The special of Chemical Review informs about studies conducted on single-electron transfer and single-electron transfer degenerative chain transfer living radical polymerization. Researchers have demonstrated that living radical polymerization (LRP) can be significantly effective for the synthesis of tailored polymers. The special issue aims at covering the latest progress in two related polymerization methodologies that rely on single-electron transfer (SET), single-electron transfer degenerative chain transfer living radical polymerization (SET-DTLRP), and single-electron transfer living radical polymerization (SET-LRP). It is demonstrated that SET-DTLRP proceeds through SET initiation and competition of SET activation, deactivation, and degenerative transfer (DT). SET-LRP proceeds exclusively through a SET initiation, activation, and deactivation. It is also revealed that the two techniques have arose from investigations into Cu-catalyzed LRP initiated with sulfonyl halides.

Single-Electron Transfer and Single-Electron Transfer Degenerative Chain Transfer Living Radical Polymerization

Electrochemical reduction of an exemplary ATRP catalyst, C 11 Br 2 /Me 6 TREN, is shown to be an efficient process to mediate and execute an ATRP. The onset of polymerization occurs only through passage of a cathodic current achieved under a reductive potential to form Cu 1 Br 2 /Me 6 TREN, within the reaction medium. Unprecedented control over the polymerization kinetics can be attained through electrochemical methods by modulating the magnitude of the applied potential allowing polymerization rate enhancement or retardation. Additional polymerization control is gained through electrochemical “dials” allowing polymerization rate enhancements achieved by larger applied potentials and the ability to successfully switch a polymerization “on” and “off between dormant and active states by application of multistep intermittent potentials.

https://science.sciencemag.org/content/sci/332/6025/81.full.pdf

Electrochemically mediated atom transfer radical polymerization

A new polymerization process (atom transfer radical polymerization, or ATRP) based on a redox reaction between a transition metal (e.g., Cu(I)/Cu(II)), provides 'living' or controlled radical polymerization of styrene, (meth)acrylates, and other radically polymerizable monomers. Using various simple organic halides as model halogen atom transfer precursors (initiators) and transition metal complexes as a model halogen atom transfer promoters (catalysts), a 'living' radical polymerization affords (co)polymers having the predetermined number average molecular weight by Δ[M]/[I]o (up to Mn > 105) and a surprisingly narrow molecular weight distribution (Mw/Mn), as low as 1.15. The participation of free radical intermediates in ATRP is supported by end-group analysis and stereochemistry of the polymerization. In addition, polymers with various topologies (e.g., block, random, star, end-functional and in-chain functional copolymers [for example, of styrene and methyl (meth)acrylate]) have been synthesized using the present process. The polymeric products encompassed by the present invention can be widely used as plastics, elastomers, adhesives, emulsifiers, thermoplastic elastomers, etc.

Novel (co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization

Improved processes for atom (or group) transfer radical polymerization (ATRP) and novel polymers have been developed and are described. In certain embodiments, novel copolymers comprising a least one polymeric branch or polymeric block with a predominantly alternating monomer sequence are described. Novel copolymers comprising a least one polymeric branch or polymeric block with a gradient monomer structure are described. Additionally, novel copolymers comprising a least one polymeric branch or polymeric block with a predominantly periodic monomer sequence are also described. Novel copolymers having a water soluble backbone and at least two hydrophobic polymeric branches grafted to the water soluble backbone are also described.

Improved processes based on atom (or group) transfer radical polymerization and novel (co)polymers having useful structures and properties

The present invention is directed to a process of atom (or group) transfer radical polymerization for the synthesis of novel homopolymer or a block or graft copolymer, optionally containing at least one polar group, with well defined molecular architecture and narrow polydispersity index, in the presence of an initiating system comprising (i) an initiator having a radically transferrable atom or group, (ii) a transition metal compound, and (iii) a ligand; the present invention is also directed to the synthesis of a macromolecule having at least two halogen groups which can be used as a macroinitiator component (i) to subsequently form a block or graft copolymer by an atom or group transfer radical polymerization process; the present invention is also directed to a process of atom or group transfer radical polymerization for the synthesis of a branched or hyperbranched polymer; in addition, the present invention is directed to a process of atom or group transfer radical polymerization for the synthesis of a macroinitiator which can subsequently be used to produce a block or graft copolymer.

M. Asscher

Papers

954. Chlorine-activation by redox-transfer. Part IV. The addition of sulphonyl chlorides to vinylic monomers and other olefins