Precision Polymer Synthesis by Degenerative Transfer Controlled/Living Radical Polymerization Using Organotellurium, Organostibine, and Organobismuthine Chain-Transfer Agents

Yamago, Shigeru

doi:10.1021/cr9001269

Cited by 422 publications

(325 citation statements)

References 183 publications

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“…[148] Polymerization Mediated by Organotellurium, Organobismuthine, and Organostibine Reagents The mechanism and application of radical polymerization mediated by organotellurium (TERP), organobismuthine, and organostibine compounds has been reviewed. [149,150] Recent papers have described the use of TERP in surfactant-free emulsion polymerization of BA [151] and St, [152,153] the preparation of polymer monoliths based on crosslinked poly (Am), [154] the use of poly(NIPAm)-b-poly(NVP) for solubilization of C 60 , [155] the use of heteroatom-metal exchange reactions in end-group transformation of polymers (poly(BA), poly (MMA), poly(HEMA), poly(NIPAm)) in organostibine or organobismuth-mediated polymerization [156] and the use of organostibine-mediated polymerization in St/MMA copolymerization. [157] The end-groups of methacrylic polymers (poly(BA), poly (MMA), poly(HEMA), poly(MAN)) formed by TERP or organostibine-mediated polymerization can be eliminated to form macromonomers in high yield through reaction with (2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) (and formation of an alkoxyamine intermediate) or the addition-fragmentation chain transfer agent, ethyl 2-[(tributylstannyl)methyl]acrylate.…”

Section: Chartmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: Chartmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…Recently, organotellurium-mediated living radical polymerization (TERP) [1][2][3] has been proposed and developed by Yamago and coworkers. as a novel controlled/living radical polymerization (CLRP) technique.…”

Section: Introductionmentioning

confidence: 99%

“…TERP has been studied mainly in homogeneous systems such as bulk and solution polymerizations since 2002. 3,[7][8][9][10] In recent years, CLRP in aqueous heterogeneous systems, such as miniemulsion polymerization, microemulsion polymerization and emulsion polymerization, has attracted a great deal of attention because the media is non-toxic and environmentally friendly. 11,12 Because the control agents used for CLRP thus far have typically been hydrophobic, most of the research efforts in this area have studied miniemulsion polymerization, which ideally proceeds in hydrophobic monomer droplets.…”

Section: Introductionmentioning

confidence: 99%

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

Moribe

Kitayama

Suzuki

et al. 2011

Polym J

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Particle formation during the initial stages of emulsifier-free organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene at 601C was investigated at two stirring rates (220 and 1000 r.p.m.), in which the styrene phase floated as a layer on an aqueous phase at 220 r.p.m. or became dispersed as droplets at 1000 r.p.m. A water-soluble TERP agent, poly(methacrylic acid) (PMAA)-methyltellanyl (PMAA 30 -TeMe) and a water-soluble thermal initiator, 4,4¢-azobis(4-cyanovaleric acid), at alkaline pH were used. The control/livingness was better at 1000 r.p.m. than at 220 r.p.m., and the particle size distribution was also affected by the stirring rate: both nanometer-sized and submicrometer-sized particles were observed at 220 r.p.m., and mainly nanometer-sized particles were observed at 1000 r.p.m. Because the percentage of PMAA 30 -TeMe consumed in the initial stage was much higher at 1000 r.p.m. than at 220 r.p.m., self-assembly nucleation preferentially occurred at 1000 r.p.m., resulting in nanometer-sized particles and good control/livingness. Stirring at 1000 r.p.m. only in the initial stage of the emulsion TERP followed by 220 r.p.m. induced good control/livingness and the formation of mainly nanometer-sized particles. It is concluded that a high stirring rate in the initial stage is important for the emulsion TERP of styrene to obtain good control/ livingness and to control the particle formation mechanism.

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“…Controlled radical polymerization CRP has become an important tool for the preparation of well-defined polymer materials [1][2][3][4][5][6][7][8][9]. The use of organometallic complexes was a significant step towards the development of CRP of various vinylic monomers [1,[9][10][11][12].…”

Section: Introductionmentioning

confidence: 99%

In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization

Kermagoret

Jérôme

Detrembleur

et al. 2015

European Polymer Journal

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a b s t r a c tOrganometallic-mediated radical polymerization (OMRP) has seen a significant growth in the last years notably due to the development of new metal complexes, especially cobalt derivatives. Despite of this, none of the reported complexes offers optimal control for monomers with very different reactivity, which somewhat limits the synthesis of copolymers. In order to expand the scope of cobalt-mediated radical polymerization (CMRP), we investigated an in situ ligand exchange reaction for modulating the properties of the cobalt complex at the polymer chain-end and adjusting the CACo bond strength involved in the control process. With the aim of improving the synthesis of poly(vinyl acetate)-b-poly (n-butyl acrylate) copolymers, bidentate acetylacetonate ligands, which impart high level of control to the polymerization of vinyl acetate (VAc), were replaced in situ at the PVAcAcobalt chain-end by tetradentate Salen type ligands that are more suited to acrylates.

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Precision Polymer Synthesis by Degenerative Transfer Controlled/Living Radical Polymerization Using Organotellurium, Organostibine, and Organobismuthine Chain-Transfer Agents

Cited by 422 publications

References 183 publications

Living Radical Polymerization by the RAFT Process – A Third Update

Living Radical Polymerization by the RAFT Process – A Third Update

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization

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