ATRP法制备含大垂饰基的螺旋聚甲基丙烯酸酯的研究

发布时间：2018-04-13 16:49

本文选题：大基团 + 原子转移自由基聚合　；参考：《湘潭大学》2011年博士论文

【摘要】：自然界中的高功能生物大分子,如蛋白质和DNA等具有高精确排列的立体结构,而螺旋结构是其中最常见的立体结构之一,并且螺旋结构常常在生命活动中扮演着重要的角色。本文综述了螺旋聚合物的研究历程以及螺旋聚合物的合成方法,开展了原子转移自由基聚合(ATRP)制备单手性螺旋过量聚合物的研究。主要研究内容有: 1)改进了甲基丙烯酸1-苯基二苯并环庚醇酯(PDBSMA)的合成工艺,将其产率由文献报道的15 %提高到了80 %。该单体是研究螺旋聚合反应较为常用的单体之一。合成了系列含大取代基的不饱和酯类单体,并研究了其聚合反应。 2)研究了以卤代烃为原子转移自由基聚合引发剂引发PDBSMA的聚合反应,讨论了引发剂结构对其引发效率的影响。研究结果表明:(a)引发剂位阻太大则不能引发含有大取代基的PDBSMA发生ATRP反应;(b)氯代烃的引发活性低于相应的溴代烃,论文所选用的几种氯代烃均不能引发PDBSMA发生ATRP反应;(c)苄位溴代烃的引发活性要高于α-位溴代酯的活性。前者作为引发剂时单体的转化率较高,并且得到的单手性螺旋过量聚合物的比旋光值也较高。 3)以带大取代基的不饱和酯为单体,研究了手性引发剂及手性配体对原子转移自由基聚合过程的立体选择性的影响。研究结果表明,手性配体或手性引发剂均可对聚合过程产生手性诱导作用。PDBSMA可以在手性配体或手性引发剂的存在下,由ATRP的聚合方式得到单手性螺旋构象过量的聚合物,。 4)发现了一种合成2-VA唑烷酮的新方法。本文在尝试合成一类含吖啶环的单体时,没有得到预期的产物,却意外的得到了2-VA唑烷酮的衍生物。该合成方法具有以下优点:(a)该方法合成条件温和,安全且无毒;(b)该反应环境污染小,原料利用率也很高,水是该反应唯一的副产物;(c)反应底物芳香胺价廉易得。一句话来概括该反应对环境友好,且具有较高的原子经济效率。论文对该方法进行了较深入的研究,制得了一系列2-VA唑烷酮类化合物。
[Abstract]:Highly functional biological macromolecules, such as protein and DNA, have highly precise arrangement in nature, and helical structure is one of the most common stereoscopic structures, and helical structure often plays an important role in life activities.In this paper, the research progress of helical polymers and the synthetic methods of helical polymers are reviewed, and the preparation of single-chiral helical excess polymers by atom transfer radical polymerization (ATRP) is carried out.The main research contents are as follows:1) the synthesis process of 1-phenyl dibenzo-cycloheptanol methacrylate (PDBSMA) was improved, and the yield of PDBSMA was increased from 15% reported in literature to 80%.The monomer is one of the commonly used monomers in the study of helical polymerization.A series of unsaturated ester monomers with large substituents were synthesized and their polymerization reactions were studied.2) the polymerization of PDBSMA initiated by halogenated hydrocarbon as atom transfer radical polymerization initiator was studied, and the effect of initiator structure on its initiation efficiency was discussed.The results show that the initiation activity of chlorinated hydrocarbons is lower than that of brominated hydrocarbons when the steric resistance of the initiator is too large to initiate the ATRP reaction of PDBSMA with large substituents.The initiated activity of benzyl brominated hydrocarbons was higher than that of 伪 -bromoesters. The selected chlorinated hydrocarbons could not initiate the ATRP reaction of PDBSMA and the activity of benzyl brominated hydrocarbons was higher than that of 伪 -bromoesters.When the former was used as initiator, the monomer conversion was higher, and the specific optical rotation value of the single chiral helical excess polymer was also higher.3) the effects of chiral initiators and chiral ligands on the stereoselectivity of atom transfer radical polymerization were studied using unsaturated esters with large substituents as monomers.The results show that chiral ligands or chiral initiators can induce the polymerization process. PDBSMA can obtain a single chiral helical conformation excess polymer in the presence of chiral ligands or chiral initiators in the presence of chiral ligands or chiral initiators.4) A new method for the synthesis of 2-VA azolone was found.In this paper, a class of monomers containing acridine ring were synthesized without the expected product, but the derivatives of 2-VA azolone were obtained unexpectedly.The synthetic method has the following advantages: the synthetic conditions are mild, the reaction is safe and non-toxic. The reaction has low environmental pollution, high utilization of raw materials, and water is the only by-product of the reaction.In one sentence, the reaction is environmentally friendly and has high atomic economic efficiency.In this paper, a series of 2-VA azolones were prepared.
【学位授予单位】：湘潭大学
【学位级别】：博士
【学位授予年份】：2011
【分类号】：O631.3

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