Leveraging Electron Push‐Pull Effect for Catalytic Polymerization and Degradation of a Cyclobutane Monomer System DOI

Teng Xie,

Shusen Chen,

Yangyang Li

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: May 10, 2024

Abstract Ring‐opening polymerization (ROP) offers a striking solution to solve problems encountered in step‐growth condensation polymerization, including precise control over molecular weight, weight distribution, and topology. This has inspired our interest ROP of cycloalkanes with an ultimate goal rethink polyolefins, which clearly poses number challenges. Practicality is actually limited by their low polymerizability elusive mechanisms arise from significantly varied ring size non‐polar C−C bonds monomers. In this work, using Lewis acid/Brønsted base/C( sp 3 )‐H initiator system previously developed laboratory, we focus on cyclobutanes explore the positional electronic effects substituents ring, namely electron push‐pull effect, promoting controlled afford densely functionalized poly(cyclobutanes), as well catalytic degradation obtained polymers for upcycling. More importantly, experiments DFT calculations unveil considerable population Lewis‐acid‐induced thermostabilized 1,4‐zwitterions, distinguish cyclopropanes others. All these findings would shed light synthesis saturated all‐carbon main‐chain polymers, small molecule transformations cyclobutanes.

Language: Английский

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

et al.

Science, Journal Year: 2025, Volume and Issue: 387(6736), P. 874 - 880

Published: Feb. 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.

Language: Английский

Citations

8
Industrial and Laboratory Technologies for the Chemical Recycling of Plastic Waste DOI Creative Commons

Mason T. Chin,

Tianning Diao

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12437 - 12453

Published: Aug. 5, 2024

Synthetic polymers play an indispensable role in modern society, finding applications across various sectors ranging from packaging, textiles, and consumer products to construction, electronics, industrial machinery. Commodity plastics are cheap produce, widely available, versatile meet diverse application needs. As a result, millions of metric tons manufactured annually. However, current approaches for the chemical recycling postconsumer plastic waste, primarily based on pyrolysis, lag efficiency compared their production methods. In recent years, significant research has focused developing milder, economically viable methods commodity plastics, which involves converting waste back into monomers or transforming it other valuable chemicals. This Perspective examines both cutting-edge laboratory-scale contributing advancements field recycling.

Language: Английский

Citations

12
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
Mechanochemical Backbone Editing for Controlled Degradation of Vinyl Polymers DOI
Zhuang Li, Xiaohui Zhang, Yajun Zhao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 27, 2024

The chemically inert nature of fully saturated hydrocarbon backbones endows vinyl polymers with desirable durability, but it also leads to their significant environmental persistence. Enhancing the sustainability these materials requires a pivotal yet challenging shift: transforming backbone into one that is degradable. Here, we present versatile platform for mechanochemically editing towards degradable polymer chains by integrating cyclobutene-fused succinimide (CBS) units along through photo-iniferter reversible addition-fragmentation chain-transfer (RAFT) copolymerization. Significantly, evenly insertion CBS does not compromise thermal or chemical stability rather offers means adjust properties polymethylacrylate (PMA). Meanwhile, reactive acyclic imide can be selectively introduced mechanochemical activation (pulse ultrasonication ball-milling grinding) when required. Subsequent hydrolysis groups enables efficient degradation, yielding telechelic oligomers. This approach holds promise inspiring design and modification more environmentally friendly editing.

Language: Английский

Citations

8
Thermal Solution Depolymerization of RAFT Telechelic Polymers DOI Creative Commons
Nethmi De Alwis Watuthanthrige, Richard Whitfield, Simon Harrisson

et al.

ACS Macro Letters, Journal Year: 2024, Volume and Issue: 13(7), P. 806 - 811

Published: June 10, 2024

Thermal solution depolymerization is a promising low-temperature chemical recycling strategy enabling high monomer recovery from polymers made by controlled radical polymerization. However, current methodologies predominantly focus on the of monofunctional polymers, limiting material scope and pathways. Herein, we report telechelic synthesized RAFT Notably, observed significant decrease in molecular weight (Mn) during recovery, which contrasts minimal Mn shift polymers. Introducing Z groups at center or both ends polymer resulted distinct kinetic profiles, indicating partial bifunctional as supported mathematical modeling. Remarkably, featuring R-terminal showed up to 68% improvement overall conversion compared their analogues, highlighting potential these materials circular economy.

