咪唑功能化介孔聚合物的合成及其在二氧化碳转化中的应用

发布时间：2018-04-26 16:50

  本文选题：有序介孔 + 咪唑功能化　； 参考：《华东师范大学》2017年硕士论文

【摘要】：介孔聚合物具有特殊的孔道结构和纯有机骨架而受到广泛的关注,由于有机骨架的易修饰性,可以通过化学修饰制备具有特定性能的功能化介孔聚合物。咪唑基团是一种重要的功能化基团,可以用于催化相关化学反应,所以制备咪唑功能化的介孔聚合物具有一定的现实意义。本论文围绕咪唑功能化介孔聚合物的合成及在二氧化碳环加成反应中的应用展开,立题依据及主要工作如下:前期工作中,我们以4-(1-氢-咪唑-1-)苯酚(4-IP)为咪唑源制备了咪唑功能化介孔聚合物(4-IP-MPs)。以4-IP作为咪唑源制备咪唑功能化介孔聚合物时,4-IP与甲醛进行聚合过程中只能由邻位生长,无法形成三维交联结构,所得咪唑功能化介孔聚合物骨架中稳定性较差。3-(1-氢-咪唑-1-)苯酚(3-IP)由于酚羟基与咪唑环处于相间位置,可以作为咪唑源制备三维交联型咪唑功能化介孔聚合物(3-IP-MPs)。考虑到咪唑环与苯环之间直接相连由于共轭效应苯环对咪唑环的性能影响可能较大,我们在咪唑环与苯环之间引入一个亚甲基,制备一种咪唑非共轭型功能化的介孔聚合物。在第二章中,将3-IP与苯酚、甲醛在碱性条件一锅法合成咪唑功能化前驱体,并与模板剂F127通过溶剂挥发诱导自组装法合成了3-IP-MPs。通过X射线衍射、氮气吸脱附表征分析考察了前驱体制备的预聚合时间、3-IP的含量以及咪唑环与酚羟基的位置对于聚合物结构影响,明确了咪唑功能化介孔聚合物的合成。通过红外分析、元素分析、碳固体核磁分析、光电子能谱分析以及热重分析证实了目标材料中含有咪唑基团,且在420 ℃下保持高度热稳定性。以碘化钾为助催化剂,考察了 3-IP-MPs在二氧化碳和环氧化物的环加成反应中的催化活性,系统的研究了温度、压强、反应时间以及底物普适性的影响。与4-IP-MPs比较,3-IP-MPs在二氧化碳的环加成反应中稳定性更高,循环使用三次活性没有明显损失。在第三章中,我们在咪唑环与苯环之间引入一个亚甲基,制备了3-((1-氢-咪唑-1-)甲基)苯酚化合物(3-IMP),并以此为咪唑源合成了咪唑非共轭型功能化的介孔聚合物(3-IMP-MPs),在咪唑源含量为5%时,目标材料具有高度有序的介孔结构,比表面积和孔容分别达到408m2/g和0.52cm3/g。系统表征证明3-IMP-MPs含有咪唑基团且具有高度热稳定性。将3-IMP-MPs用于催化二氧化碳环加成反应,考察了反应条件和底物对于催化性能的影响。功能化介孔聚合物循环使用五次转化率没有明显降低,说明3-IMP-MPs具有较高的循环稳定性。
[Abstract]:Mesoporous polymers have attracted much attention due to their special pore structure and pure organic framework. Due to the easy modification of organic frameworks, functional mesoporous polymers with specific properties can be prepared by chemical modification. Imidazole group is an important functional group, which can be used to catalyze related chemical reactions, so the preparation of imidazole-functionalized mesoporous polymers has certain practical significance. This thesis focuses on the synthesis of imidazole functionalized mesoporous polymer and its application in the cycloaddition reaction of carbon dioxide. The imidazole-functionalized mesoporous polymer (4-IP-MPsN) was prepared by using 4-H1-Imidazole-1-Phenol (4-IP) as imidazole source. When 4-IP was used as imidazole source to prepare imidazole functionalized mesoporous polymer, 4-IP could only grow from adjacent position in the process of polymerization with formaldehyde, and could not form three-dimensional cross-linking structure. The imidazole-functionalized mesoporous polymer framework was characterized by its poor stability. 3-(1-hydro-imidazole-1) phenol-3-IPP). Because the phenolic hydroxyl group and imidazole ring are in the interphase position, they can be used as imidazole source to prepare three dimensional crosslinked imidazole-functionalized mesoporous polymer (3-IP-MPsN). Considering that the direct connection between imidazole ring and benzene ring may have a great effect on the performance of imidazole ring due to the conjugation effect, we introduce a methylene between imidazole ring and benzene ring to prepare an imidazole nonconjugated mesoporous polymer. In the second chapter, 3-IP, phenol and formaldehyde were used to synthesize imidazole functionalized precursor in one pot in alkaline condition, and 3-IP-MPswere synthesized by solvent volatilization induced self-assembly with template F127. The effects of the content of prepolymerization time 3-IP and the position of imidazole ring and phenolic hydroxyl group on the structure of the polymer were investigated by X-ray diffraction and nitrogen adsorption and desorption schedule. The synthesis of imidazole functionalized mesoporous polymer was clarified. Infrared analysis, elemental analysis, carbon solid nuclear magnetic analysis, photoelectron spectroscopy and thermogravimetric analysis confirmed that the target material contained imidazole groups and maintained high thermal stability at 420 鈩，

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