In Situ Modification Assisted by HAT Chemistry for the Main Chain Initiated Depolymerization of Polymethacrylates DOI

Maxime Michelas,

Manish Kumar,

Zhisheng Lin

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 822 - 829

Published: May 29, 2025

In this study we present a novel strategy to enhance the depolymerization of nonfunctionalized poly(methyl methacrylate) (PMMA) by enabling in situ activation polymer backbone using photoinduced Hydrogen Atom Transfer (HAT) chemistry. By screening various disulfide-based RAFT agents, identified commercially available bis(dodecylsulfanylthiocarbonyl) disulfide (DisRAFT-1) as most effective, achieving up 53% monomer recovery within 5 h at 150 °C under 405 nm light irradiation tetrachloroethane (TCE). A systematic investigation key reaction parameters, including DisRAFT-1 loading, temperature, and concentration (10-200 mM), demonstrated efficiency versatility approach. Importantly, highlight that light, elevated chlorinated solvent are all essential initiate depolymerization. Moreover, temporal control over process was achieved via ON/OFF cycles, on-demand This work offers promising route toward chemical recycling polymers leveraging mild tunable conditions.

Language: Английский

Emerging Plastic Recycling Strategies Based on Photothermal Conversion DOI Creative Commons
Hanning Jiang, Yoon-Jung Jang, Clotilde Tagnon

et al.

ACS Applied Polymer Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Increasing plastic pollution presents a significant challenge for humanity and ecosystems. Photothermal (light-to-heat) conversion has emerged as promising strategy recycling waste. Upon light irradiation, photothermal agents provide intense thermal gradients localized to their surfaces, wherein the heat exceeds degradation temperature (Td) of polymers, inducing efficient depolymerization and/or degradation. Thermoplastics (including polyethylene terephthalate (PET), polypropylene (PP), (PE), polystyrene (PS), polycarbonate (PC)) thermosets (epoxy resin) are subject under mild conditions. This review summarizes some key results advancements in polymer waste mitigation using upcycling.

Language: Английский

Citations

2
Ultrafast Thermal RAFT Depolymerization at Higher Solid Contents DOI Creative Commons

Dimitra Mantzara,

Richard Whitfield, Hyun Suk Wang

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 235 - 240

Published: Feb. 10, 2025

Although thermal solution RAFT depolymerization has recently emerged as an efficient chemical recycling methodology, current approaches require specialized solvents (i.e., dioxane), typically suffer from extended reaction times, and operate exclusively under highly dilute conditions 5 mM repeat unit concentration). To circumvent these limitations, a commercial radical initiator is introduced to kinetically untrap the promote chain-end activation. By varying concentration, remarkable rate acceleration (up 72 times faster) can be observed, enabling completion of within min. Notably, 20-fold increase in concentration did not appreciably compromise final yield, while very high percentages monomer could recovered wide range solvents, including dimethyl sulfoxide, anisole, xylene, acetonitrile, toluene, trichlorobenzene. Our findings only offer intriguing mechanistic aspects, but also significantly expand scope applications depolymerization.

Language: Английский

Citations

2
Polymer Chain Modification via HAT Chemistry and Its Application in Graft Copolymer Synthesis DOI

Manish Kumar,

Maxime Michelas,

Cyrille Boyer

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 396 - 404

Published: March 15, 2025

Hydrogen atom transfer (HAT) chemistry has emerged as a powerful tool for selective molecular functionalization, with significant applications in the pharmaceutical and agricultural industries. More recently, HAT been explored polymer versatile strategy introducing targeted functional groups onto chains, enabling precise control over properties such solubility mechanical strength. This study investigates use of to synthesize reversible addition–fragmentation chain (RAFT) agents (or agents, CTAs) by modifying various substrates, including toluene, ethyl acetate, dioxane, presence bis(dodecylsulfanylthiocarbonyl) disulfide or bis(3,5-dimethyl-1H-pyrazol-1-ylthiocarbonyl) disulfide. The resulting CTAs were evaluated both thermal photoinduced electron (PET)-RAFT polymerization controlled monomers. approach was then extended functionalize polycaprolactone (PCL) polyvinyl acetate (PVAc), synthesis graft copolymers vinyl To promote HAT, range photocatalysts, iron(III) chloride (FeCl3), investigated, offering advantages conventional systems. Photocatalysis enables mild efficient radical generation under light irradiation, providing cost-effective environmentally friendly alternative expensive toxic metal catalysts.

