Page 247 - 精细化工2019年第9期

第 36 卷第 9 期 精 细 化 工 Vol.36, No.9
201 9 年 9 月 FINE CHEMICALS Sept. 2019

精细化工中间体
连续流光反应器中连续制备环丁烷四羧酸二酐

冯柏成，李春阳，侯喜超，葛平宇，金 岩

（青岛科技大学 化工学院，山东 青岛 266042）

摘要：以顺丁烯二酸酐（MA）为原料，乙酸乙酯作溶剂，在连续流光反应器中紫外光照射下连续高效地制备了
环丁烷四羧酸二酐（CBDA）。考察了溶液在管路中的停留时间、管路尺寸、反应温度、反应物浓度等对产品收
率及单位时间产品产量的影响，对比了连续流光反应器和间歇光反应器对产品收率的影响。实验结果表明，停
留时间长、管路内径小、浓度低的反应物溶液对提高产品的收率有利。当停留时间为 80 min、管路内径为 2.00 mm、
反应温度为 5 ℃、反应物质量浓度为 0.15 g/mL 时，产品的收率为 51.57%，单位时间产量 4.64 g/h。与间歇光
反应器工艺相比，连续流光反应器具有光子利用率高、光传播过程光子损失量小、光量子通量密度高、照射面
积更加充足均匀、比表面积较大、混合效率高、传热快等优点，产品的收率可提高 33%以上。
关键词：顺丁烯二酸酐；环丁烷四羧酸二酐；紫外光；连续流光反应器；精细化工中间体
中图分类号：TQ235 文献标识码：A 文章编号：1003-5214 (2019) 09-1975-06

Synthesis of Cyclobutane-1,2,3,4-tetracarboxylic Dianhydride
in Continuous Flow Photoreactor

FENG Bai-cheng, LI Chun-yang, HOU Xi-chao, GE Ping-yu, JIN Yan
（College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao 266042, Shandong, China）

Abstract: Cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) was continuously and efficiently
synthesized by photodimerization of maleic anhydride (MA) using ethyl acetate as solvent in a continuous
flow photoreactorunder UV irradiation. The influences of residence time of solution in reactor tube, tube
size, reaction temperature and mass concentration of reactants on the product yield and the unit time output
of product were studied. In addition, the effects of continuous flow photoreactor and batch photoreactor on
the product yield were compared. The results showed that longer residence time, smaller inner diameter of
the tube and lower reactant concentration were benefit to improve the yield of product. The yield and the
unit time output of product reached as high as 51.57% and 4.64 g/h under the conditions of residence time
80 min, inner diameter of reactor tube 2.00 mm, reaction temperature 5 ℃ and mass concentration of
reactants 0.15 g/mL. The continuous flow photoreactor has the advantages of high photon utilization
efficiency, small photon loss in the light propagation process, high quantum flux density, more adequate
and uniform irradiation area, large specific surface area, high mixing efficiency and heat transfer. Compared
with the batch photoreactor, the product yield was increased by more than 33%.
Key words: maleic anhydride; cyclobutane-1,2,3,4-tetracarboxylic dianhydride; UV light; continuous flow
photoreactor; fine chemical intermediates

环丁烷四羧酸二酐（CBDA）是制备聚酰亚胺 数、优异的介电性能等 [2-5] ，被广泛应用于微电子领
[1]
（PI）高分子材料的重要原料之一 ，由 CBDA 和 域和液晶显示器的取向膜材料及光电材料等高新技
其他二胺单体合成的聚酰亚胺材料具有良好的机械 术领域 [6-10] 。
性能、优异的耐热性能、优良的透光性能、稳定的 目前，国内外对于合成 CBDA 的报道主要采用
耐化学腐蚀性能、高的耐辐射性能、低的热膨胀系 间歇法将原料顺丁烯二酸酐（MA）溶于有机溶剂中，

收稿日期：2019-01-08; 定用日期：2019-03-21; DOI: 10.13550/j.jxhg.20190030
作者简介：冯柏成（1965—），男，副教授，硕士生导师，E-mail：fbc515@163.com。