双亲光电活性支化聚合物改性碳纳米管及其在电化学传感器中的应用研究

发布时间：2018-05-17 15:38

本文选题：支化聚合物 + 光电活性聚合物　；参考：《江南大学》2015年硕士论文

【摘要】：由于碳纳米管(CNT)相互之间强的范德瓦耳斯力使得其极易缠结团聚,不溶于任何溶剂或聚合物,极大的限制了CNT的应用。聚合物表面改性CNT是一种非常有效的解决CNT分散性问题的方式,然而如何在不破坏CNT固有性能的前提下获得分散性好的CNT分散体对于研究高导电率复合材料等具有重要意义。在本论文中,合成了一种双亲光电活性支化聚合物用于胶束封装多壁碳纳米管(MWCNT),聚合物分子链的共轭结构使其极易吸附在MWCNT表面从而破坏MWCNT之间的范德瓦耳斯力获得均匀稳定的MWCNT分散体,聚合物分子链上的香豆素光敏基元在紫外光照条件下发生光二聚进一步提高了MWCNT分散体的稳定性;聚合物分子链上的电活性咔唑基元可通过电化学聚合形成网状交联结构,有效改善了MWCNT复合材料的电子传输性能,并将该复合材料制备成电化学传感器,研究了其对多巴胺和扑热息痛的检测效果。具体的过程分为以下几个部分:(1)以链转移剂4-乙烯基苄硫醇(VBT)为链转移剂,疏水单体7-(4-乙烯基苄氧基)-4-甲基香豆素(VMc)和9-(4-乙烯基苄基)-9H-咔唑(VCz)分别为光敏和电活性单体,马来酸酐(MA)为亲水单体,采用链转移自由基聚合的方法,通过简单易操作的一锅法成功合成了双亲光电活性支化聚合物聚(9-(4-乙烯基苄基)-9H-咔唑/7-(4-乙烯基苄氧基)-4-甲基香豆素-alt-马来酸酐)(BP(VCz/VMc-alt-MA),BPVCM)。通过改变VBT的含量和聚合反应时间制得一系列不同支化度的聚合物,采用1H NMR、GPC/RI/MALLS/DV三联用等表征手段以及与线型聚合物特性粘度、玻璃化温度和支化因子等的比较,证明了支化聚合物的合成成功。(2)在(1)的基础上,支化聚合物BPVCM在选择性溶剂DMF/H2O中能够在多壁碳纳米管(MWCNT)表面自组装形成均匀的一个个连续球状胶束从而有效的分散MWCNT获得稳定的水溶性BPVCM/MWCNT复合分散液;此外,UV灯光照能够引发聚合物链中的光敏基团发生光二聚作用,形成的交联网状结构能够稳定胶束从而进一步提高MWCNT分散液的稳定性。(3)将(2)制备的BPVCM/MWCNT纳米复合材料用于改性玻碳电极(GCE)制备成电化学传感器,发现该传感器对多巴胺(DA)和扑热息痛(PAT)显现了优异的选择性和电催化活性以及对抗坏血酸(AA)的抗干扰性。通过电化学聚合方法制备的e-BPVCM/MWCNT/GCE电化学传感器在对实物药品制剂中的DA和PAT检测方面具有很好的检测效果,在临床诊断方面具有潜在的应用价值。
[Abstract]:Due to the strong Van der Waals force between carbon nanotubes (CNTs), it is easy to be entangled and agglomerated, insoluble in any solvent or polymer, which greatly limits the application of CNT. Polymer surface modification of CNT is a very effective way to solve the dispersion problem of CNT. However, how to obtain good dispersible CNT dispersion without destroying the inherent properties of CNT is of great significance to the study of high conductivity composites. In this paper, A amphiphilic photoactive branched polymer was synthesized for micellar encapsulation of MWCNT. The conjugated structure of polymer chains makes it easy to adsorb on the surface of MWCNT and destroy van der Waals force between MWCNT to obtain uniform and stable MWCNT dispersion. The photodimerization of coumarin Guang Min units on polymer chains further enhanced the stability of MWCNT dispersions, and the electroactive carbazole units on polymer chains formed network crosslinked structures by electrochemical polymerization. The electronic transport properties of MWCNT composites were improved effectively, and the electrochemical sensor was prepared. The detection effect of dopamine and paracetamol was studied. The specific process can be divided into the following parts: (1) the hydrophobic monomer 7-4 vinylbenzoxy-4-methylcoumarin (VMcC) and 9-4 vinylbenzylidene-9H-carbazole (VCzV) were Guang Min and electroactive monomer, respectively, using 4-vinylbenzylmercaptan (4-vinylbenzyl mercaptan) as the chain transfer agent, the hydrophobic monomer 7-4 vinylbenzylidene-4-methylcoumarin (VCZ) as the chain transfer agent. Maleic anhydride (MAA) is a hydrophilic monomer. A novel amphiphilic photoactive branched polymer, poly (9-butadiene-4-vinylbenzyl) -9H-carbazole-4-vinylbenzoxy-4-methylcoumarin, 4-methylcoumarin and maleic anhydride, was successfully synthesized by a simple and easy one-pot method. The V Mc-alt-MABPVCMs of the amphiphilic active branched polymer are V Mc-alt-MAPVCMs. A series of polymers with different branching degrees were prepared by changing the content of VBT and the time of polymerization. A series of polymers with different branching degrees were prepared by means of 1H NMRX GPC / ri / Mar LS- DV triplet and compared with the intrinsic viscosity, glass transition temperature and branching factor of linear polymers. It was proved that the branched polymer was successfully synthesized on the basis of 1). Branched polymer BPVCM can self-assemble on the surface of multi-walled carbon nanotube (MWCNT) in the selective solvent DMF/H2O to form uniform spherical micelles which can effectively disperse MWCNT to obtain stable water-soluble BPVCM/MWCNT composite dispersion. In addition, UV light can induce photodimerization of the Guang Min group in the polymer chain. The crosslinked network structure can stabilize the micelle and further improve the stability of MWCNT dispersion. It was found that the sensor exhibited excellent selectivity, electrocatalytic activity and anti-interference to ascorbic acid (AA) and dopamine (DA) and paracetamol (Pat). The electrochemical sensor of e-BPVCM/MWCNT/GCE prepared by electrochemical polymerization has a good effect on the detection of DA and PAT in real drug preparations and has potential application value in clinical diagnosis.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1;O631

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