通过溶液缩聚的方法合成了一种含烷基侧链聚芴基苯并二噁唑聚合物(PBOPFx),讨论了聚合物的光物理性能、热性能和溶解性能.结果表明,在甲基磺酸(MSA)溶液中,PBOPFx紫外吸收显示出最大吸收峰为466 nm左右的蓝光发射,与PBO相比,最大紫外吸收峰和最大荧光发射峰均发生了明显红移,这是由于芴单元的引入,提高了聚合物的共轭程度,加强了对电子的束缚能力.此外,比较了PBOPFx在320 nm处和430 nm处激发得到的荧光发射光谱,预测聚合物中存在两种共轭单元,通过测定氧化还原曲线以及讨论stokes位移,验证了这个假设,但是由于两种共轭单元并没有出现明显的分离现象,同时还伴有电子传输杂化,致使PBOPFx主要显示出共轭长度大的单元的吸收和发射.另外由于芴单元中烷基侧链的存在,聚合物(PBOPFx)的热稳定性远低于聚亚苯基苯并二噁唑聚合物(PBO),起始分解温度在350℃左右,溶解性方面,PBOPFx有了很大的改善,在大多数有机溶剂中能较好溶解.
A series of new conjugated rigid-rod polymer poly (9,9-alkyl fluorenolbenzo bisoxazole)s (PBOPFx) containing an fluorene and benzobisoxazole structures were synthesized by 4,6-diamino- 1,3-benzenediol dihydrochloride (DAR) and 9,9-dialkyl-2,7-dicarboxyl fluorine, The polymer was characterized by the elemental analysis, 1H-NMR, FTIR, thermogravimetric analysis (TGA) and photoluminescence (PL) spectra. The absorption and photoluminescence spectra of the polymers were also studied. The protonated PBOPFx in methanesulfonic acid solutions exhibits a blue emission with a peak at 466 nm or so. In contrast with that of PBO, the maximal emissions spectra and absorption spectra of PBOF red-shifted due to the introduction of the fluorene group which enhanced effective conjugation of polymer structure unit. In addition, emission spectrum of PBOPFx at 320 nm and 430 nm were compared, the Oxidation-reduction curve is observed, and at last that PBOPFx solution has two conjugated units was verified, but two conjugated units did not show a clear separation, electronic transmission occurred in hybrid, so PBOPFx mostly showed the absorption and emission of the main conjugated unit. Also as a result of existence of alkyl side chains in fluorene unit, the thermal stability of polymers (PBOPFx) is lower than polyphenylene Benzodiazepine oxazoline (PBO)polymer, the initial decomposition temperature is about 350℃, but in the respect of dissolved character, PBOPFx has a great improvement, can well dissolved in most organic solvents.