Visible Light Induced Degradation of Poly(methyl methacrylate‐co‐methyl α‐chloro acrylate) Copolymer at Ambient Temperature DOI
Zeynep Arslan, Hüseyin Cem Kılıçlar, Yusuf Yağcı

et al.

Macromolecular Rapid Communications, Journal Year: 2023, Volume and Issue: 44(9)

Published: March 21, 2023

Poly(methyl methacrylate) (PMMA) is a well-known and widely used commodity plastic. High production amount of PMMA causes excessive waste creation that highlights the necessity recycling. Conventional recycling methods require elevated temperatures to induce degradation or depolymerization. In this work, visible light induced photodegradation system by using dimanganese decacarbonyl (Mn2 (CO)10 ) with high halogen affinity reported. Halide functional photodegradable polymers are prepared copolymerization methyl methacrylate α-chloroacrylate conventional reversible addition-fragmentation chain-transfer polymerization. Synthesized copolymers efficiently degraded low molecular weight oligomers under irradiation in presence Mn2 . Characteristics precursors, polymers, kinetics depolymerization investigated gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourrier transform infrared (FTIR), proton nuclear magnetic resonance (1 H-NMR) spectroscopies. The reported approach expected trigger further development more environmentally friendly techniques near future as we moving toward greener sustainable world.

Language: Английский

Reversed Controlled Polymerization (RCP): Depolymerization from Well-Defined Polymers to Monomers DOI Creative Commons
Glen R. Jones, Hyun Suk Wang, Kostas Parkatzidis

et al.

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

Citations

103
Photoassisted Radical Depolymerization DOI
James B. Young, Jared I. Bowman, Cabell B. Eades

et al.

ACS Macro Letters, Journal Year: 2022, Volume and Issue: 11(12), P. 1390 - 1395

Published: Dec. 5, 2022

Controlled radical polymerization techniques enable the synthesis of polymers with predetermined molecular weights, narrow weight distributions, and controlled architectures. Moreover, these approaches have been routinely shown to result in retained end-group functionality that can be reactivated continue polymerization. However, reactivation end groups under conditions instead promote depropagation is a viable route initiate depolymerization potentially closed-loop recycling from polymer monomer. In this report, we investigate light as trigger for thermal prepared by reversible-addition-fragmentation chain-transfer (RAFT) We study role irradiation wavelength targeting n → π* π electronic transitions thiocarbonylthio end-groups RAFT-generated enhance via terminal bond homolysis. Specifically, explore trithiocarbonate, dithiocarbamate, p-substituted dithiobenzoate purpose increasing efficiency light. As decreases visible range UV range, rate dramatically increased. This method photoassisted allows up 87% within 1 h, results may further advancement recyclable materials life-cycle circularity.

Language: Английский

Citations

93
Bulk depolymerization of poly(methyl methacrylate) via chain-end initiation for catalyst-free reversion to monomer DOI Creative Commons
James B. Young, Rhys W. Hughes,

A. Tamura

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(9), P. 2669 - 2682

Published: Aug. 7, 2023

Language: Английский

Citations

78
Degradation of Polyacrylates by One-Pot Sequential Dehydrodecarboxylation and Ozonolysis DOI

Angie B. Korpusik,

Alafate Adili,

Kamal Bhatt

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(19), P. 10480 - 10485

Published: May 8, 2023

We establish a synthetically convenient method to degrade polyacrylate homopolymers. Carboxylic acids are installed along the polymer backbone by partial hydrolysis of ester side chains, and then, in one-pot sequential procedure, carboxylic converted into alkenes oxidatively cleaved. This process enables robustness properties polyacrylates be maintained during their usable lifetime. The ability tune degree degradation was demonstrated varying acid content polymers. is compatible with wide range polymers prepared from vinyl monomers through copolymerization acrylic different including acrylates, acrylamides, styrenics.

Language: Английский

Citations

52
Solvent‐Free Chemical Recycling of Polymethacrylates made by ATRP and RAFT polymerization: High‐Yielding Depolymerization at Low Temperatures DOI Creative Commons
Richard Whitfield, Glen R. Jones, Nghia P. Truong

et al.

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

Citations

49
Bulk Depolymerization of Methacrylate Polymers via Pendent Group Activation DOI
Rhys W. Hughes, Megan E. Lott, Isabella S. Zastrow

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6217 - 6224

Published: Feb. 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

Language: Английский

Citations

36
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

35
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

33
Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate) DOI
Kwangwook Ko,

David Lundberg,

Alayna M. Johnson

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9142 - 9154

Published: March 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.

Language: Английский

Citations

18
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