本文選題：光響應(yīng)離子液體表面活性劑 + 表面張力　； 參考：《河南師范大學(xué)》2017年碩士論文

【摘要】：從綠色化學(xué)的發(fā)展理念出發(fā),新型、環(huán)保、多功能的表面活性劑以其獨(dú)特的物理化學(xué)性質(zhì)倍受世界各地科研人員的關(guān)注。在表面活性劑的疏水鏈中嵌入光敏基團(tuán),同時(shí)在親水頭基以離子液體潤(rùn)飾,如此合成出的光響應(yīng)離子液體表面活性劑兼具了傳統(tǒng)的雙親性及特殊光學(xué)活性。本文以四丁基苯胺為原料,通過重氮偶合,威廉姆森成醚反應(yīng),取代等反應(yīng)合成的中間體與甲基咪唑反應(yīng)合成第一種產(chǎn)物:4-丁基偶氮苯-4'-(乙氧基)甲基咪唑溴化鹽(AZMIMBr),然后通過交換樹脂將產(chǎn)物AZMIMBr與氟硼酸反應(yīng)合成第二種產(chǎn)物:4-丁基偶氮苯-4'-(乙氧基)甲基咪唑四氟硼酸鹽(AZMIMBF4)。實(shí)驗(yàn)進(jìn)一步研究了十二烷基羥乙基二甲基溴化銨(C_(12)HDAB)與AZMIMBr混合后的膠束化過程,并考察了紫外光照對(duì)不同配比下膠束體系光學(xué)性質(zhì)的影響。采用核磁共振技術(shù)對(duì)已合成的兩種產(chǎn)物進(jìn)行表征,然后對(duì)產(chǎn)物的熔點(diǎn)及熱穩(wěn)定性進(jìn)行熱分析,接著,滴體積法和電導(dǎo)率法彼此驗(yàn)證,準(zhǔn)確測(cè)定其臨界膠束濃度。實(shí)驗(yàn)數(shù)據(jù)表明,兩種表面活性劑在25℃下的CMC分別為2.20、1.14 mM,由于表面活性劑的CMC主要與分子結(jié)構(gòu)有關(guān),AZMIMBr樣品溶液的CMC要大于AZMIMBF4樣品溶液的CMC,在具有相同的較大非極性基團(tuán)和咪唑陽(yáng)離子基團(tuán)的情況下,造成CMC差異的就是反離子Br-、BF4-的作用,樣品AZMIMBr中溴離子的極性較大,親水性更強(qiáng),減弱了疏水基與溶劑之間的排斥力,而樣品AZMIMBF4中氟硼酸根的極性小,有疏水作用,更加有利于膠束的形成。在電導(dǎo)率曲線圖中,臨界膠束濃度值隨溫度的增加而增大,反離子結(jié)合度β隨溫度升高而降低,這與反離子的水化半徑和極性有關(guān)。實(shí)驗(yàn)還測(cè)定了AZMIMBF4的Krafft點(diǎn)(40℃),以確定其最佳溶解溫度。由于它們的疏水鏈中特有的偶氮苯基團(tuán),通過365 nm紫外光照射,對(duì)光化學(xué)調(diào)控下的表面性質(zhì)進(jìn)行研究。對(duì)比紫外照射前后的臨界膠束濃度變化,證實(shí)了表面活性劑在紫外光照下,由穩(wěn)定的反式結(jié)構(gòu)轉(zhuǎn)變?yōu)椴环�(wěn)定的順式結(jié)構(gòu)的變化行為,并通過紫外可見吸收光譜、核磁共振儀等儀器,測(cè)定了達(dá)到光穩(wěn)態(tài)所需的紫外照射時(shí)間以及不同時(shí)間下的反轉(zhuǎn)率。結(jié)合偏光顯微鏡及小角度X射線衍射技術(shù)手段,探究了紫外光照對(duì)兩種產(chǎn)物在水溶液中構(gòu)筑成的溶致液晶體系的影響,發(fā)現(xiàn)本實(shí)驗(yàn)中所合成的表面活性劑在溶劑水體系中形成的液晶相的類型與紫外光照與否及在水中的濃度大小有很大的關(guān)系。實(shí)驗(yàn)進(jìn)一步探討了表面活性劑AZMIMBr與C_(12)HDAB復(fù)配對(duì)整個(gè)溶液體系各項(xiàng)性質(zhì)的影響以及紫外光照對(duì)混合體系分子聚集行為的影響。不同配比下的AZMIMBr/C_(12)HDAB混合溶液的臨界膠束濃度利用滴體積法和電導(dǎo)率法測(cè)出,實(shí)驗(yàn)表明隨C_(12)HDAB加入量的增加,CMC依次增大,但都位于兩者之間,偏向于單一AZMIMBr的CMC。通過對(duì)混合溶液膠束化熱力學(xué)過程進(jìn)行分析,發(fā)現(xiàn)相關(guān)參數(shù)顯示出和單一AZMIMBr變化規(guī)律相似的趨勢(shì)。同時(shí)通過紫外吸收光譜、偏光顯微鏡、動(dòng)態(tài)光散射等技術(shù)測(cè)量了紫外光誘導(dǎo)下的混合表面活性劑微觀結(jié)構(gòu)的變化,為光響應(yīng)表面活性劑在納米材料、生物醫(yī)學(xué)等領(lǐng)域中的應(yīng)用提供了一定的實(shí)驗(yàn)和理論依據(jù)。
[Abstract]:Starting from the concept of green chemistry, a new, environmentally friendly, multifunctional surface active agent has attracted the attention of researchers all over the world with its unique physical and chemical properties. The photosensitive group is embedded in the hydrophobic chain of the surfactant and the hydrophilic head base is embellished with ionic liquid, so the surface activity of the photosensitive ionic liquid has been synthesized. In this paper, four Ding Ji aniline was used as the raw material. The first product was synthesized by the reaction of diazo coupling, Williamson ethers reaction, substitution reaction, substitution reaction and methimidazole, 4- Ding Ji azobenzene -4'- (Yi Yangji) methimidazole bromide (AZMIMBr), and then produced by exchange resin. Second products were synthesized by the reaction of AZMIMBr with fluboric acid: 4- butyl azobenzene -4'- (Yi Yangji) methyl imidazole tetrafluorobate (AZMIMBF4). The micellization process of twelve alkyl hydroxyethyl two methammonium bromide (C_ (12) HDAB) and AZMIMBr was further studied, and the optical properties of the micellar system under different proportions of ultraviolet light were investigated. Two kinds of synthesized products were characterized by NMR. Then the melting point and thermal stability of the products were analyzed. Then, the