In this work, novel octadecyl amine-montmorillonite (ODA-Mt) copolymer nanocomposites were synthesised by interlamellar microwave-assisted complex-radical copolymerisation. The microwave method is found to be a facile and highly effective means to clay polymer nanocomposites (CPNs) that provide a higher rate of interlamellar copolymerisation and conversion of micro- and nanoparticles. The chemical and physical structures, surface morphologies and thermal behaviours of the prepared CPN were investigated by FTIR and H-1 (C-13) NMR spectroscopy, XRD, SEM, TEM, thermal (DSC and TGA) and dynamic mechanical (DMA) analysis methods. That copolymerisation was accompanied by in situ complex formation (charge transfer complex and H-bonding similar with known copolymerisation without ODA-Mt) and the intercalative amidisation of anhydride units with the octadecyl amine groups of Mt was determined. These observed chemical and physical interfacial interactions as effective in situ processing play an important role in the formation of hybrid systems and micro- and nanocomposites with stimuli-responsive NIPAm polymer chains. (C) 2014 Elsevier B.V. All rights reserved.