Nitroxide-Mediated Polymerization

Nicolas, Julien; Guillaneuf, Yohann; Gigmès, Didier; Charleux, Bernadette

doi:10.1016/b978-0-444-53349-4.00069-8

Cited by 32 publications

(36 citation statements)

References 576 publications

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“…New materials with the potential of revolutionizing a large part of the polymer industry continue to appear. The polymerization techniques that are receiving greatest attention are nitroxidemediated polymerization (NMP), [3][4][5][6] atom transfer radical polymerization (ATRP), [7][8][9][10][11] and reversible additionfragmentation chain transfer (RAFT).…”

Section: Introductionmentioning

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: Introductionmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…The dormant chain in the nitroxide mediated radical polymerization (NMP) is nitroxide-terminated polymer chain that exists in equilibrium with a growing chain radical (reaction Equation (2)) [12][13][14][15][16][17]. Different from equilibrium reactions in ATRP and NMP, there is an equilibrium reaction as shown in reaction Equation (3) in the reversible addition-fragmentation chain transfer (RAFT) polymerization [18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

“…In the past two decades, controlled radical polymerization has revolutionized and revitalized the field of synthetic polymer chemistry, fruitful achievements have been gained and a number of polymerization strategies were devised to control free radical polymerization process [1][2][3]. All of these synthetic strategies afford living characters by lowering the concentration of a growing radical species, which is generally achieved by introducing a population of dormant chains that is much higher in concentration relative to the growing chain radicals [4,5].…”

Section: Introductionmentioning

confidence: 99%

Allylthioketone Mediated Free Radical Polymerization of Methacrylates

2017

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By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT) has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate) (PMMA) are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate) (PGMA), and major component of the obtained polymer has the structure, (CH 3 ) 2 (CN)C-PGMA-C 7 H 9 O 3 . Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent.

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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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Nitroxide-Mediated Polymerization

Cited by 32 publications

References 576 publications

Living Radical Polymerization by the RAFT Process – A Third Update

Living Radical Polymerization by the RAFT Process – A Third Update

Allylthioketone Mediated Free Radical Polymerization of Methacrylates

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

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