Language: Английский

Citations

1
Bulk Depolymerization of Polystyrene with Comonomer Radical Triggers DOI
James B. Young, Jared I. Bowman, Megan E. Lott

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 576 - 581

Published: April 23, 2025

This study introduces a novel approach to depolymerize polystyrene in the absence of solvent at significantly reduced temperatures through incorporation thermally labile comonomer. Specifically, we employ N-(methacryloxy)phthalimide (PhthMA) as comonomer with an activated ester capable triggered decarboxylation. Thermal treatment enables generation backbone radicals that promote β-scission and subsequent unzipping. These analogs up 91% reversion monomer under 2 h lower than those required for conventional polystyrene. As compared depolymerization by decarboxylation ω-chain end, this pendent-group was considerably more efficient. The recovered styrene from bulk poly(styrene-co-PhthMA) copolymers can undergo direct repolymerization, yielding new styrenic materials. strategy extends across various copolymers, highlighting its potential broadly applicable method initiating among vinyl polymer classes.

Language: Английский

Citations

1
Tackling Waste Polystyrene with Sunlight DOI Creative Commons
Hyun Suk Wang, Athina Anastasaki

ACS Central Science, Journal Year: 2025, Volume and Issue: 11(1), P. 19 - 21

Published: Jan. 2, 2025

InfoMetricsFiguresRef. ACS Central ScienceASAPArticle This publication is Open Access under the license indicated. Learn More CiteCitationCitation and abstractCitation referencesMore citation options ShareShare onFacebookX (Twitter)WeChatLinkedInRedditEmailJump toExpandCollapse First ReactionsJanuary 2, 2025Tackling Waste Polystyrene with SunlightClick to copy article linkArticle link copied!Light-to-heat conversion by carbon black enables local heating depolymerization of polystyrene its monomer.Hyun Suk WangHyun WangLaboratory Polymeric Materials, Department ETH Zurich, Vladimir-Prelog-Weg 5 8093, SwitzerlandMore Hyun Wanghttps://orcid.org/0000-0002-2515-3906Athina Anastasaki*Athina AnastasakiLaboratory Switzerland*Email: [email protected]More Athina Anastasakihttps://orcid.org/0000-0002-6615-1026Open PDFACS ScienceCite this: Cent. Sci. 2025, XXXX, XXX, XXX-XXXClick citationCitation copied!https://pubs.acs.org/doi/10.1021/acscentsci.4c02187https://doi.org/10.1021/acscentsci.4c02187Published January 2025 Publication History Published online 2 2025newsPublished American Chemical Society. licensed CC-BY 4.0 . License Summary*You are free share (copy redistribute) this in any medium or format adapt (remix, transform, build upon) material for purpose, even commercially within parameters below:Creative Commons (CC): a Creative license.Attribution (BY): Credit must be given creator.View full license*DisclaimerThis summary highlights only some key features terms actual license. It not has no legal value. Carefully review before using these materials. underCC-BY share(copy adapt(remix, below: Attribution *DisclaimerThis creator. View PublicationsPublished SocietySubjectswhat subjectsArticle subjects automatically applied from Subject Taxonomy describe scientific concepts themes article.DepolymerizationPlasticsRecyclingStyrenesWastesYou would want touch surface car on sunny summer day─it scorching! because phenomenon called "photothermal conversion," light-to-heat pigments surface. In issue Science, Stache co-workers exploit very chemically recycle (PS) monomer, styrene, an inexpensive ubiquitous material─carbon black. (1)PS, widely recognized use packaging disposable products, presents significant environmental challenge due low recycling rates accumulation landfills. Although mechanical methods exist, they limited inevitable degradation properties each cycle. via depolymerization, (2,3) which reverts PS back into styrene monomers, offers potential infinite but typically constrained high energy demands, requiring temperatures excess 400 °C. (4) Furthermore, bulk leads uncontrolled flux reactive intermediates, leading undesirable byproducts. Photochemical have also been limited, as often produce non-monomeric products (e.g., benzoic acid) thermodynamic challenges depropagation. (5)The authors present remarkably simple approach that addresses limitations leveraging photothermal agent. Their method achieves efficient visible light irradiation, creating localized thermal hotspots while maintaining subpyrolytic (Figure 1). Carbon (CB) cost-effective pigment used commercial such coffee cup lids. However, near-zero rate makes it burden. colleagues repurposed material, utilizing efficiency (i.e., fluorescence quantum yield) drives PS. As proof concept, synthesized particles embedded varying amounts CB emulsion polymerization maximize physical contact between polymer Upon irradiating PS-CB composites white LEDs, maximum yield 57% was achieved after 30 min. Remarkably, temperature during reaction remained below 150 °C, measured thermocouple, despite purely