Anionic Synthesis of Functionalized Polymers

The synthesis of well-defined functionalized polymers is an important area of research due to their wide array of applications. The work presented herein can be divided into three categories: a) functional initiator synthesis; b) chain-end and in-chain functionalization and c) functional monomer synthesis and polymerization. All three methods involve both anionic polymerization and hydrosilation. In this work, all anionic polymerizations were performed at room temperature in hydrocarbon solvent with an alkyllithium initiator. A functional 4-pentenyllithium initiator was prepared in 70 % yield and was used for the synthesis of α and α,ω-functionalized polystyrene. 4-Pentenyllithium was used to initiate styrene polymerization in benzene in the presence of 5 equivalents of tetrahydrofuran. Narrow polydispersity indices and good agreement between calculated and observed molecular weights were observed for the methanol-terminated product. α-Triethoxysilyl-functionalized polystyrene was quantitatively prepared by hydrosilation with triethoxysilane and α-4-pentenylpolystyrene. α-4-Pentenyl-ω-silyl hydride