Supertough biocompatible and biodegradable polylactide materials were fabricated by applying a novel and facile method involving reactive blending of polylactide (PLA) and poly(ethylene glycol) diacylate (PEGDA) monomer with no addition of exogenous radical initiators. Torque analysis and FT-IR spectra confirm that cross-linking reaction of acylate groups occurs in the melt blending process according to the free radical polymerization mechanism. The results from differential scanning calorimetry, phase contrast optical microscopy and transmission electron microscopy indicate that the in situ polymerization of PEGDA leads to a phase separated morphology with cross-linked PEGDA (CPEGDA) as the dispersed particle phase domains and PLA matrix as the continuous phase, which leads to increasing viscosity and elasticity with increasing CPEGDA content and a rheological percolation CPEGDA content of 15 wt %. Mechanical properties of the PLA materials are improved significantly, for example, exhibiting improvements by a factor of 20 in tensile toughness and a factor of 26 in notched Izod impact strength at the optimum CPEGDA content. The improvement of toughness in PLA/CPEGDA blends is ascribed to the jointly contributions of crazing and shear yielding during deformation. The toughening strategy in fabricating supertoughened PLA materials in this work is accomplished using biocompatible PEG-based polymer as the toughening modifier with no toxic radical initiators involved in the processing, which has a potential for biomedical applications.

Composites consisting of polylactide (PLA) and poly(ε-caprolactone) (PCL) filled with acid-oxidized multiwalled carbon nanotubes (A-MWCNTs) were prepared through melt compounding. Phase morphologies of PLA/PCL/A-MWCNT composites with different contents of filled A-MWCNTs and PCL compositions were mainly observed by scanning electron microscope. The results show that A-MWCNTs are selectively dispersed in the PCL phase, regardingless of PCL phase domain sizes. For PLA/PCL/A-MWCNT composites with fixed PLA/PCL ratio of 95/5, the dispersed PCL phase domain sizes in the PLA matrix decrease even though a small content of A-MWCNTs is added, compared with PLA/PCL blend with the same composition, indicating that A-MWCNTs effectively prevent from coalescence of the dispersed PCL phase domains. With filling of 1.0 wt % A-MWCNTs, an interesting change of electrical conductivity for PLA/PCL/A-MWCNT composites is observed, in which the maximum conductivity is observed for PLA/PCL/A-MWCNT composite with PLA/PCL ratio of 60/40. The result is well-explained by the formed cocontinuous phase morphology and effective A-MWCNT content.

Through thermal annealing above the glass transition temperature, a supertoughened binary blend with the highest notched Izod impact strength of 98 KJ/m 2 was achieved, which was about 52 times of that of neat polylactide (PLA; 1.9 KJ/m 2 ). The binary blend was composed of biocompatible and biodegradable PLA and ethylene−acrylic ester−glycidyl methacrylate terpolymer (EGMA) elastomer at the composition of 80/20 PLA/EGMA. For one toughened binary blend with the notched Izod impact strength of 94 KJ/ m 2 , its tensile elongation at break was kept above 120%. Moreover, this supertoughened binary blend also displayed a much higher heat deflection temperature for application. Thermal annealing induced crystallization of the PLA matrix in the blend, and a linear correlation between the notched Izod impact strength and crystallinity was revealed. The possible toughening mechanism for the PLA/EGMA 80/20 blend with thermal annealing was analyzed from the viewpoint of negative pressure effects, as imposed on EGMA elastomeric particles during the quench process and thermal annealing thereafter. Decreases of the glass transition temperatures for the EGMA elastomeric particles in the blend were observed for both the quench and thermal annealing processes, which originated from asymmetric thermal shrinkages between the EGMA elastomeric phase and PLA matrix phase.