TW202311221A - Process for preparing a compound prone to polymerization - Google Patents

Abstract

The present invention relates to a process for preparing polymerization-prone, in particular hydroxyl-functional compounds, especially (meth)acrylates, using at least one suitable reactor, an intermediate vessel, in which the crude solution formed in the reactor is intermediately stored before being fed to a suitable distillative purification apparatus from which in turn the polymerization-prone compound is obtained in a form meeting specifications.

Description

製備易聚合之化合物的方法Process for preparing readily polymerizable compounds

本發明係關於使用至少一個適當的反應器及中間槽製備易聚合之化合物，特別是羥基官能性化合物，尤其是(甲基)丙烯酸酯的方法，其中在反應器中形成的粗製溶液立即儲存直到被供至適當的蒸餾性純化設備，進而得到符合規格的易聚合之化合物。 The present invention relates to a process for the preparation of readily polymerizable compounds, in particular hydroxy-functional compounds, especially (meth)acrylates, using at least one suitable reactor and intermediate tanks, wherein the crude solution formed in the reactor is immediately stored until It is supplied to appropriate distillation purification equipment to obtain easily polymerizable compounds that meet the specifications.

單體，如苯乙烯或(甲基)丙烯酸酯，具有在製備和儲存期間趨向所不欲的副反應的趨勢，延伸至褪色或過早聚合的發展。為避免此情況，在製備和後續儲存及/或進一步加工的期間內，聚合反應抑制劑用於安定化及尤其是在製程期間內實施短的停留時間。該製程此處通常由反應方法和純化方法所組成。此處，該反應方法和該純化方法之間的長時間儲存促進所不欲的副反應。Monomers, such as styrene or (meth)acrylates, have a tendency towards undesirable side reactions during production and storage, extending to the development of discoloration or premature polymerization. To avoid this, polymerization inhibitors are used for stabilization during production and subsequent storage and/or further processing and especially short residence times are implemented during the process. The process here usually consists of a reaction method and a purification method. Here, prolonged storage between the reaction method and the purification method promotes undesired side reactions.

JP 2008143814描述用於得到易聚合的環氧烷衍生物之反應方法。此文件中未進一步解釋純化方法。JP 2008143814 describes a reaction process for obtaining easily polymerizable alkylene oxide derivatives. The purification method is not further explained in this document.

JP 2008127302描述用於得到易聚合的環氧烷衍生物之方法。此處，使用批次反應器且該反應終了之後得到的粗製溶液移入單獨的蒸餾設備中並於其中分批蒸餾。JP 2008127302 describes a process for obtaining easily polymerizable alkylene oxide derivatives. Here, a batch reactor is used and the crude solution obtained after the end of the reaction is transferred to a separate distillation apparatus and distilled batchwise therein.

此外，用於純化(甲基)丙烯酸羥烷酯的較佳方法述於EP 1 090 904。根據此文件，藉由蒸餾合併薄膜蒸發器能夠特別有效率地純化包含(甲基)丙烯酸羥烷酯之反應混合物。Furthermore, a preferred process for the purification of hydroxyalkyl (meth)acrylates is described in EP 1 090 904 . According to this document, reaction mixtures comprising hydroxyalkyl (meth)acrylates can be purified particularly efficiently by distillation incorporating a thin-film evaporator.

EP 1 125 919描述經安定化的(甲基)丙烯酸羥烷酯，以該(甲基)丙烯酸羥烷酯計，各者含有濃度由0.0001重量%至2重量%的飽和羧酸的羥烷酯和濃度由0.001重量%至0.5重量%的酚化合物，其中基於該重量，該飽和羧酸的羥烷酯與該酚化合物之混合比在0.1至100的範圍內，且其中該飽和羧酸的羥烷酯係選自由乙酸羥乙酯、丙酸羥乙酯、異丁酸羥乙酯、乙酸羥丙酯、丙酸羥丙酯和異丁酸羥丙酯所組成之群組中之至少一組份。此使其得以防止或延遲所不欲的聚合反應，例如在儲存期間內。EP 1 125 919 describes stabilized hydroxyalkyl (meth)acrylates, each containing hydroxyalkyl esters of saturated carboxylic acids in concentrations of from 0.0001% to 2% by weight, based on the hydroxyalkyl (meth)acrylates and a phenolic compound at a concentration of from 0.001% by weight to 0.5% by weight, wherein the mixing ratio of the hydroxyalkyl ester of the saturated carboxylic acid to the phenolic compound is in the range of 0.1 to 100 based on the weight, and wherein the hydroxyl group of the saturated carboxylic acid The alkyl ester is at least one group selected from the group consisting of hydroxyethyl acetate, hydroxyethyl propionate, hydroxyethyl isobutyrate, hydroxypropyl acetate, hydroxypropyl propionate and hydroxypropyl isobutyrate share. This makes it possible to prevent or delay undesired polymerization reactions, for example during storage.

EP 2 857 382描述製備(甲基)丙烯酸羥烷酯之方法，其包含(甲基)丙烯酸與環氧烷在觸媒存在下反應的步驟，其中設定在總反應混合物中的水含量使其不超過0.05重量%。此得以使得在該反應期間內形成的副產物二甘醇之形成最小化。若二甘醇的存在量超過0.05重量%，則(甲基)丙烯酸羥烷酯不安定且會所不欲地在儲存期間內開始聚合。此方法的缺點在於僅能夠使用水含量極低的原料或者必須事先以昂貴且不便的方式降低這些原料中的水含量。EP 2 857 382 describes a process for the preparation of hydroxyalkyl (meth)acrylates, which comprises the step of reacting (meth)acrylic acid with alkylene oxide in the presence of a catalyst, wherein the water content in the overall reaction mixture is set such that it does not More than 0.05% by weight. This minimizes the formation of by-product diethylene glycol formed during the reaction. If diethylene glycol is present in an amount of more than 0.05% by weight, the hydroxyalkyl (meth)acrylates are unstable and undesirably start to polymerize during storage. The disadvantage of this method is that only raw materials with a very low water content can be used or the water content in these raw materials must be reduced beforehand in an expensive and inconvenient manner.

用以製備易聚合的化合物之已知方法和設備得到所欲產物之可接受的產量和品質。但是，對於進一步改良此方法之經濟性仍有持續的需求。特別地，此應該包括增加有效地使用該製法之設備組件的時間，而不是因為與方法相關的停機時間而減少使用時間。Known methods and equipment for preparing readily polymerizable compounds give acceptable yields and quality of the desired product. However, there is a continuing need to further improve the economics of this process. In particular, this should include increasing the time that the equipment components of the process are used effectively, rather than reducing the time of use due to process-related downtime.

所欲解決技術問題Want to solve technical problems

鑑於先前的技術，本發明針對的問題於是在於提供製備易聚合之化合物的方法，該方法中，以高效率方式使用該反應和純化方法的設備，且同時能夠避免在該反應和純化方法之間的儲存期間內之所不欲的副反應。In view of the prior art, the problem addressed by the present invention was thus to provide a process for the preparation of readily polymerizable compounds in which the equipment of the reaction and the purification process is used in an efficient manner and at the same time avoids an intervening time between the reaction and the purification process. Undesirable side effects during storage.

特別地，本發明一般針對的問題在於提供製備和分離易聚合的(甲基)丙烯酸酯化合物，尤其是羥基官能性(甲基)丙烯酸酯的方法，其中該反應部分以批次或半批次模式進行，而該純化處理相反地可以連續或半連續方式進行。In particular, the problem generally addressed by the present invention is that of providing a process for the preparation and isolation of readily polymerizable (meth)acrylate compounds, especially hydroxy-functional (meth)acrylates, in which the reaction is carried out partly in batches or semi-batches mode, while the purification process can be carried out in a continuous or semi-continuous manner.

自此產生了以一致的高單體品質提供分離之易聚合的(甲基)丙烯酸酯化合物及防止通常由批次或半批次模式引起的變動之進一步問題。From this arises the further problem of providing isolated, readily polymerizable (meth)acrylate compounds in a consistently high monomer quality and preventing variations usually caused by batch or semi-batch mode.

由本發明的以下描述、本發明的專利申請項、實例或整體內文顯見未明確陳述的其他問題。 發明對照先前技術之功效 Further problems not explicitly stated are apparent from the following description of the invention, from the patent claims of the invention, from the examples or from the overall text. Efficacy of inventions compared to prior art

藉由提供用於製備易聚合的化合物，尤其是(甲基)丙烯酸酯之新方法解決這些問題。此新方法始於(甲基)丙烯酸，其與環氧基官能性化合物反應。此方法至少具有以下的製程步驟： a)   在反應器中的觸媒存在下，該(甲基)丙烯酸和該環氧基官能性化合物反應，該反應器中的氣相和液相持續彼此混合。 b)   反應時間t ₁之後，藉由自該反應器移除氣相，該氣相和該液相中之環氧基官能性化合物的含量降低。根據本發明，該液相中的該(甲基)丙烯酸濃度低於1.0重量%，較佳地低於0.5重量%，特別佳地低於0.1重量%時，反應時間t ₁終了。 c)   在該反應時間t ₁之後，後續移除含(甲基)丙烯酸酯的混合物，其以液相存在於該反應器中，及將此液相轉移至中間槽中。 d)   在該混合物於該中間槽的平均停留時間t ₂之後，該混合物自該中間槽轉移至蒸餾塔I中， e)   在此蒸餾塔I中，該混合物分離成自塔頂餾份得到之含(甲基)丙烯酸酯的餾份及後續凝結此餾份並進入含有觸媒和高沸點副產物的塔底餾份中。 f)    在分離設備II中將來自製程步驟e)的塔底餾份可選地分離成另外的含有(甲基)丙烯酸酯的餾份和高沸點餾份。 These problems are solved by providing new methods for preparing readily polymerizable compounds, especially (meth)acrylates. This new method starts with (meth)acrylic acid, which is reacted with an epoxy-functional compound. The process has at least the following process steps: a) the (meth)acrylic acid and the epoxy-functional compound are reacted in the presence of a catalyst in a reactor in which the gaseous and liquid phases are continuously mixed with each other . b) After reaction time t ₁ , the content of epoxy-functional compounds in the gas phase and in the liquid phase is reduced by removing the gas phase from the reactor. According to the invention, the reaction time t ₁ ends when the (meth)acrylic acid concentration in the liquid phase is below 1.0% by weight, preferably below 0.5% by weight, particularly preferably below 0.1% by weight. c) After the reaction time t ₁ , the (meth)acrylate-containing mixture, which is present in the reactor in liquid phase, is subsequently removed and this liquid phase is transferred to an intermediate tank. d) after the average residence time _t of the mixture in the intermediate tank, the mixture is transferred from the intermediate tank to a distillation column I, e) in this distillation column I, the mixture is separated into The (meth)acrylate-containing fraction and subsequent condensation of this fraction enters the bottom fraction containing catalyst and high-boiling by-products. f) The bottom fraction from process step e) is optionally separated in a separation unit II into a further (meth)acrylate-containing fraction and a high-boiling fraction.

