本文選題：有序介孔 + 咪唑功能化�。� 參考：《華東師范大學(xué)》2017年碩士論文

【摘要】：介孔聚合物具有特殊的孔道結(jié)構(gòu)和純有機(jī)骨架而受到廣泛的關(guān)注,由于有機(jī)骨架的易修飾性,可以通過化學(xué)修飾制備具有特定性能的功能化介孔聚合物。咪唑基團(tuán)是一種重要的功能化基團(tuán),可以用于催化相關(guān)化學(xué)反應(yīng),所以制備咪唑功能化的介孔聚合物具有一定的現(xiàn)實(shí)意義。本論文圍繞咪唑功能化介孔聚合物的合成及在二氧化碳環(huán)加成反應(yīng)中的應(yīng)用展開,立題依據(jù)及主要工作如下:前期工作中,我們以4-(1-氫-咪唑-1-)苯酚(4-IP)為咪唑源制備了咪唑功能化介孔聚合物(4-IP-MPs)。以4-IP作為咪唑源制備咪唑功能化介孔聚合物時(shí),4-IP與甲醛進(jìn)行聚合過程中只能由鄰位生長,無法形成三維交聯(lián)結(jié)構(gòu),所得咪唑功能化介孔聚合物骨架中穩(wěn)定性較差。3-(1-氫-咪唑-1-)苯酚(3-IP)由于酚羥基與咪唑環(huán)處于相間位置,可以作為咪唑源制備三維交聯(lián)型咪唑功能化介孔聚合物(3-IP-MPs)�？紤]到咪唑環(huán)與苯環(huán)之間直接相連由于共軛效應(yīng)苯環(huán)對咪唑環(huán)的性能影響可能較大,我們在咪唑環(huán)與苯環(huán)之間引入一個(gè)亞甲基,制備一種咪唑非共軛型功能化的介孔聚合物。在第二章中,將3-IP與苯酚、甲醛在堿性條件一鍋法合成咪唑功能化前驅(qū)體,并與模板劑F127通過溶劑揮發(fā)誘導(dǎo)自組裝法合成了3-IP-MPs。通過X射線衍射、氮?dú)馕摳奖碚鞣治隹疾炝饲膀?qū)體制備的預(yù)聚合時(shí)間、3-IP的含量以及咪唑環(huán)與酚羥基的位置對于聚合物結(jié)構(gòu)影響,明確了咪唑功能化介孔聚合物的合成。通過紅外分析、元素分析、碳固體核磁分析、光電子能譜分析以及熱重分析證實(shí)了目標(biāo)材料中含有咪唑基團(tuán),且在420 ℃下保持高度熱穩(wěn)定性。以碘化鉀為助催化劑,考察了 3-IP-MPs在二氧化碳和環(huán)氧化物的環(huán)加成反應(yīng)中的催化活性,系統(tǒng)的研究了溫度、壓強(qiáng)、反應(yīng)時(shí)間以及底物普適性的影響。與4-IP-MPs比較,3-IP-MPs在二氧化碳的環(huán)加成反應(yīng)中穩(wěn)定性更高,循環(huán)使用三次活性沒有明顯損失。在第三章中,我們在咪唑環(huán)與苯環(huán)之間引入一個(gè)亞甲基,制備了3-((1-氫-咪唑-1-)甲基)苯酚化合物(3-IMP),并以此為咪唑源合成了咪唑非共軛型功能化的介孔聚合物(3-IMP-MPs),在咪唑源含量為5%時(shí),目標(biāo)材料具有高度有序的介孔結(jié)構(gòu),比表面積和孔容分別達(dá)到408m2/g和0.52cm3/g。系統(tǒng)表征證明3-IMP-MPs含有咪唑基團(tuán)且具有高度熱穩(wěn)定性。將3-IMP-MPs用于催化二氧化碳環(huán)加成反應(yīng),考察了反應(yīng)條件和底物對于催化性能的影響。功能化介孔聚合物循環(huán)使用五次轉(zhuǎn)化率沒有明顯降低,說明3-IMP-MPs具有較高的循環(huán)穩(wěn)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，

本文編號(hào)：1806841