In this work, bio‐based products composed of blends of a star‐shaped poly(d,l‐lactide) (star‐PDLLA) and a conventional linear poly(l‐lactide) (linear‐PLLA) are produced by typical large‐scale manufacturing techniques for thermoplastic blends. In the first case, the two polymers are blended through melt extrusion, producing pellets that are subsequently compression‐molded into the final bio‐based polymer films. Alternatively, the star/linear poly(lactide) (PLA) materials are developed by direct blending through injection molding, a process that generally applies after a preblending extrusion step to ensure proper mixing. Thermomechanical degradation induced by the different processes is evaluated, and the performances of the final star/linear PLA products are thoroughly compared. The effect of the short‐branched, amorphous, star polymeric component on thermal, mechanical, and rheological properties of the conventional PLLA is comprehensively investigated, revealing that the star‐PDLLA incorporation promotes the formation of a more flexible and tougher material with reduced capability of crystallization. Most importantly, star‐PDLLA decreases the melt viscosity of the final material, while increasing the shear‐thinning behavior, hence facilitating melt flow during manufacturing. Such properties lead to enhanced material ductility and processability, with respect to typically brittle and viscous conventional PLLA‐based materials. Moreover, the tuning of final material performances can be achieved by simply varying the star‐PDLLA content.
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