Helical polyacetylenes carrying 2,2,6,6‐tetramethyl‐1‐piperidinyloxy and 2,2,5,5‐tetramethyl‐1‐pyrrolidinyloxy moieties: Their synthesis,properties, and function |
| |
| Authors: | Jinqing Qu Toru Fujii Toru Katsumata Yuji Suzuki Masashi Shiotsuki Fumio Sanda Masaharu Satoh Jun Wada Toshio Masuda |
| |
| Institution: | 1. Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura Campus, Kyoto 615‐8510, Japan;2. Fundamental and Environmental Research Laboratories, NEC Corporation, 34, Miyukigaoka, Tsukuba, Ibaraki 305‐8501, Japan;3. Corporate Planning Department, Nippon Kasei Chemical Co., Ltd., 1‐8‐8 Shinkawa, Chuoku, Tokyo 104‐0033, Japan;4. Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura Campus, Kyoto 615‐8510, JapanDepartment of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura Campus, Kyoto 615‐8510, Japan |
| |
| Abstract: | 2,2,6,6‐Tetramethyl‐1‐piperidinyloxy (TEMPO)‐ and 2,2,5,5‐tetramethyl‐1‐pyrrolidinyloxy (PROXYL)‐containing (R)‐1‐methylpropargyl TEMPO‐4‐carboxylate ( 1 ), (R)‐1‐methylpropargyl PROXYL‐3‐carboxylate ( 2 ), (rac)‐1‐methylpropargyl PROXYL‐3‐carboxylate ( 3 ), (S)‐1‐propargylcarbamoylethyl TEMPO‐4‐carboxylate ( 4 ), and (S)‐1‐propargyloxycarbonylethyl TEMPO‐4‐carboxylate ( 5 ) (TEMPO, PROXYL) were polymerized to afford novel polymers containing the TEMPO and PROXYL radicals at high densities. Monomers 1–3 and 5 provided polymers with moderate number‐average molecular weights of 8200–140,900 in 49–97% yields in the presence of (nbd)Rh+η6‐C6H5B?(C6H5)3], whereas 4 gave no polymer with this catalyst but gave polymers possessing low Mn (3800–7500) in 56–61% yield with (nbd)RhCl]2‐Et3N. Poly( 1 ), poly( 2 ), and poly( 4 ) took a helical structure with predominantly one‐handed screw sense in THF and CHCl3 as well as in film state. The helical structure of poly( 1 ) and poly( 2 ) was stable upon heating and addition of MeOH, whereas poly( 4 ) was responsive to heat and solvents. All of the free radical‐containing polymers displayed the reversible charge/discharge processes, whose capacities were in a range of 43.2–112 A h/kg. In particular, the capacities of poly( 2 )–poly( 5 )‐based cells reached about 90–100% of the theoretical values regardless of the secondary structure of the polymer, helix and random. Poly( 1 ), poly( 2 ), and poly( 4 ) taking a helical structure exhibited better capacity tolerance towards the increase of current density than nonhelical poly( 3 ) and poly( 5 ) did. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5431–5445, 2007 |
| |
| Keywords: | charge/discharge properties conjugated polymers electrochemistry polyacetylenes PROXYL TEMPO |
|
|
