连续流高效制备成核剂中间体二芳基磷酰氯  

Highly effective preparation of nucleating agent intermediate diaryl phosphate chloride in continuous flow

作　　者：姚翰林 辛忠[1,2] YAO Hanlin;XIN Zhong(Shanghai Key Laboratory of Multiphase Materials Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;State Key Laboratory of Chemical Engineering,School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学上海市多相结构材料化学工程重点实验室,上海200237 [2]华东理工大学化工学院化学工程联合国家重点实验室,上海200237

出　　处：《精细化工》2022年第6期1290-1296,共7页Fine Chemicals

基　　金：上海市领军人才(2013);超限制造:新一代微化工芯片应用基础及器件设计评价(Y100-2-20075)。

摘　　要：设计了一种内嵌特殊连续螺旋式静态混合片的盘管式连续流反应器,并应用于成核剂中间体2,2′-亚甲基-双(4,6-二叔丁基苯氧基)磷酰氯(简称二芳基磷酰氯)的高效合成中。在流速≥0.4 m/s(180 mL/min)且沉淀含量<10%时,沉淀产物三乙胺盐酸盐在强湍动流场中可随液相稳定流动,成功解决了反应通道易堵塞的难题。毫米级尺度保持了反应器良好的传质特性,高流速下可实现反应物料的快速均匀混合,同时又大幅增加了生产通量。得到了在此连续流反应系统中的最佳合成工艺:盘管后20%管段使用空管以减小系统整体的压降,混合采用T型射流,停留时间3.5 min,反应温度90℃,n[2,2′-亚甲基-双(4,6-二叔丁基)苯酚(简称二芳基酚)]∶n(三乙胺)∶n(POCl_(3))=1∶2.8∶1.10,二芳基酚和POCl_(3)的初始进料浓度分别为0.29和0.32 mol/L。产物收率从间歇式反应的90%提升至连续流反应的96%,空时产率提升了约43倍。A coil-tube continuous flow reactor embedded with a special type of continuous spiral static mixing piece was designed and used to efficiently prepare nucleating agent intermediate 2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate chloride(abbreviated as diaryl phosphoate chloride). Under the conditions of flow rate ≥0.4 m/s(180 m L/min) and precipitation content <10%, the precipitation triethylamine hydrochloride could flow stably with liquid phase in strong turbulent flow field, which successfully solved the serious clogging problem in reaction channel. Millimeter scale of the reactor maintained the good mass transfer characteristics, and the rapid and uniform mixing of reactive materials could be realized at high flow rate, meanwhile greatly increased the throughput. The optimum synthesis process in this continuous flow reaction system was obtained. Empty pipe was used in the last 20% section of the coil tube to reduce the overall pressure drop of the reaction system, T-jet was used to mix the reaction materials, residence time was 3.5 min, reaction temperature was 90 ℃, n[2,2′-methylene-bis(4,6-di-tertburtylpheny) phenol(abbreviated as diaryl phenol)]∶n(triethylamine)∶n(POCl_(3)) =1∶2.8∶1.10, initial feed concentration of diaryl phenol and POCl_(3)were 0.29 and 0.32 mol/L, respectively. The product yield increased from nearly 90% in batch reactor to 96% in continuous flow reactor, and the space time yield increased by about 43 times.

关 键 词：二芳基磷酰氯 连续流制备 静态混合 工艺优化 沉淀反应 强湍动流场 精细化工中间体 

分 类 号：TQ265.1[化学工程—有机化工]