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A new class of polybenzoxazine/POSS nanocomposites with network structure is prepared by reacting multifunctional vinyl-terminated benzoxazine POSS (VBa-POSS) with virlyl-teminated benzoxazine monomers (VBa) at various compositional ratios.Octafunctional cubic silsesquioxane (VBa-POSS) is used as a curing agent, which is synthesized from through octa-phenol POSS with formaldehyde and allyl amine.