How to Do a<scp>RAFT</scp>Polymerization

Postma, Almar; Skidmore, Melissa A.

doi:10.1002/9783527821358.ch3

Cited by 2 publications

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“…[ 12 ] As a result, the oxygen sensitivity issues in RDRP require specialized equipment like gloveboxes, freeze–pump–thaw degassing, or inert gas sparging to achieve good control during polymerization. [ 13 ] Unfortunately, these specific setups complicate their usage by nonexperts. Additionally, conventional RDRP may not be the most efficient or cost‐effective approach for producing specialized polymers (such as protein–polymer conjugates).…”

Section: Introductionmentioning

confidence: 99%

Strategies for Achieving Oxygen Tolerance in Reversible Addition–Fragmentation Chain Transfer Polymerization

Prescott

Postma

et al. 2023

Macro Chemistry & Physics

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Reversible addition–fragmentation chain transfer polymerization (RAFT) is a popular method for the synthesis of well‐defined macromolecules, but its sensitivity to oxygen is a major limitation for many industrial applications. Recent research has focused on developing strategies to confer oxygen tolerance onto RAFT polymerization, eliminating the need for deoxygenation steps and allowing for simpler reaction conditions. This minireview highlights several promising approaches to achieve oxygen tolerance in RAFT polymerization, including enzyme‐mediated, alkylborane‐initiated, and photomediated methods. The potential applications of oxygen‐tolerant RAFT polymerization are also discussed, demonstrating the promise for significant advances in large‐scale industrial polymer synthesis.

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Section: Introductionmentioning

confidence: 99%

Strategies for Achieving Oxygen Tolerance in Reversible Addition–Fragmentation Chain Transfer Polymerization

Prescott

Postma

et al. 2023

Macro Chemistry & Physics

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“…Reversible addition–fragmentation chain-transfer (RAFT) polymerization is a powerful and versatile technique for the synthesis of well-defined polymers with complex architectures . The ease of implementation of the RAFT system and its tolerance to various conditions and monomer types has quickly made it one of the most employed reversible-deactivation radical polymerization (RDRP) techniques. − As such, its use has spread beyond the field of polymer chemistry and into more application-focused fields such as nanomedicine, theranostics, coatings, and tailored additives. − …”

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confidence: 99%

Self-Catalyzed Hydrolysis of Nitrile-Containing RAFT Chain-Transfer Agent and Its Impact upon Polymerization Control of Methacrylic Monomers

Jerlhagen,

Wilson,

Malmström

2024

ACS Macro Lett.

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Self-catalyzed hydrolysis upon storage of the common RAFT chain-transfer agent (CTA) 4-cyano-4-[(thiothiopropyl)sulfanyl] pentanoic acid (CTPPA) is confirmed, where the nitrile group is transformed into an amide by catalysis from the adjacent carboxylic acid moiety. The amide-CTA (APP) is found to poorly control molecular weight evolution during polymerization of two methacrylates, methyl methacrylate (MMA) and N,N-(dimethylamino)ethyl methacrylate (DMAEMA), likely due to poor reinitiation speed in the pre-equilibrium. However, when attached to a macromolecule, the impact of this amide moiety becomes insignificant and chain extension proceeds as expected with CTPPA. In light of CTPPA and similarly hydrolyzable CTAs being extensively employed for aqueous polymerizations of methacrylates, these findings highlight the importance of CTA purity when performing RAFT polymerizations.

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How to Do aRAFTPolymerization

Cited by 2 publications

References 108 publications

Strategies for Achieving Oxygen Tolerance in Reversible Addition–Fragmentation Chain Transfer Polymerization

Strategies for Achieving Oxygen Tolerance in Reversible Addition–Fragmentation Chain Transfer Polymerization

Self-Catalyzed Hydrolysis of Nitrile-Containing RAFT Chain-Transfer Agent and Its Impact upon Polymerization Control of Methacrylic Monomers

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