Development of Novel Halosilane Reagents and Applications to Polymer Materials

我们开发了新的合成的碘-硅烷和溴硅烷的等价物，并检测了它们的化学行为。利用烷氧基硅烷的反应合成了新型硅基聚合物。对所得聚合物的光学和热性能也进行了研究。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等价物。它们很容易与环醚反应，生成开环的卤代硅烷基化产物。聚氢硅氧烷在1当量的烯丙基溴存在下与环醚反应，在PdCl2的催化量下合成了聚溴代烷氧基硅氧烷S。对所得的聚(溴代烷氧基硅氧烷)S的进一步反应进行了研究。将二氢硅烷和三氢硅烷选择性烷氧基化用于合成主链上含有乙烯、亚苯基和金刚烷基团的聚合物。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均偶联和异偶联反应，选择性地得到了烷氧基二硅烷和三硅烷，产率较高，烷氧基硅键完整。通过亲核取代聚烷氧基硅亚苯制备了含苯并冠醚荧光团的硅聚合物。结果表明，碘硅烷、溴硅烷和烷氧基硅烷不仅是有机合成工具的有用试剂，也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.