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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Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

Chemical Science, Journal Year: 2022, Volume and Issue: 13(39), P. 11540 - 11550

Published: Jan. 1, 2022

Photoinduced atom transfer radical polymerization (photo-ATRP) has risen to the forefront of modern polymer chemistry as a powerful tool giving access well-defined materials with complex architecture. However, most photo-ATRP systems can only generate radicals under biocidal UV light and are oxygen-sensitive, hindering their practical use in synthesis biohybrids. Herein, inspired by photoinduced electron transfer-reversible addition-fragmentation chain (PET-RAFT) polymerization, we demonstrate dual photoredox/copper catalysis that allows open-air ATRP green irradiation. Eosin Y was used an organic photoredox catalyst (PC) combination copper (X-Cu

Language: Английский

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Ultrasonics in polymer science: applications and challenges

Progress in Materials Science, Journal Year: 2023, Volume and Issue: 136, P. 101113 - 101113

Published: March 22, 2023

Language: Английский

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Fast Bulk Depolymerization of Polymethacrylates by ATRP

ACS Macro Letters, Journal Year: 2023, Volume and Issue: 12(8), P. 1173 - 1178

Published: Aug. 2, 2023

Fast bulk depolymerization of poly(n-butyl methacrylate) and poly(methyl methacrylate), prepared by atom transfer radical polymerization (ATRP), is reported in the temperature range between 150 230 °C. Depolymerization Cl-terminated polymethacrylates was catalyzed a CuCl2/TPMA complex (0.022 or 0.22 equiv vs P-Cl) studied using TGA, also under isothermal conditions. Relatively rapid 5-20 min observed at 180 The preparative scale reactions were carried out short-path distillation setup with up to 84% within 15

Language: Английский

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Red-Light-Driven Atom Transfer Radical Polymerization for High-Throughput Polymer Synthesis in Open Air

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24315 - 24327

Published: Oct. 25, 2023

Photoinduced reversible-deactivation radical polymerization (photo-RDRP) techniques offer exceptional control over polymerization, providing access to well-defined polymers and hybrid materials with complex architectures. However, most photo-RDRP methods rely on UV/visible light or photoredox catalysts (PCs), which require multistep synthesis. Herein, we present the first example of fully oxygen-tolerant red/NIR-light-mediated photoinduced atom transfer (photo-ATRP) in a high-throughput manner under biologically relevant conditions. The method uses commercially available methylene blue (MB+) as PC [X-CuII/TPMA]+ (TPMA = tris(2-pyridylmethyl)amine) deactivator. mechanistic study revealed that MB+ undergoes reductive quenching cycle presence TPMA ligand used excess. formed semireduced MB (MB•) sustains by regenerating [CuI/TPMA]+ activator together provides polymerization. This dual catalytic system exhibited excellent oxygen tolerance, enabling polymerizations high monomer conversions (>90%) less than 60 min at low volumes (50-250 μL) synthesis library DNA-polymer bioconjugates narrow molecular weight distributions (Đ < 1.30) an open-air 96-well plate. In addition, broad absorption spectrum allowed ATRP be triggered UV NIR irradiation (395-730 nm). opens avenues for integration orthogonal reactions. Finally, MB+/Cu catalysis showed good biocompatibility during cells, expands potential applications this method.

Language: Английский

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Photocatalytic ATRP Depolymerization: Temporal Control at Low ppm of Catalyst Concentration

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21146 - 21151

Published: Sept. 22, 2023

A photocatalytic ATRP depolymerization is introduced that significantly suppresses the reaction temperature from 170 to 100 °C while enabling temporal regulation. In presence of low-toxicity iron-based catalysts and under visible light irradiation, near-quantitative monomer recovery could be achieved (up 90%), albeit with minimal control. By employing ppm concentrations either FeCl2 or FeCl3, during dark periods completely eliminated, thus control possibility modulate rate by simply turning "on" "off". Notably, our approach allowed preservation end-group fidelity throughout reaction, carried out at high polymer loadings 2M), was compatible various polymers sources. This methodology provides a facile, environmentally friendly, temporally regulated route chemically recycle ATRP-synthesized polymers, opening door for further opportunities.

Language: Английский

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Visible‐Light‐Mediated Controlled Radical Branching Polymerization in Water

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 16, 2023

Hyperbranched polymethacrylates were synthesized by green-light-induced atom transfer radical polymerization (ATRP) under biologically relevant conditions in the open air. Sodium 2-bromoacrylate (SBA) was prepared situ from commercially available 2-bromoacrylic acid and used as a water-soluble inibramer to induce branching during copolymerization of methacrylate monomers. As result, well-defined branched obtained less than 30 min with predetermined molecular weights (36 000

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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Stretchable phosphorescent polymers by multiphase engineering

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 15, 2024

Stretchable phosphorescence materials potentially enable applications in diverse advanced fields wearable electronics. However, achieving room-temperature simultaneously featuring long-lived emission and good stretchability is challenging because it hard to balance the rigidity flexibility same polymer. Here we present a multiphase engineering for obtaining stretchable phosphorescent by combining stiffness softness well-designed block copolymers. Due microphase separation, copolymers demonstrate an intrinsic of 712%, maintaining ultralong lifetime up 981.11 ms. This generally applicable series binary ternary initiator systems with color-tunable visible range. Moreover, these multi-level volumetric data encryption afterglow display. work provides fundamental understanding nanostructures material properties designing extends potential polymers.

Language: Английский

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Current status and outlook for ATRP

European Polymer Journal, Journal Year: 2024, Volume and Issue: 211, P. 113001 - 113001

Published: March 30, 2024

Atom transfer radical polymerization (ATRP) is one of the most often used controlled techniques. It employs very small amounts (ppm) Cu complexes in presence various chemical reducing agents but also external stimuli such as light, electrical current or mechanical forces. can be carried out bulk, solution, and dispersed media. ATRP has been successfully to prepare polymers with architecture well-defined topology, composition, functionality, well bioconjugates organic–inorganic hybrids. This article summarizes status an outlook for ATRP.

Language: Английский

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