A novel elastomer poly(diethyl itaconate-co-butyl acrylate-co-ethyl acrylate-co-glycidyl methacrylate) (PDEBEG) was designed and synthesized by redox emulsion polymerization based on bio-based diethyl itaconate, butyl acrylate, ethyl acrylate, and glycidyl methacrylate. The PDEBEG has a number average molecular weight of more than 200,000 and the yield is up to 96%. It is easy to control the glass transition temperature of the PDEBEG, which is ranged from −25.2 to −0.8 °C, by adjusting the monomer ratio. We prepared PDEBEG/CB composites by mixing PDEBEG with carbon black N330 and studied the oil resistance of the composites. The results show that the tensile strength and the elongation at break of the composites with 10 wt% diethyl itaconate can reach up to 14.5 MPa and 305%, respectively. The mechanical properties and high-temperature oil resistance of the composites are superior to that of the commercially available acrylate rubber AR72LS.
In response to increasingly stringent requirements for the sustainability and environmental friendliness of the rubber industry, the application and development of bio-based elastomers have received extensive attention. In this work, we prepared a new type of bio-based elastomer poly(dibutyl itaconate-butadiene) copolymer (PDBIB) nanocomposite using carbon black and non-petroleum-based silica with a coupling agent. Using dynamic thermodynamic analysis (DMTA) and scanning electron microscope (SEM), we studied the effects of feed ratio on dynamic mechanical properties, micro morphology, and filler dispersion of PDBIB composites. Among them, silica-reinforced PDBIB60 (weight ratio of dibutyl itaconate to butadiene 40/60) and carbon black-reinforced PDBIB70 (weight ratio of dibutyl itaconate to butadiene 30/70) both showed excellent performance, such as tensile strength higher than 18 MPa and an elongation break higher than 400%. Compared with the widely used ESBR, the results showed that PDBIB had better rolling resistance and heat generation than ESBR. In addition, considering the development of green tires, we compared it with the solution polymerized styrene–butadiene rubber with better comprehensive performance, and analyzed the advantages of PDBIB and the areas to be improved. In summary, PDBIB prepared from bio-based monomers had superior performance and is of great significance for achieving sustainable development, providing a direction for the development of high-performance green tire and holding great potential to replace petroleum-derived elastomers.
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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