Polymerization of silyl ketenes using alkoxide initiators: a combined computational and experimental study

The atomic composition and chemical structure of polymers is fundamental to dictating properties and applications. While much work has addressed controlling pendant group functionalities and polymer molecular weight, much less work has focused on novel polymer backbone chemistries. Herein we report experimental and computational investigations of the polymerization of triisopropyl silyl (TIPS) ketene, and detail products formed. TIPS ketene reacts with an alkoxide initiator to give an enolate intermediate that propagates through either the carbon or oxygen atom, giving multiple functional groups in the resulting polymer backbone. This work indicates that silyl ketenes are suitable monomers for chain growth polymerizations, and that they can polymerize through both the CC and CO to prepare multiple polymer functionalities from a single monomer.