Stapler Strategies for Upcycling Mixed Plastics

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19449 - 19459

Published: July 2, 2024

Mechanical recycling is one of the simplest and most economical strategies to address ever-increasing plastic pollution, but it cannot be applied immiscible mixed plastics suffers from property deterioration after each cycle. By combining amphiphilic block copolymer strategy reactive compatibilization strategy, we designed a series stapler for compatibilizing/upcycling plastics. First, various functionalized graft copolymers were accessed via different synthetic routes. Subsequently, addition very small amount molecules induced synergistic effect with that improved compatibility mechanical properties These highly effective binary/ternary systems can directly postconsumer waste plastics, which increase toughness by 162 times. Most importantly, also effectively impact resistance, adhesion performance, three-dimensional (3D) printing performance permitted blends 20 times minimal degradation in their properties.

Language: Английский

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Synthesis, Characterization, and Catalytic Properties of Regioisomeric β‐Ketoimine Titanium Complexes for Ethylene Polymerization

Applied Organometallic Chemistry, Journal Year: 2025, Volume and Issue: 39(2)

Published: Jan. 1, 2025

ABSTRACT Non‐metallocene catalysts have shown great potential for modulating the polymer microstructure by changing ligand structure, but effects of structure and electronic property metal center on their catalytic performance remain underexplored. Herein, we designed synthesized two pairs isomeric tridentate β‐ketoimine complexes TiL a / b c d with methylthioaniline methylthioethylamine side arms, respectively, which exhibited moderate to extremely high activity over 10 6 g (mol Ti) −1 · h ·atm polymerization ethylene copolymerization α‐olefins (1‐hexene, 1‐octene) polar comonomer (9‐decen‐1‐ol) in presence MAO, activities order: > . The regioisomers arm showed significantly higher (co)polymerization than that arm, especially or 9‐decen‐1‐ol, indicating an obvious positive “comonomer effect”. complex highest insertion rate. Structural optimization using density functional theory (DFT) calculations suggested “side arms” properties titanium played key role copolymerization.

Language: Английский

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Tailor-Made Functional Polyolefins of Complex Architectures: Recent Advances, Applications, and Prospects

Macromolecules, Journal Year: 2022, Volume and Issue: 55(16), P. 6938 - 6972

Published: Aug. 12, 2022

Polyolefins play a crucial role in the polymer industry because of their low-cost monomers and well-established production processes. Recent years have witnessed tremendous progress direct tandem copolymerization strategies that provide an opportunity developing polyolefins bearing polar groups with distinctive architectures properties. In this perspective, we first highlight new routes for proficient synthesis tailor-made functional briefly discuss designing tactics. Then, attempt to categorize these, recently appeared literature, innovative on basis applications. The prospected future applications olefin copolymers include biomedical materials, catalysts, energy storage devices, conductive polymers, which open up arenas paradigms academic research industrial products development. Critical issues concerning intelligent green chemistry are discussed, too.

Language: Английский

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Photodegradable polar-functionalized polyethylenes

National Science Review, Journal Year: 2023, Volume and Issue: 10(7)

Published: Feb. 16, 2023

The degradation of plastics has attracted much attention from the global community. Polyethylenes (PEs), as most abundant synthetic plastics, are frequently studied. PE is non-degradable and non-polar because sole presence pure hydrocarbon components. Concurrent incorporation both in-chain cleavable functional groups into chain an effective pathway to overcome issue; however, method for achieving this remains elusive. Here, we report a strictly non-alternating (>99%) terpolymerization ethylene with CO fundamental polar monomers via coordination-insertion mechanism using late transition metal catalysts, which effectively prevents formation undesired chelates originating co-monomers under low concentration. High-molecular-weight linear PEs isolated keto main-chain prepared. key low-content makes photodegradable while retaining their desirable bulk material properties, introduction considerably improves surface properties.

Language: Английский

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Advance on nickel‐ and palladium‐catalyzed insertion copolymerization of ethylene and acrylate monomers

Journal of Polymer Science, Journal Year: 2023, Volume and Issue: 61(23), P. 2987 - 3021

Published: Aug. 8, 2023

Abstract Nickel‐ and palladium‐catalyzed insertion copolymerization of ethylene acrylate comonomers for synthesis ethylene‐acrylates copolymers have attracted much academic industrial interests remained highly challenging. This review provides an overview the developments in nickel‐ comonomers. Mechanistic interpretation metal‐catalyzed is described. Late transition metal catalysts are divided to nickel‐based palladium‐based with different chelate ligands. The effects catalyst structure on performance copolymer microstructure comprehensively discussed. aims promote design development nickel palladium ethylene/acrylate copolymerizations copolymers.

