雙重刺激響應型蠕蟲狀膠束體系的研究
發(fā)布時間：2018-09-12 10:11
【摘要】：刺激響應型蠕蟲狀膠束(SWLMs)是蠕蟲狀膠束中較為特殊的一種,它的結構、性質和外觀可以針對外界的刺激而發(fā)生改變。與傳統(tǒng)的蠕蟲狀膠束相比,刺激響應型蠕蟲狀膠束的粘度可以智能調控,具有可逆,可控,可多次循環(huán)利用的優(yōu)點,引起了越來越多人的關注。然而,目前報道的刺激響應型蠕蟲狀膠束多為單響應,對多重刺激響應的報道還很少。因此,本文利用刺激響應型表面活性劑和常規(guī)表面活性劑分別構筑了一系列的雙重刺激響應型蠕蟲狀膠束體系,通過紫外可見雙光束分光光度計、電導率儀、流變儀、表面張力儀、核磁共振(1H NMR)、動態(tài)光散射儀(DLS)和冷凍透射電鏡(Cyro-TEM)等一系列手段,研究了蠕蟲狀膠束體系的流變性能和刺激響應性能,主要的研究結果如下:1刺激響應型表面活性劑構筑雙重刺激響應型蠕蟲狀膠束體系(1)合成了含偶氮苯基團的陽離子表面活性劑4-丁基-4′-(4-N,N,N-三甲基己氧基溴化銨)偶氮苯(C_4AzoC_6N),通過質譜和核磁表征確定得到的產物為所需的目標產物,且純度達到了實驗的要求;通過紫外吸收和核磁測試證明了合成的產物具有很好的光響應性能,其在水溶液中順反異構的轉化率可以達到85%左右;通過表面張力測試發(fā)現C_4AzoC_6N具有較好的降低表面張力的性能。(2)將C_4AzoC_6N分別與十二烷基氨基丙酸鈉(C_(12)NC_2COONa)和偶氮苯酚鈉(AzoONa)復配制備了兩種CO_2/N_2-光雙重刺激響應型蠕蟲狀膠束體系。實驗結果表明,AzoONa的加入對形成蠕蟲狀膠束的促進作用更強,C_4AzoC_6N-AzoONa體系的粘度最大可以達到230 Pa?s。(3)由于C_4AzoC_6N的光敏感性,兩個二元體系都具有較好的光響應性能。通過紫外光和藍光的照射可以實現蠕蟲狀膠束和球狀膠束之間的轉換,從而實現宏觀上高粘度和低粘度之間的轉變。二元體系的光響應性具有很好的重復可逆性,反復循環(huán)三次后,體系的粘度依然可以恢復到初始的數值。(4)由于C_(12)NC_2COONa和AzoONa的pH敏感性,兩個二元體系都具有很好的CO_2/N_2刺激響應性。雖然響應原理不同,但是通入CO_2后,都可以導致蠕蟲狀膠束的瓦解,宏觀上表現為溶液粘度的下降。加熱通N_2后,蠕蟲狀膠束重新形成,體系的粘度也得以恢復。反復通入CO_2和N_2,體系的粘度同樣可以在高粘度和低粘度之間轉換。2常規(guī)表面活性劑構筑雙重刺激響應型蠕蟲狀膠束體系(1)通過向典型的十六烷基三甲基溴化銨(CTAB)和肉桂酸鈉(CA)二元蠕蟲狀膠束體系(CTAB-CA)中加入十六叔胺(CDA)制備了CO_2/N_2-光雙重刺激響應型蠕蟲狀膠束體系(CTAB-CA-CDA-CO_2)。與CTAB-CA二元體系相比,三元體系的粘度大幅提升,最大粘度可以達到537 Pa?s,是二元體系的5倍。反復通入CO_2和N_2,CDA可以發(fā)生質子化和去質子化反應,導致體系中蠕蟲狀膠束的形成和破壞,因此,體系具有很好的CO_2響應性和可逆性。由于CA對紫外光敏感,因此紫外光照射后,CA由反式結構變?yōu)轫樖浇Y構,導致蠕蟲狀膠束的破壞,但是這種轉變是不可逆的。(2)將CTAB、二茂鐵甲酸(FA)和CDA混合制備了CO_2/N_2-氧化還原雙重刺激響應型蠕蟲狀膠束體系(CTAB-FA-CDA-CO_2)。雖然FA與CA分子結構相似,但是與CTAB-CA-CDA-CO_2體系相比,CTAB-FA-CDA-CO_2體系的粘度較低,最大粘度只有23 Pa?s。由于CDA的存在,CTAB-FA-CDA-CO_2體系同樣具有很好的CO_2和N_2刺激響應性。同時,因為FA的存在,體系還具有氧化還原響應性。反復向體系中加入氧化劑和還原劑,可以實現蠕蟲狀膠束與球狀膠束之間的相互轉換。但是由于添加氧化劑和還原劑的過程中不可避免的向體系中引入了雜質,因此每重復循環(huán)一次后,體系的粘度都會有所下降。
[Abstract]:Stimulus-responsive wormlike micelles (SWLMs) are a special kind of wormlike micelles. Their structure, properties and appearance can be changed by stimulation. Compared with the traditional wormlike micelles, the viscosity of the stimulation-responsive wormlike micelles can be controlled intelligently, which has the advantages of reversibility, controllability and multiple recycling. However, most of the stimulus-responsive vermicular micelles are single-response micelles and few of them are multiple-stimulus micelles. Therefore, a series of double-stimulus-responsive vermicular micelles have been constructed by using stimulus-responsive surfactants and conventional surfactants, respectively. Two-beam spectrophotometer, conductivity meter, rheometer, surface tensiometer, nuclear magnetic resonance (1H NMR), dynamic light scattering (DLS) and freezing transmission electron microscopy (Cyro-TEM) were used to study the rheological and stimulus response properties of wormlike micelles. The main results are as follows: 1. Stimulus-responsive wormlike micelle system (1) Cationic surfactant 4-butyl-4'-(4-N, N, N-trimethylhexyl ammonium bromide) azobenzene (C_4AzoC_6N) containing azophenyl group was synthesized. The product was characterized by