常压高效合成双(烷基聚氧乙烯基)仲胺  

Efficient synthesis of bis(alkyl polyoxyethylene)secondary amine via one-pot method under ambient pressure

作　　者：齐维君 吴飞飞[1] 付博[1] 陈慕华[1] 谈继淮 朱新宝[1] QI Weijun;WU Feifei;FU Bo;CHEN Muhua;TAN Jihuai;ZHU Xinbao(College of Chemical Engineering,Nanjing Forestry University,Nanjing 210037,Jiangsu,China)

机构地区：[1]南京林业大学化学工程学院,南京210037

出　　处：《精细化工》2021年第8期1716-1721,共6页Fine Chemicals

基　　金：江苏省重点研发计划项目基金(BE2019111)。

摘　　要：针对仲胺基聚醚合成存在产率低、反应条件苛刻等问题,以端伯胺基C_(12~14)烷基聚乙二醇醚(A/C_(12~14)E_(5))为原料,通过伯胺在常压条件的分子间脱氨耦合,高效地合成了双(C_(12~14)烷基聚氧乙烯基)仲胺(S/C_(12~14)E_(5))。探究了耦合温度、催化剂用量、氢气流量及反应时间对S/C_(12~14)E_(5)选择性的影响。结果表明,当反应温度为200℃,催化剂用量为原料总质量的2.5%,氢气流量为200 mL/min,反应时间为5 h时,仲胺含量(化学法)达到97.3%。在此基础上,进行了底物拓展、放大实验,并提出了可能的反应机理。In order to solve the problems of low yield and harsh reaction conditions in the synthesis of secondary amine polyether,bis(C_(12~14) alkyl polyoxyethylene)secondary amine(S/C_(12~14)E_(5))was effectively synthesized via the intermolecular deamination coupling of amine-terminated polyether with C_(12)~C_(14) alkyl group(A/C_(12~14)E_(5))under normal pressure.The effects of coupling temperature,catalyst dosage,hydrogen flow rate and reaction time on the selectivity of S/C_(12~14)E_(5) were studied.The results showed that the content of secondary amine(chemical method)reached up to 97.3% under the conditions of reaction temperature of 200℃,catalyst dosage being 2.5% of the total mass of raw materials,hydrogen flow rate of 200 mL/min and reaction time of 5 h.On this basis,the substrate scope and scale-up experiments were performed.A possible reaction mechanism was also proposed.

关 键 词：仲胺基聚醚 脱氨耦合反应 高效合成 常压反应 放大实验 精细化工中间体 

分 类 号：TQ226.3[化学工程—有机化工] TQ317