Bulk depolymerization of poly(methyl methacrylate) via chain-end initiation for catalyst-free reversion to monomer

Young, James B.; Hughes, Rhys W.; Tamura, A.; Bailey, Lisa M.; Stewart, Kevin A.; Sumerlin, Brent S.

doi:10.1016/j.chempr.2023.07.004

Cited by 56 publications

(42 citation statements)

References 75 publications

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“…Moreover, compared to well-established pyrolysis depolymerization of PMMA, in which up to 98 wt % MMA can be regenerated at 450 °C using a fluidized bed process, , the recycling efficiency has been relatively low for depolymerization of PMMA prepared via both ATRP and RAFT approaches. Thus, ongoing efforts are underway to further improve the depolymerization conditions and efficiency, − expand monomer scope, and find niche applications for depolymerizable polymers synthesized via controlled polymerizations.…”

Section: Recent Developments In Depolymerizable Backbonesmentioning

confidence: 99%

Emerging Trends in the Chemistry of End-to-End Depolymerization

Deng,

Gillies

2023

JACS Au

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Over the past couple of decades, polymers that depolymerize end-to-end upon cleavage of their backbone or activation of a terminal functional group, sometimes referred to as "self-immolative" polymers, have been attracting increasing attention. They are of growing interest in the context of enhancing polymer degradability but also in polymer recycling as they allow monomers to be regenerated in a controlled manner under mild conditions. Furthermore, they are highly promising for applications as smart materials due to their ability to provide an amplified response to a specific signal, as a single sensing event is translated into the generation of many small molecules through a cascade of reactions. From a chemistry perspective, end-to-end depolymerization relies on the principles of self-immolative linkers and polymer ceiling temperature (T c ). In this article, we will introduce the key chemical concepts and foundations of the field and then provide our perspective on recent exciting developments. For example, over the past few years, new depolymerizable backbones, including polyacetals, polydisulfides, polyesters, polythioesters, and polyalkenamers, have been developed, while modern approaches to depolymerize conventional backbones such as polymethacrylates have also been introduced. Progress has also been made on the topological evolution of depolymerizable systems, including the introduction of fully depolymerizable block copolymers, hyperbranched polymers, and polymer networks. Furthermore, precision sequence-defined oligomers have been synthesized and studied for data storage and encryption. Finally, our perspectives on future opportunities and challenges in the field will be discussed.

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Section: Recent Developments In Depolymerizable Backbonesmentioning

confidence: 99%

Emerging Trends in the Chemistry of End-to-End Depolymerization

Deng,

Gillies

2023

JACS Au

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“…This depolymerization methodology offers a facile chemical recycling approach to reach near quantitative monomer yields while also enabling temporal regulation. We believe that our work can open new avenues, for example in the field of reversed additive manufacturing and lithography …”

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confidence: 93%

“…We believe that our work can open new avenues, for example in the field of reversed additive manufacturing and lithography. 31 ■ ASSOCIATED CONTENT * sı Supporting Information…”

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confidence: 99%

Photocatalytic ATRP Depolymerization: Temporal Control at Low ppm of Catalyst Concentration

Parkatzidis,

Truong,

Matyjaszewski

et al. 2023

J. Am. Chem. Soc.

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A photocatalytic ATRP depolymerization is introduced that significantly suppresses the reaction temperature from 170 to 100 °C while enabling temporal regulation. In the presence of low-toxicity iron-based catalysts and under visible light irradiation, near-quantitative monomer recovery could be achieved (up to 90%), albeit with minimal temporal control. By employing ppm concentrations of either FeCl2 or FeCl3, the depolymerization during the dark periods could be completely eliminated, thus enabling temporal control and the possibility to modulate the rate by simply turning the light “on” and “off”. Notably, our approach allowed preservation of the end-group fidelity throughout the reaction, could be carried out at high polymer loadings (up to 2M), and was compatible with various polymers and light sources. This methodology provides a facile, environmentally friendly, and temporally regulated route to chemically recycle ATRP-synthesized polymers, thus opening the door for further opportunities.

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“…Recently, polymethacrylates synthesized by various RDRP methodologies have been actively utilized for depolymerization to monomer, exploiting their activatable end-groups, which provide a low-temperature route to introducing a chain-end radical that can trigger depolymerization. − Polymethacrylates with halogen chain ends have been depolymerized by several groups, usually in the presence of a catalyst that abstracts the halogen end-group. ,,,, For example, Matyjaszewski and co-workers recently demonstrated the depolymerization of poly(methyl methacrylate) (PMMA) and poly( n -butyl methacrylate) using an iron catalyst, reaching an impressive 70% depolymerization at 170 °C . In the RAFT arena, depolymerization of polymethacrylates with thiocarbonylthio end-groups was reported by our group and the groups of Gramlich and Sumerlin. , For instance, we recently reported the thermal depolymerization of dithiobenzoate-terminated polymethacrylates in dioxane, reaching up to 92% conversion at 120 °C, and later expanded the scope to various end-groups and solvents. , Sumerlin and co-workers reported an elegant photoassisted depolymerization of PMMA, whereby visible light irradiation enabled a reduction of the reaction temperature . In parallel, our group reported a photoaccelerated depolymerization of PMMA in the presence of a photocatalyst …”

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confidence: 99%

“…22 In the RAFT arena, depolymerization of polymethacrylates with thiocarbonylthio end-groups was reported by our group and the groups of Gramlich 25 and Sumerlin. 23,29 For instance, we recently reported the thermal depolymerization of dithiobenzoateterminated polymethacrylates in dioxane, reaching up to 92% conversion at 120 °C, and later expanded the scope to various end-groups and solvents. 14,17 Sumerlin and co-workers reported an elegant photoassisted depolymerization of PMMA, whereby visible light irradiation enabled a reduction of the reaction temperature.…”

mentioning

confidence: 99%

Fate of the RAFT End-Group in the Thermal Depolymerization of Polymethacrylates

Häfliger,

Truong,

Wang

et al. 2023

ACS Macro Lett.

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Bulk depolymerization of poly(methyl methacrylate) via chain-end initiation for catalyst-free reversion to monomer

Cited by 56 publications

References 75 publications

Emerging Trends in the Chemistry of End-to-End Depolymerization

Emerging Trends in the Chemistry of End-to-End Depolymerization

Photocatalytic ATRP Depolymerization: Temporal Control at Low ppm of Catalyst Concentration

Fate of the RAFT End-Group in the Thermal Depolymerization of Polymethacrylates

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