200829540 九、發明說明： 【發明所屬之技術領域3 技術領域 本發明係有關於生產性高、且可以穩定之製造條件來 5 製造之二烧基胺基烧基（甲基）丙稀酸醋四級鹽之製造方法 及其製造裝置。 背景技術 二烧基胺基烧基（甲基）丙烯酸酯四級鹽（以下稱作 10 「DAM」）係陽離子性聚合物之原料等，可使用於各種用途 作為高分子凝聚劑、紙張增強劑、抗靜電劑及土壤改良劑 等之製造原料。 一般而S ’藉由使用水作為溶媒，在該溶媒存在下供 應原料，去除反應熱並使其反應，可在DAM之水溶液形態 15下製造DAM。又，以往，DAM係以批式製造(例如，專利 文獻1及同2等）。 但是，由於以批式製造dam的方法係以1個反應器進 行製造，需要在每次製造dam時重新裝入原料，再於反應 結束後抽出產品，而且，為使製造條件穩定而需要長時間 20進行，在生產性上有問題。又，因為是批式，相對於反應 液之原料)辰度或反應熱等製造條件之穩定化極為困難，所 得之產品之品質容易不穩定。再者，在水或含有水之反應 溶媒系中，若原料之丙烯酸酯殘留於反應液中，則丙烯酸 酯就會水解，而容易產生丙烯酸。一旦丙烯酸作為雜質成 5 200829540 分存在於DAM產品中，在將聚合所得之高分子作為凝聚劑 使用時，就會有引起性能降低的情形。 為解決此種問題點，本發明人報告了一種製造方法， 係在含有以DAM水溶液作為反應溶媒之反應器中，連續供 5 應一燒基胺基烧基（甲基）丙烯酸酯、四級化劑及水，並連續 抽出上述反應器中之反應液，作為生產性高、且產品間品 質良莠不齊很少的高純度DAM之製造方法(專利文獻3)。 然而，該製造方法雖為優異之方法，但在以氣體供應 低沸點之四級化劑來作為四級化劑時，需要使四級化劑之 10 供應壓力比反應器内之壓力大。因此，四級化劑之供應需 要加壓，且反應液會逆流至四級化劑之供應配管中而堵塞 配管。此外，在將液體狀之四級化劑直接供應至反應器時， 反應液中之四級化劑的分散就會不充分，故反應性會降低。 因此，本發明人發現，藉由喷射器來進行四級化劑之 15 供應，反應液就不會逆流至四級化劑之供應配管中，且四 級化劑可均勻地喷灑入反應液中，提高四級化劑在反應液 中之溶解性，使反應性優異（專利文獻4)。 【專利文獻1】 特開平4-217649號公報 2〇【專利文獻2】 特開平8-268985號公報 【專利文獻3】 特開2003-342244號公報 【專利文獻4】 6 200829540 特開2004-155669號公報 【發明内容3 發明揭示 . 發明所欲解決之問題 • 5 如專利文獻4,以連續式且藉由喷射器來進行四級化劑 之供應的DAM之製造方法雖為優異之方法，但因四級化反 應為放熱反應，所以會產生在提高反應性的同時，也會使 反應裔内之溫度控制變困難的問題。通常，反應槽之冷卻 • 係使用反應槽之夾套式(jacket type)熱交換器來進行，因不 . 10易使冷卻能力（除熱量）跟上放熱量，反應器内之溫度會上 升。反應器内之溫度一旦升得過高，就會產生所生成之DAM 之聚合反應、酯之水解等問題，而不易穩定地製造高品質 之DAM。因此，長久以來便期待著一種可確實地進行反應 器内之溫度控制的方法。 I5 又’當除熱量不足時，若欲增加生產量，也會有要加 大反應器，或使用複數反應器等問題。 φ 即，本發明之目的在於提供可藉由將反應液有效率地 冷卻，來控制反應器内之溫度上升，即使在使用袖珍之反 應器時，也可以高生產性製造高純度dam的方法。又，另 20 一目的在於提供適合該製造方法之製造裝置。 - 用以解決問題之手段 本發明人為解決前述問題而進行各種檢討後，發現藉 由在反應中，從反應器中抽出一部分之反應液’將其通過 熱交換器冷卻，並藉由噴射器將該冷卻之反應液和四級化 7 200829540 劑一併供應至反應器内，可有效地進行反應器内之除熱， 以高生產性來製造高純度dam。根據此種見解再進一步進 行研究後，便完成了本發明。 即，本發明提供以下之二烷基胺基烷基（甲基）丙烯酸酯 5 四級鹽之製造方法及其製造裝置。 第1項·一種二烷基胺基烷基（甲基）丙烯酸酯四級鹽之製造 方法，係將二烷基胺基烷基（甲基）丙烯酸酯、四級化劑及水 連續供應至反應器，並將該反應器中之反應液連續抽出， 以製造二烷基胺基烷基(甲基）丙烯酸酯四級鹽的方法，該方 10 法係從該反應器中抽出一部分之反應液，再通過熱交換器 使其冷卻，然後藉由喷射器將該冷卻後之反應液和前述四 級化劑一併供應至該反應器内。 第2項·如第1項之二烷基胺基烷基（甲基）丙烯酸酯四級鹽之 製造方法，係將二烷基胺基烷基（甲基）丙烯酸酯四級鹽水溶 15 液預先裝入前述反應器後，再將前述二烷基胺基烷基（甲基） 丙烯酸酯、四級化劑及水連續供應至其中。 第3項·如第1或2項之二烧基胺基烧基（甲基）丙烯酸醋四級 鹽之製造方法，係將反應中之前述反應液的溫度維持在 30〜80〇C。 20 第4項·如第1項之二烧基胺基烧基（甲基）丙烯酸S旨四級鹽之 製造方法，係令前述反應器為密閉之反應器，並使用沸點 在25°C以下之四級化劑作為前述四級化劑，且將反應中之 前述反應器内部之壓力維持在0.10〜1MPa〇。 第5項·如第1項之—烧*基胺基炫*基（甲基）丙缔酸醋四級鹽之 8 200829540 製造方法，係令前述二燒基胺基烧基（甲基）丙烯酸_為二甲 基胺基乙基（甲基）丙烯酸酯，且令前述四級化劑為氯甲烧。 第6項·如第1〜5項中任一項之二烷基胺基烧基(甲基）丙烯酸 酯四級鹽之製造方法，係將從前述反應器中連續抽出之反 5應液供應至1個以上之密閉槽，接著再階段性地使該槽内之 反應液的壓力成為大氣壓。 ’ 第7項·一種製造裝置，係製造二烷基胺基烷基（曱基）丙烯酸 酯四級鹽的裝置，包含有：二烷基胺基烷基（甲基）丙烯酸酯 之供應口；供水口；喷射器，係用以供應四級化劑者；反 10 應液抽出口；循環泵，係用以抽出一部分之反應液者；及 反應器，係依需要而設有攪拌葉片者，且該製造裝置更包 含有：流路，係用以將利用該循環泵自該反應器中抽出之 反應液供應至該喷射器者；及熱交換器，係用以在該流路 中途將該抽出之反應液冷卻者。 15 發明效果 根據本發明之DAM之製造方法，可有效地進行反應器 φ 内之除熱。特別是，在使用噴射器供應四級化劑時，雖反 應性會提高而使放熱量變大，但此時除熱也能迅速進行。 因此，反應斋内之溫度控制極為簡便，而可以高生產性製 20 造高純度之DAM。 ' 圖式簡單說明 第1圖係顯示噴射器的模式圖。 第2圖係顯示設有本發明之噴射器及外部熱交換器反 應裝置的模式圖。 、、 9 200829540 I：實施方式】 實施發明之最佳形態 以下詳細地說明實施本發明之實施形態。該發明並不 限於該等實施形態，可在不變更該發明之要旨内實施適宜 5 變更。 此外’在本說明書中，（甲基)丙烯酸酯表示丙烯酸酯或 甲基丙烯酸酯。 1.使用原料 本發明之DAM之製造方法中，原料係使用二烷基胺基 10烷基（甲基）丙烯酸酯、四級化劑及水。 具體而言，二烷基胺基烷基（曱基）丙烯酸酯（以下稱作 「Da」）可舉例如：二甲基胺基乙基（甲基）丙烯酸酯、二乙 基胺基乙基（甲基）丙烯酸酯、二丙基胺基乙基（甲基）丙烯酸 酯及二甲基胺基丙基（甲基）丙烯酸酯等。 15 四級化劑可使用可使Da之胺基四級化之化合物。四級 化劑可為液狀者亦可為氣體狀者，在可輕易地自反應後之 反應液中去除未反應之四級化劑，並可輕易地將其供應至 噴射器，且反應液中之分散性優異的點上，以氣體狀或低 沸點之四級化劑（以下稱作「低沸點四級化劑」）為佳。具體 2〇而言，可舉例如在大氣壓下之沸點為25。(：以下，且在2(TC 以下較佳，在HTC以下更佳的四級化劑。 具體而言，四級化劑可舉例如：氣甲燒、氯乙燒等燒 基_化物；以及氯甲苯等芳基烷基豳化物等。其中，以= 基_化物為佳，且以烧基之碳數為卜5之烧基南化物為佳， 200829540 特別是以氯甲烷為佳。 對四級化劑之反應斋之供應形態可採用各種態樣。例 如，可作為氣體、液體或氣液混合物等供應。 本發明所使用之上述水最好是使用不含金屬等，盡可 5能為高純度者。具體而言，可舉蒸餾水及離子交換水等為 例。 2.DAM之製造 本發明係在將Da、四級化劑及水連續供應至反應器， 並將反應器中之反應液連續抽出之DAM之製造方法中，從 10該反應器中抽出一部分之反應液，通過熱交換器進行冷 卻，再藉由喷射器將該冷卻之反應液和四級化劑一併供應 至該反應器内。此處之「反應液」為含有各原料在反應器 中進行反應所生成之DAM的液體。 用以實施本發明之DAM之製造方法的製造裝置可舉 15 第2圖所示之製造裝置為例，該製造裝置包含有：Da供應口 (10);供水口（11);用以供應四級化劑之喷射器（1) ·，反應液 抽出口（13);用以抽出一部分之反應液的循環泵(7);及依 需要而設有攪拌葉片（9)之反應器（6)，且該製造裝置更包含 有：用以將利用該循環泵(7)自該反應器（6)中抽出之反應液 20 供應至該噴射器（1)的流路；及用以在該流路中途將該抽出 之反應液冷卻的熱交換器（8)。而且，上述製造裝置中亦可 包含有後處理(finishing)槽、熟成槽。 以下，參照第1圖及第2圖詳細地說明本發明之製造方 法及製造裝置。 11 200829540 本發明所使用之反應器的大小、材質及構造並未特別 限定’只要可使各原料反應以製造DAM即可。 在反應斋方面，其内面以玻璃或Tefl〇n(註冊商標）等条 5布及/或襯裏者，可避免金屬成分溶出所得之DAM水溶液 中’故可得到高純度之DAM水溶液而較佳。又，在使用低 沸點四級化劑作為四級化劑時·，最好是使用可密閉之裝置 或可加壓之裝置等作為反應器。此種反應器可舉高壓蒸氣 滅菌器等為例。又，以設有夾套式熱交換器者作為反應器 1〇因容易控管溫度而較佳（第2圖）。 因在本發明中係使用噴射器來供應四級化劑，故反應 杰中没有喷射器。噴射器典型之例顯示於第。在第工圖 之(1)所不之噴射器中，（2)為噴嘴部，（3)為吸引部。噴射器 亦稱作吸引器，如第〗圖所示，將反應液(4)以高速供應至噴 5嘴邛(2) ’以使喷射器内減壓，再藉由該推進力，即可將液 體、氣體或氣液混合物(5)由吸引部(3)供應至喷射器内部。 此外，反應器中只要具有丨個以上之喷射器即可，可依反應 器之大小或反應量來選擇其最適合之個數。 在本發明中，係藉由循環泵(7)將反應器内之反應液(4) 2〇抽出，再供應至喷射器之噴嘴部⑵，藉由此處所生之推進 力將四級化劑從吸引部（3)供應至反應液中。通常，反應液 抽出。卩係设於反應器之底部，而噴射器係設於反應器之上 4。噴射器之吸引部(3)可設在反應器、外。第2圖係顯示噴射 為之導入官前端（反應液排出部)位於反應液中之例，亦可設 12 200829540 在反應液面之上部。以噴射蕃之導入管前端位於反應液中 之態樣為佳，特別是以使導入管前端位於由反應器之底部 到反應液面之間的大概中間位置為佳。 在本發明中’反應器内之氣液混合單靠喷射器便已足 5狗，亦可依需要併用4片後退葉片及平翼渦輪(心加⑽) 等攪拌葷片。 原料供應 在本發明中，係將-定量之各原料連續供應至反應器 内。因此，與批式之反應相比，可抑制反應熱量變大。 10 四級化劑可通過喷射器之吸引部供應至反應器内，而200829540 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a dialkylaminoalkyl (meth) acrylate vinegar manufactured by a manufacturer having high productivity and stable manufacturing conditions. A method for producing a grade salt and a device for producing the same. BACKGROUND ART A dialkylaminoalkyl (meth) acrylate quaternary salt (hereinafter referred to as 10 "DAM") is a raw material of a cationic polymer, and can be used as a polymer flocculant or paper reinforcing agent for various purposes. , raw materials for antistatic agents and soil conditioners. In general, S' can be produced by using water as a solvent, supplying a raw material in the presence of the solvent, removing the reaction heat, and reacting it, thereby producing DAM in an aqueous solution form of DAM. Further, conventionally, DAM has been manufactured in batches (for example, Patent Document 1 and the same as 2). However, since the method of manufacturing dam by batch is manufactured by one reactor, it is necessary to refill the raw material every time dam is produced, and then extract the product after the reaction is completed, and it takes a long time to stabilize the manufacturing conditions. 