Novel Vanadium(III) Complexes with Tridentate Phenoxy-Phosphine [O,P(=O),O] Ligands: Synthesis, Characterization, and Catalytic Behavior of Ethylene Polymerization and Copolymerization with 10-Undecen-1-ol
Novel Vanadium(III) Complexes with Tridentate Phenoxy-Phosphine [O,P(=O),O] Ligands: Synthesis, Characterization, and Catalytic Behavior of Ethylene Polymerization and Copolymerization with 10-Undecen-1-ol
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新型钒(III)与三齿苯氧基膦[O,P(=O),O]配体的配合物：合成、表征以及乙烯聚合和与10-十一碳烯-1-醇共聚的催化行为
DOI：
10.1002/pola.26441
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
Li Yue-Sheng
中科院分区：
文献类型：
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作者：
Zhang Sen-Wang;Zhang Gui-Bao;Lu Ling-Pan;Li Yue-Sheng
合成了一系列新型的含三齿苯氧膦[O，P，O]配体和氧化膦-桥接双酚[O，P - O，O]配体的钒（III）配合物，它们具有不同的空间和电子性质。用傅里叶变换红外光谱（FTIR）、质谱和元素分析对这些配合物进行了表征。单晶X射线衍射表明，配合物可以围绕钒中心形成八面体结构。在乙二alcl作为助催化剂存在下，这些配合物的催化活性高达22.8 kg PE/mmolV.h。棒材用于乙烯聚合，并制成高分子量聚合物。在[O，P，O]配体的磷原子上引入额外的氧原子会导致空间/电子效应方面的显著变化，从而对聚合性能产生影响。3cand4c/Et2AlCl催化体系耐高温（70°C），并产生单峰聚乙烯，表明这些催化剂的单位点行为。通过等量的烷基铝预处理，功能化α -烯烃- 10 -十一烯- 1 -醇可以有效地结合到聚乙烯链中。在温和条件下，10 -十一烯- 1 -醇掺入率可轻松达到14.6 mol %。其他影响聚合行为的反应参数，如反应温度、Al/V（摩尔比）和共聚单体浓度，也进行了详细的研究。©2012 Wiley期刊公司高分子材料学报，2013
A series of novel vanadium(III) complexes bearing tridentate phenoxy‐phosphine [O,P,O] ligands and phosphine oxide‐bridged bisphenolato [O,PO,O] ligands, which differ in the steric and electronic properties, have been synthesized and characterized. These complexes were characterized by Fourier transform infrared spectroscopy (FTIR) and mass spectra as well as elemental analysis. Single‐crystal X‐ray diffraction revealed that complexes3cand4eadopt an octahedral geometry around the vanadium center. In the presence of Et2AlCl as a cocatalyst, these complexes displayed high catalytic activities up to 22.8 kg PE/mmolV.h.bar for ethylene polymerization, and produced high‐molecular‐weight polymers. Introducing additional oxygen atom on phosphorus atom of [O,P,O] ligands has resulted in significant changes on the aspect of steric/electronic effect, which has an impact on polymerization performance.3cand4c/Et2AlCl catalytic systems were tolerant to elevated temperature (70 °C) and yielded unimodal polyethylenes, indicating the single‐site behavior of these catalysts. By pretreating with equimolar amounts of alkylaluminums, functional α‐olefin 10‐undecen‐1‐ol can be efficiently incorporated into polyethylene chains. 10‐Undecen‐1‐ol incorporation can easily reach 14.6 mol % under the mild conditions. Other reaction parameters that influenced the polymerization behavior, such as reaction temperature, Al/V (molar ratio), and comonomer concentration, are also examined in detail. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013