本文關鍵詞：基于偶氮吡啶衍生物的超分子功能材料的研究　出處：《北京科技大學》2015年博士論文　論文類型：學位論文

  更多相關文章： 偶氮吡啶衍生物 超分子 光熱效應 自組裝纖維 鹵鍵液晶

【摘要】：近年來,發(fā)展新材料和新器件的重要手段之一就是通過分子的功能化自組裝形成規(guī)整有序的超分子結構。偶氮吡啶衍生物一方面含有光活性的偶氮基團,分子中的-N=N-雙鍵可以在光和熱的作用下進行異構體的轉變,同時又含有能夠形成氫鍵、鹵鍵等自組裝的吡啶基團,為我們設計材料提供了無限的可能。此外,當紫外光達到一定強度時,還表現(xiàn)出光熱效應。因此,受到科學工作者的廣泛關注。 雖然偶氮吡啶衍生物有著顯著的優(yōu)點,然而目前對于偶氮吡啶衍生物的研究僅限于光響應性液晶和超分子纖維兩個領域。本論文著眼于偶氮吡啶衍生物這類材料,結合偶氮吡啶衍生物的光活性和自組裝兩者的特點,用以開發(fā)和探索偶氮吡啶衍生物新的功能和應用,其研究內容如下： (1)首次研究了偶氮吡啶衍生物的光熱效應,發(fā)現(xiàn)偶氮吡啶衍生物相比于具有類似分子結構的偶氮苯衍生物具有較高的光熱轉換效率,同時研究了樣品單位面積的質量和紫外光的強度對光熱轉換效率的影響。在此基礎上,我們提出了基于偶氮吡啶衍生物光熱效應方面的兩個潛在應用,其一是應用于光控智能膠黏劑,它在兩個玻璃基板之間的剪切強度達到0.661MPa。其二是制備了具有光響應性的聚合物復合雙層膜,在紫外光照之下,由于光熱能量轉換引起的體積變化使其出現(xiàn)光致彎曲的現(xiàn)象,從而有望在光機械領域有所應用。 (2)設計合成了一系列具有不同末端烷基鏈長度的偶氮吡啶衍生物,將其與鹵素分子反應,首次制備出具有較高穩(wěn)定性的超分子溴鍵液晶,證明了本體系中的N…Br相互作用足以組裝成有序介晶相,同時制備了具有可逆光致相轉變行為的碘鍵液晶。此外,研究了末端烷基鏈對液晶行為的影響,末端取代基較短時不利于形成液晶相,隨著末端烷基鏈長度的增加,碘鍵化合物由近晶相液晶轉變?yōu)橄蛄邢嘁壕?而本體系中的溴鍵化合物均為近晶相液晶。 (3)利用偶氮吡啶衍生物的自組裝特性,研究了多種無機酸和有機溶劑對偶氮吡啶衍生物超分子自組裝行為的影響,發(fā)現(xiàn)其在不同的環(huán)境下具有不同的形貌,并且揭示了酸度離解常數(shù)(pKa)對自組裝纖維的形成有重要的影響。研究表明,有機溶劑也影響著纖維形成的過程,其中,在丙酮溶劑中的自組裝纖維材料能夠凝膠化,同時考察了末端烷基取代基對偶氮吡啶衍生物形成凝膠能力的影響,當偶氮吡啶衍生物的濃度增加為60mg/mL時,末端烷基取代基大于12的偶氮毗啶衍生物均可以使丙酮溶劑凝膠化,并且隨著末端烷基取代基增加,凝膠化能力增強,同時,偶氮吡啶衍生物作為凝膠因子的濃度越高,越容易形成凝膠。此外,結合TEM和XRD等測試手段,我們提出了超分子纖維的形成機理,即肉眼可見的微米纖維是由納米級別的纖維組成的。
[Abstract]:In recent years, one of the important means for the development of new materials and devices is through functional molecular and supramolecular structure ordered. Azo azo pyridine derivatives containing a photoactive, molecule of -N=N- can be transformed into double bond isomers in light and heat effect, but also can contain the formation of hydrogen bonds, such as halogen bond self-assembly of pyridine group, we design material provides unlimited possibilities. In addition, when the light reaches a certain intensity, but also show the photothermal effect. Therefore, attention of scientific workers.
Although azo pyridine derivatives have significant advantages, however, for the study of azo pyridine derivatives are only limited to the two areas of the liquid crystal light response and supramolecular fibers. This paper focuses on azo pyridine derivatives of this kind of material, combined with azo pyridine derivatives of optically active and self-assembly of the characteristics of both in function and application development and exploration azo pyridine derivatives, its research contents are as follows:
(1) for the first time on the thermal effect of azo pyridine derivatives, discovered azo pyridine derivatives with azobenzene derivatives compared to photothermal similar molecular structure has high conversion efficiency, and on the unit area of the sample quality and intensity of ultraviolet light on the photothermal conversion efficiency. On this basis, we propose two potential applications azo pyridine derivatives based on the photothermal effect, one is applied to intelligent light controlled adhesive, it between the two glass substrate shear strength reached 0.661MPa. the second is prepared with light responsive polymer composite bilayer membrane, under UV light, volume changes due to heat energy conversion caused by the emergence of light induced the bending phenomenon, which is expected to be used in optical mechanical field.
(2) with a series of different length of the terminal alkyl chain azo pyridine derivatives were designed and synthesized, and the halogen molecular reaction, prepared for the first time the supramolecular bromine bonds with high stability crystal, proved that the system of N... The interaction of Br to assemble into ordered mesophase, while preparing a light induced phase transition behavior of liquid crystal iodine bond. In addition, effects of the terminal alkyl chain on the liquid crystal behavior of the terminal substituent is short is not conducive to the formation of liquid crystal phase, with the increase of the length of the terminal alkyl chain transformation of iodine compounds the smectic liquid crystal nematic liquid crystal, and bromine bond compounds in this system were smectic liquid crystals.
(3) the self-assembly properties of azo pyridine derivatives, studied a variety of inorganic acids and organic solvent effect on azo pyridine derivatives supramolecular self-assembly behavior, found with different morphologies under different environment, and reveals the acidity dissociation constant (pKa) has an important influence on the formation of self-assembled fibers. Show that the organic solvent also affects the process of fiber formation, self-assembly fiber material to gelation in acetone, and investigate the influence of alkyl substituents at the end of gel forming ability of azo pyridine derivatives and azo pyridine derivatives increased when the concentration is 60mg/mL, the end of alkyl pyridine derivatives than azo 12 both can make the acetone gel, and with the end of alkyl substituents increased, the gelation ability, at the same time, azo pyridine derivatives as gelator concentration The higher the degree, the easier the formation of gel. In addition, the combination of TEM and XRD test methods, we proposed the formation mechanism of supramolecular fibers, the visible micron fiber is composed of nanoscale fibers.

【學位授予單位】：北京科技大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：O626.32;TB34

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本文編號：1387675