芘基多孔有机聚合物的合成与吸附性能研究
发布时间：2018-07-28 11:50
【摘要】：共价键联结的多孔有机聚合物材料(POPs)因其大的比表面积、可调谐的孔径尺寸、低的骨架密度、高的热稳定性以及可裁剪的构筑模块而被广泛应用于气体吸附、异相催化、光电补集等领域。POPs材料对CO2的吸附分离是气体吸附领域的研究重点。这是因为化石燃料的过度消耗向大气中排放了过量的CO2,并且造成了严峻的生态环境问题。同时,化石燃料的不可再生也迫使人类不断探寻新的清洁能源,如CH4、H2等,以此来维持人类社会的可持续发展。因此,设计合成可应用于实践的有机多孔吸附剂材料具有迫切意义。本论文以芘为核心,并利用不同类型的有机合成反应构建了三组多孔有机聚合物材料,并对这些材料的结构,热稳定性及形貌等进行了细致的表征。此外,还对这些材料的CO2吸附分离性能进行了测试与分析。以下为本论文的主要内容:(1)以1,3,6,8-四溴芘为起始原料分别与2-噻吩硼酸和3-噻吩硼酸通过Suzuki交叉耦合反应得到相应的蝴蝶状共聚单体L1和L2。L1和L2再分别通过三氯化铁催化的氧化聚合反应自缩聚成CK-COP-1与CK-COP-2。在这一组材料中L1和L2是同分异构体,但在聚合过程中因其参与聚合的活性位点数不同导致最终材料的交联程度、孔径分布、热稳定性、气体吸附分离性能等都产生较大差异。例如CK-COP-1和CK-COP-2对CO2的吸附量分别为2.85%和9.73%(273 K,1 bar)。由此得出,多孔吸附剂类材料除了依赖于特异性官能团外,构筑模块的交联程度也是吸附剂材料设计时考虑的必要因素。(2)以1,3,6,8-四(对甲酰基苯基)芘(TFPPy)为初始构建单元并分别与间苯三酚和2,5-二萘酚通过酚醛树脂类型的合成反应仅在盐酸催化的条件下直接共聚成聚合物有机框架材料ZLY-POF-1和ZLY-POF-2。尽管上述两材料均是以芘为核,但因间苯三酚和2,5-二萘酚所含羟基数量及其平面刚性程度的不同导致了聚合物最终的联结方式和孔径排布差异较大。两类材料的CO2吸附分离性能差距也较大(ZLP-POF-1:11.26%,ZLY-POF-2:7.76%,273 K 1 bar)。(3)以1,3,6,8-四乙炔基芘为构筑单元,通过钯催化的氧化耦合反应自聚成共轭微孔有机聚合物(CMPs)LKK-CMP,具有高的热稳定性以及微孔特征。LKK-CMP材料是由芘基与炔基交替“编织”成的聚合物,因此具有较好的共轭效应。构筑单体中丰富的电子可以流动于聚合物材料的整个骨架,而这一特性恰好有助于材料与缺电子的二氧化碳通过分子间相互作用力而将CO2大量吸附。基于本材料对CO2的物理吸附作用,该材料具有可低能耗循环利用的特点。LKK-CMP对CO2的吸附量在273 K,1 bar条件下可达9.78%,CO2/CH4与CO2/N2的分离性能分别可达6.8和52.8。
[Abstract]:Covalently bonded porous organic polymer (POPs) is widely used in gas adsorption, heterogeneous catalysis, due to its large specific surface area, tunable pore size, low skeleton density, high thermal stability and tailor-made building blocks. The adsorption and separation of CO2 by pops is the focus in the field of gas adsorption. This is because excessive consumption of fossil fuels releases excess CO2 into the atmosphere and causes severe ecological problems. At the same time, the non-renewable fossil fuels force mankind to explore new clean energy sources, such as CH4H _ 2, so as to maintain the sustainable development of human society. Therefore, it is urgent to design and synthesize organic porous adsorbent materials. In this paper, three groups of porous organic polymer materials were constructed by using different organic synthesis reactions and pyrene as the core. The structure, thermal stability and morphology of these materials were characterized in detail. In addition, the CO2 adsorption and separation properties of these materials were tested and analyzed. The following are the main contents of this thesis: (1) the corresponding butterfly copolymerization monomer L1 L2.L1 and L 2 were synthesized by Suzuki cross-coupling reaction with 2-thiophene boric acid and 3-thiophene boric acid respectively from the starting materials of 1ttrithiophene 8-tetrabromopyrene. Iron catalyzed oxidation polymerization was self-condensed to form CK-COP-1 and CK-COP-2. In this group of materials, L1 and L2 are isomers, but the crosslinking degree, pore size distribution, thermal stability, gas adsorption and separation performance of the final materials are different during the polymerization process due to the difference in the number of active sites involved in the polymerization. For example, the adsorption capacities of CK-COP-1 and CK-COP-2 for CO2 were 2.85% and 9.73% (273K ~ (-1) bar).), respectively. It is concluded that the porous adsorbents are not only dependent on specific functional groups, but also dependent on specific functional groups. The degree of crosslinking of the building blocks is also an essential factor in the design of adsorbent materials. (2) the initial construction unit of 1 (3) (6) -tetra (p formylphenyl) pyrene (TFPPy) and its combination with mesoglucinol and 2 (2) -dinaphthol through phenolic resin type, respectively. The polymer organic framework materials ZLY-POF-1 and ZLY-POF-2 were synthesized by direct copolymerization under the catalysis of hydrochloric acid. Although pyrene is the core of the two materials, due to the difference of hydroxyl content and plane rigidity degree between phloroglucinol and 2o 5-dinaphthol, the final bonding mode and pore size arrangement of the polymer are different greatly. The difference of CO2 adsorption and separation performance between the two kinds of materials is also large (ZLP-POF-1: 11.26 and ZLY-POF-2: 7.76 ~ 273K1 bar). (3). The conjugated microporous organic polymer (CMPs) LKK-CMP was self-polymerized by the oxidation coupling reaction catalyzed by palladium. It has high thermal stability and micropore characteristics. LKK-CMP is a polymer composed of pyrene and alkynyl alternately "braided", so it has a good conjugation effect. The construction of abundant electrons in the monomer can flow through the whole skeleton of the polymer material, and this property can help the material and the electron-deficient carbon dioxide to adsorb CO2 in large quantities through the intermolecular interaction. Based on the physical adsorption of CO2, the material has the characteristics of low energy consumption and recycling. The adsorption capacity of LKK-CMP for CO2 can reach 9.78% and 52.8% at 273 K ~ (-1) bar, respectively, and the separation properties of CO _ 2 / Ch _ 4 and CO2/N2 are 6.8 and 52.8, respectively.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631
