TY - JOUR
T1 - Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization
AU - Xu, Jiaxi
AU - Wang, Xin
AU - Hadjichristidis, Nikos
N1 - KAUST Repository Item: Exported on 2021-12-14
Acknowledgements: The research work was supported by King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia.
PY - 2021/12/8
Y1 - 2021/12/8
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/673965
UR - https://www.nature.com/articles/s41467-021-27377-3
U2 - 10.1038/s41467-021-27377-3
DO - 10.1038/s41467-021-27377-3
M3 - Article
C2 - 34880211
SN - 2041-1723
VL - 12
JO - Nature Communications
JF - Nature Communications
IS - 1
ER -