200904797 九、發明說明： [發明所屬之技術領域] 本發明係有關一種含有易聚合性化合物的液體之蒸顧 方法，詳而言之，係有關一種將含有（甲基）丙烯酸或（甲基） 丙稀酸酯等之易聚合性化合物之液體進行蒸餾之方法。更 詳而言之，係有關一種如下之蒸餾方法，係將含有如（甲基） 丙稀酸或（甲基）丙烯酸酯之易聚合性化合物的液體以分批 式進行單蒸餾之際，對於蒸餾結束後殘留於蒸餾裝置内的 蒸餾殘渣液並不直接丟棄，而是將該一部份回收至蒸餾裝 置内，藉此而有效地利用蒸餾殘渣液中所含的阻聚劑者。 [先前技術] 將如（甲基）丙烯酸或（甲基）丙稀酸醋等之易聚合性化 合物進行蒸餾並精製者在 r月衣苓隹工業上廣泛地實施，並依其產量 而選擇連續式蒸餾或分批式蒸館。 s 、，式蒸餾之具體例示係如：美國專利案第0649787號 說明書中所揭示之技術：其係在(甲基)丙稀酸酿之連續製 紅中’除了將某傲拔+ ▲拔 、 …°之罐出液所含的阻聚劑加以再利用之 外’並回收殘存於^總山 、， 、罐出液中之（曱基）丙烯酸酯者。 又如美國專利幸箪 #: ” 號說明書中所揭示之技 柯具係在（甲基）丙烯酸盥氯仆# _ c * 舻钿其 /、乳化烧撐反應所得之（甲基）丙烯 酸羥基烷酯之連續精製 狴罟盥嗜脸4 、程中’使用具有空塔部份之蒸餾 裝置與薄膜式蒸餾裝 如兮榮 置而精製（甲基）丙烯酸羥基烷酯者。 如该等之專利文獻 不’係提示在連續式的蒸餾製程 200904797 令之阻：法，以及用以得到高純度製品之技術。 而//面’在分批式蒸料’因隨著蒸館時間的增加 有的液里’因此經由高_點物質的 "Γ吏肖置内的溫度上升，而擔憂再崎蝴管 内寻、或蒸館裝置内有聚合物發生的情形。更且，因保有 液量的減少而亦擔憂循環幫㈣起孔餘（caviiation)的情 形。對於該等之各個問題雖可採取減少鶴出比例的手段而 加以解決’“此時卻會產生因增加所廢棄之廢棄油量而 使指失增大之新的問題。而且，4了提升顧出比例以改善 =二必須在蒸餾裝置内配置填充物或塔板使氣液接觸而 提南瘵餾效率。然π，此時為了抑制蒸餾裝置内聚合物的 產生而幻員導入防止聚合之複雜系統，結果使經濟效益不 佳。 [發明内容] 發明所欲解決之課題 在此，本發明之課題係提供—種含有易聚合性化合物 的液體之分批式單蒸顧方法，其係將含有（甲基）丙婦酸或 (甲基烯酸s0等之易聚合性化合物之液體以分批式進行 蒸德時’為防止篆飽g加& 、雠衷置内部中之聚合，除了選擇可成為 早純的阻聚系統之單基耶*4：、 ϊ 早…爾I式以外，並減低所廢棄之作為 廢油的蒸餾殘潰液之量。 … 用以解決課題之手段 本發明者等為解決上述之課題，經專心致志研討之結 6 200904797 果發現：含有易聚合性化合物的液體在分批式單蒸餾結束 後，將所排出之蒸餾殘渣液，在下回之後的分批式單蒸餾 中、經特定時期、較佳為特定之量，經由在蒸餾裝置内回 收’即可防止蒸餾裝置内之聚合’遂而完成本發明。 亦即’本發明係使用分批式單蒸餾形式的蒸餾裝置， 將3有易聚合性化合物的液體進行單蒸餾之含有易聚合性 化合物的液體之蒸餾方法，其特徵係·在初期饋入原料之 質里％以上餾出之際，將之前以分批式單蒸餾所得易聚合 I·生化σ物餾去後之蒸餾殘渣液供至上述蒸餾裝置並持續進 行該單蒸餾者。 發明之效果 如依本發明之崧餾方法，使用既有之分批式單蒸餾裝 並以單純的阻聚系統，即可得到精製之易聚合性化合 物。如在以不回收蒸餾殘渣液的習知方法之單蒸餾中，合 在較短時間中於蒸顧震置内產生聚合物。相對於此，如： 本卷明之瘵餾方法’藉由將蒸餾殘渣液在蒸餾裝置内回收 。使長期間文疋地運作。然而，僅將蒸德殘 二置：進行㈣，因會影響所得之精製的易聚合性化：物 奘、屯度，因此需要本發明所揭示之在特定時機於基餾 裝置内回收。 … ，即可減低所廢棄之作為廢油 ，不須特別的阻聚系統即可抑 如依本發明之蒸館方法 的蒸餾殘渣液之量，尤其是 制蒸餾裝置内的聚合。 7 200904797 [實施方式] 發明實施之最佳型態 以下’對於本發明實施型態之含有易聚合性化合物的 液體之瘵餾方法加以詳細說明。然而本發明之範圍並不僅 限於該等說明，除了下述之例示外，在無損及本發明之主 旨的範圍内，可適當地變更而實施。另外，本說明書中記 載著「X至Y」之範圍係表示「X以上Y以下」者。 本發明實施型態之含有易聚合性化合物的液體之蒸顧 方法係在初期饋入原料之70質量％以上餾出之際，將蒸館 殘渣液供至分批式單蒸餾形式的蒸餾裝置内並持續進行該 蒸餾。 上述蒸餾殘渣液係指分批式單蒸餾結束後殘留於蒸销 裝置内的液體之意。該蒸餾殘渣液在送至廢油儲存槽之 後’其中一部分供給（回收）下回的分批式單蒸餾，剩餘的 一部份當成廢油排出系統外。更且’下回的分批式單蒸館 結束後之蒸餾殘渣液同樣地送往廢油儲存槽，其中一部分 供給（回收）下回的分批式單蒸餾，剩餘的一部份當成廢油 排出系統外。之後反覆地施行此操作。 在可適用本發明實施型態之蒸餾方法的易聚合性.化合 物方面’通常包含不純物（或雜質），而只要為在用以去除 該不純物所施行的蒸餾步驟時易於聚合之液體者即可。其 例可列舉如：丙烯酸、曱基丙烯酸、馬來酸酐、丙烯腈或該 等之酯體及衍生物。丙烯酸酯方面之適用對象可列舉如：丙 烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、 8 200904797 丙烯酸2-羥基乙酯、丙烯酸2_羥基丙酯等；而曱基丙烯酸酯 方面之適用對象可列舉如：甲基丙烯酸曱酯、甲基丙烯酸丁 酯、甲基丙浠酸第三丁酯、甲基丙烯酸異丁酯、甲基丙烯 酸環己酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸2_羥基丙 酉旨等。 在含有易聚合性化合物的液體方面，可為包含更高沸 點物質、溶媒以及易聚合性物質生成時之副產物的混合物。 易聚合性化合物係如丙烯酸、曱基丙烯酸或該等之酯 體，而含有易聚合性化合物的液體方面可例示如：於此含有 溶媒或其他之不純物者。如此之不純物方面，易聚合性化 合物為丙烯酸以及丙烯酸酯時，在接觸氣相氧化反應而得 丙烯酸時所副生者可列舉如：乙酸、丙酸、丙烯醛、馬來酸、 水、福馬林。易聚合性化合物為甲基丙烯酸以及甲基丙烯 酸酯時，在接觸氣相氧化反應而得曱基丙烯酸時所副生之 不純物可列舉如：甲基丙烯醛、丙烯酸、乙酸等。另外可列 舉如：在丙烯酸或甲基丙烯酸之酯化步驟所生成之不純 物、或丙烯酸、甲基丙烯酸或該等之酯體的精製步驟所生 成之不純物。 本發明實施型態之蒸餾方法方面，為防止（甲基）丙烯 酸等之聚合性物質的聚合，一般可添加作為阻聚劑之（甲基） 丙烯酸等易聚合性化合物之習知化合物。 如此之阻聚劑方面可列舉如：酚化合物類、胺化合物 類、銅鹽化合物類' 錳鹽化合物類、氮氧基化合物類、N_ 羥基-2，2，6，6-四甲基哌啶化合物類、2，2，6 200904797 基哌啶化合物類、亞减 合物類以及該等之分解物等。 阻聚劑可使用單-種，或可併用2種以上。 〃上述齡化合物類方面雖無特別限定，惟其例可列舉如. 虱醌、甲基氫醌、第：ττ其. 弟—丁基虱醌、2, 6-二-第三丁基氫 5-一-第二丁基虱醌、2 _ 基粉等。其中亦以對甲負其私第二丁紛、對甲氧 對甲乳基酚，尤其與氮氧基化合物類以 及胺化合物類併用夕M _L 、 '類併用之際，由於阻聚效果優於氫酿，因而為 土。並且’该等之酚化合物類可併用2種以上。 上述胺化合物類方面雖無㈣限定，惟其例可列舉如· 吩喧嗔、雙·（1_甲基苯）吩售嗪、3,7-二辛基吩嗜嗪、雙仆 一甲基苯偶醯）吩噻嗪、硫撐二苯胺等。 上述銅鹽化合物類並無特別限定，可為無機鹽、有機 鹽之任-種，而可使用各式各樣者。其例可列舉如:二燒基 二硫代胺基甲酸銅、乙酸銅、環烧酸銅、丙稀酸銅、硫酸 銅、石肖酸銅、氯化銅等。該等之銅鹽化合物類亦可使用一 價、二價之任一者，在上述銅鹽化合物類中，由效果等之 點而言，則以二烷基二硫代胺基甲酸銅為佳。 二烷基二硫代胺基甲酸銅並無特別限定，其例可列舉 如：二甲基二硫代胺基甲酸銅、二乙基二硫代胺基甲酸 銅、二丙基二硫代胺基甲酸銅、二丁基二硫代胺基Τ酸鋼、 二戊基二硫代胺基甲酸銅'二己基二硫代胺基曱酸銅、二 苯基二硫代胺基甲酸銅、甲基乙基二硫代胺基甲酸銅； 基丙基二硫代胺基甲酸銅、甲基丁基二硫代胺基，酸銅、 甲基戊基二硫代胺基甲酸銅、甲基己基二硫代胺基甲酸 10 200904797 銅、甲基苯基二硫代胺基甲酸銅、乙基丙基二硫代胺基甲 酸銅、乙基丁基二硫代胺基甲酸銅、乙基戊基二硫代胺基 甲酸銅、乙基己基二硫代胺基甲酸銅、乙基苯基二硫代胺 基甲酸銅、丙基丁基二硫代胺基甲酸銅、丙基戊基二硫代 胺基曱酸銅、丙基己基二硫代胺基甲酸銅、丙基苯基二硫 代胺基甲酸銅、丁基戊基二硫代胺基曱酸銅、丁基己基二 硫代胺基甲酸銅、丁基苯基二硫代胺基甲酸銅、戊基己基 二硫代胺基甲酸銅、戊基苯基二硫代胺基甲酸銅、己基苯 基二硫代胺基甲酸銅等。該等之二烷基二硫代胺基甲酸銅 可為一價或二價之銅鹽。該等之中，由效果之點以及容易 取得之點等而言，以二甲基二硫代胺基甲酸銅、二乙基二 硫代胺基甲酸銅以及二丁基二硫代胺基甲酸銅為佳，特別 以一丁基一硫代胺基甲酸銅為更佳。 上述錳鹽化合物類並無特別限定，其例可列舉如：二烷 基二硫代胺基甲酸錳（烷基係曱基、乙基、丙基、丁基之任 -者，可為相同或互異）、^苯基二硫代職甲⑽、甲酸 錳、乙酸錳、辛酸錳、環烷酸錳、乙二胺四乙酸之錳鹽化 合物等’該等可使用一種以上者。 在N-氧化合物類方面並無特別限定，只要為一般作為 乙烯化合物之阻聚劑的習知1氧化合物類者均可使用。該 等之中 為適用 6 -四曱基娘咬氧類 以下述式（1)所示之2，2，6 200904797200904797 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for evaporating a liquid containing an easily polymerizable compound, and more specifically, a related one will contain (meth)acrylic acid or (meth) A method in which a liquid of an easily polymerizable compound such as acrylic acid ester is subjected to distillation. More specifically, it relates to a distillation method in which a liquid containing a polymerizable compound such as (meth)acrylic acid or (meth) acrylate is subjected to single distillation in a batch mode, The distillation residue liquid remaining in the distillation apparatus after the completion of the distillation is not directly discarded, but a part thereof is recovered into the distillation apparatus, whereby the polymerization inhibitor contained in the distillation residue liquid is effectively utilized. [Prior Art] Distillation and refining of an easily polymerizable compound such as (meth)acrylic acid or (meth)acrylic acid vinegar is widely practiced in the r 苓隹 苓隹 industry, and is continuously selected depending