Azo-Derived Symmetrical Trithiocarbonate for Unprecedented RAFT Control

Oleksandr Ivanchenko; Maksym Odnoroh; Sonia Mallet-Ladeira; Marc Guerre; Stéphane Mazières; Mathias Destarac

doi:10.1021/jacs.1c10031

Azo-Derived Symmetrical Trithiocarbonate for Unprecedented RAFT Control

J Am Chem Soc. 2021 Dec 15;143(49):20585-20590. doi: 10.1021/jacs.1c10031. Epub 2021 Dec 3.

Authors

Oleksandr Ivanchenko¹, Maksym Odnoroh¹, Sonia Mallet-Ladeira², Marc Guerre¹, Stéphane Mazières¹, Mathias Destarac¹

Affiliations

¹ Laboratoire des IMRCP, Université Toulouse 3-Paul Sabatier, CNRS UMR 5623, 118 route de Narbonne, 31062 Toulouse, France.
² Institut de Chimie de Toulouse (UAR 2599), Université Toulouse 3-Paul Sabatier, 118 route de Narbonne, 31062 Toulouse, France.

PMID: 34861112
DOI: 10.1021/jacs.1c10031

Abstract

Bis(2-cyanopropan-2-yl)trithiocarbonate (TTC-bCP) is a new symmetrical trithiocarbonate with the best leaving group ever reported for reversible addition-fragmentation chain transfer (RAFT) polymerization. We propose an elegant route to obtain TTC-bCP starting from 2,2'-azobis(2-methylpropionitrile) (AIBN) as a donor of the 2-cyanopropan-2-yl group. TTC-bCP allowed the preparation of a high-molar-mass (M_n ≈ 135 kg mol^-1) methyl methacrylate-n-butyl acrylate-methyl methacrylate triblock copolymer with unprecedented control (D̵ = 1.04) in reversible-deactivation radical polymerization. Rheology measurements of this triblock copolymer showed a typical thermoplastic elastomer behavior with a steady rubbery plateau up to 120 °C.