Reversible cross-linking reactions of alkoxyamine-appended polymers with low glass transition temperature (T-g) were successfully carried out under bulk conditions. The low-T-g polymers with alkoxyamine units in the side chains were synthesised by radical copolymerisation of 2-ethylhexyl acrylate and two kinds of alkoxyamine-containing acrylate monomers. By heating the low-Tg polymers under bulk conditions at 100 C, cross-linked polymers were formed by radical exchange reactions between alkoxyamine units, and a transition from a liquid-like flowable polymer state to a rubber-like polymer state was confirmed. A de-cross-linking reaction was also accomplished by radical exchange reactions between the cross-linked polymers and an added alkoxyamine-containing small molecule or stable nitroxyl radical, which resulted in transition to the flowable state again. The structural transition between low-Tg linear polymers and cross-linked polymers were characterised by H-1 and C-13 NMR spectroscopy, Fourier transform infrared spectroscopy, rheology measurement, swelling experiment, and gel permeation chromatography measurement. (c) 2014 Elsevier Ltd. All rights reserved.