本文選題：油酸衍生物 + 刺激響應(yīng)性　； 參考：《西南石油大學(xué)》2017年碩士論文

【摘要】：近年來(lái),環(huán)境刺激響應(yīng)型蠕蟲(chóng)狀膠束憑借其獨(dú)特的微觀結(jié)構(gòu)和可調(diào)控的流變性質(zhì)引起了廣泛的關(guān)注。其中的pH和CO2響應(yīng)型蠕蟲(chóng)狀膠束具有易于制備,性能可逆可控,經(jīng)濟(jì)環(huán)保等優(yōu)點(diǎn),在油氣田開(kāi)發(fā)領(lǐng)域中存在著巨大的發(fā)展?jié)摿�。因�?本論文基于兩種油酸衍生物表面活性劑,分別制備了 pH和CO2響應(yīng)型的蠕蟲(chóng)狀膠束,并對(duì)兩種體系的刺激響應(yīng)行為及其機(jī)理進(jìn)行了深入的研究,具體研究?jī)?nèi)容如下:首先,以油酸、N,N-二甲基-1,3-丙二胺為原料合成了油酸酰胺丙基二甲基氧化胺(OAPAO)表面活性劑,并對(duì)OAPAO在水溶液中的氣/液界面性質(zhì)和不同pH、溫度下的聚集行為進(jìn)行了系統(tǒng)的研究。由表面張力法和吉布斯等溫吸附方程等公式得到了OAPAO溶液在不同pH下的特性參數(shù),對(duì)比表明,pH可以調(diào)控OAPAO溶液的氣/液界面的性質(zhì),1H NMR和分子狀態(tài)分布圖證實(shí)這是由于OAPAO表面活性劑的分子狀態(tài)隨pH的改變發(fā)生了變化。不同pH下的粘度測(cè)試證明該體系具有pH響應(yīng)特性,當(dāng)PH2.1時(shí),體系為低粘度的粘彈性流體,η0=0.5074 Pa·s,當(dāng)將pH調(diào)節(jié)到6.82時(shí),溶液的粘度增大到34.49 Pa·s,實(shí)現(xiàn)了三倍數(shù)量級(jí)的增長(zhǎng),當(dāng)pH增大到11.88時(shí),溶液的粘度降低為12.0Pa·s;流變和Cryo-TEM研究表明,體系粘度的急劇增大,是因?yàn)殡S著酸性的變?nèi)?OAPAO去質(zhì)子化程度增大,溶液中質(zhì)子化的OAPAO和未質(zhì)子化的OAPAO頭基之間可以形成氫鍵,促進(jìn)蠕蟲(chóng)狀膠束的生長(zhǎng),使溶液中蠕蟲(chóng)狀膠束的長(zhǎng)度和纏繞的密度變大。不同溫度下的粘度測(cè)試證明體系還具有溫度響應(yīng)特性,在pH=6.82和pH=11.88時(shí),OAPAO溶液的粘度均隨著溫度的升高先增大后減小,粘度在35℃時(shí)達(dá)到最大值,流變測(cè)試表明這是溫度升高過(guò)程中疏水作用和分子熱運(yùn)動(dòng)相互競(jìng)爭(zhēng)的結(jié)果。其次,利用油酸鈉作為主劑,分別引入具有刺激響應(yīng)的N,N-二甲基環(huán)己胺(DMCHA)和N,N-二甲基芐胺(DMBA)制備了兩種CO2響應(yīng)型蠕蟲(chóng)狀膠束,并對(duì)濃度和摩爾比對(duì)體系粘度的影響、體系的流變學(xué)性能、CO2的響應(yīng)特性和響應(yīng)機(jī)理進(jìn)行了研究。結(jié)果表明:兩體系的粘度隨著摩爾比的增大先增大后減小,隨著濃度的增大而增大,同時(shí),相同濃度和摩爾比條件下NaOA-DMBA體系的粘度明顯優(yōu)于NaOA-DMCHA體系,這是由疏水鏈結(jié)構(gòu)不同引起的。通入CO2前,NaOA-DMCHA和NaOA-DMBA溶液均為水狀液體;通入一定時(shí)間的CO2后,兩體系均變?yōu)闊o(wú)色透明的粘彈性流體,且具有剪切稀釋特性,符合Maxwell流體模型;加熱并通入N2將CO2排出后,兩混合溶液再次變回水狀液體,如此循環(huán)三次,體系粘度幾乎沒(méi)有發(fā)生變化,證實(shí)了兩體系的CO2響應(yīng)具有循環(huán)可逆性。由流變、Cryo-TEM、DLS、分子狀態(tài)分布圖和1H-NMR研究表明,通入CO2前,OA-自組裝形成球狀膠束;通入CO2后,DMCHA或DMBA被質(zhì)子化成DMCHA-H+或DMBA·H+通過(guò)與OA-的靜電屏蔽作用和疏水作用,使得聚集體的微觀結(jié)構(gòu)相應(yīng)的從球狀膠束轉(zhuǎn)變成蠕蟲(chóng)狀膠束,混合溶液粘度變大。
[Abstract]:In recent years, environmental stimulus-responsive worm-like micelles have attracted wide attention due to their unique microstructure and controllable rheological properties. Among them, pH and CO2 responsive worm micelles have the advantages of easy preparation, reversible and controllable performance, economic and environmental protection, etc., which have great development potential in the field of oil and gas field development. Therefore, based on two kinds of surfactants of oleic acid derivatives, the wormlike micelles of pH and CO2 response were prepared, and the stimuli response behavior and mechanism of the two systems were studied. The specific research contents are as follows: firstly, oleic acid amide propyl dimethyl amine oxide (OAPAO) surfactant was synthesized from oleic acid N-dimethyl-1-methyl-3-propylenediamine. The gas / liquid interface properties of OAPAO in aqueous solution and the aggregation behavior at different pH and temperature were systematically studied. The characteristic parameters of OAPAO solution at different pH were obtained by surface tension method and Gibbs isothermal adsorption equation. The comparison shows that the pH can regulate the properties of the gas-liquid interface of OAPAO solution and the molecular state distribution diagram proves that this is due to the change of molecular state of OAPAO surfactant with the change of pH. The viscosity tests at different pH values show that the system has the characteristics of pH response. When PH2.1, the system is a viscoelastic fluid with low viscosity, 畏 _ 0 ~ (0) 0.5074 Pa / s, and when pH is adjusted to 6.82, the viscosity of the solution increases to 34.49 Pa / s, and the increase of three times order of magnitude is achieved. When pH increased to 11.88, the viscosity of the solution decreased to 12.0Pa s, and the rheological and Cryo-TEM studies showed that the viscosity of the system increased sharply because the degree of deprotonation of OAPAO increased with the weakening of acidity. A hydrogen bond can be formed between the protonated OAPAO and the unprotonated OAPAO head group, which can promote the growth of the wormlike micelles, and increase the length and the winding density of the wormlike micelles in the solution. The viscosity tests at different temperatures show that the system also has the characteristic of temperature response. The viscosity of OAPAO solution increases first and then decreases with the increase of temperature at pH=6.82 and pH = 11.88, and reaches the maximum value at 35 鈩，

本文編號(hào)：1855051