Unsaturated polyamines having hydroxyl groups were synthesized by polymerization of a bifunctional vinylepoxide, 1,4-bis(1-methyl-2-vinylepoxyethyl)benzene (1), and aliphatic amines in the presence of a Pd(0) catalyst. The polyaddition was carried out for 24 h at 90 degrees C in dioxane. Among the phosphine ligands employed, bis(2-diphenylphosphinophenyl)ether (DPEphos) was most effective and gave polyamines with high molecular weight. Benzylamine and piperazine were appropriate nucleophiles and the corresponding polyamines were obtained in moderate to high yields, the number-average molecular weights (M-n) of which were high (M-n 29,000-33,000). The polyaddition between 1 and anilines was not successful. (C) 2008 Wiley Periodicals, Inc.