Language: Английский

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Emulsion Polymerization Strategy for Heterogenization of Olefin Polymerization Catalysts

Macromolecules, Journal Year: 2023, Volume and Issue: 56(6), P. 2388 - 2396

Published: March 6, 2023

Heterogenization of homogeneous metal catalysts on solid supports has been widely studied for product morphology control in ethylene polymerization. In this contribution, an emulsion polymerization strategy was introduced to achieve heterogenization various imino-based nickel olefin catalysts. A series polymeric microspheres were prepared through copolymerization vinyl-functionalized imino ligands with comonomers such as styrene or methyl methacrylate. The corresponding heterogeneous demonstrated superior properties and 10-undecylenate. Their catalytic can be controlled by tuning the comonomer type, composition, particle size. Most importantly, avoid reactor fouling while generating polyethylene products minimum inorganic contamination. addition, introduction polymer improve mechanical surface polyolefin products.

Language: Английский

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Aqueous Coordination‐Insertion Copolymerization for Producing High Molecular Weight Polar Polyolefins

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: March 29, 2024

Hydrocarbons, when used as the medium for transition metal catalyzed organic reactions and olefin (co-)polymerization, are ubiquitous. Environmentally friendly water is highly attractive long-sought, but greatly challenging coordination-insertion copolymerization reaction of polar monomers. Unfavorable interactions from both monomer usually lead to either catalyst deactivation or formation low-molecular-weight polymers. Herein, we develop well-behaved neutral phosphinophenolato nickel catalysts, which enable aqueous ethylene diverse monomers produce significantly high-molecular-weight linear polyolefins (219-549 kDa, 0.13-1.29 mol %) in a single-component fashion under mild conditions first time. These occur better than hydrocarbons such toluene. The dual characteristics high molecular weight incorporation small amount functional group result improved surface properties while retain desirable intrinsic high-density polyethylene (HDPE).

Language: Английский

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Block Copolymers of Polyolefins with Polyacrylates: Analyzing and Improving the Blocking Efficiencies Using MILRad/ATRP Approach

Macromolecular Rapid Communications, Journal Year: 2024, Volume and Issue: 45(8)

Published: Jan. 1, 2024

Abstract Despite their industrial ubiquity, polyolefin‐polyacrylate block copolymers are challenging to synthesize due the distinct polymerization pathways necessary for respective blocks. This study utilizes MILRad, metal–organic insertion light‐initiated radical polymerization, polyolefin‐ b ‐poly(methyl acrylate) copolymer by combining palladium‐catalyzed insertion–coordination and atom transfer (ATRP). Brookhart‐type Pd complexes used living of olefins homolytically cleaved blue‐light irradiation, generating polyolefin‐based macroradicals, which trapped with functional nitroxide derivatives forming ATRP macroinitiators. in presence Cu(0), that is, supplemental activators reducing agents , is polymerize methyl acrylate. An increase functionalization efficiency up 71% demonstrated this modifying light source optimizing trapping condition. Regardless efficiency, essentially quantitative chain extension polyolefin‐Br macroinitiator acrylates consistently demonstrated, indicating successful second formation.

Language: Английский

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Upgrading Polyolefin Plastic Waste into Multifunctional Porous Graphene using Silicone‐Assisted Direct Laser Writing

Small, Journal Year: 2024, Volume and Issue: unknown

Published: May 25, 2024

Abstract The widespread use of plastics, especially polyolefin including polyethylene and polypropylene, has led to severe environmental crises. Chemical recycling, a promising solution for extracting value from plastic waste, however, is underutilized due its complexity. Here, simple approach, silicone‐assisted direct laser writing (SA‐DLW) developed, upgrade waste into multifunctional porous graphene, called laser‐induced graphene (LIG). This method involves infiltrating polyolefins with silicone, which retards ablation during the DLW process supplies additional carbon atoms, as confirmed by experimental molecular dynamic results. A remarkable conversion yield 38.3% achieved. upgraded LIG exhibited structure high conductivity, utilized fabrication diverse energy electronic devices commendable performance. Furthermore, SA‐DLW technique versatile upgrading in various types forms. Upgrading form fabric significantly simplified pre‐treatment. Finally, wearable flex sensor fabricated on non‐woven discarded medical mask, applied gesture monitoring. work offers but effective valuable products, contributing mitigation challenges posed pollution.

Language: Английский

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Impact of Labile Ligands on Catalyst Initiation and Chain Propagation in Ni-Catalyzed Ethylene/Acrylate Copolymerization

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 5000 - 5006

Published: March 29, 2023

Polar polyolefin synthesis by coordination polymerization is of high interest, but the catalysts' low activity limits industrial implementation. Herein, we demonstrate how nature labile ligand, L, impacts performance neutral nickel catalysts supported bidentate phosphine-phenoxide and phosphine-enolate ligands in ethylene/acrylate copolymerization. By tuning copolymerization reaches ∼24000 kg/(mol h). In situ studies indicate that a weaker L leads to faster chain propagation more efficient catalyst initiation. Overall, this work highlights potential strategy improve polar complementary design optimization for ligand.

Language: Английский

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