Synergistic Effect of 1-Butyl-3-methylimidazolium Hexafluorophosphate and DMSO in the SARA ATRP at Room Temperature Affording Very Fast Reactions and Polymers with Very Low Dispersity

Mendes, Joana P.; Branco, Fábio; Abreu, Carlos M. R.; Mendonça, Patrícia V.; Popov, Anatoliy V.; Guliashvili, Tamaz; Serra, Arménio C.; Coelho, Jorge F. J.

doi:10.1021/mz5002383

Cited by 28 publications

(27 citation statements)

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“…45 These salts can directly activate alkyl halides and also reduce in situ Cu(II) to Cu(I) species. 45-49 In general, sulfites are efficient, inexpensive, safe, and environmentally friendly “co-catalysts” for the synthesis of well-defined polymers both in organic solvents (e.g. DMSO) 45 and in more eco-friendly solvents like ionic liquids, 49 alcohols and alcohols/water mixtures.…”

Section: Introductionmentioning

confidence: 99%

“…7,50 Over the years, different systems have been developed to replace these volatile and potentially hazardous organic solvents by “green” solvents 10,51 like supercritical carbon dioxide, 52,53 ionic liquids 49,54-56 or water. 21,26,30,57 Aqueous ATRP usually results in polymers with relatively high dispersity ( Đ ) indicating either poor control or the loss of chain-end functionality.…”

Section: Introductionmentioning

confidence: 99%

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Aqueous SARA ATRP using inorganic sulfites

Abreu

Carmali

et al. 2017

Polym. Chem.

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Aqueous supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) using inorganic sulfites was successfully carried out for the first time. Under optimized conditions, a well-controlled poly[oligo(ethylene oxide) methyl ether acrylate] (POEOA) was obtained with <30 ppm of soluble copper catalyst using tris(2-pyridylmethyl)amine (TPMA) ligand in the presence of an excess of halide salts (e.g. NaCl). Inorganic sulfites (e.g. Na2S2O4) were continuously fed into the reaction mixture. The mechanistic studies proved that these salts can activate alkyl halides directly and regenerate the activator complex. The effects of the feeding rate of the SARA agent (inorganic sulfites), ligand and its concentration, halide salt and its concentration, sulfite used, and copper concentration, were systematically studied to afford fast polymerizations rates while maintaining the control over polymerization. The kinetic data showed linear first-order kinetics, linear evolution of molecular weights with conversion, and polymers with narrow molecular weight distributions (Đ ~1.2) during polymerization even at relatively high monomer conversions (~80%). “One-pot” chain extension and “one-pot” block copolymerization experiments proved the high chain-end functionality. The polymerization could be directly regulated by starting or stopping the continuous feeding of the SARA agent. Under biologically relevant conditions, the aqueous SARA ATRP using inorganic sulfites was used to synthesize a well-defined protein-polymer hybrid by grafting of P(OEOA480) from BSA-O-[iBBr]30.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Aqueous SARA ATRP using inorganic sulfites

Abreu

Carmali

et al. 2017

Polym. Chem.

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“…An unusual synergetic effect of DMSO and 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIM‐PF 6 ) for the SARA‐ATRP of MA has been recently reported by our research group, which enabled very fast polymerization rates for a broad range of targeted molecular weights, with a very stringent control over the dispersity during the entire course of the polymerizations . In a further contribution, a synergetic effect is observed in the mixtures of BMIM‐PF 6 and glycols which was explored to access the “flash” polymerization of MA reaching almost full conversion in only 11 min (for target DP = 222).…”

Section: Introductionmentioning

confidence: 86%

“…The absorbance was measured, in the 350‐1100 nm range, at room temperature. The E T (30) values of different mixtures were determined according to the expression: E T (30) = 28,591.5/ λ abs,máx (nm) …”

Section: Methodsmentioning

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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“…The improved control was ascribed to a faster degenerative chain transfer reaction, which is critical for control of polydispersity by TERP. The synergistic use of [BMIM]PF 6 as a solvent in supplemental activator and reducing agent (SARA) ATRP of methyl acrylate was recently reported, where very fast polymerization rates, very narrow polydispersities, and well-defined chain end functionalities were reported (61). RTILs have also been used as solvents in activators regenerated by electron transfer (ARGET) ATRP (62,63).…”

Section: Free Radical Polymerizationmentioning

confidence: 99%

Polymerization in Ionic Liquids

Zhang

Behera

Hong

et al. 2015

Encyclopedia of Polymer Science and Technology

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Room temperature ionic liquids (RTILs) have proved over recent years to be useful and unique reaction media for a variety of chemical reactions. Faster reaction rates and better selectivities are often observed in RTILs as compared to those in common organic solvents. In addition to these advantages, the low volatility, nonflammability, and recycling potential also help RTILs become a preferred alternative reaction medium to meet environmental and other requirements. This is evidenced by the ever increasing number of papers published in this area every year and interesting and important discoveries. When conventional free radical polymerizations are carried out in RTILs, there is an increase in the propagation rate due to the high polarity of the RTIL and a decrease in the termination rate because of the high viscosity of the RTILs, and thus the overall reaction rate is greatly increased along with an increase in molecular weight. For living/controlled polymerization such as atom transfer radical polymerization and radical addition‐fragmentation and transfer, the reactions in RTILs are still controllable with faster reaction rates and easy separation of catalysts and/or ligands from the resulting polymers. Nearly all types of polymerization processes have now been successfully conducted in RTILs, often with advantageous effects.

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Synergistic Effect of 1-Butyl-3-methylimidazolium Hexafluorophosphate and DMSO in the SARA ATRP at Room Temperature Affording Very Fast Reactions and Polymers with Very Low Dispersity

Cited by 28 publications

References 28 publications

Aqueous SARA ATRP using inorganic sulfites

Aqueous SARA ATRP using inorganic sulfites

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

Polymerization in Ionic Liquids

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