Effect of Cu(0) Particle Size on the Kinetics of SET-LRP in DMSO and Cu-Mediated Radical Polymerization in MeCN at 25 °C

Lligadas, Gerard; Rosen, Brad M.; Bell, Craig A.; Monteiro, Michael J.; Percéc, Virgil

doi:10.1021/ma8018365

Cited by 207 publications

(270 citation statements)

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“…10 42 exhibit amplified adsorption and desorption processes that may complement the previous studies on the elucidation of the role of the surface of Cu(0) catalyst on the activation and deactivation steps of SET-LRP. 11,[58][59][60][61] This publication reports the aqueous SET-LRP of HEA and OEOMEA mediated by "in situ" generated Cu(0) catalyst. 26,37,38 The study reported here demonstrates that the surface of Cu(0) is responsible both for the activation of the initiator and dormant growing species, as well as for the much lower extent of bimolecular termination observed during polymer synthesis by SET-LRP.…”

Section: Introductionmentioning

confidence: 99%

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

et al. 2015

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The aqueous SET-LRP catalyzed with "in situ" generated Cu(0) of the two amphiphilic monomers 2-hydroxyethyl acrylate (HEA) and oligo(ethylene oxide) methyl ether acrylate (OEOMEA) was investigated at temperatures from −22 to +25°C. while the theoretical value would have to be ∼0%. This high experimental chain-end functionality was explained by the slow desorption of the hydrophobic backbone containing the propagating radicals of these amphiphilic polymers from the surface of the catalyst due to their strong hydrophobic effect.Polymer radicals adsorbed on the surface of Cu(0) undergo monomer addition and reversible deactivation but do not undergo the bimolecular termination that requires desorption. This amplified adsorptiondesorption process that mediates both the activation and the bimolecular termination explains the unexpectedly high chain-end functionality of the polymers synthesized by SET-LRP.

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Section: Introductionmentioning

confidence: 99%

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

et al. 2015

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“…17,61,62 More recently, Percec and co-workers proposed that the Cu(0)-based living radical polymerization proceeds via a single-electron transfer mechanism under certain conditions and that their systems are highly effective for the very fast living radical polymerization of various monomers, leading to well-controlled high-molecular weight polymers with narrow MWDs. [63][64][65][66] In contrast, the Cu(I)-based systems in the presence of reducing agents, such as tin(II) 2-ethylhexanoate, ascorbic acid, Cu(0) and radical initiators, also induced an efficient living radical polymerization, in which the accumulated Cu(II) species changed into the active Cu(I) species via the reduction by these additives. [67][68][69][70] Although the working mechanisms of Cu(0) are still controversial and may depend on the conditions, it is clear that the use of lower oxidation metal species is important for constructing highly catalytic systems.…”

Section: Metal Catalytic Systemsmentioning

confidence: 99%

Recent developments in metal-catalyzed living radical polymerization

Kamigaito

2010

Polym J

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This review presents a short overview of recent developments in metal-catalyzed living radical polymerization, mainly focusing on our recent research studies related to the subject. Metal-catalyzed living radical polymerization or atom transfer radical polymerization, which was originally developed via evolution of the metal-catalyzed Kharasch or atom transfer radical addition to chain-growth polymerization via reversible activation, has now been widely developed in many aspects. The effective metal catalysts include various transition metals, such as ruthenium, copper, iron and nickel, and highly active and versatile catalytic systems have been developed by designing ligands, applying lower oxidation metal species and using additives to widen the scope of controllable monomers and to minimize the amount of metal catalysts and the residual metals in the products. The development of the initiating systems has enabled the synthesis of a wide variety of novel, well-defined polymers, including end-functionalized, block, graft and star polymers, but also more complicated polymers possessing multiple controlled structures. Furthermore, metal-catalyzed living radical polymerization has been judiciously combined with stereospecific radical polymerization based on the use of polar solvents or Lewis acid additives, resulting in the dual control of the molecular weight and the tacticity of the resulting polymers and enabling the preparation of stereoblock and stereogradient polymers. Keywords: block polymer; living radical polymerization; precision polymer synthesis; transition metal catalyst; star polymer; stereospecific polymerization INTRODUCTIONSince the discovery of metal-catalyzed living radical polymerization or atom transfer radical polymerization (ATRP), there have been many developments in this research area, including active and versatile metal catalytic systems; the scope of controllable monomers; well-defined polymers with various controlled architectures; hybridization of the controlled polymers with inorganic, metal and biomolecular compounds; and attempts or real applications to a variety of industrial materials. 1-17 Besides these metal catalytic systems, there have also been substantial developments in various living radical polymerizations, such as nitroxide-mediated polymerizations, reversible addition fragmentation chain-transfer polymerizations and others, and in all of these, there are characteristic features of the mechanisms and components. [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] The metal-catalyzed living radical polymerization was originally discovered via evolution of the metal-catalyzed Kharasch or atom transfer radical addition reaction 35 to the chain-growth polymerization of vinyl monomers (Figure 1). 1 The initiating system generally consists of a transition metal complex in a lower oxidation state and an organic halide, in which the carbon-halogen bond of the halogen compound is activated by the metal catalyst to generate the carbon radical species upon a one-e...

