Synthesis of 1-{2-[bis(2-aminoethyl)amino]ethyl} pyridinium chloride and its application in ATRP reaction

doi:10.16085/j.issn.1000-6613.2016.10.025

Chemical Industry and Engineering Progree ›› 2016, Vol. 35 ›› Issue (10): 3196-3200.DOI: 10.16085/j.issn.1000-6613.2016.10.025

• Industrial catalysis • Previous Articles Next Articles

Synthesis of 1-{2-[bis(2-aminoethyl)amino]ethyl} pyridinium chloride and its application in ATRP reaction

ZHANG Meimei¹, XUE Teng¹, TANG Erjun^1,2, YUAN Miao¹, LIU Shaojie^1,2, ZHAO Dishun^1,2

1 Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, Hebei, China;
2 Hebei Research Center of Pharmaceutical and Chemical Engineering, Shijiazhuang 050018, Hebei, China

Received:2015-12-28 Revised:2016-05-01 Online:2016-10-05 Published:2016-10-05

氯化1-{2-[双(2-氨基乙基)氨基]乙基}吡啶离子液体的合成及在ATRP反应中的应用

张美美¹, 薛腾¹, 唐二军^1,2, 袁淼¹, 刘少杰^1,2, 赵地顺^1,2

1 河北科技大学化学与制药工程学院, 河北石家庄 050018;
2 河北省药物化工工程技术中心, 河北石家庄 050018

通讯作者: 唐二军,教授。E-mail:ejtang@sohu.com
作者简介:张美美(1988-),女,硕士研究生。
基金资助:
国家自然科学基金（21304030）及河北省自然科学基金（B2013208183）项目。

Abstract

Abstract: Ionic liquid of 1-{2-[bis(2-aminoethyl)amino]ethyl} pyridinium chloride[N₃Py]Cl was synthesized by grafting the diethylenetriamine(DETA)onto 1-chloro-ethyl pyridinium chloride ionic liquid[CePy]Cl through N alkylation. The structure of the ionic liquid was characterized by FTIR,¹H NMR and MS. The redox potential(E_1/2)of complex[N₃Py] Cl/CuBr and PMDETA/CuBr was tested by cyclic voltammetry. The result indicated that the redox potential of[N₃Py]Cl/CuBr was -0.541V,lower than that of PMDETA/CuBr(-0.142V). In addition,the atom transfer radical polymerization (ATRP)of MMA was catalyzed by ionic liquid[N₃Py]Cl with CuBr in the ionic liquid[AMIM]Cl. The conversion of monomer was up to 75% with a narrow distribution of molecular weight(M_w/M_n=1.24)when the employed amount of the ligand,catalyst and solvent was n(CuBr)=0.19mmol、n([N₃Py]Cl)=1.13mmol、n([AMIM]Cl)=0.02mol,respectively,with the reaction temperature of 60℃,and reaction time of 4h. The reaction presented the characteristic of living/controlled polymerization.

Key words: ionic liquids, redox potential, complexes, catalysis, polymerization

摘要： 采用N-烷基化方法将二乙烯三胺（DETA）接枝到氯化1-氯乙基吡啶离子液体[CePy]Cl上，合成了离子液体氯化1-{2-[双（2-氨基乙基）氨基]乙基}吡啶（[N₃Py]Cl），通过FTIR、¹H NMR和MS等测试手段对合成离子液体的结构进行了表征。采用循环伏安法对离子液体配合物[N₃Py]Cl/CuBr和有机配合物PMDETA/CuBr的氧化还原电位（E_1/2）进行测试，结果表明：合成的离子液体[N₃Py]Cl和CuBr形成配合物的氧化还原电势为E_1/2=-0.541V，比常用的有机配合物PMDETA/CuBr（E_1/2=-0.142V）具有更低的氧化还原电势。将离子液体[N₃Py]Cl与CuBr配位形成催化体系，在离子液体[AMIM]Cl中催化甲基丙烯酸甲酯（MMA）的原子转移自由基聚合（ATRP）反应。结果表明，当配体、催化剂和溶剂的用量分别为n（CuBr）=0.19mmol、n（[N₃Py]Cl）=1.13mmol、n（[AMIM]Cl）=0.02mol，反应温度60℃，反应时间4h时，单体转化率高达75%，分子量分布较窄（M_w/M_n=1.24），ATRP反应具有明显的可控性能。

关键词: 离子液体, 氧化还原电位, 配合物, 催化, 聚合

CLC Number:

TQ032.4

ZHANG Meimei, XUE Teng, TANG Erjun, YUAN Miao, LIU Shaojie, ZHAO Dishun. Synthesis of 1-{2-[bis(2-aminoethyl)amino]ethyl} pyridinium chloride and its application in ATRP reaction[J]. Chemical Industry and Engineering Progree, 2016, 35(10): 3196-3200.

张美美, 薛腾, 唐二军, 袁淼, 刘少杰, 赵地顺. 氯化1-{2-[双(2-氨基乙基)氨基]乙基}吡啶离子液体的合成及在ATRP反应中的应用[J]. 化工进展, 2016, 35(10): 3196-3200.

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Synthesis of 1-{2-[bis(2-aminoethyl)amino]ethyl} pyridinium chloride and its application in ATRP reaction

氯化1-{2-[双(2-氨基乙基)氨基]乙基}吡啶离子液体的合成及在ATRP反应中的应用

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