本文编号：2150046
[Abstract]:Covalently bonded porous organic polymer (POPs) is widely used in gas adsorption, heterogeneous catalysis, due to its large specific surface area, tunable pore size, low skeleton density, high thermal stability and tailor-made building blocks. The adsorption and separation of CO2 by pops is the focus in the field of gas adsorption. This is because excessive consumption of fossil fuels releases excess CO2 into the atmosphere and causes severe ecological problems. At the same time, the non-renewable fossil fuels force mankind to explore new clean energy sources, such as CH4H _ 2, so as to maintain the sustainable development of human society. Therefore, it is urgent to design and synthesize organic porous adsorbent materials. In this paper, three groups of porous organic polymer materials were constructed by using different organic synthesis reactions and pyrene as the core. The structure, thermal stability and morphology of these materials were characterized in detail. In addition, the CO2 adsorption and separation properties of these materials were tested and analyzed. The following are the main contents of this thesis: (1) the corresponding butterfly copolymerization monomer L1 L2.L1 and L 2 were synthesized by Suzuki cross-coupling reaction with 2-thiophene boric acid and 3-thiophene boric acid respectively from the starting materials of 1ttrithiophene 8-tetrabromopyrene. Iron catalyzed oxidation polymerization was self-condensed to form CK-COP-1 and CK-COP-2. In this group of materials, L1 and L2 are isomers, but the crosslinking degree, pore size distribution, thermal stability, gas adsorption and separation performance of the final materials are different during the polymerization process due to the difference in the number of active sites involved in the polymerization. For example, the adsorption capacities of CK-COP-1 and CK-COP-2 for CO2 were 2.85% and 9.73% (273K ~ (-1) bar).), respectively. It is concluded that the porous adsorbents are not only dependent on specific functional groups, but also dependent on specific functional groups. The degree of crosslinking of the building blocks is also an essential factor in the design of adsorbent materials. (2) the initial construction unit of 1 (3) (6) -tetra (p formylphenyl) pyrene (TFPPy) and its combination with mesoglucinol and 2 (2) -dinaphthol through phenolic resin type, respectively. The polymer organic framework materials ZLY-POF-1 and ZLY-POF-2 were synthesized by direct copolymerization under the catalysis of hydrochloric acid. Although pyrene is the core of the two materials, due to the difference of hydroxyl content and plane rigidity degree between phloroglucinol and 2o 5-dinaphthol, the final bonding mode and pore size arrangement of the polymer are different greatly. The difference of CO2 adsorption and separation performance between the two kinds of materials is also large (ZLP-POF-1: 11.26 and ZLY-POF-2: 7.76 ~ 273K1 bar). (3). The conjugated microporous organic polymer (CMPs) LKK-CMP was self-polymerized by the oxidation coupling reaction catalyzed by palladium. It has high thermal stability and micropore characteristics. LKK-CMP is a polymer composed of pyrene and alkynyl alternately "braided", so it has a good conjugation effect. The construction of abundant electrons in the monomer can flow through the whole skeleton of the polymer material, and this property can help the material and the electron-deficient carbon dioxide to adsorb CO2 in large quantities through the intermolecular interaction. Based on the physical adsorption of CO2, the material has the characteristics of low energy consumption and recycling. The adsorption capacity of LKK-CMP for CO2 can reach 9.78% and 52.8% at 273 K ~ (-1) bar, respectively, and the separation properties of CO _ 2 / Ch _ 4 and CO2/N2 are 6.8 and 52.8, respectively.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631
【参考文献】
相关期刊论文 前1条
1 王晔峰,邓维,刘磊,郭庆祥;Sonogashira反应研究的最新进展[J];有机化学;2005年01期
，本文编号：2150046
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