【作者】 王娟；

【导师】 刘福德；

【作者基本信息】 天津理工大学 ， 药物化学， 2012， 硕士

【摘要】 聚噻吩衍生物具有优良的环境稳定性、可加工型及电化学性质，在聚合物光伏电池等方面有着极其广泛的应用前景，然而，作为聚合物光伏材料聚噻吩衍生物目前仍存在光电转换效率低的问题。研究表明聚合物光伏电池光电转换效率与作为给体材料的聚噻吩衍生物的带隙及ELUMO能量有关。因此设计并合成新型结构聚噻吩衍生物并测定其光电性能对筛选优良光伏电池给体材料具有重要意义。本论文将联苯、偶氮苯结构引入聚合物共轭链中合成得到新型聚噻吩衍生物，另外合成得到交联化聚噻吩衍生物，并测定其光电性能。具体研究内容如下：1.以4,4′-二溴联苯为原料，经Suzuki偶联反应，得4,4′-二（2-噻吩基）联苯；以4,4′-二溴联苯为原料，经混酸硝化得到2-硝基-4,4′-二溴联苯，2-硝基-4,4′-二溴联苯经Suzuki偶联反应得到2-硝基-4,4′-二（2-噻吩基）联苯。上述噻吩基联苯单体经三氯化铁氧化聚合，得噻吩基联苯系列聚噻吩衍生物。2.以对氨基乙酰苯胺为原料，经氧化酸解、Sandmeyer反应得4,4′-二溴偶氮苯，4,4′-二溴偶氮苯经Suzuki偶联反应得到4,4′-二（2-噻吩基）偶氮苯，再经三氯化铁氧化聚合得偶氮类聚噻吩衍生物。3.以噻吩和2-噻吩甲醛为原料，经傅克反应得交联剂三（2-噻吩基）甲烷。交联剂与3-己基噻吩交联后再经DDQ氧化，得交联化聚噻吩衍生物。所述噻吩衍生物及交联剂单体经IR、1^H NMR等进行结构表征，表明结构正确；利用扫描电镜SEM对所述聚合物形貌进行表征；利用紫外-可见吸收光谱、荧光光谱、光致发光图谱对所述聚合物光学性能进行表征；利用循环伏安曲线表征所述聚合物的电化学性能，并得到了聚合物带隙Eg、轨道能级值E_LUMO。更多还原

【Abstract】 Polythiophene derivatives have good electrochemical properties, environmental stabilityand processability, they have an extremely wide application prospect in biomedicine field,polymer photovoltaic materials.However, polythiophene derivatives for polymer photovoltaicmaterials still exist the problem of low photoelectric conversion efficiency which is inrelevance with the band gap and LUMO orbital energy of the donor material.It is significantto design and synthesis polythiophene derivatives with novel structure,and to measure theiroptical and electrical properties for selecting excellent photovoltaic materials.In the paper several novel polythiophene derivatives with biphenyl and azophenyl in theconjugated chain of polythiophene derivatives were synthesized and cross-linkedpolythiophenes were synthesized too. The optical-electrical properties of all the abovecompounds were measured.The specific research is as follows:With4,4′-dibromobiphenyl as basic materials,4,4′-di(2-thieyl)biphenyl was synthesizedvia Suzuki coupling reaction,and4,4′-di(2-thienyl)-2-nitrobiphenyl was synthesized vianitration and Suzuki coupling reaction. the two biphenylyl-thiophene derivatives werepolymerized by chemical oxidative polymerization with ferric chloride as oxidizing reagent tosynthesize polythiophenes containing biphenyl in the conjugated chain.With p-aminoacetanillide as raw material,4,4′-di (2-thienyl) azobenzene was synthesizedvia oxidation, acid hydrolysis, Sandmeyer, and Suzuki coupling reaction. Poly[4,4′-di(2-thienyl)azobenzene] was synthesized by chemical oxidative polymerization with ferricchloride as oxidizing reagent.With thiophene and2-thiophenecarboxaldehyde as basic materials, tri(2-thienyl)methanewhich is used as crosslinker was synthesized by phosphorus pentoxide as dehydrator.Thecrosslinker was crosslinked with3-hexylthiophene, then conjugated cross-linkedpoly(3-hexylthiophene) was prepared with DDQ as oxidant.All the thiophene derivatives and the cross-linker were characterization by IR and1H-NMR.The morphology of the polymers were characterized by SEM;the optical propertieswere characterized by UV-vis and fluorescence spectroscopy;the electrochemical propertieswere recorded by Cyclic voltammetry, and the band gap and orbital energy were calculated.更多还原