Low potential electrosyntheses of free‐standing poly(dibenzofuran) films in mixed electrolytes of boron trifluoride diethyl etherate and trifluoroacetic acid
Low potential electrosyntheses of free‐standing poly(dibenzofuran) films in mixed electrolytes of boron trifluoride diethyl etherate and trifluoroacetic acid
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DOI：
10.1002/pola.21210
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发表时间：
2006-02
期刊：
影响因子：
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通讯作者：
Jingkun Xu;Weiqiang Zhou;Bing Chen;S. Pu;Jingwu Wang;Yiqun Wan
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文献类型：
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作者：
Jingkun Xu;Weiqiang Zhou;Bing Chen;S. Pu;Jingwu Wang;Yiqun Wan
在含有一定量三氟乙酸(TFA)的三氟化硼乙醚(BFEE)混合电解液中，通过直接阳极氧化二苯并呋喃(PDBF)制备了聚二苯并呋喃(PDBF)自支撑膜。二苯并呋喃在纯BFEE中的氧化电位仅为1.31V，而在饱和甘汞电极上的氧化电位仅为1.31V。该值远低于在乙腈+0.1moL L-1TBATFB中测得的值(2.14V vs.SCE)。在BFEE+30%TFA的混合电解液中，TFA的加入可使单体的氧化电位进一步降低到1.07V。用该介质制备的PDBF薄膜具有良好的电化学性能、电致变色性能和热稳定性，电导率为10°S cm-1。红外光谱和核磁共振氢谱表明，聚合物主要是通过C(3)C(10)或C(4)C(9)位的偶联方式生长的(方案1)。PDBF膜部分溶于四氢呋喃(THF)或氯仿。荧光光谱研究表明，无论是可溶性的还是固态的PDBF都是很好的蓝光PDBF发射体。据我们所知，这是第一个电沉积独立的PDBF薄膜的报道。
Free-standing poly(dibenzofuran) (PDBF) films were synthesized electrochemically by direct anodic oxidation of dibenzofuran in mixed electrolytes of boron trifluoride diethyl etherate (BFEE) containing certain amount of trifluoroacetic acid (TFA). The oxidation potential of dibenzofuran in pure BFEE was measured to be only 1.31 V versus saturated calomel electrode (SCE). This value was much lower than that determined in acetonitrile + 0.1 mol L -1 TBATFB (2.14 V vs. SCE). The addition of TFA to BFEE can further decrease the oxidation potential of the monomer to 1 07 V versus SCE in the mixed electrolyte of BFEE + 30% TFA. PDBF films obtained from this medium showed good electrochemical behavior, good electrochromic properties, and good thermal stability with conductivity of 10° S cm -1 . FTIR and 1 H NMR spectra showed that the polymer was grown mainly via the coupling of the monomer at C (3) C (10) or C (4) C (9) positions (Scheme 1). As-formed PDBF films were partly soluble in tetrahydrofuran (THF) or chloroform. Fluorescent spectral studies indicated that either soluble or PDBF in solid state was a good blue light PDBF emitter. To the best of our knowledge, this is the first report that free-standing PDBF films can be electrodeposited.