应用电化学石英晶体微天平和反射光谱电化学方法研究了 0 .10molL 1四氟硼酸化四丁铵 二氯甲烷溶液中联苯和联三苯在铂电极上的氧化聚合 .结果表明 ,联苯和联三苯经氧化后在溶液中偶合成聚合物 ,生成的聚合物沉积在铂电极表面 .聚合反应是通过单体氧化后生成的自由基离子偶合进行的 .聚合物的生成量与单体氧化生成的自由基离子的量有关 .由于联三苯的氧化电位低于联苯 ,因此在相同的实验条件下前者在铂电极上的聚合沉积速度较快 .聚合过程的吸收光谱红移说明随着电解的进行 ,氧化的联苯和联三苯的自由基离子聚合成长链的聚合物
Polymers were prepared by oxidation of biphenyl and p terphenyl by consecutive cyclic voltammetry and at a constant potential in rigorously dried dichloromethane solutions. In situ studies on the polymerization properties and deposited polymer were also proceeded employing electrochemical quartz crystal micro balance, spectroelectrochemical measurements. The great mass deposition was observed as the biphenyl and p terphenyl monomers are oxidized indicating that polymers were formed by the oxidation of biphenyl and p terphenyl in the solution and then deposited on the platinum electrode surfaces. Polymerization can be further confirmed by the red shifts of spectra observed by spectroelectrochemical measurements. The polymerization might be proceeded with several steps by coupling of oxidized monomer radical cations in both case of biphenyl and p terphenyl.
[1] G .Grem ,G .Leditzky ,B .Ullrich ,etal.Blueelectroluminescentdevicebasedonaconjugatedpolymer[J].Synth .Met .,1992 ,51:383.
[2 ] P .Soubiran ,S .Aeiyach ,J .J .Aaron ,etal.Electrosynthesisandspectroscopcharacterizationofpoly para phenylenefilmsbyoxidationofbenzeneinliquidsulfurdioxide[J].J.Electroanal.Chem .,1988,2 51:89～10 2 .
[3] K .Kobayashi,T .X .Yang ,K .Maruyama ,etal.Electrochemicalpolymerizationofpoly ( para phenylene)anditselectricalproperties[J].Synth .Met.,1995,69:4 75.
[4 ] S .Aeiyach ,J .E .Dubois,P .C .Lacaze .Mediumeffectontheanodicfabricationofpoly (p phyenylene)filmsonplatinumelectrodes[J].J .Chem .Soc.,Chem .Commun .,1986,1668～ 1669.
[5] K .Ashiley .Propertiesofelectrochemicallygeneratedpoly ( p phenylene) [J].Electrochim .Acta ,198934 :599～ 610 .
[6] C .Kvarnstrom ,R .Bilger,A .Ivaskaetal.Anelectrochemicalquartzcrystalmicrobalancestudyonpolymer izationofoligo p phenylene[J].Electrochim .Acta ,1998,4 3:355～ 366.
[7] Sheng YunCui,Su MoonPark .ElectrochemicalGrowthandDopingMechanismofPolyanilineandPoly ( p phenylene)UsinginSituExperiments :DissertationforthedegreeofDoctorofphilosophyinthedepartmentofchemistry[A].Pohang ,Korea :PohangUniversityofScience&Technology ,1999.
