Design and Synthesis of a New Indazole-Decorated RAFT Agent for Highly Efficient PET-RAFT Polymerization DOI
Zipeng Zhang, Yueqin Yu, Cyrille Boyer

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(9), P. 4421 - 4429

Published: April 15, 2024

While enabling precise control and well-defined molecular weights in polymer synthesis, photocatalyzed reversible deactivation radical polymerization (photo-RDRP) suffers from slow kinetics, limiting its broader application advanced manufacturing. Despite a decade of research on photocatalyst design, progress significantly improving the kinetics photo-RDRP remains insufficient. In contrast, role initiator is often overlooked, especially photoinduced electron/energy transfer addition–fragmentation chain (PET-RAFT) polymerization, where RAFT agent serves as both agent. this work, we first designed synthesized new with an indazole Z group (InZ) for highly efficient PET-RAFT under irradiation. This strongly electron-donating accelerates initiation by facilitating π* → σ* charge systems. Compared to commonly used trithiocarbonates utilization InZ improved rates 2.7-fold. Additionally, discovered (PC) i.e., zinc 5,10,15,20-tetra(naphthalen-2-yl)porphyrin (ZnTNP), through experimental screening various porphyrin derivates. ZnTNP/InZ system exhibits temporal weight course being compatible broad range acrylates acrylamides exhibiting good oxygen tolerance. Importantly, may inspire further development high-performance agents polymerization.

Language: Английский

Light-driven polymer recycling to monomers and small molecules DOI Creative Commons
Laura Wimberger,

Gervase Ng,

Cyrille Boyer

et al.

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

Published: March 20, 2024

Abstract Only a small proportion of global plastic waste is recycled, which most mechanically recycled into lower quality materials. The alternative, chemical recycling, enables renewed production pristine materials, but generally comes at high energy cost, particularly for processes like pyrolysis. This review focuses on light-driven approaches chemically recycling and upcycling waste, with emphasis reduced consumption selective transformations not achievable heat-driven methods. We focus challenging to recycle backbone structures composed mainly C‒C bonds, lack functional groups i.e., esters or amides, that facilitate e.g., by solvolysis. discuss the use light, either in conjunction heat drive depolymerization monomers via photocatalysis transform polymers valuable molecules. structural prerequisites these are outlined, highlighting their advantages as well limitations. conclude an outlook, addressing key challenges, opportunities, provide guidelines future photocatalyst (PC) development.

Language: Английский

Citations

38
Photocatalytic Upcycling and Depolymerization of Vinyl Polymers DOI Creative Commons
Kostas Parkatzidis, Hyun Suk Wang, Athina Anastasaki

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 11, 2024

Abstract Photocatalytic upcycling and depolymerization of vinyl polymers have emerged as promising strategies to combat plastic pollution promote a circular economy. This mini review critically summarizes current developments in the degradation including polystyrene poly(meth)acrylates. Of these material classes, polymethacrylates possess unique possibility undergo photocatalytic back monomer under thermodynamically favourable conditions, thus presenting significant advantages over traditional thermal strategies. Our perspective on formidable challenges potential future directions are also discussed.

Language: Английский

Citations

34
Current status and outlook for ATRP DOI Creative Commons
Krzysztof Matyjaszewski

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

Citations

23
Visible light–triggered depolymerization of commercial polymethacrylates DOI
Hyun Suk Wang, Mikhail Agrachev, Hongsik Kim

et al.

Science, Journal Year: 2025, Volume and Issue: 387(6736), P. 874 - 880

Published: Feb. 20, 2025

The reversion of vinyl polymers with carbon-carbon backbones to their monomers represents an ideal path alleviate the growing plastic waste stream. However, depolymerizing such stable materials remains a challenge, state-of-the-art methods relying on "designer" that are neither commercially produced nor suitable for real-world applications. In this work, we report main chain-initiated, visible light-triggered depolymerization directly applicable commercial containing undisclosed impurities (e.g., comonomers, additives, or dyes). By in situ generation chlorine radicals from solvent, near-quantitative (>98%) polymethacrylates could be achieved regardless synthetic route radical ionic polymerization), end group, and molecular weight (up 1.6 million daltons). possibility perform multigram-scale depolymerizations confer temporal control renders methodology versatile general recycling.

Language: Английский

Citations

6
Atom transfer radical polymerization DOI
Simon Harrisson, Richard Whitfield, Athina Anastasaki

et al.

Nature Reviews Methods Primers, Journal Year: 2025, Volume and Issue: 5(1)

Published: Jan. 9, 2025

Language: Английский

Citations

4
The thermodynamics and kinetics of depolymerization: what makes vinyl monomer regeneration feasible? DOI Creative Commons
Victoria Lohmann, Glen R. Jones, Nghia P. Truong

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 15(3), P. 832 - 853

Published: Dec. 5, 2023

Insight into the thermodynamics and kinetics of depolymerization to understand barriers that prevent effective monomer regeneration from vinyl polymers, an exploration overcoming these limitations.

Language: Английский

Citations

41
Controlled radical depolymerization: Structural differentiation and molecular weight control DOI Creative Commons
Hyun Suk Wang, Kostas Parkatzidis, Tanja Junkers

et al.

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

Citations

34
Depolymerization of Polymethacrylates with Ball-Mill Grinding DOI
Eunsong Jung, Minyoung Cho, Gregory I. Peterson

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(7), P. 3131 - 3137

Published: March 25, 2024

In this report, we demonstrate that polymethacrylates can undergo appreciable depolymerization, with mild conditions and without reactive end groups, using ball-mill grinding (BMG). For instance, the important commercial polymer, poly(methyl methacrylate) (PMMA) underwent up to 41% depolymerization monomer within 8 min of grinding. We explored factors influence conversion found temperature (heating only 43 °C), addition a small amount liquid (μL tert-butyl alcohol), ball number/size be most parameters. also applied method other pendent substituent extent depolymerization. Addition was reverse effects were observed bulk among studied, PMMA had lowest in one highest conversions slurry. Notably, molecular weight residual polymer is remarkably low, ca. 1 kDa, demonstrating excellent degradation performance BMG. Overall, work provides mechanistic insight into reactions under ball-milling represents an step expanding BMG as tool for chemical recycling polymethacrylates.

Language: Английский

Citations

13
Photochemical upcycling and recycling of plastics: achievements and future opportunities DOI Creative Commons
Olga G. Mountanea,

Elpida Skolia,

Christoforos G. Kokotos

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(15), P. 8528 - 8549

Published: Jan. 1, 2024

Recent developments in the photochemical upcycling and recycling of plastics.

Language: Английский

Citations

13
Closed-loop recyclable polymers: from monomer and polymer design to the polymerization–depolymerization cycle DOI

Shuaiqi Yang,

Shuai Du,

Jin Zhu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(19), P. 9609 - 9651

Published: Jan. 1, 2024

We present the state-of-the-art of circular polymers based on monomer and polymer design reversible ring-opening addition polymerization reactions without involvement other reactants.

Language: Английский

Citations

11