丙烯酰胺基嫁接钌催化剂的自振荡凝胶制备与性能

发布时间：2018-04-20 18:43

本文选题：自振荡凝胶 + BZ反应催化剂　；参考：《中国矿业大学》2016年硕士论文

【摘要】：智能软物质材料自振荡凝胶,将BZ振荡反应催化剂联吡啶钌通过共价键嫁接到凝胶高分子链上,表现出无外界刺激即可产生体积自发膨胀收缩的独特性质,在生物医学、组织工程以及仿生设计等领域有着广阔的应用前景。为了构建新型自振荡凝胶,本文从自振荡反应催化剂角度进行设计,合成了六种带有不同数目双键丙烯酰胺取代基团的系列联吡啶钌催化剂,并对系列催化剂以及其构建的自振荡凝胶的性能进行了测试与研究。基于催化剂多双键基团致活性交联的思想,设计双键取代基数目由单个到六个的三联吡啶钌催化剂。首先设计并合成了两种双键基团取代联吡啶单体:单丙烯酰胺基团联吡啶与双丙烯酰胺基团联吡啶。通过三种不同取代基数目联吡啶的组合排列,模板化合成了不同双键取代基团数目的三联吡啶钌。利用电化学循环伏安测定以及均相BZ振荡反应动力学监测对不同催化剂的氧化还原性能以及BZ催化性能进行分析。六种带有不同数目取代基的催化剂均可对BZ反应进行长时间催化,但取代基团数目为一、二、四的联吡啶钌催化剂的循环伏安曲线有明显的氧化还原峰,催化BZ反应振荡振幅较大,取代基团数目为三、五、六的催化剂在这两方面表现出较弱的性能。通过合成的六种催化剂构建系列自振荡凝胶体系,控制催化剂种类与含量进行凝胶制备。发现当双键交联基团不少于三个时催化剂具有活性交联功能,即具有活性催化以及交联凝胶网络的双重作用。然后对不同数目交联基团催化剂的凝胶及不同催化剂含量的凝胶氧化还原行为及交联度进行表征,发现凝胶内部交联密度较高的情况下氧化行为不明显。催化剂交联基团数目及活性交联催化剂含量可有效控制凝胶的高分子网络交联密度。最后对凝胶温敏性进行测试,发现了活性交联催化剂凝胶系列具有与传统接枝催化剂凝胶不同的温敏性现象:氧化态与还原态体积差异随温度升高而增加,在LCST后差异明显。同时发现:接枝单丙烯酰胺基团催化剂的自振荡凝胶在24 o C时表现出了30%的氧化态还原态间的体积溶胀比;随着温度升高,三丙烯酰胺基团催化剂交联自振荡凝胶表现出了两次氧化态还原态体积温敏性反转的独特现象。
[Abstract]:Intelligent soft matter material self-oscillating gel, BZ oscillatory reaction catalyst bipyridine ruthenium grafted onto the gel polymer chain through covalent bonds, showing the unique properties of volume spontaneous expansion contraction can be produced without external stimulation, in biomedicine, Tissue engineering and bionic design have broad application prospects. In order to construct a new self-oscillating gel, six series of bipyridine ruthenium catalysts with different number of double bond acrylamide substituents were synthesized from the view of self-oscillating reaction catalyst. The properties of a series of catalysts and their self-oscillating gels were tested and studied. Based on the idea of active crosslinking induced by multi-double bond groups, a tripyridine ruthenium catalyst with the number of double bond substituents from single to six was designed. At first, two kinds of double bond group substituted bipyridine mono-acrylamide group bipyridine and bisacrylamide group bipyridine were designed and synthesized. Through the combination arrangement of three different substituents, the templates were combined to form tripyridine ruthenium with different number of double bond substituents. The redox and BZ catalytic properties of different catalysts were analyzed by electrochemical cyclic voltammetry and kinetic monitoring of homogeneous BZ oscillations. Six kinds of catalysts with different number of substituents can catalyze the BZ reaction for a long time, but the cyclic voltammetry curves of bipyridine ruthenium catalysts with one, two and four substituents have obvious redox peaks. The oscillatory amplitude of the catalytic BZ reaction is large, and the catalyst with three, five and six substituents shows weak performance in these two aspects. A series of self-oscillating gel systems were constructed by six kinds of catalysts, and the kinds and contents of the catalysts were controlled to prepare the gel. It is found that the catalyst has the function of active crosslinking when the group of double bond crosslinking is not less than three, that is, the catalyst has the dual function of active catalysis and cross-linking gel network. The redox behavior and crosslinking degree of gels with different number of cross-linking group catalysts and different catalyst contents were characterized. It was found that the oxidation behavior was not obvious when the crosslinking density was high. The crosslinking density of gel can be effectively controlled by the number of cross-linking groups and the content of active crosslinking catalyst. Finally, the temperature sensitivity of the gels was tested. It was found that the gel series of active crosslinking catalysts had different temperature sensitivity from the traditional graft catalyst gels: the volume difference between oxidized and reduced state increased with the increase of temperature, and the difference was obvious after LCST. It is also found that the self-oscillating gel of the graft monoacrylamide group catalyst exhibits a volume swelling ratio of 30% between the redox states at 24 o C, and increases with the increase of temperature. The cross-linking self-oscillating gel of triacrylamide group catalyst shows the unique phenomenon of volume temperature inversion of two redox state.
【学位授予单位】：中国矿业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O643.36;O648.17

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