on the yield thereof. Distillation or batch steaming. Specific examples of s, and distillation are as disclosed in the specification of U.S. Patent No. 0,649,787: in the continuous red making of (meth)acrylic acid brewing, except for the extraction of a certain arrogant + ▲ The polymerization inhibitor contained in the tank of the tank is reused, and the (mercapto) acrylate remaining in the total mountain, and the tank liquid is recovered. For example, the technique disclosed in the specification of the US Patent No. #: ” is a (meth)acrylic acid hydroxyalkane obtained by emulsification of (meth)acrylic acid chlorinated servant # _ c * Continuous refining of esters, fascinating face 4, Cheng Zhong' use of a distillation unit with a hollow column and a thin film distillation apparatus such as 兮Rongrong to refine (hydroxy) hydroxyalkyl acrylate. Such as the patent documents It does not indicate the resistance in the continuous distillation process of 200,904,797: the method, and the technology used to obtain high-purity products. And / / face in the batch of steamed materials because of the increase in steaming time In the case of the temperature of the high-point material, the temperature rises in the room, and there is concern about the occurrence of polymer in the tube or the steaming device. Moreover, due to the decrease in the amount of liquid retained I am also worried about the situation in which the circulation helps (4) the caviiation. For each of these problems, the means of reducing the proportion of cranes can be used to solve the problem. 'At this time, the amount of waste oil discarded is increased. A new problem of loss. Moreover, 4 increase the proportion of the improvement to improve = two must be placed in the distillation apparatus to fill or tray to make gas and liquid contact and to increase the efficiency of distillation. However, at this time, in order to suppress the generation of the polymer in the distillation apparatus, a complicated system for preventing polymerization is introduced, and as a result, the economic efficiency is not good. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The subject of the present invention is to provide a batch-type single evaporation method for a liquid containing a polymerizable compound, which will contain (meth) propyl benzoate or ( When the liquid of the polymerizable compound such as methenoic acid s0 is steamed in a batch manner, 'in order to prevent the addition of 篆 & & 雠 雠 雠 雠 雠 雠 雠 雠 雠 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合In addition to the type I, the amount of the distillation residue that is discarded as a waste oil is reduced. The means for solving the problem is solved by the inventors of the present invention. Research Conclusion 6 200904797 It is found that after the batch-type single distillation is completed, the liquid containing the polymerizable compound is discharged in the batch-type single distillation after the next time, preferably for a certain period of time, preferably In a specific amount, the present invention is completed by recovering 'in the distillation apparatus to prevent polymerization in the distillation apparatus'. That is, the present invention uses a distillation apparatus in a batch-type single distillation form, and 3 has an easily polymerizable compound. Liquid A method for distilling a liquid containing a polymerizable compound in a single distillation, characterized in that, when the amount of the material fed into the raw material is initially distilled, the previously obtained mono-distillation of the easily polymerizable I·biochemical σ substance The distilled residue liquid after distillation is supplied to the above distillation apparatus and the single distillation is continued. The effect of the invention is as follows. According to the distillation method of the present invention, an existing batch type single distillation apparatus is used and a simple polymerization inhibition system is used. A purified polymerizable compound can be obtained. For example, in a single distillation in a conventional method in which the distillation residue liquid is not recovered, a polymer is produced in a vaporization chamber in a short period of time. The distillation method of the invention is carried out by recovering the distillation residue liquid in a distillation apparatus, and the operation is carried out for a long period of time. However, only the vaporization residue is set to be carried out: (4), since the resulting polymerization is easily polymerized. : 奘 屯 屯 , , , , , , , , , 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本It The amount of the distillation residue liquid in the distillation method, in particular, the polymerization in the distillation apparatus. 7 200904797 [Embodiment] The best mode of the invention is as follows. 