶份。過濾時爲了 效率良好地濾除不溶份，較好使用矽藻土等過濾助劑。 接著，針對進行含有乙烯醚之（甲基）丙烯酸酯之脫 乙烯化反應，獲得羥基烷基（甲基）丙烯酸酯之方法加以 說明。 本發明之脫乙烯化反應係在酸觸媒存在下，使二醇共 存而進行。二醇存在下進行脫乙烯化反應時所生成之甲基 乙縮醛可藉由使反應系統內減壓而去除，但二醇會與由脫 201209035 乙烯化反應生成之羥基烷基（甲基）丙烯酸酯反應 羥基烷基（甲基）丙烯酸酯甲基乙縮醛（乙縮醛二 。殘留有乙縮醛二聚物時，聚合時由於交聯反應而 黏度化或凝膠化等之異常。乙縮醛二聚物化反應爲 應，在酸觸媒下容易經脫乙縮醛化。 本發明之脫乙烯化反應之際可使用之酸觸媒通 爲硫酸、硫酸氫鈉、對甲苯磺酸、苯磺酸、甲烷磺 體酸（沸石、amberlite®、Amberlyst®、Nafion®等 ，使用之觸媒量相對於經反應之含有乙烯醚之（甲 烯酸酯較好爲0.1重量％〜10重量％，更好爲0.5 〜3重量％。使用之觸媒量未達〇.1重量％時，脫乙 應性顯著下降，反應變極慢。又，多於10質量％ 有大量生成乙縮醛二聚物等副產物之傾向。 本發明之脫乙烯化反應時之二醇只要是例如乙 丙二醇、丁二醇等可輕易取得之二醇即無限制，亦 複數種該等化合物使用。考慮與乙烯基之反應性、 物之安定性時較好使用乙二醇。又，二醇之使用量 含有乙烯醚之（甲基）丙烯酸酯只要爲等莫耳以上 別限制，但以相對於含有乙烯醚之（甲基）丙烯酸 1.05〜3.0莫耳當量’可加速脫乙烯化反應之進行， 制乙縮醛二聚物之生成量。二醇之使用量相對於含 醚之（甲基）丙烯酸酯爲等莫耳以下時，脫乙烯化 緩慢，使用超過3.0莫耳當量時，沒有促進脫乙烯 之效果，且反應後必需去除過量之二醇而無效率。 ，形成 聚物） 出現高 可逆反 常列舉 酸、固 )。又 基）丙 重量％ 烯化反 時，會 二醇、 可組合 或反應 相對於 即無特 酯使用 且可抑 有乙烯 之進行 化反應 -12- 201209035 本發明之脫乙烯化反應爲放熱反應，反應生成之甲基 乙縮醛有必要使系統內減壓而去除。使反’應溫度控制在 6 0°C以下，較好控制在20°C〜40°C，可獲得高純度之羥基 烷基（甲基）丙烯酸酯。控制反應溫度之方法列舉爲使反 應器冷卻，或者將含有乙烯醚之（甲基）丙烯酸酯緩慢添 加於觸媒水溶液中之方法。另外，發熱結束後，以溫浴等 加溫以保持溫度。反應溫度若在2〜40°C之範圍則可以 系統內壓力於20〜40 kP a左右有效地去除甲基乙縮醛。 本發明之特徵爲在進行脫乙烯化反應後，進一步添加 二醇進行脫乙縮醛化反應。二醇之添加量並無特別限制， 但以含有乙烯醚（甲基）丙烯酸酯爲基準較好爲3〜30重 量％。二醇之使用量在該範圍外時，無法效率良好地進行 脫乙縮醛化反應。又，二醇之添加方法可爲緩慢滴加之方 法，亦可爲一次添加之方法。另外，必須有效率地去除脫 乙縮醛化時生成之甲基乙縮醛，故更好使系統內之壓力成 爲10kPa以下。本乙縮醛化反應中使用之二醇種類較好與 上述脫乙烯化反應時所使用者相同，但亦可使用不同者。 本發明之脫乙烯化反應及脫乙縮醛反應之際，較好與 酯交換反應時同樣吹入少量分子狀氧，以防止反應中反應 液之聚合。 脫乙烯化反應結束後，必須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，爲了提高分離能，可 -13- 201209035 單獨或組合兩種以上使用例如甲苯或二甲苯等之溶劑，且 ，可使用利用添$卩氯化鈉等增大水層比重之方法。 中和後，可藉由濃縮餾除過量水分，或於使用溶劑時 則餾除溶劑。濃縮較好在常壓或減壓下，一面使液溫維持 在90°C以下一面進行，更好爲65t〜85°C之範圍內。液溫 超過90 °C時，引起羥基烷基（甲基）丙烯酸酯著色或聚合 之可能性高。 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。 本發明之羥基烷基（甲基）丙烯酸酯之製造方法由於 可藉由使用二醇進行脫乙烯化反應及脫乙縮醛化反應，獲 得高純度之羥基烷基（甲基）丙烯酸酯，故不需要過濾以 外之生成步驟，但可視需要實施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。 [製造例1] (甲基丙烯酸乙烯氧基丁基酯之合成） 於4L之四頸圓底可分離燒瓶中饋入4-羥基丁基乙烯 基醚（九善石油化學製造之HBVE) 1 000g、甲基丙烯酸 甲酯30 00g、氫醌甲基醚〇.65g，且設置精餾塔（15段） -14 - 201209035 、攪拌機、空氣導入管、溫度計。在攪拌下，一 ml/分鐘導入乾燥空氣一面開始加熱，以使回流 內之液溫成爲75°C之方式將壓力調整成40kPa左 系統內之水分。確認系統內之水分爲300ppm以 入四異丙氧化鈦8.6g作爲觸媒，使反應溫度成: 之方式將燒瓶內之壓力控制在60kPa左右。監控 時精餾塔上部之溫度（塔頂溫度）時，由於生成 甲基丙烯酸甲酯之共沸溫度相近，故以使塔頂 6 0°C左右之方式調節回流比，邊使甲醇成爲與甲 甲酯之共沸物餾除邊進行反應。反應經4小時後 開始上升，故緩慢加大回流比繼續反應。以氣相 反應第5小時之反應液，酯轉化率爲99.2%，故 。將反應液冷卻，使液溫成爲7 5 °C後添加1 7質 鹽水25 0g使觸媒水解。靜置1 5分鐘後，以傾析 倒入梨型燒瓶中’使用旋轉蒸發器減壓餾除過量 烯酸甲酯後’以抽氣過濾而過濾梨型燒瓶內之液 1522g之標的甲基丙烯酸乙烯基氧基丁基酯。 [實施例1] (使用乙二醇合成甲基丙烯酸4 -羥基丁基酯） 於1L·之四頸可分離燒瓶中饋入對甲苯磺酸 二醇101g，且設置攪拌機、溫度計、空氣導入 卻阱之真空泵。一面進行攪拌一面以使液溫調節 40亡下將製造例1合成之甲基丙烯酸乙烯基氧 面以100 時之燒瓶 右，去除 下後，饋 U 9 5 ± 5 °C 加熱回流 之甲醇與 溫度成爲 基丙烯酸 塔頂溫度 層析分析 結束反應 量％之食 將有機層 之甲基丙 體，獲得 2.5g、乙 管、附冷 在保持於 基丁基酯 -15- 201209035 2 5 0g緩慢添加於燒瓶中。添加結束後，減壓至30kPa，一 面以100 ml/分鐘導入乾燥空氣一面持續攪拌一小時，以 氣體層析儀分析反應液，結果未發現甲基丙烯酸乙烯基氧 基丁基酯之峰。然而，以液體層析儀分析可確認到生成 14.4%之乙縮醛二聚物，故添加乙二醇25.2g，使壓力成 爲5kPa進行脫乙縮醛化反應。反應2小時後分析結果， 乙縮醛二聚物之峰幾乎消失，故結束反應。於反應結束之 液體中饋入碳酸氫鈉1 . 8 g及純水8 g中和洗淨後，混合1 7 %之食鹽水78g，且靜置10分鐘直至油水完全分離。以 氣體層析儀分析有機層，結果由於殘留過量之乙二醇，故 以10%食鹽水120g洗淨去除乙二醇。以傾析將有機層倒 入梨型燒瓶中，使用旋轉蒸發器，減壓餾除水分後，以抽 氣過濾過濾梨型燒瓶內之液體，以收率87%獲得標的物 質 1 86g。 [實施例2] (使用丙二醇合成甲基丙烯酸4-羥基丁基酯） 於1L之四頸可分離燒瓶中饋入對甲苯磺酸2.5g、丙 二醇124g，且設置攪拌機、溫度計、空氣導入管、附冷 卻阱之真空泵。一面進行攪拌一面以使液溫調節在保持於 40°C下將製造例1合成之甲基丙烯酸乙烯基氧基丁基酯 2 5 0g緩慢添加於燒瓶中。添加結束後，減壓直至30kPa， 一面以100 ml/分鐘導入乾燥空氣一面持續攪拌一小時， 以氣體層析儀分析反應液，結果未發現甲基丙烯酸乙烯基 -16- 201209035 氧基丁基酯之峰。然而，以液體層析儀分析可確認到生成 16.2%之乙縮醛二聚物，故添加丙二醇31g，使壓力成爲 5kPa進行脫乙縮醛化反應。反應2小時後分析結果，乙 縮醛二聚物之峰幾乎消失，故結束反應。於反應結束之液 體中饋入碳酸氫鈉1 .8g及純水8g中和洗淨後，混合17% 之食鹽水7 8 g，且靜置1 0分鐘直至油水完全分離。以氣 體層析儀分析有機層後，由於殘留過量之丙二醇，故以 1 0%食鹽水1 20g洗淨去除丙二醇。以傾析將有機層倒入 梨型燒瓶中，使用旋轉蒸發器，減壓餾除水分，以抽氣過 濾過濾梨型燒瓶內之液體，以收率84 %獲得標的物質 1 8 0g。以液體層析儀分析最終之乙縮醛二聚物爲0.12%。 [比較例1 ] 於1L之四頸可分離燒瓶中饋入對甲苯磺酸2.5g、乙 二醇l〇lg，且設置攪拌機、溫度計、空氣導入管、附冷 卻阱之真空泵。