Vanadium-Catalyzed Terpolymerization of ?,?-Dienes with Ethylene and Cyclic Olefins: Ready Access to Polar-Functionalized Polyolefins

?,?-Dienes are an important class of monomers due to their utility in the synthesis cyclopolyolefins and reactive polyolefin intermediates. In this contribution, terpolymerization two ?,?-dienes (i.e., 1,5-hexadiene 1,7-octadiene) with ethylene various cyclic olefins [i.e., norbornene (NB), 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD)] catalyzed by a chelated imido vanadium complex has been examined. The ENB DCPD diene termonomers provide additional sites for post-polymerization functionalization. Vanadium-catalyzed investigated yields polyolefins high molecular weight (Mw up 200 × 103 g mol–1), unimodal narrow distribution, subambient glass transition temperatures (?30 < Tg °C ?3), proper content C?C bonds. Comprehensive NMR investigation obtained polymers revealed that subtle changes ?,?-diene size have effects on numerous combinations insertion paths (ring closure vs ring opening), from which different repeating units bond side or main polymer chain installed. Finally, poly(ethylene-ter-1,5-hexadiene-ter-NB) was subjected thiol-ene addition using thioglycolic acid, methyl thioglycolate, N-acetyl-l-cysteine access polar-functionalized degree functionalization properties dependent thiol substitution.