The heterogeneous grafting of chitosan with thermoresponsive (oligoethylene)glycol methacrylate (OEGMA)/diethyleneglycol methacrylate (MEO(2)MA)/acrylonitrile (AN) was accomplished by nitroxide mediated polymerization (NMP) with SG1-based BlocBuilder unimolecular initiators. Homogeneous OEGMA/MEO(2)MA/AN terpolymerizations in solution were done first at 120 degrees C to confirm the cloud point temperatures (CPTs) of the thermoresponsive chains that were to be grafted onto the chitosan (CPT tuning from 30 to 65 degrees C was done by varying OEGMA:MEO(2)MA in the initial monomer composition). Grafting was accomplished by reacting chitosan with acryloyl choride and the subsequent acrylamide grafted chitosan was reacted by a 1,2 intermolecular radical addition with BlocBuilder followed by NMP OEGMA/MEO(2)MA/AN monomers. TGA revealed 65-80% of the composite material was due to the grafted polymer. CPTs of the chitosan-graft-poly(OEGMA-ran-MEO(2)MA-ran-AN) reflected those of the homogeneous case, but there was extensive hysteresis as the composite particles could not readily disentangle upon cooling below the CPT. (C) 2016 Elsevier Ltd. All rights reserved.