20, there is a problem in productivity. Further, since it is a batch type, it is extremely difficult to stabilize the production conditions such as the raw material of the reaction liquid or the reaction heat, and the quality of the obtained product is liable to be unstable. Further, in water or a reaction medium containing water, if the acrylate of the raw material remains in the reaction liquid, the acrylate is hydrolyzed, and acrylic acid is easily generated. Once acrylic acid is present as an impurity in the DAM product, when the polymer obtained by polymerization is used as a coagulant, there is a case where the performance is lowered. In order to solve such a problem, the present inventors have reported a manufacturing method in which a continuous charge of a sulfonylaminoalkyl (meth) acrylate, a four-stage, is contained in a reactor containing a DAM aqueous solution as a reaction solvent. The method of producing a high-purity DAM having high productivity and low quality between products is obtained by continuously extracting the reaction liquid in the above-mentioned reactor as a chemical agent and water (Patent Document 3). However, this production method is an excellent method. However, when a lower boiling four-stage agent is supplied as a quaternizing agent by gas, it is necessary to make the supply pressure of the quaternizing agent 10 larger than the pressure in the reactor. Therefore, the supply of the quaternizing agent needs to be pressurized, and the reaction liquid flows back into the supply pipe of the quaternizing agent to block the pipe. Further, when the liquid quaternizing agent is directly supplied to the reactor, the dispersion of the quaternizing agent in the reaction liquid is insufficient, so that the reactivity is lowered. Therefore, the inventors have found that the supply of the quaternizing agent 15 by the ejector does not reverse the flow to the supply pipe of the quaternizing agent, and the quaternizing agent can be uniformly sprayed into the reaction liquid. In the middle, the solubility of the quaternizing agent in the reaction liquid is improved, and the reactivity is excellent (Patent Document 4). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Invention 3] The present invention discloses a problem to be solved by the invention. 5. As disclosed in Patent Document 4, a DAM manufacturing method in which a quaternizing agent is continuously supplied by an ejector is an excellent method, but Since the quaternization reaction is an exothermic reaction, there is a problem in that the reactivity is improved and the temperature control in the reaction state is difficult. Usually, the cooling of the reaction tank is carried out using a jacket type heat exchanger of the reaction tank, because it is easy to make the cooling capacity (heat removal) keep up with the heat release, and the temperature inside the reactor rises. When the temperature in the reactor is too high, problems such as polymerization of the produced DAM and hydrolysis of the ester occur, and it is not easy to stably produce high-quality DAM. Therefore, a method for reliably controlling the temperature in the reactor has been expected for a long time. I5 And when there is insufficient heat, if you want to increase the production volume, there will be problems such as increasing the reactor or using a complex reactor. φ That is, an object of the present invention is to provide a method for controlling the temperature rise in the reactor by efficiently cooling the reaction liquid, and to produce high-purity dam with high productivity even when a compact reactor is used. Further, another object of the invention is to provide a manufacturing apparatus suitable for the manufacturing method. - Means for Solving the Problems After conducting various reviews to solve the aforementioned problems, the inventors found that by extracting a part of the reaction liquid from the reactor in the reaction, it is cooled by a heat exchanger, and by an ejector The cooled reaction liquid and the quaternized 7 200829540 agent are supplied to the reactor together, and the heat removal in the reactor can be efficiently performed to produce high-purity dam with high productivity. The present invention has been completed after further research based on such findings. That is, the present invention provides a method for producing the following dialkylaminoalkyl (meth) acrylate 5 quaternary salt and a device for producing the same. Item 1 A method for producing a dialkylaminoalkyl (meth) acrylate quaternary salt by continuously supplying a dialkylaminoalkyl (meth) acrylate, a quaternizing agent, and water to a reactor, and the reaction liquid in the reactor is continuously withdrawn to produce a dialkylaminoalkyl (meth) acrylate quaternary salt, and the method 10 extracts a part of the reaction from the reactor The liquid is further cooled by a heat exchanger, and then the cooled reaction liquid and the above-mentioned quaternizing agent are supplied together into the reactor by an ejector. Item 2: The method for producing a dialkylaminoalkyl (meth) acrylate quaternary salt according to the item 1, wherein the dialkylaminoalkyl (meth) acrylate tetrabasic salt solution is dissolved in 15 After the foregoing reactor is previously charged, the aforementioned dialkylaminoalkyl (meth) acrylate, quaternizing agent and water are continuously supplied thereto. Item 3: The method for producing a bis-alkylaminoalkyl methacrylate quaternary salt according to the first or second item, wherein the temperature of the reaction solution in the reaction is maintained at 30 to 80 〇C. Item No. 4: The method for producing a quaternary salt of the alkylaminoalkyl methacrylate (meth) acrylate according to the first item, wherein the reactor is a closed reactor and a boiling point of 25 ° C or less is used. The quaternizing agent is used as the quaternizing agent, and the pressure inside the reactor in the reaction is maintained at 0.10 to 1 MPa. Item 5: as in Item 1 - Burning *Amino-based xyl (methyl) propionic acid vinegar quaternary salt 8 200829540 Manufacturing method, the above-mentioned dialkylaminoalkyl (meth)acrylic acid _ is dimethylaminoethyl (meth) acrylate, and the above quaternizing agent is chloroform. Item 6. The method for producing a dialkylamine-based alkyl (meth) acrylate quaternary salt according to any one of items 1 to 5, which is a supply of a reverse-phase liquid which is continuously withdrawn from the foregoing reactor In a sealed tank of one or more, the pressure of the reaction liquid in the tank is gradually increased to atmospheric pressure. Item 7. A manufacturing apparatus for producing a dialkylaminoalkyl (mercapto) acrylate quaternary salt, comprising: a supply port of a dialkylaminoalkyl (meth) acrylate; The water supply port; the ejector is used to supply the quaternization agent; the anti-10 liquid extraction port; the circulation pump is used to extract a part of the reaction liquid; and the reactor is provided with the stirring blade as needed. And the manufacturing apparatus further includes: a flow path for supplying the reaction liquid extracted from the reactor by the circulation pump to the injector; and a heat exchanger for using the flow path in the middle of the flow path The extracted reaction solution is cooled. Advantageous Effects of Invention According to the method for producing DAM of the present invention, heat removal in the reactor φ can be efficiently performed. In particular, when the quaternizing agent is supplied by the ejector, the reaction is increased and the amount of heat generation is increased, but at this time, heat removal can be quickly performed. Therefore, the temperature control in the reaction chamber is extremely simple, and the high-purity DAM can be produced with high productivity. 