Development of Novel Halosilane Reagents and Applications to Polymer Materials

我们开发了新的合成碘和溴硅烷等价物，并研究了它们的化学行为。利用氧基硅烷的反应合成了新型硅基聚合物。研究了所得聚合物的光学和热性能。我们发现二氨基硅烷/MeI和二氨基硅烷/烯丙基溴的混合物表现为二溴硅烷和二碘硅烷的合成当量。它们很容易与环醚反应形成开环的卤硅化产物。发现聚（氢硅氧烷）在1等量烯丙基溴和催化量PdCl2存在下与环醚反应生成聚（溴烷氧基硅氧烷）s，收率高。对得到的聚溴烷氧硅氧烷的进一步反应进行了研究。采用二氢硅和三氢硅的选择性烷氧基化反应合成了以乙烯苯和金刚烷为主链单元的聚合物。这些聚合物分别表现出有趣的光学性质和高耐热性。研究了烷氧基氯硅烷的电化学同偶联和异偶联，选择性地得到了产率较高的烷氧基二烷和三硅烷，且烷氧基硅键完整。采用聚烷氧基乙烯基亲核取代法制备了具有二苯冠荧光基团的硅聚合物。这些聚合物选择性地响应碱和碱土金属离子，以显示其作为离子传感器的潜在应用。这些结果表明，碘硅烷、溴硅烷和烷氧硅烷不仅是有机合成工具的有用试剂，而且是形成功能聚合物的有用试剂。

We developed novel synthetic equivalents of iodo-and bromosilanes and examined their chemical behaviors. Novel silicon-based polymers were synthesized utilizing the reactions of alxoxysilanes. The optical and thermal properties of the resulting polymers were also studied.1. We found that mixtures of diaminosilane/MeI and diaminosilane/allylBr behave as synthetic equivalents of dibromo-and diiodosilanes. They react readily with cyclic ethers to form ring-opened halosilylation products. Poly(hydrosiloxane) was found to react with cyclic ethers in the presence of 1 equiv of allylBr and a catalytic amount of PdCl2 to produce poly(bromoalkoxysiloxane) s in goo yield. Further reactions of the resulting poly(bromoalkoxysiloxane)s were studied.2. Selective alkoxylation of di-and trihydrosilens was applied to the synthesis of polymers with vinylenephenylene and adamantane units in the backbone. These polymers exhibit interesting optical properties and high heat resistance, respectively.3. Electrochemical homo- and hetrerocoupling of alkoxychlorosilanes was studies, which proceeded selectively to give alkoxydi- and trisilanes in good yield with alkoxy-Si bonds intact.4. Silicon polymers having benzocrown fluorophors were prepare by nucleophilc substitution of poly(alkoxysilylenephenylene). These polymers respond to alkali and alkali earth metal ions, selectively, to show their potential utilities as ion-sensors was studied.These results indicate that iodosilane, bromosilane, and alkoxysilane are useful reagents not only for organic synthetic tools but also for the formation of functional polymers.