Facile synthesis and comparative study of poly(l-lactide) with linear-comb and star-comb architecture†
Abstract
In this work, two series of linear-comb and star-comb well defined graft poly(L-lactide) (PLLA) have been synthesized conveniently by one-pot ring-opening polymerization (ROP) of L-lactide using functionalized polybutadiene macroinitiators. The used organocatalyst of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) allows the polymerization of L-lactide to proceed rapidly at room temperature. Kinetic studies of the ROP reaction in this system indicate first-order kinetics in monomer concentration. 1H NMR and GPC techniques are employed to characterize the synthesized polymers, validating the formation of the desired comb structures with controllable chain length. Linear-comb and star-comb graft PLLA were comparatively studied as well as with linear PLLA by DSC and POM. The results reveal that the comb structure gives a remarkable improvement of PLLA crystallization ability in both crystallinity and growth rate of spherulites. Furthermore, the more compacted star-comb structure imposes restriction on chain mobility, which weakens the growth effect to some extent. It is found that the glass transition temperature (Tg) and melting temperature (Tm) significantly depend on the side chain length and backbone structure. Rheological studies of both melt and instinct viscosity of the solution show that star-comb PLLA has the lowest hydrodynamic volume compared with linear-comb PLLA and linear PLLA.