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

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(7), P. 4393 - 4478

Published: March 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.

Language: Английский

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Semi-Interpenetrating Polyurethane Network with Fatigue Elimination and Upcycled Mechanical Performance

Macromolecules, Journal Year: 2024, Volume and Issue: 57(10), P. 5063 - 5072

Published: April 25, 2024

Recyclable elastomers based on adaptable covalent networks fabricated via different types of dynamic bonds have been designed and prepared to resolve the urgent problems generated by waste elastomers. However, due inevitable side reactions during thermal recycling (e.g., oxidation, permanent cross-linking), mechanical recovery efficiency after is normally <90% for most recyclable elastomers, making it difficult achieve comparable performance. Herein, we report a novel semi-interpenetrating network design that achieves reinforcement topology isomerization formation new cross-linking points. The includes an aromatic disulfide bond-containing polyurethane long linear chains with side-chain vinyl groups. Triggered heat reprocessing, inside cross-linked break phenyl sulfur radicals undergo thiol–ene groups in chains, resulting increased density. Electron paramagnetic resonance testing, situ Fourier transform infrared spectrometry, high-temperature stress relaxation density measurements were utilized monitor process. tensile strength extensibility efficiencies reached 186 131% original values reprocessing twice, realizing recycling. Interestingly, similar mechanism, fatigue repeated stretch release cycles was efficiently eliminated upon treatment. Such strategy achieving polymer reinforced physical properties will benefit practical applications sustainable other thermosetting materials.

Language: Английский

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Sustainable, recyclable and biodegradable castor oil-derived elastomers enabled by dynamic acetoacetyl formed amides

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 491, P. 152195 - 152195

Published: May 12, 2024

Language: Английский

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Electrocatalysis enables polyvinyl chloride functionalization

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102435 - 102435

Published: Feb. 1, 2025

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Tunable and Degradable Dynamic Thermosets from Compatibilized Polyhydroxyalkanoate Blends

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: 13(9), P. 3817 - 3829

Published: Feb. 27, 2025

Polyhydroxyalkanoates (PHAs) are versatile, biobased polyesters that often targeted for use as degradable thermoplastic replacements polyolefins. Given the substantial chemical diversity of PHA, their potential cross-linked polymers could also enable similar platforms reversible, thermosets. In this work, we genetically engineered Pseudomonas putida KT2440 to synthesize poly(3-hydroxybutyrate-co-3-hydroxyundecenoate) (PHBU), which contains both 3-hydroxybutyrate and unsaturated 3-hydroxyundecenoate components. To reduce brittleness polymer, physically blended PHBU with soft copolymer poly(3-hydroxydecanonate-co-3-hydroxyundecenoate) in mass ratios 1:3, 1:1, 3:1. Upon observing varying degrees immiscibility by scanning electron microscopy, installed dynamic boronic ester cross-links via thiol–ene click chemistry, resulted compatibilized thermoset blends ranging hard, medium, rubber or elastomer thermomechanical profiles. These were subjected controlled biological degradation experiments freshwater conditions, achieving timely loss despite architectures. Overall, work highlights a two-component platform production reprocessable suitable several classes polymer technologies from tailored, PHA copolymers.

Language: Английский

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Molecular Reconstruction for the High‐Performance Recycled Fluororubbers

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Abstract To address the challenges associated with difficult recycling of fluorinated specialty materials and subpar performance recycled products, a molecular reconstruction strategy oxidative degradation, fluorination addition is reported, end‐group transformation, which upcycled waste fluororubber into high‐performance, chemically awakenable amino‐terminated low‐molecular‐weight fluoropolymer (ATLF‐Boc). Leveraging chemical properties vinylidene fluoride structure in fluororubber, carboxyl‐terminated (CTLF) controlled weight content are synthesized. Further, whole chain structurally strengthened at scale to achieve higher fluorine thermal stability, saturated (SCTLF) Subsequently, balance high reactivity stable storage, high‐performance ATLF‐Boc synthesized, realizing upcycling fluororubber. After upcycling, awakened ATLF exhibits (66.95%), cured shows regulation surface hydrophilicity hydrophobicity (between 43° 114°), tensile strength 13.3 MPa, an excellent stability (T 10% = 359 °C). In this study, novel solution for fluororubbers fabricating functional offered, great significance field materials.

