Aqueous one-pot synthesis of epoxy-functional diblock copolymer worms from a single monomer: new anisotropic scaffolds for potential charge storage applications

Hatton, Fiona L.; Park, Albert M.; Zhang, Yiren; Fuchs, Gregory D.; Ober, Christopher K.; Armes, Steven P.

doi:10.1039/c8py01427b

Cited by 36 publications

(56 citation statements)

References 41 publications

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“…For PGMA‐ b ‐PGlyMA, reaction with NaN 3 provided azide‐functionalized nanoparticles, and the possibility to crosslink the particle core by the addition of diamines was evidenced. Interestingly, using a shorter PGMA block led to the formation of worms, a morphology that is not obtained very often by emulsion polymerization . Subsequent reaction with 4‐amino‐2,2,6,6‐tetramethylpiperidin‐1‐oxyl produced crosslinked worms bearing a high local concentration of stable nitroxide groups within the worm cores.…”

Section: Reactive/functional Nanoobjectsmentioning

confidence: 99%

RAFT‐Mediated Polymerization‐Induced Self‐Assembly

2020

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After a brief history that positions polymerization‐induced self‐assembly (PISA) in the field of polymer chemistry, this Review will cover the fundamentals of the PISA mechanism. Furthermore, this Review will also give an overview of some of the features and limitations of RAFT‐mediated PISA in terms of the choice of the components involved, the nature of the nanoobjects that can be obtained and how the syntheses can be controlled, as well as some potential applications.

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Section: Reactive/functional Nanoobjectsmentioning

confidence: 99%

RAFT‐Mediated Polymerization‐Induced Self‐Assembly

2020

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“…The strategy developed in the present contribution is to directly synthesize PTMA‐based nano‐objects in suspension in an aqueous medium by copolymerizing it with a hydrophilic polymer block using the PISA process. Our approach is complementary to the one recently reported by Armes and coworkers where a three‐step one‐pot PISA of glycidyl methacrylate (GlyMA) is used . In a first step, GlyMA is converted into glycerol methacrylate (GMA) and a water‐soluble PGMA macro‐initiator is prepared by RAFT polymerization.…”

Section: Introductionmentioning

confidence: 93%

“…Our approach is complementary to the one recently reported by Armes and coworkers where a three-step one-pot PISA of glycidyl methacrylate (GlyMA) is used. [25] In a first step, GlyMA is converted into glycerol methacrylate (GMA) and a water-soluble PGMA macroinitiator is prepared by RAFT polymerization. This PGMA is further used for PISA polymerization of water-insoluble GlyMA to afford worm-like micelles containing a reactive PGlyMA core and a hydrophilic PGMA corona.…”

Section: Introductionmentioning

confidence: 99%

“…The GlyMA units are further derivatized with 4-amino-TEMPO to introduce nitroxide radicals in the core of the worm-like micelles. [25] In our approach, we report the RAFT PISA of the 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (TMPM) monomer which is the precursor of PTMA. Two types of water-soluble macro-CTAs are synthesized, that is, poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) ( Figure 1a) and cationic poly[(4-methacryloyloxy)-2,2,6,6-tetramethylpiperidinium chloride] (PTMPM + Cl − ) ( Figure 1b).…”

Section: Introductionmentioning

confidence: 99%

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Redox Polymer–Based Nano‐Objects via Polymerization‐Induced Self‐Assembly

