9,9-二(丙酸六氟丁酯)芴共聚物的合成及荧光性能

采用迈克尔加成反应合成了含氟芴单体2,7-二溴-9,9-二(丙酸六氟丁酯)芴(FHFBP),进一步采用铃木反应制备了不同FHFBP结构单元含量的9,9-二(丙酸六氟丁酯)芴-9,9-二辛基芴共聚物(PF8FHFBP)。通过红外光谱、核磁氢谱、紫外光谱和荧光光谱等方法对其结构和性能进行了表征。结果表明,成功合成了相对分子质量较高的含氟聚芴PF8FHFBP,并且在甲苯、四氢呋喃(THF)和氯仿等常用的有机溶剂中具有良好的溶解性。含氟侧链的引入有效地提高了聚合物的疏水性,但使得波长440 nm处聚芴的荧光峰渐渐消失,在530 nm附近出现了1个新的峰。可能是含氟侧链的引入使聚合物侧链产生结晶现象,主链之间更加致密的堆砌产生出激基缔合物,通过不同浓度共聚物溶液的荧光光谱与共聚物的差示扫描量热测试作了进一步分析讨论。

Synthesis and Photoluminescene of Poly[(9,9-bis(hexafluorobutylpropanoate)-2,7-fluorene)-co-2,7-(9,9-dioctylfluorene)]Copolymers

2,7-Dibromo-9,9-bis(hexafluorobutylpropanoate)fluorene was synthesized by Michael addition reaction,and poly[(9,9-bis(hexafluorobutylpropanoate)-2,7-fluorene)-co-2,7-(9,9-dioctylfluorene)]copolymers with different contents of the 9,9-bis(hexafluorobutylpropanoate)fluorene structural unit were synthesized through Suzuki coupling.The structure and properties of polymers were characterized by FT-IR,1H-NMR,ultraviolet-visible spectroscopy and photoluminescence spectroscopy.The results show that fluorine-containing polyfluorenes with high molecular weight were successfully synthesized.The copolymers have good solubility in common organic solvents such as toluene,THF and chloroform.The hydrophobicity of copolymers is increased with the introduction of fluorine-containing side chains.And the fluorescence spectra of the copolymers show that the fluorescent emission peak at 440 nm of the polyfluorene structural unit disappears,and a new fluorescent emission peak at 530 nm appears after the introduction of the fluorine-containing side chain.This new emission peak was supposed to be caused by the formation of excimer arising from the denser packing between polyfluorene backbones,which was induced by the introduction of the fluorine-containing side chains and the crystallization of the side chains.This phenomena were further investigated by the fluorescence spectra of PF8FHFBP with different concentrations in THF solution and DSC results.