藉此新方法能夠以前所未見的方式簡單且有效率地製備易聚合的化合物。此外，該方法提供非常一致的產物品質。使用根據本發明之方法，令人訝異地有效率地防止副反應和褪色。This new method enables the simple and efficient preparation of easily polymerizable compounds in a way never seen before. Furthermore, this method provides very consistent product quality. Using the method according to the invention, side reactions and fading are surprisingly effectively prevented.

根據本發明之方法特別適合用於製備(甲基)丙烯酸羥烷酯。此處的術語"(甲基)丙烯酸羥烷酯"涵蓋甲基丙烯酸羥烷酯、丙烯酸羥烷酯、及其混合物。這同樣適用於措辭"(甲基)丙烯酸"，其涵蓋甲基丙烯酸和丙烯酸或其混合物。The process according to the invention is particularly suitable for the preparation of hydroxyalkyl (meth)acrylates. The term "hydroxyalkyl (meth)acrylate" herein encompasses hydroxyalkyl methacrylates, hydroxyalkyl acrylates, and mixtures thereof. The same applies to the expression "(meth)acrylic acid", which covers methacrylic acid and acrylic acid or mixtures thereof.

在專業領域中，(甲基)丙烯酸羥烷酯為習知之(甲基)丙烯酸的酯類，其醇基具有至少一個羥基。例如，較佳的(甲基)丙烯酸羥烷酯包括甲基丙烯酸2-羥乙酯、丙烯酸2-羥乙酯、甲基丙烯酸羥丙酯(尤其是甲基丙烯酸2-羥丙酯和甲基丙烯酸3-羥丙酯)、和/或丙烯酸羥丙酯(尤其是丙烯酸2-羥丙酯和丙烯酸3-羥丙酯)。In the professional field, hydroxyalkyl (meth)acrylates are known esters of (meth)acrylic acid, the alcohol group of which has at least one hydroxyl group. For example, preferred hydroxyalkyl (meth)acrylates include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate (especially 2-hydroxypropyl methacrylate and methyl 3-hydroxypropyl acrylate), and/or hydroxypropyl acrylate (especially 2-hydroxypropyl acrylate and 3-hydroxypropyl acrylate).

該環氧基官能性化合物較佳為環氧烷，特別佳為環氧乙烷或環氧丙烷。對應地，該(甲基)丙烯酸酯較佳為經羥烷基取代的(甲基)丙烯酸酯，特別佳為甲基丙烯酸2-羥乙酯或甲基丙烯酸羥丙酯。而甲基丙烯酸羥丙酯可為甲基丙烯酸2-羥丙酯、甲基丙烯酸3-羥丙酯或其異構混合物。The epoxy-functional compound is preferably an alkylene oxide, particularly preferably ethylene oxide or propylene oxide. Correspondingly, the (meth)acrylate is preferably a hydroxyalkyl-substituted (meth)acrylate, particularly preferably 2-hydroxyethyl methacrylate or hydroxypropyl methacrylate. The hydroxypropyl methacrylate can be 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate or an isomeric mixture thereof.

該(甲基)丙烯酸的總用量與該環氧基官能性化合物的總用量之莫耳比可較佳地在2:1至1:2的範圍內，特別佳地在1.1:1至0.9:1的範圍內。The molar ratio of the total amount of (meth)acrylic acid to the total amount of the epoxy-functional compound may preferably be in the range of 2:1 to 1:2, particularly preferably in the range of 1.1:1 to 0.9: 1 range.

所提到的破壞性副產物的例子可為(甲基)丙烯酸二甘醇酯或者是作為特別的關鍵副產物的二(甲基)丙烯酸乙二醇酯。此處，二(甲基)丙烯酸乙二醇酯特別關鍵，此因為其為一種交聯劑，由於交聯，其能夠嚴重破化該終產物的性質，尤其在所欲的聚合方法中。Examples of damaging by-products mentioned may be diethylene glycol (meth)acrylate or, as a particularly critical by-product, ethylene glycol di(meth)acrylate. Ethylene glycol di(meth)acrylate is particularly critical here, since it is a crosslinking agent which, due to crosslinking, can severely disrupt the properties of the end product, especially in the desired polymerization process.

在製程步驟a)中，較佳地，該甲基丙烯酸與觸媒和可選的輔助劑(如，安定劑)一起供應。達到在反應溫度T ₁範圍內的反應開始溫度之後，開始添加該環氧基官能性化合物，例如藉由均勻計量。根據本發明之反應時間t ₁始於該添加開始之時。理論上，該添加可以均勻計量或以單獨批次添加的方式進行直到t ₁結束。但是，該添加通常在t ₁過去很久之前就結束。或者，但是，亦可採用隨後添加該甲基丙烯酸和/或該觸媒的其他方法。也可以有初時引入所有的原料及藉由提高該溫度而開始該反應之變體。此較後提到的情況中，t ₁可以始於首次記錄放熱的時刻。 In process step a), preferably the methacrylic acid is supplied together with a catalyst and optionally auxiliary agents such as stabilizers. After reaching the reaction start temperature in the range of the reaction temperature T ₁ , the addition of the epoxy-functional compound is started, for example by uniform metering. The reaction time t ₁ according to the invention begins at the start of the addition. In theory, this addition can be metered uniformly or in separate batch additions until the end of _t1 . However, this addition usually ends long before _t1 has elapsed. Alternatively, however, other methods of subsequently adding the methacrylic acid and/or the catalyst may also be used. There is also a variant of introducing all the starting materials initially and starting the reaction by raising the temperature. In this latter case, t ₁ may begin at the moment when the exotherm is first recorded.

所用觸媒較佳係含金屬的化合物。或者，亦可使用例如二或更多種含金屬的化合物。較佳的觸媒尤其揭示於EP 12 312 04。The catalyst used is preferably a metal-containing compound. Alternatively, two or more metal-containing compounds, for example, may also be used. Preferred catalysts are disclosed inter alia in EP 12 312 04 .

更佳地，製程步驟a)中之反應的實施溫度T ₁係介於40和120℃之間，較佳地介於50和100℃之間，且特別佳地介於60和80℃之間。此處的該溫度T ₁不是恆定溫度，而是在t ₁期間內進行反應的溫度範圍。T ₁僅可以在這個範圍內變化，尤其是作為計量添加、該反應的放熱性、和在該反應器中之蒸發程序的結果。亦未將溫度升高至略高於100℃達極短時間(即，不到5分鐘)排除在外。但是，較佳地避免反應發生這種情況。 More preferably, the reaction in process step a) is carried out at a temperature _T1 between 40 and 120°C, preferably between 50 and 100°C, and particularly preferably between 60 and 80°C . The temperature T ₁ here is not a constant temperature, but a temperature range in which the reaction proceeds during t ₁ . T ₁ can only be varied within this range, especially as a result of the metered addition, the exothermic nature of the reaction, and the evaporation procedure in the reactor. Nor is it excluded that the temperature is raised to slightly above 100° C. for a very short period of time (ie less than 5 minutes). However, it is preferred to avoid such a reaction.

(甲基)丙烯酸可以連續或批次或半批次地與環氧化物反應。由於設備的操作簡單及該反應可進行到所欲終點，所以該批次或半批次操作模式已建立成商業模式。用於製備(甲基)丙烯酸羥烷酯之方法可以整體模式進行，即，未使用其他溶劑。有須要時，亦可使用惰性溶劑。轉化率，基於(甲基)丙烯酸，較佳為至少99 mol%，特別佳為至少99.5 mol%。特別可以經由該反應持續時間和該反應溫度而調整該轉化率。(Meth)acrylic acid can be reacted with epoxides continuously or batchwise or semi-batchwise. Due to the simple operation of the equipment and the fact that the reaction can be carried out to the desired end point, the batch or semi-batch operation mode has been established as a commercial mode. The process for the preparation of hydroxyalkyl (meth)acrylates can be carried out in bulk mode, ie without using other solvents. Inert solvents can also be used when necessary. The conversion, based on (meth)acrylic acid, is preferably at least 99 mol%, particularly preferably at least 99.5 mol%. In particular the conversion can be adjusted via the reaction duration and the reaction temperature.

根據本發明之批次或半批次模式中的該反應時間t ₁係基本上介於2和10小時之間，較佳為4至8小時。製備該(甲基)丙烯酸羥烷酯所用壓力較佳地在0.5至25 bar的範圍內，特別佳地在1至3 bar的範圍內，這些數值分別為絕對壓力。 The reaction time t ₁ in the batch or semi-batch mode according to the invention is substantially between 2 and 10 hours, preferably 4 to 8 hours. The pressure used for the preparation of the hydroxyalkyl (meth)acrylate is preferably in the range of 0.5 to 25 bar, particularly preferably in the range of 1 to 3 bar, these values being absolute pressures in each case.

