Abstract

AbstractPolylactide (PLA) is a fully bio‐derived polyester with great biodegradability, biocompatibility, and mechanical properties. Synthesis of stereoregular PLA by highly stereoselective organocatalyzed ring opening polymerization (ROP) of racemic lactide (rac‐LA) at room temperature is challenging despite some important developments in the past few years. In this contribution, two bulky phenyl diphosphazene bases,p‐PDPBandm‐PDPB,were conveniently synthesized by the Staudinger reaction. In combination with different hydrogen‐bond donors such as ureas and squaramides, they could mediate the stereocontrolled ROP ofrac‐LA in THF at room temperature. Semicrystalline PLAs with narrow dispersity and high tacticity (Pmup to 0.84) were successfully synthesized in a well‐controlled manner using phenyl diphosphazene based/urea binary catalytic system. Structural analysis verified the linear structure and high end‐group fidelity of the resulting polymers. Moreover, the minimal transesterification of the polymer backbone proved by the MALDI‐TOF MS analysis indicated the good controllability of the phenyl diphosphazene based binary catalytic system.

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