芘标记有机硅聚合物的合成和荧光氧猝灭特性

Synthesis and Fluorescence Quenching Behaviors of Pyrene-labelled Polysiloxanes

合成了丙烯酸芘甲酯、二甲基乙烯基芘甲氧基硅烷、10-十一碳烯酸芘甲酯三种含芘单体,用硅氢加成方法制备了一系列含芘封端侧链的聚二甲基硅氧烷光-氧敏感高分子,并分别用四乙氧基硅烷和甲基含氢硅油A交联.对基于上述高分子的压力敏感涂料(PSP)的荧光氧猝灭和光物理行为进行了研究.结果表明,芘封端的侧基结构和交联剂对此类PSP的性能,包括激基缔合物荧光强度和氧猝灭灵敏度、Stern-Volmer关系的线性和贮存稳定性等都有明显的影响.含长碳链芘甲酯侧链的聚合物显示较高激基缔合物荧光强度和氧灵敏度;以甲基含氢硅油A作为交联剂,既能提高PSP的储存稳定性,又能提高氧猝灭灵敏度.

A series of fluorescent polymers composed of polydimethylsiloxane（ PDMS） with a pyreneterminated side chain were synthesized and characterized. The oxygen quenching of the fluorescence emission and the photophysics behaviors of the pressure sensitive paints（ PSP） based on these polymers were investigated. The results showed that the side chain structure of the polymer not only affected significantly the emission intensity,oxygen quenching sensitivity and Stern-Volmer linearity,but also the storage stability of the PSP. The polymers with a longer alkylpyrene side chain terminated by pyrene chromosphere showed higher excimer emission intensity and oxygen quenching sensitivity. Otherwise,the crosslinker for the polymer filming also has some influence on the PSP properties. When tetraethyl orthosilicate（ TEOS） was added for the polymer crosslinking,the storage stability of the PSP decreased obviously. But,when polyhydromethylsiloxane（ PHMS A） was used,the PSP showed higher oxygen quenching sensitivity and storage stability. All of the data indicated that the pyrene- terminated alkyl side chain structure of the polymers is favorable to the stable aggregation in the condensed state,at the same time,inhibits the aggregation of the pyrene chromospheres,the PSP should have high emission intensity,oxygen quenching sensitivity,Stern-Volmer linearity and storage stability.