The electron-beam irradiation of polymers generates modification effects in the macromolecular structure and material properties. Therefore, irradiation processing is mostly realized in the polymer solid state. In this way, the modification of linear polypropylene may result in long-chain branching of polypropylene macromolecules. The objective of this article is to investigate the effect of a polymer in the molten state during electron-beam irradiation on the macromolecular structure and material properties of polypropylene. For this procedure, a special irradiation vessel (BG3) has been developed in which a rapid transfer of polymer films from the solid state to the molten state and a defined temperature during electron-beam irradiation are realizable. The irradiated samples have been analyzed by high-temperature size exclusion chromatography coupled with a multi-angle laser light scattering detector and differential scanning calorimetry (DSC) measurements. With an increasing irradiation dose, a high reduction of the molar mass and an increasing amount of long-chain branching are found. Compared with irradiation in the solid state, the modification in the molten state leads to a higher degree of branching. The rheological experiments in elongation flow clearly exhibit the existence of long-chain branching. Furthermore, DSC measurements show that the glass-transition temperature and peak temperatures of melting and crystallization decrease. (c) 2005 Wiley Periodicals, Inc.