用於混合該氣相和該液相，注射器-混合器噴嘴特別適合。較佳的注射器-混合器噴嘴之構造和幾何形狀經理想地配置，以達到相對高的抽取比。該抽取比(SR)定義為SR = V1 [m ³/h] / V2 [m ³/h]，其中 V1=來自反應器的抽取之體積流率； V2=移動的介質之體積流率 For mixing the gas phase and the liquid phase, syringe-mixer nozzles are particularly suitable. The configuration and geometry of the preferred injector-mixer nozzles are ideally configured to achieve relatively high extraction ratios. The extraction ratio (SR) is defined as SR = V1 [m ³ /h] / V2 [m ³ /h], where V1 = volume flow rate of extraction from the reactor; V2 = volume flow rate of moving medium

該注射器-混合器噴嘴通常具有氣體供應器及用於液流的供應器。此外，該注射器-混合器噴嘴的氣體供應器經由連接至至少一個反應物進料管線的氣體管線連接至該反應器的氣體空間，使得該液流可經由該注射器-混合器噴嘴的該氣體供應器自該反應器抽出氣體。特別有利的是在該氣體管線中配置節流閥，該節流閥連接該反應器的氣體空間和該注射器-混合器噴嘴。因此，該氣體管線中的該氣流尤其可獨立地調整該液體流向該注射器-混合器噴嘴的循環。較佳地，除了該注射器-混合器噴嘴以外，該反應器可具有例如可配備於該反應器中的攪拌器。The syringe-mixer nozzle typically has a gas supply and a supply for the liquid flow. Furthermore, the gas supply of the injector-mixer nozzle is connected to the gas space of the reactor via a gas line connected to at least one reactant feed line, so that the liquid flow can be via the gas supply of the injector-mixer nozzle The gas is withdrawn from the reactor. It is particularly advantageous to arrange a throttle valve in the gas line, which connects the gas space of the reactor with the injector-mixer nozzle. Thus, the gas flow in the gas line can in particular independently regulate the circulation of the liquid flow to the injector-mixer nozzle. Preferably, in addition to the injector-mixer nozzle, the reactor can have, for example, a stirrer that can be equipped in the reactor.

這些注射器-混合器噴嘴僅為用於混合該氣相和液相之設備之特別佳的例子。此設備的其他例子為嫻熟於此領域之人士習知者。例如，特別的攪拌器幾何形狀就可以單獨導致此混合。也可以簡單地抽出氣相並將其注回，例如，於該反應器底部處，較佳地確保特別小的氣泡。These syringe-mixer nozzles are only particularly good examples of equipment for mixing the gas and liquid phases. Other examples of such devices are known to those skilled in the art. For example, a particular stirrer geometry alone can cause this mixing. It is also possible to simply withdraw the gaseous phase and inject it back, for example, at the bottom of the reactor, preferably ensuring particularly small gas bubbles.

本方法之特別的變體中，有超過一個反應器，此情況中，所有的這些反應器彼此平行設置。此意謂該反應可以在一個反應器或複數個反應器中進行，且該等反應器全數皆經由一或多個管線連接至該中間槽，且各個液相經清空進入該中間槽。In a particular variant of the process, there is more than one reactor, in which case all these reactors are arranged parallel to each other. This means that the reaction can be carried out in one reactor or in a plurality of reactors, all of which are connected to the intermediate tank via one or more pipelines, and the respective liquid phases are emptied into the intermediate tank.

(甲基)丙烯酸可以在聚合反應抑制劑存在下與環氧化物反應，在許多情況中，這些可能已用於該反應器。所用的該聚合反應抑制劑較佳地尤其包括酚化合物，例如氫醌、氫醌醚(如，氫醌一甲醚)、三級丁基氫醌、2,6-二-三級丁基氫醌、2,5-二-三級丁基氫醌、2,4-二甲基-6-三級丁基酚或二-三級丁基兒茶酚；對-苯二胺，例如N,N'-二苯基-對-苯二胺、N,N'-二-2-萘基-對-苯二胺、N,N'-二-對-甲苯基-對-苯二胺、N-1,3-二甲基丁基-N'-苯基-對-苯二胺和N-1,4-二甲基戊基-N'-苯基-對-苯二胺；胺，例如巰基二苯胺和酚噻

(phenothiazine)；二烷基二巰基胺甲酸銅，例如二甲基二巰基胺甲酸銅、二乙基二巰基胺甲酸銅和二丁基二巰基胺甲酸銅；亞硝基化合物，例如亞硝基二苯胺、異戊基亞硝酸鹽、N-亞硝酸基環己基羥基胺、N-亞硝酸基-N-苯基-N-羥基胺和其鹽；及N-氫氧基化合物，例如2,2,4,4-四甲基氮雜環丁烷 1-氧、2,2-二甲基-4,4-二丙基氮雜環丁烷 1-氧、2,2,5,5-四甲基吡咯烷 1-氧、2,2,5,5-四甲基-3-氧吡咯烷 1-氧、2,2,6,6-四甲基哌啶 1-氧、4-羥基-2,2,6,6-四甲基哌啶 1-氧、6-氮雜-7,7-二甲基螺[4.5]癸烷 6-氧、2,2,6,6-四甲基-4-乙醯氧基哌啶 1-氧和2,2,6,6-四甲基-4-苯甲醯基氧基哌啶 1-氧；伸甲基藍、油溶苯胺黑BA(nigrosin base BA)、1,4-苯醌、立體阻礙酚(例如，2,4-二甲基-6-三級丁酚和/生育酚化合物，較佳者為α-生育酚)。(Meth)acrylic acid can be reacted with epoxides in the presence of polymerization inhibitors, and in many cases these may have been used in the reactor. The polymerization inhibitors used preferably include especially phenolic compounds such as hydroquinone, hydroquinone ethers (e.g. hydroquinone monomethyl ether), tertiary butylhydroquinone, 2,6-di-tertiary butylhydroquinone quinone, 2,5-di-tertiary butyl hydroquinone, 2,4-dimethyl-6-tertiary butylphenol or di-tertiary butyl catechol; p-phenylenediamines such as N, N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-p-tolyl-p-phenylenediamine, N -1,3-Dimethylbutyl-N'-phenyl-p-phenylenediamine and N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine; amines such as Mercaptodiphenylamine and phenothiazine

(phenothiazine); copper dialkyldimercaptocarbamate, such as copper dimethyldimercaptocarbamate, copper diethyldimercaptocarbamate, and copper dibutyldimercaptocarbamate; nitroso compounds, such as nitroso Diphenylamine, isopentyl nitrite, N-nitrosocyclohexylhydroxylamine, N-nitroso-N-phenyl-N-hydroxylamine and their salts; and N-hydroxy compounds such as 2, 2,4,4-tetramethylazetidine 1-oxo, 2,2-dimethyl-4,4-dipropylazetidine 1-oxo, 2,2,5,5- Tetramethylpyrrolidine 1-oxygen, 2,2,5,5-tetramethyl-3-oxopyrrolidine 1-oxygen, 2,2,6,6-tetramethylpiperidine 1-oxygen, 4-hydroxyl -2,2,6,6-tetramethylpiperidine 1-oxygen, 6-aza-7,7-dimethylspiro[4.5]decane 6-oxygen, 2,2,6,6-tetramethyl Dimethyl-4-acetyloxypiperidine 1-oxygen and 2,2,6,6-tetramethyl-4-benzoyloxypiperidine 1-oxygen; methylene blue, oil-soluble nigrosine BA (nigrosin base BA), 1,4-benzoquinone, sterically hindered phenols (for example, 2,4-dimethyl-6-tertiary butylphenol and/tocopherol compounds, preferably α-tocopherol).

該聚合反應抑制劑可以單獨使用或以混合物形式使用，且通常可在市場上購得。其他細節可見於相關的專業文件，尤其是Römpp-Lexikon Chemie; editors: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996)；關鍵字“抗氧化劑”及其中所標註的參考文獻。The polymerization inhibitor can be used alone or in admixture, and is generally available on the market. Additional details can be found in the relevant specialist papers, especially Römpp-Lexikon Chemie; editors: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996); keyword "antioxidants" and references noted therein .

尤其藉由較佳含有1至5000ppm，特別佳地5至1000ppm，且極特別佳地10至200ppm的聚合反應抑制劑之反應混合物，可達到令人驚訝的優點。Surprising advantages are achieved in particular by reaction mixtures which preferably contain 1 to 5000 ppm, particularly preferably 5 to 1000 ppm and very particularly preferably 10 to 200 ppm, of polymerization inhibitors.

關於製程步驟b)，應注意的是，該液相中的(甲基)丙烯酸濃度低於1.0重量%的時間點最初可藉由例如採樣、測量pH或測量折射指數、或其他光學方法而定出測得。由對於反應機制的更多經驗，嫻熟於此技術者可以在該反應期間內由外部，理想上未採樣，簡單地基於溫度曲線和/或其他易測量的程序參數而定出該時間點。製程步驟b)較佳地於介於60和100℃之間的溫度T ₂進行，即於類似於真實反應溫度且將該反應的放熱本質列入考慮之可絕對甚至高於在該反應開始期間內之該反應器內部溫度的溫度。 With regard to process step b), it should be noted that the point in time at which the concentration of (meth)acrylic acid in the liquid phase falls below 1.0% by weight can initially be determined, for example, by sampling, measuring the pH or measuring the refractive index, or other optical methods measured out. With more experience with the reaction mechanism, the skilled person can determine the time point during the reaction externally, ideally without sampling, simply based on the temperature profile and/or other easily measurable process parameters. Process step b) is preferably carried out at a temperature _T2 between 60 and 100° C., i.e. at a temperature similar to the actual reaction temperature and taking into account the exothermic nature of the reaction may be absolutely even higher than during the initiation of the reaction The temperature inside the reactor internal temperature.

