两性离子液体的自组装结构及其功能化研究
发布时间：2018-08-08 10:54
【摘要】：经过多年的发展,离子液体不再被仅仅看作是"绿色溶剂"。研究人员开始针对特定的应用,有目的性地设计离子液体的阴、阳离子结构。一系列新型离子液体被设计合成出来,包括手性离子液体、磁性离子液体、氨基酸离子液体、金属配位离子液体以及具有氧化还原活性的离子液体等,极大地拓展了离子液体的应用范围。同时,为了改善传统离子液体的缺陷,多种新型的离子液体衍生结构也引起了研究人员的广泛关注,比如两性离子液体、聚离子液体等。关于离子液体有序分子聚集体的研究经过近十年的快速发展,研究方向也不再仅仅局限于发现新的聚集体形貌,而是更加关注如何将离子液体独特的物理化学性质与有序分子聚集体的结构、尺寸效应相结合。一方面,基于离子液体的可设计性,将具有不同功能基团的离子液体引入到分子有序聚集体中,是实现有序分子聚集体功能化的有效途径。另一方面,得益于有序聚集体的结构效应和尺寸效应,也进一步拓展了离子液体的应用。本论文以离子液体的可设计性为基础,设计合成了多种具有特定功能的两性离子液体以及聚离子液体,系统研究了离子液体结构变化对其聚集体结构和功能的影响。开展了以下四部分的工作:1.锂离子传导离子液体液晶的构筑。采用两性离子液体结构,通过咪唑两性离子(3-(1-Dodecyl-3-imidazolio)propanesulfonate,C12IPS)与锂盐(LiTFSI)"中和"的方法,合成了含有锂离子的室温离子液体[C12IPS][LiTFSI]。C12IPS与LiTFSI室温时均为固体粉末,等摩尔混合后,根据软硬酸碱理论软亲软、硬亲硬的原则,两性离子中的咪唑阳离子会优先与TFSI-阴离子相互作用,从而使体系的晶格能显著降低,形成室温离子液体。由于两性离子整体呈电中性,其在电场中并不迁移,因而可以实现锂离子的选择性传输。由于C12IPS具有典型的双亲分子结构,随着[C12IPS][LiTFSI]/H20体系中离子液体浓度的不断增大,观察到了由蠕虫状胶束到六角液晶相、Ia3d双连续立方液晶相以及层状液晶相的转变。采用POM、SAXS、流变等表征方法系统研究温度和浓度对这种离子液体液晶相行为的影响,并以此为基础探究了液晶微观结构对其电导率和传导机理的影响。结果表明,液晶有序微观结构的引入显著提高了锂离子的传输效率,所有液晶样品的电导率都呈现出明显的结构依赖性。其中,Ia3d双连续立方液晶由于具有三维连续离子通道,与其他液晶相态相比电导率更高,离子传导过程的表观活化能更低。2.质子传导液晶体系的构筑。在上一部分工作的基础上,进一步探索了两性离子液体结构变化对其聚集体形貌和功能的调控作用,构筑了质子传导液晶体系。合成了一系列不同烷基链长的咪唑两性离子(CnIPS,n=12,14,16),并通过与不同取代基结构的磺酸(CH3SO3H,C6H5SO3H,CF3SO3H)"中和"的方法合成了一系列含有质子的离子液体,探究了抗衡离子结构变化和烷基链长对离子液体的物理化学性质以及聚集行为的影响。其中[C12IpS][CH3SO3H]呈现出最丰富的相行为。这种双亲性离子液体可以在水溶液中自组装形成六角相和Pm3n立方相结构的质子传导液晶。采用POM和SAXS系统研究了这种离子液体参与构筑的液晶体系的相行为并计算了相关机构参数,并以此为基础探究了液晶微观结构对其电导率和传导机理的影响。液晶有序微观结构的引入显著提高了其电导率,并促成了质子传导由扩散机理向跳跃机理的转变,同时也观察到了基于液晶相变过程的温度响应性质子传导行为。3.聚离子液体微观有序阴离子传导膜的构筑。设计合成了一系列不同烷基链长的可聚合咪唑离子液体(3-n-alkyl-1-vinylimidazoliumbromide,CnVIMBr)。借助于这种离子液体的双亲性,构筑了可聚合的六角液晶相和层状液晶相,通过液晶原位光聚合的方法制备了自支持的聚离子液体膜。聚离子液体膜中液晶微观结构的保留通过SAXS、POM和SEM表征得到了确认。虽然在C12VIMBr/H20的二元体系中只观察到了六角和层状液晶相,我们在尝试过多种不同种类的添加剂之后,发现适量对二甲苯的加入可以在C12VIMBr/H20体系中诱导产生可聚合的Im3m双连续立方液晶相,从而首次成功制备了具有双连续立方液晶相结构的阴离子传导膜。对保留有六角、层状和立方液晶微观结构的阴离子传导膜的电导率、溶胀率和碱稳定性等测试表明,液晶结构的引入有效改善了其综合性能,与没有液晶结构的对照组相比,具有液晶相结构的阴离子传导膜在实现高电导率的同时保持了极低的溶胀率。特别是具有Im3m双连续立方液晶微观结构的阴离子传导膜,借助于三维连续的氢键网络促成了其氢氧根离子传导由扩散机理向跳跃机理的转变。4.两性离子软模板制备贵金属纳米材料。受两性离子液体结构特点的启发,通过两性离子与贵金属前驱体离子之间的静电相互作用,构筑了抗衡离子为贵金属前驱体离子的有序分子聚集体。通过分步还原法控制反应速率,实现了以有序分子聚集体为模板的软模板法制备贵金属纳米材料。在第一节中,合成了一种分子尾链末端带有羟基的咪唑两性离子,借助于羟基之间的氢键作用,在不加任何添加剂的情况下,这种两性离子与等摩尔的HAuC14在水中可以自组装形成多室囊泡。由于羟基具有一定的还原性,在体系中观察到了以囊泡双分子层为模板的金纳米片的自还原过程,并进一步通过两步还原法实现了囊泡到球状金纳米颗粒的形态复制。在第二节中,通过调节两性离子中的阳离子结构,成功得到了抗衡离子为AuCl4-,PtCl62-PdCl42-的蠕虫状胶束体系。并以蠕虫胶束为模板得到了形貌规整的金、铂、钯及其合金的纳米线网络结构。证明了双亲分子有序聚集体作为软模板结构易于调控和普适性的特点。
[Abstract]:After years of development, ionic liquids are no longer regarded as only "green solvents". Researchers have begun to purposefully design the anion and cation structure of ionic liquids for specific applications. A series of new ionic liquids have been designed and synthesized, including chiral ionic liquids, magnetic ionic liquids, amino acid ionic liquids and metal coordination. Subliquid and ionic liquid with redox activity have greatly expanded the application range of ionic liquids. At the same time, in order to improve the defects of traditional ionic liquids, a variety of new ionic liquid derivatization structures have attracted the attention of researchers, such as amphoteric liquid, polyionic liquids, etc.. On ionic liquids order. After nearly ten years of rapid development of molecular aggregation, the research direction is not only limited to the discovery of new aggregates, but more concerned with how to combine the unique physical and chemical properties of ionic liquids with the structure and size effect of ordered molecules. The ionic liquids of the same functional groups are introduced into the molecular