【作者】 李红坤；

【导师】 唐本忠； 秦安军； 孙景志；

【作者基本信息】 浙江大学 ， 高分子材料， 2012， 博士

【摘要】 发展新的聚合反应对于高分子化学来说是非常重要的。几乎所有新的聚合反应都起源于已知的有机小分子的反应。Cu(I)催化的叠氮-炔的“点击反应”,由于反应原料易得、反应条件温和、后处理简单和具有立体专一性等优点,被广泛应用于药物及生物复合物的合成、表面改性和聚合物后功能化修饰等方面。同时该点击反应也用于制备线形和超支化聚合物。利用该反应制备的聚合物,金属催化剂往往很难去除干净,由于铜离子会产生细胞毒性和影响聚合物的光电性能,极大地限制了该反应在生物和光电高分子领域中的应用。解决的方法之一是发展无金属催化的“点击聚合”反应。本文建立了一种无金属催化的丙炔酸酯-叠氮的点击聚合反应,制备了一系列的功能化线形和超支化聚三唑甲酸酯。我们首先设计并合成了四种芳香族和脂肪族的二丙炔酸酯化合物,尝试了该类单体与二叠氮化合物在加热条件下的聚合反应,系统研究了单体浓度、反应时间和溶剂对聚合物的产率、分子量及立构规整性的影响,确定了最佳的聚合条件,并且该聚合反应可以在空气氛围中进行,大大简化了反应过程。该聚合反应所制备的聚三唑甲酸酯可在碱液中快速降解。含有聚集诱导发光(AIE)性能的四苯基乙烯(TPE)单元的二叠氮与二丙炔酸酯单体进行无金属催化的点击聚合,高产率地制备了具有较高分子量和立构规整性的聚三唑甲酸酯。由于分子结构中含有TPE单元,该聚三唑甲酸酯具有AIE性能,并且该聚合物可作为化学传感器,高灵敏度地检测爆炸物。通过分子结构设计,合成了四种含二苯甲酮、硫原子的功能化的二叠氮单体,利用无金属催化的点击聚合反应,制备了具有高透光率、较高的折光指数和较低的色散系数,并且可以形成光致抗蚀图案的聚三唑甲酸酯,该类聚合物有望用于光学材料。利用含二茂铁的二叠氮化合物与二丙炔酸酯单体进行无金属催化的点击聚合反应,高产率地得到了较高分子量、较低分子量分布和高立构规整性的二茂铁基聚三唑甲酸酯,所制备的聚合物具有较高的热稳定性和电化学活性。探索了三丙炔酸酯单体与含TPE单元的二叠氮化合物的无金属催化的点击聚合反应,系统研究了聚合反应温度、时间和单体浓度对聚合物的溶解性、产率、分子量及分子量分布的影响,确定了最佳的聚合条件,发展了一种无金属催化的丙炔酸酯-叠氮的点击聚合制备超支化聚合物的方法。所制备的聚合物具有较高的折光指数和较低的色散性,并且可形成光致抗蚀图案；该聚合物具有聚集诱导发光性能,可用于高灵敏度地检测爆炸物。更多还原

【Abstract】 The development of new polymerization reactions is a constant theme in current polymer chemistry. Most of the new polymerization reactions, if not all, are derived from the established organic reactions.The Cu(Ⅰ)-catalyzed azide-alkyne cycloaddition, i.e. the click reaction, enjoys such advantageous characteristics as high efficiency, atom economy, regioselectivity, and functionality tolerance as well as mild reaction conditions, fast reaction rates and simple product isolation procedures. The click reaction has been actively utilized to synthesize bioconjugates and dendrimers, to decorate surfaces and nanoparticles, and to post-modify preformed polymers. This reaction has also been developed to a polymerization technique for the preparation of linear and hyperbranched polymers. However. it is very difficult to completely remove metallic catalysts after polymerization. The catalyst residues can cause cytotoxicity and deteriorate the photophysical properties of resulting polymers. The development of the metal-free click polymerization process is thus highly desired.In this paper, an efficient metal-free click polymerization of propiolates and azides was developed. Linear and hyperbrached poly(aroxycarbonyltriazole)s (PACTs) with advanced functional properties were prepared by the metal-free click polymerization.We firstly synthesized four aromatic and aliphatic propiolates. The thermally activated click polymerization of propiolates and azides were carried out. The effect of monomer concentration, reaction time and solvent on the yield, molecular weight and regioregularity of the polymer was studied. An optimal polymerization conditions were obtained. It is worthy noting that this polymerization reaction is insensitive to oxygen and moisture and can be carried out in open atmosphere, which further simplify the polymerization. The resulting PACTs could be rapidly degraded in the presence aqueous solution of potassium hydroxide.The metal-free click polymerization of4,4’-isopropylidenediphenyl dipropiolate and tetraphenylethene (TPE)-containing diazides were carried out in a DMF and toluene mixture at100℃for6h. affording PACTs with high molecular weights and regioregularities in high yields. Thanks to the aggregation-induced emission (AIE) feature of contained TPE units, the PACTs are also AIE-active and can serve as fluorescent chemosensors for superamplified detection of explosives.A series of functional PACTs were prepared by the metal-free click polymerization. The resulting PACTs are photo-sensitive and could generate three-dimensional phtotopattern upon UV irradiation. They also show high refractive indices and low optical dispersion, making them promising for photonic applications.Ferrocene-based PACTs with high molecular weights and low polydispersity indices, were synthesized by the metal-free click polymerization of bipropioiates and ferrocene-containing diazides. The ferrocene-based PACTs showed high resistance to thermolysis and electrochemical activity.We attempted the metal-free click polymerization of tripropiolates and diazide, and studied the effect of monomer concentration, reaction time and temperature on the yield, molecular weight and solubility of the polymers. The produced hyperbranched PACTs showed high resistance to thermolysis, high refractive index values and low optical dispersion, and could generate two-dimensional phtotopattern by UV irradiation. Moreover, the PACTs could be rapidly degraded in the presence of potassium hydroxide aqueous solution, showed AIE characteristics and worked as explosive sensors with high sensitivity.更多还原