Current Challenges and Perspectives in CO₂-Based Polymers

Macromolecules, Journal Year: 2023, Volume and Issue: 56(5), P. 1759 - 1777

Published: Feb. 28, 2023

Carbon dioxide (CO2) is considered a renewable one-carbon building block for chemical synthesis owing to its abundance, low toxicity, nonflammability, and availability. The incorporation of CO2 into the polymer backbone affords various ester- or carbonyl-containing moieties, which create desired material properties impart unique degradability after use under microbial conditions. In this Perspective, we focus on critical advances in CO2-derived polymers highlight catalytic strategies, novel conceptual routes, potential application fields. outlook perspective are provided describe future challenges new strategies establishing CO2-based with performances economic competitiveness comparable that petroleum-based materials.

Language: Английский

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Organoboron-mediated polymerizations

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(7), P. 3384 - 3456

Published: Jan. 1, 2024

The scientific community has witnessed extensive developments and applications of organoboron compounds as synthetic elements metal-free catalysts for the construction small molecules, macromolecules, functional materials over last two decades. This review highlights achievements organoboron-mediated polymerizations in past several decades alongside mechanisms underlying these transformations from standpoint polymerization mode. Emphasis is placed on free radical polymerization, Lewis pair ionic (cationic anionic) polyhomologation. Herein, alkylborane/O

Language: Английский

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New sustainable polymers with on-demand depolymerization property

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(9), P. 2803 - 2841

Published: Aug. 12, 2024

Language: Английский

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High Molar Mass Polycarbonates as Closed-Loop Recyclable Thermoplastics

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 8381 - 8393

Published: March 14, 2024

Using carbon dioxide (CO2) to make recyclable thermoplastics could reduce greenhouse gas emissions associated with polymer manufacturing. CO2/cyclic epoxide ring-opening copolymerization (ROCOP) allows for >30 wt % of the polycarbonate derive from CO2; so far, field has largely focused on oligocarbonates. In contrast, efficient catalysts high molar mass polycarbonates are underinvestigated, and resulting thermoplastic structure–property relationships, processing, recycling need be elucidated. This work describes a new organometallic Mg(II)Co(II) catalyst that combines productivity, low loading tolerance, highest polymerization control yield number average molecular weight (Mn) values 4 130 kg mol–1, narrow, monomodal distributions. It is used in ROCOP CO2 bicyclic epoxides produce series samples, each Mn > 100 poly(cyclohexene carbonate) (PCHC), poly(vinyl-cyclohexene (PvCHC), poly(ethyl-cyclohexene (PeCHC, by hydrogenation PvCHC), poly(cyclopentene (PCPC). All these materials amorphous thermoplastics, glass transition temperatures (85 < Tg 126 °C, differential scanning calorimetry) thermal stability (Td 260 °C). The cyclic ring substituents mediate materials' chain entanglements, viscosity, temperatures. Specifically, PCPC was found have 10× lower entanglement (Me)n 100× zero-shear viscosity compared those PCHC, showing potential as future thermoplastic. polymers fully recyclable, either reprocessing or using highly selective depolymerizations CO2. shows fastest depolymerization rates, achieving an activity 2500 h–1 >99% selectivity cyclopentene oxide

Language: Английский

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Evolution of Copolymers of Epoxides and CO₂: Catalysts, Monomers, Architectures, and Applications

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 25, 2024

The copolymerization of CO

Language: 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, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 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.

Language: Английский

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Recyclable, Fire-Resistant, Superstrong, and Reversible Ionic Polyurea-Based Adhesives

Chemistry of Materials, Journal Year: 2023, Volume and Issue: 35(3), P. 1218 - 1228

Published: Jan. 13, 2023

Carbon dioxide (CO2) as a sustainable comonomer for the synthesis of polycarbonates, polyurea, and polyurethane is attracting continuous interest, whereas development multifunctional polymers directly from CO2 remains challenging its inherent inertness. Herein, we report characterization recyclable, nonflammable, superstrong, reversible adhesive via polycondensation an amino-functionalized ionic liquid. The resulting CO2-sourced polyurea (CIPUa) with commutative urea groups species in skeleton shows much higher shear strength on various substrates even below −80 °C than commercial hot-melt adhesives excellent nonflammability antibacterial ability isocyanate-derived nonionic polyurea. CIPUa also demonstrates facile degradation ZnSO4 aqueous solution can be recycled into fresh CIPUa. These properties are mainly endowed by enhanced electrostatic interaction attenuated hydrogen bonds between chains. This study provides effective strategy designing polymer multiple functions broad applications.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: April 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.

Language: Английский

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Advances in the Synthesis of Chemically Recyclable Polymers

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(3)

Published: Jan. 9, 2023

Abstract The development of modern society is closely related to polymer materials. However, the accumulation materials and their evolution in environment causes not only serious environmental problems, but also waste resources. Although physical processing can be used reuse polymers, properties resulting polymers are significantly degraded. Chemically recyclable a type that degrades into monomers, an effective solution degradation caused by recycling polymers. ideal chemical i. e., quantitative conversion monomers at low energy consumption repolymerization formed with comparable original, attractive research goal. In recent years, significant progress has been made design enabling regulation “polymerization‐depolymerization” equilibrium closed‐loop under mild conditions. This review will focus on following aspects poly(sulfur) esters, polycarbonates, polyacetals, polyolefins, poly(disulfide) polymer, illustrate challenges this area, provide outlook future directions.

Language: Английский

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Insights into substitution strategy towards thermodynamic and property regulation of chemically recyclable polymers

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 2, 2023

The development of chemically recyclable polymers serves as an attractive approach to address the global plastic pollution crisis. Monomer design principle is key achieving chemical recycling monomer. Herein, we provide a systematic investigation evaluate range substitution effects and structure-property relationships in ɛ-caprolactone (CL) system. Thermodynamic recyclability studies reveal that substituent size position could regulate their ceiling temperatures (Tc). Impressively, M4 equipped with tert-butyl group displays Tc 241 °C. A series spirocyclic acetal-functionalized CLs prepared by facile two-step reaction undergo efficient ring-opening polymerization subsequent depolymerization. resulting demonstrate various thermal properties transformation mechanical performance from brittleness ductility. Notably, toughness ductility P(M13) comparable commodity isotactic polypropylene. This comprehensive study aimed guideline future monomer towards polymers.

Language: Английский

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