The past 5 years have seen a significant increase in the understanding of the fate of so‐called mid‐chain radicals (MCR), which are formed during the free radical polymerization of monomers that form highly reactive propagating radicals and contain an easily abstractable hydrogen atom. Among these monomers, acrylates are, beside ethylene, among the most prominent. Typically, a secondary propagating acrylate‐type macroradical (SPR) can easily transfer its radical functionality via a six‐membered transition state to a position within the polymer chain (in a so‐called backbiting reaction), creating a tertiary MCR. Alternatively, the radical function can be transferred intramolecularly to any position within the chain (also forming an MCR) or intermolecularly to another polymer strand. This article aims at providing a comprehensive overview of the up‐to‐date knowledge about the rates at which MCRs are formed, their secondary reactions as well as the consequences of their occurrence under variable reaction conditions. We explore the latest aspects of their detection (via electron spin resonance spectroscopy) as well as the characterization of the polymer structures to which they lead (via high resolution mass spectrometry). The presence of MCRs leads to the formation of branched polymers and the partial formation of polymer networks. They also limit the measurement of kinetic parameters (such as the SPR propagation rate coefficient) with conventional methods. However, their occurrence can also be used as a synthetic handle, for example, the high‐temperature preparation of macromonomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7585–7605, 2008

Photo-induced copper-mediated radical polymerization of methyl acrylate (MA) is carried out in DMSO at 15 °C in a tubular photo-flow reactor as well as in a glass-chip based microreactor. Polymerization reactions proceed rapidly to approximately 90% monomer conversion within 20 minutes of reactor residence time. Control of reactions is high as evidenced by ideal polymerization kinetics, low dispersities of the obtained polymers (in the range of 1.1) and linear evolution of number average molecular weights during polymerization reactions. Poly(MA) with average molecular weights between a few hundred and ∼5000 g mol⁻¹ was obtained under retention of pristine end group fidelity. Besides homopolymers, block copolymers can also be successfully synthesized and poly(methyl acrylate)-b-poly(butyl acrylate) block copolymers with a similar low dispersity are obtained. Reactions proceed under homogeneous reaction conditions. This feature allows the reaction to be carried out in milli- and also in microflow devices. In both cases, equally good control is achieved with only minimal adaptation of the reaction protocol, underpinning the simplicity and fast adaptability of the protocol to different flow reactors.