'Simple diagram of the diagram Figure 1 shows a schematic diagram of the injector. Fig. 2 is a schematic view showing an ejector and an external heat exchanger reaction apparatus provided with the present invention. 9 200829540 I: BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. The invention is not limited to the embodiments, and modifications may be made without departing from the spirit of the invention. Further, in the present specification, (meth) acrylate means acrylate or methacrylate. 1. Raw material used In the method for producing DAM of the present invention, a dialkylamino 10 alkyl (meth) acrylate, a quaternizing agent and water are used as a raw material. Specifically, the dialkylaminoalkyl (mercapto) acrylate (hereinafter referred to as "Da") may, for example, be dimethylaminoethyl (meth) acrylate or diethylaminoethyl. (Meth) acrylate, dipropylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate. As the quaternizing agent, a compound which can quaternize the amine group of Da can be used. The quaternizing agent may be in the form of a liquid or a gas, and the unreacted quaternizing agent may be easily removed from the reaction liquid after the reaction, and may be easily supplied to the ejector, and the reaction liquid Among the points excellent in dispersibility, a gas-like or low-boiling four-stage agent (hereinafter referred to as "low-boiling four-stage agent") is preferred. Specifically, for example, the boiling point at atmospheric pressure is 25. (The following is a quaternary agent which is preferably 2 or less, more preferably less than HTC. Specific examples of the quaternizing agent include a calcination group such as gas-fired or chloroeth-butyl; An arylalkyl halide such as chlorotoluene, etc., wherein the alkyl group is preferred, and the alkyl group having a carbon number of the alkyl group is preferably 5, and 200829540 is preferably methyl chloride. The supply form of the leveling agent can be used in various forms, for example, it can be supplied as a gas, a liquid or a gas-liquid mixture, etc. The above-mentioned water used in the present invention is preferably made of metal-free, etc. For example, distilled water and ion-exchanged water are exemplified. 2. Production of DAM The present invention continuously supplies Da, a quaternizing agent and water to a reactor, and reacts in the reactor. In the method for producing DAM in which the liquid is continuously extracted, a part of the reaction liquid is taken out from the reactor, cooled by a heat exchanger, and the cooled reaction liquid and the quaternizing agent are supplied together by the ejector. In the reactor, the "reaction liquid" here contains all the raw materials in the reaction. The liquid of the DAM produced by the reaction. The manufacturing apparatus for carrying out the manufacturing method of the DAM of the present invention is exemplified by the manufacturing apparatus shown in Fig. 2, which comprises: a Da supply port (10); Water supply port (11); ejector (1) for supplying a quaternizing agent, a reaction liquid extraction port (13); a circulation pump (7) for extracting a part of the reaction liquid; and stirring as needed a reactor (6) of the blade (9), and the manufacturing apparatus further comprises: a reaction liquid 20 for extracting the reaction liquid (20) withdrawn from the reactor (6) by the circulation pump (7) to the injector (1) And a heat exchanger (8) for cooling the extracted reaction liquid in the middle of the flow path. Further, the manufacturing apparatus may include a finishing tank and a forming tank. The production method and manufacturing apparatus of the present invention will be described in detail with reference to Figures 1 and 2. 11 200829540 The size, material and structure of the reactor used in the present invention are not particularly limited as long as the respective raw materials can be reacted to produce DAM. In terms of reaction, the inside is made of glass or Tefl〇n (registered trademark) It is preferable to use a low-boiling quaternizing agent as the quaternizing agent in order to avoid the elution of the metal component in the DAM aqueous solution obtained by the stripping of the metal component. Preferably, a reactor or a pressurizable device or the like is used as the reactor. Such a reactor may be exemplified by a high pressure steam sterilizer, etc. Further, a reactor having a jacket type heat exchanger is used as the reactor 1 It is preferable because it is easy to control the temperature (Fig. 2). Since the ejector is used to supply the quaternizing agent in the present invention, there is no ejector in the reaction. A typical example of the ejector is shown in the first. In the ejector which is not shown in (1), (2) is a nozzle portion, and (3) is a suction portion. The injector is also called an aspirator. As shown in the figure, the reaction liquid (4) is supplied to the nozzle 5 (2) at a high speed to decompress the inside of the injector, and then by the propulsive force, A liquid, gas or gas-liquid mixture (5) is supplied from the suction portion (3) to the inside of the injector. Further, as long as there are more than one ejector in the reactor, the optimum number of reactors can be selected depending on the size of the reactor or the amount of reaction. In the present invention, the reaction liquid (4) in the reactor is extracted by a circulation pump (7), and then supplied to the nozzle portion (2) of the ejector, and the quaternizing agent is used by the propulsion force generated here. It is supplied from the suction portion (3) to the reaction liquid. Usually, the reaction liquid is withdrawn. The ruthenium is placed at the bottom of the reactor and the ejector is placed above the reactor 4 . The suction portion (3) of the ejector can be disposed outside the reactor. Fig. 2 shows an example in which the injection front end (reaction liquid discharge portion) is placed in the reaction liquid, and 12 200829540 may be provided above the reaction liquid surface. It is preferred that the front end of the introduction tube is located in the reaction liquid, and it is particularly preferable that the leading end of the introduction tube is located at an approximate intermediate position from the bottom of the reactor to the surface of the reaction liquid. In the present invention, the gas-liquid mixture in the reactor alone is sufficient for the dog, and the four pieces of the retracting blade and the flat-blade turbine (heart plus (10)) can be used as needed to stir the bracts. Feedstock Supply In the present invention, each of the raw materials is quantitatively supplied to the reactor. Therefore, the heat of reaction can be suppressed from being increased as compared with the reaction of the batch type. 10 The quaternizing agent can be supplied to the reactor through the suction part of the ejector, and
