Radical polymerization of vinyl monomers initiated by a mono-captodatively substituted ethane
TL;DR: In this article, a mono-captodatively (cd) substituted ethane bearing nitrile and ethylsulfenyl substituents on the same carbon atom was found to accelerate both styrene and methyl methacrylate polymerization with no induction period.
Abstract: Homopolymerization of styrene and methyl methacrylate was carried out at 60–130°C in the presence of a mono-captodatively (cd) substituted ethane bearing nitrile and ethylsulfenyl substituents on the same carbon atom. It was found that the cd-ethane accelerated both styrene and methyl methacrylate polymerizations with no induction period, but the polymerization mode of methyl methacrylate was different from that of styrene. The polymerization rate of styrene was proportional to the 0.46th power of the cd-ethane concentration. However, the cd-ethane produced a reversible radical termination in the case of methyl methacrylate. The mechanism of both polymerizations is discussed in terms of the kinetic and ESR data. © 1996 John Wiley & Sons, Inc.
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TL;DR: In this article, the authors describe the concept of iniferters and the model for living radical polymerization in a homogeneous system, which was proposed in 1982 by one of the authors to enable the controlled synthesis and molecular design of polymers through the radical polymerisation process.
Abstract: In this review, we describe the concept of iniferters and the model for living radical polymerization in a homogeneous system, which was proposed in 1982 by one of the authors to enable the controlled synthesis and molecular design of polymers through the radical polymerization process. The iniferters are classified into several types: thermal or photoiniferters; mono-, di-, tetra-, or polyfunctional iniferters; monomeric, polymeric, or gel iniferters; monomer or macromonomer-iniferters, leading to the syntheses of monofunctional, telechelic, and polyfunctional polymers, block and graft copolymers, and branched, star, and cross-linked polymers. Phenylazotriphenylmethane and tetraphenylethane derivatives serve as thermal iniferters, and some organic sulfur compounds act as photoiniferters. Among the iniferters, several compounds containing N,N-diethyldithiocarbamyl groups were found to be excellent for the synthesis of polymers with well-controlled structures. The synthesis of various types of block, star, and graft polymers with a controlled chain structure through living radical polymerization using dithiocarbamate compounds as photoiniferters is described. In the last section, the recent developments in living radical polymerization using nitroxides and transition-metal complexes since 1993 up to 1997 have also been reviewed.
149 citations
TL;DR: In this article, a review relates generally to improved processes in which it is possible to control the growth steps of a radical polymerization to produce relatively monitored chain-length homopolymers and copolymers.
109 citations
TL;DR: The captodative effect in radical polymerization and polymer properties is reviewed in this article, where the authors show that captodation with olefins and methanes can promote a radical polymerisation, in spite of resonance stabilization of the resulting radicals and sterically hindered 1,1-disubstituted molecules.
29 citations
TL;DR: In this paper, a new electrocatalytic reaction affording tetraarylsuccinonitriles in 80-100% yields by the oxidation of diarylacetonitrile in an undivided cell with sodium halides as mediators is described.
6 citations
TL;DR: In this paper, the authors studied the reaction of methyl methacrylate (MMA) by captodatively substituted morpholino succinonitrile (MCS) domant.
Abstract: Radical polymerization of methyl methacrylate (MMA) by captodatively substituted morpholino succinonitrile was studied kinetically at 90 and 130°C by comparison with that of styrene. The polymerizations of MMA and styrene at 90°C proceeded at moderate rates to give polymers which show unimodal size exclusion chromatography (SEC) curves. Both polymerizations at 130°C were significantly fast to give polymers with bimodal SEC curve. A higher molecular weight fraction of the obtained polymer may mostly formed by a spontaneous thermal polymerization in styrene polymerization, but in MMA polymerization produced mainly by dissociation of the domant species. The rate constant of the activation of captodative-capped poly(MMA) domant was smaller than that reported for nitroxide-mediated styrene polymerization.
3 citations