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This study aims at obtaining cross‐linked polymeric materials of biomass origin. For this purpose, one‐pot polyesterification of methyl ricinoleate and methyl 12‐hydroxystearate using titanium isopropoxide as a catalyst is performed leading to polyesters known as estolides. The obtained estolides are successfully cross‐linked using dicumyl peroxide or a sulfur vulcanization system. The so‐formed bio‐based elastomers appear to exhibit promising properties. The latter are analyzed by mechanical tensile tests and thermal techniques (TGA, DSC, DMA) and show high thermal stability ( T  5%  = 205–318 °C), tailored physico‐mechanical properties (low glass transition temperature in the range from −69 to −54 °C), and good tensile strength (0.11–0.40 MPa). Networks prepared from high molecular weight estolides appear to be promising bio‐based elastomers.   Practical Applications : The vegetable oil‐based estolides described in this contribution are new fully bio‐based precursors for further elastomers synthesis. The resulting estolide networks (obtained by peroxide or sulfur cross‐linking) exhibit tailored thermo‐mechanical properties.

Cross‐Linking of Polyesters Based on Fatty Acids