Air‐Mediated Biomimetic Synthesis of Polyhydroxyalkanoate with C4 Diol DOI Open Access
Huilin Xie, Kai Zhong,

Sijie Niu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Abstract Poly(4‐hydroxybutyrate) (P4HB) is a high‐performance, well‐recyclable, and biodegradable polyhydroxyalkanoate (PHA). However, conventional bioproduction of homopolymeric P4HB involves complex costly processes with C4 feedstocks, particularly 1,4‐butanediol (BDO), enzyme‐coenzyme systems in genetically engineered bacteria. An alternative extracellular chemical route utilizing aerial oxidation BDO offers cost energy benefits but struggle conversion efficiency. Inspired by efficient intracellular primary alcohols, we propose ruthenium‐phosphine synergistic catalytic system that mimics functionality. This effectively catalyzed the air‐mediated, solvent‐free to produce γ‐butyrolactone (γ‐BL) oligomeric P4HB, space‐time yield (10.37 g [γ‐BL unit] −1 catalyst h ) surpassing values (<5.5) previous approaches. The oligomer‐containing products were reversibly converted γ‐BL then (28.9 kDa) via ring‐opening polymerization, exceeding reported (<16 kDa). study provides potential for large‐scale synthesis high‐value PHAs from diverse non‐grain‐based diols, offering economic environmental advantages.

Language: Английский

Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics DOI

Tianxiang Fang,

Weipo Jiang,

Tengfei Zheng

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(46)

Published: Aug. 4, 2024

Poly(ethylene terephthalate) (PET) is an important polymer with annual output second only to polyethylene. Due its low biodegradability, a large amount of PET recycled for sustainable development. However, current strategies recycling are limited by added value or small product scale. It urgent make breakthrough on the principle macromolecular reaction and efficiently prepare products high wide applications. Here, catalyst- solvent-free synthesis biodegradable plastics reported through novel carboxyl-ester transesterification between waste bio-based hydrogenated dimer acid (HDA), which can directly substitute some terephthalic (TPA) units in chain HDA unit. This be facilely carried out equipment polyester industry without any additional catalyst solvent, thus enabling low-cost large-scale production. Furthermore, semi-bio-based copolyester shows excellent mechanical properties, regulable flexibility good expected poly(butylene adipate-co-terephthalate) (PBAT) plastic as value-added materials. work provides environmental-friendly economic strategy upcycling waste.

Language: Английский

Citations

9
Accessing a Carboxyl‐Anhydride Molecular Switch‐Mediated Recyclable PECT Through Upcycling End‐of‐Use PET DOI Open Access
Hongjie Zhang,

Mingyuan Fang,

Sijie Niu

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Poly(ethylene terephthalate) (PET), with an annual production of exceeding 70 million tons, is mainly utilized in disposable fields and subsequently contribute to severe environmental pollution. Conventional chemical recycling, which typically involves depolymerizing polymer into monomers, limited due the intricate recycling process, excess using unrecyclable solvents low conversion. Inspired by protein's molecular switches, we propose a novel polymer-to-polymer strategy based on polycondensation principles upcycling waste PET high-value recyclable poly(ethylene-co-1,4-cyclohexanedimethanol derivatives containing switches. Upon deactivating switch, acidification reaction occurs within system, leading rapid controllable reduction weight imbalance reactive group. Conversely, activating switch triggers ring-closing that detaches acid anhydrides, bringing about equal molar ratio groups thereby facilitating increase weight. By simply incorporating condensation products melt polycondensation, closed-loop capability achieved without necessitating excessive organic or complex depolymerization processes. The present study not only presents pathway for end-of-use but also introduces innovative concept switching recyclability polymers, demonstrating significant potential large-scale implementation.

Language: Английский

Citations

0
Accessing a Carboxyl‐Anhydride Molecular Switch‐Mediated Recyclable PECT Through Upcycling End‐of‐Use PET DOI Open Access
Hongjie Zhang,

Mingyuan Fang,

Sijie Niu

et al.

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Abstract Poly(ethylene terephthalate) (PET), with an annual production of exceeding 70 million tons, is mainly utilized in disposable fields and subsequently contribute to severe environmental pollution. Conventional chemical recycling, which typically involves depolymerizing polymer into monomers, limited due the intricate recycling process, excess using unrecyclable solvents low conversion. Inspired by protein's molecular switches, we propose a novel polymer‐to‐polymer strategy based on polycondensation principles upcycling waste PET high‐value recyclable poly(ethylene‐ co ‐1,4‐cyclohexanedimethanol derivatives containing switches. Upon deactivating switch, acidification reaction occurs within system, leading rapid controllable reduction weight imbalance reactive group. Conversely, activating switch triggers ring‐closing that detaches acid anhydrides, bringing about equal molar ratio groups thereby facilitating increase weight. By simply incorporating condensation products melt polycondensation, closed‐loop capability achieved without necessitating excessive organic or complex depolymerization processes. The present study not only presents pathway for end‐of‐use but also introduces innovative concept switching recyclability polymers, demonstrating significant potential large‐scale implementation.

Language: Английский

Citations

0
Trendbericht: Organische Chemie 2025 DOI Open Access
Martin Breugst, Jennifer N. Andexer,

Lena Barra

et al.

