Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations
Among various catalyst design strategies used in the α-diimine nickel(II) and palladium(II) catalyst systems, the unsymmetrical strategy is an effective and widely utilized method. In this contribution, unsymmetrical nickel and palladium α-diimine catalysts (<b>Ipty/<i><sup>i</s...
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MDPI AG
2022-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/24/8942 |
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| author | Xin Ma Yixin Zhang Zhongbao Jian |
| author_facet | Xin Ma Yixin Zhang Zhongbao Jian |
| author_sort | Xin Ma |
| collection | DOAJ |
| description | Among various catalyst design strategies used in the α-diimine nickel(II) and palladium(II) catalyst systems, the unsymmetrical strategy is an effective and widely utilized method. In this contribution, unsymmetrical nickel and palladium α-diimine catalysts (<b>Ipty/<i><sup>i</sup></i>Pr-Ni</b> and <b>Ipty/<i><sup>i</sup></i>Pr-Pd</b>) derived from the dibenzobarrelene backbone were constructed via the combination of pentiptycenyl and diisopropylphenyl substituents, and investigated toward ethylene (co)polymerization. Both of these catalysts were capable of polymerizing ethylene in a broad temperature range of 0–120 °C, in which <b>Ipty/<i><sup>i</sup></i>Pr-Ni</b> could maintain activity in the level of 10<sup>6</sup> g mol<sup>−1</sup> h<sup>−1</sup> even at 120 °C. The branching densities of polyethylenes generated by both nickel and palladium catalysts could be modulated by the reaction temperature. Compared with symmetrical <b>Ipty-Ni</b> and <b><i><sup>i</sup></i>Pr-Ni</b>, <b>Ipty/<i><sup>i</sup></i>Pr-Ni</b> exhibited the highest activity, the highest polymer molecular weight, and the lowest branching density. In addition, <b>Ipty/<i><sup>i</sup></i>Pr-Pd</b> could produce copolymers of ethylene and methyl acrylate, with the polar monomer incorporating both on the main chain and the terminal of branches. Remarkably, the ratio of the in-chain and end-chain polar monomer incorporations could be modulated by varying the temperature. |
| first_indexed | 2024-03-09T16:01:54Z |
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| language | English |
| last_indexed | 2024-03-09T16:01:54Z |
| publishDate | 2022-12-01 |
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| series | Molecules |
| spelling | doaj.art-0c2c0e827b1c45d0b38fae0930b378f32023-11-24T17:00:10ZengMDPI AGMolecules1420-30492022-12-012724894210.3390/molecules27248942Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)PolymerizationsXin Ma0Yixin Zhang1Zhongbao Jian2State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5625, Changchun 130022, ChinaState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5625, Changchun 130022, ChinaState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5625, Changchun 130022, ChinaAmong various catalyst design strategies used in the α-diimine nickel(II) and palladium(II) catalyst systems, the unsymmetrical strategy is an effective and widely utilized method. In this contribution, unsymmetrical nickel and palladium α-diimine catalysts (<b>Ipty/<i><sup>i</sup></i>Pr-Ni</b> and <b>Ipty/<i><sup>i</sup></i>Pr-Pd</b>) derived from the dibenzobarrelene backbone were constructed via the combination of pentiptycenyl and diisopropylphenyl substituents, and investigated toward ethylene (co)polymerization. Both of these catalysts were capable of polymerizing ethylene in a broad temperature range of 0–120 °C, in which <b>Ipty/<i><sup>i</sup></i>Pr-Ni</b> could maintain activity in the level of 10<sup>6</sup> g mol<sup>−1</sup> h<sup>−1</sup> even at 120 °C. The branching densities of polyethylenes generated by both nickel and palladium catalysts could be modulated by the reaction temperature. Compared with symmetrical <b>Ipty-Ni</b> and <b><i><sup>i</sup></i>Pr-Ni</b>, <b>Ipty/<i><sup>i</sup></i>Pr-Ni</b> exhibited the highest activity, the highest polymer molecular weight, and the lowest branching density. In addition, <b>Ipty/<i><sup>i</sup></i>Pr-Pd</b> could produce copolymers of ethylene and methyl acrylate, with the polar monomer incorporating both on the main chain and the terminal of branches. Remarkably, the ratio of the in-chain and end-chain polar monomer incorporations could be modulated by varying the temperature.https://www.mdpi.com/1420-3049/27/24/8942nickel and palladium catalystsunsymmetricalethylene polymerizationpolar monomerpolyolefin |
| spellingShingle | Xin Ma Yixin Zhang Zhongbao Jian Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations Molecules nickel and palladium catalysts unsymmetrical ethylene polymerization polar monomer polyolefin |
| title | Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations |
| title_full | Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations |
| title_fullStr | Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations |
| title_full_unstemmed | Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations |
| title_short | Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations |
| title_sort | unsymmetrical strategy on α diimine nickel and palladium mediated ethylene co polymerizations |
| topic | nickel and palladium catalysts unsymmetrical ethylene polymerization polar monomer polyolefin |
| url | https://www.mdpi.com/1420-3049/27/24/8942 |
| work_keys_str_mv | AT xinma unsymmetricalstrategyonadiiminenickelandpalladiummediatedethylenecopolymerizations AT yixinzhang unsymmetricalstrategyonadiiminenickelandpalladiummediatedethylenecopolymerizations AT zhongbaojian unsymmetricalstrategyonadiiminenickelandpalladiummediatedethylenecopolymerizations |