Electrochemically Induced Functionalization of Fluorocontaining Polyolefins
Electrochemically Induced Functionalization of Fluorocontaining Polyolefins
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DOI：
10.1080/10601329508018951
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发表时间：
1995-07
期刊：
影响因子：
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通讯作者：
A. Pud;O. Mikulina;G. S. Shapoval
中科院分区：
文献类型：
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作者：
A. Pud;O. Mikulina;G. S. Shapoval
研究了聚偏氟乙烯（PVDF）、聚偏氟乙烯（PVF）、偏氟乙烯（VDF）与四氟乙烯（TFE）的共聚物和六氟丙烯（HFP）在不同性质的阴极上，在0，1M（C4H9）4NClO4存在下的电化学转化机理.研究发现，在研究的条件下，共聚物、PVF和PVDF的含氢氟键能够在阴极进行脱氟化氢反应。其主要原因是在二甲基甲酰胺电化学还原时形成的带负电荷的亲核产物对大分子的攻击。全氟TFE和HFP的连接通过两个不可逆阶段进行直接电化学还原，随后氟阴离子消除和多共轭键形成。基于电化学和光谱数据，提出了含氟碳链聚合物在阴极转化的两种不同机理。总的来说，所获得的数据证明了利用聚合物电化学转化来实现其功能化的可能性。
Mechanistic aspects of electrochemical transformations of polyvinylidonefluoride (PVDF), polyvinylfluoride (PVF), copolymers of vinylidenefluoride (VDF) with tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) at a cathodes of different nature in dimethylformamide in the presence of 0,1 M (C 4 H 9 ) 4 NClO 4 , have been investigated. It is found that hydrogenfluorocontaining links of the copolymer, PVF and PVDF are able to dehydrofluorination at a cathode in investigated conditions. The main reason of this is an attack of macromolecules by negatively charged nucleophilic products that are formed at the dimethylformamide electrochemical reduction. Perfluorinative TFE and HFP links undergo direct electrochemical reduction through two irreversible stages with subsequent fluorine anions elimination and polyconjugated bonds formation. Based on the electrochemical and spectral data two different mechanisms of fluorocontaining carbochain polymers transformation at a cathode were suggested. On the whole, the obtained data testify to the possibility of an employment of polymer electrochemical transformations to realize their functionalization.