Metal and Ligand Effects of Photoactive Transition Metal Carbonyls in the Iodine Degenerative Transfer Controlled Radical Polymerization and Block Copolymerization of Vinylidene Fluoride
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- 作者：Christopher P. Simpson ; Olumide I. Adebolu ; Joon-Sung Kim ; Vignesh Vasu ; Alexandru D. Asandei
- 刊名：Macromolecules
- 出版年：2015
- 出版时间：September 22, 2015
- 年：2015
- 卷：48
- 期：18
- 页码：6404-6420
- 全文大小：836K
- ISSN：1520-5835
文摘
The metal and ligand effect of a series of transition metal carbonyls in conjunction with alkyl and perfluoroalkyl halides was investigated in the initiation and control of the visible light, radical photopolymerizations of vinylidene fluoride (VDF) and respectively, in the synthesis of PVDF block copolymers. No polymerization was observed for CpMn(CO)3, CpCo(CO)2, Cp2Fe2(CO)4, Cp*2Cr2(CO)4, Mo(CO)6, Fe(CO)5, Cr(CO)6, Co2(CO)8, Co4(CO)12, Fe3(CO)12, Ru3(CO)12, (PPh3)2Ni(CO)2, Cp2Ti(CO)2, and Au(CO)Cl. A free radical polymerization, and respectively an iodine degenerative transfer, controlled radical polymerization was obtained for Mn2(CO)10 鈭?Re2(CO)10 鈮?Cp2Mo2(CO)6 鈮?Cp2W2(CO)6 with CH3(CH2)5鈥揃r, CH3(CH2)5鈥揑, CH3鈥揑, CCl3鈥揅l, CCl3鈥揃r, Br鈥?CF2)6鈥揃r, and respectively with CF3(CF2)3鈥揑 and I鈥?CF2)4,6鈥揑. Furthermore, while Fe(CO)5, Cp*Cr2(CO)4 and Co4(CO)12 led to 鈭?CF2鈥揑 bond insertion, Re2(CO)10, Mn2(CO)10, Cp2W2(CO)6, Cp2Mo2(CO)6 and Cp2Fe2(CO)4 provided quantitative radical activation of both PVDF鈥揅H2鈥揅F2鈥揑 and PVDF鈥揅F2鈥揅H2鈥揑 chain ends, and were employed in the synthesis of well-defined ABA triblock PVDF copolymers with vinyl acetate, tert-butyl acrylate, methyl methacrylate, isoprene, styrene, and acrylonitrile.