Da及水可依常法供應。各原料之供應順序並未特別限定， 例如，在使用低沸點四級化劑作為本發明之四級化劑時， 係透過噴射益將上述低沸點四級化劑供應至反應器内，將 反應器内之壓力保持在一定，之後連續供應〇&及水。 15 而且，在使用低沸點四級化劑作為本發明之四級化劑 時，係使用密閉之反應器作為反應器，再將反應中之反應 器内部之壓力維持在0.1〜IMPaG為佳，且以〇1〜㈣碰⑷較 佳，並以0.1〜0.6MPaG更佳。藉此，即可增加反應液中之四 級化劑的溶解量。 20 在本發明中，最好是將DAM水溶液預先裝入反應器作 為反應溶媒，再將Da、四級化劑及水連續供應至其中。在 以無溶媒使原料反應時，因所得之DAM為結晶狀者，且具 吸溼性，故會附著於反應器内壁上而不易除熱。不僅如此， 因DAM為結晶狀而呈無氧狀態，故有DAM會聚合的問題。 13 200829540 又，為解決該問題，也有以水作為溶媒之方法，此時，原 料之Da會水解，而有生成物之純度降低的問題。對此，在 本發明中，藉由使用DAM水溶液作為反應溶媒，可有效地 生產高純度之DAM，故以其為佳。 5 上述0八鰱水溶液中所含之DAM種類並未特別限定，通 常係與所得之DAM為同一種DAM。又，上述DAM水溶液 的濃度並未特別限定，可依需要設定各種範圍。通常，上 述DAM水溶液之濃度為50〜84重量％，且以75〜84重量％為 佳，更以78〜83重量％為佳。又，供應原料進行反應所得之 10 DAM水溶液的濃度也是調製成在上述範圍内。 在本發明中，將作為反應溶媒之上述DAM水溶液及各 原料裝入反應器内的順序並未特別限定，只要各原料之反 應可進打即可。具體而言，可舉例如：預先將上述dam水 溶液裝入反應器，然後再連續供應各原料的方法；及在供 I5應上述原料的同時、或正在供應上述原料的時候，將〇舰 水溶液裝入反應器内的方法等。 上述各原料之供應速度只要依各原料之特性、反應器 之大小及每一單位時間之生產量等適宜地設定即可。例 如，Da之供應速度以相對於反應器中之反應液的質量為 20 3·0〜70質量％/小時較佳，且以5〇〜35質量％/小時更佳。 四級化劑之供應速度以相對於反應器中之反應液的質 量為1 ·〇〜30質量％/小時較佳，且以2.0〜15質量％/小時更佳。 水之供應速度以相對於反應器中之反應液的質量為 1.0〜30質量％/小時較佳，且以2〇〜15質量％/小時更佳。 14 200829540 藉由將各原料之供應速度設在上述範圍内，以適切之 原料比例進行反應，故可以高生產性來製造高純度之DAM 而較佳。而且，相對於Da之四級化劑的供應比例，以在反 應液中大致為等莫耳的比例較佳。 5 又’ Da、四級化劑及水可供應至反應液中，亦可供應 至反應為中之反應液上部的空間。如上述，因四級化劑係 透過嘴射裔、供應至反應液，故最好是供應至反應液中。又， 關於Da ’為了避免DAC之結晶在其供應過程中析出而堵塞 導入管，最好是將Da之導入管前端置於反應液上部之空 10 間，再由該處供應Da。 外部熱交換器 在將各原料連續供應至反應器内，再藉由噴射器供應 四級化劑時，四級化反應之反應性會增大，每一單位時間 之反應熱量亦有變大的傾向。但是，在本發明中，係藉由 15外部熱父換益冷部一部分之反應液，再經由噴射器循環供 應至反應益内，故反應熱之除熱可極為快速地進行。因此， 反應溫度的控制極為容易。在只有使用設有夾套式熱交換 窃之反應姦時，很難控管溫度，特別是生產量一變多，就 必須大量地進行除熱，故會有需要增大反應器，或使用複 20 數反應器的問題。 在本發明中，包含有用以將利用循環泵(7)自反應器（6) 中抽出之反應液供應至該喷射器（i)的流路；及在該流路中 途將該抽出之反應液冷卻的熱交換器（8)。亦可在該流路中 設置1或2個以上之熱交換器。 15 200829540 藉由猶環泵可從反應器中抽出一部分之反應液，接著 供應至”、、父換器。熱交換器以不鑛鋼製、欽製或玻璃概裡 製者等為佳’可舉多管式熱交換器、板式熱交換器及螺旋 式熱交換器等為例。 5 通過熱交換器後之冷卻反應液係直揍以高壓狀態供應 至喷射器之噴嘴部，生出用以吸引噴嘴部之四級化劑之高 推進力（第2圖）。 如此，本發明係在短時間將大量之反應液連續以外部 熱交換器冷卻、循環，故即使在反應熱量增大時，除熱效 1〇率也極高。因此，本發明可在將各原料連續供應至反應器 内之步驟、反應步驟中，將反應器内保持在一定溫度。此 日守之溫度以30〜80°C為佳，且以40〜70°C更佳。 尾崖液之柄屮 本發明係供應各原料並同時將反應器中之反應液抽 15出。抽出反應液的時期並未特別限定，可在各原料開始供 應時同時抽出，亦可在各原料開始供應後等一小段時間再 抽出。又，反應液之抽出可連續進行，亦可依需要間歇地 j出。職出之-部分之反驗會通環隸應至喷射 器⑴之噴嘴部(2)。 20 反應液之抽出速度只要依目的適宜設定即可。反應液 之抽出速度相對於反應器中之反應液質量以5〇〜13〇質量 小時為佳，且以9.0〜65質量％/小時更佳。藉此，因係以 適切之原料比例進行反應，故可以高生產性製造高純度之 dam 〇 16 200829540 後處理槽 在本發明中，最好是將從反應器中連續抽出之反應液 供應至密閉之1個以上的後處理槽，接著將該後處理槽内之 反應液之壓力設為大氣壓。此處之後處理槽為與反應器及/ 5 或後述之熟成槽連結的槽，該槽之目的在於，藉由使反應 液之壓力降為大氣壓，再依需要進行曝氣，以去除存在於 反應液中之四級化劑等反應後之未反應物，特別是去除在 使用低沸點四級化劑作為四級化劑時之未反應低沸點四級 化劑。 10 例如，在使用氯甲烷作為低沸f點四級化劑時，反應器 内之反應液中溶解存在有未反應之氣甲烷。反應液中之未 反應之氯曱烷就會水解變成氯化氫，在最後產品之品質上 較為不佳。因此，需要去除未反應之氯甲烷，但若立刻將 反應液之壓力回到大氣壓，氯甲炫就會一口氣揮散掉，此 15時反應液中之溶氧也會一同揮散掉，反應液就會呈低氧狀 態，因此反應液中之dam會有聚合的情形。 另一方面，使用後處理槽可使所抽出之反應液的壓力 階段性地降低，而可解決前述問題。反應液對後處理槽之 供應，可連續性亦可間歇性地進行，在連續供應時可穩定 20 地製造DAM而較佳。 後處理槽之數量至少有1個即可，從可去除反應後之未 反應物，特別疋使用低彿點四級化劑作為四級化劑時之未 反應四級化劑14-點來看，槽的數量以多者較佳。 槽之數量通常為1個以上，且以2個以上為佳，更以3個以上 17 200829540 為佳。又，後處理槽之大小’材質及構造只要依使用原料 及DAM之生產量等目的適宜選擇即可。具體而言，可使用 與上述反應器所例示者相同者。 又’後處理槽内部之壓力並未特別限定，以反應器内 5 之壓力以下的壓力為佳，且以大氣壓〜0.7MPaG為佳，更以 大氣壓為佳。藉由設在此範圍，可防止反應液中之dam之 聚合。 又，在本發明中，可將至少含有氧的氣體噴灑入移送 至後處理槽之反應液中。藉此，可將氧供應至後處理槽中 10之反應液，以防止DAM之聚合，且可去除反應後之未反應 物’特別是使用低沸點四級化劑作為四級化劑時之未反應 四級化劑而較佳。上述氣體中，關於其種類並未特別限定， 只要至少含有氧即可’通常是使用空氣。 如前述，因可在反應器中抑制Da之水解，故可使DAM 15以咼濃度反應而較佳，而對於最後產品來說，為使其黏度 降低以易於操作，且為防止其在冬季結晶化，最好是將D A M 設為60〜80質量％。此時，最好是在後處理槽添加水，使其 為最後產品濃度。 熟成槽 20 在本發明中，最好是將從反應器中連續抽出之反應液 再供應至密閉之1個以上的熟成槽。熟成槽為與反應器及後 處理槽連結的槽，且係指用以進行如下操作的槽，該操作 係使反應率較從反應器中抽出之反應液中之dam之反應率 更高（熟成)者。通常，係以反應器、熟成槽及後處理槽的順 18 200829540 序連結。 具體而言，例如，將熟成槽内之壓力維持在較反應器 内之壓力低的壓力，且將熟成槽内之溫度設為反應器内之 溫度以下的溫度，即可使反應熟成。 5 若使用熟成槽，則即使在反應由於反應器中之反應條 件等而未充分進行時，也可利用熟成槽使反應能充分地進 行，而可抑制未反應之各原料殘留在產品中而較佳。此外， 反應液對熟成槽的供應，可連續性亦可間歇性地進行，在 連續供應時，可穩定地製造DAM而較佳。 1〇 關於熟成槽内之壓力及溫度並未特別限定。熟成槽内 之壓力通常為較反應器内之壓力低的壓力，在使用熟成槽 ’亦可在热成槽中設為大氣壓。壓力以大氣壓〜dMpaG 為佳，且以大氣壓〜〇.6MPaG為佳。又，熟成槽内之溫度通 苇要為反應器内之溫度以下的溫度即可，且以30〜60°C較 15佳。而且，熟成槽内之壓力最好是保持在一定壓力，且熟 成槽内之溫度最好是維持在一定。 又，在本發明中，最好是將反應液供應至熟成槽，使 上述反應液熟成後’再將反應液供應至後處理槽。藉此， 除了熟成槽之效果外，還有後處理槽之效果，即，防止反 20應液中之DAM之聚合，且可去除反應後之未反應物，特別 是使用低沸點四級化劑作為四級化劑時之未反應四級化劑 而較佳。 此時，最好是階段性地使反應器、熟成槽及後處理槽 内之壓力降低。藉此，〉谷解存在於反應液中之四級化劑即 19 200829540 可一口氣揮散掉，此時，反應液中之溶氧也會一同揮散掉， 而可防止起因於反應液呈低氧狀態之DAM之聚合。此時之 上述各槽内之壓力只要在反應器、熟成槽及後處理槽内之 較佳壓力的範圍即可。此外，在熟成槽中為大氣壓時，只 5要在後處理槽進行曝氣及添加水即可。 在本發明中，熟成槽之數量至少有丨個即可’從可提高 生產性這一點來看，槽之數量以較多者為佳。熟成槽之數 ϊ通常在1個以上，且以2個以上為佳，更以3個以上為佳。 _ 最好是連結2個以上熟成槽再階段性地降低壓力。具體而 10言，在連結2個熟成槽時，最好是將第丨個熟成槽設為 0·05〜0.8MPaG，且將第2個熟成槽設為大氣壓〜〇.5卿犯。 又，熟成槽之大小、材質及構造只要依使用原料及 DAM之生產鮮目的適宜選擇即可。具體而言，可使用反 應器所例示者相同者。 15 本發明之滯留時間([反應液質量]/[反應液抽出速度（質 量/小時)])可依反應條件、後處理槽或熟成槽之數量等設成 • 各種範圍。通常，在為具有後處理槽之2槽連續製程時，上 述滯留時間通常在4小時以上，且以4.5小時以上為佳，更 以5小時以上為佳。又’在為具有熟成槽和後處理槽之3槽 20連續製程時，上述滯留時間通常在1小時以上，且以 時以上為佳’更以2小時以上為佳，尤以2〜15小時為佳。將 上述滯留時間設定在此範圍内時，可減低來自於上述原料 之丙稀酸殘量而較佳。又’藉由本發明所得之DAM中之來 自於上述原料之丙烯酸殘量通常在15〇〇ppm以下，且以 20 200829540 1200ppm以下為佳，更以ΙΟΟΟρρπι以下為佳。 【實施例】 以下，藉由實施例詳細地說明本發明。此外，只有「％」 的記載係指「質量％」。 5 [實施例1] 使用第2圖所示之反應裝置，進行二甲基胺基乙基丙稀 酸酯之氯曱烷加成物（以下稱作「DAC」）的製造。 反應槽(6)係使用内部設有攪拌機(9)，並附帶有爽套式 熱交換器（14)，且内部壁面經玻璃襯裏之i〇m3槽型反應 10器。反應槽(6)係使用更設有噴射器（1)、作為外·部熱交換器 之多管式熱交換器（8)(總傳熱係數（u)x傳熱面積 (Α)=5,9721ο^1/1ιγΧ：)及循環泵⑺者。在多管式熱交換器 中，係藉由泵（圖未示)使以鹽水冷卻後之2〇。〇水循環。 將DAC之79%水溶液8,000kg裝入反應槽⑹，密閉後加 15 溫至50°C。 接著，藉由上述反應槽（6)之攪拌機⑼攪拌DAC水溶 液，並啟動循環泵(7)，將DAC水溶液通過多管式熱交換器 (8)供應至喷射器（1)之噴嘴部，開始循環。經由噴射器（1) 之吸引部(3) ’將氯甲燒(以下簡稱「MC」）由供應管⑽供 2〇應至密閉之反應槽（6)，使反應槽⑹内部之壓力為 0.28MPaG。以274kg/小時的供應速度連續供應㈣，又，只 供應反應所消耗之量，使反應槽（6)内部之壓力保持在 0_28MPaG。 之後，以730kg/小時的供應速度將二甲基胺基乙基丙 21 200829540 5 条 〇 10 烯酸酯(以下稱作「DA」）通過供應管（10)連續供應至反應 槽(6)，並同時以263kg/小時的供應速度將水通過供應管（η) 連續供應至反應槽(6)。使用夾套式熱交換器（14)及多管式 熱交換器（8)讓冷卻水循環，以使反應溫度為5(TC。所得之 DAC水溶液之DAC濃度為80%，再由配管（13)連續抽出。 連續抽出之DAC水溶液係供應至熟成槽（圖未示），並 減壓至O.lMPaG使其熟成，再將熟成後之反應液供應至後 處理槽（圖未示），使其為大氣壓，然後添加水使DAC濃度為 79%。 結果，可在反應溫度50°C下，以l，250kg/小時的比例穩 定地連續製造79%DAC水溶液。 [實施例2] 在實施例1中，除了將DA、MC及水的供應速度分別設 為876kg/小時、329kgM、時及316kg/小時之外，用和實施例 15 • 1相同的方法進行DAC的製造。 結果，冷卻水用循環泵之能力用到最大限度，可在反 應溫度51°C下，以l，5001g/小時的比例穩定地連續製造 79%DAC水溶液。 [比較例1] 20 除了使用在實施例1中沒有多管式熱交換器之反應裝 置，且將DA、MC及水的供應速度分別設為526kg/小時、 197kg/小時及190kg/小時，並且只使用夾套式熱交換器（14) 使冷卻水循環，以使反應溫度為50°C之外，用和實施例1相 同的方法進行DAC的製造。 22 200829540 結果，雖以900kg/小時的比例開始連續製造79%dac水溶 液’但在製造途中超過目的之反應溫度變成54°C，而且反應溫 度沒有停止上升，冷卻不足，而無法控管溫度，故中止操作。 [比較例2] 5 因在比較例1中反應液之溫度上升，故嘗試降低生產能 力來連續製造DAC。 