Photocontrolled RAFT polymerization: past, present, and future

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(9), P. 3035 - 3097

Published: Jan. 1, 2023

In this review, we provide a brief history, progress, and applications, discuss the remaining challenges of photocontrolled reversible addition-fragmentation chain transfer (RAFT) polymerization (i.e., photoinduced electron/energy transfer-RAFT (PET-RAFT), photoiniferter, photomediated cationic RAFT polymerization). Among these, visible-light-driven has attracted particular attention in recent years due to its benefits, including low energy consumption safe reaction procedure. Moreover, incorporation visible-light photocatalysis conferred attractive features, such as spatiotemporal control oxygen tolerance; however, clear understanding mechanism not been completely provided. We also present research efforts elucidate mechanisms with aid quantum chemical calculations combined experimental evidence. This review offers an insight into better design systems for desired applications helps realize full potential both academic- industrial-scale applications.

Language: Английский

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Precision polymer synthesis by controlled radical polymerization: Fusing the progress from polymer chemistry and reaction engineering

Progress in Polymer Science, Journal Year: 2022, Volume and Issue: 130, P. 101555 - 101555

Published: May 7, 2022

Language: Английский

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Reversed Controlled Polymerization (RCP): Depolymerization from Well-Defined Polymers to Monomers

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 9898 - 9915

Published: May 1, 2023

Controlled polymerization methods are well-established synthetic protocols for the design and preparation of polymeric materials with a high degree precision over molar mass architecture. Exciting recent work has shown that end-group fidelity and/or functionality inherent in these techniques can enable new routes to depolymerization under relatively mild conditions. Converting polymers back pure monomers by is potential solution environmental ecological concerns associated ultimate fate polymers. This perspective focuses on emerging field from synthesized controlled polymerizations including radical, ionic, metathesis polymerizations. We provide critical review current literature categorized according technique explore numerous concepts ideas which could be implemented further enhance lower temperature systems, catalytic depolymerization, increasing polymer scope, depolymerization.

Language: Английский

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Driving Polymer Brushes from Synthesis to Functioning

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: March 23, 2023

The great success of controlled radical polymerizations has encouraged researchers to develop more facile and robust approaches for surface-initiated (SIPs) fabricate polymer brushes, even non-experts. In recent years, external-stimuli-mediated polymerization methods have come the fore as SIPs because their less rigorous synthetic procedures high controllability, which expand opportunities synthesizing macromolecules with desired chemical compositions structures, well tailor-made polymers bioconjugates that show broad applicability physiological compatibility. This review discusses latest developments in methods, particular, external-stimuli mediated atom transfer (ATRP), photo-induced polymerizations, reversible addition-fragmentation chain (RAFT) polymerization, other combination application surface grafting. implementation these is interest due unique possibilities temporally control a process, fast straightforward environmentally benign features, lead established emerging applications biolubrication, antifouling, biosensing.

Language: Английский

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Solvent‐Free Chemical Recycling of Polymethacrylates made by ATRP and RAFT polymerization: High‐Yielding Depolymerization at Low Temperatures

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: July 31, 2023

Although controlled radical polymerization is an excellent tool to make precision polymeric materials, reversal of the process retrieve starting monomer far less explored despite significance chemical recycling. Here, we investigate bulk depolymerization RAFT and ATRP-synthesized polymers under identical conditions. RAFT-synthesized undergo a relatively low-temperature solvent-free back thanks partial in situ transformation end-group macromonomer. Instead, can only depolymerize at significantly higher temperatures (>350 °C) through random backbone scission. To aid more complete even lower temperatures, performed facile quantitative modification strategy which both ATRP end-groups were successfully converted macromonomers. The macromonomers triggered temperature with onset 150 °C yielding up 90 % regeneration. versatility methodology was demonstrated by scalable (≈10 g polymer) retrieving 84 intact could be subsequently used for further polymerization. This work presents new low-energy approach depolymerizing creates many future opportunities as high-yielding, methods are sought.

