【作者】 林奇；

【导师】 张有明； 魏太保；

【作者基本信息】 西北师范大学 ， 高分子化学与物理， 2009， 博士

【摘要】 本论文在研究总结近年来国内外乙烯聚合/齐聚催化剂的研究进展的基础上,设计合成了一系列新型的基于不对称二齿配体3-芳基亚氨基甲基-5-氯-2羟基苯甲醛的三苯基膦萘中性镍(II)配合物(2a~2f)。用X-射线单晶衍射确定了配合物的结构。研究了这些配合物的乙烯齐聚活性。在甲基铝氧烷(MAO)做助催化剂的条件下这些配合物都有较好的乙烯齐聚活性。通过考查铝镍比、反应时间、反应温度和反应压强等实验条件,选出了最佳反应条件,在此条件时的最高催化活性为4.6×106 g mol-1h-1。另外,本论文在总结阴离子识别的最新进展的基础上,还设计合成了一系列基于酚羟基和酰腙基、腙基、酰胺基硫脲基和缩氨基硫脲基的钳形或单臂型阴离子受体。结果表明,受体F3溶于N,N’-二甲基甲酰胺(DMF)形成质量百分比浓度为0.2~1.5%的溶液在室温下可形成有机凝胶。在该凝胶中加入F-、AcO-和H2PO4-等阴离子时,凝胶由凝胶态转变成液态,同时颜色由黄色变为紫红色。因此,该凝胶能用于裸眼检测氟离子,醋酸根离子和磷酸二氢根离子。该凝胶稳定性好,易于储存和携带,方便使用,具有很好的应用价值。受体L1和L2在DMSO/H2O(9:1 v/v)的体系中对氯离子有选择性识别能力。L1, L2和L4在DMSO/H2O (7.5:2.5 v/v)的含水介质中对醋酸根有很好的选择性比色识别能力。制备了基于受体L1和L2的阴离子检测试纸,此类试纸能比色检测DMSO中的氟离子和醋酸根离子,还能选择性比色检测DMSO/H2O (7.5:2.5 v/v)的含水介质中的醋酸根离子。该试纸可作为一种方便、快捷、有效的氟离子和醋酸根的检测工具。受体M1和M3可在乙腈溶液中高选择性的比色识别碘离子.另外,在DMSO溶液中,受体M1和M3可选择性比色识别氯离子,在DMSO/H2O(7:3)的含水介质中, M1和M3能选择性裸眼识别醋酸根离子.此类阴离子受体具有合成方法简便,产率高,识别效果好等优点.以5-硝基取代苯基呋喃为信号报告基团,以缩氨基硫脲基团为识别位点的受体3a~3f可选择性比色识别氟离子、醋酸根和磷酸二氢根。通过晶体结构确定了3a~3f的结构。晶体结构研究表明,在晶体中,受体分子通过氢键和π-π作用自组装成了网状或链状的超分子结构。基于缩氨基硫脲和酚羟基的钳状阴离子受体A1~A5,此类受体对阴离子不仅有比色响应,而且还具有荧光识别性能。其中部分受体对硝酸根和氟离子具有选择性很强的荧光识别能力。总之,本论文中开发出的阴离子受体可选择性的识别氟离子、氯离子、碘离子、醋酸根、磷酸二氢根和硝酸根等阴离子,这些受体合成方法简单,易于制备。开发的基于这些受体的有机凝胶和阴离子比色检测试纸制备简单,便于储存、携带和使用,而且检测效果也很好,具有很好的应用前景。更多还原

【Abstract】 A series of new neutral arylnickel(II) phosphine complexes bearing non-symmetric bidentate chelate ligands 3-aryliminomethyl-5-chloro-2-hydroxy- benzaldehyde have been synthesized, and the structure of representative complexes (2b and 2d) have been confirmed by X-ray crystallographic analysis. These neutral arylnickel(II) phosphine complexes have been investigated as catalysts for ethylene oligomerization. Using methylaluminoxane (MAO) as a cocatalyst, these complexes display high ethylene oligomerization activities. Catalytic activity of up to 4.6×106 g mol-1h-1 has been observed. The influence of Al/Ni molar ratio, reaction temperature, reaction period and pressure on catalytic activity was investigated. Moreover, a series of novel colorimetric anion sensors which bearing phenol O-H, hydrazone N-H groups, thiourea groups and thiosemicarbazones were designed and synthesized via simple processes. The receptor F3 could form supramolecular organic gel in DMF or DMSO solution. This organic gel possesses solution-Gel transition response upon the addition of anion. This organic gel could efficient detect F-, AcO- and H2PO4- conveniently. The receptors L1 and L2 could selectively“naked eyes”recognize Cl- in DMSO/H2O (9:1, v/v) solutions and AcO- in DMSO/H2O (7.5:2.5, v/v) solutions. A test paper based on L1 was developed which could detect F- and AcO- conveniently. Receptors M1 and M3 showed colorimetric single selectivity for I–. Moreover, M1 and M3 could selectively colorimetric detect Cl-, F- and AcO- in DMSO or DMSO/H2O solutions. Receptors 3a~3f employ 5-nitrophenylfural as signal group and thiosemicarbazone group as binding sites. Some of them could selectively colorimetric recognizes F-, AcO- and H2PO4- in DMSO solutions. The structures of these receptors were confirmed by single crystal X-ray diffraction. In the crystal, the molecular of the receptor self-assembled as link like or network supramolecular by hydrodgen bonds andπ-πstack action. The pincer type receptors A1~A5 which employ thiosemicarbazone group and phenol O-H group as binding sites, these receptors possess selective fluorescent recognition ability for F- and NO3-. In summar, in a series of anion receptors were synthesized, these receptor could selectively recognize F-, Cl-, I-, AcO-, H2PO4- and NO3-. The organic gel and anion test paper could efficiently and conveniently sense anions.更多还原