一面進行攪拌一面以使液溫調節在保持於 40°C下將製造例1合成之甲基丙烯酸乙烯基氧基丁基酯 250g緩慢添加於燒瓶中。添加結束後，減壓直至30kPa， 一面以100 ml/分鐘導入乾燥空氣一面持續攪拌一小時， 以氣體層析分析反應液，結果未發現甲基丙烯酸乙烯基氧 基丁基酯之峰，故結束反應。饋入碳酸氫鈉1.8g及純水 8g中和洗淨後’混合17%之食鹽水78g ’且靜置10分鐘 直至油水完全分離。以氣體層析儀分析有機層後’由於殘 留過量之乙二醇，故以10%食鹽水12〇g洗淨去除乙二醇 -17- 201209035 。以傾析將有機層倒入梨型燒瓶中，使用旋轉蒸發器，減 壓餾除水分後’以抽氣過濾過濾梨型燒瓶內之液體，以收 率93 %獲得標的物質1 99g。以液體層析儀分析所得物質 後，存在17.1%之乙縮醛二聚物之峰。 [比較例2](利用專利文獻7之製造方法） 於1L之四頸可分離燒瓶中饋入硫酸〇.〇6g、乙二醇 8 5 g，且設置攪拌機、溫度計、附冷卻阱之真空泵。一面 進行攪拌一面在室溫下緩慢添加製造例1中合成之甲基丙 烯酸乙烯基氧基丁基酯 25 0g。添加結束後，減壓直至 1 kPa，持續攪拌2小時時以氣體層析分析反應液後，未發 現甲基丙烯酸乙烯基氧基丁基酯之峰。另外，以液體層析 儀分析乙縮醛二聚物爲22.6%，但該分析過程中反應系統 凝膠化，隨後之處理變得困難。 表1] 項目 實施例1 實施例2 比較例1 比較例2 標的物質 4HBMA 4HBMA 4HBMA 4HBMA 脫乙烯化率[%] 100 100 100 100 乙縮酸二聚物[%] 0.12 0.16 17.1 22.6(凝膠化） 4HBMA:甲基丙烯酸4_羥基丁基酯 由上表1可了解’脫乙嫌化反應後進而添加二醇進行 脫乙縮醛化之實施例1及2中之乙縮酸二聚物大幅減少。 -18-ΟΗ Formula (II) (In the formula (Π), Α represents a cyclopentyl group or a cyclohexyl group). Specific examples of the lower (meth) acrylate used in the transesterification method include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. . That is, the lower (meth) acrylate referred to in the present application means an alkyl group having a carbon number of 4 or less. 201209035 During the transesterification reaction, low-grade (meth)acrylic acid is preferably used in an equivalent amount to an excess amount with respect to the vinyl ether-containing alcohol compound in terms of a short reaction time, a high ester conversion ratio, and a post-reaction treatment. ester. Specifically, the lower (meth) acrylate is usually used in an amount of from 1.0 to 20 mol per mol of the hydroxyl group of the vinyl ether-containing alcohol compound. When the amount of the lower (meth) acrylate is less than 1.0 mol with respect to the hydroxyl group of the vinyl ether-containing alcohol compound, the reaction does not proceed sufficiently, and when it exceeds 20 mol, the concentration step after the reaction takes a long time. To make the production worse. As the catalyst to which the transesterification method is applied, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate; lithium pentoxide or methoxide; Alkali metal alkoxides such as sodium, sodium ethoxide and potassium butoxide; alkali metal amides such as lithium amide, sodium amide, potassium amide; tetramethyl orthotitanate; tetraethyl orthotitanate Alkyl titanate such as tetrapropyl titanate, tetraisopropyl orthotitanate or tetrabutyl orthotitanate; other alkane alumina; alkoxy tin oxide. The side reaction is suppressed as much as possible, and after the reaction, water may be added to easily remove the catalyst, and more preferably a titanium alkoxide or an alkane oxide. Further, the amount of the catalyst used is usually in the range of from 〜1 to 5.0% by mass based on the total amount of the lower (meth) acrylate and the vinyl ether-containing alcohol compound. Even if the amount of the catalyst is more than necessary, the reaction speed is hardly affected. On the contrary, a large amount of water is required for the removal, and it is only uneconomical. In the transesterification reaction of the present invention, a conventional polymerization inhibitor -9-201209035 may be added or used. The polymerization inhibitor is exemplified by a phenol such as hydroquinone or hydroquinone monomethyl ether (also referred to as "p-methoxyphenol"); a sulfur compound such as phenothiazine or ethyl thiourea: dibutyl group a copper salt such as copper thiocarbamate; a manganese salt such as manganese acetate; a nitro compound, a nitroso compound, a 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy