Liu Ming, Sun Min, Ma Yanping, Wang Yizhou, Li Mingfeng, Sun Wen-Hua
State Key Laboratory of Petroleum Molecular & Process Engineering, SINOPEC Research Institute of Petroleum Processing Co., Ltd., Beijing 100083, China.
Key Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, China.
Molecules. 2025 Jun 23;30(13):2706. doi: 10.3390/molecules30132706.
A series of -trifluoromethoxy-substituted and fluorobenzhydryl-functionalized 1,2-bis(imine)acenaphthene ligands: 1-[2,6-{(4-F-CH)CH}-4-FCOCHN]-2-(ArN)CCH (Ar = 2,6-MeCH, 2,6-EtCH, 2,6-iPrCH, 2,4,6-MeCH, 2,6-Et-4-MeCH), were synthesized and used to generate their corresponding nickel(II) bromide complexes (-). Elemental analysis, F NMR, and FT-IR spectroscopy were employed to characterize these five nickel complexes. Single-crystal X-ray diffraction of and confirmed distorted tetrahedral geometries. Upon activation with either EtAlCl (ethylaluminum dichloride) or EASC (ethyl aluminum sesquichloride), these complexes showed exceptional high activities (up to 22.0 × 10 g PE mol (Ni) h) and remarkable thermal stability (4.82 × 10 g PE mol(Ni) h 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 ( 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.
一系列含三氟甲氧基取代和氟代二苯甲基官能化的1,2 - 双（亚胺）苊配体：1 - [2,6 - {（4 - F - C6H4）CH} - 4 - F - C6H4 - CHN] - 2 - （ArN）C6H4 （Ar = 2,6 - Me2C6H3，2,6 - Et2C6H3，2,6 - iPr2C6H3，2,4,6 - Me3C6H2，2,6 - Et - 4 - MeC6H2）被合成，并用于生成它们相应的溴化镍（II）配合物（ - ）。采用元素分析、氟核磁共振和傅里叶变换红外光谱对这五种镍配合物进行表征。对[具体配合物1]和[具体配合物2]的单晶X射线衍射证实了扭曲的四面体几何结构。在用二氯乙基铝（EtAlCl）或倍半氯乙基铝（EASC）活化后，这些配合物对乙烯聚合表现出极高的活性（高达22.0×106 g PE mol-1（Ni）-1 h-1）和显著的热稳定性（80℃下为4.82×106 g PE mol-1（Ni）-1 h-1）。所得聚乙烯高度支化，支化的类型和程度可通过温度、溶剂和助催化剂的选择进行调节。此外，这些聚合物表现出优异的拉伸强度（高达20.7 MPa）和弹性回复率（高达58%），具有热塑性弹性体（TPE）的特征。这些结果突出了三氟甲氧基和氟代二苯甲基基团在提高催化性能和聚合物性能方面的双重作用。
