Catalyst Influence on the Crystallization Behaviors and Mechanical Properties of Polyethylene Vitrimers

Polyethylene (PE)-derived vitrimers represent a promising class of reprocessable materials that combine the desirable properties of semicrystalline polyolefins with dynamic covalent networks. In this study, we investigate the influence of transesterification catalyst identity and loading on the crystallization behavior and mechanical properties of vitrimers formed from maleated linear low-density PE crosslinked with diglycidyl ether bisphenol A (DGEBA). Four catalysts, including zinc-(II) stearate, zinc-(II) acetylacetonate, zinc-(II) acetate, and manganese-(II) acetate, were studied across a range of loadings. Through thermal and mechanical characterization, we demonstrate that catalyst selection can play a critical role in controlling network formation and crystallization kinetics, in part due to their ability to act as nucleating agents and influence crystallization activation energies across varying cooling rates. These insights contribute to a deeper understanding of how dynamic chemistry of vitrimers can be leveraged to impact processing conditions and mechanical performance of semicrystalline polyolefin systems.