group or the like N- An oxy compound or the like. The amount of the polymerization inhibitor added is preferably 0.1% by mass or less based on the ester to be produced. When it exceeds 0.1% by mass, coloring may occur due to an additive. At the time of the transesterification reaction, a small amount of molecular oxygen is preferably blown in to prevent polymerization of the reaction liquid in the reaction. Molecular oxygen is preferably used in a diluted state, and it is appropriate to use air. Further, it is preferable to blow in the molecular oxygen to prevent the polymerization of (meth) acrylate which is vaporized and which is condensed on the upper wall surface or the like by evaporation. Molecular oxygen means a triplet oxygen molecule (〇2) in a basal state formed by two oxygen atoms, and means that it can directly participate in the reaction directly in this state, but by interaction with a catalyst or a reagent, An oxygen molecule that participates in the reaction after being converted into a singlet oxygen molecule or an oxygen atom, a superoxide, a peroxide, or the like. The introduction amount of molecular oxygen is also affected by the shape of the reactor and the stirring power, but it is preferably 5 to 500 ml/min (25 to 2500 in terms of air) relative to the vinyl ether-containing alcohol 1 mol of the raw material. The speed of ml/min) is blown in. When the introduction amount of molecular oxygen is less than 5 ml/min, the polymerization inhibiting effect is insufficient. When the amount exceeds 500 ml/min, the effect of lowering the lower (meth) acrylate out of the system becomes stronger, resulting in a lower level (methyl) as a raw material. ) The loss of acrylic vinegar. 10-201209035 The transesterification reaction of the present invention is preferably carried out at 60 to 12 ° C under normal pressure or reduced pressure. When the temperature is less than 6 (the reaction rate at TC makes the reaction extremely slow, and when it exceeds 120 ° C, the polymerization of the vinyl ether-containing (meth) acrylate obtained in the transesterification reaction is likely to occur, and coloring is likely to occur. The form of the transesterification reaction can be carried out by a method generally known to those skilled in the art for the manufacture of (meth) acrylate. The transesterification reaction must be such that the by-product lower alcohol is azeotroped with a lower (meth) acrylate and/or solvent. Therefore, a fractional reaction tank such as an additional rectification column is used as a reaction apparatus. After the end of the transesterification reaction, the catalyst is deactivated by water, and excess low-boiling components are distilled off by a concentrating device. The concentration of the concentrating device is preferably carried out under normal pressure or reduced pressure while maintaining the liquid temperature below 90 ° C, 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 vinyl ether-containing (meth) acrylate becomes high. The vinyl ether-containing (meth) acrylate which is distilled off by the low-boiling component can be removed by filtration to remove the residual deactivated catalyst. In order to filter out the insoluble matter in an efficient manner during filtration, it is preferred to use a filter aid such as diatomaceous earth. Next, a dehydroxylation reaction of a (meth) acrylate containing a vinyl ether is carried out to obtain a hydroxyalkyl group ( The method of the methyl acrylate is described. The de-ethylation