Over the past few years, cobalt-mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the reason for this success and the intimate mechanism remained basically speculative. Herein, two mechanisms are shown to coexist: the reversible termination of the growing poly(vinyl acetate) chains by the Co(acac)2 complex (acac: acetylacetonato), and a degenerative chain-transfer process. The importance of one contribution over the other strongly depends on the polymerization conditions, including complexation of cobalt by ligands, such as water and pyridine. This significant progress in the CMRP mechanism relies on the isolation and characterization of the very first cobalt adducts formed in the polymerization medium and their use as CMRP initiators. The structure proposed for these adducts was supported by DFT calculations. Beyond the control of the VAc polymerization, which is the best ever achieved by CMRP, extension to other monomers and substantial progress in macromolecular engineering are now realistic forecasts.

Controlled Radical Polymerization (CRP) techniques offer today a unique opportunity to properly design polymer chains and to adjust their chemical and physical properties. Among these techniques, cobalt-mediated radical polymerization (CMRP) distinguished itself by the high level of control imparted to the polymerization of acrylic and vinyl ester monomers, even for high molar masses. This article summarizes for the first time the advances in understanding and synthetic scope of CMRP since its discovery. Notably, the cobalt-carbon bond formation by dual contribution of reversible termination and degenerative chain transfer is discussed, as well as the impact of additives able to coordinate the metal. The potential of computational chemistry in the field of CMRP as a rationalization and predicting tool is also presented. These mechanistic considerations and achievements in macromolecular engineering will be discussed along with challenges and future prospects in order to assess the CMRP system as a whole.

A poly(vinyl acetate) macroinitiator, preformed by a cobalt‐mediated technique, facilitates controlled radical polymerization of vinyl acetate (VAc) in suspension in water. The molar mass increases with monomer conversion, as demonstrated by size exclusion chromatograms (see picture), and the polydispersity remains low at 1.2–1.4. Moreover, the VAc polymerization rate is much higher in suspension than in the bulk.

Reversible end‐capping of the growing polymer chains to form dormant species (see scheme) lowers the radical concentration. Thus, cobalt(II) acetylacetonate efficiently controls the bulk radical polymerization of vinyl acetate. The molar mass of the poly(vinyl acetate) increases linearly with monomer conversion, polydispersity is as low as 1.15, and polymerization can be resumed by preformed vinyl acetate oligomers. acac=acetylacetonate.

The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

Poly(N-vinylcaprolactam) (PNVCL) is a thermoresponsive and biocompatible polymer that raises an increasing interest in the biomedical area, especially in drug delivery systems (DDS) that include micelles, hydrogels, and hybrid particles. The thermoresponsiveness of PNVCL, used alone or in combination with other stimuli- responsive polymers or particles (pH, magnetic field, or chemicals), is often key in the loading and/or release process in these DDS. The renewed focus on this polymer, which is known for decades, is to a large extent due to recent progress in synthetic strategies. Especially, the advent of efficient controlled radical polymerization (CRP) methods for NVCL monomer gives now access to unprecedented well-defined NVCL-based copolymers with unique properties. This Review article addresses up-to-date synthetic aspects, biological features, and biomedical applications of the latest NVCL-containing systems.

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried out starting from a conventional azo-initiator (V-70) in the presence of bis(acetylacetonato)cobalt(II) ([Co(acac)(2)]) but also by using organocobalt(III) adducts. Molar concentration ratios of the reactants, the temperature, and the solvent were tuned, and the effect of these parameters on the course of the polymerization is discussed in detail. The best level of control was observed when the AN polymerization was initiated by an organocobalt(III) adduct at 0 degrees C in dimethyl sulfoxide. Under these conditions, poly(acrylonitrile) with a predictable molar mass and molar mass distribution as low as 1.1 was prepared. A combination of kinetic data, X-ray analyses, and DFT calculations were used to rationalize the results and to draw conclusions on the key role played by the solvent molecules in the process. These important mechanistic insights also permit an explanation of the unexpected "solvent effect" that allows the preparation of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) by CMRP.

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