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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Copolymerization Involving Sulfur-Containing Monomers

Chemical Reviews, Год журнала: 2023, Номер 123(24), С. 14038 - 14083

Опубликована: Ноя. 2, 2023

Incorporating sulfur (S) atoms into polymer main chains endows these materials with many attractive features, including a high refractive index, mechanical properties, electrochemical and adhesive ability to heavy metal ions. The copolymerization involving S-containing monomers constitutes facile method for effectively constructing polymers diverse structures, readily tunable sequences, topological structures. In this review, we describe the recent advances in synthesis of via or multicomponent polymerization techniques concerning variety monomers, such as dithiols, carbon disulfide, carbonyl sulfide, cyclic thioanhydrides, episulfides elemental (S8). Particularly, significant focus is paid precise control main-chain sequence, stereochemistry, structure achieving high-value applications.

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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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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Ring‐opening Polymerization of Enantiopure Bicyclic Ether‐ester Monomers toward Closed‐loop Recyclable and Crystalline Stereoregular Polyesters via Chemical Upcycling of Bioplastic

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Апрель 5, 2023

Although great successes have been achieved, the preparation of closed-loop recyclable polyesters with high working temperatures still remains as a big challenge. Herein, we present syntheses series enantiopure bicyclic ether-ester monomers by upcycling poly(3-hydroxybutyrate) bioplastic. The "living"/controlled ring-opening polymerizations these to produce stereoregular controlled molecular weights and well-defined chain ends were achieved. effects stereoconfiguration substituent on polymerization kinetics thermodynamics well thermal properties resultant investigated. Of note, are semi-crystalline materials melting up 176 °C, even higher than commodity polyolefin plastics. These can be depolymerized back recover pristine monomers, thus successfully establishing life cycle.

Язык: Английский

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Chemically Recyclable Polymer System Based on Nucleophilic Aromatic Ring-Opening Polymerization

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(25), С. 13950 - 13956

Опубликована: Июнь 12, 2023

The development of chemically recyclable polymers with desirable properties is a long-standing but challenging goal in polymer science. Central to this challenge the need for reversible chemical reactions that can equilibrate at rapid rates and provide efficient polymerization depolymerization cycles. Based on dynamic chemistry nucleophilic aromatic substitution (SNAr), we report polythioether system derived from readily accessible benzothiocane (BT) monomers. This represents first example well-defined monomer platform capable chain-growth ring-opening through an SNAr manifold. polymerizations reach completion minutes, pendant functionalities are easily customized tune material or render amenable further functionalization. resulting materials exhibit comparable performance commercial thermoplastics be depolymerized original monomers high yields.

Язык: Английский

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Hybrid Monomer Design Synergizing Property Trade‐offs in Developing Polymers for Circularity and Performance

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(31)

Опубликована: Апрель 19, 2023

Abstract Current search for more sustainable plastics seeks to redesign polymers possessing both chemical recyclability monomer a circular economy and desirable performance that can rival or even exceed today's non‐recyclable hard‐to‐recycle petroleum‐based incumbents. However, within traditional framework it is challenging optimize, concurrently , contrasting polymerizability/depolymerizability recyclability/performance properties. Here, we highlight the emerging hybrid design strategy develop intrinsically with tunable properties, aiming unify desired, but otherwise conflicting, properties in single monomer. Conceptually, this hybridizes parent pairs of contrasting, mismatching, matching into offspring monomers not only above‐described conflicting also radically alter resultant polymer far beyond limits what either homopolymers their copolymers achieve.

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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Acid‐Cleavable Aromatic Polymers for the Fabrication of Closed‐Loop Recyclable Plastics with High Mechanical Strength and Excellent Chemical Resistance

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)

Опубликована: Дек. 22, 2023

Although closed-loop recycling of dynamic covalent bond-based plastics does not require catalysts, their mechanical strength and chemical stability remain a major concern. In this study, recyclable poly(aryl imine) (PAI) with high excellent resistance are fabricated by copolymerizing aromatic amines aldehydes through imine bonds. The resulting PAI plastic tensile 58.2 MPa exhibits in acidic basic aqueous solutions various organic solvents. can be depolymerized mixed solvent tetrahydrofuran (THF)/HCl solution the dissociation bonds, monomers facilely recovered purity isolated yields due to solubility difference between selective efficient also realized monomer conversion because hydrolysis generates amines. used re-fabricate original plastics. This selectively from complicated polymer waste streams mild depolymerization conditions its most

Язык: Английский

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Performance‐Advantaged Stereoregular Recyclable Plastics Enabled by Aluminum‐Catalytic Ring‐Opening Polymerization of Dithiolactone

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)

Опубликована: Апрель 14, 2023

Chemically recyclable polymers that can depolymerize into their constituent monomers are attractive candidates to replace non-recyclable petroleum-derived plastics. However, the physical properties and mechanical strengths of depolymerizable commonly insufficient for practical applications. Here we demonstrate by proper ligand design modification, aluminum complexes catalyse stereoretentive ring-opening polymerization dithiolactone, yielding highly isotactic polythioesters with molar masses up 45.5 kDa. This material form crystalline stereocomplex a Tm 94.5 °C, exhibits performances comparable petroleum-based low density polyethylene. Exposure polythioester precatalyst used synthesized it resulted in depolymerization pristine chiral dithiolactone. Experimental computational studies suggest have appropriate binding affinity sulfide propagating species, thereby avoiding catalyst poisoning minimizing epimerization reactions, which has not been accessible using other metal catalysts. Overall, catalysis provides access performance-advantaged stereoregular plastics as promising alternative petrochemical plastics, thus incentivizing improved plastic sustainability.

Язык: Английский

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