Light-accelerated depolymerization catalyzed by Eosin Y

Bellotti, Valentina; Parkatzidis, Kostas; Wang, Hyun Suk; Watuthanthrige, Nethmi De Alwis; Orfano, Matteo; Monguzzi, Angelo; Truong, Nghia P.; Simonutti, Roberto; Anastasaki, Athina

doi:10.1039/d2py01383e

Cited by 60 publications

(81 citation statements)

References 54 publications

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“…These techniques have been routinely shown to retain end-group functionality that can be reactivated to continue polymerization or initiate depolymerization and enable closed-loop recycling. , Depolymerization allows the retrieval of starting monomers from synthesized polymers, which can increase the recyclability of materials and potentially enable their industrial implementation. While most methods rely on high temperatures (typically from 120 to 180 °C) to trigger efficient depolymerization, recent studies by the Sumerlin and Anastasaki groups have shown that light can also be used to trigger faster and more efficient thermal depolymerization of polymers prepared by RAFT polymerization. These studies have made significant progress in the development of recyclable materials and in promoting a circular life cycle.…”

Section: Future Direction Of Raft-mediated 3d Printingmentioning

confidence: 99%

Application of RAFT in 3D Printing: Where Are the Future Opportunities?

Bagheri

2023

Macromolecules

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Research into 3D printing using reversible addition−fragmentation chain transfer (RAFT) polymerization has garnered interest since it was first reported in 2019. This technique was initially developed to expand the scope of light-based 3D printing technologies by producing materials that can be modified postprinting, termed "living" 3D printing. The livingness can be achieved by incorporating reactivatable RAFT functionalities within the polymer networks, enabling 3D materials to be modified after printing. As the field of RAFTmediated 3D printing has progressed, further studies have revealed its applications in advanced materials. These include spatially resolved surface functionalization and patterning, self-healing, welding, and nano-and microscale structuring of 3D polymers. Additionally, RAFT-mediated 3D printing enables the production of scaffolds with controlled interconnected channel-pore architecture, suitable for customized drug delivery. This Perspective provides a review of the chemical mechanisms employed in RAFT-mediated 3D printing and highlights the advanced materials manufactured through this technology. Potential research directions in this field are also discussed and organized for future investigation.

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Section: Future Direction Of Raft-mediated 3d Printingmentioning

confidence: 99%

Application of RAFT in 3D Printing: Where Are the Future Opportunities?

Bagheri

2023

Macromolecules

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“…[31][32][33] In addition, polymers obtained from RAFT polymerization have been depolymerized by our laboratory and those of Gramlich and Sumerlin. [34][35][36][37][38] Notably, these methods have been developed to recover as much as 90% of the original monomer at temperatures as low as 120 ˚C, or even at 100 ˚C in the presence of UV or blue light irradiation. [34][35][36][37][38] Despite the aforementioned outstanding results, the vast majority of current approaches operate best in specific solvents, such as dioxane, while significantly lower depolymerization conversions are reported in alternate media, thus limiting the scope of depolymerizable materials.…”

Section: Introductionmentioning

confidence: 99%

“…[34][35][36][37][38] Despite the aforementioned outstanding results, the vast majority of current approaches operate best in specific solvents, such as dioxane, while significantly lower depolymerization conversions are reported in alternate media, thus limiting the scope of depolymerizable materials. [35][36][37][38] In addition, very high polymer dilutions (i.e. 0.1 mM polymer concentration or 5 mM repeat unit concentration) are typically essential to favour a successful depolymerization.…”

Section: Introductionmentioning

confidence: 99%

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Solvent-Free Chemical Recycling of Polymers made by ATRP and RAFT polymerization: High-Yielding Depolymerization at Low Temperatures

Whitfield

Jones

Truong

et al. 2023

Preprint

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Although controlled radical polymerization is an excellent tool to make precision polymeric materials, reversal of the process to retrieve the starting monomer is far less explored despite the significance of chemical recycling. Current depolymerization approaches typically require elevated temperatures (>350 ˚C), high dilutions in specific solvents (typically 0.1-25 mM polymer concentrations), and/or expensive catalysts. Here, we report that RAFT-synthesized polymers can undergo a low-temperature solvent-free depolymerization back to monomer thanks to the partial in-situ transformation of the RAFT end-group to macromonomer. To aid a more complete depolymerization, we performed a facile and quantitative end-group modification strategy with the modified RAFT polymers exhibiting significantly higher depolymerization conversions (~90%) at comparable temperatures. The end-group transformation was applied to polymers synthesized by ATRP triggering an efficient low-temperature bulk depolymerization (~90% of monomer regeneration) with an onset at 150 ˚C, in contrast to previous reports where depolymerization could only be triggered at much higher temperatures (> 350 ˚C). The versatility of the methodology was demonstrated by a scalable depolymerization (~10 g of starting polymer) retrieving 84% yield of the starting monomer intact which could be subsequently used for further polymerization. This work presents a new low-energy approach for depolymerizing controlled radical polymers and creates many future opportunities as high-yielding, solvent-free and scalable depolymerization methods are sought.

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“…A recent repor t on photo-assisted depolymerization by Anastasaki exhibited the importance of organodyes as catalysts in RAFT depolymerization system. 42 Herein we report a novel approach to take advantage of the previously reported charge transfer reactions and halogen abstracting capabilities of thus formed ionic radical species. Radical formed on the polymer main chain initiates degradation in diluted reaction conditions.…”

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confidence: 99%