Synthesis and charge/discharge properties of polyacetylenes carrying 2,2,6,6-tetramethyl-1-piperidinoxy radicals
Synthesis and charge/discharge properties of polyacetylenes carrying 2,2,6,6-tetramethyl-1-piperidinoxy radicals
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DOI：
10.1002/chem.200700698
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Masuda, Toshio
中科院分区：
文献类型：
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作者：
Qu, Jinqing;Katsumata, Toru;Masuda, Toshio
含2,2,6,6-四甲基-1-哌啶氧基(TEMPO)的炔属单体HC相当于CC6H3-p,m-(CONH-4-TEMPO)(2)(1)，HC相当于CC6H3-p,m-(COO-4-TEMPO)(2)(2)，(S,S,S,S)-HC相当于 CC6H3-p,m-[CO-NHCH{COO-(4-TEMPO)}CH2COO-(4-TEMPO)](2) (3), (S,S)-HC 相当于 CC6H4CO-NHCH{COO-(4-TEMPO)} CH2COO-(4-TEMPO) (4), HC 相当于 CC6H4-p-OCO-4-TEMPO (5)、相当于 CCH2C(CH3)(CH2OCO-4-TEMPO)(2) (6) 的 HC、相当于 CCH2NHCO-4-TEMPO (7) 的 HC 和相当于 CCH2OCO-4-TEMPO (8) 的 HC 在高温下聚合，得到含有 TEMPO 自由基的新型聚合物 密度。在铑催化剂存在下，单体1、3-6和8以62-99％的产率提供平均分子量为10000-136500的聚合物，而单体2和7以100％的产率提供不溶性聚合物。根据热重分析 (TGA)，所形成的聚合物在高达约 274 摄氏度的温度下保持热稳定性。所有含TEMPO的聚合物均表现出可逆充放电过程，其放电容量为21.3-108 A h kg(-1)。特别是，聚(1)、聚(4)和聚(5)基电池的容量分别达到108、96.3和89.3Ahkg(-1)，这实际上与其理论值一致。
The 2,2,6,6-tetramethyl-1-piperidinoxy (TEMPO)-containing acetylenic monomers HC equivalent to CC6H3-p,m- (CONH-4-TEMPO)(2) (1), HC equivalent to CC6H3-p,m-(COO-4-TEMPO)(2) (2), (S,S,S,S)-HC equivalent to CC6H3-p,m-[CO-NHCH{COO-(4- TEMPO)}CH2COO-(4-TEMPO)](2) (3), (S,S)-HC equivalent to CC6H4CO-NHCH{COO-(4-TEMPO)} CH2COO-(4-TEMPO) (4), HC equivalent to CC6H4-p-OCO-4-TEMPO (5), HC equivalent to CCH2C(CH3)(CH2OCO-4-TEMPO)(2) (6), HC equivalent to CCH2NHCO-4-TEMPO (7), and HC equivalent to CCH2OCO-4-TEMPO (8) were polymerized to afford novel polymers containing the TEMPO radical at high densities. Monomers 1, 3-6, and 8 provided polymers with average molecular weights of 10000-136500 in 62-99% yield in the presence of a rhodium catalyst, whereas monomers 2 and 7 gave insoluble polymers in 100% yield. The formed polymers were thermally stable up to approximately 274 degrees C according to thermogravimetric analysis (TGA). All the TEMPO-containing polymers demonstrated reversible charge/discharge processes, whose discharge capacities were 21.3-108 A h kg(-1). In particular, the capacity of poly(1)-, poly(4)-, and poly(5)-based cells reached 108, 96.3, and 89.3Ahkg(-1), respectively, which practically coincided with their theoretical values.