ordered aggregates, which are an effective way to realize the functionalization of ordered molecules. On the other hand, the application of ionic liquids is further expanded thanks to the structural and dimensional effects of ordered aggregates. This paper is based on the design of ionic liquids and has been designed and synthesized. The effects of the structural changes of ionic liquids on the structure and function of the polymer were systematically investigated. The following four parts were carried out: 1. the construction of liquid crystal of lithium ion conduction ion liquid liquid crystal, amphoteric ionic liquid structure, and imidazole amphoteric ions (3- (1-Dodecyl-3-imidaz) Olio) Propanesulfonate, C12IPS) and the method of "Neutralization" with lithium salt (LiTFSI), synthesis of a room temperature ionic liquid containing lithium ion, [C12IPS][LiTFSI].C12IPS and LiTFSI at room temperature, are solid powders. After isormole mixing, the imidazole cations in the amphoteric ions will give priority to TFSI- detachment according to the softness and hardness principle of the theory of soft and hard acid and alkali. The lattice energy of the system is significantly reduced and the room temperature ionic liquid is formed. Because the amphoteric ion is neutral in the whole, it does not migrate in the electric field, and thus the selective transfer of lithium ion can be realized. Since C12IPS has a typical parent molecular structure, the ionic liquid concentration in the C12IPS][LiTFSI]/H20 system does not. The transition from vermicular micelle to six angle liquid crystal phase, Ia3d double continuous cubic liquid crystal phase and lamellar liquid crystal phase were observed. The influence of temperature and concentration on the liquid crystal phase behavior of this ionic liquid was systematically studied by means of POM, SAXS, rheology and so on. The results show that the introduction of the ordered microstructures of the liquid crystal significantly improves the transmission efficiency of the lithium ion, and the conductivity of all the liquid crystal samples shows a distinct structural dependence. In this case, the Ia3d double continuous cubic liquid crystal has a higher conductivity compared with the other liquid crystalline phase because of the three dimensional continuous ion channel, and the ion conduction process is higher than that of other liquid crystalline phase states. The structure of the.2. proton conducting liquid crystal system with apparent activation energy is lower. On the basis of the previous work, the regulation of the structure change of the amphoteric ionic liquid to its aggregate morphology and function is further explored. The proton conducting liquid crystal system is constructed. A series of CnIPS, n=12,14,16, which are different alkyl chain long, are synthesized. A series of ionic liquids containing protons were synthesized by the neutralization method of sulfonic acid (CH3SO3H, C6H5SO3H, CF3SO3H) with different substituent groups. The effects of the changes in the structure and the length of the alkyl chain on the physical and chemical properties of the ionic liquids and the aggregation behavior of the ionic liquids were investigated. Among them, [C12IpS][CH3SO3H] showed the most abundant phase behavior. A two parent ionic liquid can be self assembled in a aqueous solution to form a proton conducting liquid crystal with six angular phases and a Pm3n cubic phase structure. The phase behavior of the liquid crystal system constructed by this ionic liquid is studied by POM and