双重刺激响应型蠕虫状胶束体系的研究
发布时间：2018-09-12 10:11
【摘要】：刺激响应型蠕虫状胶束(SWLMs)是蠕虫状胶束中较为特殊的一种,它的结构、性质和外观可以针对外界的刺激而发生改变。与传统的蠕虫状胶束相比,刺激响应型蠕虫状胶束的粘度可以智能调控,具有可逆,可控,可多次循环利用的优点,引起了越来越多人的关注。然而,目前报道的刺激响应型蠕虫状胶束多为单响应,对多重刺激响应的报道还很少。因此,本文利用刺激响应型表面活性剂和常规表面活性剂分别构筑了一系列的双重刺激响应型蠕虫状胶束体系,通过紫外可见双光束分光光度计、电导率仪、流变仪、表面张力仪、核磁共振(1H NMR)、动态光散射仪(DLS)和冷冻透射电镜(Cyro-TEM)等一系列手段,研究了蠕虫状胶束体系的流变性能和刺激响应性能,主要的研究结果如下:1刺激响应型表面活性剂构筑双重刺激响应型蠕虫状胶束体系(1)合成了含偶氮苯基团的阳离子表面活性剂4-丁基-4′-(4-N,N,N-三甲基己氧基溴化铵)偶氮苯(C_4AzoC_6N),通过质谱和核磁表征确定得到的产物为所需的目标产物,且纯度达到了实验的要求;通过紫外吸收和核磁测试证明了合成的产物具有很好的光响应性能,其在水溶液中顺反异构的转化率可以达到85%左右;通过表面张力测试发现C_4AzoC_6N具有较好的降低表面张力的性能。(2)将C_4AzoC_6N分别与十二烷基氨基丙酸钠(C_(12)NC_2COONa)和偶氮苯酚钠(AzoONa)复配制备了两种CO_2/N_2-光双重刺激响应型蠕虫状胶束体系。实验结果表明,AzoONa的加入对形成蠕虫状胶束的促进作用更强,C_4AzoC_6N-AzoONa体系的粘度最大可以达到230 Pa?s。(3)由于C_4AzoC_6N的光敏感性,两个二元体系都具有较好的光响应性能。通过紫外光和蓝光的照射可以实现蠕虫状胶束和球状胶束之间的转换,从而实现宏观上高粘度和低粘度之间的转变。二元体系的光响应性具有很好的重复可逆性,反复循环三次后,体系的粘度依然可以恢复到初始的数值。(4)由于C_(12)NC_2COONa和AzoONa的pH敏感性,两个二元体系都具有很好的CO_2/N_2刺激响应性。虽然响应原理不同,但是通入CO_2后,都可以导致蠕虫状胶束的瓦解,宏观上表现为溶液粘度的下降。加热通N_2后,蠕虫状胶束重新形成,体系的粘度也得以恢复。反复通入CO_2和N_2,体系的粘度同样可以在高粘度和低粘度之间转换。2常规表面活性剂构筑双重刺激响应型蠕虫状胶束体系(1)通过向典型的十六烷基三甲基溴化铵(CTAB)和肉桂酸钠(CA)二元蠕虫状胶束体系(CTAB-CA)中加入十六叔胺(CDA)制备了CO_2/N_2-光双重刺激响应型蠕虫状胶束体系(CTAB-CA-CDA-CO_2)。与CTAB-CA二元体系相比,三元体系的粘度大幅提升,最大粘度可以达到537 Pa?s,是二元体系的5倍。反复通入CO_2和N_2,CDA可以发生质子化和去质子化反应,导致体系中蠕虫状胶束的形成和破坏,因此,体系具有很好的CO_2响应性和可逆性。由于CA对紫外光敏感,因此紫外光照射后,CA由反式结构变为顺式结构,导致蠕虫状胶束的破坏,但是这种转变是不可逆的。(2)将CTAB、二茂铁甲酸(FA)和CDA混合制备了CO_2/N_2-氧化还原双重刺激响应型蠕虫状胶束体系(CTAB-FA-CDA-CO_2)。虽然FA与CA分子结构相似,但是与CTAB-CA-CDA-CO_2体系相比,CTAB-FA-CDA-CO_2体系的粘度较低,最大粘度只有23 Pa?s。由于CDA的存在,CTAB-FA-CDA-CO_2体系同样具有很好的CO_2和N_2刺激响应性。同时,因为FA的存在,体系还具有氧化还原响应性。反复向体系中加入氧化剂和还原剂,可以实现蠕虫状胶束与球状胶束之间的相互转换。但是由于添加氧化剂和还原剂的过程中不可避免的向体系中引入了杂质,因此每重复循环一次后,体系的粘度都会有所下降。
[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.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O647.2
本文编号：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.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O647.2
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