A series of novel naphthoxazine monomers containing allyl functionalities were synthesized from the reaction of 1-naphthol, 2-naphthol, and 1,5-diheroxynaphthalene with allylamine and formalin. Anothe series of naphthoxazines were similarly prepared by using aniline instead of allylamine for comparison. The chemical structures of these novel monomers were confirmed by IR, H-1 NMR, and elemental analysis. DSC of the aniline- based naphthoxazines; showed an exotherm due to the ring-opening polymerization of oxazine. For allylamine-based naphthoxazines, two exotherms were observed. The first exotherm is attributed to the thermal crosslinking of the allyl group and the second is due to the ring- opening polymerization of oxazine. The thermal cure of the allylamine-based naphthoxazine monomers gave thermoset resins with novel structure comprising of polynaphthoxazine with extended network via the polymerization of allyl- functionalities. Dynamic mechanical analyses and thermogravimetric analyses showed that the thermosets derived from allyl- functional naphthoxazines have high T-g's and stable storage moduli to higher temperature as well as better thermal stability than that of aniline-based naphthoxazines. (c) 2006 Wiley Periodicals, Inc.