此外，已證實有利的情況為，製程步驟b)中之環氧基官能性化合物含量的降低與壓力降低合併執行。溶於該液相中的環氧基官能性化合物另經脫氣及與該氣相自該反應器移除。Furthermore, it has proven to be advantageous if the reduction of the content of epoxy-functional compounds in process step b) is carried out in combination with the reduction of the pressure. Epoxy functional compounds dissolved in the liquid phase are additionally degassed and removed from the reactor with the gas phase.

關於製程步驟c)，尤其關於該中間槽的設計和操作，已證實特別有利的情況為該反應器中的壓力p ₁大於該中間槽中的壓力p ₂。一樣有利的是該中間槽中的內部溫度T ₃低於移除氣相的期間內(即，製程步驟b))之該反應器的內部壓力T ₂。該中間槽亦可選地配備冷卻和/或加熱元件，其裝設於內部或外部，以外部為佳。 With regard to process step c), especially with regard to the design and operation of the intermediate tank, it has proven to be particularly advantageous if the pressure p ₁ in the reactor is greater than the pressure p ₂ in the intermediate tank. It is also advantageous that the internal temperature T ₃ in the intermediate tank is lower than the internal pressure T ₂ of the reactor during the removal of the gaseous phase (ie process step b)). The intermediate tank is also optionally equipped with cooling and/or heating elements, which are installed internally or externally, preferably externally.

根據本發明，較佳地，該中間槽的內部體積與該反應器的工作體積之比為介於1:1和20:1之間，較佳地介於1.5:1和10:1之間，且極特別佳地介於1:2和5:1之間。在具有複數個並聯反應器之變體的情況中，這些數值係關於該中間槽的內部體積與所有反應器的工作體積總和之比。應理解此處的工作體積係各反應器的最大充填體積。此使得反應程序和純化程序之間的停留時間得以維持短時間，並因而避免所不欲的副反應。According to the invention, preferably, the ratio of the internal volume of the intermediate tank to the working volume of the reactor is between 1:1 and 20:1, preferably between 1.5:1 and 10:1 , and very particularly preferably between 1:2 and 5:1. In the case of a variant with a plurality of parallel reactors, these values relate to the ratio of the internal volume of the intermediate tank to the sum of the working volumes of all reactors. It should be understood that the working volume here refers to the maximum filling volume of each reactor. This allows the residence time between the reaction procedure and the purification procedure to be kept short and thus avoid undesired side reactions.

根據一個特別的配置，在該反應設備或用於中間儲存的該槽中之該反應程序之後及在該純化程序之前(即製程步驟b)和c)之間、製程步驟c)的期間內和/或製程步驟d)的期間內)分別存在的該液相可經氣體處理。此處，尤其是，空氣或氮可通過該液相。此配置得以在此處存在的液相進行進一步的純化處理(較佳為蒸餾處理)之前，自彼移除氣體或高揮發性組成份。According to a particular configuration, after the reaction procedure in the reaction plant or in the tank for intermediate storage and before the purification procedure (i.e. between process steps b) and c), during process step c) and and/or the liquid phase respectively present during process step d)) can be gas-treated. Here, in particular, air or nitrogen can pass through the liquid phase. This configuration enables removal of gases or highly volatile constituents from the liquid phase present there before it is subjected to further purification treatment, preferably distillation treatment.

關於製程步驟d)，較佳地，該停留時間t ₂少於200小時，較佳地少於100小時且特別佳地少於50小時。關於製程步驟d)，較佳地，該停留時間t ₂與該反應時間t ₁的比低於25，較佳地低於12，特別佳地低於6。 With regard to process step d), preferably, this residence time t ₂ is less than 200 hours, preferably less than 100 hours and particularly preferably less than 50 hours. With regard to process step d), it is preferred that the ratio of the residence time t ₂ to the reaction time t ₁ is lower than 25, preferably lower than 12, particularly preferably lower than 6.

此處，該中間槽經由一或多個管線連接至一或多個蒸餾塔I。Here, the intermediate tank is connected to one or more distillation columns I via one or more lines.

可以思及，雖根據本發明非必須者並因此相對不是較佳的，使用超過一個中間槽，類似地彼此平行設置。與此無關地，也可以使用複數個(超過一個)彼此平行設置的蒸餾塔I。It is conceivable, although not necessary according to the invention and thus relatively not preferred, to use more than one intermediate groove, similarly arranged parallel to each other. Independently of this, it is also possible to use a plurality (more than one) of distillation columns I arranged parallel to one another.

用於製程步驟e)，較佳地，至少一個來自蒸餾塔I之含觸媒的塔底餾份的子流連續或不連續循環至該反應器中。較佳地，本發明之配置包含使用內部具有分離作用的塔，該塔例如構成分離階段或對應於分離階段。For process step e), preferably at least one substream of the catalyst-containing bottom fraction from distillation column I is recycled continuously or discontinuously into the reactor. Preferably, the arrangement according to the invention comprises the use of a column having a separation effect inside, for example constituting or corresponding to a separation stage.

關於製程步驟e)中使用的蒸餾塔I，藉由此蒸餾塔I之特別可選的設計，例如具有低的分離性能，可達到令人訝異的優點。此配置的結果為設備的產能和能量效率特別可獲得改良。據此，所用的該蒸餾塔I具有不超過4個分離階段，特別佳地不超過3個分離階段。根據特別的態樣，所用塔較佳地具有至少2個分離階段。本發明中，瞭解分離階段的數目係盤塔中的盤數或在包含結構化的充填物之塔或包含隨機充填物之塔的情況中之理論分離階段數。With regard to the distillation column I used in process step e), surprising advantages can be achieved by a particularly optional design of this distillation column I, for example with a low separation performance. As a result of this configuration, the productivity and energy efficiency of the plant can be improved in particular. Accordingly, the distillation column I used has no more than 4 separation stages, particularly preferably no more than 3 separation stages. According to a particular aspect, the column used preferably has at least 2 separation stages. In the present invention, the number of separation stages is known to be the number of trays in a trayed column or the theoretical number of separation stages in the case of a column comprising a structured packing or a column comprising a random packing.

該粗製溶液可以在上述內部構件上方或下方供入該蒸餾塔I中，取決於這些內部構件的本質，也可以將該粗製溶液引至該內部構件的區域中。尤其當該粗製溶液於該內部構件上方供至該蒸餾塔I中時，可達到特別的優點。術語"該內部構件上方"是指該引入的組成物的高沸點構份通過該內部構件之後才自該蒸餾塔I排出。此能夠以對於產量和純度特別有利的方式達成。此外，能夠特別有效率地進行該程序。The crude solution can be fed into the distillation column I above or below the aforementioned internals, depending on the nature of these internals, the crude solution can also be introduced into the region of the internals. Particular advantages are achieved in particular when the crude solution is fed into the distillation column I above the internals. The term "above the internal member" means that the high-boiling components of the introduced composition are discharged from the distillation column 1 after passing through the internal member. This can be achieved in a particularly advantageous manner with regard to yield and purity. Furthermore, the procedure can be carried out particularly efficiently.

本發明之該蒸餾塔I可以在具有或不具有塔回流的情形下操作，其中不具有塔回流的實施例可達到令人訝異之特別高的純度。藉由將本發明之組成物自高於可能存在之任何內部構件處供入該蒸餾塔I可較佳地達到這些優點。The distillation column I of the invention can be operated with or without column reflux, wherein surprisingly particularly high purities are achieved in the embodiment without column reflux. These advantages are preferably achieved by feeding the composition of the invention into the distillation column I above any internals that may be present.

根據本發明之特別的方面，該蒸餾塔I較佳地以不超過2 Pa ^0.5的氣體載量因子(gas load factor)操作。權宜之計為，操作該第二蒸發器的該氣體載量因子較佳地在0.8至1.8 Pa ^0.5的範圍內。該氣體載量因子(F因子(F factor))係由氣體速度計算，其係基於用於移除氣體之管線的清空截面乘以該氣體密度的平方根。 According to a particular aspect of the invention, the distillation column I is preferably operated with a gas load factor of not more than 2 Pa ^0.5 . Expediently, the gas loading factor for operating the second evaporator is preferably in the range of 0.8 to 1.8 Pa ^0.5 . The gas loading factor (F factor) is calculated from the gas velocity based on the cleared cross-section of the line used to remove the gas multiplied by the square root of the gas density.

較佳地，進行該蒸餾的溫度係在40至130℃的範圍內，特別佳地在60至110℃的範圍內，且極特別佳地在80至95℃的範圍內，這些數值係基於塔底溫度且可因製造的終產物而不同。進行該蒸餾的絕對壓力可較佳地在0.1至20 mbar的範圍內，特別佳在0.5至10 mbar的範圍內且極佳地在1至5 mabr的範圍內，這些數值係基於塔頂壓力。Preferably, the distillation is carried out at a temperature in the range of 40 to 130°C, particularly preferably in the range of 60 to 110°C, and very particularly preferably in the range of 80 to 95°C, these values being based on column base temperature and may vary depending on the end product being manufactured. The absolute pressure at which the distillation is carried out can preferably be in the range of 0.1 to 20 mbar, particularly preferably in the range of 0.5 to 10 mbar and very preferably in the range of 1 to 5 mabr, these values being based on the pressure at the top of the column.

