二茂铁基多孔有机高分子的可控合成与及其性能研究

发布时间：2018-05-16 14:57

本文选题：多孔有机高分子 + 二茂铁　；参考：《湖南科技大学》2017年硕士论文

【摘要】：近年来,因为多孔高分子材料在气体的存储和分离等方面具有潜在的应用前景,基于”Bottom-Up”合成新型多孔有机高分子材料得到广泛关注对于新能源的开发,缓解温室效应有重要的意义。本文以采用二茂铁单元为链接单体一步法合成金属多孔聚合物(Metal-containing Porous Organic Polymers)高分子材料,目的在于探索有机多孔高分子材料的结构多样性、聚合反应的多样性、材料稳定性、孔隙率以及其在与能源和环境相关领域的应用,并对材料进行了基本的表征及相关性质的研究。1.以“三明治”结构1,1’-二茂铁二甲醛和氮掺杂程度不同的间二胺单体为基础,成功实现醛胺脱水缩合得到了新型的二茂铁基多孔聚合物(MPOPs)。采用气体吸附仪测试了微孔孔隙率及其H2、CO_2、CH4吸附性能分析,表明以二茂铁为构筑单元明显提高材料的孔隙率(BET比表面积与孔体积)。MPOPs表现出优越的CO_2吸附性能,MPOP-3对二氧化碳的吸附值达到14.8wt%(273K/1bar),且MPOP-1和MPOP-2分别达到11.6wt%和10.4wt%,超过了绝大多数的有机多孔聚合物材料。MPOP-1表现出优秀的气体选择性吸附,即S(CO_2/CH4)和S(CO_2/N2)为5.95和40.2(273K/1bar)。氮掺杂高的聚合物,其单位微孔比表面积对CO_2吸附量大。MPOPs中含有大量的C=N和铁元素能极大地提高对CO_2的吸附能力。2.以1,1’-二溴二茂铁和共轭程度不同的芳香端位炔基为基础,成功实现通过Sonogashrira偶联反应制备了新型的磁性二茂铁基共轭微孔聚合物(MF-CMP-1与MF-CMP-2)。随后,对材料进行了基本的表征及相关性质的研究。MF-CMPs材料表现出优秀的孔隙率,MF-CMP-1与MF-CMP-2的BET比表面积分别达519m2/g与356 m2/g,孔体积分别为0.57cm3/g与0.4 cm3/g。MF-CMP-1的CO_2饱和吸附值为1.45mmol/g(6wt%,273K/1bar),CO_2的吸附焓为27.2k J/mol,且CO_2对CH4的选择吸附性值为4.35。磁响应研究表明,共轭程度大的饱和磁化率高。MF-CMP-1与MF-CMP-2的饱和磁化率分别为0.805emu/g与2.41 emu/g。磁性多孔高分子材料将在工业废水吸附处理及快速磁分离等领域存在潜在的价值。3.以具有含氮富电子平面大环卟啉为中心单体与二茂铁二甲醛链接单体制备层状磁性二茂铁基亚胺共价有机网络(FMI-CON),对材料采用TGA、FIIR、13C CP/MAS NMR、XPS、TGA、SEM、HR-TEM及气体吸脱附等手段进行了表征。HR-TEM图片表明,FMI-CON显示出纳米级别的层状结构。FIM-CON的BET比表面积为602m2/g,孔体积为0.4 cm3/g。其中,微孔面积与微孔体积分别为263m2/g和0.12 cm3/g。FMI-CON材料的CO_2与CH4的饱和吸附值分别为11.2wt%与1.11wt%(273K/1bar),CO_2对CH4的选择吸附性值为4.97,CO_2对N2的选择吸附性值为27.98。磁响应研究表明,FMI-CON材料的饱和磁化率为1.82 emu/g。
[Abstract]:In recent years, due to the potential applications of porous polymer materials in gas storage and separation, the synthesis of new porous organic polymer materials based on "Bottom-Up" has received extensive attention for the development of new energy sources. Relieving Greenhouse Effect is of great significance. In this paper, metal porous polymer Metal-containing Porous Organic Polymers) polymer materials were synthesized by one-step method using ferrocene unit as linked monomer. The purpose of this study was to explore the structural diversity, polymerization diversity and material stability of organic porous polymer materials. Porosity and its applications in energy and environment related fields, and the basic characterization and properties of the materials were studied. A novel ferrocenyl porous polymer (MPOPsN) was successfully obtained by dehydration condensation of aldehydes based on "sandwich" structure (1), ferrocene-ferrocene (1) -ferrocene diformaldehyde and m-diamine monomer with different degree of nitrogen doping. The micropore porosity and the adsorption properties of H _ 2O _ 2C _ 2CH _ 4 were measured by gas adsorption apparatus. The results showed that ferrocene was used as the building unit to improve the porosity of the