Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene Elastomers
A series of <i>para</i>-trifluoromethoxy-substituted and fluorobenzhydryl-functionalized 1,2-bis(imine)acenaphthene ligands: 1-[2,6-{(4-F-C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>CH}<sub>2</sub>-4-F<sub>3</sub>COC<sub>6</...
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2025-06-01
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| author | Ming Liu Min Sun Yanping Ma Yizhou Wang Mingfeng Li Wen-Hua Sun |
| author_facet | Ming Liu Min Sun Yanping Ma Yizhou Wang Mingfeng Li Wen-Hua Sun |
| author_sort | Ming Liu |
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| description | A series of <i>para</i>-trifluoromethoxy-substituted and fluorobenzhydryl-functionalized 1,2-bis(imine)acenaphthene ligands: 1-[2,6-{(4-F-C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>CH}<sub>2</sub>-4-F<sub>3</sub>COC<sub>6</sub>H<sub>2</sub>N]-2-(ArN)C<sub>2</sub>C<sub>10</sub>H<sub>6</sub> (Ar = 2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <b>L1</b>, 2,6-Et<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <b>L2</b>, 2,6-iPr<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <b>L3</b>, 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub> <b>L4</b>, 2,6-Et<sub>2</sub>-4-MeC<sub>6</sub>H<sub>2</sub> <b>L5</b>), were synthesized and used to generate their corresponding nickel(II) bromide complexes (<b>Ni1</b>–<b>Ni5</b>). Elemental analysis, <sup>19</sup>F NMR, and FT-IR spectroscopy were employed to characterize these five nickel complexes. Single-crystal X-ray diffraction of <b>Ni2</b> and <b>Ni4</b> confirmed distorted tetrahedral geometries. Upon activation with either EtAlCl<sub>2</sub> (ethylaluminum dichloride) or EASC (ethyl aluminum sesquichloride), these complexes showed exceptional high activities (up to 22.0 × 10<sup>6</sup> g PE mol<sup>−1</sup> (Ni) h<sup>−1</sup>) and remarkable thermal stability (4.82 × 10<sup>6</sup> g PE mol<sup>−1</sup>(Ni) h<sup>−1</sup> at 80 °C) towards ethylene polymerization. The resulting polyethylenes are highly branched, with the type and extent of branches tunable by temperature, solvent, and co-catalyst choice. Moreover, these polymers demonstrated excellent tensile strength (<i>σ<sub>b</sub></i> up to 20.7 MPa) and elastic recovery (up to 58%), characteristic of thermoplastic elastomers (TPEs). These results highlight the dual role of trifluoromethoxy and fluorobenzhydryl groups in enhancing catalytic performance and polymer properties. |
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| spelling | doaj-art-d5e7ab7d5d7447e4a3cc5120084d759a2025-08-20T03:28:25ZengMDPI AGMolecules1420-30492025-06-013013270610.3390/molecules30132706Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene ElastomersMing Liu0Min Sun1Yanping Ma2Yizhou Wang3Mingfeng Li4Wen-Hua Sun5State Key Laboratory of Petroleum Molecular & Process Engineering, SINOPEC Research Institute of Petroleum Processing Co., Ltd., Beijing 100083, ChinaState Key Laboratory of Petroleum Molecular & Process Engineering, SINOPEC Research Institute of Petroleum Processing Co., Ltd., Beijing 100083, ChinaKey Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, ChinaKey Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, ChinaState Key Laboratory of Petroleum Molecular & Process Engineering, SINOPEC Research Institute of Petroleum Processing Co., Ltd., Beijing 100083, ChinaKey Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, ChinaA series of <i>para</i>-trifluoromethoxy-substituted and fluorobenzhydryl-functionalized 1,2-bis(imine)acenaphthene ligands: 1-[2,6-{(4-F-C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>CH}<sub>2</sub>-4-F<sub>3</sub>COC<sub>6</sub>H<sub>2</sub>N]-2-(ArN)C<sub>2</sub>C<sub>10</sub>H<sub>6</sub> (Ar = 2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <b>L1</b>, 2,6-Et<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <b>L2</b>, 2,6-iPr<sub>2</sub>C<sub>6</sub>H<sub>3</sub> <b>L3</b>, 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub> <b>L4</b>, 2,6-Et<sub>2</sub>-4-MeC<sub>6</sub>H<sub>2</sub> <b>L5</b>), were synthesized and used to generate their corresponding nickel(II) bromide complexes (<b>Ni1</b>–<b>Ni5</b>). Elemental analysis, <sup>19</sup>F NMR, and FT-IR spectroscopy were employed to characterize these five nickel complexes. Single-crystal X-ray diffraction of <b>Ni2</b> and <b>Ni4</b> confirmed distorted tetrahedral geometries. Upon activation with either EtAlCl<sub>2</sub> (ethylaluminum dichloride) or EASC (ethyl aluminum sesquichloride), these complexes showed exceptional high activities (up to 22.0 × 10<sup>6</sup> g PE mol<sup>−1</sup> (Ni) h<sup>−1</sup>) and remarkable thermal stability (4.82 × 10<sup>6</sup> g PE mol<sup>−1</sup>(Ni) h<sup>−1</sup> at 80 °C) towards ethylene polymerization. The resulting polyethylenes are highly branched, with the type and extent of branches tunable by temperature, solvent, and co-catalyst choice. Moreover, these polymers demonstrated excellent tensile strength (<i>σ<sub>b</sub></i> up to 20.7 MPa) and elastic recovery (up to 58%), characteristic of thermoplastic elastomers (TPEs). These results highlight the dual role of trifluoromethoxy and fluorobenzhydryl groups in enhancing catalytic performance and polymer properties.https://www.mdpi.com/1420-3049/30/13/2706nickel catalystsdual steric-electronic tuninghighly branched polyethyleneshigh-temperature polymerizationthermoplastic elastomers (TPEs) |
| spellingShingle | Ming Liu Min Sun Yanping Ma Yizhou Wang Mingfeng Li Wen-Hua Sun Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene Elastomers Molecules nickel catalysts dual steric-electronic tuning highly branched polyethylenes high-temperature polymerization thermoplastic elastomers (TPEs) |
| title | Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene Elastomers |
| title_full | Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene Elastomers |
| title_fullStr | Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene Elastomers |
| title_full_unstemmed | Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene Elastomers |
| title_short | Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene Elastomers |
| title_sort | trifluoromethoxy and fluorobenzhydryl tuned nickel catalysts for polyethylene elastomers |
| topic | nickel catalysts dual steric-electronic tuning highly branched polyethylenes high-temperature polymerization thermoplastic elastomers (TPEs) |
| url | https://www.mdpi.com/1420-3049/30/13/2706 |
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