Hybrid inorganic/organic diblock copolymers. Nanostructure in polyhedral oligomeric silsesquioxane polynorbornenes

Our main approach to the synthesis and study of hybrid organic/inorganic materials involves incorporating nano-size inorganic polyhedral oligomeric silsesquioxane (POSS) clusters into various polymeric resins. A typical POSS cluster is a discrete silicon and oxygen framework solubilized with organic groups and contains a single reactive site. This lone site of reactivity is used to covalently attach the inorganic macromers pendent to a polymer backbone without causing any crosslinking. This strategy permits the synthesis of melt processable, linear hybrid polymers containing pendent inorganic clusters, and allows us to study the effect these clusters have on chain motion, polymer properties and morphology. The synthesis of norbornenyl-based (POSS) macromers, their ring opening metathesis copolymerizations with varying amounts of norbornene, and analysis of the effect of the pendent POSS group is presented. Ring opening metathesis polymerization permits the easy synthesis of both random and diblock copolymers. Transmission electron microscopy (TEM) clearly images POSS-rich domains against the POSS-free regions. Major differences in polymer morphology are observed as the amount of inorganic POSS is varied, between random and diblock copolymers, as well as between polymers that differ only in the solubilizing cycloalkyl groups on the POSS cluster.