The rapid, living, anionic polymerization of 2‐vinylnaphthalene at ambient temperature: Characterization of an n‐butyllithium/tetrahydrofuran system in 1,2,3,4‐tetrahydronaphthalene

We report the first well‐controlled room temperature anionic polymerization of 2‐vinylnaphthalene (2‐VNP), using alkyllithium (RLi) initiators. The nucleophilicity and solubility of the RLi as well as that of the 2‐vinylnaphthalenyllithium (VNPLi) and poly(2‐vinylnaphthalenyl)lithium (PVNPLi) propagating species were found to be very important factors in this reaction. An initiator system composed of n ‐butyllithium ( n ‐BuLi) with tetrahydrofuran (THF) in 1,2,3,4‐tetrahydronaphthalene (THN) was determined to be the most effective of the various systems examined. The n ‐BuLi/THF complex initiates polymerization and the resulting VNPLi/THF and PVNPLi/THF complexes act as propagating species at room temperature. These species offer adequate nucleophilicity and stability without promoting side reactions. As a result, rapid anionic polymerization was achieved. Various poly(2‐VNP) products with well‐defined polymeric chain structures were synthesized by this process at room temperature.