The Intrinsic Mechanochemical Reactivity of Vinyl-Addition Polynorbornene.

Herein we report the discovery of the intrinsic mechanochemical reactivity of vinyl-addition polynorbornene (VA-PNB), which has strained bicyclic ring repeat units along the polymer backbone. VA-PNBs with three different side chains were found to undergo ring-opening olefination upon sonication in dilute solutions. The sonicated polymers exhibited spectroscopic signatures consistent with conversion of the bicyclic norbornane repeat units into the ring-open isomer typical of polynorbornene made by ring-opening metathesis polymerization (ROMP-PNB).

Accessing Siloxane Functionalized Polynorbornenes via Vinyl-Addition Polymerization for CO Separation Membranes.

The vinyl addition polymerization of norbornyl-based monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst -[Ni(CF)(SbPh)]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxane-substituted polymers with molecular weights exceeding 100 kg/mol.