醋酸丙炔酯低聚物的合成及其湿敏性

采用新的过渡金属钯σ 键合炔酯单体络合物 Pd(C≡CCH2 OOCCH3 ) 2 (PPh3 ) 2 ](PPA) ]作为催化剂 ,合成了主链含π 共轭结构、可溶的醋酸丙炔酯低聚物 (OPAT) ,其重均分子量为 4 50 0 ,聚合度约为 4 5.研究了这一新聚合反应的特征、动力学行为和产物的湿敏特性 .聚合反应的表观速率方程为 :Rp=kpPAT]1.5PPA]1.5,其中表观速率常数kp=6 58× 1 0 -4 L2 mol-2 s-1,表观活化能为 1 1 0 2kJ/mol.低聚物经无水三氯化铁掺杂后 ,在几乎全部湿度范围内 (RH % :1 1 %～ 96% )显示良好湿敏响应 .

SYNTHESIS AND HUMI-SENSITIVITY OF OLIGOMER OF PROPARGYL ACETATE

A π-conjugated soluble oligomer of propargyl acetate(OPAT) was synthesized with a novel palladium acetylide catalyst Pd(C≡CCH-2OOCCH-3)-2(PPh-3)-2](PPA). Its molecular weight (-w) is 4500. Some features and kinetic behavior of PAT polymerization with PPA catalyst are described and discussed. The overall polymerization activation energy was found to be 110\^2kJ/mol and the rate equation can be expressed as R p=k p\\+\{1.5\}\\+\{1.5\},where k\-p=6 58×10\+\{-4\}L\+2mol\+\{-2\}s\+\{-1\}.The oligomer (OPAT) doped with a solution of FeCl\-3 in THF exhibits humi\|sensitivity. The impedance of doped OPAT(DOPAT) varies about two orders of magnitude (10\+6～10\+4Ω), when relative humidity(RH%) changes from 11% to 96%.