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A facile N 2 flow-accelerated N -carboxyanhydride ring opening polymerization (NCA ROP) is demonstrated, herein, with rigorous kinetic studies to evaluate the methodology in detail. By using n -hexylamine as initiator and γ-benzyl-L-glutamate N -carboxyanhydride (BLG-NCA) as monomer, the NCA ROP via a normal amine mechanism (NAM) reached 90% conversion in 2 h under N 2 flow at room temperature in a fume hood, much shorter than the time required for the same polymerization conducted in a glove box (14 h). The efficient removal of CO 2 from the reaction by N 2 flow drove the carbamic acid-amine equilibrium toward the formation of active nucleophilic amino termini and promoted polymerization. The detailed kinetic studies of the polymerization with different feed ratios and N 2 flow rates were conducted, demonstrating the living feature of the NCA ROP and the tuning of the polymerization rate by simply changing the flow rate of N 2 . Maintenance of the reactivity of the amino ω-chain terminus and control during a subsequent polymerization were confirmed by performing chain extension reactions. The N 2 flow method provides a new straightforward strategy to synthesize well-defined polypeptides with predictable molecular weights and narrow molecular weight distributions (PDI &lt; 1.19).

macromolecules

A Facile Glovebox-Free Strategy To Significantly Accelerate the Syntheses of Well-Defined Polypeptides by <i>N</i>-Carboxyanhydride (NCA) Ring-Opening Polymerizations

A Facile Glovebox-Free Strategy To Significantly Accelerate the Syntheses of Well-Defined Polypeptides by N-Carboxyanhydride (NCA) Ring-Opening Polymerizations