基于小分子掺杂及聚电介质模板导向的水溶性聚苯胺的CPO酶促氧化合成及结构性能表征

Synthesis,Structure and Performance of Soluble Polyaniline by CPO-catalyzed Oxidation Using Small Molecule as Dopant or Polyelectrolyte as Template

以氯过氧化物酶(CPO)催化H2O2氧化对苯二胺(PPD)单体,建立了一个水溶性聚苯胺(PANI)的绿色合成体系,通过添加小分子和引入模板剂导向合成目标产物,并经紫外-可见光谱、循环伏安测量、电镜扫描、热重分析及电导率测定等进行表征,结果表明,产物的各项性能均比本征态有明显改善.以高氯酸钠为掺杂剂,且n(对苯二胺)∶n(高氯酸钠)=1∶1时,产物具有明显的片层状结构,电化学活性最好,具有很强的可逆氧化还原能力;以聚苯乙烯磺酸钠(SPS)为模板剂导向合成的聚苯胺的热稳定性好,电导率高,水溶性大大增强.另外基于CPO的活性中心结构分析了PPD的聚合机理.

A green enzymatic approach for the synthesis of soluble polyaniline （PANI） from p-phenylene diamine（PPD） monomer by chloroperoxidase （CPO）-catalyzed H202-oxidation was proposed. The performance of aim product was improved compared io that of eigenstate polymer by the introduction of small molecule as dopant or polyelectrolyte as template, which was testified by UV-Vis spectra, cyclic vohammetry curve, electron microscope scanning, thermal gravimetric analysis and conductivity measurement. Sodium perchlorate was screened as the most effective dopant, and the corresponding product when n（PPD） ： n（ NaC104 ）= 1 ： 1 had fine layer structure and strong reversible redox capacity; The PANI obtained with polystyrene sulfonate （SPS） as the template had the best thermal stability and solubility as well as maximum con- ductivity. The enzymatic polymerization was analyzed according to the structure of active site in CPO.