reaction of the present invention is carried out by coexisting a diol in the presence of an acid catalyst, and the methyl acetal formed during the de-ethylation reaction in the presence of a diol It can be removed by depressurizing the reaction system, but the diol will react with the hydroxyalkyl (meth) acrylate formed by the ethylene reaction of 201209035 to react with hydroxyalkyl (meth) acrylate methyl acetal ( Acetal aldehyde 2. When an acetal dimer remains, the viscosity during the polymerization is abnormal due to the crosslinking reaction, such as viscosity or gelation. The acetal dimerization reaction is suitable, and it is easy to remove under the acid catalyst. Acetalization. The acid catalyst used in the deethylation reaction of the present invention is sulfuric acid, sodium hydrogen sulfate, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid (zeolite, amberlite®, Amberlyst®, Nafion®, etc. The amount of the catalyst is relative to the reacted vinyl ether-containing (methic acid ester is preferably from 0.1% by weight to 10% by weight, more preferably from 0.5% to 3% by weight. The amount of the catalyst used is less than 0.1% by weight. In addition, the decoupling property is remarkably lowered, and the reaction becomes extremely slow. Further, more than 10% by mass tends to generate a large amount of by-products such as an acetal dimer. The diol in the deethylation reaction of the present invention is, for example, The diol which can be easily obtained, such as ethylene propylene glycol and butane diol, is not limited, and a plurality of such compounds are used. It is preferable to use ethylene glycol in consideration of reactivity with a vinyl group and stability of a substance. The amount of (meth) acrylate containing a vinyl ether to be used may be accelerated by a dealkylation reaction with respect to 1.05 to 3.0 mol equivalents of (meth)acrylic acid containing vinyl ether, as long as it is equal to or higher than the molar amount. The amount of acetal dimer produced. When the amount of the diol used is less than or equal to the molar amount of the ether-containing (meth) acrylate, the deethylation is slow, and when the amount is more than 3.0 moles, the effect of deacetylation is not promoted, and the excess must be removed after the reaction. Glycol is not efficient. , formation of a polymer) appears highly reversible anomaly list acid, solid). Further, when the olefination is reversed, the diol may be combined or reacted with respect to the unesterified ester and the progress of the ethylene may be inhibited. -12-201209035 The deethylation reaction of the present invention is an exothermic reaction. The methyl acetal formed by the reaction needs to be removed by decompression in the system. The high-purity hydroxyalkyl (meth) acrylate can be obtained by controlling the temperature at 60 ° C or lower, preferably at 20 ° C to 40 ° C. The method of controlling the reaction temperature is exemplified by cooling the reactor or slowly adding a vinyl ether-containing (meth) acrylate to the aqueous solution of the catalyst. Further, after the end of the heat generation, the temperature is maintained by a warm bath or the like to maintain the temperature. When the reaction temperature is in the range of 2 to 40 ° C, the methyl acetal can be effectively removed at a pressure of about 20 to 40 kPa in the system. The present invention is characterized in that after the de-ethylation reaction, a diol is further added to carry out a deacetalization reaction. The amount of the diol