Effects of Branches on the Crystallization Kinetics of Polypropylene-g-Polystyrene and Polypropylene-g-Poly(n-butyl acrylate) Graft Copolymers with Well-defined Molecular Structures

Effects of branches on the crystallization kinetics of polypropylene-g-polystyrene (PP-g-PS) and polypropylene-gpoly( n-butyl acrylate) (PP-g-PnBA) graft copolymers with well-defined molecular structures were systematically investigated by DSC. The Avrami equation was used to analyze the isothermal crystallization process, while the analysis of nonisothermal crystallization process was based on the Jeziorny-modified Avrami model and Mo model. The kinetics results of isothermal and nonisothermal crystallization verified the peculiar effects of branches on the crystallization process of PP backbones in PP-g-PS and PP-g-PnBA graft copolymers: on one hand, the interaction between branches (pi-pi interaction between PS branches, or dipole-dipole interaction between PnBA branches) restrained the mobility and reptation ability of the PP backbones, which hindered the crystallization process; on the other hand, the heterogeneous nucleation effect resulting from the branched structure and fluctuation-assisted nucleation mechanism (caused by microphase separation between the PS or PnBA rich phase and the PP rich phase) became more pronounced with increasing branch length, which facilitated the crystallization process