The synthesis of copolymers between lignin and electron poor alkenes is described. Lignin from steam-exploded pine, from steam-exploded straw, and organosolv were used as starting materials. Beforehand, lignins were fully characterized by using elemental analysis, ultraviolet spectroscopy, gel permeation chromatography (GPC), Fourier transform infrared (FTIR), and both(1)H and C-13 nuclear magnetic resonance (NMR) spectroscopy. The synthesis of copolymers was performed using a previously described procedure utilizing calcium chloride and hydrogen peroxide as reagents. FTIR of copolymers showed absorptions due to the presence of both lignin and the electron withdrawing group on the alkene. GPC analysis showed the presence of fractions with high molecular weights: the M-z of lignin from pine was 3729 while the copolymer with methyl acrylate showed M-z = 383790. Differential calorimetry showed the presence of glass transitions in the range of -9 to 4.5degreesC due to the presence of grafted polyalkene chains. When acrylonitrile was used as starting material DSC analysis of the product showed a glass transition at 119degreesC, which can be attributed to grafted polyacrylonitrile chain. Lignin from steam explosion could be a good raw material in the preparation of graft copolymers. Furthermore, lignin from pine gave better results than that from straw. Finally, lignin from steam explosion gave better results than organosolv lignin. These results can be explained on the basis of the structural properties of used lignins. Both UV and C-13 NMR spectra showed that lignin from pine contained a consistent amount of double bonds. (C) 2003 Wiley Periodicals, Inc.