to be added is not particularly limited, but is preferably from 3 to 30% by weight based on the weight of the vinyl ether (meth) acrylate. When the amount of the diol used is outside the range, the acetalization reaction cannot be carried out efficiently. Further, the method of adding the diol may be a method of slowly dropping or a method of adding one time. Further, it is necessary to efficiently remove the methyl acetal formed during the acetalization, so that the pressure in the system is more preferably 10 kPa or less. The type of the diol used in the acetalization reaction is preferably the same as that of the user in the above deethylation reaction, but different ones may be used. In the deethylation reaction and the deacetalization reaction of the present invention, it is preferred to blow a small amount of molecular oxygen in the same manner as in the transesterification reaction to prevent polymerization of the reaction liquid in the reaction. After the end of the de-ethylation reaction, the acid catalyst must be neutralized with a base and separated. 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, in the case of separating and removing the water layer after neutralization, in order to improve the separation energy, a solvent such as toluene or xylene may be used alone or in combination of two or more kinds, and the use of sodium, sodium chloride or the like may be used. The method of the proportion of large water layers. After the neutralization, excess water can be distilled off by concentration, or the solvent can be distilled off when a solvent is used. The concentration is preferably carried out under normal pressure or reduced pressure while maintaining the liquid temperature at 90 ° C or lower, more preferably in the range of 65 t to 85 ° C. When the liquid temperature exceeds 90 °C, the possibility of coloring or polymerizing the hydroxyalkyl (meth) acrylate is high. After concentration, the residue and the insoluble matter such as salt can be removed by filtration. In order to efficiently remove the insoluble matter during filtration, it is preferred to use a filtration aid such as diatomaceous earth. The method for producing a hydroxyalkyl (meth) acrylate of the present invention can obtain a high-purity hydroxyalkyl (meth) acrylate by performing a de-ethylation reaction and a deacetalization reaction using a diol. The production step other than filtration is not required, but a general purification method such as distillation may be carried out as needed. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. [Production Example 1] (Synthesis of ethylene oxybutyl methacrylate) 4-hydroxybutyl vinyl ether (HBVE manufactured by Jiushan Petrochemical Co., Ltd.) was fed into a 4 L four-neck round bottom separable flask (1 000 g) Methyl methacrylate 30 00g, hydroquinone methyl ether 〇.65g, and set up the distillation column (15 segments) -14 - 201209035, mixer, air inlet tube, thermometer. Under agitation, one ml/min was introduced into the dry air to start heating, and the pressure in the reflux was adjusted to 75 ° C to adjust the pressure to 40 kPa of water in the left system. It was confirmed that the water content in the system was 300 ppm, and 8.6 g of titanium tetraisopropoxide was used as a catalyst, and the pressure in the flask was controlled to about 60 kPa so that the reaction temperature became: When monitoring the temperature at the top of the rectification column (the temperature at the top of the column), since the azeotropic temperature of methyl