SAXS systems, and the parameters of the related mechanism are calculated. The conductivity of the liquid crystal ordered microstructures was greatly improved, and the transformation of proton conduction from the diffusion mechanism to the jumping mechanism was promoted. At the same time, the structure of the micro ordered anion conduction membrane of the.3. polyionic liquid based on the temperature responsive proton conduction behavior of the liquid crystal phase transition process was also observed. A series of polymerizable imidazole ionic liquids (3-n-alkyl-1-vinylimidazoliumbromide, CnVIMBr) with different alkyl chain lengths were used to construct a polymerizable six angle liquid crystal phase and lamellar liquid crystal phase. A self supported polyionic liquid film was prepared by the method of liquid crystal in situ polymerization. Liquid membrane in polyionic liquid membrane was prepared. The retention of crystal microstructure was confirmed by the characterization of SAXS, POM and SEM. Although only six angles and lamellar liquid crystals were observed in the two element system of C12VIMBr/H20, we found that a proper amount of para xylene could be induced to produce polymerizable Im3m double connections in the C12VIMBr/H20 system after a variety of different kinds of additives were tried. The anion conducting membrane with a double continuous cubic liquid crystal phase structure was successfully prepared for the first time, and the conductivity, swelling rate and alkali stability of the anion conducting membrane with six angle, layered and cubic liquid crystal microstructures were tested. The results showed that the introduction of liquid crystal structure improved its comprehensive performance and no liquid crystal. Compared with the structure of the control group, the anion conduction membrane with the liquid crystal phase structure keeps a very low swelling rate while realizing high conductivity. Especially, the anion conduction membrane with the Im3m double continuous cubic liquid crystal microstructure has contributed to the mechanism of the hydrogen oxygen radical ion conduction from the diffusion mechanism to the hopping mechanism by the three-dimensional continuous hydrogen bond network. The.4. amphoteric ion soft template is used to prepare the noble metal nanomaterials. Inspired by the structure characteristics of the amphoteric ionic liquid, the ordered molecular aggregates are constructed by the electrostatic interaction between the amphoteric ions and the noble metal precursor ions. The reaction rate is controlled by the stepwise reduction method. In the first section, a kind of imidazole amphoteric ion with hydroxyl group was synthesized in the first section. With the aid of hydrogen bonding between hydroxyl groups, the amphoteric ions and isomole HAuC14 can be self assembled in water without any additives. As the hydroxyl group has a certain reducibility, the self reduction process of the gold nanoscale with the bimolecular layer of the vesicle is observed in the system, and the form of the spherical gold nanoparticles is replicated by the two step reduction method. In the second section, the cationic structure in the amphoteric ion is successfully regulated. The worm like micelle system with a counterion of AuCl4- and PtCl62-PdCl42- was obtained. The morphology of gold, platinum, palladium and its alloy nanowires was obtained by using worm micelle as a template. It was proved that the ordered aggregation of parent molecules was easy to regulate and universality as a soft template.
