对苯醌二亚胺与3,4-乙撑二氧噻吩共聚物的合成及表征

Synthesis and Characterization of Copolymers Consisting of N,N′-p-Benzoquinonediimine and 3,4-Ethylenedioxythiophene Unit

以N,N′-二氯对苯醌二亚胺、2,5-二甲基-N,N′-二氯对苯醌二亚胺与2,5-二溴-3,4-乙撑二氧噻吩为单体,1,3-二(二苯基膦)丙烷二氯化镍(Ⅱ)为催化剂,采用金属配合物催化法合成了聚(N,N′-对苯醌二亚胺-3,4-乙撑二氧噻吩)和聚(2,5-二甲基-N,N′-对苯醌二亚胺-3,4-乙撑二氧噻吩)两种共聚物。通过红外光谱(FT-IR)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)、X射线衍射(XRD)、紫外分光光度计(UV-Vis)和循环伏安(CV)等测试对其进行了结构表征及性能测试。结果表明,两种共聚物在CF3COOH(TFA)溶液中的UV-Vis最大吸收波长分别在500 nm和511 nm处;氧化还原峰出现在-0.2 V-0.8 V之间;通过碘掺杂后共聚物的电化学窗口拓宽,电化学活性提高。

The π-conjugated polymers of p-benzoquinone diimines and 3,4-ethylenaedioxythiophene （EDOT） were synthesized by metal complex catalysis with Ni （ Ⅱ ） catalyst. The poly （n, n＇-dichloro-benzoquinonediimine-3,4- ethylenedioxythiophene） and poly （ 2,5-dimethyl-N, N＇-dichloro-benzoquinonediimine-3,4-ethylenedioxythiophene） were characterized by 1H-NMR, FT-IR, UV-vis absorption, XRD, gel permeation chromatography （GPC） and cyclic voltammetry. The maximum UV-vis absorption of these polymers appears in the range of 500 nm- 511 nm in CF3COOH solution. CV results suggest that the copolymers have certain electrochemical activity and exhibit redox peaks in the range of -0.2 V-0.8 V. The electrochemical window of doped copolymers with iodine widens evidently, and the electrochemical activity of iodine-doped polymers also is greatly improved as compared with that of the un-doped precursors.