Recyclable, Reprocessable, Anticorrosive, and Hydrolysis-Resistant Long-Chain Aliphatic Polycarbonates as Polyethylene-like Materials

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(2), P. 1551 - 1562

Published: Jan. 4, 2024

Disposable plastic items (packages in particular) cause serious resource waste and environmental pollution. Alternative materials resembling macroscopic properties of traditional plastics while possessing degradability recyclability are anticipated to address such global challenges. Herein, we presented facile synthesis long-chain aliphatic polycarbonates via fluoride-promoted carbonylation polymerization by using 1,1′-carbonyldiimidazole cesium fluoride as the activator catalyst, respectively. This mild preparation process circumvents several deficiencies owned conventional polycondensation for polycarbonate synthesis, manipulation corrosive/toxic reagents, high energy consumption, time cost. The as-prepared showed molecular weights good thermal stabilities. Key parameters crystallization/melting temperatures enthalpies were positively associated with methylene spacer lengths repeating units these polymers. In particular, a plausible odd–even effect was observed from wide-angle X-ray diffraction patterns specimens. These polyethylene-like virtually bridged gap between polycondensates polyolefins that samples displayed comparable crystal morphology, film-forming property, reprocessability, surface wettability, hydrolysis resistance, anticorrosiveness high-density polyethylene. Meanwhile, polyethylene mimics manifested remarkable through alkaline upon heating almost complete recovery (>96%) diol achieved each case. On other hand, inorganic fillers, including toner, phosphor, magnetite, silver powders micro/nanoparticles homogeneously dispersed matrices vortex mixing create colored, phosphorescent, magnetic, conductive composite films,

Language: Английский

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CO₂ and Lignin‐Based Sustainable Polymers with Closed‐Loop Chemical Recycling

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: March 19, 2024

Abstract This work highlights the conversion method of chaining up greenhouse gas CO 2 with biomass lignin to develop new sustainable, recyclable polymers from abundant and non‐food based renewable resources. A cyclic carbonate monomer has synthesized using a cost‐effective, non‐phosgene‐based, greener approach under atmospheric pressure room temperature. The fully programable ring‐opening polymerization is accomplished by varying catalyst (DBU TBD), loading (0.5–5.0%) reaction time (2–40 min). best polymer obtained in 1% TBD 30‐min reaction. precise characterization polymers' structure are established spectroscopic analyses including 1 H, 13 C, 2D HSQC NMR, FT‐IR, GPC. exhibit high molecular weights ( M n : 120.34–154.58 kDa) adequate thermal stabilities T d5% 244–277 °C TGA g 33–52 DSC), rendering them advantageous for practical applications. Significantly, lignin‐based have successfully recycled circular plastic economy heating at 90 12 h presence DBU. process yields original monomers another without unwanted changes chemical structures, presenting an ultimate sustainable solution.

Language: Английский

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Sustainable Plastics with High Performance and Convenient Processibility

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: July 19, 2024

Abstract Designing and making sustainable plastics is especially urgent to reduce their ecological environmental impacts. However, it remains challenging construct with simultaneous high sustainability outstanding comprehensive performance. Here, a composite strategy of in situ polymerizing petroleum‐based monomer the presence an industrialized bio‐derived polymer quasi‐solvent‐free system introduced, affording plastic excellent mechanical robustness, impressive thermal solvent stability, as well low energy, consumes during production, processing, recycling. Particularly, can be easily processed into diverse shapes through 3D printing, injection molding, etc. polymerization further reprocessed other complex structures via eco‐friendly hydrosetting. In addition, mechanically robust Young's modulus up 3.7 GPa tensile breaking strength 150.2 MPa, superior many commercially available plastics. It revealed that hierarchical hydrogen bonds predominate well‐balanced This work provides new path for fabricating high‐performance toward practical applications, contributing circular economy.

Language: Английский

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Easy Synthetic Access to High‐Melting Sulfurated Copolymers and their Self‐Assembling Diblock Copolymers from Phenylisothiocyanate and Oxetane

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: March 23, 2024

Abstract Although sulfurated polymers promise unique properties, their controlled synthesis, particularly when it comes to complex and functional architectures, remains challenging. Here, we show that the copolymerization of oxetane phenyl isothiocyanate selectively yields polythioimidocarbonates as a new class sulfur containing polymers, with narrow molecular weight distributions ( M n =5–80 kg/mol Đ ≤1.2; ,max =124 kg/mol) high melting points up 181 °C. The method tolerates different substituent patterns on both isothiocyanate. Self‐nucleation experiments reveal π‐stacking substituents, presence unsubstituted polymer backbones, kinetically linkage selectivity are key factors in maximising points. increased tolerance macro‐chain transfer agents propagation allows synthesis double crystalline amphiphilic diblock copolymers, which can be assembled into micellar‐ worm‐like structures amorphous cores water. In contrast, crystallization driven self‐assembly ethanol gives cylindrical micelles or platelets.

Language: Английский

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Harnessing Borane-Potassium Cooperativity for Sulfurated Ring-Opening Copolymerisation

Green Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Catalysts combining commercial borane Lewis acids and potassium acetate complexes achieve the selective ring-opening copolymerization (ROCOP) of oxetanes with diverse sulfur-containing monomers.

