多胺类配位功能离子液体的合成及其结构对ATRP反应影响研究

发布时间：2018-04-22 18:57

  本文选题：配体 + 离子液体　； 参考：《河北科技大学》2017年硕士论文

【摘要】：原子转移自由基聚合(ATRP)反应是近几年迅速发展起来的一种重要的活性聚合技术,具有对反应活性可控的优点,可合成特定的功能性聚合物材料。在ATRP反应体系中配体对反应可控性起着重要的作用,本文针对离子液体体系中的ATRP反应所用有机配体的不足,合成了两类七种不同胺类配位功能离子液体,替代传统有机配体,研究了不同结构配位离子液体与CuBr的配位机理以及对ATRP反应影响。以N-甲基咪唑为骨架引入1,2-二氯乙烷,合成了中间体:氯化1-氯乙基-3-甲基咪唑离子液体([CeMIM]Cl),再与不同结构的脂肪多胺反应合成了含N的胺类配位功能离子液体:氯化1-(乙基氨基)乙基-3-甲基咪唑([N2C2MIM]Cl)、氯化1-(丙基氨基)乙基-3-甲基咪唑([N2C3MIM]Cl)、氯化1-(2-甲基丙基氨基)乙基-3-甲基咪唑([N2MeC3MIM]Cl)、氯化1-(1,2-二甲基丙基氨基)乙基-3-甲基咪唑([N2Me2C3MIM]Cl)、氯化1-[(二乙氨基)氨基]乙基-3-甲基咪唑([N3MIM]Cl)、氯化1-[(五甲基二乙基)氨基]乙基-3-甲基咪唑[N3Me5MIM]Cl、氯化1-(三乙基四氨基)乙基-3-甲基咪唑([N4MIM]Cl)。通过FT-IR、1HNMR对胺类配位离子液体的结构进行分析测试,确证了其化学结构;并通过正交实验测定了其最优合成工艺条件为:[CeMIM]Cl与脂肪多胺物质的量配比1:1、反应时间20h、反应温度80℃。采用循环伏安法(CV)分别测定了多胺类配位离子液体和有机配体与Cu+配位的氧化还原电势(E1,2),结果表明:配位功能离子液体相比于传统有机配体具有较好的配位性能,随着多胺类配位离子液体中含N个数的增多,配位能力增强;配位离子液体C链的增长,可提高其配位能力,而随着多胺类配位离子液体中取代基的增多,配位能力减弱。将配位离子液体分别与CuBr配位应用于[AMIM]Cl离子液体溶剂中MMA的ATRP反应,测得该聚合反应速率与单体MMA的浓度符合一级动力学关系,经凝胶渗透色谱(GPC)测得所合成的聚合物分子量分布Mw/Mn为1.50—1.90,表明配位离子液体对ATRP反应具有良好的可控性,并且随着多胺类配位离子液体中C链的增长,可控性变强;而随着取代基的增多,可控性变差。其次经原子吸收光谱AAS测得聚合产物PMMA中Cu2+的残留量,配位离子液体有利于催化剂与聚合产物的分离,并且随着配位离子液体与Cu+的配位性越好,对聚合产物与催化剂的分离性能越好。该配位离子液体克服了传统有机配体有毒有害、兼容性差、不利于催化剂与聚合产物分离等不足,在ATRP领域具有广阔的应用前景。
[Abstract]:Atom transfer radical polymerization (ATRP) is an important active polymerization technology developed rapidly in recent years. It has the advantage of controllable reaction activity and can be used to synthesize specific functional polymer materials. Ligands play an important role in the controllability of the ATRP reaction system. In this paper, two kinds of seven kinds of amines coordination functional ionic liquids were synthesized to replace the traditional organic ligands, aiming at the deficiency of the organic ligands used in the ATRP reaction of ionic liquids. The coordination mechanism of different structure coordination ionic liquids with CuBr and its effect on ATRP reaction were studied. N- methylimidazole was used as skeleton to introduce 1 ~ (2 +) -dichloroethane. The intermediate, 1-chloroethyl-3-methylimidazole ionic liquid (CeMIM), was synthesized by reaction with different structure aliphatic polyamines to synthesize N-containing amine coordination functional ionic liquids: 1-ethylamino ethyl-3-methyl imidazole chloride ([N2C2MIM] CLA, chlorine). 1-( propylamino) ethyl -3-methyl imidazole (N2C3MIM), 1-chloride-2-methylpropylamino ethyl-3-methylimidazole ([N2MeC3MIM] CLA, 1-PHENYL 2-dimethyl propyl amino group) ethyl-3-methyl imidazole (N2Me2C3MIM), 1- [(diethylamino) amino] ethyl-3-methylimidazole chloride, [N2Me2C3MIM] CLO, 1- [(diethylamino) amino] ethyl-3-methylimidazole ([N3MIM] CLO, 1- [(pentamethyldiethylamino) amino] ethyl-3-methyl imidazole [N3Me5MIM] Cl, 1-( triethyltetraamino) ethyl -3-methyl imidazole ([N4MIM] CLA]). The structure of amines coordination ionic liquids was analyzed and tested by FT-IRN 1H NMR, and the optimum synthesis conditions were determined by orthogonal experiment: the ratio of [CeMIM] Cl to aliphatic polyamines was 1: 1, the reaction time was 20 h, the reaction temperature was 80 鈩，

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