Ultra-High Molecular Weights via Aqueous Reversible-Deactivation Radical Polymerization

Carmean, R. Nicholas; Becker, Troy E.; Sims, Michael B.; Sumerlin, Brent S.

doi:10.1016/j.chempr.2016.12.007

Cited by 243 publications

(244 citation statements)

References 49 publications

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“…[9] Especially the use of light as an initiation source has recently gotten into the focus of research. [13][14][15][16] Much less studied are the slower monomers,s uch as methacrylates,f or which as ignificant improvement was made only recently. An inarguable improvement compared to thermally initiated RDRPs is that the radical concentration can be adjusted independently from temperature,promoting fast and highly controlled chain propagation.…”

mentioning

confidence: 99%

Ultrafast PhotoRAFT Block Copolymerization of Isoprene and Styrene Facilitated through Continuous‐Flow Operation

Lauterbach¹,

Rubens

Abetz³

et al. 2018

Angew Chem Int Ed

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Polymers made from isoprene and styrene resemble an important class of synthetic macromolecules found in a wide range of everyday commodity products. Their synthesis is usually limited to radical emulsion or anionic polymerization. Herein, we report on ultrafast photoiniferter reversible addition-fragmentation chain transfer (RAFT) polymerization of isoprene and styrene in a continuous-flow microreactor. The cooperative action of a high photoinitiation efficiency and use of elevated temperatures considerably reduces the reaction times to less than half an hour to give high monomer conversions, allowing for the first time polyisoprene to be yielded from controlled radical polymerization in high definition and reasonable reaction times. High chain-end fidelities are maintained and block copolymers were prepared including a polystyrene-block-polyisoprene-block-polystyrene (PS-b-PI-b-PS) triblock copolymer.

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confidence: 99%

Ultrafast PhotoRAFT Block Copolymerization of Isoprene and Styrene Facilitated through Continuous‐Flow Operation

Lauterbach¹,

Rubens

Abetz³

et al. 2018

Angew Chem Int Ed

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“…[24] Regardless of the radical-concentration profile,w ell-defined polymers were obtained in all cases, indicating the strength of the RAFT agent in controlling propagating radicals through ap rocess of rapid degenerativec hain transfers (Table 1). [29] Using am ild UV-light source, an analogousp hoto-RAFT reaction was conducted in the absence of the Fe 2 + /H 2 O 2 initiation system. Further investigations into the loading level of Fe 2 + ( Table S2 in the Supporting Information) and the ratio between H 2 O 2 and Fe 2 + (TableS3i nt he Supporting Information) demonstrated the importance of the catalytic system for both activation and deactivationo fa ctive (initiating and propagating) radicals in the system and were consistentw ith reports on free radicalp olymerization demonstrated by Dainton et al [25] Careful analysiso ft he resultsr evealed that for successful polymerization H 2 O 2 must be employed in molar excess relative to Fe 2 + ,w ith an optimum molar ratio determined to be at hreefold excess of H 2 O 2 (Entry 15, Ta ble S3 in the Supporting Information),a chieving ac onversion of 85 %w ithin 5min.…”

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confidence: 99%

Fenton‐RAFT Polymerization: An “On‐Demand” Chain‐Growth Method

Reyhani

McKenzie

Ranji‐Burachaloo

et al. 2017

Chemistry A European J

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Fine control over the architecture and/or microstructure of synthetic polymers is fast becoming a reality owing to the development of efficient and versatile polymerization techniques and conjugation reactions. However, the transition of these syntheses to automated, programmable, and high-throughput operating systems is a challenging step needed to translate the vast potential of precision polymers into machine-programmable polymers for biological and functional applications. Chain-growth polymerizations are particularly appealing for their ability to form structurally and chemically well-defined macromolecules through living/controlled polymerization techniques. Even using the latest polymerization technologies, the macromolecular engineering of complex functional materials often requires multi-step syntheses and purification of intermediates, and results in sub-optimal yields. To develop a proof-of-concept of a framework polymerization technique that is readily amenable to automation requires several key characteristics. In this study, a new approach is described that is believed to meet these requirements, thus opening avenues toward automated polymer synthesis.

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Section: Aqueous Photoatrp and Photoraftmentioning

confidence: 99%

“…In 2017, Sumerlin and co‐workers reported an aqueous iniferter RAFT using near UV light (365 nm) at 35 °C . This system was designed to access ultrahigh molecular weight (UHMW) polymers with good control.…”

Section: Aqueous Photoatrp and Photoraftmentioning

confidence: 99%

Photochemistry for Well‐Defined Polymers in Aqueous Media: From Fundamentals to Polymer Nanoparticles to Bioconjugates

Burridge

Wright

Page

et al. 2018

Macromol. Rapid Commun.

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This review article highlights recent developments in the field of photochemistry and photochemical reversible deactivation radical polymerization applied to aqueous polymerizations. Photochemistry is a topic of significant interest in the fields of organic, polymer, and materials chemistry because it allows challenging reactions to be performed under mild conditions. Aqueous polymerization is of significant interest because water is an environmentally benign solvent, and the use of water enables complex polymer self-assembly and bioconjugation processes to occur. This review focuses on powerful new developments in photochemical aqueous polymerization reactions and their applications to the synthesis of well-defined polymer nano-objects and bioconjugates. It is anticipated that these aqueous photopolymerizations will enable the next generation of self-assembled structures and biohybrid materials to be developed under mild and environmentally friendly conditions.

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Ultra-High Molecular Weights via Aqueous Reversible-Deactivation Radical Polymerization

Abstract: 2017-08-30T02:06:43

Cited by 243 publications

References 49 publications

Ultrafast PhotoRAFT Block Copolymerization of Isoprene and Styrene Facilitated through Continuous‐Flow Operation

Ultrafast PhotoRAFT Block Copolymerization of Isoprene and Styrene Facilitated through Continuous‐Flow Operation

Fenton‐RAFT Polymerization: An “On‐Demand” Chain‐Growth Method

Photochemistry for Well‐Defined Polymers in Aqueous Media: From Fundamentals to Polymer Nanoparticles to Bioconjugates

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