ORGANIC ELECTROCHEMISTRY IN THE SOLID STATE-OVEROXIDATION OF POLYPYRROLE
ORGANIC ELECTROCHEMISTRY IN THE SOLID STATE-OVEROXIDATION OF POLYPYRROLE
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DOI：
10.1002/bbpc.19870910927
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发表时间：
1987-09-01
期刊：
影响因子：
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通讯作者：
OBERST, M
中科院分区：
文献类型：
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作者：
BECK, F;BRAUN, P;OBERST, M
详细研究了在H2O、OH−、CH3OH、CH3O−、Br2−和CN−等亲核试剂存在下，聚吡咯的阳极过氧化反应。在高达2.1V(vs.SCE)的电位下，在铂上观察到具有200 nm层的不可逆阳极峰。在大多数情况下，最初在可逆电位区氧化为自由基阳离子的单体单位总数为OFZ=4-6F/mol。只有每三个环才涉及到这种方式。在水体系中的特征产物是吡咯烷酮(3位含酮基团)，z=4，以及4位进一步羟化的产物(z=6)。在其他亲核试剂存在的情况下，似乎会产生相应的取代产物。中心反应中间体似乎就是标记物。IRRAS结果证实了这一方案的显著偏离，似乎是在存在像OH−这样的强亲核试剂的情况下进行的，它最初添加到自由基阳离子中，并且在强极化时进行，这可能导致其他环的攻击和/或聚合物的破坏。聚合物的改性和电池材料的优化具有实际意义。
Anodic overoxidation of polypyrrole in the presence of nucleophiles such as H2O, OH−, CH3OH, CH3O−, Br−and CN−has been studied in detail. At potentials up to 2.1 V (vs. SCE), irreversible anodic peaks are observed with 200 nm layers on Pt. In most of the cases, a total ofz= 4 – 6F/mol monomer unit initially oxidized in the reversible potential region to the radical cation has been evaluated. Only every third ring is involved by this way. Characteristic products in aqueous systems are pyrrolinones (with a keto group in 3‐position),z= 4, and the product of further hydroxylation in 4‐position (z= 6). In the presence of the other nucleophiles, corresponding substitution products seem to be generated. The central reactive intermediate seems to be the dication. Pronounced deviations from this scheme, which is confirmed by IRRAS results, seem to proceed in the presence of strong nucleophiles as OH−, which add initially to the radical cation, and upon strong polarization, which may lead to an attack of the other rings and/or polymer destruction. Practical implications are due to polymer modification and battery material optimization.