基于取代炔螺旋聚合物纳米粒子的制备及性能研究

发布时间：2018-08-25 12:17

【摘要】：取代聚炔是一类独特的聚合物,其主链通常以螺旋结构构成,往往表现出良好的光学活性,在手性领域如不对称催化,诱导结晶,手性控释等领域发挥着重要作用。另一方面,聚合物纳米粒子由于特有的表面效应与小尺寸效应,拥有着其他粒径粒子所不及的特性,在近些年吸引了越来越多的关注,并在众多领域有着重要的应用价值。但是到目前为止,绝大多数聚合物纳米粒子均是基于烯类聚合物制备的,基于取代炔类聚合物报道还比较少,制备手段也较为匮乏。鉴于此,设计合成新型取代聚炔纳米粒子对于手性化学,材料科学等领域具有重要意义。本论文基于不同的聚合手段制备了两类螺旋取代聚炔纳米粒子,主要研究内容如下:1、以两种芳香炔烃苯乙炔和1-乙炔基萘为单体,通过悬浮聚合法制备了两种取代聚炔纳米粒子。通过FTIR,NMR,SEM, UV-vis等测试方法对粒子进行了结构与形貌的表征。此外,实验分别研究了分散剂与搅拌速度对于悬浮聚合制备纳米粒子的影响,确定了在聚乙烯吡咯烷酮为分散剂下,选用500 rpm转速是芳香炔烃单体制备纳米粒子的最佳条件。2、分别以手性取代炔单体和苯乙炔为单体,通过乳液聚合法制备了两种取代聚炔纳米空心粒子。实验以150 nm左右的二氧化硅粒子作为模板,制备了二氧化硅/取代聚炔纳米核壳粒子,再通过氢氟酸在适宜的条件下去核最终得到了取代聚炔纳米空心粒子。TEM测试表征了粒子的空心结构,证明了制备的成功;CD与UV-vis谱图表明在去核后,构成空心粒子的聚合物主链以过量的单手螺旋构象存在,并且具有良好的光学活性。
[Abstract]:Substituted polyacetylene is a kind of unique polymer, its main chain is usually made up of helical structure, and often shows good optical activity. It plays an important role in chiral fields such as asymmetric catalysis, induced crystallization, chiral controlled release and so on. On the other hand, polymer nanoparticles have attracted more and more attention in recent years because of their unique surface effects and small size effects, which have attracted more and more attention in recent years, and have important application value in many fields. However, up to now, most polymer nanoparticles are based on alkenes, and there are few reports based on substituted acetylene polymers, and the preparation methods are relatively scarce. In view of this, the design and synthesis of novel substituted polyacetylene nanoparticles are of great significance in chiral chemistry, material science and other fields. In this thesis, two kinds of helically substituted polyacetylene nanoparticles were prepared by different polymerization methods. The main contents of this study are as follows: 1. Two aromatic alkynes, phenylethynes and 1-acetylnaphthalene, were used as monomers. Two substituted polyacetylene nanoparticles were prepared by suspension polymerization. The structure and morphology of the particles were characterized by FTIR,NMR,SEM, UV-vis and other methods. In addition, the effects of dispersant and agitation speed on the preparation of nanoparticles by suspension polymerization were studied, and polyvinylpyrrolidone was used as dispersant. The optimum conditions of preparing nano-particles with aromatic alkynes were selected at the rotational speed of 500 rpm. Two kinds of hollow polyacetylene nanoparticles were prepared by emulsion polymerization with chiral substituted acetylene and chiral substituted acetylene as monomers respectively. The silica / polyacetylene nano-core-shell particles were prepared by using the silica particles of about 150 nm as the template. The hollow structure of polyacetylene nanocrystalline was characterized by TEM, and the results of CD and UV-vis spectra showed that after nucleation, the hollow structure of the particles was characterized by dihydrofluoric acid under suitable conditions. The main chain of the hollow particles is in excess of single-handed helical conformation and has good optical activity.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O632.17

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