氯化1-{2-[双(2-氨基乙基)氨基]乙基}吡啶离子液体的合成及在ATRP反应中的应用

Synthesis of 1-{2-[bis(2-aminoethyl)amino]ethyl} pyridinium chloride and its application in ATRP reaction

采用N-烷基化方法将二乙烯三胺(DETA)接枝到氯化1-氯乙基吡啶离子液体[Ce Py]Cl上,合成了离子液体氯化1-{2-[双(2-氨基乙基)氨基]乙基}吡啶([N3Py]Cl),通过FTIR、1H NMR和MS等测试手段对合成离子液体的结构进行了表征。采用循环伏安法对离子液体配合物[N3Py]Cl/Cu Br和有机配合物PMDETA/Cu Br的氧化还原电位(E1/2)进行测试,结果表明:合成的离子液体[N3Py]Cl和Cu Br形成配合物的氧化还原电势为E1/2=-0.541V,比常用的有机配合物PMDETA/Cu Br(E1/2=-0.142V)具有更低的氧化还原电势。将离子液体[N3Py]Cl与Cu Br配位形成催化体系,在离子液体[AMIM]Cl中催化甲基丙烯酸甲酯(MMA)的原子转移自由基聚合(ATRP)反应。结果表明,当配体、催化剂和溶剂的用量分别为n(Cu Br)=0.19mmol、n([N3Py]Cl)=1.13mmol、n([AMIM]Cl)=0.02mol,反应温度60℃,反应时间4h时,单体转化率高达75%,分子量分布较窄(Mw/Mn=1.24),ATRP反应具有明显的可控性能。

Ionic liquid of 1-{2-[bis（2-aminoethyl）amino]ethyl} pyridinium chloride [N3Py]Cl was synthesized by grafting the diethylenetriamine（DETA）onto 1- chloro-ethyl pyridinium chloride ionic liquid [Ce Py]Cl through N alkylation. The structure of the ionic liquid was characterized by FTIR,1H NMR and MS. The redox potential（E1/2）of complex [N3Py] Cl/Cu Br and PMDETA/Cu Br was tested by cyclic voltammetry. The result indicated that the redox potential of [N3Py]Cl/Cu Br was –0.541 V,lower than that of PMDETA/Cu Br（–0.142V）. In addition,the atom transfer radical polymerization（ATRP）of MMA was catalyzed by ionic liquid [N3Py]Cl with Cu Br in the ionic liquid [AMIM]Cl. The conversion of monomer was up to 75% with a narrow distribution of molecular weight（Mw/Mn = 1.24）when the employed amount of the ligand,catalyst and solvent was n（Cu Br）=0.19mmol、n（[N3Py]Cl）=1.13mmol、n（[AMIM]Cl）=0.02 mol,respectively,with the reaction temperature of 60℃,and reaction time of 4h. The reaction presented the characteristic of living/controlled polymerization.