In the rubber industry, the substitution of traditional engineering rubbers derived from fossil resources with novel biobased elastomers is considered for sustainable development, which largely relies on a straightforward and environmentally friendly synthesis procedure and the availability of material properties. In the research, semi-biobased elastomers, poly(dibutyl fumarate-co-butadiene)s (PDBFBs), were prepared by redox emulsion polymerization of dibutyl fumarate obtained from fumaric acid esterified with n-butanol and partially petroleumderived butadiene. The microscopic structures of PDBFBs were verified by FTIR, NMR, and GPC analyses. The T g values of PDBFBs were in the range of −73 and −58 °C. Additionally, the reactivity ratios of two comonomers in PDBFBs were evaluated by two methods: the Fineman−Ross and Kelen−Tudos methods. The macroscopic properties of semi-biobased elastomers, such as thermal and mechanical performances, were meticulously regulated via molecular design. To achieve the desired properties, silica was incorporated into the PDBFBs to prepare strong nanocomposites. These nanocomposites displayed adequate tensile strength (14.3−31.6 MPa), adequate elongation at break (338−457%), low rolling resistance, and excellent thermoresistant oxygen aging performance. These results showed that PDBFB nanocomposites possessed quite good properties and had the potential for practical applications. This work provides a facile, efficient, solvent-less green synthesis route to design new-generation promising sustainable engineering elastomers for the rubber industry.

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