Language: Английский

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Robust β‐myrcene block copolymer elastomeric vitrimers

Polymer International, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

Abstract As a terpene‐based conjugated diene, β ‐myrcene (Myr) is promising renewable building block for synthetic rubbers. However, the high entanglement molecular weight of poly(Myr) limits its mechanical properties and applications. This work aims to improve dimensional stability recyclable bio‐based Myr elastomers by incorporating vitrimer chemistry copolymer self‐assembly. Linear prepolymers statistical diblock terpolymers Myr, styrene (S) ‐ketoester functional (acetoacetoxy)ethyl methacrylate (AAEMA) were synthesized using nitroxide‐mediated polymerization. The resulting (P(S‐ co ‐Myr‐ ‐AAEMA)) (PS‐ b ‐P(Myr‐ had comparable number‐average weights ( M n ~ 20–27 kg mol −1 ) similar overall compositions. PS‐ ‐AAEMA) underwent microphase separation into lamellae, as confirmed small‐angle X‐ray scattering atomic force microscopy. Vinylogous urethane vitrimers formed crosslinking AAEMA units in with vegetable oil‐derived difunctional amines (Priamine 1075). networks could be remolded hot pressing at 125 °C least 4 cycles while retaining thermomechanical properties. exhibited tensile stress 3.1 ± 0.6 MPa, which was four times higher than that P(S‐ ‐AAEMA). also nearly ten hardness, strain break 90%), compared terpolymer‐based vitrimer. addition glassy PS domains effectively anchored network, 18–35% lower creep highlights potential Myr‐based creating robust, elastomers. © 2025 Author(s). Polymer International published John Wiley & Sons Ltd on behalf Society Chemical Industry.

Language: Английский

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Assessment of Lab-Scale Medium-Chain-Length Polyhydroxyalkanoate Production from Food Wastewater

ACS ES&T Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

Language: Английский

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Biodegradable Polyester-Based Vitrimers Exhibiting Transesterification-Induced Topography Isomerization under Recycling

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(15), P. 9191 - 9199

Published: July 25, 2024

In this work, biodegradable and polyester-based vitrimers possessing dynamic ester bonds are prepared by chemically cross-linking −OH-containing poly(glycerol sebacate) (PGS) with the formation of interchain bonds. enzymatic biodegradation tests, demonstrate high extents degradation (of about 85–90 wt %) after 60 days at 37 °C. The excess hydroxyl groups in bring a catalytic effect to transesterification. catalyst-free exhibit stress relaxation time 390 s 190 °C, an activation energy 45.0 kJ mol–1, glass transition temperature 8.0 topology freezing 48.7 Possessing both PGS main chains side sites, topography isomerization changes their mechanical properties under thermally recycling processes. has been demonstrated as effective precursor for preparation corresponding vitrimers. Moreover, processes could be interest further studies potential applications.

Language: Английский

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Investigation on Polyether Sulfone Toughening Epoxy Vitrimer: Curing and Dynamic Properties

Macromolecular Rapid Communications, Journal Year: 2024, Volume and Issue: 45(23)

Published: Oct. 7, 2024

Abstract Diglycidyl ether of bisphenol A crosslinking with glutaric anhydride is used to form the conventional “covalent adaptive network”, polyether sulfone (PES) by coiling and aggregating on network significantly increase uncured resin viscosity for improving processability epoxy resin, but inevitably affecting curing reaction dynamic transesterification reaction. This study investigates crucial roles PES in dynamics stress relaxation behavior. The results indicate that although does not directly participate polyester‐based vitrimers. Moreover, isothermal studies reveal addition can greatly bring forward rate peak from conversion α = 0.6 0.2, meaning mechanism transfers chemical control diffusion control. Dynamic property analysis shows accelerates relaxation, especially at lower temperatures, leading low viscous flow activation energy E τ relatively insensitive behavior temperature. Introducing into vitrimer improves density (2.31 × 10⁴ mol m − 3 ), enhancing glass transition temperature (82.68 °C), tensile strength (68.66 MPa), fracture toughness (6.25%). Additionally, modified exhibits satisfying shape memory performance reprocessing capability.

Language: Английский

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