Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization

Jiaxi Xu, Xin Wang, Nikos Hadjichristidis

Research output: Contribution to journalArticlepeer-review

34 Scopus citations


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 ($\textit{N}$-sulfonyl aziridines; cyclic anhydrides and epoxides), with $\textit{tert}$-butylimino-tris(dimethylamino)phosphorene ($\textit{t}$-BuP$_1$) 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 ($\textit{Ð}$ < 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.
Original languageEnglish (US)
JournalNature Communications
Issue number1
StatePublished - Dec 8 2021

ASJC Scopus subject areas

  • Biochemistry, Genetics and Molecular Biology(all)
  • Chemistry(all)
  • Physics and Astronomy(all)


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