nature process. at noteworthy, particularly when compared conventional pyrolysis methods. Other reaction, including trimers, dimers, toluene, α-methylstyrene, accounted approximately 30% total small-molecule products. could reused multiple cycles, highlighting robustness methodology.Figure 1Figure 1. Depolymerization (co)polymers agents, developed co-workers. (1) Copyright 2024. The Authors. Society.High Resolution ImageDownload MS PowerPoint SlideThe agent.The versatility CB-based process demonstrated through application various styrene-based copolymers containing comonomers notoriously ceiling propensity depropagation). Copolymers incorporating methyl acrylate, acrylonitrile, isoprene were successfully depolymerized regenerate both comonomers, minor reduction overall efficiency.The methodology further validated postconsumer plastics. Black foam trays, food containers, lids─materials already contain black─were effectively 2). Even clear plastics addition CB. Importantly, robust against common contaminants, soy sauce sugar, yields their presence. Additionally, mixed plastic waste streams little 10% weight comparable yields. suggested contamination beneficial enhancing recycling. demonstration process's sustainability, sunlight instead LEDs source. By focusing natural onto Fresnel lens, impressive 80%. contribution direct effects concentrated unclear, photolysis backbone high-energy rays (λ < 300 nm) can ruled out lens made plastic.Figure 2Figure 2. either already-present additional black.High SlideThis recycling.The work team represents advancement chemical recycling, next step potentially involve scaling technology industrial applications. Light penetration carbon-black-filled inherently necessitating development specialized reactor designs extended times ensure consistent processing. Nevertheless, simplicity effectiveness method, coupled compatibility current streams, position promising candidate future technologies. addressing technical challenges, pave way scalable, energy-efficient solutions.The technologies.Author InformationClick section linkSection copied!Corresponding AuthorAthina Anastasaki - Laboratory Switzerland; https://orcid.org/0000-0002-6615-1026; Email: protected]AuthorHyun Wang https://orcid.org/0000-0002-2515-3906ReferencesClick copied! references other publications. 1Oh, S.; Jiang, H.; Kugelmass, L. Stache, E. Recycling Post-Consumer Using Commercial Plastic Additives. 2024, DOI: 10.1021/acscentsci.4c01317 Google ScholarThere corresponding record reference.2Coates, G. W.; Getzler, Y. D. J. N. R. M. monomer ideal, circular economy. Nat. Rev. Mater. 2020, (7), 501– 516, 10.1038/s41578-020-0190-4 Scholar2Chemical economyCoates, Geoffrey Yutan L.Nature Reviews Materials (2020), 501-516CODEN: NRMADL; ISSN:2058-8437. (Nature Research) Abstr.: majority post-consumer recycled. Impediments commodity polymers include sepn., impurities degrdn. macromol. structures, all neg. affect recycled An attractive alternative transform monomers purify them repolymn. form chem. we term (CRM). Material exhibits loss properties, Review our vision realizing economy based CRM. We examine energetics polymn. developing practical scalable CRM processes. briefly attempts achieve polymers, polyolefin thermolysis nylon 6 ring-closing depolymn., closely recent flourishing new-to-the-world polymers. benefits heterocycle ring-opening discussed synthetic control kinetically accessible polymer-backbone functionality. Common structural characteristics CRM-compatible ring-opening-polymn. identified, liabilities recyclable discussed. conclude perspective ideals opportunities field. >> SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXntVOmt7Y%253D&md5=ce62cb9ab02615ebcde8b8dd674aa2523Lohmann, V.; Jones, R.; Truong, P.; Anastasaki, A. thermodynamics kinetics depolymerization: what vinyl regeneration feasible?. Chem. 15 (3), 832– 853, 10.1039/D3SC05143A reference.4Lu, C.; Xiao, Chen, X. Simple valuable chemicals. e-Polym. 2021, 21 (1), 428– 432, 10.1515/epoly-2021-0037 reference.5Parkatzidis, K.; Wang, H. Photocatalytic Upcycling Vinyl Polymers. Angew. Chem., Int. Ed. 63 (19), e202402436 10.1002/anie.202402436 reference.Cited Click copied!This yet cited publications.Download PDFFiguresReferences Get e-AlertsGet e-AlertsACS copied!https://doi.org/10.1021/acscentsci.4c02187Published 2025Published Article Views-Altmetric-Citations-Learn about metrics closeArticle Views COUNTER-compliant sum text downloads since November 2008 (both PDF HTML) across institutions individuals. These regularly updated reflect usage up last few days.Citations number articles citing article, calculated Crossref daily. Find more information counts.The Altmetric Attention Score quantitative measure attention research received online. Clicking donut icon will load page altmetric.com details score social media presence article. how calculated.Recommended Articles FiguresReferencesAbstractHigh SlideFigure SlideReferences There 2Chemical reference.

