【作者】 申震； 李君； 刘正平；

【Author】 Zhen Shen;Jun Li;Zhengping Liu;Bejing Key Laboratory of Energy Conversion and Storage Materials, Institute of Polymer Chemistry and Physics, College of Chemistry, Beijing Normal University;

【机构】 能量转换与储存北京市重点实验室,北京师范大学化学学院高分子化学与物理研究所；

【摘要】 目前,有机锑调控的可控/活性自由基聚合（SBRP）还未见室温下反应的研究报导。本文以过硫酸铵（APS）为引发剂,以乙基-2-二甲基锑-2-甲基异丁酸酯（EMSMP）为链转移剂,在1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim]PF₆）离子液体中成功实现了甲基丙烯酸甲酯（MMA）、甲基丙烯酸缩水甘油酯（GMA）、丙烯酸甲酯（MA）等丙烯酸酯类单体的室温可控SBRP。室温下不加入离子液体时,本体或是有机溶剂THF、CHCl₃中的聚合反应均可控性差或者不发生反应。而在离子液体中28°C下,MMA聚合24小时产率为94.01wt%,产物的相对分子质量为27600,相对分子质量分布为1.30;GMA聚合6小时产率达到85.46 wt%,产物相对分子质量为20800,相对分子质量分布为1.39。聚合反应动力学研究表明反应具有可控/活性自由基聚合的特点。研究发现,有机锑化合物在作为链转移剂的同时也具有还原剂的作用。进一步结合UV-Vis、¹H NMR、¹⁹F NMR和³¹P NMP等测试手段,研究了引发剂、链转移剂和离子液体之间的相互作用,阐明离子液体中室温可控SBRP的聚合机理。更多还原

【Abstract】 Organostibine-mediated controlled/living radical polymerization（SBRP） of acrylates has been realized at room temperature using ammonium persulfate（APS） as the initiator, ethyl-2-dimethylstibanyl-2-methylpropionate（EMSMP） as the chain transfer agent and ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate（[Bmim]PF₆） as the solvent. The polymerization of methyl methacrylate or glycidyl methacrylate did not happen or was out of control without the addition of ionic liquid at 28 °C. On the contrary, the polymerization was under good control in ionic liquid and showed typical living polymerization characteristics. The polydispersity indices of polymers are less than 1.40. Furthermore, EMSMP was found as the role of not only chain transfer agent, but also reducing agent. UV-vis, ¹H NMR, ¹⁹ F NMR and ³¹ P NMP methods were used to explore the interaction of initiator, ionic liquid and organostibine and the polymerization mechanism.更多还原