'The distillation of the liquid containing the polymerizable compound of the embodiment of the present invention. The present invention is not limited to the scope of the invention, and may be appropriately modified and implemented within the scope of the gist of the invention. The range of X to Y" is "X or more and Y or less". The method of evaporating the liquid containing the polymerizable compound according to the embodiment of the present invention is to be distilled at 70% by mass or more of the initial feedstock. The steaming residue liquid is supplied to the distillation apparatus of the batch type single distillation type and the distillation is continued. The above-mentioned distillation residue liquid means the liquid remaining in the steaming pin apparatus after the completion of the batch type single distillation. The distillation residue is subjected to a batch-type single distillation in which a part of the distillation residue is supplied (recovered), and the remaining portion is discharged as waste oil out of the system. Moreover, the distillation residue after the end of the batch-type single-steaming plant is sent to the waste oil storage tank, and a part of it is supplied (recovered) to the next batch of single-distillation, and the remaining part is regarded as waste oil. Out of the system. Then do this again and again. The polymerizable property of the distillation method to which the embodiment of the present invention can be applied generally contains impurities (or impurities) as long as it is a liquid which is easily polymerized in the distillation step for removing the impurities. Examples thereof include acrylic acid, methacrylic acid, maleic anhydride, acrylonitrile or the like and derivatives thereof. Examples of the acrylate target include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 8 200904797 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and the like; Examples of the acrylate target include decyl methacrylate, butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, and methacrylic acid 2 - hydroxyethyl ester, 2-hydroxypropyl methacrylate, and the like. In the case of a liquid containing a polymerizable compound, it may be a mixture of a higher boiling point substance, a solvent, and a by-product of the formation of an easily polymerizable substance. The polymerizable compound is, for example, acrylic acid, methacrylic acid or the like, and the liquid containing the polymerizable compound can be exemplified by a solvent or other impurities. In the case of such an impurity, when the polymerizable compound is acrylic acid or acrylate, the by-producer may be exemplified by acetic acid, propionic acid, acrolein, maleic acid, water, and formalin when exposed to a gas phase oxidation reaction to obtain acrylic acid. . When the polymerizable compound is methacrylic acid or methacrylic acid ester, impurities which are by-produced when contacted with a gas phase oxidation reaction to obtain mercaptoacrylic acid include, for example, methacrolein, acrylic acid, acetic acid and the like. Further, impurities such as impurities formed in the esterification step of acrylic acid or methacrylic acid or impurities obtained by the purification steps of acrylic acid, methacrylic acid or the like may be mentioned. In the distillation method of the embodiment of the present invention, in order to prevent polymerization of a polymerizable substance such as (meth)acrylic acid, a conventional compound which is an easily polymerizable compound such as (meth)acrylic acid as a polymerization inhibitor can be added. Examples of such a polymerization inhibitor include phenol compounds, amine compounds, copper salt compounds, manganese salt compounds, oxynitrides, N-hydroxy-2,2,6,6-tetramethylpiperidine. Compounds, 2, 2, 6 200904797 Piperidine compounds, sub-halogens, and the like, and the like. The polymerization inhibitor may be used singly or in combination of two or more. The compound of the above-mentioned age is not particularly limited, and examples thereof include, for example, hydrazine, methylhydroquinone, and ττ. 弟-butyl hydrazine, 2,6-di-t-butylhydrogen 5- One-second butyl hydrazine, 2 _ base powder, and the like. Among them, it is also better for the anti-agglomeration effect of the second, the methoxy-p-methyl-based phenol, especially with the oxynitrides and the amine compounds, and the combination of the M-L and 'classes. Hydrogen is brewed and thus is soil. Further, these phenol compounds may be used in combination of two or more kinds. Although there are no (4) restrictions on the above amine compounds, examples thereof include, for example, bismuth, bis(1-methylphenyl) phenazine, 3,7-dioctylphenazine, bis-monomethylbenzene. Occasionally) phenothiazine, thiodiphenylamine, and the like. The copper salt compound is not particularly limited, and may be any of an inorganic salt or an organic salt, and various types can be used. Examples thereof include copper dithiodithiocarbamate, copper acetate, copper succinic acid, copper acrylate, copper sulfate, copper lithosperate, copper chloride and the like. The copper salt compound may be either monovalent or divalent. Among the above copper salt compounds, copper dialkyldithiocarbamate is preferred from the viewpoint of effects and the like. . The copper dialkyldithiocarbamate is not particularly limited, and examples