Harnessing the Interaction between Surfactant and Hydrophilic Catalyst To Control <i>e</i>ATRP in Miniemulsion

Fantin, Marco; Chmielarz, Paweł; Wang, Yi; Lorandi, Francesca; Isse, Abdirisak Ahmed; Gennaro, Armando; Matyjaszewski, Krzysztof

doi:10.1021/acs.macromol.7b00530

Cited by 103 publications

(103 citation statements)

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“…A controlled polymerization was even obtained with [SDS] as low as 1.15 wt % relative to monomer, which is below the critical micellar concentration (cmc) of the surfactant in the polymerization media (cmc = 8.9 mM for SDS in water + 0.1 M NaBr, T = 65 °C, which corresponds to 1.46 wt % relative to BA). 45 Reducing [SDS] resulted in decreased control because less ion pairs were formed and less catalyst was bound to the surface of the droplets. Polymerization rate decreased because the droplets size increased, lowering the overall interfacial area, which slowed down the kinetics of mass transport.…”

Section: Resultsmentioning

confidence: 99%

“…Despite its insoluble nature in n -butyl acrylate (BA), the catalyst enters hydrophobic BA droplets when combined with an anionic surfactant, sodium dodecyl sulfate (SDS). 45 The interaction between catalyst and SDS formed neutral ion pairs, Br–Cu II TPMA + /DS − , that resided either at the surface or inside the BA droplets. This concept could be considered as a paradigm shift for miniemulsion ATRP, which previously required very hydrophobic catalysts that were predominately confined to the organic phase.…”

Section: Introductionmentioning

confidence: 99%

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Miniemulsion ARGET ATRP via Interfacial and Ion-Pair Catalysis: From ppm to ppb of Residual Copper

et al. 2017

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It was recently reported that copper catalysts used in atom transfer radical polymerization (ATRP) can combine with anionic surfactants used in emulsion polymerization to form ion pairs. The ion pairs predominately reside at the surface of the monomer droplets, but they can also migrate inside the droplets and induce a controlled polymerization. This concept was applied to activator regenerated by electron transfer (ARGET) ATRP, with ascorbic acid as reducing agent. ATRP of n-butyl acrylate (BA) and n-butyl methacrylate (BMA) was carried out in miniemulsion using CuII/tris(2-pyridylmethyl)amine (TPMA) as catalyst, with several anionic surfactants forming the reactive ion-pair complexes. The amount and structure of surfactant controlled both the polymerization rate and the final particle size. Well-controlled polymers were prepared with catalyst loadings as low as 50 ppm, leaving only 300 ppb of Cu in the precipitated polymer. Efficient chain extension of a poly(BMA)-Br macroinitiator confirmed high retention of chain-end functionality. This procedure was exploited to prepare polymers with complex architectures such as block copolymers, star polymers, and molecular brushes.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Miniemulsion ARGET ATRP via Interfacial and Ion-Pair Catalysis: From ppm to ppb of Residual Copper

et al. 2017

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“…e ATRP has also been successfully used in both dispersed and homogeneous aqueous media . In particular, the aqueous e ATRP of oligo(ethylene glycol)methyl ether methacrylate (OEOMA) and the detailed electrochemical analysis of the properties of common ATRP catalysts in pure water and H 2 O/OEOMA mixtures have fundamentally contributed to understanding and winning the challenges of aqueous ATRPs .…”

Section: Introductionmentioning

confidence: 99%

Biocompatible polymers via aqueous electrochemically mediated atom transfer radical polymerization

Michieletto

Lorandi

Bon

et al. 2019

Journal of Polymer Science

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The preparation of well‐defined polymers via aqueous atom transfer radical polymerization (ATRP) is challenging due to the high activity and limited stability of ATRP catalysts in water. Optimized conditions previously reported for the ATRP of some water‐soluble monomers cannot be regarded as universal conditions. Indeed, well‐controlled electrochemically mediated ATRP (eATRP) of oligo(ethylene oxide)methyl ether acrylate (OEOA) and 2‐hydroxyethyl methacrylate (HEMA) were achieved by adjusting the conditions in relation to the solubility and reactivity of these monomers and corresponding polymers. Importantly, PEOA with low dispersity and predetermined molecular weight was obtained even with low catalyst loading and high monomer content (up to 50 vol %). Moreover, >90% conversion of HEMA was obtained within 6–7 h, giving PHEMA with dispersity 1.2–1.3. This work confirms eATRP as a versatile, clean technique applicable to a range of water‐soluble, biocompatible monomers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 114–123

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“…Last, the reaction can be stopped and restarted on demand, by appropriately adjusting the applied potential or current. This technique was applied to several monomers in organic solvents, water (at both neutral and very acidic pH), oil‐in‐water miniemulsion and ionic liquids …”

Section: Introductionmentioning

confidence: 99%

Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate: The Importance of Catalytic Halogen Exchange

2019

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Electrochemically mediated atom transfer radical polymerization (eATRP) of methyl methacrylate (MMA) was studied in 1‐butyl‐3‐methylimidazolium triflate ([BMIm][OTf]) and ethanol. When 2‐bromopropionitrile and ethyl 2‐bromoisobutyrate were used as initiators, poorly controlled or uncontrolled polymerizations yielding polymers with molecular weights largely exceeding the theoretical values were obtained. Poor control was attributed to a reactivity mismatch between initiator and dormant species, which was successfully suppressed by combining eATRP with catalytic halogen exchange. Well‐defined polymers (Mn>30000 and Ð<1.2) were obtained in both solvents under optimized conditions. The possibility of using PMDETA as an inexpensive ligand in combination with ethyl α‐bromophenylacetate as initiator was also successful. Good chain‐end fidelity during eATRP was confirmed by chain extension of PMMA‐Cl macroinitiator with MMA in ethanol. Polymers prepared in both solvents were found to be mainly syndiotactic, without any solvent effect on tacticity.

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Harnessing the Interaction between Surfactant and Hydrophilic Catalyst To Control eATRP in Miniemulsion

Cited by 103 publications

References 32 publications

Miniemulsion ARGET ATRP via Interfacial and Ion-Pair Catalysis: From ppm to ppb of Residual Copper

Miniemulsion ARGET ATRP via Interfacial and Ion-Pair Catalysis: From ppm to ppb of Residual Copper

Biocompatible polymers via aqueous electrochemically mediated atom transfer radical polymerization

Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate: The Importance of Catalytic Halogen Exchange

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