含醚双取代聚炔的功能化后修饰
发布时间：2018-08-31 15:34
【摘要】：双取代聚炔(PDSAs)相比于单取代聚炔具有显著提高的稳定性和特有的发光性能,这使PDSAs获得成为一类特殊光电功能高分子的发展机遇,功能化也因此成为目前PDSAs的主导研究方向。但催化双取代炔单体聚合的过渡金属催化剂对水、氧和极性基团相当敏感,这极大地制约了新型功能化PDSAs的发展。聚合后修饰方法的引入很好地解决了这一难题。通过一个含有反应性基团的前驱体聚合物,可以衍生出多种具有特定功能的聚合物。目前,如钯催化的偶联反应,铜催化的叠氮-炔点击反应,烯烃和巯基的点击反应等聚合后修饰方法已应用到功能化双取代聚炔的合成制备中。但受限于各种反应的适用范围,目前可以进行功能化后修饰的聚炔种类还相当有限,探索新型的双取代聚炔前驱体进行后修饰尝试的工作依然具有很重要的意义。基于此,本文以合成双取代聚炔含醚前驱体为出发点,分别探索合成了含酚羟基官能团和环氧基团的双取代聚炔,并对其进行相应的后修饰反应,以期进一步丰富功能化双取代聚炔的合成路线。本文首先合成了含不同保护基的双取代炔单体,经探索后发现含硅醚保护基的单体可以在WCl6-Ph4Sn催化体系中顺利聚合。之后将所得聚合物进行一步简单的脱保护反应,即得含酚羟基的PDSA。酚羟基具有较高的反应活性,可以进行酯化、加成等多种反应。本文首次应用了酚-炔点击反应来进行后修饰,在温和条件下,聚合侧链上的酚羟基与活性炔(羰基与端三键直接相连形成的化合物)在4小时内发生近100%的点击反应。进而用凝胶色谱、核磁、红外等手段表征了聚合物结构,证明得到了预期产物,并研究了酚-炔点击反应产物的结构。环氧基团和巯基的点击反应条件温和,效率高,在聚合物后修饰领域十分常见,同时含环氧基团的双取代聚炔还未被报道过。因此,第二个工作的目的是先合成侧链为烯丙基醚基团的双取代聚炔,并探索控制其环氧化程度的条件,得到具有点击修饰功能的双取代聚炔。在经过核磁红外等手段表征后,证实成功得到了同时含环氧和双键的双取代聚炔。
[Abstract]:Compared with the monosubstituted polyacetylene (PDSAs), the disubstituted polyacetylene has better stability and unique luminescence performance, which makes PDSAs become a kind of special optoelectronic functional polymer development opportunity. Therefore, functionalization has become the leading research direction of PDSAs at present. However, the transition metal catalysts which catalyze the polymerization of disubstituted acetylene monomers are very sensitive to water, oxygen and polar groups, which greatly restrict the development of new functionalized PDSAs. The introduction of post-polymerization modification method solves this problem well. A variety of polymers with specific functions can be derived by a precursor polymer containing reactive groups. At present, such post-modification methods as palladium catalyzed coupling reaction, copper-catalyzed azido-acetylene click reaction, olefin and mercapto reaction have been applied to the synthesis and preparation of functionalized disubstituted polyacetylene. However, limited by the application of various reactions, the types of polyacetylene that can be functionalized and modified are still very limited, so it is still of great significance to explore new disubstituted polyacetylene precursors for post-modification. Based on this, the disubstituted polyacetylene containing phenolic hydroxyl group and epoxy group were synthesized from the precursor of disubstituted polyacetylene with ether as the starting point, and the corresponding post-modification reaction was carried out. In order to further enrich the functionalized disubstituted polyacetylene synthesis route. In this paper, disubstituted alkyne monomers with different protective groups were synthesized. It was found that the monomers containing silicoether protected groups could be successfully polymerized in WCl6-Ph4Sn catalyst system. The obtained polymer was then deprotected by a simple deprotection reaction, that is, PDSA. containing phenolic hydroxyl groups was obtained. Phenolic hydroxyl groups have high reaction activity and can be used for esterification and addition. In this paper, the phenol-acetylene click-through reaction was used for the first time. Under mild conditions, the phenolic hydroxyl group in the polymerization side chain and the active acetylene (the compound formed by the direct connection of carbonyl group to the end three bonds) occurred nearly 100% of the click-through reaction within 4 hours. The structure of the polymer was characterized by gel chromatography, NMR and IR. The expected product was obtained and the structure of phenol-acetylene click-through reaction product was studied. The reaction conditions of epoxy group and sulfhydryl group are mild and high efficiency, which is very common in the field of post-modification of polymer, and disubstituted polyacetylene containing epoxy group has not been reported. Therefore, the aim of the second work is to synthesize disubstituted polyacetylene with side chain as allyl ether group, and to explore the conditions of controlling its epoxidation degree to obtain the polyacetylene with click-modification function. It is proved that the disubstituted polyacetylene containing both epoxy and double bonds has been successfully obtained by means of nuclear magnetic infrared spectroscopy.
