含吡咯基团导电性聚磷腈的合成及化学氧化聚合

A NEW CONDUCTIVE POLYPHOSPHAZENE CONTAINING PYRROLE GROUP AND ITS CHEMICAL OXIDATIVE POLYMERIZATION

采用热开环聚合物方法,合成反应性无机聚合物聚(二氯)磷腈。通过高分子亲核取代反应合成了含吡咯基团的聚磷腈。并采用NMR(1H,31P)、FT-IR、DSC、TGA、GPC等对聚合物的结构和性能进行了表征。聚合物的分子量Mn=4.1×105,Mw=9.2×105,Mw/Mn=2.24,Tg为-36℃。聚合物具有优良的成膜性能。经过FeCl3氧化交联,聚合物薄膜的颜色由无色透明变成黑色,导电率(σ)达到10-6S/cm,比氧化聚合前提高了近105倍,交联后的聚合物具有优良的热稳定性。

Reactive inorganic polymer-poly(dichloro)phosphazene was prepared through ring-opening polymerization at high temperature. Then a new conductive polyphosphazene containing pyrrole group was synthesized by nucleophilic reaction between the inorganic polymer and N-hydroxyethylpyrrole. The chemical structure and properties of all polymers were characterized by NMR(()~1H,()^(31)P),FT-IR,DSC,TGA and GPC. Using FeCl_3 as oxidiant, the polymer film underwent crosslinking reaction to form conjugated polypyrrole. The experimental results indicate that: the molecular weight of pyrrole-containing soluble polymer are _n=4.1×10~5, _w=(9.2)×10~5(_w/_n=(2.24)), and the T_g is (-36) ℃. The soluble polymer is an excellent film-former. After oxidative reaction, the color of polymer film turned into light black from almost transparent and the conductivity was determined to be (1.7)×10^(-5) S/cm, it is 10~5 times greater than that of the original film. The crosslinked polymer shows high thermal stability.