Light-Driven Polymer Recycling to Monomers and Small Molecules DOI Creative Commons
Laura Wimberger,

Gervase Ng,

Cyrille Boyer

и другие.

Опубликована: Фев. 22, 2024

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, mainly C‒C, 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 development.

Язык: Английский

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

Gervase Ng,

Cyrille Boyer

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 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.

Язык: Английский

Процитировано

38

Bulk Depolymerization of Methacrylate Polymers via Pendent Group Activation DOI
Rhys W. Hughes, Megan E. Lott, Isabella S. Zastrow

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(9), С. 6217 - 6224

Опубликована: Фев. 21, 2024

In this study, we present an efficient approach for the depolymerization of poly(methyl methacrylate) (PMMA) copolymers synthesized via conventional radical polymerization. By incorporating low mol % phthalimide ester-containing monomers during polymerization process, colorless and transparent polymers closely resembling unfunctionalized PMMA are obtained, which can achieve >95% reversion to methyl methacrylate (MMA). Notably, our catalyst-free bulk method exhibits exceptional efficiency, even high-molecular-weight polymers, including ultrahigh-molecular-weight (10

Язык: Английский

Процитировано

37

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

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Март 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.

Язык: Английский

Процитировано

34

Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate) DOI
Kwangwook Ko,

David Lundberg,

Alayna M. Johnson

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9142 - 9154

Опубликована: Март 25, 2024

The development of cleavable comonomers (CCs) with suitable copolymerization reactivity paves the way for introduction backbone deconstructability into polymers. Recent advancements in thionolactone-based CCs, exemplified by dibenzo[c,e]-oxepine-5(7H)-thione (DOT), have opened promising avenues selective deconstruction multiple classes vinyl polymers, including polyacrylates, polyacrylamides, and polystyrenics. To date, however, no thionolactone CC has been shown to copolymerize methacrylates an appreciable extent enable polymer deconstruction. Here, we overcome this challenge through design a new class benzyl-functionalized thionolactones (bDOTs). Guided detailed mechanistic analyses, find that radical-stabilizing substituents bDOTs enables markedly increased tunable methyl methacrylate (MMA). Through iterative optimizations molecular structure, specific bDOT, F-p-CF3PhDOT, is discovered efficiently MMA. High molar mass deconstructable PMMA-based copolymers (dPMMA, Mn > 120 kDa) low percentages F-p-CF3PhDOT (1.8 3.8 mol%) are prepared using industrially relevant bulk free radical conditions. thermomechanical properties dPMMA similar PMMA; former degrade fragments (<6.5 under mild aminolysis This work presents first example ring-opening capable nearly random MMA without possibility cross-linking provides workflow mechanism-guided future.

Язык: Английский

Процитировано

19

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

и другие.

Science, Год журнала: 2025, Номер 387(6736), С. 874 - 880

Опубликована: Фев. 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.

Язык: Английский

Процитировано

6

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

Elpida Skolia,

Christoforos G. Kokotos

и другие.

Green Chemistry, Год журнала: 2024, Номер 26(15), С. 8528 - 8549

Опубликована: Янв. 1, 2024

Recent developments in the photochemical upcycling and recycling of plastics.

Язык: Английский

Процитировано

13

Photoiniferter Polymerization: Illuminating the History, Ascendency, and Renaissance DOI
Rhys W. Hughes, Megan E. Lott,

Rebecca A. Olson S

и другие.

Progress in Polymer Science, Год журнала: 2024, Номер 156, С. 101871 - 101871

Опубликована: Авг. 22, 2024

Язык: Английский

Процитировано

13

Harnessing Non-Thermal External Stimuli for Polymer Recycling DOI Creative Commons
Glen R. Jones, Richard Whitfield, Hyun Suk Wang

и другие.

Macromolecules, Год журнала: 2025, Номер 58(5), С. 2210 - 2223

Опубликована: Фев. 18, 2025

Polymeric materials have become indispensable due to their versatility and low cost, yet environmental impact presents a significant global challenge. Traditional chemical recycling methods typically rely on heat as stimulus; for instance, pyrolysis is popular methodology which faces limitations high energy consumption, product selectivity, the generation of undesirable byproducts. In response, recent advances in promotion depolymerization degradation through alternative stimuli such light, electrochemistry, mechanical force, shown promising potential more efficient selective polymer breakdown, yielding either starting monomers or valuable small molecules. This perspective explores key examples these emerging strategies, highlighting improve upon current protocols offer pathways under milder conditions, while identifying challenges that future research must address translate chemistry into viable broadly applicable strategies.

Язык: Английский

Процитировано

1

Chemical recycling of bromine-terminated polymers synthesized by ATRP DOI Creative Commons
Stella Afroditi Mountaki, Richard Whitfield, Kostas Parkatzidis

и другие.

RSC Applied Polymers, Год журнала: 2024, Номер 2(2), С. 275 - 283

Опубликована: Янв. 1, 2024

Efficient, fast and versatile depolymerization of bromine-terminated polymers.

Язык: Английский

Процитировано

9

Enhancing photothermal depolymerization with metalloporphyrin catalyst DOI Creative Commons

Gervase Ng,

Stuart W. Prescott, Almar Postma

и другие.

Journal of Polymer Science, Год журнала: 2024, Номер 62(17), С. 3920 - 3928

Опубликована: Май 22, 2024

Abstract The ability to revert polymers their original monomers represents a crucial chemical recycling technique, promoting sustainability and offering the chance convert used materials into valuable products. In recent years, numerous studies have explored use of synthesized via reversible deactivation radical polymerization (RDRP) techniques facilitate efficient depolymerization reactions. Herein, we report photocatalyst, zinc tetraphenylporphyrin (ZnTPP), along with light irradiation accelerate prepared by addition‐fragmentation chain transfer (RAFT) polymerization. We explore various parameters affecting efficiency, including solvents, reaction temperature (80, 100, 120°C), presence photocatalysts (ZnTPP Eosin Y), type RAFT end‐groups, namely trithiocarbonate, dithiobenzoate, 1 H ‐pyrazole‐1‐carbodithioate. For instance, when PMMA was diluted 25 mM in 1,4‐dioxane heated 120°C under green ZnTPP (200 ppm), rapid exceeding 70% occurred within h. Without ZnTPP, similar conditions, required over 8 h achieve slightly lower yield. Furthermore, this method confers moderate oxygen tolerance system, enabling proceed without need deoxygenation, albeit at rate consequently lesser monomer recovery (31%).

Язык: Английский

Процитировано

8