Synthesis of methyl imidazole amine ionic liquid for ATRP reaction system

doi:10.3969/j.issn.0438-1157.20161132

Abstract

Abstract:

1-(Propyl amine)ethyl-3-methyl chloride ionic liquid ([N₂C₃MIM]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 1,3-propanediamine.The chemical structure of [N₂C₃MIM]Cl was confirmed by FT-IR and ¹H NMR.[N₂C₃MIM]Cl possessed a lower REDOX potential (-0.522 V) through cyclic voltammetry measurement,[N₂C₃MIM]Cl presented a perfect coordination property compared with organic ligands.The obtained ionic liquid[N₂C₃MIM]Cl coordinated with CuBr was used to catalyze atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA)and it indicated by gel permeation chromatography (GPC) that the coordination ionic liquid[N₂C₃MIM]Cl presented the perfect controllability to the ATRP reactions.The residues of Cu²⁺ in polymerization product PMMA was only 270 mg·kg^-1 by atomic absorption spectrometry determination.It showed that[N₂C₃MIM]Cl was conducive to the separation of catalyst from the obtained product compared with the traditional organic ligands.

Key words: complexes, ionic liquids, ATRP, cyclic voltammetry, GPC, polymers

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1，3-丙二胺反应合成了氯化1-（丙基氨基）乙基-3-甲基咪唑离子液体（[N₂C₃MIM]Cl）。通过FT-IR、¹H NMR对[N₂C₃MIM]Cl进行分析测试，确证了其化学结构。通过循环伏安法测得[N₂C₃MIM]Cl具有较低的氧化还原电势，为-0.522 V，与有机配体相比[N₂C₃MIM]Cl具有较好的配位性能。将[N₂C₃MIM]Cl与CuBr配位用于催化甲基丙烯酸甲酯（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[N₂C₃MIM]Cl对ATRP反应具有较好的可控性。原子吸收光谱测定聚合产物PMMA中Cu²⁺的残留量仅为270 mg·kg^-1，表明与传统有机配体相比，[N₂C₃MIM]Cl有利于催化剂与聚合产物的分离。

关键词: 配位物, 离子液体, ATRP, 循环伏安法, GPC, 聚合物

CLC Number:

TQ032.4

XUE Teng, ZHOU Jian, FU Tantan, TANG Erjun, ZHAO Dishun. Synthesis of methyl imidazole amine ionic liquid for ATRP reaction system[J]. CIESC Journal, 2016, 67(S2): 159-163.

薛腾, 周剑, 付坦坦, 唐二军, 赵地顺. 甲基咪唑胺类离子液体的合成及其对ATRP反应的影响[J]. 化工学报, 2016, 67(S2): 159-163.

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