Systematic study on chemical oxidative and solid-state polymerization of poly(3,4-ethylenedithiathiophene)
Systematic study on chemical oxidative and solid-state polymerization of poly(3,4-ethylenedithiathiophene)
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聚(3,4-乙撑二硫噻吩)化学氧化固相聚合的系统研究
DOI：
10.1002/pola.25971
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发表时间：
2012-05-15
影响因子：
--
通讯作者：
Xu, Jingkun
中科院分区：
文献类型：
--
作者：
Chen, Shuai;Lu, Baoyang;Xu, Jingkun
系统研究了3,4-乙撑二硫噻吩（EDTT）在表面活性剂存在或无存在下的化学氧化聚合，以及2,5-二溴-3,4-乙撑二硫噻吩（DBEDTT）和2,5-二碘-3,4-乙撑二硫噻吩（DIEDTT）在无溶剂和无溶剂条件下的固相聚合。 对无氧化剂条件进行了研究。讨论了氧化剂(Fe3+盐、过硫酸盐、过氧化物、Ce4+盐)、溶剂(H2O、CH3CN/H2O、CH3CN)、表面活性剂等对聚(3,4-乙烯二硫噻吩)(PEDTT)聚合反应和性能的影响。表征表明，FeCl3 是更适合 EDTT 氧化聚合的氧化剂，而 CH3CN 是形成具有更高收率和电导率的 PEDTT 粉末的更好溶剂。将这些粉末分散在聚苯乙烯磺酸（PSSH）水溶液中，比十二烷基硫酸钠和十二烷基苯磺酸钠表现出更好的稳定性和成膜性能。 EDTT在PSSH水溶液中氧化聚合形成可溶液加工的PEDTT分散体，具有良好的储存稳定性和成膜性能。溶剂处理对自支撑 PEDTT 薄膜的电导率影响不显着。固相聚合合成的PEDTT与氧化聚合相比，具有相似的电导率，稳定性较差，但热电性能更好。相比之下，由DIEDTT合成的PEDTT表现出比DBEDTT更高的电导率（0.18 S cm-1），DBEDTT表现出更好的热电性能和更高的功率因数值（6.7 X 10-9 W m-1 K-2）。 (c) 2012 年 Wiley periodicals, Inc. J Polym Sci A 部分：Polym Chem，2012 年
Systematic research on the synthesis, chemical oxidative polymerization of 3,4-ethylenedithiathiophene (EDTT) in the presence of surfactants or not, and solid-state polymerization of 2,5-dibromo-3,4-ethylenedithiathiophene (DBEDTT) and 2,5-diiodo-3,4-ethylenedithiathiophene (DIEDTT) under solventless and oxidant-free conditions has been investigated. Effects of oxidants (Fe3+ salts, persulfate salts, peroxides, and Ce4+ salts), solvents (H2O, CH3CN/H2O, and CH3CN), surfactants, and so forth on polymerization reactions and properties of poly(3,4-ethylenedithiathiophene) (PEDTT) were discussed. Characterizations indicated that FeCl3 was more suitable oxidant for oxidative polymerization of EDTT, while CH3CN was a better solvent to form PEDTT powders with higher yields and electrical conductivities. Dispersing these powders in aqueous polystyrene sulfonic acid (PSSH) solution showed better stability and film-forming property than sodium dodecylsulfate and sodium dodecyl benzene sulfonate. Oxidative polymerization of EDTT in aqueous PSSH solutions formed the solution processable PEDTT dispersions with good storing stability and film-forming performance. Solvent treatment showed indistinctive effect on electrical conductivity of free-standing PEDTT films. As-formed PEDTT synthesized from solid-state polymerization showed similar electrical conductivity, poorer stability, but better thermoelectric property than oxidative polymerization. Contrastingly, PEDTT synthesized from DIEDTT showed higher electrical conductivity (0.18 S cm-1) than DBEDTT which showed better thermoelectric property with higher power factor value (6.7 X 10-9 W m-1 K-2). (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012