Electrochemically Controlled Cationic Polymerization of Vinyl Ethers

Peterson, Brian M.; Lin, Song; Fors, Brett P.

doi:10.1021/jacs.8b00173

Cited by 115 publications

(119 citation statements)

References 46 publications

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“…[1] Recently,c hemists have developed systems that gain spatiotemporal control over polymer chain growth with various external stimuli, adding to the repertoire of methods to control macromolecular structure. [2][3][4][5][6][7][8][9] These techniques have proven useful in av ariety of applications such as biological assays,p hotoresponsive materials,a nd surface patterning based on the ability to externally regulate chain-growth. Light is arguably one of the most powerful external stimuli used for polymerizations and new developments in this area will enable the synthesis of new functional materials.…”

Section: Enhancing Temporal Control and Enablingchain-end Modificatiomentioning

confidence: 99%

Enhancing Temporal Control and Enabling Chain‐End Modification in Photoregulated Cationic Polymerizations by Using Iridium‐Based Catalysts

2018

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Gaining temporal control over chain growth is a key challenge in the enhancement of controlled living polymerizations. Though research on photocontrolled polymerizations is still in its infancy, it has already proven useful in the development of previously inaccessible materials. Photocontrol has now been extended to cationic polymerizations using 2,4,6-triarylpyrylium salts as photocatalysts. Despite the ability to stop polymerization for a short time, monomer conversion was observed over long dark periods. Improved catalyst systems based on Ir complexes give optimal temporal control over chain growth. The excellent stability of these complexes and the ability to tune the excited and ground state redox potentials to regulate the number of monomer additions per cation formed allows polymerization to be halted for more than 20 hours. The excellent stability of these iridium catalysts in the presence of more nucleophilic species enables chain-end functionalization of these polymers.

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Section: Enhancing Temporal Control and Enablingchain-end Modificatiomentioning

confidence: 99%

Enhancing Temporal Control and Enabling Chain‐End Modification in Photoregulated Cationic Polymerizations by Using Iridium‐Based Catalysts

2018

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“…Instead of using reductive conditions and radical intermediates, a RAFT cationic polymerization was successfully triggered by either direct or mediated oxidation of a dithiocarbamate CTA, resulting in well‐defined polyvinyl ethers with a temporal control over the polymerization. However, under such oxidative conditions the monomer propagated via cationic intermediates, instead of radical species.…”

Section: Introductionmentioning

confidence: 99%

Synergy between Electrochemical ATRP and RAFT for Polymerization at Low Copper Loading

Wang

Fantin

Matyjaszewski

2018

Macromol. Rapid Commun.

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A dual-concurrent atom transfer radical polymerization/reversible addition-fragmentation chain-transfer (ATRP/RAFT) system is used to control a radical polymerization by electrochemical reduction of small amount of copper complexes in the presence of a chain transfer agent (CTA). Electrochemical ATRP conditions provide a continuous supply of radicals, while the CTA aids the control over molecular weight and dispersity of poly(n-butyl acrylate), even in the presence of low ppm amounts of catalyst. The polymerization could be turned "on" and "off" by shifting electrolysis potential. With as low as 10 ppm of Cu catalyst, addition of only 2% CTA (with respect to the ATRP initiator) improves control by decreasing dispersity from Ð = 1.41 to Ð = 1.25.

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“…Thef irst reports of polymer-analogous reactions by Staudinger are nearly ac entury old. [2][3][4] Despite the history and commercial relevance of the CÀHf unctionalization of polymers,t he field does not have clearly defined common criteria and objectives.N ow is an opportune time to outline previous contributions and define new directions,asadvances in radical chemistry, [166] photoredox catalysis, [167][168][169][170] organic electrochemistry, [171][172][173] and CÀHf unctionalization [14][15][16] have provided unprecedented bond disconnections for constructing small molecules.T ranslating these concepts to the functionalization of commodity polymers will leverage the existing production capacity of plastics to transform the properties of existing polymers,d iscover new material properties,and upcycle post-consumer plastic waste.…”

Section: Outlook and Future Directionsmentioning

confidence: 99%

C−H Functionalization of Commodity Polymers

et al. 2019

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Synthetic manipulation of polymer substrates is one of the oldest and most reliable methods to increase the functional diversity of soft materials. Modifying the chemical structure of polymers that are already produced on a commodity scale leverages the current high‐volume and low‐cost production of commodity plastics for the discovery of modern materials. A myriad of polymer C−H functionalization methods have been developed which enable the modification of material properties on both a laboratory and industrial scale. More recently, driven by advances in C−H activation, photoredox catalysis, and radical chemistry, chemoselective approaches have emerged as a means to impart precise functionality onto commodity polymer substrates. This Review discusses the historical significance of and contemporary advances in the C−H functionalization of commodity polymers. The conceptual approach outlined herein presents exciting new directions for the field, including increasing the value of otherwise pervasive materials, uncovering entirely new material properties, and a viable path to upcycle post‐consumer plastic waste.

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Electrochemically Controlled Cationic Polymerization of Vinyl Ethers

Cited by 115 publications

References 46 publications

Enhancing Temporal Control and Enabling Chain‐End Modification in Photoregulated Cationic Polymerizations by Using Iridium‐Based Catalysts

Enhancing Temporal Control and Enabling Chain‐End Modification in Photoregulated Cationic Polymerizations by Using Iridium‐Based Catalysts

Synergy between Electrochemical ATRP and RAFT for Polymerization at Low Copper Loading

C−H Functionalization of Commodity Polymers

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