萘酰亚胺类凝胶因子的结构与性能调控
发布时间：2018-11-24 17:33
【摘要】：超分子化学是一门新兴的学科,它涵盖了比分子本身更加复杂的物理、化学、生物、材料和信息特征,模糊了有机化学、生物化学和材料学之间的界限,为分子器件、材料科学等的发展拓宽了道路。首先,萘酰亚胺类衍生物优良的光电性能,可作为功能基团引入凝胶因子分子骨架,其次,其大的分子共平面特性与三嗪基团的特有的氢键特性相互协同作用对调控凝胶材料的性质的影响也极具研究意义。因此,论文在综合文献的基础上,设计合成了五种由三嗪基团修饰的萘酰亚胺类凝胶因子,并通过试管倒转法对其凝胶性能和凝胶能力进行了测试,观察了其凝胶的微观形貌,利用紫外吸收光谱和荧光光谱考察了其溶液及凝胶状态下的光谱学特性,具体内容如下：1、以三聚氯氰为原料,合成了四种不同官能团修饰的三嗪衍生物,以EDC与HOBT为酰胺键的偶联剂,再与1,4,5,8-萘四甲酸酐缩合得五种目标产物NDI-1、NDI-2、NDI-3、NDI-4和NDI-M。并对其结构进行了确认。2、采用试管倒转法对五种凝胶因子在一系列有机溶剂中的凝胶行为进行了测试,同时对其临界凝胶浓度和临界凝胶温度进行了测定。结果表明：五种凝胶因子都能在甲苯,二甲苯等溶剂中形成热稳定的透明凝胶,在乙酸乙酯,乙酸丁酯,甲基丙烯酸丁酯中形成热稳定的不透明凝胶。其中NDI-4的凝胶能力最强,NDI-M的凝胶能力最弱。NDI-2的凝胶性能最强,NDI-M的凝胶性能最差。NDI-3在二甲苯中表现出随时间变化凝胶颜色由黄色变为红色凝胶的特殊现象。3、利用SEM电镜观察五种凝胶因子在多种溶剂中形成凝胶的微观形貌。结果表明,萘酰亚胺类凝胶因子在不同溶剂中能得到三维网络状和针织状两种特殊结构的凝胶。适当降低烷基链的长度对凝胶的微观形貌影响不明显。改变三嗪基团上的取代基,对凝胶的微观形貌有一定的影响。4、利用紫外吸收光谱和荧光光谱考察五种凝胶因子的光物理性能。研究发现,在三氯甲烷中,五种萘酰亚胺分子都呈现单分子状态。在凝胶状态下,萘酰亚胺基团都因氢键的制约采用J型堆积模式。另外,萘酰亚胺类凝胶的光谱学性质与其分子的聚集状态和溶剂极性有关。通过上述研究结果表明,萘酰亚胺基团因其特殊的分子结构和优良的光化学物理性能,能够为功能性光物理材料的发展带来极大的促进作用。另外其作为凝胶因子也能为凝胶材料的发展提供重要的科学依据。
[Abstract]:Supramolecular chemistry is an emerging discipline that covers physical, chemical, biological, material and information characteristics that are more complex than the molecules themselves, blurring the boundaries between organic chemistry, biochemistry and materials for molecular devices. The development of material science has widened the road. First of all, naphthalimide derivatives have excellent photoelectric properties and can be used as functional groups to introduce gel factor molecular skeleton. The synergistic interaction between its large molecular coplanar properties and the unique hydrogen bonding properties of triazine groups is also of great significance in regulating the properties of gel materials. Therefore, five kinds of naphthalimide gel factors modified by triazine groups were designed and synthesized on the basis of comprehensive literature. The gel properties and gel properties were tested by the method of tube inversion, and the microcosmic morphology of the gel was observed. The spectroscopic properties of its solution and gel state were investigated by UV absorption and fluorescence spectra. The main contents were as follows: 1. Four triazine derivatives modified by different functional groups were synthesized by using cyanuric chloride as raw material. Five target products, NDI-1,NDI-2,NDI-3,NDI-4 and NDI-M., were synthesized by condensation of EDC and HOBT as amide bond and condensed with 1 ~ 4 ~ (4) O ~ (5) N _ (8) -naphthalene tetracarboxylic anhydride. The gel behavior of five kinds of gel factors in a series of organic solvents was measured by the method of tube inversion. The critical gel concentration and the critical gel temperature were also determined. The results show that all of the five gel factors can form heat-stable transparent gel in toluene, xylene and other solvents, and in ethyl acetate, butyl acetate and butyl methacrylate to form heat-stable opaque gel. The gel ability of NDI-4 is the strongest, that of NDI-M is the weakest, and that of NDI-2 is the strongest. The gel properties of NDI-M were the worst. NDI-3 showed a special phenomenon that the gel color changed from yellow to red with time in xylene. 3. SEM electron microscope was used to observe the micromorphology of the gel formed by five gel factors in a variety of solvents. The results show that the gel factors of naphthalimide can be used in different solvents to obtain two kinds of special gels with three dimensional network and knitted structure. Proper reduction of the length of alkyl chain has no obvious effect on the micromorphology of the gel. Changing the substituents on the triazine group has a certain influence on the micromorphology of the gel. 4. The photophysical properties of the five gel factors were investigated by UV and fluorescence spectra. It is found that all five naphthalimide molecules present a monolayer state in trichloromethane. In the gel state, the naphthalimide groups all adopt the J-type stacking mode because of the restriction of hydrogen bond. In addition, the spectroscopic properties of naphthalene imide gels are related to their molecular aggregation state and solvent polarity. The results show that the naphthalimide group can greatly promote the development of functional photophysical materials because of its special molecular structure and excellent photochemical physical properties. In addition, as a gel factor, it can also provide an important scientific basis for the development of gel materials.
