Abstract

N-Butyl N-carboxyanhydride (Bu-NCA) was polymerized in THF to produce poly(N-butylglycine) using benzyl alcohol initiator and 1,1,3,3-tetramethylguanidine (TMG) promoter. Poly(N-butylglycine) species (PNBG) with controlled molecular weight (Mn = 2.9–20.5 kg mol–1) and narrow molecular weight distribution (PDI = 1.04–1.08) were obtained by controlling the initial monomer-to-initiator ratio and conversion. The reaction exhibits characteristics of a living polymerization, as evidenced by the linear increase of Mn with conversion and successful chain extension experiments. Kinetic studies revealed a first-order dependence of propagation rate on the monomer and benzyl alcohol concentration and zero-order dependence on the TMG concentration, consistent with a controlled polymerization where the TMG does not influence the chain propagation. It was further revealed that the polymerization activities and Mn control are strongly dependent on the structure of the alcohol initiators. Primary alcohols (e.g., methanol,...

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