thereof include copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and dipropyldithioamine. Copper formate, dibutyldithiocarbamic acid, copper dipentyldithiocarbamate, copper dihexyldithiocarbamate, copper diphenyldithiocarbamate, A Copper ethyl thiodithiocarbamate; copper propyl dithiocarbamate, methyl butyl dithio amine, copper acid, copper methyl pentyl dithiocarbamate, methyl hexyl Dithiocarbamic acid 10 200904797 Copper, copper methyl phenyl dithiocarbamate, copper ethyl propyl dithiocarbamate, copper ethyl butyl dithiocarbamate, ethyl amyl Copper dithiocarbamate, copper ethylhexyl dithiocarbamate, copper ethyl phenyl dithiocarbamate, copper propyl butyl dithiocarbamate, propyl pentyl dithio Copper amidinate, copper propylhexyldithiocarbamate, copper propylphenyldithiocarbamate, copper butylpentyldithiocarbamate, butylhexyldithioamino Acid copper, butylphenyl dithio carbamic acid copper, pentyl hexyl dithiophosphoric acid copper amine, pentylphenyl dithio carbamic acid copper, hexylphenyl dithio carbamic acid copper. The copper dialkyldithiocarbamate may be a monovalent or divalent copper salt. Among these, copper, dimethyldithiocarbamate, copper diethyldithiocarbamate, and dibutyldithiocarbamic acid are used in terms of the point of effect and the point of easy availability. Copper is preferred, and copper monobutyl monothiocarbamate is particularly preferred. The manganese salt compound is not particularly limited, and examples thereof include manganese dialkyldithiocarbamate (alkyl group, ethyl group, propyl group, and butyl group), which may be the same or "Different", phenyldithiocarbamate (10), manganese formate, manganese acetate, manganese octoate, manganese naphthenate, manganese salt compound of ethylenediaminetetraacetic acid, etc., may be used. The N-oxygen compound is not particularly limited, and any of the conventional oxygen compounds which are generally used as a polymerization inhibitor of a vinyl compound can be used. Among these, it is suitable for the application of 6-tetraki-kidini, which is represented by the following formula (1), 2, 2, 6 200904797
R1R1
H3Cxl Uch3H3Cxl Uch3
HbC^n^CHs o (惟式中之 Ri 表示 CHOU、CHCi^OH、（：ίί(：Ή：2(：ϋ20ίΙ、 CHOCH2OH、CHOCH2CH2OH、CHCOOH、或 C=〇; R2 表示 H或CHaOH)。如為N-氧化合物類者，則無特別限定而均 可使用。為得到良好的阻聚效果，宜使用2，2，6，6_四= *基:辰啶氧化合物、4_羥基_2’2,6’6_四甲基哌啶氧化合物甲 4_；n_(2 ’ 2 ’ 6 ’ 6_四甲基哌啶氧基）癸二酸酯、4,4，，4，，_ 6四曱基D底D定氧基）鱗酸醋中之一種 上者。 但次—種以 N-羥基 _2，2，6 〔 6 -四甲基派π定化合物類 列舉如：1,4-二羚其9 。 碉之代表例可 .,m 工土 ，2 ’ 6，6_四甲基哌啶、其。 6 ’6-四曱基哌 ^基-2’ 2, 疋專。該等N_羥基_2 化合物可單獨使 6 6-四甲基哌啶 m，6,6:甲Λ可混合二種以上使用。 2, 6, 6_四甲基呢二咬化合物類之具體例可列舉如 並可使用該等之—種/羥基_2’ 2, 6, 6_四甲基哌啶等， 四甲基娘咬化合物類或^。另外，Ν-經基_2,2,6,6_ 有含於市售之Ν•氧，:’ 6’ 6_四甲基派啤化合物類亦 品中作為不純物之情形。在如 12 200904797 此之情況下，經由使用市售之冰氧化合物，而可與N_羥基 -2 ’ 2 ’ 6，6-四’基哌啶化合物或2，2，6，6-四甲基哌啶 化合物併用。 上述之亞硝基化合物類方面並無特別限定，其例可列 舉如：對亞靖基齡、亞確基苯、N-亞靖基二苯胺、亞靖酸異 壬酯、N-亞石肖基環己基經基胺、N_亞石肖基苯基經基胺以及 該等之銨鹽等，並可使用該等之一種以上者。 如使用上述之阻聚劑，其添加量係依操作條件等而適 當地調整，並無特別限定，而相對於每批之初期饋入原料， 以0.0001至1質量％為佳，以〇 〇〇1至〇 5質量％更佳。 在上述之阻聚劑之添加方法方面並無特別限定，當阻 聚劑為固體時，宜以固體（粉體）或以溶於液體之狀態（母液） 而添加’而且亦可導入分解氣體。當阻聚劑為液體時，宜 以直接狀態或以溶於液體之狀態（母液）而添加，當阻聚劑 為氣體時，宜以氣體之狀態而添加。 對於上述阻聚劑之添加時機方面亦無特別限定，可在 瘵餾步驟中之任意時點進行添加，惟當阻聚劑為固體時， 可先與初期饋入成分同時添加於蒸餾裝置内。 本發明之實施型態的蒸顧方法中，如有必要亦可在上 述阻聚劑中與分子狀氧併用。 本發明之實施型態的蒸餾方法申，Λ τ 馮徒咼阻聚效果， 可在上述阻聚劑中與酸類併用。酸類方面並無特別限定， 其例可列舉如：乙二酸、乙二酸酐、丙二酸'丁二酸、丁二 酉文酐、反丁細二酸、順丁稀二酸、順丁嫌_紋 ，钸一酸酐、辛酸、 13 200904797 己二酸、癸二酸、十四烷二羧酸、1，2,4-丁烷三羧酸、丨，3,6-己炫三羧酸、1,2,3,4-丁烷四羧酸、1，2,3,4-戊烷四羧酸、 1,6,7,12 -十—貌四叛酸、苯曱酸、鄰苯乙酸、間苯乙酸、 對苯乙酸、笨二甲酸、苯二甲酸酐、異苯二甲酸、對苯二 甲酸、2,6-萘二羧酸、均苯四甲酸、均苯四曱酸酐、 苯三叛酸、1，4,5,8-萘四羧酸、1,3,5,7-萘四綾酸、水楊酸、 醋酸等之羧酸類以及羧酸酐類。該等可單使用一種，亦可 將二種以上併用。 如使用上述酸類’該添加量可依使用之阻聚劑種類、 添加量等之條件而適當地調整，並無特別限定，而相對於 每批之初期饋入原料，酸類之總添加量以〇 〇〇〇丨至i質量 %為佳’以0.001至〇.5質量％更佳。如A 〇 〇〇〇1質量％以 上時，目可獲得充分之阻聚效果而佳。且如為i質量％以 下時，因難以使蒸餾殘留液引起性狀惡化而佳。 上述酸類之添加方法方面並無特別限定，可一次投入 (添加），亦可分成二次以上投入。 本發明之實施型態的蒸餾係在真空下進行，該HbC^n^CHs o (Ri in the formula denotes CHOU, CHCi^OH, (: ίί(:Ή:2(:ϋ20ίΙ, CHOCH2OH, CHOCH2CH2OH, CHCOOH, or C=〇; R2 represents H or CHaOH). For the N-oxygen compound, it can be used without particular limitation. To obtain a good polymerization inhibitory effect, it is preferred to use 2,2,6,6_tetra=*yl: phenidine oxy compound, 4-hydroxyl-2 '2,6'6_Tetramethylpiperidinyloxymethyl 4_;n_(2 ' 2 ' 6 ' 6-tetramethylpiperidinyloxy)sebacate, 4,4,,4,,_ 6 One of the tetradecyl D bottom D-oxygen sulphate vinegars. However, the sub-species are N-hydroxy-2,2,6 [6-tetramethylpyridine compounds such as: 1,4 - Erling its 9. The representative example of 碉 can be., m soil, 2 '6,6_tetramethylpiperidine, which is 6 '6-tetradecylpiperidinyl-2' 2, 疋. The N-hydroxyl-2 compound may be used alone or in combination with two or more kinds of 6 6-tetramethylpiperidine m,6,6:formamidine. Specific examples of the 2,6,6-tetramethyl bismuth compound For example, it is possible to use such a kind of /hydroxy-2' 2,6,6-tetramethylpiperidine, etc., tetramethyl mother bite compound or ^. Ν-经基基_2,2,6,6_ is included in the commercially available Ν•Oxygen, as in the case of '6' 6_Tetramethyl beer compound, as in the case of impurities. In the case of 12 200904797 The above may be used in combination with an N-hydroxy-2' 2 ' 6,6-tetra'-piperidine compound or a 2,2,6,6-tetramethylpiperidine compound by