含膦酰杂菲侧基的4-炔基苯甲酸酯对聚叠氮缩水甘油醚点击接枝反应及其聚集诱导发光增强性能  

SYNTHESIS OF PHOSPHAPHENANTHRENE-CONTAINING 4-ETHYNYLBENZONATE GRAFTED GLYCIDYL AZIDE POLYMERS BY CLICK CHEMISTRY AND THEIR AGGREGATIONINDUCED EMISSION ENHANCEMENT PROPERTIES

作　　者：许亮鑫[1] 朱宇峰[1] 申进波[1] 石建兵[1] 佟斌[1] 支俊格[2] 董宇平[1] 

机构地区：[1]北京理工大学材料科学与工程学院,北京100081 [2]北京理工大学理学院,北京100081

出　　处：《高分子学报》2011年第7期740-744,共5页Acta Polymerica Sinica

基　　金：国家自然科学重点基金(基金号20634020);北京理工大学基础研究基金(基金号20070442004)资助项目

摘　　要：在CuI催化作用下,实现了含膦酰杂菲侧基的4-炔基苯甲酸酯(MAT4)与聚叠氮缩水甘油醚(GAP)的点击接枝反应,得到新型接枝聚合物G-M4,并由红外谱图确定了等摩尔反应.由于分子内含膦酰杂菲基团侧基之间较强的π-π和极性共同相互作用以及聚醚主链的柔顺性,使G-M4分子链内侧基之间相对空间位置比较固定,分子链构型规整,使分子链之间的排列趋于规整,分子的内旋转受到限制,进而降低了热运动所引起的能量损失,导致聚合物的荧光强度明显增加,呈现具有聚集诱导发光增强特性.同时由于G-M4分子链之间采取J-聚集,使分子链之间趋于规整聚集,部分分子链之间形成超分子结构,当沉淀剂正己烷含量超过70%时,在荧光光谱长波区域出现归属于超分子结构的发射峰,并随正己烷含量增加,该荧光强度增强.Phosphaphenanthrene-containing 4-ethynylbenzonate（MAT4） was grafted to glycidyl azide polymer（GAP） by click chemistry in the presence of CuI as catalyst.FT-IR analytical results confirmed the structure of the grafting polymer（G-M4） and revealed the click reaction between GAP and MAT4 in equal molar ratio.Compared with MAT4,the UV-Vis absorbance and the photoluminescence strength of G-M4 in dichloromethylene solution are obviously increased because the formation of triazole induces the increasing of total conjugated degree.When G-M4 molecules aggregate to a certain degree in a mixture of dichloromethylene and n-hexane,the photoluminescence strength of G-M4 proportionally increases,which shows obvious aggregation-induced emission enhancement（AIEE） property because the aggregation state of G-M4 restricts the intramlecular rotation of phosphaphenanthrene groups based on the π-π stacking and polarity interaction between the molecules.Due to J-aggregation,supramolecular structure between triazole rings in G-M4 and phosphaphenanthrene groups in adjacent G-M4 based on donor-accept interaction is formed.When the content of n-hexane is over 70%,the photoluminescence spectra of G-M4 obviously show two peaks,which are attributed to photoluminescence emission of intra-and extra-chains of G-M4,respectively.This novel phenomenon may enable the polymer to find applications in chemosensor,optical display and rewritable optical media.

关 键 词：膦酰杂菲 苯乙炔衍生物 聚叠氮缩水甘油醚 点击化学 聚集诱导发光增强 

分 类 号：O631.3[理学—高分子化学]