基于Salen基有机多孔聚合物材料的合成及性能研究

发布时间：2018-03-16 22:49

本文选题：有机多孔聚合物　切入点：共轭微孔聚合物　出处：《吉林大学》2017年硕士论文　论文类型：学位论文

【摘要】：信息、材料和能源是人类社会发展的三大支柱,而材料则是最基础的。多孔材料因具有吸附性能优异、比表面积高、材料质量轻等特性,从众多的材料之中脱颖而出,在近几年成了科学界的热点领域。特别是有机多孔聚合物可通过简单的结构单元用共价键连接形成高分子多孔材料而逐渐得到研究者的重视,越来越多的多孔材料的合成及运用在近些年发展迅速。有机多孔聚合物(Porous organic polymers,POPs)在各种气体的存储与释放、有机光电器件、非均相催化、荧光传感和危险品包装等众多方面展现出重要的应用前景。在最近几十年报道中,在催化领域所使用的各种金属Salen配合物具有良好的催化性能。通过催化环氧化物与胺类化合物发生开环反应,从而简单、方便及高效的得到β-氨基醇,是目前工业上采用的最主要方法;所得到的产物可直接应用于医药、二次化学品、香料及手性辅助剂等产品的生产及制备。从以前的报道中不难发现,催化开环反应最重要的就是金属离子,并且一般选用贵金属或毒性金属,从而限制了其广泛应用。在众多金属基催化剂中,Fe(III)具有丰度高、无毒、廉价及无污染等特性,可将其络合到Salen结构中。我们合成了一种基于Salen修饰的咔唑单体,采用无水三氯化铁做氧化偶联试剂,在氧化聚合过程中,无水三氯化铁是过量的,由此可直接得到负载有Fe(III)的有机多孔聚合物材料,此材料具有较大的比表面积、良好的热稳定性及负载率,因此具有非常好的气体吸附能力及催化性能。将其应用于催化开环反应,所得的β-氨基醇具有较高的产率,且当催化剂循环多次时,产率没有明显下降。本论文的后一部分,利用Salen结构可络合金属的特性,我们合成了一种可用于荧光检测的有机多孔聚合物材料,将Salen双醛与1,3,5-三-(4-氨基苯基)三嗪通过常规的溶剂热法合成有机多孔材料,合成的材料具有独立的发光单元和螯合单元,具有非常好的荧光及金属螯合性能。此材料对于金属铜离子具有非常好的检测效果,当在溶液中有铜离子存在时,发生非常强的荧光淬灭效应,在其他金属阳离子或阴离子存在的情况下,不会干扰对Cu2+的选择性。而且当加入强络合剂的时候,荧光强度能恢复,可用于第二次检测,具有非常好的重复利用性。此种多孔材料应用于金属离子检测领域,扩大了多孔材料的应用范围,具有非常重要的意义。
[Abstract]:Information, materials and energy are the three pillars of the development of human society, and materials are the most basic. Porous materials stand out from many materials because of their excellent adsorption properties, high specific surface area, light material mass, etc. In recent years, organic porous polymers have become a hot topic in the scientific community. In particular, organic porous polymers can be formed by covalent bonding of simple structural units to form polymer porous materials, which have gradually attracted the attention of researchers. More and more porous materials have been synthesized and applied in recent years. The organic porous polymer Porous organic polymers are stored and released in various gases, organic optoelectronic devices, heterogeneous catalysis. Fluorescent sensing and packaging of dangerous goods show important application prospects. In recent decades, All kinds of metal Salen complexes used in the field of catalysis have good catalytic performance. Through the ring-opening reaction between epoxides and amine compounds, 尾 -aminols can be obtained easily, conveniently and efficiently. The products obtained can be directly used in the production and preparation of medicines, secondary chemicals, spices and chiral auxiliaries. The metal ions are most important in the catalytic ring-opening reaction, and the noble metal or toxic metal is generally used, which limits its wide application. It has the characteristics of high abundance, non-toxic, cheap and pollution-free in many metal-based catalysts. A carbazole monomer modified by Salen was synthesized. Anhydrous ferric chloride was used as oxidative coupling reagent. In the process of oxidative polymerization, anhydrous ferric chloride was excessive. Therefore, the organic porous polymer materials supported on FeHII I) can be directly obtained. The material has a large specific surface area, good thermal stability and loading rate. Therefore, the 尾 -aminoalcohol has a high yield when it is applied to the catalytic ring-opening reaction, and the yield does not decrease obviously when the catalyst circulates for many times. An organic porous polymer material, which can be used for fluorescence detection, was synthesized by using the properties of complex metal with Salen structure. The organic porous materials were synthesized by conventional solvothermal method from Salen dialdehydes and 1 ~ (3) C ~ (3 +) -trichloro-4-aminophenyl) triazine. The synthesized materials have independent luminescence units and chelating units, and have excellent fluorescence and metal chelating properties. A very strong fluorescence quenching effect occurs in the presence of other metal cations or anions that does not interfere with the selectivity to Cu2. Moreover, when a strong complexing agent is added, the fluorescence intensity recovers and can be used for the second detection. This kind of porous material is applied in the field of metal ion detection, which expands the application scope of porous material and has very important significance.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.3

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