在比較例1中，除了將DA、MC及水的供應速度分別設 為94kg/小時、148kg/小時及142kg/小時之外，用和比較例1 相同的方法進行DAC的製造。Da and water can be supplied according to the usual method. The order of supply of the respective raw materials is not particularly limited. For example, when a low-boiling quaternizing agent is used as the quaternizing agent of the present invention, the low-boiling quaternizing agent is supplied to the reactor through the injection benefit, and the reaction is carried out. The pressure inside the device is kept constant, and then 〇& and water are continuously supplied. Further, when a low-boiling quaternizing agent is used as the quaternizing agent of the present invention, a closed reactor is used as the reactor, and it is preferred to maintain the pressure inside the reactor in the reaction at 0.1 to IMPaG, and It is preferable to use 〇1 to (4) touch (4), and more preferably 0.1 to 0.6 MPaG. Thereby, the amount of the quaternizing agent dissolved in the reaction liquid can be increased. In the present invention, it is preferred to previously charge the aqueous DAM solution to the reactor as a reaction medium, and to continuously supply Da, the quaternizing agent and water thereto. When the raw material is reacted in the absence of a solvent, since the obtained DAM is crystalline and hygroscopic, it adheres to the inner wall of the reactor and does not easily remove heat. In addition, since DAM is crystalline and is in an anaerobic state, there is a problem that DAM is polymerized. 13 200829540 In order to solve this problem, there is also a method in which water is used as a solvent. At this time, Da of the raw material is hydrolyzed, and the purity of the product is lowered. On the other hand, in the present invention, it is preferable to use a DAM aqueous solution as a reaction solvent to efficiently produce high-purity DAM. 5 The type of DAM contained in the above aqueous solution of octahydrate is not particularly limited, and is usually the same DAM as the obtained DAM. Further, the concentration of the aqueous DAM solution is not particularly limited, and various ranges can be set as needed. Usually, the concentration of the above aqueous DAM solution is 50 to 84% by weight, preferably 75 to 84% by weight, more preferably 78 to 83% by weight. Further, the concentration of the 10 DAM aqueous solution obtained by supplying the raw material for the reaction was also adjusted to be within the above range. In the present invention, the order of charging the above-mentioned DAM aqueous solution and each raw material as a reaction solvent into the reactor is not particularly limited as long as the reaction of each raw material can be carried out. Specifically, for example, a method in which the aqueous solution of dam described above is charged into a reactor in advance, and then each raw material is continuously supplied; and when the raw material for I5 is supplied or the raw material is supplied, the aqueous solution of the ship is loaded. The method of entering the reactor, and the like. The supply rate of each of the above raw materials may be appropriately set depending on the characteristics of each raw material, the size of the reactor, the production amount per unit time, and the like. For example, the supply speed of Da is preferably from 20 3 to 70% by mass/hour with respect to the mass of the reaction liquid in the reactor, and more preferably from 5 to 35% by mass/hour. The supply rate of the quaternizing agent is preferably from 1 to 30% by mass/hour based on the mass of the reaction liquid in the reactor, and more preferably from 2.0 to 15% by mass/hour. The water supply rate is preferably 1.0 to 30% by mass/hour with respect to the mass of the reaction liquid in the reactor, and more preferably 2 to 15% by mass/hour. 14 200829540 By setting the supply speed of each raw material within the above range and reacting at a suitable ratio of raw materials, it is preferable to produce high-purity DAM with high productivity. Further, the ratio of the supply of the quaternizing agent to Da is preferably a ratio which is substantially equal to the molar amount in the reaction liquid. 5 Further, Da, the quaternizing agent and water may be supplied to the reaction liquid, or may be supplied to the space above the reaction liquid in the reaction. As described above, since the quaternizing agent is supplied to the reaction liquid through the mouth, it is preferably supplied to the reaction liquid. Further, in order to prevent the DAC crystal from being deposited in the supply process and clogging the introduction tube, it is preferable to place the leading end of the introduction tube of Da in the space 10 of the upper portion of the reaction liquid, and then supply Da from there. When the external heat exchanger continuously supplies each raw material into the reactor, and the quaternizing agent is supplied by the ejector, the reactivity of the quaternization reaction increases, and the heat of reaction per unit time also increases. tendency. However, in the present invention, the reaction liquid of a part of the cold portion is exchanged by the external heat master and then supplied to the reaction benefit via the ejector cycle, so that the heat removal by the reaction heat can be carried out extremely quickly. Therefore, the control of the reaction temperature is extremely easy. It is difficult to control the temperature when only the use of jacketed heat exchange stealing is used, especially if the production volume is increased, it is necessary to carry out a large amount of heat removal, so there is a need to increase the reactor, or use the complex 20 number of reactor problems. In the present invention, a flow path for supplying a reaction liquid extracted from the reactor (6) by the circulation pump (7) to the ejector (i) is included; and the reaction liquid to be withdrawn in the middle of the flow path Cooled heat exchanger (8). It is also possible to provide one or more heat exchangers in the flow path. 15 200829540 A part of the reaction liquid can be withdrawn from the reactor by the helium ring pump, and then supplied to the ",, the parent exchanger. The heat exchanger is preferably made of non-mineral steel, made or glass." For example, a multi-tube heat exchanger, a plate heat exchanger, and a spiral heat exchanger are used. 5 The cooling reaction liquid after passing through the heat exchanger is supplied to the nozzle portion of the injector at a high pressure, and is generated to attract The high thrust of the quaternizing agent in the nozzle portion (Fig. 2). Thus, the present invention continuously cools and circulates a large amount of the reaction liquid in