A general strategy for access intrinsically antioxidant polyolefins.

Abstract

The long-term stability of various polyolefins relies on antioxidants. Traditional methods such as physical blending or chemical modification often suffer from non-uniform dispersion, migration, or lack of universality, especially for ultra-high molecular weight polyethylene (UHMWPE). Developing a general strategy to access various polyethylene types bearing intrinsically antioxidant properties (defined as polyolefins with antioxidant properties produced via polymerization, without postpolymerization antioxidant addition) remains a challenge. Here, we present a Catalyst-Enabled Antioxidation Strategy (CEAS) using phenolic hydroxy-functionalized dual-functional catalysts that both catalyze polymerization and provide antioxidant capacity, enabling the production of various types of intrinsically antioxidant polyolefins. We further develop enhancement strategies via auxiliary antioxidants and biomass-supported heterogeneous catalysis to boost antioxidant properties. This approach ensures uniform dispersion, overcomes processing limitations, retains mechanical properties, and enhances antioxidant performance. Notably, CEAS-synthesized UHMWPE demonstrates resistance to oxidation during demanding processing such as high-temperature spinning and radiation-induced crosslinking.