Development of Novel Halosilane Reagents and Applications to Polymer Materials

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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.