新型荧光超支化聚苯醚的合成与性能研究

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389nm和443nm。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393nm和450nm。

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

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 443nm, 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 7nm. In addition, the absorption spectrum of 9-anthracenemethanol fortuitously overlaps the emission spectrum of HPPO-OH, and the emission at about 365nm from HPPO-OH was not observed in the emission spectrum of FHPPO, which suggests that FHPPO possesses a hybridstructure 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.