an external heat exchanger in a short time, so that even when the heat of reaction increases, The heat efficiency rate is also extremely high. Therefore, the present invention can maintain the temperature inside the reactor at a certain temperature in the step of continuously supplying each raw material into the reactor, and the reaction step is 30 to 80 ° C. Preferably, it is preferably 40 to 70 ° C. The tail liquid of the tail liquid The present invention supplies each raw material and simultaneously extracts the reaction liquid in the reactor. The period of extracting the reaction liquid is not particularly limited, and may be Each raw material is taken out at the same time as it is supplied, or After the raw materials are started to be supplied, they are taken out for a short period of time. Further, the extraction of the reaction liquid can be carried out continuously, or intermittently if necessary. The back-part of the service will be passed to the nozzle of the injector (1). Part (2). 20 The extraction rate of the reaction liquid may be appropriately set according to the purpose. The extraction speed of the reaction liquid is preferably 5 〇 to 13 〇 mass hours with respect to the mass of the reaction liquid in the reactor, and is 9.0 to 65 mass. %/hour is better. Thereby, since the reaction is carried out in a suitable ratio of raw materials, high-purity dam 〇16 can be produced with high productivity. 200829540 After-treatment tank In the present invention, it is preferable to continuously extract from the reactor. The reaction liquid is supplied to one or more sealed post-treatment tanks, and then the pressure of the reaction liquid in the post-treatment tank is set to atmospheric pressure. Here, the treatment tank is connected to the reactor and / or a mature tank to be described later. The purpose of the tank is to reduce the pressure of the reaction liquid to atmospheric pressure and then aerate as needed to remove the unreacted material after the reaction such as the quaternizing agent present in the reaction liquid, in particular, use When the boiling point quaternizing agent is used as a quaternizing agent, the unreacted low-boiling quaternizing agent is used. 10 For example, when methyl chloride is used as the low-boiling f-point quaternizing agent, the reaction liquid in the reactor is dissolved or not. Methane in the reaction gas. The unreacted chlorodecane in the reaction solution is hydrolyzed to hydrogen chloride, which is not good in the quality of the final product. Therefore, it is necessary to remove unreacted methyl chloride, but if the pressure of the reaction liquid is immediately returned At atmospheric pressure, the chloroform will be volatilized in one breath. At this time, the dissolved oxygen in the reaction solution will also be volatilized together, and the reaction solution will be in a low oxygen state, so the dam in the reaction solution will be polymerized. On the one hand, the use of the post-treatment tank can reduce the pressure of the extracted reaction liquid stepwise, and the above problem can be solved. The supply of the reaction liquid to the post-treatment tank can be continuously performed intermittently, during continuous supply. It is preferable to manufacture DAM stably 20 times. The number of post-treatment tanks may be at least one, from the point of view of the unreacted quaternizing agent when the unreacted material after the reaction can be removed, especially when the low-foaming quaternizing agent is used as the quaternizing agent. The number of slots is preferably greater. The number of the grooves is usually one or more, and preferably two or more, and more preferably three or more 17 200829540. Further, the size and material structure of the post-treatment tank may be appropriately selected depending on the purpose of using the raw material and the production amount of DAM. Specifically, the same as those exemplified in the above reactor can be used. Further, the pressure inside the post-treatment tank is not particularly limited, and is preferably a pressure equal to or lower than the pressure in the reactor 5, and is preferably from atmospheric pressure to 0.7 MPaG, more preferably at atmospheric pressure. By setting it in this range, polymerization of dam in the reaction liquid can be prevented. Further, in the present invention, at least a gas containing oxygen may be sprayed into the reaction liquid transferred to the post-treatment tank. Thereby, oxygen can be supplied to the reaction liquid in the post-treatment tank 10 to prevent the polymerization of DAM, and the unreacted reactant after the reaction can be removed, especially when the low-boiling quaternizing agent is used as the quaternizing agent. It is preferred to react a quaternizing agent. The type of the gas is not particularly limited as long as it contains at least oxygen. Usually, air is used. As described above, since the hydrolysis of Da can be suppressed in the reactor, DAM 15 can be preferably reacted at a ruthenium concentration, and for the final product, it is easy to handle in order to reduce its viscosity, and to prevent it from crystallizing in winter. Preferably, the DAM is set to 60 to 80% by mass. At this time, it is preferable to add water to the post-treatment tank to make it the final product concentration. In the present invention, it is preferred that the reaction liquid continuously withdrawn from the reactor be supplied to one or more of the closed forming tanks. The ripening tank is a tank connected to the reactor and the post-treatment tank, and refers to a tank for performing a reaction rate higher than that of the dam in the reaction liquid withdrawn from the reactor (cooking )By. Usually, the reactor, the matured tank and the post-treatment tank are connected in the order of 2008 200829540. Specifically, for example, the pressure in the ripening tank is maintained at a pressure lower than the pressure in the reactor, and the temperature in the ripening tank is set to a temperature equal to or lower than the temperature in the reactor, whereby the reaction can be matured. 5 When the ripening tank is used, even if the reaction is not sufficiently carried out due to the reaction conditions in the reactor, etc., the reaction tank can be sufficiently carried out by using the ripening tank, and the unreacted raw materials can be suppressed from remaining in the product. good. Further, the supply of the reaction liquid to the ripening tank can be carried out intermittently, and it is preferable to stably produce DAM during continuous supply. 