Synthesis and properties of polyacetylene and polynorbornene derivatives carrying 2,2,5,5-tetramethyl-1-pyrrolidinyloxy moieties
Synthesis and properties of polyacetylene and polynorbornene derivatives carrying 2,2,5,5-tetramethyl-1-pyrrolidinyloxy moieties
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DOI：
10.1021/ma062357e
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发表时间：
2007-05-01
期刊：
影响因子：
5.5
通讯作者：
Masuda, Toshio
中科院分区：
文献类型：
--
作者：
Qu, Jinqing;Katsumata, Toru;Masuda, Toshio
PROXYL-containing炔丙基酯HCCCH2OCO-3-PROXYL (1) N-propargylamide HCCCH2NHCO-3-PROXYL (2), 1-pentyne-4, 4-dimethyl酯HCCCH2C (CH3) (CH2OCO-3-PROXYL)(2)(3),和norbornene二元酸酯单体NB-2, 3-exo,外(CH2OCO-3-PROXYL) (2) (4), NB-2, 3-endo, endo - (CH2OCO-3-PROXYL)(2)(5),和NB-2, 2 - (CH2OCO-3-PROXYL) (2) (6) (NB = norbornene PROXYL = 2, 2, 5, 5-tetramethyl-1-pyrrolidinyoxy)是聚合买得起小说聚合物包含PROXYL激进的密度很高。在Rh催化剂的作用下，单体1和2的数均分子量为3300- 29800，产率为60-65%；单体4-6的数均分子量为209000 - 272000，产率为90-94%。根据热重热分析，形成的聚合物热稳定性高达约220摄氏度，可溶于常见的有机溶剂，包括甲苯，CHCl3和THF。聚(1)、聚(2)和聚(4)-聚(6)在400 nm以上几乎没有吸收，这与它们的颜色很浅相对应。在循环伏安图中，聚合物的氧化/还原间隙小至0.072 ~ 0.092 V，表明电极反应速率大。所有含proxyl的聚合物均表现出可逆的充放电过程，其容量均大于85 A h/kg。其中，聚(1)-和聚(4)基电池的最大容量分别达到117和107 A h/kg，与理论容量值（分别为119和109 A h/kg）基本吻合。
PROXYL-containing propargyl ester HCCCH2OCO-3-PROXYL (1), N-propargylamide HCCCH2NHCO-3-PROXYL (2), 1-pentyne-4,4-dimethyl ester HCCCH2C(CH3)(CH2OCO-3-PROXYL)(2) (3), and norbornene diester monomers NB-2,3-exo,exo-(CH2OCO-3-PROXYL)(2) (4), NB-2,3-endo,endo-(CH2OCO-3-PROXYL)(2) (5), and NB-2,2-(CH2OCO-3-PROXYL)(2) (6) (NB = norbornene, PROXYL = 2,2,5,5-tetramethyl-1-pyrrolidinyoxy) were polymerized to afford novel polymers containing the PROXYL radical at high densities. While 1 and 2 provided polymers with number-average molecular weights of 3300-29 800 in 60-65% yields in the presence of a Rh catalyst, monomers 4-6 gave polymers with number-average molecular weights up to 209 000-272 000 in 90-94% yields with a Ru catalyst. The formed polymers were thermally stable up to ca. 220 degrees C according to TGA and soluble in common organic solvents including toluene, CHCl3, and THF. Poly(1), poly(2), and poly(4)-poly(6) hardly exhibited absorption above 400 nm, which corresponds with their very light color. The oxidation/reduction gaps in the cyclic voltammograms of the present polymers were as small as 0.072-0.092 V, indicating large electrode reaction rates. All the PROXYL-containing polymers demonstrated the reversible charge/discharge processes, whose capacities were larger than 85 A h/kg. In particular, the maximum capacity of poly(1)- and poly(4)-based cells reached 117 and 107 A h/kg, which practically coincided with the theoretical capacity values (119 and 109 A h/kg, respectively).