mass spectrometry and nuclear magnetic resonance, and its purity met the experimental requirements. Magnetic test showed that the synthesized product had good photoresponse, and its cis-trans isomerization conversion in aqueous solution could reach about 85%; surface tension test showed that C_4AzoC_6N had better performance of reducing surface tension. (2) C_4AzoC_6N was separately compared with sodium dodecyl aminopropionate (C_ (12) NC_2COONa) and sodium Azophenol (Na_2COONa). The results show that the addition of AzoONa can promote the formation of wormlike micelles more strongly, and the maximum viscosity of C_4AzoC_6N-AzoONa system can reach 230 Pa?S. (3) Because of the photosensitivity of C_4AzoC_6N, both binary systems have better photoresponse. The photoresponsiveness of the binary system is very reversible, and the viscosity of the system can still be restored to the initial value after three cycles. Both binary systems exhibit good CO_2/N_2 stimulus responsiveness to the pH sensitivities of C_ (12) NC_2COONa and AzoONa. Although the response principle is different, the wormlike micelles can disintegrate after CO_2 is introduced and the macroscopic viscosity of the solution decreases. The viscosity of the system can also be changed between high viscosity and low viscosity by repeating CO_2 and N_2. 2 The double stimulus-responsive wormlike micelle system was constructed by conventional surfactants (1) by adding hexadecyl trimethyl ammonium bromide (CTAB) and sodium cinnamate (CA) into the typical binary wormlike micelle system (CTAB-CA). Comparing with CTAB-CA-CDA-CO_2 binary system, the viscosity of the ternary system was greatly increased, and the maximum viscosity was 537 Pa?S, which was 5 times higher than that of the binary system. When CO_2 and N_2 were repeatedly injected into the system, the protonation and deprotonation reactions of CDA could occur, resulting in worm-like micelles in the system. Because CA is sensitive to ultraviolet light, it changes from trans-structure to cis-structure after ultraviolet irradiation, resulting in the destruction of wormlike micelles, but this transformation is irreversible. (2) CTAB, ferrocene formic acid (FA) and CDA were mixed to prepare CO_2/N_2-oxide. CTAB-FA-CDA-CO_2 micelle system (CTAB-FA-CDA-CO_2). Although FA is similar to CA, the viscosity of CTAB-FA-CDA-CO_2 system is lower than that of CTAB-CA-CDA-CO_2 system. The maximum viscosity of CTAB-FA-CDA-CO_2 system is only 23 Pa?S. Because of the presence of CDA, CTAB-FA-CDA-CO_2 system also has good CO_2 and N_2 stimulation responsiveness. FA exists in the system, and the system is also redox-responsive. Repeated addition of oxidants and reductants to the system can achieve the conversion between wormlike micelles and spherical micelles. However, due to the inevitable introduction of impurities into the system during the addition of oxidants and reductants, the viscosity of the system after each repetition of the cycle. There will be a drop.
