【作者】 张洁；

【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， 2019， 博士

【摘要】 溴代炔类化合物是一类活化炔类单体,可在无复杂催化剂的情况下参与聚合反应,完美地避免了聚合物中重金属催化剂残留以及其对其在生物和光电等重要领域应用限制的问题,成为发展新型聚合反应的新构筑基元。基于溴代炔类单体,本文主要致力于新型聚合反应的开发,并制备了一系列功能性线形和超支化聚合物。首先,建立了一个基于溴代炔类单体的新型聚合反应。在该聚合反应中,水首次作为单体来构筑聚合物。在氟化铯的促进下,溴代炔、异腈与水在较温和的条件下便可高产率制备得到分子量高、溶解性良好的聚酰胺。该聚合反应具有很好的立体选择性,所得聚合物中Z式异构体的含量高达80%。此外,基于聚合物中所含的溴代烯基,通过简单的偶联或取代反应即可实现聚合后修饰。因此,本工作不仅建立了新型的基于溴代炔单体的聚合反应,同时为在较温和条件下制备功能化聚酰胺提供了一种崭新的方法。其次,我们成功发展了一类无过渡金属催化的溴代炔与酚类单体的高效聚合反应。在碳酸铯的介导下,双官能团的溴代炔与双酚单体在加热条件下即可顺利发生聚合反应,在1h内便可以95.2%的产率得到可溶的、热稳定好的、高分子量高达47600的聚合物。功能性基团四苯基乙烯的引入使得所得聚合物具有聚集诱导发光(AIE)的特性,且利用该AIE聚合物成功制备了高分辨率2D荧光图案。此外,基于所得聚合物结构中含有溴代烯基团,同样采用非常简单的反应对其进行了后修饰,得到的新聚合物具有比原聚合物更高的折光指数。再次,成功开发了一种溴代炔与硫酚的高效新型聚合反应。该反应只需在有机碱的作用下便可以非常高的产率得到分子量高达44500的聚合物。值得一提的是,溴代炔为单官能团单体,可设计性强,一些杂原子可以很容易地通过单体设计引入到聚合物中。所得聚合物具有优异的透光性和极高的折光指数(最高可达1.8351)。利用这一光学特性我们成功将其应用于聚合物光波导,表现出了比商业材料SU-8更低的光传输损耗。该聚合反应为含硫高折光指数聚合物的合成打开了一片广阔的天地,有望在光学集成领域得以应用。最后,我们利用单溴代炔双官能度的特点,采用双溴代炔与双硫酚的单体组合策略,便可以非常高的产率得到高分子量的超支化聚合物。通过单体设计将AIE基元引入聚合物结构中,使所得聚合物也都相应地展现出AIE或聚集增强发光(AEE)的特性。更多还原

【Abstract】 Bromoalkynes,as a kind of activated alkynes,could be easily polymerized without using transition-metal catalysts,making the resultant polymers suffer from the ditemental of transition-metallic residues,greatly broadening their applications in optoelectronic and biologic fields.Thus,bromoalkynes become an outstanding building block for establishing powerful and efficient polymerizations.In this thesis,we focus on the development of novel polymerizations based on bromoalkynes,and a series of linear and hyperbranched polymers with advanced functions were prepared.First,a novel CsF-mediated polymerization of bromoalkyne,isocayanide and water was developed under mild reaction conditions,and soluble polyamides with high weight-average molecular weights(Mw)were produced in high yields.This new polymerization is stereoselective,and the fraction of Z-stereoregular isomers in the resultant polymers is generally higher than 80%.Furthermore,the polymers can be postmodified via Sonogashira coupling or substitution reactions.Thus,we not only established a new stereoselective polymerization of water and triple-bond based monomers but also provided a powerful strategy for the preparation of functional polyamide under mild reaction conditions.Second,a Cs2CO3-mediated polymerization of bromoalkynes and phenols was established,from which polymers with high Mw up to 47600 were obtained in the yields up to 95.2%in as short as 1 h.All the resultant polymers are soluble in commonly used organic solvents and thermally stable with high degradation temperatures.The polymerization also exhibits excellent functional group tolerance,and the moieties such as tetraphenylethylene(TPE)could be facilely introduced into the polymer,endowing it with aggregation-induced emission(AIE)feature,too.The AIE-polymer could be used to fabricate a 2D fluorescent photopattern with high resolution.Moreover,the resultant polymers could be easily post-modified because of their containing bromovinyl groups in each repeating unit.Interstingly,the post-modified polymer possesses a higher refractive index than that of pristine one.Third,a simple and powerful organobase-catalyzed polymerization of bromoalkynes and thiols was established,and polymers with high Mw up to 44500 were produced in excellent yields.The resultant polymers exhibit high optical transparency and high refractive indices(n,up to 1.8351)in the visual and near IR region.Benefiting from above merits,polymeric optical waveguides using the polymers with high n were successfully fabricated.The propagation loss of the fabricated waveguides was remarkably reduced compared with that of a famous commercial SU-8.Thus,this polymerization opens a new scope in the synthesis of processable polymers with high n,which are potentially applicable in photonic integrated field.Finally,a series of hyperbranched polymers with high molecular weights were obtained in excellent yields via the polymerization of bis(bromoalkyne)s and dithiols.Thanks to its functional tolerance of used polymerization,diverse functional moieties could be facilely introduced into the polymers,endowing them with AIE or aggregation-enhanced emission(AEE)activity.更多还原