新型烷氧基胺的合成及对甲基丙烯酸甲酯的调控聚合  

Synthesis of Novel Alkoxyamine and Its Controlled Polymerization of Methyl Methacrylate

作　　者：罗菊香[1,2] 赵磊 肖旺钏 程德书[1,3] LUO Juxiang;ZHAO Lei;XIAO Wangchuan;CHENG Deshu(School of Resourses and Chemical Engineering,Sanming University,Sanming 365004,China;College of Chemical Engineering,Fuzhou University,Fuzhou 350108,China;College of Materials Science and Engineering,State Key Laboratory of Advanced Fiber Materials,Donghua University,Shanghai 201620,China)

机构地区：[1]三明学院资源与化工学院,三明365004 [2]福州大学化工学院,福州350108 [3]东华大学材料科学与工程学院,先进纤维材料国家重点实验室,上海201620

出　　处：《高等学校化学学报》2025年第5期140-148,共9页Chemical Journal of Chinese Universities

基　　金：三明学院科学研究项目(批准号:KD23028P);福建省自然科学基金(批准号:2022J011174);福建区域发展项目(批准号:2022Y3003)资助.

摘　　要：单分子烷氧基胺调控的可逆失活自由基聚合工艺简单,制备的聚合物颜色浅、气味小且不含金属离子杂质,但设计合成可调控聚合甲基丙烯酸酯类单体的烷氧基胺是一项具有挑战性的工作.本文通过席夫碱还原、过氧单磺酸钾(Oxone)氧化和自由基偶联三步反应合成了一种新型的烷氧基胺{3-[(2-氰基丙烷-2-基)氧基](异丙基)氨基}-2,2-二甲基-3-苯基丙腈(CPDMN),研究了其对甲基丙烯酸甲酯(MMA)聚合的调控性能.研究结果表明,单体转化率随聚合时间的延长线性增加;聚合物分子量随着聚合时间的延长而增大,凝胶色谱流出曲线峰形对称,没有明显的拖尾现象;聚合反应具有可控/“活性”自由基聚合的特点.聚甲基丙烯酸甲酯大分子引发剂(PMMA-ONR)对MMA、苯乙烯(St)和甲基丙烯酸乙酯(EMA)的再引发实验进一步证明聚合物末端的烷氧基胺保留率良好.在有氧和CPDMN存在的条件下,MMA单体转化率达91.2%,PMMA分子量分布小于1.5,表明CPDMN可以在有氧条件下调控MMA的聚合.该烷氧基胺拓展了氮氧自由基聚合调控单体的范围,在功能聚合物材料的合成方面具有良好的应用前景.Reversible-deactivation radical polymerization(R DRP)regulated by single-molecule alkoxyamine features a simple process,produces polymers with light color and minimal odor,and is free of metal ion impurities.However,the design and synthesis of alkoxyamines capable of regulating the polymerization of methacrylate monomers remains a challenging task.In this paper,an innovative type of alkoxyamine{3-[(2-cyanopropan-2-yl)oxy](isopropyl)amino}-2,2-dimethyl-3-phenylpropanenitrile(CPDMN)was synthesized via Schiff base reduction,potassium persulfate complex oxidation and radical coupling,and then the controlled polymerization behavior of methyl methacrylate(MMA)mediated by CPDMN was investigated.The experimental results demonstrate that the monomer conversion rate increases linearly with polymerization time,while the polymer molecular weight grows with prolonged reaction duration.Gel permeation chromatography traces exhibit symmetrical peaks without significant tailing,indicating characteristic features of controlled/living radical polymerization.Subsequent re-initiation experiments using poly(methyl methacrylate)macroinitiator(PMMA-ONR)with MMA,styrene(St),and ethyl methacrylate(EMA)further confirm the effective retention of alkoxyamine end-groups in the resulting polymers.Finally,the regulation performance of CPDMN on MMA in the presence of oxygen was investigated,achieving a monomer conversion rate of 91.2%and a PMMA molecular weight distribution of less than 1.5,which demonstrates that CPDMN can control the polymerization of MMA with oxygen tolerance.The as-synthesized CPDMN extends the range of monomers applicable to nitroxide-mediated polymerization(NMP),demonstrating promising potential for the synthesis of functional polymeric materials.

关 键 词：氮氧稳定自由基聚合 甲基丙烯酸甲酯 可逆失活自由基聚合 有氧自由基聚合 

分 类 号：O631[理学—高分子化学]