methacrylate is similar, the reflux ratio is adjusted so that the top of the column is about 60 ° C. The reaction is carried out while distilling off the azeotrope of the methyl ester. The reaction started to rise after 4 hours, so the reaction was continued by slowly increasing the reflux ratio. In the reaction liquid of the fifth hour of the gas phase reaction, the ester conversion rate was 99.2%. The reaction solution was cooled, and the temperature of the solution was changed to 75 ° C, and then 25 g of 1 7 brine was added to hydrolyze the catalyst. After standing for 15 minutes, it was poured into a pear-shaped flask by decantation. After distilling off excess methyl enoate under reduced pressure using a rotary evaporator, '1522 g of the target methacrylic acid in a pear-shaped flask was filtered by suction filtration. Vinyloxybutyl ester. [Example 1] (Synthesis of 4-hydroxybutyl methacrylate using ethylene glycol) 101 g of p-toluenesulfonic acid diol was fed into a four-neck separable flask of 1 L·, and a stirrer, a thermometer, and an air introduction were provided. The vacuum pump of the trap. While stirring, the liquid temperature was adjusted to 40, and the methacrylic acid vinyloxy surface synthesized in Example 1 was applied to the right side of the flask for 100 hours. After removing the mixture, the methanol and the temperature were heated and refluxed at U 9 5 ± 5 °C. The base of the acrylic acid was subjected to temperature analysis at the end of the temperature analysis. The methyl group of the organic layer was obtained, and 2.5 g of the organic layer was obtained, and the tube was cooled, and the cold was added to the base butyl ester-15-201209035 250g. In the flask. After the completion of the addition, the pressure was reduced to 30 kPa, and dry air was introduced at 100 ml/min while stirring for one hour, and the reaction liquid was analyzed by a gas chromatograph. As a result, no peak of vinyl oxy methacrylate was observed. However, it was confirmed by liquid chromatograph that 14.4% of an acetal dimer was formed. Therefore, 25.2 g of ethylene glycol was added, and the pressure was changed to 5 kPa to carry out a deacetalization reaction. After the reaction for 2 hours, the peak of the acetal dimer almost disappeared, and the reaction was terminated. After the reaction was completed, sodium hydrogencarbonate (1.8 g) and pure water (8 g) were neutralized and washed, and then 78 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 analyzed by a gas chromatograph, and as a result, since ethylene glycol remained in an excess amount, 120 g of 10% saline solution was washed to remove ethylene glycol. 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. Then, the liquid in the pear-shaped flask was filtered by suction filtration to obtain a substance of 86 g in a yield of 87%. [Example 2] (Synthesis of 4-hydroxybutyl methacrylate using propylene glycol) In a 1 L four-neck separable flask, 2.5 g of p-toluenesulfonic acid and 124 g of propylene glycol were fed, and a stirrer, a thermometer, an air introduction tube, and the like were placed. Vacuum pump with cooling trap. While stirring, the solution was adjusted to a temperature of 40 ° C, and 250 g of vinyl methacrylate methacrylate synthesized in Production Example 1 was slowly added to the flask. After the completion of the addition, the pressure was reduced to 30 kPa, and while introducing dry air at 100 ml/min, stirring was continued for one hour, and the reaction liquid was analyzed by a gas chromatograph. As a result, no