未防止待純化之可聚合的化合物之所不欲的聚合反應，聚合反應抑制劑可選地加至上述程序。可較佳地使用之聚合反應抑制劑包括以上所示者或這些安定劑中之二或更多者之混合物。除了，或較不佳地作為替代方案，計量添加至該反應器以外，該計量添加的執行方式亦可為計量添加至該中間槽或該蒸餾塔I。在該抑制劑計量添加至該蒸餾塔I的情況中，其較佳地在該塔頂部進行。高沸點物(如，添加的抑制劑)可藉慣用方法(例如，藉薄膜蒸發器或針對類似任務的設備(其將蒸發的物質循環進入精餾塔並排放非蒸發的高沸點物))自該塔底部排出。Instead of preventing undesired polymerization of the polymerizable compound to be purified, polymerization inhibitors are optionally added to the above procedure. Polymerization inhibitors that can be preferably used include those shown above or a mixture of two or more of these stabilizers. In addition to, or less preferably as an alternative to, metering into the reactor, the metering can also be carried out by metering into the intermediate tank or the distillation column I. In case the inhibitor is metered into the distillation column I, it preferably takes place at the top of the column. High boilers (e.g. added inhibitors) can be autoclaved by customary methods (e.g. by means of a thin-film evaporator or similar task-oriented equipment which recycles evaporated substances into a rectification column and discharges non-evaporated high boilers). The bottom of the column is discharged.

關於可選的製程步驟f)，該分離設備II較佳地為第二蒸餾塔、薄膜蒸發器或短程蒸發器。此處，特別佳地，自此分離設備II得到之含(甲基)丙烯酸酯的餾份循環進入該中間槽及進入該蒸餾塔I，特別地，來自分離設備II的塔頂餾份的至少一個子流循環進入中間槽和/或進入蒸餾塔I。若實施可選的製程步驟f)，則特別有利地，來自該分離設備II之含觸媒的塔底餾份的至少一個子流連續或不連續循環進入該反應器。此亦可如前述者與來自該蒸餾塔I的塔底餾份之對應子流一起進行。With regard to optional process step f), the separation device II is preferably a second distillation column, a thin-film evaporator or a short-path evaporator. Here, particularly preferably, the (meth)acrylate-containing fraction obtained from the separation device II is recycled into the intermediate tank and into the distillation column I, in particular at least A substream is recycled into the intermediate tank and/or into the distillation column I. If optional process step f) is carried out, it is particularly advantageous if at least one substream of the catalyst-containing bottom fraction from the separation device II is recycled continuously or discontinuously into the reactor. This can also be done as before with a corresponding substream of the bottom fraction from the distillation column I.

在此製程步驟f)中，自蒸餾塔I的塔底餾份得到之組成物的一部分因此可選但較佳地使用至少一個蒸發器(例如，薄膜蒸發器或循環蒸發器)用於提高轉變成氣相的產量。據此，用於進行純化(甲基)丙烯酸羥烷酯之程序的較佳設備包括薄膜蒸發器和/或循環蒸發器。In this process step f), a part of the composition obtained from the bottom fraction of the distillation column I is therefore optionally but preferably used at least one evaporator (for example, a thin-film evaporator or a circulation evaporator) for increasing the conversion yield in the gas phase. Accordingly, preferred equipment for carrying out the procedure for purifying hydroxyalkyl (meth)acrylates includes thin film evaporators and/or circulation evaporators.

製程步驟e)和f)中使用的組份的可轉移例尤其可見於EP 1 090 904。Transferable examples of components used in process steps e) and f) can be found inter alia in EP 1 090 904 .

根據此描述，進行根據本發明之方法時，即使沒有該較佳實施例，通常可觀察到該反應器中使用之新鮮的觸媒至少某些程度地包括與該蒸餾塔I及/或分離設備II的塔底餾份中存在的觸媒不同的陰離子。特別地，該蒸餾塔I及/或分離設備II的塔底餾份中存在的觸媒整體或部分為(甲基)丙烯酸金屬鹽。According to this description, when carrying out the process according to the invention, even without the preferred embodiment, it can generally be observed that the fresh catalyst used in the reactor is at least to some extent included with the distillation column I and/or separation equipment Catalyst-different anions present in the bottom fraction of II. In particular, the catalyst present in the bottom fraction of the distillation column I and/or the separation apparatus II is wholly or partly a metal (meth)acrylate salt.

根據本發明之方法之特別佳的配置之特徵在於製程步驟a)至c)係以半連續方式進行，其進行方式為清空在製程步驟c)中的反應器之後，該反應器在t ₃時間內直接再度充填以直接再度進行製程步驟a)。此處，t ₃應比t ₁短。此特別佳的情況中，製程步驟d)至f)可接著以連續方式進行。 A particularly preferred configuration of the process according to the invention is characterized in that process steps a) to c) are carried out in a semi-continuous manner in that after emptying the reactor in process step c), the reactor is at time _t directly refill in order to directly perform process step a) again. Here, _t3 should be shorter than _t1 . In this particularly preferred case, process steps d) to f) can then be carried out in a continuous manner.

此程序的進行方式可為在該反應終了之後，該液相自該反應器輸出進入該中間槽及在僅短時間且無停機時間之後，可在該反應器中接著進行新的批次或半批次程序。同時，該中間槽將粗製溶液供應至由一或多個蒸餾性純化系統所組成的該純化程序。理想上，該產物在製程步驟d)、和e)，或至f)中之處理係以連續方式進行。This procedure can be carried out in such a way that after the reaction is over, the liquid phase is output from the reactor into the intermediate tank and after only a short time and without downtime, a new batch or semi-period can be followed in the reactor batch program. At the same time, the intermediate tank supplies the crude solution to the purification process consisting of one or more distillative purification systems. Ideally, the treatment of the product in process steps d), and e), or to f) is carried out in a continuous manner.

在此連續進行的處理中，在製程步驟d)至e)或f)中，根據本發明之方法的效率源自於此純化程序的處理輸出。必須避免因為粗製溶液產物過低而導致的停機時間。此外，該粗製溶液產製必須不大於該純化程序的處理輸出，否則粗製溶液會累積於該中間槽中。此可藉由較佳地使用平行操作的複數個反應器及尤其是補償時間而具有更多的彈性而抵消。因此，較佳地，每小時以噸計之該純化程序的該處理輸出至少與每小時以噸計之該反應程序排放的液相的該生產輸出一樣多。此處，該反應程序的該生產輸出係各個反應器的生產輸出隨時間平均的總和。In this continuous treatment, in process steps d) to e) or f), the efficiency of the method according to the invention is derived from the treatment output of this purification procedure. Downtime due to low crude solution product must be avoided. Furthermore, the crude solution production must not be greater than the process output of the purification procedure, otherwise the crude solution will accumulate in the intermediate tank. This can be counteracted by preferably using multiple reactors operating in parallel and especially having more flexibility in compensating time. Therefore, preferably, the process output of the purification process in tons per hour is at least as much as the production output of the liquid phase discharged by the reaction process in tons per hour. Here, the production output of the reaction program is the time-averaged sum of the production outputs of the individual reactors.

如同本發明之方法，本發明之構成亦係用於實施此程序之設備。此設備具有至少一個反應器、一個中間槽和至少一個蒸餾塔I。該設備之特徵在於 (I)   反應器和中間槽藉管線連接在一起，在於 (II) 該中間槽的內部體積與該反應器的內部體積的比係介於1和20之間，該中間槽的設計使得該蒸餾塔I能夠不中斷地連續操作和製程步驟a)至c)能夠以半連續方式進行，在製程步驟c)和a)之間不存在干擾，及在於 (III) 壓力控制閥，其可選地位於介於反應器I和中間槽I之間的管線上。 Like the method of the present invention, the constitution of the present invention is also an apparatus for implementing this procedure. This plant has at least one reactor, one intermediate tank and at least one distillation column I. The device is characterized by (I) The reactor and the intermediate tank are connected together by pipelines, in that (II) The ratio of the internal volume of the intermediate tank to the internal volume of the reactor is between 1 and 20, the intermediate tank is designed such that the distillation column I can be operated continuously without interruption and process steps a) to c ) can be carried out in a semi-continuous manner without interference between process steps c) and a), and in that (III) A pressure control valve, optionally located on the line between reactor I and intermediate tank I.

該設備較佳地亦另外包括以下特點： (IV) 該中間槽和該蒸餾塔I藉管線連接在一起。 (V)  蒸餾塔I的設計使得在t ₁期間內進入蒸餾塔I的進料流的體積至少和在製程步驟a)期間內在該反應器中的該液相的體積一樣多。 (VI) 壓力控制閥，其可選地位於介於中間槽和蒸餾塔I之間的管線上。 The device preferably additionally includes the following features: (IV) The intermediate tank and the distillation column I are connected together by a pipeline. (v) Distillation column I is designed such that the volume of the feed stream entering distillation column I during _t1 is at least as much as the volume of the liquid phase in the reactor during process step a). (VI) A pressure control valve, optionally located in the line between the intermediate tank and distillation column I.

特別佳地，此設備另具有彼此平行配置的複數個反應器。這些反應器皆連接至該中間槽或可選地連接至彼此平行配置的複數個中間槽。但是，極特別佳地，該一或多個中間槽直接連接至僅一個蒸餾塔I。Particularly preferably, the plant additionally has a plurality of reactors arranged parallel to each other. These reactors are all connected to the intermediate tank or alternatively to a plurality of intermediate tanks arranged in parallel to each other. Very particularly preferably, however, the one or more intermediate tanks are directly connected to only one distillation column I.

實例example

在不構成限制的情況下，以下使用實例和比較例描述本發明。The present invention is described below using examples and comparative examples without limitation.

