邻苯二胺及其金属配位型含氟聚酰胺磺酰胺的合成与荧光性能

采用溶解聚合法使β-四氟乙烷磺内酯分别与邻苯二胺、二氯-邻苯二胺合锌(Ⅱ)和二氯-邻苯二胺合镉(Ⅱ)开环缩聚,制备出邻苯二胺型和金属配位邻苯二胺型含氟聚酰胺磺酰胺聚合物。通过红外光谱、核磁共振氢谱、电感耦合等离子体发射光谱仪、凝胶渗透色谱等手段,确定其分子链为同时含有酰胺、磺酰胺、氟碳基团、芳环和金属离子的特殊结构;采用紫外-可见分光光度计和荧光分光光度计分析表明:邻苯二胺型含氟聚酰胺磺酰胺具有高荧光量子产率0.65,Cd2+配位后荧光量子产率保持0.65,而络合Zn2+的邻苯二胺型含氟聚酰胺磺酰胺的荧光量子产率降低为0.39,Zn2+对该类聚合物的荧光性能具有选择性。

Synthesis and Fluorescent Properties of o-Phenylenediamine and Its Metal Coordination-Complexes Based Fluoropoly(amide-sulfonamide)s

Novel fluorine-containing polymers,o-phenylenediamine and its metal coordination-complexes based fluoropoly(amide-sulfonamide)s were synthesized for the first time by solution polycondensation of β-hydroxytetrafluoroethanesulfonic acid sultone(TFE-sultone)and o-phenylenediamine, Zn(o-PDA)Cl_2 and Cd(o-PDA)Cl_2.Chemical structures of the obtained F-PASAs were characterized by GPC,FT-IR,~1H-NMR and ICP-AES in detail.Fluorescence quantum yields were investigated by UV-Vis and Fluorospectrophotometer.Results show that these functionalized fluoropolymers possess distinctive structures as well as unique fluorescent properties.o-Phenylenediamine based fluoropoly(amide-sulfonamide)S show a high fluorescence quantum yield of 0.65,and Cd(o-PDA)Cl_2 based fluoropoly(amide-sulfonamide)S display the same fluorescence quantum yield,while fluorescence quantum yield of Zn(o-PDA)Cl_2 based ones are decreased to 0.39,which indicate the negative influence of Zn~(2+) on fluorescence quantum yield.