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Vanadium(V) tetra-phenolate complexes: synthesis, structural studies and ethylene homo-(co-) polymerization capability

机译：钒（V）四酚络合物：合成，结构研究和乙烯同源 - （共）聚合能力

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摘要

Reaction of a,a,a0,a0-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-p-xylene (p-L1H4) with two equivalents of [VO(OR)3] (R nPr, tBu) in refluxing toluene afforded, after work-up, the complexes {[VO(OnPr)(THF)]2(m-p-L1)}$2(THF) (1$2(THF)) or {[VO(OtBu)]2(m-p-L1)}$2MeCN (2$2MeCN), respectively in moderate to good yield. A similar reaction using the meta pro-ligand, namely a,a,a0,a0-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-mxylene (m-L2H4) afforded the complex {[VO(OnPr)(THF)]2(m-p-L2)} (3). Use of [V(Np-R1C6H4)(tBuO)3] (R1 Me, CF3) with p-L1H4 led to the isolation of the oxo-imido complexes {[VO(tBuO)][V(Np-R1C6H4) (tBuO)](m-p-L1)} (R1 Me, 4$CH2Cl2; CF3, 5$CH2Cl2), whereas use of [V(Np-R1C6H4)Cl3] (R1 Me, CF3) in combination with Et3N/p-L1H4 or p-L1Na4 afforded the diimido complexes {[V(Np-MeC6H4)(THF)Cl]2(m-p-L1)}$4toluene (6$4toluene) or {[V(Np-CF3C6H4)(THF)Cl]2(m-p-L1)} (7). For comparative studies, the complex [(VO)(m-OnPr) L3]2 (8) has also been prepared via the interaction of [VO(nPrO)3] and 2-(a-(2-hydroxy-3,5-di-tertbutylphenyl) benzyl)-4,6-di-tert-butylphenol (L3H2). The crystal structures of 1$2THF, 2$2MeCN, 3, 4$CH2Cl2, 5$CH2Cl2, 6$4toluene$THF, 7 and 8 have been determined. Complexes 1-3 and 5-8 have been screened as pre-catalysts for the polymerization of ethylene in the presence of a variety of co-catalysts (with and without a re-activator), including DMAC (dimethylaluminium chloride), DEAC (diethylaluminium chloride), EADC (ethylaluminium dichloride) and EASC (ethylaluminium sesquichloride) at various temperatures and for the co-polymerization of ethylene with propylene; results are compared versus the benchmark catalyst [VO(OEt) Cl2]. In some cases, activities as high as 243 400 g mmol~1 V~1 h~1 (30.43 kgPE mmol V~1 h~1 bar~1) were achievable, whilst it also proved possible to obtain higher molecular weight polymers (in comparable yields to the use of [VO(OEt)Cl2]). In all cases with dimethylaluminium chloride (DMAC)/ethyltrichloroacetate (ETA) activation, the activities achieved surpassed those of the benchmark catalyst. In the case of the copolymerization of ethylene with propylene, complexes 1-3 and 5-8 showed comparable or higher molecular weight than [VO(OEt)Cl2] with comparable catalytic activities or higher in the case of the imido complexes 6 and 7.
机译：A，A，A，A，A0，A0-四（3,5-二叔 - 丁基-2-羟基苯基）-P-二甲苯（P-L1H4）的反应，具有两当量的[VO（或）3]（R NPR， TBU）在回流甲苯中，完成后，复合物{[VO（ONPR）（THF）] 2（MP-L1）} 2美元（THF）（1美元））或{[VO（OTBU）] 2（MP-L1）} 2mcecn（2美元2mmcn），分别以中等到良好的收益率。使用Meta pro-an-pibland，即a，a，a0，a0-四（3,5-二叔 - 丁基-2-羟基苯基）-mxylene（m-l2h4）的类似反应得到了复合物{[vo（onpr ）（THF）] 2（MP-L2）}（3）。使用[V（NP-R1C6H4）（TBUO）3]（R1 ME）3]（R1 ME，CF3）导致氧代-Imido复合物的分离{[VO（TBUO）] [V（NP-R1C6H4）（TBUO ）]（MP-L1）}（R1 ME，4 $ CH2CL2; CF3,5 $ CH2CL2），而使用[V（NP-R1C6H4）CL3]（R1 ME，CF3）与ET3N / P-L1H4或P-L1NA4提供二咪唑络合物{[V（NP-MEC6H4）（THF）Cl] 2（MP-L1）} $ 4Toluene（6 $ 4Toluene）或{[V（NP-CF3C6H4）（THF）CL] 2（ MP-L1）}（7）。对于比较研究，还通过[VO（NPRO）3]和2-（A-（2-羟基-3,5）的相互作用来制备复合体[（VO）（M-ONPR）L3] 2（8）。（a-（2-羟基-3,5 -di-叔丁基苯基）苄基）-4,6-二叔丁基苯酚（L3H2）。晶体结构为1美元，2美元2mMec，3,4 $ CH2CL2,5 $ CH2CL2,6 $ 4toluene $ THF，7和8。已经筛选到乙烯在各种助催化剂（具有和无活化剂）存在下筛选乙烯的催化剂，包括DMAC（二甲基铝），DEAC（二乙基丙烯氯化物），Eadc（二氯乙烯）和EASC（乙基丙氨酸）在各种温度下和具有丙烯的乙烯的共聚聚合;结果与基准催化剂[VO（OET）CL2]比较。在某些情况下，可实现高达243 400g摩尔〜1〜1 h〜1（30.43kgpe mmol V〜1 h〜1 bar〜1）的活动，同时证明可以获得更高的分子量聚合物（in使用[VO（OET）Cl2]的可比产率。在所有含二甲基铝（DMAC）/乙基三氟乙酸酯（ETA）活化的情况下，所达到的活性超过了基准催化剂的活性。在用丙烯的乙烯共聚的情况下，复合物1-3和5-8显示比在Imido复合物6和7的情况下具有比较催化活性或更高的相当或更高的分子量或更高的分子量或更高的分子量。

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  • 来源
    《RSC Advances》 |2015年第109期|共14页
  • 作者

    Carl Redshaw; Mark J. Walton; Mark R. J. Elsegood;

  • 作者单位

    Department of Chemistry University of Hull Hull HU6 7RX UK.;

    Energy Materials Laboratory School of Chemistry University of East Anglia Norwich NR4 7TJ UK;

    Chemistry Department Loughborough University Loughborough Leicestershire LE11 3TU UK;

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  • 正文语种 eng
  • 中图分类 化学;
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