Dual roles of trifluoroborate in nickel-catalyzed ethylene polymerization: Electronic perturbation and anchoring for heterogenization

Hong, Changwen; Wang, Zihao; Jiang, Hui; Si, Guifu; Mao-Ping, Song; Chen, Changle

doi:10.1016/j.cclet.2022.107918

Cited by 4 publications

(5 citation statements)

References 37 publications

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“…For example, potassium trifluoroborate substituent was introduced into the α-diimine nickel catalyst (Figure 2, Ni5@SiO 2 ). 51 The ionic properties of the potassium trifluoroborate group enabled strong catalyst interaction with the solid supports, and the catalyst loading was up to ca. 1 μmol nickel per 10 mg of SiO 2 .…”

Section: Ionic Anchoring Strategymentioning

confidence: 99%

“…(H) Radar plots for comparison of polymerization performances of heterogeneous trifluoroborate potassium anchored α-diimine catalyst Ni5@SiO 2 , homogeneous catalyst Ni5 and classical α-diimine catalyst Ni-NN. Data source: ref . (I) Image of polyethylene samples prepared from catalyst Ni4@SiO 2 .…”

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

confidence: 99%

“…To demonstrate the general applicability of the ionic anchoring strategy, other ionic groups were explored. For example, potassium trifluoroborate substituent was introduced into the α-diimine nickel catalyst (Figure , Ni5@SiO 2 ) . The ionic properties of the potassium trifluoroborate group enabled strong catalyst interaction with the solid supports, and the catalyst loading was up to ca.…”

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%

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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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Section: Ionic Anchoring Strategymentioning

confidence: 99%

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

confidence: 99%

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

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Heterogenization Strategies for Nickel Catalyzed Synthesis of Polyolefins and Composites

2023

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“…However, industrial olefin polymerization processes generally use heterogeneous catalytic systems because of the need to achieve continuous polymerization processes by controlling polymer morphology and avoiding reactor fouling. [36][37][38][39][40][41][42][43][44][45] Heterogenization of nickel catalysts can be achieved by bonding them with solid supports. Interestingly, some recent reports show that heterogenization effect may significantly improve the catalytic performances of various nickel-based olefin polymerization catalysts (Chart 1a,H-K).…”

Section: Introductionmentioning

confidence: 99%

Positional heterogenization effect in salicylaldimine nickel catalyzed ethylene polymerization

Yu,

Gong,

Liu

et al. 2024

J of Applied Polymer Sci

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Heterogenization of nickel‐based olefin polymerization catalysts has received increasing attention in recent years. In this contribution, positional heterogenization effect in salicylaldimine nickel catalyzed ethylene polymerization is studied. The salicylaldimine nickel pre‐catalysts bearing anchor groups are synthesized, characterized, and investigated in heterogeneous catalytic ethylene polymerization. The anchoring groups are installed at different positions, including the 4‐position of the salicylaldehyde moiety and the 4‐position of the aniline moiety. It is shown that the positions of the anchoring groups have significant effects on heterogeneous ethylene polymerization catalyzed by SiO2‐supported salicylaldimine nickel catalysts. This provides a strategy worth considering for the design of high‐performance heterogeneous catalysts in the future.

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A “Catalyst+Support” Strategy for Salicylaldimine Nickel Catalyzed Ethylene Polymerization and Copolymerization with Polar Monomers

Wang

Yang

et al. 2023

Chem. Res. Chin. Univ.

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Dual roles of trifluoroborate in nickel-catalyzed ethylene polymerization: Electronic perturbation and anchoring for heterogenization

Cited by 4 publications

References 37 publications

Heterogenization Strategies for Nickel Catalyzed Synthesis of Polyolefins and Composites

Heterogenization Strategies for Nickel Catalyzed Synthesis of Polyolefins and Composites

Positional heterogenization effect in salicylaldimine nickel catalyzed ethylene polymerization

A “Catalyst+Support” Strategy for Salicylaldimine Nickel Catalyzed Ethylene Polymerization and Copolymerization with Polar Monomers

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