實例1Example 1

甲基丙烯酸與環氧乙烷在圖1的裝置中反應。此處，5300 kg(61.6 kmol)的甲基丙烯酸經由供料管線1添加至反應器A(工作體積為8 m ³)，於其中添加12 kg (52.4 mol)的乙酸鉻作為觸媒，經由供料管線3添加2.5 kg (20.1 mol)的氫醌單甲醚(HQME)作為安定劑，且此混合物加熱至70℃的溫度。然後開始經由外部迴路進行該混合物的抽取循環，設定循環體積流率約70 m ³/h，且該混合物經由注射器-混合噴嘴計量回到該反應器頂部。然後，經由供料管線2添加2720 kg(61.7 kmol)的環氧乙烷。選擇計量輸入的量以使得反應溫度不超過70℃。計量數量設定於約900 kg/h(20.4 kmol/h)。自填充該甲基丙烯酸至計量輸入該環氧乙烷終了的時間為3小時。 Methacrylic acid is reacted with ethylene oxide in the apparatus of Figure 1. Here, 5300 kg (61.6 kmol) of methacrylic acid was added to reactor A (with a working volume of 8 m ³ ) via feed line 1, 12 kg (52.4 mol) of chromium acetate was added as a catalyst, and via feed line 1 2.5 kg (20.1 mol) of hydroquinone monomethyl ether (HQME) was added to feed line 3 as stabilizer and this mixture was heated to a temperature of 70°C. The withdrawal cycle of the mixture via the external loop is then started, setting a circulation volume flow rate of about 70 m ³ /h, and the mixture is metered back to the top of the reactor via the injector-mixing nozzle. Then, 2720 kg (61.7 kmol) of ethylene oxide were added via feed line 2 . The amount metered in is chosen such that the reaction temperature does not exceed 70°C. The metered quantity was set at about 900 kg/h (20.4 kmol/h). The time from filling the methacrylic acid to the end of metering in the ethylene oxide was 3 hours.

在添加上述量之後，該反應混合物進一步於70℃的溫度通過上述的外部迴路。再3小時之後，每小時自該反應器內容物取得樣品，並藉酸-鹼滴定分析殘留的甲基丙烯酸含量。第一個樣品之殘留的甲基丙烯酸含量為0.63重量%，7小時之後的第二個樣品為0.18重量%，而8小時之後的第三個樣品為0.05重量%。因此在5小時之後終止此製程步驟。After addition of the above-mentioned amount, the reaction mixture was further passed through the above-mentioned external loop at a temperature of 70°C. After a further 3 hours, hourly samples were taken from the reactor contents and analyzed for residual methacrylic acid content by acid-base titration. The residual methacrylic acid content of the first sample was 0.63% by weight, the second sample after 7 hours was 0.18% by weight, and the third sample after 8 hours was 0.05% by weight. This process step was therefore terminated after 5 hours.

然後，該反應混合物冷卻至60℃。之後經由配置於該反應設備的蓋子上的針閥以幾分鐘的時間緩慢洩壓。此處的廢氣經由管線送至滌氣設備。Then, the reaction mixture was cooled to 60°C. Thereafter, the pressure was slowly released over several minutes through a needle valve provided on the cover of the reaction apparatus. The exhaust gas here is sent to the scrubber through the pipeline.

得到的8噸粗製溶液之後經由管線4進入體積為10m ³的中間槽B。此程序費時15分鐘。然後，如上述地在反應器A中直接進行甲基丙烯酸與環氧乙烷的新反應。 The obtained 8 tons of crude solution then enter the intermediate tank B with a volume of 10 m ³ via line 4 . This procedure takes 15 minutes. The fresh reaction of methacrylic acid with ethylene oxide is then carried out directly in reactor A as described above.

分析得到的該粗製溶液，甲基丙烯酸2-羥乙酯的比例為約95.4重量%。此係藉GC-FID(氣體層析術合並併火燄離子化偵測器)測量。所形成的甲基丙烯酸二乙二醇酯佔副產物的最大比例，比例為約3.60重量%。特別關鍵的副產物係二甲基丙烯酸乙二醇酯，其比例約0.11重量%。其他副產物列於表1。Analyzing the obtained crude solution, the proportion of 2-hydroxyethyl methacrylate was about 95.4% by weight. This is measured by GC-FID (Gas Chromatography Incorporated Flame Ionization Detector). Diethylene glycol methacrylate formed represented the largest proportion of by-products, with a proportion of about 3.60% by weight. A particularly critical by-product is ethylene glycol dimethacrylate, the proportion of which is about 0.11% by weight. Other by-products are listed in Table 1.

該粗製溶液接著由該用於中間儲存的槽供至連續操作的蒸餾性純化設備。該蒸餾性純化設備由蒸餾塔、塔頂冷凝器、和薄膜蒸發器所組成。該粗製溶液以970 kg/h的計量流經由管線5進入該蒸餾塔(其於此處配備分離技術中約相當於分離階段的內部組件)。於該內部組件的上方供應該組成物。該塔頂餾出產物在該頂部冷凝器中冷卻並經由管線6由該設備排出。該塔底產物主要含有高沸點的次要組份和觸媒，該觸媒極實質程度地以甲基丙烯酸鉻的形式存在。The crude solution is then supplied from the tank for intermediate storage to a continuously operating distillative purification plant. The distillative purification equipment consists of a distillation tower, a tower top condenser, and a thin film evaporator. The crude solution enters the distillation column (which is equipped here with internals approximately corresponding to the separation stage in separation technology) at a metered flow of 970 kg/h via line 5 . The composition is supplied over the internal component. The overhead product is cooled in the overhead condenser and withdrawn from the apparatus via line 6. The bottom product mainly contains high-boiling secondary components and the catalyst which is present to a very substantial extent in the form of chromium methacrylate.

該第一批次的該粗製溶液的純化處理終了之後，不中斷地立即進行已被抽取進入該中間槽之該第二批次的蒸餾性純化處理。持續此程序直到製得和純化10個批次。因此，在90.75小時之後純化了80噸的粗製溶液。Immediately after the purification of the first batch of the crude solution is completed, the distillative purification of the second batch that has been drawn into the intermediate tank is carried out without interruption. This procedure was continued until 10 batches were prepared and purified. Thus, 80 tons of crude solution were purified after 90.75 hours.

純化處理之後，得到純度為98.8%的甲基丙烯酸2-羥乙酯，其含有約50ppm的氫醌一甲醚。其他副產物列於表1。藉DE 10 131 479中所示方法測量所得該甲基丙烯酸2-羥乙酯的色度。其色度低於5。After the purification work-up, 2-hydroxyethyl methacrylate with a purity of 98.8% was obtained, which contained about 50 ppm of hydroquinone monomethyl ether. Other by-products are listed in Table 1. The color of the 2-hydroxyethyl methacrylate obtained was measured by the method described in DE 10 131 479 . Its chroma is below 5.

經由測量色度來測定此組成物的儲存性。該儲存性藉此於30℃測量6個月。此處，25g的該組成物填入30ml瓶(棕色廣口瓶)中。在空氣循環乾燥箱中於30℃儲存。6個月之後測量色度。此色度再度低於5。The storability of the composition was determined by measuring the chromaticity. The shelf life is thereby measured at 30° C. for 6 months. Here, 25 g of the composition was filled into a 30 ml bottle (brown jar). Store at 30°C in an air-circulating drying cabinet. Colorimetry was measured after 6 months. The chroma is again below 5.

比較例1Comparative example 1

基本上重複實例1，反應結束後的該粗製溶液在8小時之後以1000 kg/h的計量流直接轉移進入該蒸餾性純化設備。Example 1 was basically repeated, and the crude solution after the reaction was directly transferred into the distillative purification device with a metered flow of 1000 kg/h after 8 hours.

分析所得的該粗製溶液-如實例1中所示-甲基丙烯酸2-羥乙酯的比例為約95.4重量%。所形成的甲基丙烯酸二乙二醇酯的比例為約3.60重量%，二甲基丙烯酸乙二醇酯的比例為約0.12重量%。其他副產物列於表1。The resulting crude solution analyzed - as shown in Example 1 - had a proportion of 2-hydroxyethyl methacrylate of about 95.4% by weight. The proportion of diethylene glycol methacrylate formed was about 3.60% by weight and that of ethylene glycol dimethacrylate was about 0.12% by weight. Other by-products are listed in Table 1.

僅在一個批次完全純化之後才進行下一個批次的處理。因此，80噸的粗製溶液在160小時之後被完全純化。相較於實例1中之連續操作模式，在啟動和關閉程序中之該蒸餾性純化設備的圓筒操作導致產量損失約5%。Only after one batch has been completely purified is the next batch processed. Thus, 80 tons of crude solution were completely purified after 160 hours. Compared to the continuous mode of operation in Example 1, the drum operation of the distillative purification plant during the start-up and shutdown procedures resulted in a yield loss of about 5%.

純化之後，得到的甲基丙烯酸2-羥乙酯純度為98.8重量%，其含有約50ppm的氫醌一甲醚。其他副產物列於表1。所得甲基丙烯酸2-羥乙酯的色度(如實例1中之測量)低於5。After purification, 2-hydroxyethyl methacrylate was obtained with a purity of 98.8% by weight, which contained about 50 ppm of hydroquinone monomethyl ether. Other by-products are listed in Table 1. The resulting 2-hydroxyethyl methacrylate had a color (as measured in Example 1) of less than 5.

6個月之後，該色度(如實例1中之測量)為6。After 6 months, the chroma (measured as in Example 1) was 6.

實例2Example 2

基本上重複實例1，在該反應之後，10個批次全數先轉移進入儲存槽及之後藉由自該儲存槽供料而進行該蒸餾性純化處理。以該最後批次計，此處的該停留時間t ₂超過200小時。 Example 1 was essentially repeated, after the reaction, all 10 batches were first transferred into a storage tank and then subjected to the distillative purification treatment by feeding from the storage tank. Based on the last batch, the residence time t ₂ here exceeds 200 hours.

自該儲存槽得到的該粗製溶液經分析之後才進行該蒸餾性純化處理，甲基丙烯酸2-羥乙酯的比例為約95.0重量%，此係藉GC-FID(氣體層析術合並併火燄離子化偵測器)測量。所形成的甲基丙烯酸二乙二醇酯佔副產物的最大比例，比例為約3.95重量%。特別關鍵的副產物係二甲基丙烯酸乙二醇酯，其比例約0.16重量%。其他副產物列於表1。The distillative purification was carried out after analysis of the crude solution obtained from the storage tank, the proportion of 2-hydroxyethyl methacrylate was about 95.0% by weight, which was combined by GC-FID (gas chromatography and flame ionization detector) measurement. Diethylene glycol methacrylate formed represented the largest proportion of by-products, with a proportion of about 3.95% by weight. A particularly critical by-product is ethylene glycol dimethacrylate, the proportion of which is about 0.16% by weight. Other by-products are listed in Table 1.

