A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: April 12, 2022

The heterogenization of homogeneous metal complexes on solid supports presents an efficient strategy for bridging catalysts with industrially-preferred heterogeneous catalysts; however, a series drawbacks restrict their implementation in olefin polymerization, particularly copolymerization polar comonomers. In this contribution, we report ionic anchoring that is highly versatile, generally applicable to different systems, and enables strong catalyst-support interactions while tolerating various functional groups. addition greatly enhanced polymerization properties, the supported achieved higher comonomer incorporation than unsupported counterparts. This enabled at high temperatures large scale great control over product morphology, facile synthesis polyolefin composites. More importantly, dispersion fillers matrix produced material properties even low composite loadings. It expected will find applications catalytic systems advanced engineering materials.

Language: Английский

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Material Properties of Functional Polyethylenes from Transition-Metal-Catalyzed Ethylene–Polar Monomer Copolymerization

Macromolecules, Journal Year: 2022, Volume and Issue: 55(6), P. 1910 - 1922

Published: March 1, 2022

Polyethylenes enjoy wide applications due to their many superior properties. The incorporation of some polar functional groups into the otherwise nonpolar polyethylene backbone can significantly improve important properties and further broaden applications. During past few decades, catalyst systems have been demonstrated with capabilities copolymerizing ethylene monomers. As a result, numerous functionalized polyethylenes prepared bearing various groups. However, studies material from transition-metal-catalyzed ethylene–polar monomer copolymerization not received much attention until recently. After brief discussions selected examples potent catalysts suitable monomers, this Perspective summarizes recent advances in improvements surface compatibilities (hydrophilicity, adhesion, dyeability, compatibility other types polymers) induced through group as well custom-made such elastic, flame-retardant, antibacterial, antioxidant, cross-linking, self-healing, light response, dynamic photodegradation

Language: Английский

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An Ionic Cluster Strategy for Performance Improvements and Product Morphology Control in Metal-Catalyzed Olefin–Polar Monomer Copolymerization

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2245 - 2254

Published: Jan. 24, 2022

Product morphology control represents a critical challenge for polyolefin production, but it has remained largely unexplored in the field of ethylene-polar monomer copolymerization. Herein, an ionic cluster strategy was designed to product during synthesis polar-functionalized polyolefins via precipitation polymerization. In addition control, simultaneous improvements catalytic copolymerization performance (activities, copolymer molecular weights, and comonomer incorporation ratios) were achieved. These results due less poisoning metal-salt-based comonomers compared with their ester counterparts high local concentration alkene induced by formation. Moreover, is generally applicable various systems, greatly enhances catalyst's thermal stability at temperatures (90-150 °C), enables homopolymerization both terminal internal olefins. Finally, composites (generated from tandem process combining prepolymerization step subsequent polymerization) developed, which showed tunable mechanical properties great potential as compatibilizing agents mixtures other types polymers.

Language: Английский

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Advances on Controlled Chain Walking and Suppression of Chain Transfer in Catalytic Olefin Polymerization

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 14304 - 14320

Published: Nov. 7, 2022

Precise synthesis of the complex polymer structure has been long-sought. In late transition-metal catalyzed olefin polymerization, chain walking and transfer are two important processes that affect architectures, molecular weights distributions, respectively. However, both uncontrolled presence make it difficult to precisely synthesize desired polyolefin materials. How address these key events is a long-standing challenge. This Perspective highlights advances on controlled suppression reactions in late-transition-metal-mediated polymerization prepare well-defined polyolefins. Fruitful catalyst strategies versatile techniques powerful tools accomplish elusive control over architectures.

Language: Английский

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High activity and stability in Ni2P/(Co,Ni)OOH heterointerface with a multiple-hierarchy structure for alkaline hydrogen evolution reaction

Nano Research, Journal Year: 2023, Volume and Issue: 16(5), P. 6552 - 6559

Published: Feb. 22, 2023

Language: Английский

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

Trends in Chemistry, Journal Year: 2023, Volume and Issue: 5(2), P. 147 - 159

Published: Jan. 7, 2023

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Heterogenization Strategies for Nickel Catalyzed Synthesis of Polyolefins and Composites

Accounts of Materials Research, Journal Year: 2023, Volume and Issue: 4(6), P. 496 - 506

Published: May 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.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: March 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.

Language: Английский

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Heterogeneous Nickel Catalysts for the Synthesis of Ethylene-Based Polyolefin Elastomers

Macromolecules, Journal Year: 2024, Volume and Issue: 57(3), P. 1080 - 1086

Published: Feb. 1, 2024

Ethylene-based polyolefin elastomers (EPOEs) represent a novel class of material prepared using ethylene as the only feedstock and bear comparable mechanical elastic properties versus traditional (POEs). EPOEs are from late-transition-metal (nickel or palladium)-catalyzed chain walking polymerization ethylene. However, literature-reported potent catalysts homogeneous systems that operate at relatively low temperatures (<90 °C), while industrial production POE materials requires high (>120 °C). In this contribution, we install some OM (M = H, Na, K) tags in an α-diimine ligand framework, enabling facile heterogenization nickel complexes onto MgCl2-based solid support. The resulting heterogeneous highly active demonstrate much better thermal stability (up to 150 °C) than their counterparts. More importantly, polyethylene products super-stretchability 2160%) maintaining tensile strength 15.4 MPa) elasticity (strain recovery value up 83%). These EPOE can also be used toughen polypropylene, well compatibilize blends polypropylene.

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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