【學位授予單位】：江南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O647.2
本文編號：2238689
[Abstract]:Stimulus-responsive wormlike micelles (SWLMs) are a special kind of wormlike micelles. Their structure, properties and appearance can be changed by stimulation. Compared with the traditional wormlike micelles, the viscosity of the stimulation-responsive wormlike micelles can be controlled intelligently, which has the advantages of reversibility, controllability and multiple recycling. However, most of the stimulus-responsive vermicular micelles are single-response micelles and few of them are multiple-stimulus micelles. Therefore, a series of double-stimulus-responsive vermicular micelles have been constructed by using stimulus-responsive surfactants and conventional surfactants, respectively. Two-beam spectrophotometer, conductivity meter, rheometer, surface tensiometer, nuclear magnetic resonance (1H NMR), dynamic light scattering (DLS) and freezing transmission electron microscopy (Cyro-TEM) were used to study the rheological and stimulus response properties of wormlike micelles. The main results are as follows: 1. Stimulus-responsive wormlike micelle system (1) Cationic surfactant 4-butyl-4'-(4-N, N, N-trimethylhexyl ammonium bromide) azobenzene (C_4AzoC_6N) containing azophenyl group was synthesized. The product was characterized by mass spectrometry and nuclear magnetic resonance, and its purity met the experimental requirements. Magnetic test showed that the synthesized product had good photoresponse, and its cis-trans isomerization conversion in aqueous solution could reach about 85%; surface tension test showed that C_4AzoC_6N had better performance of reducing surface tension. (2) C_4AzoC_6N was separately compared with sodium dodecyl aminopropionate (C_ (12) NC_2COONa) and sodium Azophenol (Na_2COONa). The results show that the addition of AzoONa can promote the formation of wormlike micelles more strongly, and the maximum viscosity of C_4AzoC_6N-AzoONa system can reach 230 Pa?S. (3) Because of the photosensitivity of C_4AzoC_6N, both binary systems have better photoresponse. The photoresponsiveness of the binary system is very reversible, and the viscosity of the system can still be restored to the initial value after three cycles. Both binary systems exhibit good CO_2/N_2 stimulus responsiveness to the pH sensitivities of C_ (12) NC_2COONa and AzoONa. Although the response principle is different, the wormlike micelles can disintegrate after CO_2 is introduced and the macroscopic viscosity of the solution decreases. The viscosity of the system can also be changed between high viscosity and low viscosity by repeating CO_2 and N_2. 2 The double stimulus-responsive wormlike micelle system was constructed by conventional surfactants (1) by adding hexadecyl trimethyl ammonium bromide (CTAB) and sodium cinnamate (CA) into the typical binary wormlike micelle system (CTAB-CA). Comparing with CTAB-CA-CDA-CO_2 binary system, the viscosity of the ternary system was greatly increased, and the maximum viscosity was 537 Pa?S, which was 5 times higher than that of the binary system. When CO_2 and N_2 were repeatedly injected into the system, the protonation and deprotonation reactions of CDA could occur, resulting in worm-like micelles in the system. Because CA is sensitive to ultraviolet light, it changes from trans-structure to cis-structure after ultraviolet irradiation, resulting in the destruction of wormlike micelles, but this transformation is irreversible. (2) CTAB, ferrocene formic acid (FA) and CDA were mixed to prepare CO_2/N_2-oxide. CTAB-FA-CDA-CO_2 micelle system (CTAB-FA-CDA-CO_2). Although FA is similar to CA, the viscosity of CTAB-FA-CDA-CO_2 system is lower than that of CTAB-CA-CDA-CO_2 system. The maximum viscosity of CTAB-FA-CDA-CO_2 system is only 23 Pa?S. Because of the presence of CDA, CTAB-FA-CDA-CO_2 system also has good CO_2 and N_2 stimulation responsiveness. FA exists in the system, and the system is also redox-responsive. Repeated addition of oxidants and reductants to the system can achieve the conversion between wormlike micelles and spherical micelles. However, due to the inevitable introduction of impurities into the system during the addition of oxidants and reductants, the viscosity of the system after each repetition of the cycle. There will be a drop.
【學位授予單位】：江南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O647.2
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