高炭产率多功能聚荧蒽的化学氧化合成

项目名称： 高炭产率多功能聚荧蒽的化学氧化合成

项目编号： No.50873077

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 金属学与金属工艺

项目作者： 李新贵

作者单位： 同济大学

项目金额： 37万元

中文摘要： 从分子设计角度出发，精心选取仅含碳氢两种元素、理论炭含量高达95％的现成易得的稠环化合物荧蒽，将简易的化学氧化聚合法引入到荧蒽的高效化学聚合中，突破其无反应性取代基的难点，高产率地合成了聚荧蒽。寻求并优化了对荧蒽的化学氧化聚合具有特异氧化作用的氧化剂体系，揭示了氧化剂用量、聚合条件等对聚荧蒽的残炭率、耐热性以及导电性和荧光性等功能的影响规律。揭示了荧蒽氧化反应活性位点和数量，推测并探讨了聚合机理。论证了稠环芳烃形成的大分子链共轭结构对其强耐热性、高炭产率的贡献及热解机理。挖掘并优化了具有不同分子量聚荧蒽的功能性，拓展了一类新型耐高温、高残炭、抗静电、显荧光、可成型的有机聚合物多功能材料。另辟蹊径克服了目前所研究的高残炭有机聚合物如聚芳基乙炔、聚对苯、硼酚醛树脂等不溶不熔难以成型加工的难题，突破此项目之前荧蒽只能微小规模电聚合的缺憾。该研究突破了稠环芳烃的难溶解性及难聚合性，开拓了新型芳香聚合物的多功能性，为共轭聚合物家族成员增添了新秀。相关研究在影响因子12.186和8.486等的刊物上发表论文8篇。发明专利6项，其中国际专利2项。获上海市自然科学奖。

中文关键词： 聚荧蒽；化学氧化聚合；炭产率；荧光性;化学传感器

英文摘要： In the point of molecular design, an inexpensive polycyclic aromatic hydrocarbon - fluoranthene (FA) monomer that only consists of carbon and hydrogen elements with theoretical carbon content of as high as 95% is carefully selected to synthesize high-performance conjugated polymers. A facile chemical oxidative synthesis is introduced into an effective chemical polymerization of FA monomer, thereby overcoming the difficulty of lack of reacting groups on FA and productively obtaining polyfluoranthene (PFA). A specific oxidation system for chemical oxidative polymerization of FA monomer has been elaborately established, and the influence of oxidant dosage and polymerization conditions on the char yield, heat-resistance, electrical conductivity, and fluorescence of the PFA has been revealed. At the same time, reactive site and its quantity, and polymerization mechanism of FA monomer have also been demonstrated. The functionality of PFA with various molecular weight or tacticity has been optimized. Novel multifunctional organic polymer materials with strong heat resistance, high char yield, antistatic property, fluorescence, and processing property have been developed. This project has explored a specific way to solve the current processing problems (i.e., insolubility and infusibility) in some high char-yield organic polymers such as polyarylacetylene, poly(p-phenylene), and boron phenolic resin. Herein this technique has broken through a "bottlenecks" of only electrically synthesizing PFA on a small scale so far. New novel multifunctional polymer materials have be exploited. The study has overcome the insolubility and thus difficult polymerization of anthraquinone, and developed a new type of aromatic polymer with multifunctionality. The polyfluoranthene has become a new robust member in the conjugated polymers. Eight full articles related to this investigation have been published on the international academic journals including the journals with impact factor of 12.186 and 8.486,two on the domestic academic journals, and eight articles have been indexed by SCI. Six patents, including two international patents, have been authorized or filed. The project leader won a Natural Science Prize of Shanghai in China.

英文关键词： polyfluoranthene; chemical oxidative polymerization; char yield; fluorescence；chemosensor