有机分子凝胶的制备、组装机理及掺杂功能化研究

发布时间：2018-06-19 07:25

本文选题：分子凝胶 + 自组装机理　；参考：《浙江工业大学》2017年硕士论文

【摘要】：本文通过分子设计合成了几种不同结构类型的凝胶因子,研究了分子结构与凝胶性能之间的关系,考察了溶剂、掺杂剂等条件对于凝胶自组装过程的影响,并赋予凝胶体系光致发光的性能。具体研究内容如下:(1)设计合成了两种以谷氨酸为主链,侧基分别接有苄氧羰基和磷酸二苯酯基的长链型凝胶因子Glu-CBZ和Glu-DPA。对其凝胶性能及自组装机理的研究表明,溶剂内部、凝胶因子内部以及溶剂与凝胶因子之间的相互作用力会对凝胶的热稳定性能和微观形貌产生影响;侧基中较多的苯环数目产生明显的位阻效应,使得Glu-DPA中自组装驱动力密度下降,导致其热稳定性能弱于Glu-CBZ。因此,Glu-CBZ的自组装方式为致密的六方堆积,而Glu-DPA则以自由空间更大的立方堆积模式堆积;而在流变测试的动态过程中,剪切作用提供了足够大的活化能来破坏凝胶因子之间的氢键和配位作用,使那些可以提供驱动的基团重新裸露,重排并重新相互作用形成密度更大的相互作用,因此导致Glu-DPA的机械强度和自修复性能优于Glu-CBZ。(2)在Glu-CBZ和Glu-DPA凝胶体系中掺入手性因子ZAO-CC,研究手性因子的加入对于自组装网络形貌的影响。结果表明AZO-CC的加入会诱导Glu-CBZ和Glu-DPA在甲苯中形成的自组装结构产生螺旋结构。(3)设计合成了含有可与金属元素产生配位络合作用的三联吡啶基团的胆固醇类凝胶因子CHO-TPY,研究掺杂金属离子对于凝胶性能的影响。结果表明金属离子的加入产生了金属配位作用,从而使得凝胶体系的流变学性能和自组装有序程度提高,同时由于凝胶网络的存在使得稀土金属离子能够均匀地分散在网络结构中。(4)研究了CHO-TPY/Eu、CHO-TPY/Tb两种凝胶的荧光性质。通过荧光光谱表征可知,两种金属杂化凝胶体系中确实出现了稀土金属离子特征的电子跃迁峰。同时通过调控两种稀土元素的比例,我们制备了一系列具备不同发光特性的配位凝胶。当Eu~(III):Tb~(III)=1.6:1时,可以得到发近白光的凝胶。这在固态光源领域存在潜在应用。
[Abstract]:In this paper, several kinds of gel factors of different structural types were synthesized by molecular design, the relationship between molecular structure and gel properties was studied, and the effects of solvent and dopant on the self-assembly process of gel were investigated. The photoluminescent properties of the gel system were also given. Two kinds of long chain gel factors Glu-CBZ and Glu-DPA-DPA with benzoxycarbonyl and diphenyl phosphate groups were designed and synthesized. The study on the gel properties and self-assembly mechanism showed that the thermal stability and micromorphology of the gel were influenced by the internal solvent, the internal gel factor and the interaction force between the solvent and the gel factor. The higher number of benzene rings in the side group has a significant steric resistance effect, which decreases the driving force density of self-assembly in Glu-DPA, resulting in its thermal stability weaker than that of Glu-CBZ. Therefore, the self-assembly mode of Glu-CBZ is a dense hexagonal packing, while Glu-DPA is stacked in the cubic packing mode with larger free space, while in the dynamic process of rheological testing, Shear provides a sufficiently large activation energy to break down the hydrogen bond and coordination between the gel factors, so that the groups that can provide the drive are exposed, rearranged, and re-interacted to form more dense interactions. Therefore, the mechanical strength and self-repair property of Glu-DPA are superior to those of Glu-CBZ. 2) the chiral factor ZAO-CCin Glu-CBZ and Glu-DPA gel system is added to study the effect of chiral factor on the morphology of self-assembled network. The results show that the addition of AZO-CC can induce the formation of self-assembly structure in toluene by Glu-CBZ and Glu-DPA. The effect of doped metal ions on the gel properties was studied by CHO-TPY. The results showed that the addition of metal ions resulted in metal coordination, which improved the rheological properties and self-assembly order of the gel system. At the same time, the fluorescence properties of CHO-TPY / Eu-CHO-TPY / TB gels were studied because of the existence of gel network, which made rare earth metal ions dispersed uniformly in the network structure. The fluorescence spectra show that the electronic transition peaks of rare earth metal ions do occur in the two metal hybrid gel systems. At the same time, a series of coordination gels with different luminescence properties were prepared by adjusting the ratio of two rare earth elements. The gel with near white light can be obtained when the EU is in the presence of 1: 1. This has potential applications in the field of solid state light sources.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O648.17

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