【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O645.1
，
本文编号：2171575
[Abstract]:After years of development, ionic liquids are no longer regarded as only "green solvents". Researchers have begun to purposefully design the anion and cation structure of ionic liquids for specific applications. A series of new ionic liquids have been designed and synthesized, including chiral ionic liquids, magnetic ionic liquids, amino acid ionic liquids and metal coordination. Subliquid and ionic liquid with redox activity have greatly expanded the application range of ionic liquids. At the same time, in order to improve the defects of traditional ionic liquids, a variety of new ionic liquid derivatization structures have attracted the attention of researchers, such as amphoteric liquid, polyionic liquids, etc.. On ionic liquids order. After nearly ten years of rapid development of molecular aggregation, the research direction is not only limited to the discovery of new aggregates, but more concerned with how to combine the unique physical and chemical properties of ionic liquids with the structure and size effect of ordered molecules. The ionic liquids of the same functional groups are introduced into the molecular ordered aggregates, which are an effective way to realize the functionalization of ordered molecules. On the other hand, the application of ionic liquids is further expanded thanks to the structural and dimensional effects of ordered aggregates. This paper is based on the design of ionic liquids and has been designed and synthesized. The effects of the structural changes of ionic liquids on the structure and function of the polymer were systematically investigated. The following four parts were carried out: 1. the construction of liquid crystal of lithium ion conduction ion liquid liquid crystal, amphoteric ionic liquid structure, and imidazole amphoteric ions (3- (1-Dodecyl-3-imidaz) Olio) Propanesulfonate, C12IPS) and the method of "Neutralization" with lithium salt (LiTFSI), synthesis of a room temperature ionic liquid containing lithium ion, [C12IPS][LiTFSI].C12IPS and LiTFSI at room temperature, are solid powders. After isormole mixing, the imidazole cations in the amphoteric ions will give priority to TFSI- detachment according to the softness and hardness principle of the theory of soft and hard acid and alkali. The lattice energy of the system is significantly reduced and the room temperature ionic liquid is formed. Because the amphoteric ion is neutral in the whole, it does not migrate in the electric field, and thus the selective transfer of lithium ion can be realized. Since C12IPS has a typical parent molecular structure, the ionic liquid concentration in the C12IPS][LiTFSI]/H20 system does not. The transition from vermicular micelle to six angle liquid crystal phase, Ia3d double continuous cubic liquid crystal phase and lamellar liquid crystal phase were observed. The influence of temperature and concentration on the liquid crystal phase behavior of this ionic liquid was systematically studied by means of POM, SAXS, rheology and so on. The results show that the introduction of the ordered microstructures of the liquid crystal significantly improves the transmission efficiency of the lithium ion, and the conductivity of all the liquid crystal samples shows a distinct structural dependence. In this case, the Ia3d double continuous cubic liquid crystal has a higher conductivity compared with the other liquid crystalline phase because of the three dimensional continuous ion channel, and the ion conduction process is higher than that of other liquid crystalline phase states. The structure of the.2. proton conducting liquid crystal system with apparent activation energy is lower. On the basis of the previous work, the regulation of the structure change of the amphoteric ionic liquid to its aggregate morphology and function is further explored. The proton conducting liquid crystal system is constructed. A series of CnIPS, n=12,14,16, which are different alkyl chain long, are synthesized. A series of ionic liquids containing protons were synthesized by the neutralization method of sulfonic acid (CH3SO3H, C6H5SO3H, CF3SO3H) with different substituent groups. The