Atom Transfer Radical Polymerization Enabled by Sonochemically Labile Cu-carbonate Species

Zhenhua Wang; Francesca Lorandi; Marco Fantin; Zongyu Wang; Jiajun Yan; Zhanhua Wang; Hesheng Xia; Krzysztof Matyjaszewski

doi:10.1021/acsmacrolett.9b00029

Atom Transfer Radical Polymerization Enabled by Sonochemically Labile Cu-carbonate Species

ACS Macro Lett. 2019 Feb 19;8(2):161-165. doi: 10.1021/acsmacrolett.9b00029. Epub 2019 Jan 22.

Authors

Zhenhua Wang^{1

2}, Francesca Lorandi², Marco Fantin², Zongyu Wang², Jiajun Yan², Zhanhua Wang¹, Hesheng Xia¹, Krzysztof Matyjaszewski²

Affiliations

¹ The State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute, Sichuan University, Chengdu 610065, China.
² Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.

PMID: 35619423
DOI: 10.1021/acsmacrolett.9b00029

Abstract

Atom transfer radical polymerization (ATRP) has been previously mediated by ultrasound using a low concentration of copper complex in water (sono-ATRP) or by addition of piezoelectric materials in organic solvents (mechano-ATRP). However, these procedures proceeded slowly and yielded polymers contaminated by new chains initiated by hydroxyl radicals or by residual piezoelectrics. Unexpectedly, in the presence of sodium carbonate, rapid sono-ATRP of methyl acrylate in DMSO was achieved (80% conversion in <2 h) with excellent control of molecular weights and low dispersities (M_w/M_n < 1.2). The in situ formed Cu^II/L-CO₃ complex in the the presence of ultrasound generated Cu^I/L species as activators for ATRP and carbonate radical anions. The latter were scavenged by DMSO that was oxidized to dimethyl sulfone. This simple and robust process employs low-intensity ultrasound, air-stable Cu^II/L catalysts, and carbonate or bicarbonate salts (washing soda or baking soda) to prepare well-defined polyacrylates.