Synthesis of Polyarylene sulfonium as a Novel Polymer and Its Properties based on the Hyper-polarizedpi-Conjugate Structure

以芳基亚砜为原料，通过亚砜-酸反应合成了聚芳砜基或烷基4-（苯硫基）苯锍三氟甲磺酸盐。研究了所得聚锍盐的亲核反应，以阐明其化学反应性。锍盐与亲核试剂如卤离子的脱烷基化有效地发生以产生聚（亚芳基硫醚），这也与相应的单体锍盐的受控反应进行比较。动力学分析表明，通过紫外-可见光谱表明，脱烷基化进行定量转化硫醚键从锍之一。卤离子脱烷基反应速率常数的顺序为I > Br > CL。苯允许与甲烷亚磺酸钠在三氟甲烷磺酸中反应。首先通过简单的一步合成得到了含硫基团的苯撑聚合物。我们还发现许多硫鎓化合物是通过硫化物和醚的过酸化反应直接合成的。新型硫鎓化合物的性质正在研究中。

Poly[ary] or alkyl 4-(phenylthio)phenylsulfonium trifluoromethanesulfonate]s were synthesized by a sulfoxide-acid reaction from the corresponding arylsulfoxides. The nucleophilic reaction of the resulting poly(sulfonium) salts were investigated in order to elucidate the chemical reactivity. The dealkylation of the sulfonium salts with a nucleophile such as halide ions takes place effectively to yield poly(arylene sulfide), which is also compared to the controlled reaction of the corresponding monomeric sulfonium salts. Kinetic analysis by means of UV-vis spectroscopy reveals that the dealkylation proceeds quantitatively to convert to the thioether bond from the sulfonium one. The reaction rate constants of the dealkylation by the halide ions are in the order of I > Br > CLWe developed the direct synthesis of polysulfonium ion. Benzene allows to react with sodium methanesulfinate in trifluoromethane sulfonic acid. First phenylene polymers linked by sulfonium group were obtained by the simple and one-post synthesis. We also found that many sulfonium compounds were synthesized by the superacidified reaction of sulfides and ethers as a direct synthesis of sulfonium derivatives. The properties of novel sulfonium compounds are investigated in progress.