Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Chemical Reviews, Год журнала: 2024, Номер 124(7), С. 4393 - 4478

Опубликована: Март 22, 2024

Polyesters carrying polar main-chain ester linkages exhibit distinct material properties for diverse applications and thus play an important role in today's plastics economy. It is anticipated that they will even greater tomorrow's circular economy focuses on sustainability, thanks to the abundant availability of their biosourced building blocks presence bonds can be chemically or biologically cleaved demand by multiple methods bring about more desired end-of-life plastic waste management options. Because this potential promise, there have been intense research activities directed at addressing recycling, upcycling biodegradation existing legacy polyesters, designing biorenewable alternatives, redesigning future polyesters with intrinsic chemical recyclability tailored performance rival commodity are either petroleum based and/or hard recycle. This review captures these exciting recent developments outlines challenges opportunities. Case studies poly(lactic acid), poly(3-hydroxyalkanoate)s, poly(ethylene terephthalate), poly(butylene succinate), poly(butylene-adipate presented, emerging recyclable comprehensively reviewed.

Язык: Английский

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Ring-Opening Polymerization of Lactones to Prepare Closed-Loop Recyclable Polyesters

Macromolecules, Год журнала: 2024, Номер 57(5), С. 1919 - 1940

Опубликована: Фев. 22, 2024

The large production and indiscriminate disposal of plastics have resulted in serious resource global environmental crises, which has raised a demand to develop more sustainable circular economy. An ideal strategy address the end-of-life issue is next-generation polymers with closed-loop life cycles, can be selectively depolymerized back monomers at end their service life. Aliphatic polyesters prepared by ring-opening polymerization (ROP) moderately strained lactones shown great potential recyclable polymers. This Perspective highlights recent achievements for that are derived from four-, five-, six-, seven-membered focusing on discussion thermodynamic kinetic considerations, monomer design principles polymer preparations, material properties, chemical recyclability. Finally, current challenges possible directions also discussed.

Язык: Английский

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Redesigned Nylon 6 Variants with Enhanced Recyclability, Ductility, and Transparency

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(17)

Опубликована: Фев. 29, 2024

Abstract Geminal ( gem −) disubstitution in heterocyclic monomers is an effective strategy to enhance polymer chemical recyclability by lowering their ceiling temperatures. However, the effects of specific substitution patterns on monomer's reactivity and resulting polymer's properties are largely unexplored. Here we show that, systematically installing ‐dimethyl groups onto ϵ‐caprolactam (monomer nylon 6) from α ϵ positions, both redesigned lactam ‐nylon 6’s highly sensitive position, with ranging non‐polymerizable polymerizable inferior far superior parent 6. Remarkably, 6 ‐dimethyls substituted at γ position amorphous optically transparent, a higher T g (by 30 °C), yield stress 1.5 MPa), ductility 3×), lower depolymerization temperature 60 °C) than conventional

Язык: Английский

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

JACS Au, Год журнала: 2023, Номер 3(9), С. 2436 - 2450

Опубликована: Авг. 23, 2023

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

Язык: Английский

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New sustainable polymers with on-demand depolymerization property

Science China Chemistry, Год журнала: 2024, Номер 67(9), С. 2803 - 2841

Опубликована: Авг. 12, 2024

Язык: Английский

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Perspectives on sustainable plastic treatment: A shift from linear to circular economy

TrAC Trends in Analytical Chemistry, Год журнала: 2024, Номер 173, С. 117631 - 117631

Опубликована: Март 5, 2024

The pervasive presence of plastics in the environment, particularly microplastics, has become a significant global challenge, demanding innovative solutions for their management and upcycling. While traditional methods including landfill incineration face limitations environmental impact, emerging technologies offer promising pathways conversion into valuable chemicals fuels, operating under ambient conditions often utilizing sustainable energy sources. Considering current research progress plastic upgrading, it is necessary to summarize chemical upcycling waste. To this end, review provides an overall examination methodologies treatment, pyrolysis, hydrogenolysis, photocatalysis, electrocatalysis. Existing knowledge gaps future directions are then proposed. Overall, highlights potential these novel approaches aligning with principles circular economy.

Язык: Английский

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Enabling Closed‐Loop Circularity of “Non‐Polymerizable” α, β‐Conjugated Lactone Towards High‐Performance Polyester with the Assistance of Cyclopentadiene

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(22)

Опубликована: Март 16, 2024

Abstract Chemical recycling of polymers to monomers presents a promising solution the escalating crisis associated with plastic waste. Despite considerable progress made in this field, primary efforts have been focused on redesigning new produce readily recyclable polymers. In contrast, limited research into potential seemingly “non‐polymerizable” has conducted. Herein, we propose paradigm that leverages “chaperone”‐assisted strategy establish closed‐loop circularity for α, β‐conjugated lactone, 5,6‐dihydro‐2H‐pyran‐2‐one (DPO). The resulting PDPO, structural analogue poly(δ‐valerolactone) (PVL), exhibits enhanced thermal properties melting point ( T m ) 114 °C and decomposition temperature d,5% 305 °C. Notably, owing similarity between DPO δ‐VL, copolymerization generates semi‐crystalline P(DPO‐ co ‐VL)s irrespective incorporation ratio. Intriguingly, inherent C=C bonds enable their convenient post‐functionalization via Michael‐addition reaction. Lastly, PDPO was demonstrated be chemically ring‐closing metathesis (RCM), representing significant step towards pursuit enabling lactones without altering ultimate polymer structure.

Язык: Английский

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Closed-loop recyclable polymers: from monomer and polymer design to the polymerization–depolymerization cycle

Chemical Society Reviews, Год журнала: 2024, Номер 53(19), С. 9609 - 9651

Опубликована: Янв. 1, 2024

We present the state-of-the-art of circular polymers based on monomer and polymer design reversible ring-opening addition polymerization reactions without involvement other reactants.

Язык: Английский

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Topology-Accelerated and Selective Cascade Depolymerization of Architecturally Complex Polyesters

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9261 - 9271

Опубликована: Март 22, 2024

Despite considerable recent advances already made in developing chemically circular polymers (CPs), the current framework predominantly focuses on CPs with linear-chain structures of different monomer types. As polymer properties are determined by not only composition but also topology, manipulating topology single-monomer-based CP systems from to architecturally complex could potentially modulate resulting without changing chemical composition, thereby advancing concept monomaterial product design. To that end, here, we introduce a hyperbranched polyester (HBPE), synthesized mixed chain-growth and step-growth polymerization rationally designed bicyclic lactone pendent hydroxyl group (BiLOH). This HBPE exhibits full recyclability despite its architectural complexity, showing quantitative selectivity for regeneration BiLOH, via unique cascade depolymerization mechanism. Moreover, distinct differences materials performance arising topological variations between HBPE, hb-PBiLOH, linear analogue, l-PBiLOH, have been revealed where generally branched structure led more favorable interchain interactions, topology-amplified optical activity has observed chiral (1S, 4S, 5S)-hb-PBiLOH. More intriguingly, l-PBiLOH proceeds through an unexpected, initial transformation polymer, followed faster pathway adopted hb-PBiLOH. Overall, these results demonstrate design can go beyond typical polymers, redesigned, their may synergistically impart advantages topology-augmented acceleration exclusive regeneration.

Язык: Английский

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Mono-material product design with bio-based, circular, and biodegradable polymers

One Earth, Год журнала: 2023, Номер 6(6), С. 582 - 586

Опубликована: Июнь 1, 2023

Язык: Английский

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