Overview of cobalt-mediated radical polymerization: Roots, state of the art and future prospects

Debuigne, Antoine; Poli, Rinaldo; Jérôme, Christine; Jérôme, Robert; Detrembleur, Christophe

doi:10.1016/j.progpolymsci.2008.11.003

Cited by 353 publications

(281 citation statements)

References 114 publications

Supporting

Mentioning

281

Contrasting

Order By: Relevance

“…Numerous recent studies have focused on complex polymer architectures with original solid state morphologies [30][31][32][33], PVA-based surfactants [34,35] or poly(vinyl ester)s with enhanced solubility in scCO 2 [3][4][5][6][7][8]. To date, iodine-transfer polymerization (ITP) [36], organoheteroatom-mediated polymerization (OMRP) [28,37], cobalt-mediated polymerization (CoMRP) [38] and reversible addition-fragmentation chain transfer (RAFT) polymerization [39] have been proven efficient in the radical polymerization of vinyl esters. However, ITP, OMRP and CoMRP suffer drawbacks of different kinds.…”

Section: Introductionmentioning

confidence: 99%

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

View full text Add to dashboard Cite

This article is the first comprehensive review on the study and use of vinyl ester monomers in reversible addition fragmentation chain transfer (RAFT) polymerization. It covers all the synthetic aspects associated with the definition of precision polymers comprising poly(vinyl ester) building blocks, such as the choice of RAFT agent and reaction conditions in order to progress from simple to complex macromolecular architectures. Although vinyl acetate was by far the most studied monomer of the range, many vinyl esters have been considered in order to tune various polymer properties, in particular, solubility in supercritical carbon dioxide (scCO 2 ). A special emphasis is given to novel poly(vinyl alkylate)s with enhanced solubilities in scCO 2 , with applications as reactive stabilizers for dispersion polymerization and macromolecular surfactants for CO 2 media. Other miscellaneous uses of poly(vinyl ester)s synthesized by RAFT, for instance as a means to produce poly(vinyl alcohol) with controlled characteristics for use in the biomedical area, are also covered.

show abstract

Section: Introductionmentioning

confidence: 99%

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

View full text Add to dashboard Cite

show abstract

“…Cobalt coordination compounds in general have become popular for H 2 conversion research [4][5][6][7][8], alkene hydrogenation [9][10][11][12][13], controlled radical polymerisation [14][15][16][17][18][19] and carbene-and nitrene-transfer reactions [20][21][22][23][24]. Cobaltmediated hydroformylation is well-known and has been continuously reviewed [25][26][27].…”

Section: Introductionmentioning

confidence: 99%

Hydroformylation of 1-Octene Mediated by the Cobalt Complex [CoH(dchpf)(CO)2]

Kluwer¹,

Krafft

Hartenbach

et al. 2016

Top Catal

View full text Add to dashboard Cite

Hydroformylation of 1-octene with the heterodinuclear (Fe, Co) complex [CoH(dchpf)(CO) 2 ] (1) was investigated (dchpf = 1,1 0 -bis(dicyclohexylphosphino)ferrocene). In agreement with this cobalt complex possessing a preformed hydride as well as carbonyl ligands, the preactivated catalyst does not require any induction process or activation treatment to become reactive in hydroformylation. The catalyst activity and (chemo-)selectivity proved to be strongly dependent on the applied reaction conditions. Higher syngas pressures suppress alkene isomerization and favor the hydroformylation reaction. The overall regio-selectivity remains very similar within the investigated reaction space, with the C1-selectivity varying between 48 and 69 %. An increase of the reaction temperature at 40 bars results in a progressive decrease of the C1-selectivity and an increase in the C2-and C3-selectivity due to a higher isomerization activity at elevated temperatures. Furthermore, at high temperatures (170°C) and low syngas pressures (10-20 bar) the main oxygenated products are the alcohols, resulting from reduction of the aldehydes. However, when using a combination of higher syngas pressures and intermediate temperatures, the reaction could be optimized towards the formation of aldehydes. At 140°C and 40 bars syngas pressure quite selective hydroformylation of 1-octene could be achieved, yielding 57 % aldehydes and only 1.3 % over-reduction to the corresponding alcohol.

show abstract

“…The use of organometallic complexes was a significant step towards the development of CRP of various vinylic monomers [1,[9][10][11][12]. CRP mediated by transition metal complexes can be classified in two families [13], i.e., atom transfer radical polymerization (ATRP) [14][15][16] and organometallic mediated radical polymerization (OMRP) [11,12,17,18]. The role of the metal center consists in the transformation of the radical species into dormant species through a halogen exchange between the metal center and the radical for the ATRP mechanism (Eq.…”

Section: Introductionmentioning

confidence: 99%

“…Cobalt mediated radical polymerization (CMRP) [45,46] is extensively studied especially for its high ability to control the polymerization of a large range of monomers including acrylic monomers [47][48][49][50] and vinyl esters [12,17,46,51,52]. Depending on the reaction conditions, the CMRP process follows a reversible termination (RT) mechanism (Eq.…”

Section: Introductionmentioning

confidence: 99%

“…The role of the ligand is crucial and determines the ability of the cobalt complex to control http://dx.doi.org/10.1016/j.eurpolymj.2014.08.003 0014-3057/Ó 2014 Elsevier Ltd. All rights reserved. the polymerization by affecting the stability of the cobaltAcarbon bond of the dormant species, and therefore the active/dormant species equilibrium [12]. Cobalt complexes bearing high electron donating ligands such as porphyrin derivatives [49,55], cobaloximes [56] or 1,3-bis(2-pyridilimino)isoindolate ligands [57] (Fig.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Kermagoret

Jérôme

Detrembleur

et al. 2015

European Polymer Journal

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Overview of cobalt-mediated radical polymerization: Roots, state of the art and future prospects

Cited by 353 publications

References 114 publications

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

Hydroformylation of 1-Octene Mediated by the Cobalt Complex [CoH(dchpf)(CO)2]

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

Contact Info

Product

Resources

About