功能离子液体[N4MIM]Cl的合成及其配合Cu 催化ATRP反应研究

Synthesis of Functional Ionic Liquid [N4MIM]Cl and Cooperated with Cu for Catalyzing ATRP Reaction

摘要:

以N-甲基咪唑为骨架引入1,2-二氯乙烷合成中间体氯化1-氯乙基-3-甲基咪唑([CeMIM]Cl)，再与三乙烯四胺反应合成了氯化1-（三乙基四氨基）乙基-3-甲基咪唑离子液体（[N4MIM]Cl）。通过红外光谱IR、核磁共振氢谱1HNMR对[N4MIM]Cl进行分析测试，确证了[N4MIM]Cl的化学结构。通过循环伏安法测得[N4MIM]Cl具有较低的氧化还原电势,E1,2为-0.472V，与有机配体相比[N4MIM]Cl具有较好的配位性能。将[N4MIM]Cl与CuBr配位用于催化氯化1-烯丙基-3-甲基咪唑离子液体（[AMIM]Cl）体系中甲基丙烯酸甲酯（MMA）的原子转移自由基聚合（ATRP）反应，经凝胶渗透色谱法（GPC）测试证明[N4MIM]Cl对ATRP反应具有较好的可控性。原子吸收光谱（AAS）测定聚合产物聚甲基丙烯酸甲酯（PMMA）中Cu2 的残留量仅为360mg穔g-1，表明与传统有机配体相比，[N4MIM]Cl有利于催化剂与聚合产物的分离。

Abstract:

1-(triethyl four amine) ethyl-3-methyl chloride ionic liquid ([N4MIM]Cl) was prepared on the base of N-methylimidazole by 1,2-dichloroethane to obtain the intermediates 1-chloro-ethyl-3-methyl chloride ionic liquid ([CeMIM]Cl) and then reacting with triethylene tetramine. The chemical structure of [N4MIM]Cl was confirmed by FT-IR and 1HNMR. [N4MIM]Cl possessed a lower REDOX potential through cyclic voltammetry (CV) measurement, E1,2 -0.472V. [N4MIM]Cl presented a perfect coordination property compared with organic ligands. The obtained ionic liquid [N4MIM]Cl coordinated with CuBr was used to catalyze atom transfer radical polymerization (ATRP) of methyl爉ethacrylate (MMA) in 1-allyl-3-methylimidazolium chloride ([AMIM]Cl) and it indicated by gel permeation chromatography (GPC) that the coordination ionic liquid [N4MIM]Cl presented the perfect controllability to the ATRP reactions. The residues of Cu2 in polymerization product polymethyl methacrylate (PMMA) was only 360 mg穔g-1 by atomic absorption spectrometry (AAS) determination. It showed that [N4MIM]Cl was conducive to the separation of catalyst from the obtained product compared with the traditional organic ligands.