Sustainable developments in polyolefin chemistry: Progress, challenges, and outlook

Progress in Polymer Science, Год журнала: 2023, Номер 143, С. 101713 - 101713

Опубликована: Июнь 25, 2023

Язык: Английский

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‘Catalyst + X’ strategies for transition metal-catalyzed olefin-polar monomer copolymerization

Trends in Chemistry, Год журнала: 2023, Номер 5(2), С. 147 - 159

Опубликована: Янв. 7, 2023

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Light, Heat, and Force‐Responsive Polyolefins

Advanced Science, Год журнала: 2024, Номер 11(11)

Опубликована: Янв. 6, 2024

Abstract Stimuli‐responsive polymers have found applications as shape‐memory materials, optical switches, and sensors, but the installation of these responsive properties in non‐polar inert polyolefins is challenging. In this contribution, a series spiropyran (SP)‐based comonomers are synthesized copolymerized with ethylene or ethylene/cyclic monomers. addition to great mechanical surface properties, functionalized responded light, heat, force, which induced changes polymer structure transmit color signals. These interesting also installed commercial polyolefin materials through reactive extrusion, making scalable production possible.

Язык: Английский

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Synthesis and characterization of polyolefin thermoplastic elastomers: A review

The Canadian Journal of Chemical Engineering, Год журнала: 2023, Номер 101(9), С. 4886 - 4906

Опубликована: Янв. 4, 2023

Abstract Polyolefin thermoplastic elastomers (TPE‐Os) are high‐performance polyolefins consisting of both plastic and rubber phases. Compared with other elastomers, the TPE‐Os possess better chemical stability, transparency, re‐processability, electrical insulation, which renders their broad applications possible. By manipulating chain structures topologies TPE‐Os, differently structured improved thermal mechanical properties have been developed, including ethylene α‐olefin random copolymers (POEs), olefin block (OBCs), comb‐shaped polyolefin (CPOEs), dynamically cross‐linked elastomers. Herein, we review synthesis POE, OBC, CPOE, dynamical elastomer, catalyst systems, polymerization techniques, processes, kinetic modelling. The characterization relationships between TPE‐O structure, aggregated state, product performance discussed. future development higher‐performance is envisaged.

Язык: Английский

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Chemical Modification of Oxidized Polyethylene Enables Access to Functional Polyethylenes with Greater Reuse

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(39), С. 21527 - 21537

Опубликована: Сен. 21, 2023

Polyethylene is a commodity material that widely used because of its low cost and valuable properties. However, the lack functional groups in polyethylene limits use applications include adhesives, gas barriers, plastic blends. The inertness makes it difficult to install would enhance properties enable programmed chemical decomposition. To overcome these deficiencies, installation pendent imbue with enhanced an attractive strategy inherent limitations. Here, we describe strategies derivatize oxidized contains both ketones alcohols monofunctional variants bulk superior those unmodified polyethylene. Iridium-catalyzed transfer dehydrogenation acetone furnished polyethylenes only ketones, ruthenium-catalyzed hydrogenation hydrogen alcohols. We demonstrate ratio can be controlled by reduction stoichiometric hydride-containing reagents. serve as sites introduce esters oximes onto polymer, thereby improving surface over These were removed hydrolysis regenerate original oxygenated polyethylenes, showing how functionalization lead materials circularity. Waste equally amenable oxidative derivatization material, this low- or negative-value feedstock prepare higher value. Finally, derivatized polymers distinct solubilities separated from mechanically mixed blends selective dissolution, demonstrating novel approaches for distinguishing separating mixture.

Язык: Английский

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Diverse functional polyethylenes by catalytic amination

Science, Год журнала: 2023, Номер 381(6665), С. 1433 - 1440

Опубликована: Сен. 28, 2023

Functional polyethylenes possess valuable bulk and surface properties, but the limits of current synthetic methods narrow range accessible materials prevent many envisioned applications. Instead, these are often used in composite films that challenging to recycle. We report a Cu-catalyzed amination form mono- bifunctional containing series polar groups substituents. Designed catalysts with hydrophobic moieties enable linear branched without chain scission or cross-linking, leading otherwise inaccessible combinations functional architectures. The resulting tunable including toughness, adhesion metal, paintability, water solubility, which could unlock applications for reduce need complex composites.

