甲基咪唑胺类离子液体的合成及其对ATRP反应的影响

Synthesis of methyl imidazole amine ionic liquid for ATRP reaction system

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([N_2C_3MIM]Cl)。通过FT-IR、1 H NMR对[N_2C_3MIM]Cl进行分析测试,确证了其化学结构。通过循环伏安法测得[N_2C_3MIM]Cl具有较低的氧化还原电势,为-0.522V,与有机配体相比[N_2C_3MIM]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[N_2C_3MIM]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Cu^(2+)的残留量仅为270mg·kg^(-1),表明与传统有机配体相比,[N_2C_3MIM]Cl有利于催化剂与聚合产物的分离。

1-(Propyl amine)ethyl-3-methyl chloride ionic liquid ([N2 C3 MIM]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 [N2 C3 MIM]Cl was confirmed by FT-IR and 1 H NMR. [N2 C3 MIM]Cl possessed a lower REDOX potential (-0.522 V)through cyclic voltammetry measurement,[N2 C3 MIM]Cl presented a perfect coordination property compared with organic ligands.The obtained ionic liquid [N2 C3 MIM]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 [N2 C3 MIM ]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 [N2 C3 MIM]Cl was conducive to the separation of catalyst from the obtained product compared with the traditional organic ligands.