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“…[1][2][3][4][5][6][7][8][9] The simple and highly versatile SET-LRP process based on the catalysis by Cu(0) powder or wire is remarkably effective for synthesis of polyacrylate. [10][11][12][13][14][15][16][17] As we all know, the LRP is the significant and useful procedure to synthesize polymers with controlled molecular weight and narrow molecular weight distribution. However, it has been accomplished only for activated monomers.…”

Section: Introductionmentioning

confidence: 99%

Single electron transfer-living radical polymerization of acrylonitrile catalyzed by lanthanum powder

Zhang

Hao

Chen

2013

J. Polym. Sci. Part A: Polym. Chem.

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INTRODUCTIONIn recent years, single electron transfer-living radical polymerization (SET-LRP) has received great attention for its distinct advantages, including low temperature, ultrafast polymerization, and high molecular weight polymers with narrow molecular weight distribution. [1][2][3][4][5][6][7][8][9] The simple and highly versatile SET-LRP process based on the catalysis by Cu(0) powder or wire is remarkably effective for synthesis of polyacrylate. [10][11][12][13][14][15][16][17] As we all know, the LRP is the significant and useful procedure to synthesize polymers with controlled molecular weight and narrow molecular weight distribution. However, it has been accomplished only for activated monomers. [18][19][20][21][22][23] The defective has been perfected by SET-LRP for its polymerization of nonactivated vinyl chloride. [24][25][26] From the mechanism of SET-LRP, activation of initiator and dormant halide chain ends is catalyzed by the out-sphere electron transfer (OSET). 27 Compared to the inner-sphere electron transfer (ISET) of atom transfer radical polymerization (ATRP), SET-LRP has lower activation energy. The SET process occurs in the presence of solvents and ligands that facilitate the disproportionation of Cu(I) species to Cu(0) and Cu(II). [28][29][30][31] To establish the proper equilibrium between active and inactive chains, suitable solvents and ligands that enhance the disproportionation of Cu(I) complexes must be used. For this purpose, solvents like dimethyl sulfoxide (DMSO), 32,33 trifluoroethanol, 34 alcohol, 35-37 water, 38-42 ionic liquid, 43,44 and the combination of organic solvent mixture, 45,46 and ligands such as tris(2-(dimethylamino)ethyl)amine, 47,48 tris(2-aminoethyl)amine, 49-51 and polyetherimide 52 have been successfully applied. Effects of ligand on the apparent rate constant of propagation of SET-LRP of methyl acrylate (MA) in DMSO have been reported. 46,53 However, SET-LRP process is mainly catalyzed by Cu or Fe, few studies on other metals or metallic derivatives have been attempted. [54][55][56][57] In this study, SET-LRP of AN catalyzed by La(0) powder in N,N-dimethylformamide (DMF) with carbon tetrachloride (CCl 4 ) as initiator, and hexamethylenetetramine (HMTA) as ligand was investigated. Polyacrylonitrile (PAN) with well-defined molecular weight is successfully obtained. EXPERIMENTAL MaterialsAnalytical reagent grade AN (98%, Tianjin FuChen Chemical Reagents, Tianjin, China) was distilled under normal pressure and stored at 5 C. CCl 4 (>99.5%), methanol (CH 3 OH) (>99.5%), and DMF (>99.5%) were purchased from Tianjin Chemical Reagents and used as received. HMTA and La(0) powder were purchased from Aladdin Chemistry and used without further purification.UV-Vis Spectroscopic Analysis of LaCl 2 /HMTA and LaCl 3 / HMTA in AN/DMF The typical example is as follows: LaCl 2 (77.76 mg, 0.380 mmol) or LaCl 3 (93.20 mg, 0.380 mmol) was added into a dry two-neck round-bottom flask, followed by 0.2662 g of HMTA (1.90 mmol), 10 mL of AN, and 10 mL of DMF. Then the flask was ...

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Effect of Cu(0) Particle Size on the Kinetics of SET-LRP in DMSO and Cu-Mediated Radical Polymerization in MeCN at 25 °C

Cited by 207 publications

References 24 publications

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

Recent developments in metal-catalyzed living radical polymerization

Single electron transfer-living radical polymerization of acrylonitrile catalyzed by lanthanum powder

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