Language: Английский

Citations

0
The Plastic Problem in Research Laboratories: A Call for Sustainability DOI

Veda V. Dasari,

Anil K. Suresh

ACS Sustainable Resource Management, Journal Year: 2025, Volume and Issue: unknown

Published: April 4, 2025

Language: Английский

Citations

0
Tuning the Thermal Properties of Polymethacrylates With Bicyclobutane Monomers DOI Creative Commons
Sewon Oh, Erin E. Stache

Journal of Polymer Science, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

ABSTRACT Developing novel yet recyclable plastics is necessary as society advances and increases reliance on materials. Using new classes of monomers enables the synthesis unprecedented polymers for applications. Here, we report copolymerization with bicyclo[1.1.0]butane to make strained backbone units analyze thermal property changes based % incorporation monomers. We discover that even low (5%–20%) methyl bicyclobutane‐1‐carboxylate (MBC) poly(methyl methacrylate) (PMMA) degradation temperature while decreasing glass transition temperature. Efficient depolymerization achieved copolymers 20% or fewer MBC under photothermal conversion. Other comonomers (2‐methoxyethyl methacrylate oligo(ethylene glycol) monomethyl ethyl are also copolymerized MBC, assess in their properties, including lower critical solution temperatures (LCSTs). Our work expands understanding how monomer plays a role copolymerization, characteristics, copolymers.

Language: Английский

Citations

0
Electrochemical Commodity Polymer Up‐ and Re‐Cycling: Toward Sustainable and Circular Plastic Treatment DOI Creative Commons
Maxime Hourtoule, Sven Trienes, Lutz Ackermann

et al.

Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Abstract The demand for commodity plastics reaches unprecedented dimensions. In contrast to the well‐developed plethora of methods polymer synthesis, sustainable strategies end‐of‐life management continue be scarce. While mechanical re‐cycling often results in downgraded materials, chemical or up‐cycling offers tremendous potential an efficient and green approach, thereby addressing precarious treatment post‐use within a circular carbon economy. Recently, electrochemistry surfaced as uniquely powerful tool via functionalization degradation obtaining either novel polymers with valorized properties high‐value recycled small molecules, respectively. discussing recent progress that domain, future perspectives electrochemical modifications until January 2025 are outlined herein.

Language: Английский

Citations

0
In Situ Modification Assisted by HAT Chemistry for the Main Chain Initiated Depolymerization of Polymethacrylates DOI

Maxime Michelas,

Manish Kumar,

Zhisheng Lin

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 822 - 829

Published: May 29, 2025

In this study we present a novel strategy to enhance the depolymerization of nonfunctionalized poly(methyl methacrylate) (PMMA) by enabling in situ activation polymer backbone using photoinduced Hydrogen Atom Transfer (HAT) chemistry. By screening various disulfide-based RAFT agents, identified commercially available bis(dodecylsulfanylthiocarbonyl) disulfide (DisRAFT-1) as most effective, achieving up 53% monomer recovery within 5 h at 150 °C under 405 nm light irradiation tetrachloroethane (TCE). A systematic investigation key reaction parameters, including DisRAFT-1 loading, temperature, and concentration (10-200 mM), demonstrated efficiency versatility approach. Importantly, highlight that light, elevated chlorinated solvent are all essential initiate depolymerization. Moreover, temporal control over process was achieved via ON/OFF cycles, on-demand This work offers promising route toward chemical recycling polymers leveraging mild tunable conditions.

Language: Английский

Citations

0