純化處理之後，得到純度為98.2%的甲基丙烯酸2-羥乙酯，其含有約50ppm的氫醌一甲醚。藉DE 10 131 479中所示方法測量所得該甲基丙烯酸2-羥乙酯的色度。其色度低於5。After the purification work-up, 2-hydroxyethyl methacrylate was obtained with a purity of 98.2%, which contained about 50 ppm of hydroquinone monomethyl ether. The color of the 2-hydroxyethyl methacrylate obtained was measured by the method described in DE 10 131 479 . Its chroma is below 5.

經由測量色度來測定此組成物的儲存性。該儲存性藉此於30℃測量6個月。此處，25g的該組成物填入30ml瓶(棕色廣口瓶)中。在空氣循環乾燥箱中於30℃儲存。6個月之後測量色度。其色度為8。The storability of the composition was determined by measuring the chromaticity. The shelf life is thereby measured at 30° C. for 6 months. Here, 25 g of the composition was filled into a 30 ml bottle (brown jar). Store at 30°C in an air-circulating drying cabinet. Colorimetry was measured after 6 months. Its chroma is 8.

相較於實例1，實例2的結果展現良好顏色安定性的同時，其於超過200小時的加長停留時間t ₂情況中不理想，且反而會導致終產物儲存時間相對較長而導致色度變差。相較於實例1，本發明的此實施例因此而為較不優者。

E1          實例1 E2          實例2 CE1        比較例1 EO          環氧乙烷 MAA        甲基丙烯酸 HEMA     甲基丙烯酸2-羥乙酯 DEGMA   甲基丙烯酸二乙二醇酯 EGDMA   二甲基丙烯酸乙二醇酯 EG          乙二醇 HEAc      乙酸羥乙酯 CN          製備之後直接測得的色度 CN 6m     6個月之後測得的色度 Compared with Example 1, while the results of Example 2 exhibited good color stability, it was not ideal in the case of extended residence time _t beyond 200 hours, and would instead lead to a relatively long storage time of the final product resulting in color change Difference. Compared to Example 1, this embodiment of the invention is therefore less favorable.

E1 Example 1 E2 Example 2 CE1 Comparative Example 1 EO ethylene oxide MAA methacrylate HEMA 2-hydroxyethyl methacrylate DEGMA diethylene glycol methacrylate EGDMA ethylene glycol dimethacrylate EG ethylene glycol HEAc Hydroxyethyl acetate CN Color measured directly after preparation CN 6m Color measured after 6 months

1:原料1的供料管線 2:原料2的供料管線 3:輔助劑(如，安定劑、觸媒)的供料管線 A:反應器 4:來自反應器A的粗製溶液進入中間槽B的管線 B:中間槽B 5:來自中間槽B的粗製溶液進入蒸餾性純化設備C的管線 C:蒸餾性純化設備C 6:符合規格的易聚合之化合物(=目標產物)之移除管線 7:高沸點渣質之移除管線 8:可選：用於循環的高沸點流之管線 與圖2相關的其他項目： 11,21:原料1進入兩個不同的反應器A1和A2之供料管線 12,22:原料2進入兩個不同的反應器A1和A2之供料管線 13,23:輔助劑(如，安定劑、觸媒)進入兩個不同的反應器A1和A2之供料管線 A1,A2:平行操作的反應器A1和A2 4:粗製溶液自反應器進入中間槽B之管線 18,28:可選：用於循環的高沸點流之管線 1: Feed line for raw material 1 2: Feed line for raw material 2 3: Supply pipeline for auxiliary agents (such as stabilizers, catalysts) A: Reactor 4: The crude solution from reactor A enters the pipeline of intermediate tank B B: middle slot B 5: The crude solution from intermediate tank B enters the pipeline of distillative purification equipment C C: Distillative purification equipment C 6: Removal line for easily polymerizable compounds (= target products) that meet the specifications 7: High boiling point slag removal pipeline 8: Optional: pipeline for circulating high boiling point stream Other items related to Figure 2: 11,21: Feedstock 1 enters feed lines of two different reactors A1 and A2 12,22: Feedstock 2 enters feed lines of two different reactors A1 and A2 13,23: Auxiliary agents (e.g., stabilizers, catalysts) enter the feed lines of two different reactors A1 and A2 A1, A2: Reactors A1 and A2 operated in parallel 4: The crude solution enters the pipeline of intermediate tank B from the reactor 18,28: Optional: Lines for recirculating high-boiling streams

在不構成限制的情況下，以附圖1為基礎地例示說明製備易聚合的化合物之較佳裝置：[圖1]係適用於製備易聚合的化合物且具有反應設備之裝置的示意圖。Without limitation, a preferred apparatus for preparing easily polymerizable compounds is illustrated on the basis of accompanying drawing 1: [FIG. 1] is a schematic diagram of an apparatus suitable for preparing easily polymerizable compounds and having reaction equipment.

原料1和原料2各者經由供料管線1和2進入反應器A，在其中以批次或半批次模式進行反應程序。輔助劑(如，觸媒和/或安定劑)可經由另一供料管線3供至該反應設備。該反應程序終了之後的粗製溶液經由管線4轉移進入中間槽B。自此中間槽B，該粗製溶液經由管線5連續轉移進入蒸餾性純化設備C。由該蒸餾性純化設備C，經由管線6得到符合規格的該易聚合之化合物。經由管線7自該蒸餾性純化設備移除高沸點渣質。可選地，高沸點渣質可經由管線8全數或部分循環進入該反應設備A。Each of feedstock 1 and feedstock 2 enters reactor A via feed lines 1 and 2, where the reaction procedure is carried out in batch or semi-batch mode. Auxiliaries such as catalysts and/or stabilizers can be fed to the reaction apparatus via a further feed line 3 . The crude solution after the end of the reaction program is transferred via line 4 into intermediate tank B. From this intermediate tank B, the crude solution is continuously transferred via line 5 into a distillative purification plant C. From the distillative purification equipment C, the readily polymerizable compound meeting the specifications is obtained via line 6 . High boiling residues are removed from the distillative purification unit via line 7 . Optionally, the high-boiling point slag can be fully or partially recycled into the reaction device A through the pipeline 8 .

在不構成限制的情況下，另以附圖2例示說明製備易聚合的化合物之特別佳的裝置：[圖2]係適用於製備易聚合的化合物且具有兩個反應器之裝置的示意圖。Without being limiting, a particularly preferred apparatus for the preparation of easily polymerizable compounds is illustrated in Figure 2: [Figure 2] is a schematic diagram of an apparatus suitable for the preparation of easily polymerizable compounds and having two reactors.

原料1和原料2各者經由供料管線11和21、及12和22進入反應器A1和A2，在其中以批次或半批次模式進行反應程序。輔助劑(如，觸媒和/或安定劑)可經由其他供料管線13和23供至各反應器。該反應程序終了之後的粗製溶液經由管線14和24進入中間槽B。自此中間槽B，該粗製溶液經由管線5連續轉移進入蒸餾性純化設備C。由該蒸餾性純化設備，經由管線6得到符合規格的該易聚合之化合物。經由管線7自該蒸餾性純化設備移除高沸點渣質。可選地，高沸點渣質可經由管線18和28全數或部分循環進入該反應器A1和/或A2。Each of feedstock 1 and feedstock 2 enters reactors A1 and A2 via feed lines 11 and 21 , and 12 and 22, where the reaction procedure is carried out in batch or semi-batch mode. Auxiliary agents such as catalysts and/or stabilizers can be fed to each reactor via further feed lines 13 and 23 . The crude solution after the end of the reaction program enters intermediate tank B via lines 14 and 24 . From this intermediate tank B, the crude solution is continuously transferred via line 5 into a distillative purification plant C. From the distillative purification equipment, the readily polymerizable compound that meets the specifications is obtained via line 6. High boiling residues are removed from the distillative purification unit via line 7 . Alternatively, the high boiling slag can be fully or partially recycled into the reactors A1 and/or A2 via lines 18 and 28 .

