Page 224 - 《精细化工》2022年第6期

第 39 卷第 6 期 精 细 化 工 Vol.39, No.6
2022 年 6 月 FINE CHEMICALS June 2022

精细化工中间体
连续流高效制备成核剂中间体二芳基磷酰氯

1
姚翰林 ，辛 忠 1,2*
（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）

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。
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
中图分类号：TQ265.1 文献标识码：A 文章编号：1003-5214 (2022) 06-1290-07

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

1
YAO Hanlin , XIN Zhong 1,2*
（1. Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and
Technology, Shanghai 200237, China; 2. State Key Laboratory of Chemical Engineering, School of Chemical Engineering,
East China University of Science and Technology, Shanghai 200237, China）

Abstract: 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′-methylene-
bis(4,6-di-tert-butylphenyl) phosphate chloride (abbreviated as diaryl phosphoate chloride). Under the
conditions of flow rate ≥0.4 m/s (180 mL/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-tert-
burtylpheny) 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.
Key words: diaryl phosphate chloride; continuous-flow synthesis; static mixing; process optimization;
precipitation reaction; strong turbulent flow field; fine chemical intermediates

收稿日期：2021-12-17; 定用日期：2022-01-25; DOI: 10.13550/j.jxhg.20211296
基金项目：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）
作者简介：姚翰林（1993—），男，博士生，E-mail：18818205845@163.com。联系人：辛 忠（1962—），男，教授，E-mail：xzh@
ecust.edu.cn。