effects of the changes in the structure and the length of the alkyl chain on the physical and chemical properties of the ionic liquids and the aggregation behavior of the ionic liquids were investigated. Among them, [C12IpS][CH3SO3H] showed the most abundant phase behavior. A two parent ionic liquid can be self assembled in a aqueous solution to form a proton conducting liquid crystal with six angular phases and a Pm3n cubic phase structure. The phase behavior of the liquid crystal system constructed by this ionic liquid is studied by POM and SAXS systems, and the parameters of the related mechanism are calculated. The conductivity of the liquid crystal ordered microstructures was greatly improved, and the transformation of proton conduction from the diffusion mechanism to the jumping mechanism was promoted. At the same time, the structure of the micro ordered anion conduction membrane of the.3. polyionic liquid based on the temperature responsive proton conduction behavior of the liquid crystal phase transition process was also observed. A series of polymerizable imidazole ionic liquids (3-n-alkyl-1-vinylimidazoliumbromide, CnVIMBr) with different alkyl chain lengths were used to construct a polymerizable six angle liquid crystal phase and lamellar liquid crystal phase. A self supported polyionic liquid film was prepared by the method of liquid crystal in situ polymerization. Liquid membrane in polyionic liquid membrane was prepared. The retention of crystal microstructure was confirmed by the characterization of SAXS, POM and SEM. Although only six angles and lamellar liquid crystals were observed in the two element system of C12VIMBr/H20, we found that a proper amount of para xylene could be induced to produce polymerizable Im3m double connections in the C12VIMBr/H20 system after a variety of different kinds of additives were tried. The anion conducting membrane with a double continuous cubic liquid crystal phase structure was successfully prepared for the first time, and the conductivity, swelling rate and alkali stability of the anion conducting membrane with six angle, layered and cubic liquid crystal microstructures were tested. The results showed that the introduction of liquid crystal structure improved its comprehensive performance and no liquid crystal. Compared with the structure of the control group, the anion conduction membrane with the liquid crystal phase structure keeps a very low swelling rate while realizing high conductivity. Especially, the anion conduction membrane with the Im3m double continuous cubic liquid crystal microstructure has contributed to the mechanism of the hydrogen oxygen radical ion conduction from the diffusion mechanism to the hopping mechanism by the three-dimensional continuous hydrogen bond network. The.4. amphoteric ion soft template is used to prepare the noble metal nanomaterials. Inspired by the structure characteristics of the amphoteric ionic liquid, the ordered molecular aggregates are constructed by the electrostatic interaction between the amphoteric ions and the noble metal precursor ions. The reaction rate is controlled by the stepwise reduction method. In the first section, a kind of imidazole amphoteric ion with hydroxyl group was synthesized in the first section. With the aid of hydrogen bonding between hydroxyl groups, the amphoteric ions and isomole HAuC14 can be self assembled in water without any additives. As the hydroxyl group has a certain reducibility, the self reduction process of the gold nanoscale with the bimolecular layer of the vesicle is observed in the system, and the form of the spherical gold nanoparticles is replicated by the two step reduction method. In the second section, the cationic structure in the amphoteric ion is successfully regulated. The worm like micelle system with a counterion of AuCl4- and PtCl62-PdCl42- was obtained. The morphology of gold, platinum, palladium and its alloy nanowires was obtained by using worm micelle as a template. It was proved that the ordered aggregation of parent molecules was easy to regulate and universality as a soft template.
【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O645.1
，
本文编号：2171575
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