using a commercially available ice oxide compound. The nitroso compound is not particularly limited, and examples thereof include: for the Jingjing age, the azobenzene, the N-orthoylene diphenylamine, the isodecyl phthalate, and the N- succinyl cyclohexyl group. The above-mentioned polymerization inhibitor is used, and the amount of addition is appropriately adjusted depending on the operating conditions and the like, and the like, and the above-mentioned polymerization inhibitor is used. It is not particularly limited, and it is preferably 0.0001 to 1% by mass, more preferably 〇〇〇1 to 〇5% by mass, based on the initial feed of the batch, and is not added to the above-mentioned polymerization inhibitor. Particularly, when the polymerization inhibitor is a solid, it is preferably added as a solid (powder) or in a liquid-soluble state (mother liquor). The decomposition gas may be introduced. When the polymerization inhibitor is a liquid, it is preferably added in a direct state or in a liquid-soluble state (mother liquor), and when the polymerization inhibitor is a gas, it is preferably added in a gas state. The addition timing of the agent is not particularly limited, and may be added at any time in the retort step. However, when the polymerization inhibitor is a solid, it may be added to the distillation apparatus at the same time as the initial feed component. In the vaporization method of the state, if necessary, it may be used in combination with molecular oxygen in the above polymerization inhibitor. The distillation method of the embodiment of the present invention can be used in combination with an acid in the above polymerization inhibitor. The acid is not particularly limited, and examples thereof include oxalic acid, oxalic anhydride, malonic acid 'succinic acid, butyl phthalic anhydride, butyl bromide, cis-butyl diacid, and cis-butyl , phthalic anhydride, octanoic acid, 13 200904797 adipic acid, sebacic acid, tetradecane dicarboxylic acid, 1,2,4-butane tricarboxylic acid, hydrazine, 3,6-hexatricarboxylic acid, 1, 2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 1,6,7,12-deca-tetracarboxylic acid, benzoic acid, o-phenylacetic acid, Phenylacetic acid, p-phenylacetic acid, stearic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, pyromellitic acid, pyromellitic anhydride, benzene tricarboxylic acid And carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid, 1,3,5,7-naphthalenetetradecanoic acid, salicylic acid, acetic acid, and the like. These may be used alone or in combination of two or more. The amount of the above-mentioned acid can be appropriately adjusted depending on the conditions of the type of the polymerization inhibitor to be used, the amount to be added, and the like, and is not particularly limited, and the total amount of the acid added is 相对 with respect to the initial feed of each batch. It is preferable that 〇〇〇丨 to i mass% is preferably 0.001 to 〇.5 mass%. When A 〇 〇〇〇 1% by mass or more, the target can obtain a sufficient effect of blocking. In the case of i mass% or less, it is difficult to deteriorate the properties of the distillation residual liquid. The method of adding the above-mentioned acids is not particularly limited, and may be carried out at once (addition) or may be divided into two or more injections. The distillation system of the embodiment of the present invention is carried out under vacuum, which
較為理想。 之實施型態的蒸餾方法。 的系統圖，然並不僅限於 依據圖式而加以說明本發明之實 第1圖係呈不本發明之蒸餾方法 14 200904797 此，在無損於本發明之要旨之範圍内可適當地More ideal. An embodiment of the distillation method. The system diagram is not limited to the description of the present invention. Fig. 1 is a distillation method not according to the present invention. 14 200904797 Therefore, it is possible to appropriately deviate from the gist of the present invention.
又尺而貫施C 弟1圖中，將含有易聚合性化合物的液 W饮體，例如含有（甲 基）丙婦酸或（甲基）丙烯酸酯等之粗製液 從（以下，亦可將該含 有易聚合性化合物的液體稱為「初期饋入液」）由管路9饋 入批式單蒸餾襄置(以下，亦可單稱為「蒸餾裴置」”中貝 此處，將含有易聚合性化合物的液體之單蒸館以二式進’ 行。在蒸鶴裝置1之下部令，使蒸餾裳置内液流出，並使 德壤幫浦5與加熱源之再沸器4介由循環管路6連接 蒸氣等之熱媒體導人再㈣4並將饋人液進行加熱、基館。 蒸餾餾出液係經由馏出管路8而送至製品儲存槽2 中。/比式單蒸顧結束時，將殘留於蒸館褒置内之蒸館殘清 以下亦稱為「蒸餾底殘液」)、經由循環管路6、蒸餾底殘 液之送液管路10送至廢油儲"" 赝庙储存槽3並儲存於此。另外， 1圖中雖無圖示，而實際上 乐 观戒保存槽3中備有冷卻 置’其係在蒸顧結束後如有苒、、w — ^ 交$有间/皿之療餾底殘液的混入亦可 立即冷卻並保存於低溫中。 在本發明之實施型態的蒸館 、， 诩万，去方面，百先，將含有 易聚合性化合物的液體饋蒸 ▲微展置1中’於此，將初 饋入液之蒸餾以批式進行， ^ 甘汾 餾出物迓至製品儲存槽2,且 G餘結束後之蒸顧底殘液 ^ ^ 达至廢油儲存槽3後，在廢油儲 存槽3内進行冷卻並保存。 接著，將新的饋入液奘 ^ 夜裝入瘵餾裝置I中，即開始抵式 早Q館。此處，將蒸鶴開 卩古 Ί始别的初期饋入液量作為V。茈 時，餾出物之液量成為〇 XV以上之際，將廢油儲存槽3 15 200904797 中之蒸館底殘液的至少—却八 刀經由廢油供給幫浦11、廢油 回收管路7而供至蒸餾裝置卜再持續進行蒸館。其中， 在第！圖中，雖由循環幫浦5之吸入側所供給，然並不限 二：亦可直接供至蒸餾裝置i。蒸餾結束後，蒸餾底殘 液送至廢油儲存槽3德，ώ 炎，、儲存於廢油儲存槽3之液體混 合後，再進行冷卻、保存。 其後，反覆地進行上述之操作。 本么月之實施型態的批式單蒸餾中，蒸餾底殘液的供 給係館出物之液|，以# & 、 為0·7χν至〇.95χν之時點而開始 ‘”、，以成為0.75XV至0·9χν之時點而開始者為更佳。 在晚於0 7xV之赂讲士 ρ日，， 白1又才開始進行供給日寺，因可使所得精製 性化合物更進—步提高其純度，因而為佳。而且， 在早於0.95xV之於μ & 1¾奴開始進行供給時，因有關對保 顧…之液量的增加，液面亦高於再沸器管板，因此； 蒸館裝置1内可避免聚合物的發生之虞。更且，亦可避免 使蒸館底殘液循環之循環幫浦5引發氣钱（cavitati〇n)之危 險性，因而為佳。 本發明之實施型態的蒸餾底殘液之供給，係可將蒸餾 底殘液投人_裝置内者即可，而無特別限定，例如可使 用一般所㈣之送液幫浦或壓送者。而且，上述蒸館底殘 液之供給，可為遠縫# > 為連續式投入或間歇式投入之任一種，而無 ^ At疋另外，連續式投入係指每次少量且連續投入之 里心、間歇式投人係指脈衝式或間歇性地分成任意次數投 入之型態。 16 200904797 本發明之實施型離的成 液即可，而甘/ 存槽3如可儲存蒸餾底殘 ^ m ^ .