Getting faster: low temperature copper-mediated SARA ATRP of methacrylates, acrylates, styrene and vinyl chloride in polar media using sulfolane/water mixtures

Mendes, Joana P.; Mendonça, Patrícia V.; Maximiano, Pedro; Abreu, Carlos M. R.; Guliashvili, Tamaz; Serra, Arménio C.; Coelho, Jorge F. J.

doi:10.1039/c5ra20872f

Cited by 34 publications

(32 citation statements)

References 19 publications

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“…Mechanistically, the increased rate of polymerization was due to the gradual reduction of the deactivator, X‐Cu II L + . The proposed dominant mechanism of ATRP in the presence of Cu 0 is shown in Scheme .…”

Section: Development Of Atrp Initiation Systemsmentioning

confidence: 99%

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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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Section: Development Of Atrp Initiation Systemsmentioning

confidence: 99%

“…Inorganic sulfites such as Na 2 S 2 O 4 can also be used in SARA ATRP with a similar role of both reducing agents and supplemental activators …”

Section: Development Of Atrp Initiation Systemsmentioning

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

View full text Add to dashboard Cite

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“…A recent study revealed an unusual increase in polarity, when DMSO/BMIM‐PF 6 /glycol mixtures are used in the SARA ATRP of MA which allows very fast and controlled polymerizations . Furthermore, the presence of water in the sulfolane reactions also contributes to an increase of the rate of polymerization catalyzed by zerovalent metals . Here, we investigated the influence of both TEG and water in the SARA ATRP of MA with Cu(0) and CuBr 2 /Me 6 TREN catalytic system at room temperature (Table ).…”

Section: Resultsmentioning

confidence: 99%

“…Aiming to avoid some important limitations of using DMSO as solvent for ATRP methods (e.g., the poor solubility of styrene), sulfolane was introduced in the ATRP arena as an “universal” and industrial solvent for SARA‐ATRP of meth(acrylate)s, styrene (Sty), and vinyl chloride (VC) …”

Section: Introductionmentioning

confidence: 99%

Ambient temperature SARAATRP for meth(acrylates), styrene, and vinyl chloride using sulfolane/1-butyl-3-methylimidazolium hexafluorophosphate-based mixtures

Mendes

Góis

Costa

et al. 2017

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

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The supplemental activator reducing agent atom transfer radical polymerization (SARA ATRP) with catalytic system composed of Cu(0) and CuBr2/Me6TREN at room temperature using different sulfolane/co‐solvent‐based mixtures is reported. Three different co‐solvents were studied: 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIM‐PF6), water, and tetraethylene glycol (TEG). The results revealed a synergistic effect between sulfolane and BMIM‐PF6, which enhanced the polymerization rate several times while maintaining a stringent control over the polymerization. The catalytic system was used as proof‐of‐concept for the SARA‐ATRP of methyl methacrylate (MMA), styrene (Sty), and vinyl chloride (VC). The addition of 10% of water (or TEG) to the sulfolane/BMIM‐PF6 mixture resulted in fast polymerization rates. The results presented in this manuscript highlight the importance of the sulfolane as an universal industrial solvent for SARA‐ATRP of different monomer families. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1322–1328

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“…[16][17][18][19][20][21][22][23][24][25] ATRP is catalyzed by transition metal complexes and many metals have been tested [26] but over the years the process has been refined to use small amounts of copper complexes with polydentate amine ligands. [27] Indeed, techniques such as initiators for continuous activator regeneration (ICAR) ATRP, [28,29] activators regenerated by electron transfer (ARGET) ATRP, [30][31][32][33] supplemental activator and reducing agent (SARA) ATRP, [34][35][36][37][38][39][40] photoATRP, [41][42][43][44] electrochemically mediated ATRP (eATRP), [45][46][47][48][49][50][51][52] mechanoATRP, [53] sono-ATRP [54][55][56][57][58] allowed well-controlled polymerizations with catalyst amounts down to parts per million levels relative to the monomer. Scheme 1 illustrates the mechanism of eATRP catalyzed by Cu complexes with multidentate nitrogen-based ligands (L).…”

Section: Introductionmentioning

confidence: 99%

Electrochemically Mediated Aqueous Atom Transfer Radical Polymerization of N,N‐Dimethylacrylamide

et al. 2020

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Electrochemically mediated atom transfer radical polymerization (ATRP) of N,N‐dimethylacrylamide (DMAA) catalyzed by copper complexes with polydentate amine ligands was studied systematically in water, investigating several reaction parameters such as applied potential, catalyst concentration, ligand structure, monomer and initiator concentrations. Electropolymerizations were successfully performed under both potentiostatic and galvanostatic conditions; in both eATRP modes, reactions were fast (monomer conversion >90 % in less than 1 h) and well‐controlled, providing polymers with narrow molecular weight distributions. Despite the low dispersity, chain extension attempts of the obtained polymer were not successful because of partial loss of C−Br chain‐end functionality, due to an intramolecular nucleophilic attack. This is an intrinsic drawback of ATRP of acrylamides and although the electrochemical approach allowed preparation of well‐defined polymers in a very short time (down to ca. 15 min), loss of chain‐end functionality was unavoidable.

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Getting faster: low temperature copper-mediated SARA ATRP of methacrylates, acrylates, styrene and vinyl chloride in polar media using sulfolane/water mixtures

Abstract: Supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) of acrylates, methacrylates, styrene and vinyl chloride was successfully performed in sulfolane/water mixtures using ppm amounts of soluble copper.

Cited by 34 publications

References 19 publications

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

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

Ambient temperature SARAATRP for meth(acrylates), styrene, and vinyl chloride using sulfolane/1-butyl-3-methylimidazolium hexafluorophosphate-based mixtures

Electrochemically Mediated Aqueous Atom Transfer Radical Polymerization of N,N‐Dimethylacrylamide

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