1〇 The pressure and temperature in the cooked tank are not particularly limited. The pressure in the ripening tank is usually a pressure lower than the pressure in the reactor, and may be set to atmospheric pressure in the hot forming tank using the cooked tank. The pressure is preferably atmospheric pressure ~ dMpaG, and is preferably atmospheric pressure ~ 〇. 6MPaG. Further, the temperature in the cooked tank is preferably a temperature lower than the temperature in the reactor, and is preferably 15 to 60 °C. Further, it is preferable that the pressure in the cooked tank is maintained at a constant pressure, and the temperature in the cooked tank is preferably maintained constant. Further, in the present invention, it is preferred that the reaction liquid is supplied to the ripening tank, and the reaction liquid is cooked, and then the reaction liquid is supplied to the post-treatment tank. Thereby, in addition to the effect of forming the trough, there is also the effect of the post-treatment tank, that is, preventing the polymerization of DAM in the counter- 20 liquid, and removing the unreacted material after the reaction, especially using the low-boiling quaternizing agent. It is preferred as the unreacted quaternizing agent in the case of the quaternizing agent. At this time, it is preferable to gradually reduce the pressure in the reactor, the ripening tank, and the after-treatment tank. Therefore, the quaternary agent present in the reaction solution, ie, 19 200829540, can be volatilized in one breath. At this time, the dissolved oxygen in the reaction solution is also volatilized together, and the reaction solution is prevented from being hypoxic. The aggregation of the state's DAM. The pressure in each of the above tanks at this time may be in the range of a preferred pressure in the reactor, the ripening tank and the post-treatment tank. In addition, when the solidification tank is at atmospheric pressure, only 5 should be aerated and water added in the post-treatment tank. In the present invention, the number of the matured grooves may be at least one. The number of the grooves is preferably from the viewpoint of improving productivity. The number of cooked grooves is usually one or more, and two or more are preferable, and three or more are preferable. _ It is best to connect more than 2 matured tanks to reduce the pressure step by step. Specifically, in the case of connecting two ripening tanks, it is preferable to set the second ripening tank to 0·05 to 0.8 MPaG, and to set the second ripening tank to atmospheric pressure to 大.5. Moreover, the size, material, and structure of the cooked tank may be appropriately selected depending on the raw materials used and the production of DAM. Specifically, the same as those exemplified by the reactor can be used. The residence time ([reaction liquid mass] / [reaction liquid extraction rate (mass/hour)]) of the present invention can be set to various ranges depending on the reaction conditions, the amount of the post-treatment tank or the number of the matured tanks. Usually, in the case of a continuous process of 2 tanks having a post-treatment tank, the residence time is usually 4 hours or longer, preferably 4.5 hours or more, more preferably 5 hours or more. Further, when the process is continuous for 3 tanks 20 having a mature tank and a post-treatment tank, the residence time is usually 1 hour or more, and it is preferably more than 2 hours, especially 2 to 15 hours. good. When the residence time is set within this range, the residual amount of acrylic acid derived from the above raw material can be reduced, which is preferable. Further, the residual amount of acrylic acid derived from the above-mentioned raw materials in the DAM obtained by the present invention is usually 15 〇〇 ppm or less, and preferably 20 200829540 1200 ppm or less, more preferably ΙΟΟΟρρπι or less. [Examples] Hereinafter, the present invention will be described in detail by way of examples. In addition, only the record of "%" means "% by mass". [Example 1] Using a reaction apparatus shown in Fig. 2, a chlorodecane adduct of dimethylaminoethyl acrylate (hereinafter referred to as "DAC") was produced. The reaction tank (6) is internally provided with a stirrer (9), and is provided with a cool-type heat exchanger (14), and the inner wall is glass-lined with an i〇m3 tank type reaction device. The reaction tank (6) uses a multi-tube heat exchanger (8) equipped with an ejector (1) as an external heat exchanger (total heat transfer coefficient (u) x heat transfer area (Α) = 5 , 9721ο^1/1ιγΧ:) and circulation pump (7). In the multi-tube heat exchanger, it is cooled by brine (2) by means of a pump (not shown). Drowning cycle. 8,000 kg of a 79% aqueous solution of DAC was charged into the reaction vessel (6), and after sealing, 15 temperature was added to 50 °C. Next, the DAC aqueous solution is stirred by the stirrer (9) of the reaction tank (6), and the circulation pump (7) is started, and the DAC aqueous solution is supplied to the nozzle portion of the ejector (1) through the multi-tube heat exchanger (8), and starts. cycle. The chloroform (hereinafter referred to as "MC") is supplied from the supply pipe (10) to the closed reaction vessel (6) via the suction portion (3) of the ejector (1), so that the pressure inside the reaction vessel (6) is 0.28. MPaG. The supply was continuously supplied at a supply rate of 274 kg/hour (4), and only the amount consumed by the reaction was supplied, so that the pressure inside the reaction tank (6) was maintained at 0_28 MPaG. Thereafter, dimethylaminoethyl propyl 21 200829540 5 decyl enoate (hereinafter referred to as "DA") was continuously supplied to the reaction tank (6) through a supply pipe (10) at a supply rate of 730 kg / hour. At the same time, water was continuously supplied to the reaction tank (6) through the supply pipe (η) at a supply rate of 263 kg/hour. The jacketed heat exchanger (14) and the multi-tube heat exchanger (8) are used to circulate the cooling water so that the reaction temperature is 5 (TC. The obtained DAC aqueous solution has a DAC concentration of 80%, and then the piping (13) Continuously withdrawing. The continuously extracted DAC aqueous solution is supplied to a ripening tank (not shown), and is decompressed to O.lMPaG for ripening, and then the matured reaction liquid is supplied to a post-treatment tank (not shown) to make it At atmospheric pressure, water was added to adjust the DAC concentration to 79%. As a result, a 79% aqueous DAC solution was stably produced at a reaction temperature of 50 ° C at a ratio of 1,250 kg / hr. [Example 2] In Example 1 In the same