Polyacetylene and polynorbornene derivatives carrying TEMPO. Synthesis and properties as organic radical battery materials

Polyacetylene and polynorbornene derivatives carrying TEMPO. Synthesis and properties as organic radical battery materials
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DOI:
10.1002/marc.200600286
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发表时间:
2006-08-02
影响因子:
4.6
通讯作者:
Masuda, Toshio
Masuda, Toshio
中科院分区:
化学3区
文献类型:
--
作者:
Katsumata, Toru;Satoh, Masaharu;Masuda, Toshio

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含有N-炔丙基酰胺HC= CCH 2 NHCO-4-TEMPO(1)、炔丙基酯HC= CCH 2 OCO-4-克里思(2)、苯乙炔衍生物HC= CC 6 H 3 - 3,4-(CO2-4-克里思)(2)(3),和异戊烯二酯单体,NB-2,3-exo,exo-(CH(2)OCO 4-克里思)(2)(4),NB-2,3-endo,exo-合成了(COO-4-克里思)(2)(5a),NB-2,3-endo,endo-(COO-4-克里思)(2)(5 b)(NB =降冰片烯,克里思= 2,2,6,6-四甲基-1-哌啶氧基),并在铑和钌催化剂作用下进行聚合。单体2、5a和5 b以59-100%产率得到数均分子量为47000-185000的聚合物,而单体1、3和4以88-100%产率得到不溶于普通有机溶剂的聚合物。用聚(1)、聚(2)和聚(3)制造的电池的容量为67、82和23 Ah。kg(-1),分别按重量计。电池容量达到理论值(109 Ah . kg(-1))的聚合物。
2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO)containing N-propargylamide HC=CCH2NHCO-4-TEMPO (1), propargyl ester HC=CCH2OCO-4-TEMPO (2), phenylacetylene derivative HC=CC6H3-3,4-(CO2-4-TEMPO)(2) (3), and norbornene diester monomers, NB-2,3-exo,exo-(CH(2)OCO4-TEMPO)(2) (4), NB-2,3-endo,exo-(COO-4-TEMPO)(2) (5a), NB-2,3-endo,endo-(COO-4-TEMPO)(2) (5b) (NB = norbornorbornene, TEMPO= 2,2,6,6-tetramethyl-1-piperidinyloxyl) were synthesized and polymerized with rhodium and ruthenium catalysts. Monomers 2, 5a, and 5b gave polymers with number-average molecular weights of 47000-185000 in 59-100% yields, while 1, 3, and 4 gave polymers insoluble in common organic solvents in 88-100% yields. The capacities of cells fabricated with poly(l), poly(2), and poly(3) were 67, 82, and 23 Ah . kg(-1) based on the weight, respectively. The capacity of poly(5a)-based cell reached the theoretical value (109 Ah . kg(-1)) of the polymer.