Language: Английский

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Design of Antimicrobial Polymers

Macromolecular Chemistry and Physics, Journal Year: 2022, Volume and Issue: 224(3)

Published: Aug. 12, 2022

Abstract Antibiotic resistance has become a critical issue, alarming the healthcare and agriculture sectors worldwide. Thanks to rapid advancements in polymer science, antimicrobial polymers (AMPs) have been developed as mimic version of host‐defense peptides (a part natural immune systems multicellular organisms) mitigate antibiotic resistance. By exploiting advanced polymerization techniques, structures are easily manipulated well‐defined controlled manner, enabling precise accurate evaluation structure–activity relationship. Recent years witnessed blossoming development. This review provides comprehensive insight into from concept structure design, biofunction control. Along with optimization intrinsic factors, including compositional topological features, external factors like induced conformation upon exposure specific targeting pathogens should be considered AMP design optimization. Furthermore, new approaches smart response platforms (or bacterial‐induced triggering systems) administration dosage forms for also discussed prospective strategies address remaining challenge toxicity while maintaining or even enhancing potency.

Language: Английский

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Controlled radical depolymerization: Structural differentiation and molecular weight control

Chem, Journal Year: 2023, Volume and Issue: 10(1), P. 388 - 401

Published: Oct. 26, 2023

Depolymerization of polymers synthesized by reversible deactivation radical polymerization (RDRP) has recently emerged as a promising chemical recycling method for circular economy. However, current depolymerization reactions are typically uncontrolled (i.e., molecular weight remains unchanged), thus providing no handle over the and limiting further applications. Herein, we report controlled addition-fragmentation chain-transfer (RAFT) that enables gradual decrease in weight, resembling reverse process polymerization. The key to our strategy is enhance chain depropagation employing RAFT agents with high activity, resulting unzipping polymer chains linear time. As an exemplary application, demonstrate structural characterization various copolymers AB diblock versus BA statistical gradient) facilitating sequential release monomers from end, pushing boundaries unlocking new

Language: Английский

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Shaping the Structure and Response of Surface-Grafted Polymer Brushes via the Molecular Weight Distribution

JACS Au, Journal Year: 2023, Volume and Issue: 3(2), P. 333 - 343

Published: Feb. 6, 2023

Breadth in the molecular weight distribution is an inherent feature of synthetic polymer systems. While past this was typically considered as unavoidable consequence synthesis, multiple recent studies have shown that tailoring can alter properties brushes grafted to surfaces. In Perspective, we describe advances methods control surface-grafted polymers and highlight reveal how shaping generate novel or enhanced functionality these materials.

Language: Английский

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Acid-triggered radical polymerization of vinyl monomers

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(3), P. 347 - 356

Published: Jan. 4, 2024

Abstract Reversible addition–fragmentation chain-transfer (RAFT) polymerization is one of the most versatile and robust controlled radical methods owing to its broad material scope high tolerance various functionalities impurities. However, operate RAFT polymerization, a constant supply radicals required, typically via exogenous thermal initiators that are not only challenging transport store, but also primarily responsible for termination end-group heterogeneity. Here we present an acid-triggered operates in dark without any conventional initiator. Abundant acids (for example, sulfuric acid) shown have dual role initiating accelerating polymerization. The polymers prepared low dispersity fidelity. method compatible with wide range vinyl monomers solvents, can be applied synthesis well-controlled molecular weight block copolymers, as well free

Language: Английский

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Future Directions for Atom Transfer Radical Polymerizations

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(4), P. 1775 - 1778

Published: Feb. 27, 2024

ADVERTISEMENT RETURN TO ISSUEEditorialNEXTFuture Directions for Atom Transfer Radical PolymerizationsKrzysztof Matyjaszewski*Krzysztof MatyjaszewskiDepartment of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States*Email: [email protected]More by Krzysztof Matyjaszewskihttps://orcid.org/0000-0003-1960-3402Cite this: Chem. Mater. 2024, 36, 4, 1775–1778Publication Date (Web):February 27, 2024Publication History Received17 December 2023Published online27 February 2024Published inissue 27 2024https://doi.org/10.1021/acs.chemmater.3c03213Copyright © Published 2024 American Chemical Society. This publication is available under these Terms Use. Request reuse permissions free to access through this site. Learn MoreArticle Views1083Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF and HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated Crossref daily. Find more information about citation counts.The Altmetric Attention Score a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (940 KB) Get e-AlertscloseSUBJECTS:Chemical biology,Copolymers,Monomers,Polymers,Radical polymerization e-Alerts

Language: Английский

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