Abstract: | New heat‐reversibly crystalline poly‐(alkylated phenylene oxide)s are described. the oxidative polymerization of 2,5‐dimethylphenol catalyzed by (1,4,7‐triisopropyl‐1,4,7‐triazacyclononane) copper dichloride produced poly(2,5‐dimethyl‐1,4‐phenylene oxide), which showed heat‐reversible crystallinity with a high melting point at ca. 300°C, although the isomeric polymer, poly(2,6‐dimethyl‐1,4‐phenylene oxide), never recrystallizes once melted. The polymerization of 2,5‐diethylphenol and 2,5‐dipropylphenol gave the polymers consisting of 1,4‐phenylene oxide units; the latter polymer possessed heat‐reversible crystallinity, however, the former one did not. |