Language: Английский

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Multicomponent Polymerizations Provide Sustainable Sulfur (Selenium)-Containing Polyesters

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

ConspectusWith the rapid development of polymer industry, contradiction between synthetic polymers and sustainable human society is becoming more prominent. The advancement degradable plastics greatly contributes to sustainability our society. Synthetic containing precisely placed in-chain ester groups are expected be in a controlled manner. Their potential as environmentally benign significant. For this purpose, there clear need for their improved performance. Incorporating sulfur functional into polyesters can improve diverse crucial properties counterparts. However, lack related high-efficiency synthesis methods.In response issue, we designed series multicomponent polymerization methods library with tunable structure properties. This Account summarizes recent efforts discover approach. method uses readily available monomers including diols, diamines, H2O, diacrylates, carbonyl sulfide (COS), cyclic thioanhydrides, CO, selenium powder. usually carried out under mild conditions: at 60 90 °C, 2 12 h, using organobases catalysts or catalyst-free. approach achieves simultaneous incorporation sulfur/selenium thiocarbonate, thioether, thioester, thiourethane, selenoether.The has wide monomer scope yields structures. obtained possess weight-average molecular weights up 175.4 kDa. Most these thermally stable, exhibiting decomposition temperatures >200 °C. Due diversity structure, demonstrate extensively performance covering crystalline plastics, thermoplastic elastomers, amorphous plastics. These exhibit range glass-transition -60 72 °C melting 43 274 Notably, long alkyl chains (number carbon atoms ≥ 9) polyethylene-like crystallinity mechanical thiourethane amide enable enhanced thermal due inter/intramolecular hydrogen bonding. also easy degrade via alkali hydrolysis, alcohol enzymatic oxidation, etc. degradation products often have well-defined value-added even directly used repolymerization achieve closed-loop chemical cycle. Overall, presented furnishes facile versatile

Language: Английский

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Processing Plastic Wastes into Value-Added Carbon Adsorbents by Sulfur-Based Solvothermal Synthesis

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(30), P. 11207 - 11218

Published: July 18, 2023

Efficient strategies (degradation or recycling) for converting multifarious plastic wastes are imperative due to the resulting detriments environment and human life. With this in mind, versatile sulfur-mediated conversion of into value-added adsorbents is presented. The essential sulfur medium promotes thermal polycondensation polymer chains leads an impressive carbonization yield 91%, significantly exceeding control process without (0–12%). final sublimation endowed carbon materials with high porosity (SBET up 888 cm2/g), while attack radicals naturally results a content (8.66–12.08%) framework. Interestingly, polar interactions (CO2 sulfoxides, sulfones, sulfonic) ensured S-doped good performance CO2 adsorption (up 4.6 mmol/g at 273 K), coordinating role sulfide group contributed heavy metal [removal efficiency 99.5% Pb(II) 99.8% Cd(II)].

Language: Английский

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EtOS₂K as a C1 Source: Solvent- and Temperature-Controlled Selective Synthesis of Quinoline-2-thione and Quinoline-2-one Derivatives

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1985 - 1990

Published: Feb. 23, 2024

Herein, we disclosed a highly chemoselective synthesis of quinoline-2-one and quinoline-2-thione derivatives using EtOS2K as the C1 source. Quinoline-2-one were synthesized selectively with NaCl catalyst in solvent DMSO/H2O, while produced without need for any an environmentally friendly EtOH/H2O. The reaction conditions mild had good functional group tolerance.

Language: Английский

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Heteroleptic Calcium Complexes Supported by a Phenoxy-Imine NON Ligand: Polymerization of Cyclic Esters by a Ligand-Assisted, Activated-Monomer Mechanism

Organometallics, Journal Year: 2024, Volume and Issue: 43(9), P. 1005 - 1020

Published: April 15, 2024

Phenoxy-imine NON pro-ligands HR,DippL [1-OH-2,6-(HC═NDipp)-4-R-C6H2, where R = H, Me, or tBu] were deprotonated using KH to afford the corresponding potassium salts R,DippLK·thfx [R H (1·thfx), Me (2·thfx), and tBu (3·thfx)]. The addition of crown ether (18-c-6) these allowed for structures resulting adducts be elucidated in solid state: [1(18-c-6)]n, [2(18-c-6)]n, [3(18-c-6)(thf)]. derivatives with smaller para-substituents found 1D coordination polymers stabilized by unusual non-covalent interactions between diisopropyl-methyl groups center. Heteroleptic calcium complexes R,DippLCaI(thf)3 (4), (5), (6)] prepared salt metathesis reaction 1–3·thfx CaI2. Complexes 4–6 evaluated as initiators ring-opening polymerization lactide monomers all active; benzyl alcohol resulted large rate increases, e.g., ∼12-fold difference 6 (0.70 vs 0.06 h–1). propagation constants lie within range 88–135 M–1 h–1. Variation co-initiator concentration revealed only a fractional dependence; this agrees other experimental observations, which suggest that heteroleptic catalysts work via "ligand-assisted, activated monomer" mechanism.

Language: Английский

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Unsaturated sulfur-containing polymers from modular alcohol click chemistry

Polymer Chemistry, Journal Year: 2024, Volume and Issue: 15(20), P. 2055 - 2062

Published: Jan. 1, 2024

A modular and efficient click reaction for connecting primary secondary alcohols with activated alkynes via carbonyl sulfide (COS) was developed. Polythiocarbonates were synthesized by the step-wise polyaddition of diols, dipropiolates, COS.

Language: Английский

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