、 之’為了抑制含於蒸餾底 殘履中之阻聚劑的變質 冷卻裝置。在A卻^太具有將蒸館底殘液進行冷卻之 進行的方、> 並無特別限定，可採用一般所 進仃的方法。在冷卻溫度方面， 易聚合性化合物後之装餘殘、杳η/ 館底殘液(餾去 ㈣之相殘邊液）冷卻至50t以下之溫度 =圭，：冷卻至抑以下之溫度者更佳，以冷卻至2。 所要的者4特^ ° ^ 4 ’對於冷卻溫度達到如上述 厅要的ί现度為止之時間墓 ⑽底殘液之移送結束之時點 乍為起點’以在1.0小時之内為佳，〇 5小時之内為更佳。 、且’以在與冷卻後之溫度相同之溫度下儲存者為佳。冷 部溫度為娜以下時，則含於廢油中之阻聚劑因不易變質 而可充分發揮阻聚效果，因而為佳。 、本發明之實施型態中的再沸器4,可有效地加熱饋入 ::可’其型態並無特別限定。例如:可使用強制循環式多 g式再彿器 '自然循環式多管式再彿器等。而且，加熱源 :面’除了再沸器之外’亦可使用旋管（c〇il)或套管（★㈣ 〇 本發明並非僅限於上述之實施型態者，在申請專利範 圍所=之範圍内可作各種變更。亦即’在申請專利範圍所 不之範圍内，將經適當地變更之技術手段組合所得之實施 型態’亦包含在本發明之技術範圍。 [實施例] 以下，依製造例、實施例以及比較例而更詳加說明本 17 200904797 發明，然本發明並不僅限於該等之實施例。 製造例 將容量2000L之SUS316製蒸餾裝置（單蒸餾形式。設 有多管式再熱器作為加熱源，並使用循環幫浦使之強制循 環）之内壓進行真空吸引至5.33hPa後，饋入曱基丙烯酸與 玉哀氧乙烷反應而得之含有甲基丙烯酸羥乙酯（以下記載為 「HEMA」）之液體1150kg(93 5質量％)、作為阻聚劑之對 甲氧基酚0.12 kg，以及吩噻嗪〇.2〇 kg，將蒸氣通過再沸 器’開始上述含有HEMA之液體的蒸館。 從液溫達到70°C之時點，即開始餾出，之後在85七則 為固定。餾出量成為980 kg (初期饋入液之85 2質量％)之 時點即結束蒸餾，得到蒸餾底殘液17G kg。爾後，將所得 蒸餾底殘液全部移往廢油儲存槽中，使液溫冷卻至48。〇。 同時，瘵餾底殘液之送液剛結束後之廢油儲存槽内之溫度 升至75°C，30分鐘後成為48t：。 X 實施例1 (首次蒸餾） 在與製造例相同的蒸餾裝置中，饋入甲基丙締酸與環 氧乙院反應而得之含有HEMA之液體U5〇kg、作為阻聚 劑之對甲氧基盼G.12kg，以及吩嗟嗪〇.2Gkg後開始蒸館。 k餾出液量成為810 kg (初期饋入液之7〇·4質量％)之 時點’即將製造例中所得蒸德底殘液62 kg (初期饋入液之 5·4質里％) ’以达液幫浦供給至蒸餾裝置，並持續蒸餾。從 18 200904797 開始餾出經過3.5小時後，在餾出液量成為11〇〇 kg (初期 饋入液之95.7質量％)之時點即停止蒸鶴。 蒸餾結束後，殘留於蒸餾裝置内之蒸餾底殘液i I2 kg 移送至與製造例相同之廢油儲存槽中，使液溫冷卻至18 °C。同時，蒸餾底殘液之送液剛結束後之廢油儲存槽内之 溫度升至7〇°C，40分鐘後成為18t❶爾後，將廢油儲存 槽中所存之液體5 0kg作為廢油排出系統外。 (第2次以後之蒸餾） 在與首次瘵餾相同之蒸餾裝置中，饋入含有HEMA之 液體1150 kg (93.5質量％)、作為阻聚劑之對甲氧基酚〇12 kg，以及吩噻嗪0.20 kg後開始蒸館。 從餾出液量成為810 kg之時點，即將廢油儲存槽中所 存之蒸餾底殘液621^(初期饋入液之54質量％)，以送液 幫1供給至蒸餾裝置，並持續蒸餾。從開始餾出經過3 5 小時後，在餾出液量成為1100 kg(初期饋入液之95 7質量 /〇)之時點即停止蒸館。 蒸館結束後，$留於蒸顧裝置内之蒸餾底殘液112kg 移送至廢油儲存槽中，使液溫冷卻至。_，蒸館底 殘液之送液剛結束後之廢油儲存槽内之溫度升至贼，40 分鐘後成為18°C °爾後’將廢油儲存槽液50 kg作為廢油 排出系統外。 甘其後，反覆進行上述之操作，總共實施150批次，在 G餾裝置内並不產±聚合物而穩定地運作。 而且，此時所得製品HEMAi純度為97.8質量 19 200904797 實施例2 除了將蒸餾中供給之蒸餾底殘液改為2】〇 kg (初期饋 入液之18.3質量％)之外，與實施例！進行同樣之操作。 總共實施150批次，在蒸餾裝置内並不產生聚合物而 穩定地運作。 而且，此時所得製品HEMA之純度為97.3質量。/〇。 實施例3 除了將蒸餾底殘液之供給改為餾出液量成為1〇5〇kg (初期饋入液之91.3質量％)之時點之外，與實施例】進行 同樣之操作。 總共實施15〇批次，在蒸館裝置内並不產生聚合 穩定地運作。 而且，此時所得製品HEMA之純度為97.4質量％。 比較例1 除了不供給蒸餾底殘液之外，與實施例丨進行同樣之 操作。 7 在經過3(U比次之時點，因確認出蒸傭裝置内的聚合而 停土蒸餚。 口 比較例2 承了將蒸館底殘液之供給改為與含有HEMa之液體的 20 200904797 饋入時期同時實施之外’與實施例】進行同樣之操作 在經過1 50批次後，在蒸餾裝置内雖未見到聚人 產生，然此時所得製品HEMA之純度卻降低至95 f的 •貝量％。 比較例3 除了將蒸餾底殘液之供給改為在顧出 /、如址 置成為690 kg ^饋人液之㈣質量％)之時點而開始之外，與實施例i 進订同樣之操作。 东在經過150批次後，在蒸鶴襄置内雖未見到聚合物的 生’然此時所得製品HEMA之純度卻降低至95_8質量。A 同時，本申請案係依據2007年6月u日申請之日本 專利申請案第2OO7-I54453號者，苴想—如〜 ^ 具揭不内容經參昭而全 文引用。 … [圖式之簡單說明] 第1圖係本發明之蒸餾方法的— 「- μ ~ 巧種型態之系統圖 [凡件付號之說明] 2 製品儲存槽 4再沸器 6循環管路 8餾出管路 1 〇送液管路 1 蒸餾裝置 3 廢油儲存槽 5循環幫浦 7 廢油回收管路 9管路 11廢油供給幫浦 21In addition, the liquid W drink body containing a polymerizable compound, for example, a crude liquid containing (meth) propyl benzoic acid or (meth) acrylate, etc. (hereinafter, may also be used) The liquid containing the polymerizable compound is referred to as "initial feed solution") and is fed into the batch single distillation unit by the line 9 (hereinafter, may also be referred to simply as "distillation unit"". The single-steaming of the liquid of the polymerizable compound is carried out in two ways. In the lower part of the steaming crane device 1, the liquid in the distillation is discharged, and the reboiler 5 of the German soil pump 5 and the heating source are introduced. A heat medium such as steam is connected to the circulation line 6 to guide the liquid (4) 4, and the donor liquid is heated, and the base liquid is distilled. The distilled distillate is sent to the product storage tank 2 through the distillation line 8. At the end of the steaming, the steaming residue remaining in the steaming chamber is also referred to as the "distillate bottom liquid", and is sent to the waste oil through the circulation line 6 and the liquid supply line 10 of the distillation bottom liquid. Store "" Temple Storage Tank 3 and store it here. In addition, although there is no illustration in Fig. 1, in fact, there is a cooling device in the optimistic or preservation tank 3, which is after the end of the steaming, if there is a sputum, w-^ The mixing of the liquid can also be cooled immediately and stored at low temperature. In the embodiment of the present invention, the steaming hall, the 10,000, the first, the liquid containing the polymerizable compound is steamed ▲ micro-expanded in the middle of this, the first feed into the distillation of the batch In the formula, ^ the glycoside distillate is poured into the product storage tank 2, and after the end of the G, the bottom liquid residue is reached, and after reaching the waste oil storage tank 3, it is cooled and stored in the waste oil storage tank 3. Next, the new feed solution is charged into the distillation unit I, and the start of the early Q Pavilion is started. Here, the initial feed amount of the steamed crane is the same as V. When the amount of liquid in the distillate becomes 〇XV or more, at least the eight-knife of the bottom liquid in the waste oil storage tank 3 15 200904797 is supplied to the pump 11 and the waste oil recovery line via the waste oil. 7 and supply to the distillation unit and continue to steaming. Among them, in the first! In the figure, although it is supplied from the suction side of the circulation pump 5, it is not limited to two: it can be directly supplied to the distillation apparatus i. After the end of the distillation, the distillate bottom liquid is sent to the waste oil storage tank 3, the sputum, and the liquid stored in the waste oil storage tank 3 are mixed, and then cooled and stored. Thereafter, the above operation is repeated. In the batch type single distillation of the implementation type of this month, the supply of the distillation bottom liquid is the liquid of the library, starting with # &, from 0. 