本文選題：配體 + 離子液體�。� 參考：《河北科技大學(xué)》2017年碩士論文

【摘要】：原子轉(zhuǎn)移自由基聚合(ATRP)反應(yīng)是近幾年迅速發(fā)展起來的一種重要的活性聚合技術(shù),具有對反應(yīng)活性可控的優(yōu)點,可合成特定的功能性聚合物材料。在ATRP反應(yīng)體系中配體對反應(yīng)可控性起著重要的作用,本文針對離子液體體系中的ATRP反應(yīng)所用有機(jī)配體的不足,合成了兩類七種不同胺類配位功能離子液體,替代傳統(tǒng)有機(jī)配體,研究了不同結(jié)構(gòu)配位離子液體與CuBr的配位機(jī)理以及對ATRP反應(yīng)影響。以N-甲基咪唑為骨架引入1,2-二氯乙烷,合成了中間體:氯化1-氯乙基-3-甲基咪唑離子液體([CeMIM]Cl),再與不同結(jié)構(gòu)的脂肪多胺反應(yīng)合成了含N的胺類配位功能離子液體: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)。通過FT-IR、1HNMR對胺類配位離子液體的結(jié)構(gòu)進(jìn)行分析測試,確證了其化學(xué)結(jié)構(gòu);并通過正交實驗測定了其最優(yōu)合成工藝條件為:[CeMIM]Cl與脂肪多胺物質(zhì)的量配比1:1、反應(yīng)時間20h、反應(yīng)溫度80℃。采用循環(huán)伏安法(CV)分別測定了多胺類配位離子液體和有機(jī)配體與Cu+配位的氧化還原電勢(E1,2),結(jié)果表明:配位功能離子液體相比于傳統(tǒng)有機(jī)配體具有較好的配位性能,隨著多胺類配位離子液體中含N個數(shù)的增多,配位能力增強;配位離子液體C鏈的增長,可提高其配位能力,而隨著多胺類配位離子液體中取代基的增多,配位能力減弱。將配位離子液體分別與CuBr配位應(yīng)用于[AMIM]Cl離子液體溶劑中MMA的ATRP反應(yīng),測得該聚合反應(yīng)速率與單體MMA的濃度符合一級動力學(xué)關(guān)系,經(jīng)凝膠滲透色譜(GPC)測得所合成的聚合物分子量分布Mw/Mn為1.50—1.90,表明配位離子液體對ATRP反應(yīng)具有良好的可控性,并且隨著多胺類配位離子液體中C鏈的增長,可控性變強;而隨著取代基的增多,可控性變差。其次經(jīng)原子吸收光譜AAS測得聚合產(chǎn)物PMMA中Cu2+的殘留量,配位離子液體有利于催化劑與聚合產(chǎn)物的分離,并且隨著配位離子液體與Cu+的配位性越好,對聚合產(chǎn)物與催化劑的分離性能越好。該配位離子液體克服了傳統(tǒng)有機(jī)配體有毒有害、兼容性差、不利于催化劑與聚合產(chǎn)物分離等不足,在ATRP領(lǐng)域具有廣闊的應(yīng)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，

本文編號：1788490