新型荧光超支化聚苯醚的合成与性能研究

Preparation and characterization of a novel fluorescent hyperbranched poly(phenylene oxide)

以9-蒽甲醇为改性单体,通过与末端为酚羟基的超支化聚苯醚发生Mitsunobu反应,制得了末端含蒽生色团的新型荧光超支化聚合物。热重分析(TGA)表明该聚合物具有良好的热稳定性,氮气和氧气环境下5%的热失重温度均约为257℃。在DMF溶液中,该聚合物的吸收光谱和发射光谱均表现出蒽单元的光谱特性,其最大吸收和发射波长分别为389 nm和443 nm。研究还发现,所得荧光超支化聚苯醚在激发-发射过程中发生了分子内能量迁移或转移,表现出了典型的主客体发射体系的特性。该聚合物薄膜的最大吸收和发射波长分别是393 nm和450 nm。

A novel fluorescent hyperbranched poly（phenylene oxide） （FHPPO） was prepared by a Mitsunobu reaction of 9-anthracenemethanol and HPPO-OH using triphenylphosphine and diisopropyl azodicarboxylate as the catalysts in THF. The resulted polyether was characterized by ^1H-NMR, FT-IR, and TGA analyses. It showed good solubility in common organic solvents, such as THF, DMF, CHCl3, and toluene, and exhibited good thermal stability. Study of its optical properties showed the hyperbranched polyether in DMF solution exhibited intense absorption and fluorescence with maxima at 389 and 443 nm, respectively. A red shift for the maxima of absorption and emission was observed in the polymer thin film. In contrast, its absorption band at shorter wavelength corresponding to a π→π^＊ transition from phenoxy units showed a blue shift of about 7 nm. In addition, the absorption spectrum of 9-anthracenemethanol fortuitously overlaps the emission spectrum of HPPO-OH, and the emission at about 365 nm from HPPO-OH was not observed in the emission spectrum of FHPPO, which suggests that FHPPO possesses a hybrid structure based on HPPO-OH host and 9-anthracenemethanol guest motifs with a host-guest emission system. The hyperbranched polyether may be a potential useful blue-emitting material.