【作者】 诸佩菊；

【导师】 毛志平；

【作者基本信息】 东华大学 ， 应用化学， 2010， 硕士

【摘要】 近年来,在新材料制备领域中,无机—有机高分子杂化材料受到了高度的重视。由于金属高分子配合物兼具了无机金属与高分子材料的特征,在电学、光学、磁性等方面表现出独特性能,使得它们在诸多领域具有广阔的应用前景和价值,对新型复合材料的开发具有十分重要的意义。所以,这方面的研究异常活跃,形成了一个高分子化学与配位化学相互渗透的前沿领域。键合型金属高分子配合物是由稳定的小分子配合物单体通过加聚或缩聚等反应形成的高分子配合物,具有清晰的结构。但是,合成这类高分子配合物时要求参与反应的小分子配合物单体有活性基团,而且要有一定的溶解度或热稳定性,所以关于键合形式合成金属高分子配合物的研究相对较少。本文合成了两种具有缩聚活性的过渡金属配合物单体,主要选择一种以Yamazaki膦酰化聚合体系与其他单体共缩聚制得键合型金属高分子聚芳酰胺,对配合物单体和聚合物的结构和性质进行了探讨,为应用于纺丝及功能膜材料提供了理论和实践基础。本文第一部分是选用了过渡金属铜和钴为中心离子,两种芳香羧酸—对氨基苯甲酸和对羟基苯甲酸作为配体,合成了三种小分子过渡金属配合物。通过元素分析、红外光谱（IR）,以及X-射线单晶衍射测定其晶体结构,并通过紫外可见光谱和热重分析探讨了配合物的紫外性能和热稳定性质。结果表明,对氨基苯甲酸与钴离子配位以后形成的是配位聚合物,无法作为金属配合物单体进行下一步聚合物反应;对氨基苯甲酸和对羟基苯甲酸与铜离子配位以后分别形成两边留有活性羧基和活性羟基的小分子过渡金属配合物单体,可进一步反应形成键合型的高分子配合物。本文第二部分是选择了对氨基苯甲酸铜配合物单体（[Cu（NH₂C₆H₄COOH）₂Cl₂]）与对苯二胺、间苯二胺单体通过缩聚反应形成含有金属铜的聚芳酰胺,但其分子量较低;通过加入第三单体对苯二甲酸共聚可以提高聚合物的分子量;用金属元素分析、红外光谱、¹H NMR对聚合物的组成和结构进行了表征;同时探讨了对氨基苯甲酸铜配合物单体-间苯二胺-对苯二甲酸共聚物的特性粘度随单体浓度、反应温度、缩合剂用量和配合物单体含量等因素的影响,确定了合理的反应条件;并做了相关的热性能、紫外吸收性能研究。结果表明,经过渡金属配合物单体共缩聚后形成的聚芳酰胺的溶解性能较相似结构的PPTA好;改用间苯二胺单体以后,溶解性进一步提高,并且能得到中等分子量的聚芳酰胺,这有利于后期成膜,可用于开发新型膜材料;配合物的引入使得聚合物紫外性能明显提高,可用作良好的紫外防护材料。更多还原

【Abstract】 In recent years, organic-inorganic composites or hybrids have attracted extensive attention in the field of material chemistry. The incorporation of metal atoms into synthetic polymer chains leads to macromolecular structures in which metals are not only incorporated via the use of traditional covalent bonds but also by potentially reversible coordination interactions. Metal-containing polymers display unique electrical, optical, magnetic propertie, generating a new and versatile class of functional materials. But there is little study focused on bonding-type metal macromolecular complex, which is known for their clear structure. Because there are some special requirements for the metal containing monomers, such as good solubility or thermal stability.In our work, transition metal coordination complex monomers with active groups for polycondenstation ware prepared, fristly. Then novel metal-containing polyamides were synthesized by co-polycondensate the coordination complex monomers with other monomers in N-methyl-2-pyrrolidone （NMP） with triphenyl phosphite and pyridine as condensing agents. The structure and characterization of complexes and co-polymers were studied.Firstly, three new transition metal coordination complexes [Co（NH₂C₆H₄COO）₂（H₂O）₃]（1）, [Cu（NH₂C₆H₄COOH）₂Cl₂]（2） and {[Cu（HOC₆H₄COO）₂（NH₃）₂H₂O]₄H₂O}（3） have been preperd by the reaction of Co（NO₃）₂·6H₂O, CuCl₂·2H₂O and two functional ligands, p-aminobenzoic acid p-hydroxybenzoic acid. The complexes have been fully characterized by elemental analysis, IR, TG, UV and single crystal X-ray diffraction. The thermal stability and UV absorbility of complex （2） was studied. Experimental results showed that the complex （1） is a kind of coordination polymer, formed by self-assembly of transition metal and organic ligand. The Cu-complex （2） containing carboxylic groups and the Cu-complex （3） containing hydroxyl groups have strong potential as a monomer for the synthesis of metal-containing polyamide.Secondly, novel metal-containing polyamides were synthesized by the polycondensation of complex （2） monomer containing carboxylic group and two aromatic diamine monomers, p-phenylene diamine and m-phenylene diamine, respectively. The introduction of p-phthalic acid unit into aromatic polyamide backbones would be expected to get a highter molecular weight. The structure and property of transition metal-containing polymers were characterized by elemental analysis, IR, ¹H NMR, TG, UV and inherent viscosity. Then influencing factors of inherent viscosity of the co-polyamides reacted with complex （2） monomer, m-phenylene diamine and p-phthalic acid were investigated in detail. The results show that the prepared polyamides have increased solubility because of the presence of complex unit. By introduction of m-phenylene diamine in these aromatic polyamides makes them soluble in several polar aprotic solvents because of strong intermolecular interactions, and the polymers were produced with high yields and moderate viscosities, which indicated that the co-polyamides could be proposally used as films, fibers or other applications. It revealed the UV absorption properties of co-polyamides have been enhanced significantly by the incorporation of Cu-complex unit into the polymer chains. Thus, the metal-containing polyamide may be used as new UV protection polymeric materials.更多还原