Living cationic polymerization of vinyl ethers with a naphthyl group: Decisive effect of the substituted position on naphthalene ring

Living cationic polymerization of a vinyl ether with a naphthyl group [2‐(2‐naphthoxy)ethyl vinyl ether, βNpOVE] was achieved using base‐assisting initiating systems with a Lewis acid. The Et_1.5AlCl_1.5/1,4‐dioxane or ethyl acetate system induced the living cationic polymerization of βNpOVE in toluene at 0 °C. The living nature of this reaction was confirmed by a monomer addition experiment, followed by ¹H NMR and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry (MALDI‐TOF‐MS) analyses. In contrast, the polymerization of αNpOVE was not fully controlled; under similar conditions, it produced polymers with broad molecular weight distributions. The ¹H NMR and MALDI‐TOF‐MS spectra of the resultant poly(αNpOVE) revealed that the products had undesirable structures derived from Friedel–Crafts alkylation. The higher reactivity of αNpOVE in electrophilic substitution reactions, such as the Friedel–Crafts reaction, was attributable to the greater electron density of the naphthyl ring, which was calculated based on frontier orbital theory. The naphthyl groups significantly affected the properties of the resultant polymer. For example, the glass transition temperatures (T_g) of poly(NpOVE)s are higher by approximately 40 °C than that of poly(2‐phenoxyethyl vinyl ether). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012