1:原料1的供料管線 1: Feed line for raw material 1

2:原料2的供料管線 2: Feed line for raw material 2

3:輔助劑(如，安定劑、觸媒)的供料管線 3: Supply pipeline for auxiliary agents (such as stabilizers, catalysts)

A:反應器 A: Reactor

4:來自反應器A的粗製溶液進入中間槽B的管線 4: The crude solution from reactor A enters the pipeline of intermediate tank B

B:中間槽B B: middle slot B

5:來自中間槽B的粗製溶液進入蒸餾性純化設備C的管線 5: The crude solution from intermediate tank B enters the pipeline of distillative purification equipment C

C:蒸餾性純化設備C C: Distillative purification equipment C

6:符合規格的易聚合之化合物(=目標產物)之移除管線 6: Removal line for easily polymerizable compounds (= target products) that meet the specifications

7:高沸點渣質之移除管線 7: High boiling point slag removal pipeline

8:可選：用於循環的高沸點流之管線 8: Optional: pipeline for circulating high boiling point stream

Claims (18)

一種製備(甲基)丙烯酸酯之方法，其始於(甲基)丙烯酸和環氧基官能性化合物，具有製程步驟 a)   在反應器中的觸媒存在下，該(甲基)丙烯酸和該環氧基官能性化合物反應，該反應器中的氣相和液相持續彼此混合， b)   反應時間t ₁之後，藉由自該反應器移除氣相，該液相中的該(甲基)丙烯酸濃度為低於1.0重量%，該氣相和該液相中之環氧基官能性化合物的含量降低， c)   後續移除含(甲基)丙烯酸酯的混合物，其在該反應時間t ₁之後以液相存在於該反應器中，及將該液相轉移至中間槽中， d)   在該混合物於該中間槽的平均停留時間t ₂之後，該混合物自該中間槽轉移至蒸餾塔I中， e)   經由該蒸餾塔I的塔頂將該混合物分離成含(甲基)丙烯酸酯的餾份及後續凝結該餾份並進入含有觸媒和高沸點副產物的塔底餾份中，以及 f)    在分離設備II中將來自製程步驟e)的塔底餾份可選地分離成另外的含有(甲基)丙烯酸酯的餾份和高沸點餾份。 A process for the preparation of (meth)acrylates starting from (meth)acrylic acid and an epoxy-functional compound, having process step a) the (meth)acrylic acid and the The epoxy-functional compound is reacted, the gas and liquid phases in the reactor are continuously mixed with each other, b) after a reaction time t ₁ , the (methyl ) the concentration of acrylic acid is lower than 1.0% by weight, the content of epoxy-functional compounds in the gas phase and the liquid phase is reduced, c) the subsequent removal of the (meth)acrylate-containing mixture, which at the reaction time t ₁ is then present in the reactor in a liquid phase and the liquid phase is transferred to an intermediate tank, d) after the average residence time _t of the mixture in the intermediate tank, the mixture is transferred from the intermediate tank to a distillation column In I, e) separation of the mixture via the top of the distillation column I into a (meth)acrylate-containing fraction and subsequent condensation of this fraction into a bottom fraction containing catalyst and high-boiling by-products , and f) optionally separating the bottom fraction from process step e) in a separation device II into a further (meth)acrylate-containing fraction and a high-boiling fraction. 如請求項1之方法，其中該環氧基官能性化合物係環氧化物，較佳為環氧乙烷或環氧丙烷，及該(甲基)丙烯酸酯係經羥烷基取代的(甲基)丙烯酸酯，較佳為甲基丙烯酸2-羥乙酯或甲基丙烯酸羥丙酯。The method of claim 1, wherein the epoxy-functional compound is an epoxy, preferably ethylene oxide or propylene oxide, and the (meth)acrylate is a hydroxyalkyl-substituted (methyl) ) acrylate, preferably 2-hydroxyethyl methacrylate or hydroxypropyl methacrylate. 如請求項1或2之方法，其中該觸媒係一或多種含金屬的化合物及該製程步驟a)中之反應係於介於50和100℃的溫度T ₁進行。 The method according to claim 1 or 2, wherein the catalyst is one or more metal-containing compounds and the reaction in step a) of the process is carried out at a temperature _T1 between 50 and 100°C. 如請求項1至3中之至少一項之方法，其中來自該蒸餾塔I及/或該分離設備II之含觸媒的塔底餾份的至少一個子流連續或不連續循環至該反應器中。The method of at least one of claims 1 to 3, wherein at least one substream of the catalyst-containing bottom fraction from the distillation column I and/or the separation device II is continuously or discontinuously recycled to the reactor middle. 如請求項1至4中之至少一項之方法，其中該分離設備II係第二蒸餾塔、薄膜蒸發器或短程蒸發器，及自該分離設備得到之該含(甲基)丙烯酸酯的餾份循環進入該中間槽及/或進入該蒸餾塔I。The method of at least one of claims 1 to 4, wherein the separation device II is a second distillation column, a thin-film evaporator or a short-path evaporator, and the (meth)acrylate-containing distillate obtained from the separation device A portion of circulation enters the intermediate tank and/or enters the distillation column 1. 如請求項1至5中之至少一項之方法，其中在反應器I中的壓力p ₁高於在該中間槽中的壓力p ₂。 Process according to at least one of claims 1 to 5, wherein the pressure p ₁ in the reactor I is higher than the pressure p ₂ in the intermediate tank. 如請求項1至6中之至少一項之方法，其中製程步驟b)係於介於60和100℃之間的溫度T ₂進行，及該中間槽的內部溫度T ₃低於T ₂。 Process according to at least one of claims 1 to 6, wherein process step b) is carried out at a temperature _T2 between 60 and 100°C, and the internal temperature _T3 of the intermediate tank is lower than _T2 . 如請求項1至7中之至少一項之方法，其中在該反應時間t ₁之後，該反應器中之該液相中的該(甲基)丙烯酸濃度為低於0.5重量%，較佳地低於0.1重量%。 The method according to at least one of claims 1 to 7, wherein after the reaction time t ₁ , the (meth)acrylic acid concentration in the liquid phase in the reactor is lower than 0.5% by weight, preferably Less than 0.1% by weight. 如請求項1至8中之至少一項之方法，其中在製程步驟b)中藉壓力降低而減少環氧基官能性化合物的該含量。Process according to at least one of claims 1 to 8, wherein the content of epoxy-functional compounds is reduced in process step b) by pressure reduction. 如請求項1至9中之至少一項之方法，其中該中間槽的內部體積與該反應器的內部體積之比為介於1:1和20:1之間。Process according to at least one of claims 1 to 9, wherein the ratio of the internal volume of the intermediate tank to the internal volume of the reactor is between 1:1 and 20:1. 如請求項1至10中之至少一項之方法，其中該停留時間t ₂少於200小時，較佳地少於100小時且特別佳地少於50小時。 Process according to at least one of claims 1 to 10, wherein the residence time t ₂ is less than 200 hours, preferably less than 100 hours and particularly preferably less than 50 hours. 如請求項1至11中之至少一項之方法，其中該停留時間t ₂與該反應時間t ₁的比低於25，較佳地低於6。 The method according to at least one of claims 1 to 11, wherein the ratio of the residence time _t2 to the reaction time _t1 is lower than 25, preferably lower than 6. 如請求項1至12中之至少一項之方法，其中來自該分離設備II之該塔頂餾份的至少一個子流循環進入該中間槽及/或進入該蒸餾塔I。Process according to at least one of claims 1 to 12, wherein at least one substream of the overhead fraction from the separation device II is recycled into the intermediate tank and/or into the distillation column I. 如請求項1至13中之至少一項之方法，其中新鮮地用於該反應器的該觸媒至少某些程度包括來自存在於該蒸餾塔I及/或該分離設備II的該塔底餾份中之觸媒之不同的陰離子，及存在於該蒸餾塔I及/或該分離該設備II的該塔底餾份中之該觸媒整體或部分以(甲基)丙烯酸金屬鹽存在。The method of at least one of claims 1 to 13, wherein the catalyst freshly used in the reactor comprises at least to some extent the bottoms from the distillation column I and/or the separation device II The different anions of the catalyst in the fraction, and the catalyst present in whole or in part in the bottom fraction of the distillation column I and/or the separation device II as a metal (meth)acrylate salt. 如請求項1至14中之至少一項之方法，其中製程步驟a)至c)係以半連續方式進行，其進行方式為清空在製程步驟c)中的反應器之後，該反應器在t ₃時間內直接再度充填和進行製程步驟a)，t ₃比t ₁短，及製程步驟d)至f)係以連續方式進行。 The method of at least one of claims 1 to 14, wherein the process steps a) to c) are carried out in a semi-continuous manner by emptying the reactor in process step c), the reactor at t ₃ time is directly refilled and process step a) is carried out, _t3 is shorter than _t1 , and process steps d) to f) are carried out in a continuous manner. 一種用於實施如請求項1至15中之至少一項之方法之設備，其具有反應器、中間槽和至少一個蒸餾塔I，其中 (I)   該反應器和該中間槽藉管線連接在一起， (II) 該中間槽的內部體積與該反應器的內部體積的比係介於1和20之間，該中間槽的設計使得該蒸餾塔I能夠不中斷地連續操作和製程步驟a)至c)能夠以半連續方式進行，在製程步驟c)和a)之間不中斷，以及 (III) 壓力控制閥，其可選地位於介於反應器I和中間槽I之間的管線上。 A kind of equipment for carrying out the method of at least one in claim item 1 to 15, it has reactor, intermediate tank and at least one distillation column I, wherein (I) The reactor and the intermediate tank are connected together by pipelines, (II) The ratio of the internal volume of the intermediate tank to the internal volume of the reactor is between 1 and 20, the intermediate tank is designed such that the distillation column I can be operated continuously without interruption and process steps a) to c ) can be performed in a semi-continuous manner without interruption between process steps c) and a), and (III) A pressure control valve, optionally located on the line between reactor I and intermediate tank I. 如請求項16之設備，其中 (IV) 該中間槽和該蒸餾塔I藉管線連接在一起， (V)  該蒸餾塔I的設計使得在t ₁期間內進入蒸餾塔I的進料流的體積至少和在製程步驟a)期間內在該反應器中的該液相的體積一樣多，以及 (VI) 壓力控制閥，其可選地位於介於中間槽和蒸餾塔I之間的管線上。 As the equipment of claim item 16, wherein (IV) the intermediate tank and the distillation column 1 are connected together by a pipeline, (V) the design of the distillation column 1 makes the volume of the feed stream entering the distillation column ₁ during t1 At least as much as the volume of the liquid phase in the reactor during process step a), and (VI) a pressure control valve, optionally located in the line between the intermediate tank and the distillation column I. 如請求項16或17之設備，其中該設備具有複數個反應器，該等反應器彼此平行配置且皆連接至該中間槽或可選地連接至複數個彼此平行配置的中間槽，及該一或多個中間槽直接連接至僅一個蒸餾塔I。The equipment as claimed in claim 16 or 17, wherein the equipment has a plurality of reactors, the reactors are arranged in parallel with each other and are all connected to the intermediate tank or optionally connected to a plurality of intermediate tanks arranged in parallel with each other, and the one or several intermediate tanks are directly connected to only one distillation column I.

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