Solution-based synthesis of a four-arm star-shaped poly(L-lactide)

The mechanical properties of biocompatible poly(L-lactide) (PLA) could be dramatically enhanced by cross-linking and interesting network structures might be achieved via the formation of branched and star-shaped structures prior to such cross-linking. However, the synthesis of a four-armed star-shaped PLA is limited to bulk melt polymerization at relatively high temperatures that may degrade the monomer and render the reaction kinetics difficult to control. In this work, a solution-based polymerization approach is introduced with dimethylformamide as the solvent for the initiator and all other reactants. Varying the reactant concentrations and reaction temperature, four-arm PLA star structures were produced in solution and their properties were analyzed. The progress of the polymerization reaction was studied using the ¹H NMR and Fourier transform infrared spectroscopy. The quantitative evaluation of the monomer conversion was discussed on theoretical basis. The thermal properties and the crystallinity of the product polymers were evaluated using differential scanning calorimetry. Results indicate polymerization and cross-linking of the four-armed PLA were successful. The introduced solution-based method could open venues for better controlled and more economic reactions of star-shaped and cross-linked PLA.