7χν to 〇.95χν," It is better to start at the time of 0.75XV to 0.9χν. At the time of the lecturer ρ, which is later than 0 7xV, the white 1 is only available for the supply of the Japanese temple, because the refined compound can be further advanced. It is better to increase the purity. Moreover, when the supply of μ & 13⁄4 slaves is earlier than 0.95xV, the liquid level is higher than that of the reboiler tube plate due to the increase in the amount of liquid for the protection. Therefore, it is possible to avoid the occurrence of the polymer in the steaming device 1, and it is also preferable to avoid the risk of causing the gas circulation (cavitati〇n) to circulate the bottom liquid of the steaming liquid. The supply of the distillation bottom liquid of the embodiment of the present invention may be carried out by adding the residual liquid of the distillation bottom to the inside of the apparatus, and is not particularly limited. For example, the liquid delivery pump or the pressure transmitter of the general (4) can be used. Moreover, the supply of the residual liquid at the bottom of the steaming chamber may be Yuanshang # > for continuous or intermittent input In addition, the continuous input refers to a type in which a small amount of continuous input, a intermittent input means a pulse type or an intermittent division into an arbitrary number of inputs. 16 200904797 Implementation of the present invention The type of separation liquid can be used, and the sugar/storage tank 3 can store the distillation bottom residue, and the 'deterioration cooling device for suppressing the polymerization inhibitor contained in the residue in the distillation bottom. The method of cooling the bottom liquid of the steaming base is not particularly limited, and a method of generally performing the enthalpy can be employed. In terms of the cooling temperature, the residual polymer after the polymerizable compound, the 杳η/ the bottom of the museum The liquid (distilled (4) phase residual liquid) is cooled to a temperature below 50t = gui:, it is better to cool to the temperature below, to cool to 2. The required one is 4 ° ^ ° ^ 4 ' for the cooling temperature For the time of the above-mentioned hall, the time of the end of the transfer of the tomb (10) at the end of the tomb is the starting point' is preferably within 1.0 hours, and within 5 hours is better. It is better to store the temperature at the same temperature after the temperature. The cold part temperature is Na In the case of the following, the polymerization inhibitor contained in the waste oil is more likely to be deteriorated to exhibit a polymerization inhibitory effect. Therefore, the reboiler 4 in the embodiment of the present invention can be efficiently heated and fed: The type can be 'specially limited. For example, a forced circulation type multi-g type Buddha can be used, 'natural circulation type multi-tube type Buddha device, etc. Moreover, the heating source: the surface 'except the reboiler' A coil (c〇il) or a sleeve (★(4) can be used. The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the patent application scope. The implementation form obtained by combining the technical means appropriately modified is also included in the technical scope of the present invention. [Examples] Hereinafter, the invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to the examples. In the production example, a 2000 L SUS316 distillation apparatus (in a single distillation form, a multi-tube reheater was used as a heating source, and a circulation pump was used for forced circulation) was vacuum-applied to 5.33 hPa, and fed. 1150 kg (93 5 mass%) of a liquid containing hydroxyethyl methacrylate (hereinafter referred to as "HEMA") and 0.10 kg of p-methoxyphenol as a polymerization inhibitor obtained by reacting mercaptoacrylic acid with sulfonate And phenothiazine 〇.2〇kg, the vapor is passed through the reboiler' to start the steaming chamber containing the above HEMA liquid. When the liquid temperature reached 70 ° C, the distillation started, and then it was fixed at 85 ° C. When the amount of distillation was 980 kg (85 2% by mass of the initial feed solution), the distillation was terminated, and a distillation bottom residue of 17 G kg was obtained. Thereafter, the resulting distillate bottoms were all transferred to a waste oil storage tank, and the liquid temperature was cooled to 48. Hey. At the same time, the temperature in the waste oil storage tank immediately after the liquid supply of the bottom liquid was raised to 75 ° C, and became 48 t after 30 