This work describes the synthesis of poly(lactic acid) by the ring-opening polymerization of L-lactide in the presence of oligo(butylene succinate) with two different molecular weights (Mn = 6100 and 16300 g/mol) as a macroinitiator during reactive processing. The macroinitiators were added in concentrations 1 wt%, 2.5 wt%, 5 wt%, 10 wt% and 15 wt% in respect to the L-lactide mass in the premix. The properties of the received copolymers were extensively studied with spectroscopic techniques, GPC, DSC, XRD, TGA as well as nanoindentation. Blocky copolymers were received with number average molecular weights ranging from 30 to 100 kg/mol, which decreased with increasing the PBSu content in the feed. The introduction of the flexible PBSu chains decreased the single glass transition detected, while DSC and XRD gave indications that both components crystallized in the copolymers with PBSu premix content > 5 wt%. Thermal stability was maintained and depended on the composition and molecular weight. Nanoindentation showed that despite the decreasing trend of hardness and elastic modulus with increasing PBSu content, the PLA-PBSu 2.5% copolymers had simultaneously higher elasticity modulus and strength compared to the other compositions, possibly because of a complementary effect of their high molecular weight and crystallinity. These copolymers were promising for production with continuous reactive extrusion, a novel, fast and economically viable method to commercially produce PLA-based polymers.
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