【摘要】：共價(jià)鍵聯(lián)結(jié)的多孔有機(jī)聚合物材料(POPs)因其大的比表面積、可調(diào)諧的孔徑尺寸、低的骨架密度、高的熱穩(wěn)定性以及可裁剪的構(gòu)筑模塊而被廣泛應(yīng)用于氣體吸附、異相催化、光電補(bǔ)集等領(lǐng)域。POPs材料對(duì)CO2的吸附分離是氣體吸附領(lǐng)域的研究重點(diǎn)。這是因?yàn)榛剂系倪^度消耗向大氣中排放了過量的CO2,并且造成了嚴(yán)峻的生態(tài)環(huán)境問題。同時(shí),化石燃料的不可再生也迫使人類不斷探尋新的清潔能源,如CH4、H2等,以此來維持人類社會(huì)的可持續(xù)發(fā)展。因此,設(shè)計(jì)合成可應(yīng)用于實(shí)踐的有機(jī)多孔吸附劑材料具有迫切意義。本論文以芘為核心,并利用不同類型的有機(jī)合成反應(yīng)構(gòu)建了三組多孔有機(jī)聚合物材料,并對(duì)這些材料的結(jié)構(gòu),熱穩(wěn)定性及形貌等進(jìn)行了細(xì)致的表征。此外,還對(duì)這些材料的CO2吸附分離性能進(jìn)行了測(cè)試與分析。以下為本論文的主要內(nèi)容:(1)以1,3,6,8-四溴芘為起始原料分別與2-噻吩硼酸和3-噻吩硼酸通過Suzuki交叉耦合反應(yīng)得到相應(yīng)的蝴蝶狀共聚單體L1和L2。L1和L2再分別通過三氯化鐵催化的氧化聚合反應(yīng)自縮聚成CK-COP-1與CK-COP-2。在這一組材料中L1和L2是同分異構(gòu)體,但在聚合過程中因其參與聚合的活性位點(diǎn)數(shù)不同導(dǎo)致最終材料的交聯(lián)程度、孔徑分布、熱穩(wěn)定性、氣體吸附分離性能等都產(chǎn)生較大差異。例如CK-COP-1和CK-COP-2對(duì)CO2的吸附量分別為2.85%和9.73%(273 K,1 bar)。由此得出,多孔吸附劑類材料除了依賴于特異性官能團(tuán)外,構(gòu)筑模塊的交聯(lián)程度也是吸附劑材料設(shè)計(jì)時(shí)考慮的必要因素。(2)以1,3,6,8-四(對(duì)甲�；交�)芘(TFPPy)為初始構(gòu)建單元并分別與間苯三酚和2,5-二萘酚通過酚醛樹脂類型的合成反應(yīng)僅在鹽酸催化的條件下直接共聚成聚合物有機(jī)框架材料ZLY-POF-1和ZLY-POF-2。盡管上述兩材料均是以芘為核,但因間苯三酚和2,5-二萘酚所含羥基數(shù)量及其平面剛性程度的不同導(dǎo)致了聚合物最終的聯(lián)結(jié)方式和孔徑排布差異較大。兩類材料的CO2吸附分離性能差距也較大(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為構(gòu)筑單元,通過鈀催化的氧化耦合反應(yīng)自聚成共軛微孔有機(jī)聚合物(CMPs)LKK-CMP,具有高的熱穩(wěn)定性以及微孔特征。LKK-CMP材料是由芘基與炔基交替“編織”成的聚合物,因此具有較好的共軛效應(yīng)。構(gòu)筑單體中豐富的電子可以流動(dòng)于聚合物材料的整個(gè)骨架,而這一特性恰好有助于材料與缺電子的二氧化碳通過分子間相互作用力而將CO2大量吸附�；诒静牧蠈�(duì)CO2的物理吸附作用,該材料具有可低能耗循環(huán)利用的特點(diǎn)。LKK-CMP對(duì)CO2的吸附量在273 K,1 bar條件下可達(dá)9.78%,CO2/CH4與CO2/N2的分離性能分別可達(dá)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.
【學(xué)位授予單位】：山西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631

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相關(guān)期刊論文 前1條

1 王曄峰,鄧維,劉磊,郭慶祥;Sonogashira反應(yīng)研究的最新進(jìn)展[J];有機(jī)化學(xué);2005年01期

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本文編號(hào)：2150046