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(3), P. 40 - 70

Published: Feb. 28, 2025

Abstract Highlights von November 2023 bis 2024: die erste Einelektron‐C–C‐σ‐Bindung und Anti‐Bredt‐Verbindung; gesättigte Heterocyclen elektrochemisch funktionalisieren; Ausrichten diskotischer Flüssigkristalle; enantioselektive Wagner‐Meerwein‐Umlagerung reiner Aliphaten; photokatalytisch Furanen zu Pyrrolen; mit Ammoniak primären Arylaminen; Metallschrott recyceln ionischen Flüssigkeiten; terminale Alkene Ni‐Katalysatoren zum (Z)‐ oder (E)‐Alken isomerisieren;neue Fungizide, Medikamente Alkaloide.

Citations

0
Upcycling of Waste PET via Reprocessable Thermoset-like Covalent Adaptable Networks (CANs) DOI

Vini Gupta,

Soumabrata Majumdar, Debabrota Das

et al.

Polymer, Journal Year: 2025, Volume and Issue: unknown, P. 128438 - 128438

Published: April 1, 2025

Language: Английский

Citations

0
Catalyst-Free Upcycling of Poly(ethylene terephthalate) (PET) Waste into Degradable PET-Based Engineering Plastics via the Solvothermal Method DOI
Bingying Gao, Yunyun Sun,

Qiyi Lu

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Language: Английский

Citations

0
Closed-loop recycling for poly(ethylene terephthalate) (PET) plastic: depolymerization, monomer separation, and recycled PET (rPET) DOI
Taishun Yang, Qingming Fan, Hao He

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 163038 - 163038

Published: April 1, 2025

Language: Английский

Citations

0
Hydrogenating Polyethylene Terephthalate into Degradable Polyesters DOI

Zhenbo Guo,

Hao-Ran Zhang,

Haoyu Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 4, 2024

The recycling and upcycling of polyethylene terephthalate (PET), the most widely used polyester plastic globally, has attracted growing attention concerning its disposal as non-degradable waste in natural environment. Transforming end-of-life PET into (bio)degradable offers a novel approach to managing waste. In this study, we introduce simple process capable converting degradable polyester, terephthalate-polyethylene-1,4-cyclohexanedicarboxylate (PET-PECHD), by partly hydrogenating aromatic rings (x) aliphatic ones (y). polyesters with variable x/y compositions ranging from 100/0 0/100 can be achieved, molecular weight (Mw) maintained when >87/13 due nonobvious depolymerization. Pronounced depolymerization would occur deeper hydrogenation, which generates blend PET-PECHD polyethylene-1,4-cyclohexanedicarboxylate (PECHD) lower Mw, finally single-type polymer PECHD. demonstrates comparable thermal stability mechanical strength compared PET, along superior extensibility, barrier properties, (bio)degradability acidic, alkaline solutions, moist soil. This research highlights potential for cost-effective, large-scale production real-life

Language: Английский

Citations

1
Hydrogenating Polyethylene Terephthalate into Degradable Polyesters DOI Open Access

Zhenbo Guo,

Haoran Zhang,

Haoyu Chen

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 4, 2024

Abstract The recycling and upcycling of polyethylene terephthalate (PET), the most widely used polyester plastic globally, has attracted growing attention concerning its disposal as non‐degradable waste in natural environment. Transforming end‐of‐life PET into (bio)degradable offers a novel approach to managing waste. In this study, we introduce simple process capable converting degradable polyester, terephthalate‐polyethylene‐1,4‐cyclohexanedicarboxylate (PET‐PECHD), by partly hydrogenating aromatic rings ( x ) aliphatic ones y ). polyesters with variable / compositions ranging from 100/0 0/100 can be achieved, molecular weight (Mw) maintained when >87/13 due nonobvious depolymerization. Pronounced depolymerization would occur deeper hydrogenation, which generates blend PET‐PECHD polyethylene‐1,4‐cyclohexanedicarboxylate (PECHD) lower Mw, finally single‐type polymer PECHD. demonstrates comparable thermal stability mechanical strength compared PET, along superior extensibility, barrier properties, (bio)degradability acidic, alkaline solutions, moist soil. This research highlights potential for cost‐effective, large‐scale production real‐life

Language: Английский

Citations

0
Air‐Mediated Biomimetic Synthesis of Polyhydroxyalkanoate with C4 Diol DOI Open Access
Huilin Xie, Kai Zhong,

Sijie Niu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Abstract Poly(4‐hydroxybutyrate) (P4HB) is a high‐performance, well‐recyclable, and biodegradable polyhydroxyalkanoate (PHA). However, conventional bioproduction of homopolymeric P4HB involves complex costly processes with C4 feedstocks, particularly 1,4‐butanediol (BDO), enzyme‐coenzyme systems in genetically engineered bacteria. An alternative extracellular chemical route utilizing aerial oxidation BDO offers cost energy benefits but struggle conversion efficiency. Inspired by efficient intracellular primary alcohols, we propose ruthenium‐phosphine synergistic catalytic system that mimics functionality. This effectively catalyzed the air‐mediated, solvent‐free to produce γ‐butyrolactone (γ‐BL) oligomeric P4HB, space‐time yield (10.37 g [γ‐BL unit] −1 catalyst h ) surpassing values (<5.5) previous approaches. The oligomer‐containing products were reversibly converted γ‐BL then (28.9 kDa) via ring‐opening polymerization, exceeding reported (<16 kDa). study provides potential for large‐scale synthesis high‐value PHAs from diverse non‐grain‐based diols, offering economic environmental advantages.

Language: Английский

Citations

0