Stereoselective Ring-Opening Polymerization of rac-Lactide Using Organocatalytic Cyclic Trimeric Phosphazene Base

Phosphazene base is an important organocatalyst in polymer chemistry owing to its high activity and versatility. In this contribution, we demonstrate that cyclic trimeric phosphazene base (CTPB) can catalyze stereoselective ring-opening polymerization (ROP) of rac-lactide (rac-LA) to produce isotactic stereoblock PLA (P_i up to 0.93). The polymerizations are highly controlled, as evidenced by linear relationship between molecular weights (MW) and monomer conversions and the narrow dispersity (Đ = M_w/M_n) of the resulted polymers with high fidelity of end groups. The investigations on polymerization parameters show that the tacticity of produced PLA depends on the polymerization temperatures and solvents, while the kinetic studies reveal a faster rate for ROP of l-LA as compared to rac-LA under same conditions. Based on these results, the chain end control mechanism is proposed to explain the production of isotactic stereoblock PLA from rac-LA by an achiral catalyst.