minutes. X Example 1 (First Distillation) In the same distillation apparatus as in the production example, a liquid U5〇kg containing HEMA and a methoxy group as a polymerization inhibitor were obtained by feeding methyl cyanoic acid and epoxy epoxide. Kipan G.12kg, and phenoxazine 〇.2Gkg began to steam. When the amount of k distillate is 810 kg (7 〇·4 mass% of the initial feed solution), the steam residue bottom liquid obtained in the production example is 62 kg (5% of the initial feed solution is 5%). The liquid pump is supplied to the distillation unit and continuously distilled. After 3.5 hours from the start of the distillation in 200904797, the steamer was stopped when the amount of the distillate became 11 〇〇 kg (95.7 mass% of the initial feed liquid). After the end of the distillation, the distillation bottom residue i I2 kg remaining in the distillation apparatus was transferred to the same waste oil storage tank as in the production example, and the liquid temperature was cooled to 18 °C. At the same time, the temperature in the waste oil storage tank immediately after the liquid supply of the distillate bottom liquid is raised to 7 ° C, and after 40 minutes, it becomes 18 t, and the liquid stored in the waste oil storage tank is 50 kg as the waste oil discharge system. outer. (Distillation after the second time) In the same distillation apparatus as the first distillation, 1150 kg (93.5 mass%) of liquid containing HEMA, 12 kg of p-methoxyphenolphthalein as a polymerization inhibitor, and phenothiazine were fed. After the azine was 0.20 kg, the steaming was started. When the amount of the distillate was 810 kg, the distillate bottom liquid 621 (the mass of the initial feed liquid) stored in the waste oil storage tank was supplied to the distillation apparatus and the distillation was continued. After 35 hours from the start of the distillation, the steaming was stopped when the amount of the distillate became 1,100 kg (95 7 mass / 初期 of the initial feed liquid). After the steaming hall is finished, 112kg of the distillation bottom residue remaining in the steaming device is transferred to the waste oil storage tank to cool the liquid temperature. _, at the bottom of the steaming chamber, the temperature in the waste oil storage tank immediately after the liquid supply of the residual liquid rises to the thief. After 40 minutes, it becomes 18 °C °, and then 50 kg of the waste oil storage tank liquid is discharged as waste oil. After that, the above operation was repeated, and a total of 150 batches were carried out, and the polymer was stably produced without producing a polymer in the G distillation apparatus. Further, the purity of the obtained product HEMAi at this time was 97.8 mass. 19 200904797 Example 2 Except that the distillation bottom liquid supplied in the distillation was changed to 2 〇 kg (18.3 mass% of the initial feed liquid), and the examples! Do the same. A total of 150 batches were carried out, and no polymer was produced in the distillation apparatus to operate stably. Further, the purity of the obtained product HEMA at this time was 97.3 mass. /〇. (Example 3) The same operation as in Example was carried out except that the supply of the distillation bottom liquid was changed to a point at which the amount of the distillate was 1 〇 5 〇 kg (91.3% by mass of the initial feed liquid). A total of 15 batches were implemented, and polymerization did not occur stably in the steaming plant. Further, the purity of the obtained product HEMA at this time was 97.4% by mass. Comparative Example 1 The same operation as in Example 除了 was carried out except that the distillation bottom liquid was not supplied. 7 After passing 3 (U times the time, it was confirmed that the polymerization in the steaming device was stopped and steamed.) Comparative example 2 was carried out to change the supply of the bottom liquid residue to the liquid containing HEMa 20 200904797 In the same period of the feeding period, the same operation was carried out as in the example. After 150 batches, although no aggregation occurred in the distillation apparatus, the purity of the obtained product HEMA was reduced to 95 f. • % of the amount of the sample. Comparative Example 3 In addition to the start of the supply of the bottom liquid residue in the case of taking care of /, if the site is 690 kg ^ (4) mass %), Order the same operation. After 150 batches in the east, although no polymer was found in the steamed crane, the purity of the HEMA obtained at this time was reduced to 95_8 mass. A At the same time, this application is based on the Japanese Patent Application No. 2OO7-I54453 filed on June 5, 2007, and the imaginary—such as ~ ^ has not been disclosed. ... [Simple description of the drawing] Fig. 1 is the distillation method of the present invention - "- μ ~ system type diagram of the skill type [description of the part number] 2 product storage tank 4 reboiler 6 circulation line 8 distillate line 1 〇 liquid supply line 1 distillation unit 3 waste oil storage tank 5 circulation pump 7 waste oil recovery line 9 line 11 waste oil supply pump 21