Analysis of the Cu(0)-Catalyzed Polymerization of Methyl Acrylate in Disproportionating and Nondisproportionating Solvents

Nguyen, Nga H.; Levere, Martin E.; Kulis, Jakov; Monteiro, Michael J.; Percéc, Virgil

doi:10.1021/ma3003714

Cited by 139 publications

(192 citation statements)

References 71 publications

(268 reference statements)

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“…147,149 Nevertheless, in order to expand the scope of SET-LRP to a larger diversity of monomers and polymers, new solvents and solvent combinations with different solubility profiles are required to facilitate the synthesis of novel materials. Thus, when solvents that do not favor the disproportionation of Cu I Br are needed to enhance the solubility of more hydrophobic monomers (e.g., ethyl acetate (EA), 149,156 MeCN, 147,148,157 acetone, 151 97 3.2.2. Complex Solvents.…”

Section: Solvent Compatibilitymentioning

confidence: 99%

Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis

et al. 2015

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Section: Solvent Compatibilitymentioning

confidence: 99%

Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis

et al. 2015

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“…74,126,127 The key features of the SET-LRP mechanism are outlined in Scheme 5, presented in the same way as in Scheme 4, although some reactions are omitted in SET-LRP schematics, as shown in the middle part of Scheme 3. Therefore, SET-LRP does not include any significant kinetic contributions from alkyl halide activation by Cu I .…”

Section: Macromoleculesmentioning

confidence: 99%

“…66 Preservation of Chain-End Functionality. One of the key features of RDRP in the presence of Cu 0 is the high endgroup functionality that can be attained, 74 giving the technique access to polymers with complex architectures such as multiblock copolymers or stars. 62,98,106 This is possible for acrylic polymers due to their high rate coefficient of propagation, relative to the rate coefficient of termination, as highlighted in the monomers section.…”

Section: ■ Features Of Rdrp In the Presence Of Cumentioning

confidence: 99%

Reversible-Deactivation Radical Polymerization in the Presence of Metallic Copper. A Critical Assessment of the SARA ATRP and SET-LRP Mechanisms

et al. 2013

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Reversible-deactivation radical polymerization (RDRP) in the presence of Cu0 is a versatile technique that can be used to create well-controlled polymers with complex architectures. Despite the facile nature of the technique, there has been a vigorous debate in the literature as to the\ud mechanism of the reaction. One proposed mechanism, named supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP), has CuI as the major activator of alkyl halides, Cu0 acting as a supplemental activator, an inner-sphere electron transfer occurring during the activation step, and relatively slow comproportionation and disproportionation. In SARA ATRP slow activation of alkyl halides by Cu0 and comproportionation of CuII with Cu0 compensates for the small number of radicals lost to termination reactions. Alternatively, a mechanism named single electron transfer living radical polymerization (SET-LRP) assumes that the CuI species do not activate alkyl halides, but undergo instantaneous disproportionation, and that the relatively rapid polymerization is due to a fast reaction between alkyl halides and “nascent” Cu0 through an outer-sphere electron transfer. In this article a critical assessment of the experimental data are presented on the polymerization of methyl acrylate in DMSO with Me6TREN as the ligand in the presence of Cu0, in order to discriminate between these two mechanisms. The experimental data agree with the SARA ATRP mechanism, since the activation of alkyl halides by CuI species is significantly faster than Cu0, the activation step involves inner-sphere electron transfer rather than an outer-sphere electron transfer, and in DMSO comproportionation is slow but occurs faster than disproportionation, and activation by CuI species is much faster than disproportionation. The rate of deactivation by CuII is essentially the same as the rate of activation by CuI, and the system is under ATRP equilibrium. The role of Cu0 in this system is to slowly and continuously supply CuI activating species and radicals, by supplemental activation and comproportionation, to compensate for CuI lost due to\ud the unavoidable radical termination reactions. With the mechanistic understanding gained by analyzing the experimental data in the literature, the reaction conditions in SARA ATRP can be tailored toward efficient synthesis of a new generation of complex architectures and functional materials

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“…1,2,26,37,38,47 It is important to mention that from many LRP methods that provide polymers with narrow molecular weight distribution, only SET-LRP generates polymers with both narrow molecular weight distribution and quantitative or near quantitative chain-end functionality. 6,7,[48][49][50][51]57,[71][72][73][74][75][76][77] Narrow molecular weight distribution is an important feature of the polymers prepared by LRP but the most significant structural parameter of these polymers is the quantitative or near quantitative chain-end functionality combined with narrow molecular weight distribution. Chain-end functionality is the major parameter of a polymer that allows the construction of complex architectures such as multiple block copolymers, 64,73,[76][77][78][79] and dendrimers by iterative synthesis.…”

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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Analysis of the Cu(0)-Catalyzed Polymerization of Methyl Acrylate in Disproportionating and Nondisproportionating Solvents

Cited by 139 publications

References 71 publications

Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis

Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis

Reversible-Deactivation Radical Polymerization in the Presence of Metallic Copper. A Critical Assessment of the SARA ATRP and SET-LRP Mechanisms

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

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