本文關(guān)鍵詞： 三元凝膠 氫鍵 主-客體作用 雜化凝膠 可聚合AuNPs 催化　出處：《中國科學(xué)技術(shù)大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：凝膠是具有三維網(wǎng)狀結(jié)構(gòu)、富含液體的軟物質(zhì)材料。在目前已報道文獻(xiàn)中,水凝膠的種類繁多,應(yīng)用廣泛。本論文致力于構(gòu)建基于多重交聯(lián)作用的水凝膠體系,從凝膠網(wǎng)絡(luò)的交聯(lián)機(jī)理和應(yīng)用兩方面對水凝膠進(jìn)行有益探索,具體工作內(nèi)容和結(jié)果分為以下兩個部分:1)構(gòu)建基于多重物理相互作用的三元水凝膠poly[acrylamide-co-2-(dimethylamino)ethyl methacrylate][P(AM-co-DMAEMA)]和 poly(vinyl alcohol)(PVA)和β-cyclodextrin(β-CD),其中以β-CD接枝的PVA作為超分子受體、以AM與DMAEMA的共聚物作為超分子授體,引入主客體作用;通過低溫處理,引入PVA結(jié)晶的交聯(lián)作用;各組分間固有的氫鍵對交聯(lián)也有貢獻(xiàn)。以傅立葉變換紅外光譜(FTIR)研究了各組分間的氫鍵作用,二維核磁共振氫譜(2H NOESY)確認(rèn)β-CD與DMAEMA側(cè)基之間的主客體作用,X射線衍射(XRD)則反映出PVA組分在低溫處理過程中結(jié)晶。綜上所述,通過冷凍聚合制備凝膠,對凝膠進(jìn)行冷凍-融化循環(huán)處理,結(jié)合流變性能測試和熱失重分析,系統(tǒng)研究了體系中的各種相互作用對凝膠性能的影響。作為對比,我們構(gòu)建了 P(AM-co-DMAEMA)/PVA//β-CD 三元凝膠和 P(AM-co-DMAEMA)/PVA 二元水凝膠,進(jìn)一步揭示了各種相互作用對凝膠性能的貢獻(xiàn)。PVA的結(jié)晶受體系中多重相互作用的限制,所以P(AM-co-DMAEMA)和PVA二元凝膠的機(jī)械性能最好。2)以DMAEMA為還原劑和單體,在室溫下對HAuCl4進(jìn)行還原,由此得到尺寸均勻分布的可聚合金納米粒子(AuNPs)。以紫外-可見光譜(UV-Vis)與核磁共振氫譜(1HNMR)對AuNPs的反應(yīng)過程進(jìn)行了實時跟蹤,確定了制備AuNPs的最佳反應(yīng)條件。傅立葉變換紅外光譜(FTIR)和熱失重分析(TGA)證實了在AuNPs上DMAEMA單體的存在。在此基礎(chǔ)上,我們分別制備了以可聚合的AuNPs交聯(lián)和化學(xué)交聯(lián)劑交聯(lián)的兩種單交聯(lián)的雜化凝膠,以及兩種交聯(lián)作用結(jié)合的雙交聯(lián)凝膠,研究了雜化凝膠的催化性能。掃描電鏡(SEM)和透射電鏡(TEM)結(jié)果顯示,雙交聯(lián)凝膠孔壁更厚,孔尺寸更小。受甲基橙結(jié)構(gòu)的影響,經(jīng)過多次催化循環(huán)后,以N,N'-亞甲基雙丙烯酰胺和雙甲基丙烯酸乙二醇酯化學(xué)交聯(lián)的雙交聯(lián)凝膠的催化活性有所降低;以N.N'-雙丙烯酰胱胺雙交聯(lián)凝膠中具有可還原基團(tuán),在催化過程中交聯(lián)程度降低,促進(jìn)了反應(yīng)物向凝膠內(nèi)部擴(kuò)散,所以催化活性良好。單交聯(lián)凝膠的交聯(lián)程度低,有利于反應(yīng)物向凝膠內(nèi)部擴(kuò)散,所以經(jīng)過多次循環(huán)后仍然具有良好的催化活性。
[Abstract]:Gel is a kind of soft material with three-dimensional network structure and rich in liquid. There are many kinds of hydrogels and they are widely used in the literature. This paper is devoted to the construction of hydrogel system based on multiple cross-linking. This paper makes a beneficial exploration on hydrogel from the crosslinking mechanism and application of gel network. The specific work and results are divided into the following two parts: 1) A ternary hydrogel poly based on multiple physical interactions is constructed. [Acrylamide-co-2-(dimethylamino)ethyl methacrylate]. [) and poly(vinyl alcohol) and 尾 -cyclodextrin (尾 -CDD). The 尾 -CD grafted PVA was used as supramolecular receptor, and the copolymer of AM and DMAEMA was used as supramolecular donor to introduce host and guest interaction. The crosslinking effect of PVA crystallization was introduced through low temperature treatment. The inherent hydrogen bonds among the components also contributed to the cross-linking. The hydrogen bonding between the components was studied by Fourier transform infrared spectroscopy (FTIR). Two-dimensional nuclear magnetic resonance (1H-NMR) 2H NOESYS confirmed the host and guest interaction between 尾 -CD and the lateral base of DMAEMA. X-ray diffraction (XRD) showed that the PVA component crystallized in the process of low temperature treatment. In conclusion, gel was prepared by freezing polymerization, and the gel was treated by freeze-melting cycle. The effects of various interactions on gel properties were systematically studied by means of rheological test and thermogravimetric analysis. We have constructed the ternary gels of PAM-co-DMAEMAE / PVA / 尾 -CD and binary hydrogels of PVA / AM-co-DMAEMAA / PVA / PVA / 尾 -CD ternary gels. It is further revealed that the contribution of various interactions to gel properties. The crystallization of PVA is limited by the multiple interactions in the system. Therefore, the mechanical properties of DMAEMA and PVA binary gels were the best. 2) DMAEMA was used as reducing agent and monomer to reduce HAuCl4 at room temperature. The size distribution of polymerizable gold nanoparticles was obtained. UV-Visand 1HNMRs were obtained by UV-Visand 1HNMRs. The reaction process of AuNPs is tracked in real time. The optimum reaction conditions for the preparation of AuNPs were determined. Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The existence of DMAEMA monomer on AuNPs was confirmed. We prepared two kinds of mono-crosslinked hybrid gels crosslinked by polymerizable AuNPs and crosslinked by chemical crosslinking agent, and two kinds of cross-linked gels combined with crosslinking respectively. The catalytic properties of hybrid gels were studied. The results of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the pore wall of double crosslinked gel was thicker and the pore size was smaller, which was influenced by the structure of methyl orange. After several catalytic cycles, the catalytic activity of the bicrosslinked gels which were chemically crosslinked with N- Na-methylene bisacrylamide and ethylene glycol dimethacrylate was decreased. The reducible group was found in the N (N) -diacrylyl cysteine (N) -diacryloyl cysteamine (BAC) cross-linked gel, which decreased the cross-linking degree during the catalytic process and promoted the diffusion of reactants to the gel. Therefore, the catalytic activity is good, and the crosslinking degree of single crosslinked gel is low, which is beneficial to the diffusion of reactants into the gel, so it still has good catalytic activity after many cycles.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O648.17

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