Issue 43, 2021

Controlling dispersity in aqueous atom transfer radical polymerization: rapid and quantitative synthesis of one-pot block copolymers

Abstract

The dispersity (Đ) of a polymer is a key parameter in material design, and variations in Đ can have a strong influence on fundamental polymer properties. Despite its importance, current polymerization strategies to control Đ operate exclusively in organic media and are limited by slow polymerization rates, moderate conversions, significant loss of initiator efficiency and lack of dispersity control in block copolymers. Here, we demonstrate a rapid and quantitative method to tailor Đ of both homo and block copolymers in aqueous atom transfer radical polymerization. By using excess ligand to regulate the dissociation of bromide ions from the copper deactivator complexes, a wide range of monomodal molecular weight distributions (1.08 < Đ < 1.60) can be obtained within 10 min while achieving very high monomer conversions (∼99%). Despite the high conversions and the broad molecular weight distributions, very high end-group fidelity is maintained as exemplified by the ability to synthesize in situ diblock copolymers with absolute control over the dispersity of either block (e.g. low Đ → high Đ, high Đ → high Đ, high Đ → low Đ). The potential of our approach is further highlighted by the synthesis of complex pentablock and decablock copolymers without any need for purification between the iterative block formation steps. Other benefits of our methodology include the possibility to control Đ without affecting the Mn, the interesting mechanistic concept that sheds light onto aqueous polymerizations and the capability to operate in the presence of air.

Graphical abstract: Controlling dispersity in aqueous atom transfer radical polymerization: rapid and quantitative synthesis of one-pot block copolymers

Supplementary files

Article information

Article type
Edge Article
Submitted
03 Aug. 2021
Accepted
23 Sept. 2021
First published
23 Sept. 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2021,12, 14376-14382

Controlling dispersity in aqueous atom transfer radical polymerization: rapid and quantitative synthesis of one-pot block copolymers

H. S. Wang, K. Parkatzidis, S. Harrisson, N. P. Truong and A. Anastasaki, Chem. Sci., 2021, 12, 14376 DOI: 10.1039/D1SC04241F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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