【作者】 杨利国；

【导师】 张万金； 危岩； 王策；

【作者基本信息】 吉林大学 ， 高分子化学与物理， 2010， 博士

【摘要】 本文中我们以联萘基团作为手性源,聚合得到了一种新型主链含手性联萘基团和吡啶基团的螺旋共聚物R-poly-6。通过NMR、元素分析、GPC、CD等测试方法对目标产物进行了表征,其中CD测试表明聚合物为螺旋聚合物。之后进一步研究了R-poly-6热处理前后对D(L)酒石酸、(CH3CN)2PdCl2以及R-poly-6对PdSO4、CuCl2的识别。通过分析CD谱图中不同峰的峰位移动和峰强度变化,发现R-poly-6热处理前后对D(L)酒石酸均没有识别作用;R-poly-6热处理前对(CH3CN)2PdCl2具有识别作用,热处理后基本没有识别作用;R-poly-6对CuCl2具有识别作用。通过Yamamoto型Ullman偶联反应得到两亲性咔唑聚合物4-poly-5,经循环制备柱分离得到不同分子量的聚合物,通过IR、NMR、GPC、MS等测试方法对聚合物的结构和聚合物的分子量进行了表征。利用UV-Vis和1H-NMR测试方法研究了分子量Mn=1.37×104的聚合物组分4-poly-5-a在不同比例的CHCl3和DMSO混合溶液中的构象变化。结果表明4-poly-5-a在CHCl3中以无规线团形式存在,当混合溶液中的DMSO比例增加到40-50%时,溶液中的4-poly-5-a转变为螺旋构象的聚合物。分别以左旋、右旋樟脑磺酸和盐酸为掺杂剂,以不同侧基的苯胺衍生物为反应单体,通过原位化学氧化聚合法合成了一系列带有侧基的掺杂态聚苯胺衍生物,并且通过氨水脱掺杂得到了带有对应侧基的EB态聚苯胺衍生物。通过GPC和IR测试,研究了处于不同取代位置的推电子侧基、吸电子侧基对上述聚苯胺衍生物分子量及分子结构的影响,并分析了产生相应影响的原因。通过UV-Vis和CD测试,研究了手性樟脑磺酸诱导合成的不同侧基的聚苯胺衍生物的手性构象,实验结果表明推电子侧基邻位取代的聚苯胺衍生物和吸电子侧基间位取代的聚苯胺衍生物可以被手性分子诱导,形成单一方向螺旋过量的复合物。本文中合成的三类聚合物,其主体都带有功能性基团,为进一步研究螺旋结构对于此类材料的各种功能的影响打下了一定的材料基础。更多还原

【Abstract】 Helical is the essential attribute of the material, which is formed by the main chain continuous rotation rules. As the unique properties of helical materials, they draw more and more attention from a growing number of scientists. In addition to gain the structural material, chemists are now more prone to introduce the functional groups to the helical materials. In recent years, people focus on such work including (1) electrical activity helical materials: chiral switching spiral materials driven by electricity, chiral conductive spiral material; (2) optical activity helical material: spiral photochromic materials, optical information storage spiral material, spiral fluorescent probe material, the new LCD and LED spiral materials; (3) irritating the corresponding helical materials and (4) molecules, ion recognition helical materials and so on.In this paper, we adopted three methods to design and synthesize three types of functional spiral material, including (1) direct synthesis of helix polymers containing the chiral component, (2) non-chiral polymer induced spiralization by different solvents and (3) synthesis of chiral dopant-induced spiral compounds and made some meaningful results.(1) Synthesis and properties study of a polypyridine with binaphthyl moietie In this paper we synthesized a new chiral R-poly-6 polymer having pyridine and binaphthyl moietiefor by the Suzuki cross-coupling reaction, which was characterized with EA, IR, 1H-NMR and 13C-NMR spectroscopies. The CD and UV-Vis absorption spectra of the R-poly-6 result show it have the visible positive and negative Cotton effect in the 260-500 nm, which proof the R-poly-6 is a helical polymer.We attributed to each peak, and further studied the R-poly-6’s indentification before and after annealing treatment on D(L) tartaric acid and (CH3CN)2PdCl2 by studying different peak peak movement and size changes of peak intensity in the CD spectra as well as R-poly-6’s recognition on PdSO4 and CuCl2. In the third experiment, we found R-poly-6 have different effect capabilities with two kinds of ions, which indicates this polymer can be used as a potential chiral ion probe.(2) Synthesis of amphiphilic poly-carbazole and the study of the conformation spiralization induced by external environmental changesIn this paper we have synthesized the amphiphilic poly-carbazole 4-Poly-5 used the excellent optical properties hydrophobic carbazole as main part and the hydrophilic TEG as the side chain by Yamamoto-type Ullman polycondensation reaction and isolated different molecular weight of polymer used cycle of preparative column, whose structure and molecular weight were characterized by IR, NMR, GPC and MS tests. And then, we studied the conformational change of 4-Poly-5-a which the Number average molecular weight is 1.37×104 in the different ratios of mixed solvents of CHCl3 and DMSO.Studies have shown that polymer in the non-polar solvent CHCl3 showed random coil structure and the polymer conformation gradually turned into helical structure from random coil structure when DMSO/CHCl3 V/V is 40-50%. Such structural change is due to the hydrophobic force changes between the polymer and solvent.(3) Acid-induced synthesis of the different side aniline derivatives by chiral camphor sulfonic A series of aniline-based compounds with a different side were synthesizd using in-situ synthesis method with L-and D camphor sulfonic acid and hydrochloric acid as dopants We researched the electron-pushing side, electron-withdrawing hydrophilic side and electron-withdrawing hydrophobic side’s effect on the molecular weight and structure of the compounds, ammonia dedoped compounds and second doped compounds by GPC and IR experments.The GPC results show the electron-pushing side aniline derivatives have the larger molecular weight and the electron-withdrawing hydrophilic side and electron-withdrawing hydrophobic side aniline derivatives have the smaller molecular weight. In addition, IR results show that the action between the dopant and polymer is also stronger in the electron-pushing side aniline derivatives polymers.(4) Chiral helical conformation study of the different side aniline derivatives synthesizd by chiral camphor sulfonic acid-inducedHelical conductive polyaniline and its derivatives have many unique excellent properties, in addition to electrical properties of polyaniline such as catalytic properties, electromagnetic shielding, electrochromic color and absorbing performance, they also have optical activity, which make them have the potential applications on the chiral recognition, membrane separation technology, bio-sensors, electrochemical polymerization and other fields. In this paper, we studied the chiral helical conformation of the different side aniline derivatives which were synthesized through chiral camphor sulfonic acid-induced by UV-Vis and CD experiments. The experiment results show that the electron-pushing ortho-substituent aniline derivatives and electron-withdrawing meta-substituent aniline derivatives can be induced the spiral of the main compound.Through the work of this paper, we have prepared three types helical materials with the main functional groups, which lay a certain functional materials foundation for the further study on the functional properties effect of the helical structure for such materials.更多还原