A siloxane-containing diphenol is synthesized from 1,1,3,3-tetramethyldisiloxane and o-allylphenol, followed by the Mannich condensation with aniline, methylamine, and formaldehyde yielding two siloxane-containing benzoxazines. The onset polymerization temperature of aniline-based benzoxazine is higher than that of the methylamine counterpart. The dynamic mechanical properties of the polybenzoxazines depend on the structure of the starting primary amines. Both polybenzoxazines exhibit one-way dual-shape memory behavior in response to changes in temperature, and they show excellent shape fixity ratios in bending, tension, and tensile stress-strain tests, high shape recovery ratios in bending and tension tests, but relatively low shape recovery ratios in tensile stress-strain test. The network chain segments including the alkylsiloxane units serve as a thermal control switch based on the glass transition temperatures (39 and 53 degrees C) for the polybenzoxazines. (C) 2016Wiley Periodicals, Inc.