【学位授予单位】：湖南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O648.17
，
本文编号：2354493
[Abstract]:Supramolecular chemistry is an emerging discipline that covers physical, chemical, biological, material and information characteristics that are more complex than the molecules themselves, blurring the boundaries between organic chemistry, biochemistry and materials for molecular devices. The development of material science has widened the road. First of all, naphthalimide derivatives have excellent photoelectric properties and can be used as functional groups to introduce gel factor molecular skeleton. The synergistic interaction between its large molecular coplanar properties and the unique hydrogen bonding properties of triazine groups is also of great significance in regulating the properties of gel materials. Therefore, five kinds of naphthalimide gel factors modified by triazine groups were designed and synthesized on the basis of comprehensive literature. The gel properties and gel properties were tested by the method of tube inversion, and the microcosmic morphology of the gel was observed. The spectroscopic properties of its solution and gel state were investigated by UV absorption and fluorescence spectra. The main contents were as follows: 1. Four triazine derivatives modified by different functional groups were synthesized by using cyanuric chloride as raw material. Five target products, NDI-1,NDI-2,NDI-3,NDI-4 and NDI-M., were synthesized by condensation of EDC and HOBT as amide bond and condensed with 1 ~ 4 ~ (4) O ~ (5) N _ (8) -naphthalene tetracarboxylic anhydride. The gel behavior of five kinds of gel factors in a series of organic solvents was measured by the method of tube inversion. The critical gel concentration and the critical gel temperature were also determined. The results show that all of the five gel factors can form heat-stable transparent gel in toluene, xylene and other solvents, and in ethyl acetate, butyl acetate and butyl methacrylate to form heat-stable opaque gel. The gel ability of NDI-4 is the strongest, that of NDI-M is the weakest, and that of NDI-2 is the strongest. The gel properties of NDI-M were the worst. NDI-3 showed a special phenomenon that the gel color changed from yellow to red with time in xylene. 3. SEM electron microscope was used to observe the micromorphology of the gel formed by five gel factors in a variety of solvents. The results show that the gel factors of naphthalimide can be used in different solvents to obtain two kinds of special gels with three dimensional network and knitted structure. Proper reduction of the length of alkyl chain has no obvious effect on the micromorphology of the gel. Changing the substituents on the triazine group has a certain influence on the micromorphology of the gel. 4. The photophysical properties of the five gel factors were investigated by UV and fluorescence spectra. It is found that all five naphthalimide molecules present a monolayer state in trichloromethane. In the gel state, the naphthalimide groups all adopt the J-type stacking mode because of the restriction of hydrogen bond. In addition, the spectroscopic properties of naphthalene imide gels are related to their molecular aggregation state and solvent polarity. The results show that the naphthalimide group can greatly promote the development of functional photophysical materials because of its special molecular structure and excellent photochemical physical properties. In addition, as a gel factor, it can also provide an important scientific basis for the development of gel materials.
【学位授予单位】：湖南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O648.17
，
本文编号：2354493
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