【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O632.17
本文编号：2215421
[Abstract]:Compared with the monosubstituted polyacetylene (PDSAs), the disubstituted polyacetylene has better stability and unique luminescence performance, which makes PDSAs become a kind of special optoelectronic functional polymer development opportunity. Therefore, functionalization has become the leading research direction of PDSAs at present. However, the transition metal catalysts which catalyze the polymerization of disubstituted acetylene monomers are very sensitive to water, oxygen and polar groups, which greatly restrict the development of new functionalized PDSAs. The introduction of post-polymerization modification method solves this problem well. A variety of polymers with specific functions can be derived by a precursor polymer containing reactive groups. At present, such post-modification methods as palladium catalyzed coupling reaction, copper-catalyzed azido-acetylene click reaction, olefin and mercapto reaction have been applied to the synthesis and preparation of functionalized disubstituted polyacetylene. However, limited by the application of various reactions, the types of polyacetylene that can be functionalized and modified are still very limited, so it is still of great significance to explore new disubstituted polyacetylene precursors for post-modification. Based on this, the disubstituted polyacetylene containing phenolic hydroxyl group and epoxy group were synthesized from the precursor of disubstituted polyacetylene with ether as the starting point, and the corresponding post-modification reaction was carried out. In order to further enrich the functionalized disubstituted polyacetylene synthesis route. In this paper, disubstituted alkyne monomers with different protective groups were synthesized. It was found that the monomers containing silicoether protected groups could be successfully polymerized in WCl6-Ph4Sn catalyst system. The obtained polymer was then deprotected by a simple deprotection reaction, that is, PDSA. containing phenolic hydroxyl groups was obtained. Phenolic hydroxyl groups have high reaction activity and can be used for esterification and addition. In this paper, the phenol-acetylene click-through reaction was used for the first time. Under mild conditions, the phenolic hydroxyl group in the polymerization side chain and the active acetylene (the compound formed by the direct connection of carbonyl group to the end three bonds) occurred nearly 100% of the click-through reaction within 4 hours. The structure of the polymer was characterized by gel chromatography, NMR and IR. The expected product was obtained and the structure of phenol-acetylene click-through reaction product was studied. The reaction conditions of epoxy group and sulfhydryl group are mild and high efficiency, which is very common in the field of post-modification of polymer, and disubstituted polyacetylene containing epoxy group has not been reported. Therefore, the aim of the second work is to synthesize disubstituted polyacetylene with side chain as allyl ether group, and to explore the conditions of controlling its epoxidation degree to obtain the polyacetylene with click-modification function. It is proved that the disubstituted polyacetylene containing both epoxy and double bonds has been successfully obtained by means of nuclear magnetic infrared spectroscopy.
【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O632.17
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