Язык: Английский

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Heterogenization Strategies for Nickel Catalyzed Synthesis of Polyolefins and Composites

Accounts of Materials Research, Год журнала: 2023, Номер 4(6), С. 496 - 506

Опубликована: Май 20, 2023

ConspectusPolyolefin is one of the most common synthetic polymers. However, polyolefins are nonpolar materials, which leads to poor compatibility with polar thus limiting their application in some fields. Polar functionalized can lead significantly improved dyeability, adhesiveness and fillers, realize customized properties polyolefin materials. Transition-metal-catalyzed coordination copolymerization olefin comonomers represents a direct potentially economic route synthesize polar-functionalized has attracted great attention recent decades. Literally hundreds nickel palladium catalysts have been synthesized investigated olefin-polar monomer achieve high efficiency by tuning molecular structures catalysts. In particular, earth-abundant low-cost nickel-based hold potential for industrial applications. research efforts focus on homogeneous catalysts, while industrially preferred heterogeneous systems remained largely unexplored. With objective bridging this gap, our group recently developed series heterogenization strategies synthesis high-performance taking advantage hydrogen bond anchoring, ionic coanchoring, cocatalyst, cluster formation. These involve known or easily accessible be adapted various catalytic systems, simultaneous enhancement all parameters such as thermal stability, activity, comonomer incorporation ratio, copolymer weight versus counterparts. addition, performance tuned changing type support, thereby facilitating discovery Most importantly, product morphology control achieved. This desirable polymerization processes because it avoids reactor fouling results significant improvements safety operational processes. Finally, these give access materials (polar-functionalized polyolefins, in-reactor blends polyolefin-based functional composites) custom-made properties. Compared melt blending, composites obtained situ better material By using prepared situ. applications many fields, electrical conductivity, photodegradation, flame retardancy, barrier, etc. It expected that continuous mechanism/catalysts, heterogenizatioin will eventually commercialization nickel-catalyzed production composites.

Язык: Английский

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Outer‐Shell Self‐Supported Nickel Catalysts for the Synthesis of Polyolefin Composites

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Март 3, 2023

In situ heterogeneous olefin polymerization has attracted much attention for the synthesis of polyolefin composites. However, complicated syntheses specially designed catalysts or detrimental effects interactions between catalyst and solid supports pose great challenges. this contribution, an outer-shell self-supporting strategy was to heterogenize nickel on different fillers via precipitation homopolymerization ionic cluster type polar monomer. These demonstrated high activity, good product morphology control, stable performances in ethylene copolymerization. Moreover, various composites with mechanical customized properties can be efficiently synthesized.

Язык: Английский

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Synthesis of Polar-functionalized Isotactic Polypropylenes Using Commercial Heterogeneous Ziegler–Natta Catalyst

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6837 - 6845

Опубликована: Март 1, 2024

The efficient synthesis of polar-functionalized polypropylenes with high molecular weight and stereoregularity represents a challenging task. This challenge becomes even more daunting when pursuing an industrially preferred heterogeneous process. study demonstrated the realization these goals through use commercial Ziegler–Natta catalysts in copolymerization propylene ionic cluster polar monomers. results revealed activity (∼1.1 × 107 g mol–1 h–1), moderate monomer incorporation ratios (∼4.9 mol %), copolymer (Mw > 105 mol–1), ([mmmm] ∼ 96%), melting temperature range (150–162 °C). utilization monomers improved thermal stability as well stereoselectivity catalyst. Moreover, catalyst can homopolymerize activities (>104 h–1). resulting isotactic (iPP) exhibited superior tensile strength, impact creep resistance, transparency, crystallinity compared nonpolar iPP. enhancement was attributable to dual roles unit, serving both transparent nucleating agent dynamic cross-linking functionality. Furthermore, iPP compatibility materials, offering benefits for applications composites, recycling mixed plastic wastes, 3D printing, other fields. offered comprehensive solution future industrial production via copolymerization, bridging gap between practical process from synthetic chemistry perspective enhanced material properties application perspective.

Язык: Английский

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Noncovalent Ni–Phenyl Interactions Promoted α-Diimine Nickel-Catalyzed Copolymerization of Ethylene and Methyl Acrylate

Macromolecules, Год журнала: 2024, Номер 57(11), С. 5279 - 5288

Опубликована: Май 20, 2024

As a widely used functional polyolefin, the industrial ethylene (E)-methyl acrylate (MA) copolymer (EMA), prepared by free radical polymerization under harsh conditions, is lightly branched with in-chain and terminal MA incorporation. Metal-catalyzed E/MA copolymerization as an alternative technique highly attractive challenging. Herein, we first report efficient direct using "sandwich" dibenzobarrelene-derived α-diimine nickel catalysts. The produced EMA copolymers in-chain, pendant, units have chain structure very similar to EMA, which not previously reported palladium Experimental results support that noncovalent Ni–phenyl interactions in catalysts promote copolymerization. Density theory studies clearly illuminate crucial role of well explain formation chain.

Язык: Английский

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