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

• Published in: Nature communications Vol. 12; no. 1; pp. 7124 - 10
• Main Authors: Xu, Jiaxi, Wang, Xin, Hadjichristidis, Nikos
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 08.12.2021; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/455/941; 639/638/77/889; Block copolymers; Catalysts; Chemical synthesis; Copolymerization; Epoxides; Humanities and Social Sciences; Molecular weight; Molecular weight distribution; Monomers; multidisciplinary; NMR; Nuclear magnetic resonance; Phosphorene; Polymerization; Ring opening; Science; Science (multidisciplinary); Selectivity; Switches; Terpolymerization; Terpolymers
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-021-27377-3

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 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 ( 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. One-pot/one-step polymerizations are ideal with regards to efficiency and simplicity of copolymerization, but can be difficult for the practitioner to control. Here the authors perform one-pot/one-step polymerizations with three monomers, producing diblock dialternating terpolymers with precise alternating structure.