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活性炔与叠氮单体的无金属催化聚合反应研究

Synthesis of Novel Polymers Based on Monomers Bearing Carbonyl Alkyne by Metal-Free Catalyst

【作者】 魏强

【导师】 秦安军; 唐本忠; 孙景志;

【作者基本信息】 浙江大学 , 高分子材料, 2012, 硕士

【摘要】 探索新的聚合反应是高分子合成化学研究的一个重要方向。一价铜催化的叠氮和炔烃的点击反应具有高效、原子经济性、副产物少、分离简单、立体选择性以及官能团容忍性好等优点而备受关注,已经应用于各个学科领域。该反应也已经发展成为一种点击聚合。但是,一价铜催化的点击聚合所得聚合物中残留的催化剂除去比较困难。一个很好的解决方法就是发展无金属催化的点击聚合反应。我们课题组成功地建立了活泼端炔与叠氮的无金属催化的点击聚合。在前期工作的基础上,本文首先以活泼的双炔酮和三叠氮为单体,通过优化的无金属催化的点击聚合高产率地制备了可溶的、具有较高分子量的超支化聚三唑。所得的聚合物具有抗表面刮伤以及自愈合的性能。其次,根据1,3-偶极环加成反应的机理,首次建立了活泼内炔和叠氮的高效的环加成聚合反应。对所得聚合物的结构进行了详细表征,所得聚合物中含有的苯甲酰三唑基团使得其具有高的折光指数以及光交联图案化的性能。本文中所得的聚合物不受金属催化剂残留的影响,所以可以广泛应用于生物和光电等领域。

【Abstract】 Exploration of new polymerization reaction is one of the most import research areas of polymer chemistry. Because of its remarkable advantages, such as high yield, atomic economic, benign byproduct, simple isolation procedure, regioselectivity and tolerance of many functional groups, Cu(Ⅰ)-catalyzed azide-alkyne click react has attracted lot of attentions and has been widely used in diverse research areas. The removals of metal residuals from obtained polymers after polymerizaiton is, however, difficult. One way to surmount this difficulty is to develop metal-free click polymerization. We have successfully established a metal-free click polymerization of active external alkynes with azides in our previous works.On the basis of our previous works, we prepared soluble hyperbranched polytriazoles with high molecular weights by metal-free click polymerization of bis(aroylacetylene)s and triazide in high yield. The obtained polymers exhibit the ability of anti-scratching on their film surfaces and self-healing. Furthermore, according to reaction mechanism of1,3-dipolar cycloaddition, we established an efficient1,3-dipolar polycycloaddition reaction for the first time and prepared functional polytriazoles. Their structures were fully characterized by spectroscopies. Thanks to the containing benzoyltriazole units, the polymers show unique properties of high refractive indices and photopatternability.The prepared polymers are promising to be used in biological and opto-electronic fields because they do not contain metal-catalyst residues and thus suffer free from their detriment.

  • 【网络出版投稿人】 浙江大学
  • 【网络出版年期】2012年 11期
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