drop volume method and the conductivity method were verified with each other to accurately determine the critical micelle concentration. The experimental data showed that the CMC of the two surface activator at 25 C was 2.20,1.14 mM, respectively. The CMC of the surface active agent is mainly related to the molecular structure. The CMC of the AZMIMBr sample solution is greater than the CMC of the AZMIMBF4 sample solution. In the case of the same large non polar group and the imidazole cationic group, the CMC difference is the reaction of the reverse ion Br-, the action of BF4-, the sample AZMIMBr is more polar, more hydrophilic and weaker. The repellent force between the hydrophobic group and the solvent, and the polarity of the fluorobate root in the sample AZMIMBF4 is small and has the effect of hydrophobicity, which is more beneficial to the formation of the micelle. In the conductivity curve, the critical micelle concentration increases with the increase of temperature, and the anti ion binding degree decreases with the increase of temperature, which is related to the hydration radius and polarity of the reverse ion. The experiment also determined the Krafft point of AZMIMBF4 (40 degrees C) to determine the optimum dissolution temperature. The surface properties under photochemical regulation were studied by 365 nm UV irradiation due to the unique azobenzene group in their hydrophobic chain. The changes of the critical micelle concentration before and after UV irradiation were compared. At the same time, the stable trans structure is transformed into an unstable CIS structure, and the UV irradiation time and the reversal rate are measured by UV visible absorption spectroscopy and nuclear magnetic resonance apparatus. Ultraviolet light microscopy and small angle X ray diffraction techniques have been used to explore ultraviolet light. According to the effect of the lyotropic liquid crystal constructed by the two products in aqueous solution, it is found that the type of the liquid crystal phase formed in the solvent water system in this experiment has a great relationship with the ultraviolet light or not and the concentration of the water in the water. The experiment further explored the combination of surfactant AZMIMBr and C_ (12) HDAB. The effects on the properties of the whole solution system and the influence of ultraviolet light on the aggregation behavior of the mixed system. The critical micelle concentration of AZMIMBr/C_ (12) HDAB mixed solution under different proportions is measured by the drop volume method and the conductivity method. The experiment shows that CMC increases with the increase of the amount of C_ (12) HDAB, but both are located between the two. By analyzing the thermodynamic process of micellization of mixed solution, CMC., which is biased toward a single AZMIMBr, found that the related parameters showed a similar trend with the single AZMIMBr change law. At the same time, the microstructure of the mixed surfactant induced by ultraviolet light was measured by UV absorption spectroscopy, polarizing microscope and dynamic light scattering. It provides some experimental and theoretical basis for the application of photoresponse surfactants in nanomaterials, biomedicine and other fields.

【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O647.2

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本文編號(hào)：1828684