material obviously. The specific surface area and pore volume of the material showed excellent CO_2 adsorption performance. The adsorption value of carbon dioxide by MPOP-3 reached 14.8 wtcm / 1 barge, and the MPOP-1 and MPOP-2 reached 11.6wt% and 10.4wtrespectively, which exceeded the absolute value. Most organic porous polymer materials. MPOP-1 exhibit excellent gas selective adsorption. This is 5.95 and 40.2 / 273K / 1 / 1 / 1 / 1 of S / CO _ 2 / Ch _ 4 and S _ CO _ 2 / N _ 2 respectively. When the nitrogen doped polymer has high specific surface area, the adsorption capacity of CO_2 can be greatly improved by the large amount of Con N and Fe elements in the adsorbed amount of Con N and Fe in the polymer with large specific surface area per unit micropore. A novel magnetic ferrocenyl conjugated microporous polymer, MF-CMP-1 and MF-CMP-2N, was successfully prepared by Sonogashrira coupling reaction based on 1hlb-dibromoferrocenyl ferrocene and aromatic terminal alkynyl groups with different conjugation degree. Then, The basic characterization and related properties of MF-CMPs were studied. MF-CMPs showed excellent porosity. The specific surface area of MF-CMP-1 and MF-CMP-2 was 519m2/g and 356m2 / g, respectively, and the saturated adsorption value of CO_2 with pore volume of 0.57cm3/g and 0.4 cm3/g.MF-CMP-1 was 1.45 mmol / g and 0.4 cm3/g.MF-CMP-1, respectively. The adsorption enthalpy of MF-CMP-1 and MF-CMP-2 was 273K / 1 Barco _ 2. It is 27.2kJ / mol, and the selective adsorption of CH4 by CO_2 is 4.35. The results of magnetic response show that the saturation susceptibility of MF-CMP-1 and MF-CMP-2 with high conjugation degree is 0.805emu/g and 2.41 emu / g, respectively. Magnetic porous polymer materials will have potential value in industrial wastewater adsorption treatment and rapid magnetic separation. The layered magnetic ferrocenyl imide covalent organic network (FMI-CON) was prepared by using nitrogen-rich electron plane macrocyclic porphyrin as the central monomer and ferrocene diformaldehyde linked monomer. The material was characterized by TGA FIIR13C CP/MAS NMRX XPSN TGA TGA Sem HR-TEM and gas desorption. HR-TEM images show that FMI-CON shows a nanoscale layered structure. FIM-CON has a BET surface area of 602m2 / g and a pore volume of 0.4 cm ~ 3 / g. The saturated adsorption values of CO_2 and CH4 for 263m2/g and 0.12 cm3/g.FMI-CON materials are 11.2wt% and 1.11wt%, respectively. The selective adsorbability of CH4 for CO2 is 4.97% and 27.98wt% for N2, respectively. The magnetic response shows that the saturation susceptibility of FMI-CON is 1.82 emu / g.
【学位授予单位】：湖南科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O634

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