Cobalt(I)‐mediated living radical polymerization of methyl methacrylate

Matsubara, Kouki; Matsumoto, Megumi

doi:10.1002/pola.21498

Cited by 27 publications

(10 citation statements)

References 47 publications

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“…the association of the halide anion to the catalyst in the higher oxidation state, should be sufficiently high to provide efficient deactivation. Examples of other metals successfully used in ATRP include Fe, [240] Ru, [241] Co, [242] Ti, [243] Ni, [244] Mo, [245,246] Re, [247] Rh, [248] Pd, [249] and Os. [250] Cu complexes are most commonly utilized in ATRP, owing to their availability, low cost, [19,22,23] In such a case, the ligand should be selected to ensure that the Cu II /L deactivator species is present in the same phase as the growing radicals for efficient deactivation.…”

Section: Monomersmentioning

confidence: 99%

Kinetics of Atom Transfer Radical Polymerization

Krys

2017

European Polymer Journal

213

142

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This review encompasses the fundamentals of kinetics of atom transfer radical polymerization (ATRP). ATRP is a versatile reversible-deactivation radical polymerization (RDRP) technique, frequently utilized to synthesize advanced functional materials. Detailed mechanistic investigations over the past two decades allowed for an in-depth understanding of the underlying processes and rational design of the reaction conditions. Various aspects of ATRP kinetics are reviewed such as initiation modes, methods allowing to decrease catalyst concentration, influence of the initiator, catalyst (transition metal, ligand, counterion), solvent, additives, type of monomer, and effect of temperature and pressure. Techniques utilized to determine kinetic parameters of catalytic systems are discussed. Finally, guidelines for synthesis of polymers with targeted architectures, predetermined molecular weights, narrow molecular weight distributions, and high retained chain end functionality are presented.

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Section: Monomersmentioning

confidence: 99%

Kinetics of Atom Transfer Radical Polymerization

Krys

2017

European Polymer Journal

213

142

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“…Therefore, both the activator and deactivator forms of the catalyst are necessary. Various transition metals have been used in ATRP such as Cu, Ru, Fe, Ni, Os, Re, Rh, Pd, Co, Ti, and Mo . Copper is the most widely studied due to its availability, low cost, and robustness…”

Section: Introductionmentioning

confidence: 99%

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Ribelli

Lorandi

Fantin

et al. 2018

Macromol. Rapid Commun.

226

184

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polymerizing styrene in the presence of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) radicals. [10] Later, Wayland et al. used a cobalt(II) porphyrin complex to reversibly trap radical species during the polymerization of acrylate monomers, which showed living features: i) linear increase of polymer MW with monomer conversion, and ii) narrow MWD. [11] These techniques set the basis for the development of nitroxide-mediated polymerization (NMP) [12,13] and organometallic mediated radical polymerization (OMRP). [14][15][16] Within the past three decades, controlled radical polymerization (CRP) has been established as a new field in polymer chemistry, in which exceptional control was achieved over polymer architectures, thus enabling the preparation of commercially relevant polymer-based materials for advanced applications. Following IUPAC recommendations, CRP should be termed as reversible deactivation radical polymerization (RDRP). [17] Besides the aforementioned NMP and OMRP, the most affirmed RDRPs are atom transfer radical polymerization (ATRP) [18][19][20] and reversible additionfragmentation chain transfer (RAFT) polymerization. [21] RDRP ensures comparable degree of control as living ionic polymerization, while retaining the versatility and the scope of conventional radical polymerization. The fraction of terminated chains in RDRP is small, typically below a few mol%. Polymers and copolymers prepared by RDRP methods can have defined topologies (stars, brushes, networks, combs), compositions (block, gradient, graft, alternate) and chain-end functionalities. [22] This review will focus on ATRP, with particular attention to the design and application of progressively more active and selective copper-based catalysts, and the development of novel, more benign initiation systems. The correlation between the structure of Cu complexes and their catalytic activity will be discussed in detail, also taking into account the effect of solvent and, when present, surfactants and other additives. Mechanisms of Reversible Deactivation Radical Polymerization ProcessesThe core of all RDRP systems is the increase of chain lifetime by reversibly deactivating the propagating radical species, thus forming dormant species that can be subsequently reactivated. As opposed to conventional RP in which the 25 Years of ATRP Approaching 25 years since its invention, atom transfer radical polymerization (ATRP) is established as a powerful technique to prepare precisely defined polymeric materials. This perspective focuses on the relation between structure and activity of ATRP catalysts, and the consequent choice of the initiating system, which are paramount aspects to well-controlled polymerizations. The ATRP mechanism is discussed, including the effect of kinetic and thermodynamic parameters and side reactions affecting the catalyst. The coordination chemistry and activity of copper complexes used in ATRP are reviewed in chronological order, while emphasizing the structure-activity correlation. ATRP-initiating systems are described, from ...

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“…This further supports the ATRP-like catalytic nature of 9h. 11 and other literature protocols 60,74 , we propose a mechanism for the polymerization of MMA with 9h (Scheme 39). Upon heating the solution, the initiator (TsCl) radicalizes.…”

Section: Polymerization Studies With a Co 2+ Catalystmentioning

confidence: 97%

Catalytic and co-ordination chemistry of enolate oxazoline K2-N,O-ligands to group 9 & 11 transition metals

May¹

2021

Preprint

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The co-ordination chemistry and resulting catalytic potential of Group 9 and 11 transition metal centered complexes with the 2-acylmethyl-2-oxazoline skeleton are detailed. Each of the synthesized ligand species were treated with either a Copper (II) or Cobalt (II) salt to promote co-ordination, in all cases deprotonation of the ligand occurred. These complexes have, thereafter, been examined by infrared spectroscopy (IR), UV-Visible spectroscopy (UV-Vis), mass spectrometry (MS), cyclic voltammetry (CV), combustion analysis (EA) and x-ray diffraction and probed for their potential redox properties. In the case of Cu(II) chelated complexes, no desirable redox behaviour was observed. Although, with respect to Co(II) complexes, one complex displayed favourable redox potential. The redox active species have been shown to effectively catalyze the polymerization of methyl methacrylate with tosyl chloride as an initiator, through an ATRP-like mechanism. Work within also reflects preliminary co-ordination to Iridium and Rhodium metal centers. Successfully synthesized Iridium complexes have been tested with respect to their oxidative properties. Positive results have been observed in their ability to perform oxidative addition with both HSnPh3 and MeI. Both small molecule species have been effectively added to an Ir(I) complex, formally changing its oxidation state to Ir(III).

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Cobalt(I)‐mediated living radical polymerization of methyl methacrylate

Cited by 27 publications

References 47 publications

Kinetics of Atom Transfer Radical Polymerization

Kinetics of Atom Transfer Radical Polymerization

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Catalytic and co-ordination chemistry of enolate oxazoline K2-N,O-ligands to group 9 & 11 transition metals

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