Design and preparation of a crosslinkable, oil-resistant, and bio-based elastomer from fumarate

Abstract

Poly(diethyl fumarate-co-methoxyethyl acrylate-co-vinyl chloroacetate) (PDEFMV), a novel bio-based elastomer with a saturated structure, was synthesized via redox emulsion polymerization. The glass-transition temperatures of PDEFMV, adjusted through the variation of the diethyl fumarate-to-methoxyethyl acrylate feeding ratio, ranged from −36.1 to −14.8 °C. The number-average molecular weights of PDEFMV ranged from 384,000 to 46,000 g/mol. In designing the molecular structure, vinyl chloroacetate was used to provide active sites for subsequent vulcanization and crosslinking. The active chlorine groups within the PDEFMV chain reacted with the crosslinking agent trithiocyanuric acid under high temperature and pressure to form a nonsulfur crosslinked three-dimensional network structure. To achieve the desired properties, carbon black (CB, N330) was incorporated to reinforce PDEFMV, leading to the formation of PDEFMV/CB composites. A comprehensive study was conducted on the high-temperature oil resistance of PDEFMV/CB composites. Following immersion in IRM903 oil at temperatures of 150 and 200 °C for 72 h, the mass and volume changes in PDEFMV/CB were lower than those observed in commercially available acrylate rubber (AR)/CB, indicating that PDEFMV exhibited superior oil resistance. Furthermore, the aging characteristics and mechanisms of oil resistance in the PDEFMV/CB and AR/CB composites were investigated at different temperatures (150, 200, and 250 °C). The results provide insights into the operational temperature ranges suitable for PDEFMV/CB and offer valuable guidance for potential industrial applications.