vinyl methacrylate--16-201209035 oxybutyl ester was found. The peak. However, it was confirmed by liquid chromatograph that 16.2% of an acetal dimer was formed. Therefore, 31 g of propylene glycol was added, and the pressure was changed to 5 kPa to carry out a deacetalization reaction. After the reaction for 2 hours, the peak of the acetal dimer almost disappeared, and the reaction was terminated. After the reaction was completed, sodium hydrogencarbonate (1.8 g) and pure water (8 g) were neutralized and washed, and then 17 g of 17% saline was mixed, and allowed to stand for 10 minutes until the oil and water were completely separated. After the organic layer was analyzed by a gas chromatograph, propylene glycol was removed by washing with 10% of 10% saline solution to remove propylene glycol. The organic layer was poured into a pear-shaped flask by decantation, and 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 a target substance of 180 g in a yield of 84%. The final acetal dimer was analyzed by liquid chromatography to be 0.12%. [Comparative Example 1] A four-neck separable flask of 1 L was fed with 2.5 g of p-toluenesulfonic acid and 100 g of ethylene glycol, and a vacuum pump equipped with a stirrer, a thermometer, an air introduction tube, and a cold trap was placed. While stirring the liquid temperature, 250 g of vinyl methacrylate methacrylate synthesized in Production Example 1 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 while introducing dry air at 100 ml/min, stirring was continued for one hour, and the reaction liquid was analyzed by gas chromatography. As a result, no peak of vinyl oxybutyl methacrylate was observed, so that the end was completed. reaction. After feeding 1.8 g of sodium hydrogencarbonate and 8 g of pure water, the mixture was washed and mixed with 17% of saline water 78 g and allowed to stand for 10 minutes until the oil and water were completely separated. After the organic layer was analyzed by a gas chromatograph, ethylene glycol -17-201209035 was removed by washing with 10 g of 10% saline solution due to excess ethylene glycol remaining. 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 to obtain a target substance of 99 g at a yield of 93%. After the obtained material was analyzed by a liquid chromatograph, a peak of 17.1% of an acetal dimer was present. [Comparative Example 2] (Using the production method of Patent Document 7) A four-neck separable flask of 1 L was fed with barium sulfate, 〇6 g, and ethylene glycol (85 g), and a stirrer, a thermometer, and a vacuum pump with a cooling trap were placed. While stirring, 25 0 g of vinyl methacrylate methacrylate synthesized in Production Example 1 was slowly added thereto at room temperature. After completion of the addition, the pressure was reduced to 1 kPa, and after stirring for 2 hours, the reaction liquid was analyzed by gas chromatography, and a peak of vinyl oxy methacrylate was not observed. Further, the acetal dimer was analyzed by liquid chromatography to be 22.6%, but the reaction system gelled during the analysis, and subsequent processing became difficult. Table 1] Example Example 1 Example 2 Comparative Example 1 Comparative Example 2 Substance 4HBMA 4HBMA 4HBMA 4HBMA Deethylation ratio [%] 100 100 100 100 Acetate dimer [%] 0.12 0.16 17.1 22.6 (gelation 4HBMA: 4-hydroxybutyl methacrylate. From the above Table 1, it can be understood that the acetal dimer in Examples 1 and 2 after the de-ethylation reaction and the addition of the diol are deacetalized. cut back. -18-