Language: Английский

Citations

7
Open-Air Chemical Recycling: Fully Oxygen-Tolerant ATRP Depolymerization DOI Creative Commons
Stella Afroditi Mountaki, Richard Whitfield, Evelina Liarou

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18848 - 18854

Published: July 3, 2024

While oxygen-tolerant strategies have been overwhelmingly developed for controlled radical polymerizations, the low concentrations typically required high monomer recovery render solution depolymerizations particularly challenging. Here, an open-air atom transfer polymerization (ATRP) depolymerization is presented, whereby a small amount of volatile cosolvent introduced as means to thoroughly remove oxygen. Ultrafast (i.e., 2 min) could efficiently proceed in open vessel, allowing very retrieval be achieved ∼91% efficiency), on par with that fully deoxygenated analogue. Oxygen probe studies combined detailed kinetics revealed importance low-boiling point removing oxygen prior reaction, thus facilitating effective depolymerization. The versatility methodology was demonstrated by performing reactions range different ligands and at polymer loadings (1 M repeat unit concentration) without significantly compromising yield. This approach provides oxygen-tolerant, facile, efficient route chemically recycle ATRP-synthesized polymers, enabling exciting new applications.

Language: Английский

Citations

7
Backbone Degradable Polymers via Chain-growth Radical Polymerization DOI
Haiwang Lai, Makoto Ouchi

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

Published: Feb. 24, 2025

Language: Английский

Citations

1
Dual Feedstock Upcycling of α-Methylstyrene-Doped Poly(methyl methacrylate) and Biomass via the Telescope of Depolymerization and Diels–Alder Reaction DOI Creative Commons
Rui Zhang,

Mason T. Chin,

Tianning Diao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

Nearly 90% of poly(methyl methacrylate) (PMMA) is not recycled and instead ends up in landfills. Conventional pyrolysis PMMA recovers impure methyl methacrylate (MMA) with low economic value. Here, we present a telescoped dual upcycling strategy that integrates depolymerization, Diels-Alder cycloaddition, aromatization to convert AMS-doped biomass-derived 2,5-dimethylfuran (DMF) into 1,2,4-trimethylbenzene (pseudocumene), valuable chemical feedstock. BBr3 proved effective promoting the challenging reaction between MMA DMF under high pressure argon.

Language: Английский

Citations

1
Leveraging Electron Push‐Pull Effect for Catalytic Polymerization and Degradation of a Cyclobutane Monomer System DOI

Teng Xie,

Shusen Chen,

Yangyang Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 10, 2024

Abstract Ring‐opening polymerization (ROP) offers a striking solution to solve problems encountered in step‐growth condensation polymerization, including precise control over molecular weight, weight distribution, and topology. This has inspired our interest ROP of cycloalkanes with an ultimate goal rethink polyolefins, which clearly poses number challenges. Practicality is actually limited by their low polymerizability elusive mechanisms arise from significantly varied ring size non‐polar C−C bonds monomers. In this work, using Lewis acid/Brønsted base/C( sp 3 )‐H initiator system previously developed laboratory, we focus on cyclobutanes explore the positional electronic effects substituents ring, namely electron push‐pull effect, promoting controlled afford densely functionalized poly(cyclobutanes), as well catalytic degradation obtained polymers for upcycling. More importantly, experiments DFT calculations unveil considerable population Lewis‐acid‐induced thermostabilized 1,4‐zwitterions, distinguish cyclopropanes others. All these findings would shed light synthesis saturated all‐carbon main‐chain polymers, small molecule transformations cyclobutanes.

Language: Английский

Citations

6
Spontaneous Amino-Acetoacetate Click Polymerization: A Powerful Tool toward Closed-Loop Recyclable Poly(vinylogous urethane)s DOI

Shihao Ji,

Linlin Wang, Shengyu Feng

et al.

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(17), P. 10718 - 10726

Published: Aug. 22, 2024

The development of click polymerization toward the creation structurally diverse closed-loop recyclable polymers is challenging yet desirable in modern polymer chemistry. In this work, we report a modular amino-acetoacetate polymerization, which proceeds under mild conditions and produces H2O as only byproduct. Through systematic optimization reaction parameters, successfully synthesized 22 poly(vinylogous urethane)s possessing high molecular weights (Mw up to 93.7 kDa) well-defined structures outstanding yields (up 98%). diacetoacetate monomers are derived from diols, both diols diamine common chemicals that can be produced renewable biomass. Notably, these exhibit ability depolymerize back their respective conditions, highlighting excellent recyclability. This enables synthesis with structures, providing versatile platform for fabrication materials such plastics, elastomers, carbon fiber-reinforced composites. methodology material innovations discussed work may benefit promotion application greatly demands scenarios.

Language: Английский

Citations

4