Ethylene homo and copolymerization by phosphorus‐benzoquinone based homogeneous and heterogeneous nickel catalysts

Wang, Quan; Wang, Wenbing; Qu, Weicheng; Pang, Wenmin; Qasim, Muhammad; Zou, Chen

doi:10.1002/pol.20220381

Cited by 7 publications

(7 citation statements)

References 69 publications

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“…The hydrogen bonding is also applied in the immobilization of olefin polymerization catalysts by catalyst–support interactions. Unlike traditional physical absorption on silicon, Cai and co-workers reported an alternative strategy for the heterogenization of late transition metal catalysts (Figure ) through hydrogen bonding interactions between the ligands and the silica. − Using this immobilization approach, pretreatment of the solid support or the use of any cocatalyst can be avoided. The supported nickel and palladium catalysts showed enhanced catalytic properties compared to their corresponding homogeneous catalysts.…”

Section: Hydrogen Bonding Interactionsmentioning

confidence: 99%

Noncovalent Interactions in Late Transition Metal-Catalyzed Polymerization of Olefins

Zheng,

Gao

2024

Macromolecules

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Transition metal-catalyzed olefin polymerization dominates in the polyolefin field, and we still have limited control over a catalyst's behavior. In addition to traditional steric and electronic modifications, developing new design strategies for transition metal catalysts is highly intriguing and may open avenues for the highly efficient synthesis of new highperformance polyolefins. In this Perspective, recent advances in weak noncovalent interactions including hydrogen bonding, π−π interactions, metal−aryl π-interactions, and electrostatic metal−X interactions (X = heteroatoms) for modulating late transition metal-catalyzed polymerization of olefins are reviewed with an emphasis on their influences on (co)polymerization of olefins. It provides a practical consultation for polymer synthesis chemists that are interested in developing weak noncovalent interaction-assisted polymerization of olefins.

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Section: Hydrogen Bonding Interactionsmentioning

confidence: 99%

Noncovalent Interactions in Late Transition Metal-Catalyzed Polymerization of Olefins

Zheng,

Gao

2024

Macromolecules

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“…In another system, heterogeneous phosphorus benzoquinone nickel catalysts anchored by carbonyl groups were prepared by hydrogen bond interactions between carbonyl groups and supports (SiO 2 , TiO 2 , Al 2 O 3 ) (Figure , Ni3@support) . These catalysts showed improved thermal stability in ethylene polymerization compared with similar homogeneous catalysts.…”

Section: Heterogenization Strategies For Nickel Catalyzed Synthesis O...mentioning

confidence: 99%

“…These interactions may lead to the deterioration of the catalyst performances. , For example, the interaction between support and catalyst may enhance the poisoning effect of polar monomers toward metal catalysts; the interaction between catalyst and polar monomers may decrease the catalyst loading efficiency on solid support; the interaction between support and polar monomers may interfere with catalyst anchoring and increase catalyst leaching. Recently, our group developed a series of heterogenization strategies for the development of high-performance heterogeneous nickel catalysts, including hydrogen bond anchoring, ,, ionic anchoring, ,, coanchoring, cocatalyst, and ionic cluster strategies . The (co)anchoring strategies are based on molecular catalysts bearing hydrogen bond or ionic anchoring groups (Figure D).…”

Section: Introductionmentioning

confidence: 99%

Heterogenization Strategies for Nickel Catalyzed Synthesis of Polyolefins and Composites

2023

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

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] In particular late transition metal catalysts based on nickel and palladium have played an important role in the field of olefin polymerization, which can easily adjust the microstructure of polyolefins and realize the copolymerization of olefins and polar monomers. [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] However, in contrast to these studies of homogeneous polymerization systems, the polyolefin industry mainly utilizes heterogeneous polymerization systems, which can further increase the polymerization activity, the molecular weight of the polymer, and effectively control the product morphology to achieve a continuous polymerization process while preventing reactor fouling. 32,33 ZieglerÀNatta (TiCl 4 /AlR 3 /MgCl 2 ) 2 and Phillips (CrO x / SiO 2 ) 3 catalysts possess multisite to produced highdensity polyethylene with broad molecular weight distributions.…”

Section: Introductionmentioning

confidence: 99%

“…While the production of polyolefin continues to increase, the development of high‐performance polyolefin catalysts continues to advance with the contributions of scientific researchers 1–16 . In particular late transition metal catalysts based on nickel and palladium have played an important role in the field of olefin polymerization, which can easily adjust the microstructure of polyolefins and realize the copolymerization of olefins and polar monomers 17–31 …”

Section: Introductionmentioning

confidence: 99%

Heterogenization of nickel catalysts with ionic liquid‐modified supports for ethylene polymerization and copolymerization

Wang

Sun

Pan

et al. 2023

Journal of Polymer Science

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The preparation of heterogeneous catalysts by loading homogeneous metal complexes on the supports is an effective strategy preferred by the polyolefin industry. In this contribution, we synthesize a series of heterogeneous nickel catalysts using the supporting strategy of ionic liquid-modified supports. These supported catalysts have polymerization activities up to 1.68 Â 10 7 g mol À1 h À1 , polymer molecular weights up to 224.1 Â 10 4 g mol À1 , and significantly, higher melting points compared to homogeneous systems. The polyolefin materials prepared by this supporting strategy possess a wide range of tunable mechanical properties, from thermoplastics to elastomers. These heterogeneous nickel catalysts can catalyze the copolymerization of ethylene and methyl 10-undecenoate.

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Ethylene homo and copolymerization by phosphorus‐benzoquinone based homogeneous and heterogeneous nickel catalysts

Cited by 7 publications

References 69 publications

Noncovalent Interactions in Late Transition Metal-Catalyzed Polymerization of Olefins

Noncovalent Interactions in Late Transition Metal-Catalyzed Polymerization of Olefins

Heterogenization Strategies for Nickel Catalyzed Synthesis of Polyolefins and Composites

Heterogenization of nickel catalysts with ionic liquid‐modified supports for ethylene polymerization and copolymerization

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