Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• weight and polymerization rate precisely. In order to solve these problems, Hawker et al. [32][33][34] proposed the concept of the unimolecular initiation system. In this system, an alkoxyamine compound is used instead of the original nitroxide radical/initiator combination. These unimolecular initiators

• can decompose to produce a stoichiometric pair of the primary initiating radical and a nitroxide radical, thus combining the roles of a conventional initiator and a control agent. The mechanism is shown in Scheme 4 [35]. Due to the steric effect of TEMPO, the dissociation rate constant, kd, of the

• acrylates, under milder conditions [37][38][39]. Grimaldi et al. [40] achieved NMP of styrene and n-butyl acrylate using SG1-type nitroxide radical (N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)nitroxide). Compared with TEMPO, SG1 was considered that it initiated the truly “living”/controlled

Structures of the reaction products of the AZADO radical with TCNQF₄ or thiourea

• Hideto Suzuki,
• Yuta Kawahara,
• Hiroki Akutsu,
• Jun-ichi Yamada and
• Shin’ichi Nakatsuji

Beilstein J. Org. Chem. 2013, 9, 1487–1491, doi:10.3762/bjoc.9.169

• compound; nitroxide radical; TCNQF4; thiourea; Introduction TEMPO radical (2,2,6,6-tetramethylpiperidinyl-N-oxyl) (1) is a typical nitroxide radical and is persistent because of the steric hindrance of the four neighboring methyl groups of the NO moiety protecting it from attack by various reagents

• including oxygen [1]. Sometimes, however, the merit turns out to be a drawback by limiting its properties and reactivity. For example, 1 is inefficient in the oxidation of sterically hindered secondary alcohols. The AZADO radical (2) [2] is an intriguing nitroxide radical with adamantane-like structure and