Triphenylphosphine (TPP) was used as reducing agent to continuously generate the Cu(I) activator in copper(II)- catalyzed activators generated by electron transfer atom transfer radical polymerization (AGET ATR...Triphenylphosphine (TPP) was used as reducing agent to continuously generate the Cu(I) activator in copper(II)- catalyzed activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). For example, the polymers prepared with a molar ratio of [MMA]0/[EBiB]0/[CuC12]o/[PMDETA]0/[TPP]o = 500/1/0.1/0.5/0.5 had controlled molecular weights and low molecular weight distribution (Mw/Mn) values (-1.2). TPP as a commercial reducing agent provides a convenient copper-catalyzed AGET ATRP procedure for the preparation of well-defined polymers.展开更多
Atom transfer radical polymerization of styrene (St) and methyl methacrylate (MMA) in bulk and in different solvents using activators generated by electron transfer (AGET ATRP) were investigated in the presence ...Atom transfer radical polymerization of styrene (St) and methyl methacrylate (MMA) in bulk and in different solvents using activators generated by electron transfer (AGET ATRP) were investigated in the presence of a limited amount of air using FeC13-6H2O as the catalyst, ascorbic acid sodium salt (AsAc-Na) as the reducing agent, and a cheap and commercially available tetrabutylammonium bromide (TBABr) as the ligand. It was found that polymerization in THF resulted in shorter induction period than that in bulk and in toluene for AGET ATRP of St, while referring to AGET ATRP of MMA, polymerization in THF showed three advantages compared with that in bulk and toluene:1) shortening the induction period, 2) enhancing the polymerization rate and 3) having better controllability. The living features of the obtained polymers were verified by chain end analysis and chain-extension experiments.展开更多
以4,4’-二甲基二苯甲酮为原料,经过溴化、选择性胺化、O-烷基化等反应,依次合成了4-(溴甲基)-4’-[双(羟乙基)氨基]二苯甲酮与4-(腰果酚基甲基)-4’-[双(羟乙基)氨基]二苯甲酮两个功能性的类米氏酮光引发剂,收率分别为58%和46%。在4-(...以4,4’-二甲基二苯甲酮为原料,经过溴化、选择性胺化、O-烷基化等反应,依次合成了4-(溴甲基)-4’-[双(羟乙基)氨基]二苯甲酮与4-(腰果酚基甲基)-4’-[双(羟乙基)氨基]二苯甲酮两个功能性的类米氏酮光引发剂,收率分别为58%和46%。在4-(溴甲基)-4’-[双(羟乙基)氨基]二苯甲酮中含有苄溴基团,因此该化合物还可作为ATRP或SET-LRP引发剂。同时,利用4-(溴甲基)-4’-[双(羟乙基)氨基]二苯甲酮作引发剂进行了腰果酚单体的AGET ATRP聚合反应,得到相应的腰果酚均聚物(Mn=20.2 k Da,PDI=1.11)。小分子化合物的结构用1H-NMR进行了表征。展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.21404051 and 21404052)the Natural Science Foundation of Shandong Province(Nos.ZR2014BQ016 and BS2014CL040)+1 种基金the Talent Introduction Special Funds of Ludong University(Nos.2014012 and 2014017)the Program for Scientific Research Innovation Team in Colleges and Universities of Shandong Province and Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application(Soochow University)
文摘Triphenylphosphine (TPP) was used as reducing agent to continuously generate the Cu(I) activator in copper(II)- catalyzed activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). For example, the polymers prepared with a molar ratio of [MMA]0/[EBiB]0/[CuC12]o/[PMDETA]0/[TPP]o = 500/1/0.1/0.5/0.5 had controlled molecular weights and low molecular weight distribution (Mw/Mn) values (-1.2). TPP as a commercial reducing agent provides a convenient copper-catalyzed AGET ATRP procedure for the preparation of well-defined polymers.
基金financially supported by the National Natural Science Foundation of China(Nos.21174096,21274100 and 21234005)the Specialized Research Fund for the Doctoral Program of Higher Education(No.20103201110005)+1 种基金the Project of International Cooperation of the Ministry of Science and Technology of China(No.2011DFA50530)the project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘Atom transfer radical polymerization of styrene (St) and methyl methacrylate (MMA) in bulk and in different solvents using activators generated by electron transfer (AGET ATRP) were investigated in the presence of a limited amount of air using FeC13-6H2O as the catalyst, ascorbic acid sodium salt (AsAc-Na) as the reducing agent, and a cheap and commercially available tetrabutylammonium bromide (TBABr) as the ligand. It was found that polymerization in THF resulted in shorter induction period than that in bulk and in toluene for AGET ATRP of St, while referring to AGET ATRP of MMA, polymerization in THF showed three advantages compared with that in bulk and toluene:1) shortening the induction period, 2) enhancing the polymerization rate and 3) having better controllability. The living features of the obtained polymers were verified by chain end analysis and chain-extension experiments.
文摘以4,4’-二甲基二苯甲酮为原料,经过溴化、选择性胺化、O-烷基化等反应,依次合成了4-(溴甲基)-4’-[双(羟乙基)氨基]二苯甲酮与4-(腰果酚基甲基)-4’-[双(羟乙基)氨基]二苯甲酮两个功能性的类米氏酮光引发剂,收率分别为58%和46%。在4-(溴甲基)-4’-[双(羟乙基)氨基]二苯甲酮中含有苄溴基团,因此该化合物还可作为ATRP或SET-LRP引发剂。同时,利用4-(溴甲基)-4’-[双(羟乙基)氨基]二苯甲酮作引发剂进行了腰果酚单体的AGET ATRP聚合反应,得到相应的腰果酚均聚物(Mn=20.2 k Da,PDI=1.11)。小分子化合物的结构用1H-NMR进行了表征。