Boujioui

Zhuge

2019

Macro Chemistry & Physics

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polymer for application as suspension electrode. Indeed, PTMA is able to undergo stable and reversible redox reactions upon electrochemical stimuli. [6] Moreover, it displays high power density with an ultra-fast electron transfer process of 10 −1 cm s −1. [7] Thus, it is also classified as a pseudocapacitive component. This allows PTMA to be widely used as cathode materials in organic radical batteries (ORB). [8,9] Schubert et al. have synthesized water-soluble statistical copolymers containing PTMA and hydrophilic comonomers [10] and have studied their electrochemical properties in water-based and in organic carbonatebased redox flow batteries. [11] While the organic carbonates are widely used due to their good stabilities, the water-based systems reveal better performances as well as positive environmental impact. Furthermore, Schubert and coworkers were able to design a full organic water-based redox flow battery by using water-soluble redox polymers both as catholyte and anolyte. [12] One of the main challenges related to redox polymer-based electrodes remains the relatively low concentration of redoxactive material that can be dissolved while keeping a sufficiently low viscosity to allow the pumping of the liquid electrode in the main electrochemical cell. Decreasing the molar mass of the polymer is not an appropriate option because the redox polymer should not pass through the semi-permeable membrane which is located in the main electrochemical cell. [12] One solution, that allows the dispersion of a high amount of redox polymer without reaching a too high viscosity, consists in tethering the redox polymer chains in a micellar design. Basically, the redox polymer chains could be incorporated into two different compartments of the micellar cargo: the micellar core or the micellar corona. In a previous work, we have designed micellar nano-objects comprising PTMA coronal chains tethered onto a polystyrene (PS) core. These objects were synthesized from PTMA-b-PS diblock copolymers containing a major PTMA block dissolved in carbonate solvents that are selective solvents for the PTMA blocks. [13] The accordingly obtained micelles were successfully tested as catholytes in redox flow batteries. [14] Such a design has the advantage of a good accessibility of the redox-active PTMA chains for redox reactions since they are located in the micellar corona. However, this design has the drawback of being limited to organic solvents for the preparation of the liquid electrodes since both PTMA and PS are hydrophobic groups. The aim of this work is to synthesize micellar nano-objects in aqueous medium containing the redox PTMA polymer. The target is to elaborate an amphiphilic block copolymer containing Redox Polymer Nanoparticles Poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl-methacrylate) (PTMA) redox polymer-based nano-objects are synthesized by polymerization-induced self-assembly with poly[oligo(ethylene glycol) methyl ether methacrylate] and poly[(4-methacryloyloxy)-2,2,6,6-tetramethylpiperidinium chloride] as hydrophili...

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“…Für PGMA‐ b ‐PGlyMA lieferte die Reaktion mit NaN 3 azidfunktionale Nanopartikel, und es wurde die Möglichkeit der Vernetzung des Partikelkerns durch Zugabe von Diaminen nachgewiesen. Interessanterweise führte die Verwendung eines kürzeren PGMA‐Blocks zur Bildung von Würmern, einer Morphologie, die nicht sehr oft durch Emulsionspolymerisation erreicht wird . Eine nachfolgende Reaktion mit 4‐Amino‐2,2,6,6‐tetramethylpiperidin‐1‐oxyl produzierte vernetzte Würmer mit einer hohen lokalen Konzentration an stabilen Nitroxidgruppen innerhalb der Wurmkerne.…”

Section: Reaktive/funktionelle Nanoobjekteunclassified

RAFT‐vermittelte polymerisationsinduzierte Selbstorganisation (PISA)

2020

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Nach einem kurzen historischen Überblick zur polymerisationsvermittelten Selbstorganisation (polymerization‐induced self assembly, PISA) im Bereich der Polymerchemie werden in diesem Aufsatz die Grundlagen des PISA‐Mechanismus erklärt. Darüber hinaus behandelt der Aufsatz einige Eigenschaften und Einschränkungen von RAFT‐vermittelten PISA‐Systemen im Hinblick auf die Auswahl der beteiligten Komponenten, die Art und Steuerung der synthetisierbaren Nanoobjekte und Morphologien sowie mögliche Anwendungen.

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Aqueous one-pot synthesis of epoxy-functional diblock copolymer worms from a single monomer: new anisotropic scaffolds for potential charge storage applications

Abstract: The one-pot synthesis of highly anisotropic epoxy-functional diblock copolymer worms is achieved directly in water using a single monomer (glycidyl methacrylate).

Cited by 36 publications

References 41 publications

RAFT‐Mediated Polymerization‐Induced Self‐Assembly

RAFT‐Mediated Polymerization‐Induced Self‐Assembly

Redox Polymer–Based Nano‐Objects via Polymerization‐Induced Self‐Assembly

RAFT‐vermittelte polymerisationsinduzierte Selbstorganisation (PISA)

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