Imidazolium ionene segmented block copolymers were synthesized from 1,1'-(1,4-butanediyl)bis(imidazole) and 1,12-dibromododecane hard segments and 2000 g/mol PTMO dibromide soft segments The polymeric structures were confirmed using H-1 NMR spectroscopy, and resonances associated with methylene spacers from 1,12-dibromododecane became more apparent as the hard segment content increased TGA revealed thermal stabilities >= 250 degrees C for all imidazolium ionene segmented block copolymers These ionene segmented block copolymers containing imidazolium cations showed evidence of microphase separation when the hard segment was 6-38 wt% The thermal transitions found by DSC and DMA analysis found that the T-g and T-m of the PTMO segments were comparable to PTMO polymers, namely approximately 80 C and 22 degrees C, respectively In the absence of PTMO soft segments the T-g increased to 27 degrees C The crystallinity of the PTMO segments was further evidence of microphase separation and was particularly evident at 6, 9 and 20 wt% hard segment, as indicated in X-ray scattering The periodicity of the microphase separation was well-defined at 20 and 38 wt% hard segment and found to be approximately 105 and 13.0 nm, respectively, for these ionenes wherein the PTMO soft segment is 2000 g/mol Finally, the 38 and 100 wt% hard segment ionenes exhibited scattering from correlations within the hard segment on a length scale of approximately 2-23 nm. These new materials present structure on a variety of length scales and thereby provide various routes to controlling mechanical and transport properties (C) 2009 Elsevier Ltd. All rights reserved