Diblock Dialternating Terpolymers by One-step/one-pot Highly Selective Organocatalytic Multimonomer Polymerization

Overview

Journal Nat Commun

Specialty Biology

Date 2021 Dec 9

PMID 34880211

Citations 6

Authors

Jiaxi Xu

Xin Wang

Nikos Hadjichristidis

Affiliations

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Abstract

The synthesis of well-defined block copolymers from a mixture of monomers without additional actions ("one-pot/one-step") is an ideal and industrially valuable method. In addition, the presence of controlled alternating sequences in one or both blocks increases the structural diversity of polymeric materials, but, at the same time, the synthetic difficulty. Here we show that the "one-pot/one-step" ring-opening terpolymerization of a mixture of three monomers (N-sulfonyl aziridines; cyclic anhydrides and epoxides), with tert-butylimino-tris(dimethylamino)phosphorene (t-BuP) as a catalyst, results in perfect diblock dialternating terpolymers having a sharp junction between the two blocks, with highly-controllable molecular weights and narrow molecular weight distributions (Ð < 1.08). The organocatalyst switches between two distinct polymerization cycles without any external stimulus, showing high monomer selectivity and kinetic control. The proposed mechanism is based on NMR, in-situ FTIR, SEC, MALDI-ToF, reactivity ratios, and kinetics studies.

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