manner as in Example 15 • 1 except that the supply speeds of DA, MC, and water were set to 876 kg/hr, 329 kgM, and 316 kg/hr, respectively, the DAC was produced. The capacity of the pump was maximized, and a 79% aqueous DAC solution was stably produced at a reaction temperature of 51 ° C at a ratio of 1,5001 g / hr. [Comparative Example 1] 20 No multi-tube was used except in Example 1. Heat exchanger reaction unit, and supply speed of DA, MC and water The same method as in Example 1 was carried out except that the cooling water was circulated only using the jacketed heat exchanger (14) so that the reaction temperature was 50 ° C, respectively, at 526 kg/hr, 197 kg/hr, and 190 kg/hr. 22 Manufacture of DAC 22 200829540 As a result, the continuous production of 79% aqueous dac solution was started at a rate of 900 kg/hour. However, the reaction temperature exceeding the purpose during the manufacturing process became 54 ° C, and the reaction temperature did not stop rising, and the cooling was insufficient. [Comparative Example 2] [5] Since the temperature of the reaction liquid increased in Comparative Example 1, it was attempted to reduce the throughput to continuously manufacture the DAC. In Comparative Example 1, except for DA, MC, and water. The production of the DAC was carried out in the same manner as in Comparative Example 1, except that the supply speeds were 94 kg/hr, 148 kg/hr, and 142 kg/hr, respectively.
I 10 結果，冷卻水循環泵之能力用到最大限度，反應溫度 為5l°c，且可以675kg/小時的比例穩定地連續製造79%DAC 水溶液。唯，要降至大概實施例一半的製造能力才能穩定 地連續製造。 上述實施例及比較例的結果顯示於第1表。 15 20 23 200829540 ΟAs a result of I 10 , the capacity of the cooling water circulation pump was maximized, the reaction temperature was 5 l ° C, and the 79% DAC aqueous solution was stably produced continuously at a ratio of 675 kg / hour. Only the manufacturing capacity to be reduced to about half of the embodiment can be stably manufactured continuously. The results of the above examples and comparative examples are shown in the first table. 15 20 23 200829540 Ο
【第1表】 _-—-rn 實施例1 實施例2 比較例1 設定產量 DAC79%產品 (kg/hr) 1,250 1,500 900 675 _______ 操 作 DA供應量 (kg/hr) 730 876 526 394 條 件 MC供應量 (kg/hr) 274 329 197 148 一 内溫設定 (°C) 50 50 50 50 _----- 冷水溫度 CC) 26 28 24 23 ___— 除 熱 内溫實績值 CC) 50 51 54 51 狀 態 冷卻條件 夾套式熱交換器 +外部熱交換器 夾套式熱交換器 +外部熱交換器 只有爽套式 熱交換器_ 只有夾套式 溫度調節狀況 沒有問題 冷卻水 擔壞果 全開 内溫超過54〇C 試驗中止 卩水循環泵 放熱量 (kcal/hr) 181,000 217,200 130,320 97,740 爽套式熱交換器 (kcal/hr) 82,800 79,350 103,500 96,600 熱 量 外部熱交換器 (kcal/hr) 143,328 137,356 - - 合計 (kcal/hr) 226,128 216,706 103,500 96,600 夾套式熱交換器容量：總傳熱係數(U)x傳熱面積(A)=3,450kcal/hr°C 外部熱交換器容量··總傳熱係數(U)x傳熱面積(人)=5,972kcal/hr.°C 5 在使用外部熱交換器之本發明之製造方法中，可充分 地將反應熱除熱，為具高生產性者。 另一方面，在只使用夾套式熱交換器之比較例1及2 中，首先，比較例1在比實施例少之DAC水溶液之生產量 (900kg/hr)的條件下，即使使用和實施例相同之反應容器， 10連續地供應氯甲烷，也無法充分地將反應熱除熱，而不易 控管溫度。假如勉強地提高生產能力而沒有用外部熱交換 器，也會無法控管溫度而產生危險。又，在比較例2中，/ 在將生產量設為約實施例一半之67 5k g / hr的情況下門私 24 200829540 可控管溫度。因此，為確保和實施例相同之生產量，需要 將反應器加大，或設置2台反應器。 接著’著眼於除熱量時，實施例认]可進行226，128及 216,706kcal/hr的除熱，而比較例丨及2只能進行約實施例一 5 半之 1〇3,500 及 965600kcal/hr 的除熱。 產業上利用之可能性 本發明之DAM之製造方法可有效地冷卻反應液，控制 反應益内之溫度上升，而可以高生產性製造高純度之dam。 【圖式簡單說明3 0 第1圖係顯示喷射器的模式圖。 第2圖係顯示設有本發明之喷射器及外部熱交換器反 應裝置的模式圖。 【主要元件符號說明】[Table 1] _---rn Example 1 Example 2 Comparative Example 1 Setting Yield DAC 79% Product (kg/hr) 1,250 1,500 900 675 _______ Operation DA Supply (kg/hr) 730 876 526 394 Condition MC Supply Amount (kg/hr) 274 329 197 148 One internal temperature setting (°C) 50 50 50 50 _----- Cold water temperature CC) 26 28 24 23 ___— Heat removal internal temperature performance value CC) 50 51 54 51 State cooling condition Jacket heat exchanger + external heat exchanger jacketed heat exchanger + external heat exchanger only cool-type heat exchanger _ Only jacketed temperature regulation condition is no problem Cooling water damage fruit full open internal temperature More than 54〇C test to stop the heat release of the hydrophobic circulation pump (kcal/hr) 181,000 217,200 130,320 97,740 Cool-type heat exchanger (kcal/hr) 82,800 79,350 103,500 96,600 Heat external heat exchanger (kcal/hr) 143,328 137,356 - - Total (kcal/hr) 226,128 216,706 103,500 96,600 Jacket heat exchanger Capacity: Total heat transfer coefficient (U) x Heat transfer area (A) = 3,450kcal/hr °C External heat exchanger capacity · Total heat transfer coefficient ( U)x heat transfer area (person) = 5,972kcal/hr. °C 5 in use The method for producing a heat exchanger unit of the present invention, the reaction heat can sufficiently heat removal for those with high productivity. On the other hand, in Comparative Examples 1 and 2 using only jacketed heat exchangers, first, Comparative Example 1 was used and implemented under the conditions of a production amount of DAC aqueous solution (900 kg/hr) which is less than that of the examples. In the same reaction vessel, 10, continuous supply of methyl chloride does not sufficiently remove the heat of reaction, and it is not easy to control the temperature of the tube. If the production capacity is barely increased without the use of an external heat exchanger, there is no danger of controlling the temperature. Further, in Comparative Example 2, / when the production amount was set to about 67 5 k g / hr of about half of the example, the door temperature 24 200829540 can be controlled. Therefore, in order to ensure the same throughput as in the examples, it is necessary to increase the reactor or to provide two reactors. Then, 'focusing on heat removal, the example recognizes that 226, 128 and 216, 706 kcal / hr of heat removal can be performed, while the comparative example 2 and 2 can only be performed about 1 半 3,500 and 965600 kcal / hr of the first embodiment In addition to heat. Industrial Applicability The manufacturing method of the DAM of the present invention can effectively cool the reaction liquid, control the temperature rise within the reaction, and can produce a high-purity dam with high productivity. [Simple diagram of the diagram 3 0 Figure 1 shows a schematic diagram of the injector. Fig. 2 is a schematic view showing an ejector and an external heat exchanger reaction apparatus provided with the present invention. [Main component symbol description]
1…噴射器 8···熱交換器 2…噴嘴部 9…攪拌葉片；攪拌機 3…吸引部 10…Da供應口；供應管 4…反應液 11…供水口；供應管 5···液、氣體或氣液混合物 12· · ·供應管 6".反應槽 13…反應液抽出口；配 7…循環泵 14…夾套式熱交換器 251...injector 8···heat exchanger 2...nozzle portion 9...agitating blade;mixer 3...suction portion 10...Da supply port; supply pipe 4...reaction liquid 11...water supply port; supply pipe 5···liquid, Gas or gas-liquid mixture 12···supply tube 6"reaction tank 13...reaction liquid extraction port; equipped with 7...circulation pump 14...jacketed heat exchanger 25