The kinetics of melt grafting acrylic acid (AA) onto linear low density polyethylene (LLDPE) by using reactive extrusion was investigated. The polymeric peroxides (POOP and POOH) generated by electron beam irradiation were used to initiate the graft reaction. The samples taken out from the barrel at five ports along screw axis were analyzed by FTIR. The spectra show that both the graft copolymerization and homopolymerization proceed in two stages: the graft degree (or mass of homopolymer) increases linearly with the reaction time in the initial stage

and then gradually in the second stage. The rate of graft copolymerization Rg is always faster than that of homopolymerization Rh in the present system and the activation energy is 131 kJ•mol1 for graft copolymerization and 127 kJ•mol1 for homopolymeirzation. These results were interpreted in terms of solubility and diffusion of monomer

as well as the reactivity and the concentration of reactive species. The relationships between reaction rate and monomer concentration and peroxide concentration were found to be: Rg  [M]1.46[POOP+POOH]0.53 and Rh  [M]1.08[POOH]0.51

which indicate that the addition of monomer to polymeric radicals is a slow step for the graft copolymerization.