We investigated the dynamics and structure of the aliphatic side chains of a randomly grafted copolymer, obtained through the chemical modification of poly(epichlorohydrin) with potassium 3,4,5-tris(dodecyloxy)benzoate, with solid-state C-13 NMR. Below 283 K, the aliphatic chains partially crystallized in an all-anti conformation. The calorimetric data were compatible with an orthorhombic packing. Below 323 K, the polymer exhibited a columnar mesophase. Spin-lattice relaxation times were determined in this temperature range and at 333 K, that is, in the isotropic phase. In the liquid-crystalline state, some carbons exhibited a double decay in the spin-lattice relaxation, and this was attributed to presence of the liquid-crystalline phase. This hypothesis was supported by a conformational analysis performed by molecular modeling. The activation energies of the relaxation processes in the mesophase were also estimated. (c) 2005 Wiley Periodicals, Inc.