含醚雙取代聚炔的功能化后修飾
發(fā)布時間：2018-08-31 15:34
【摘要】：雙取代聚炔(PDSAs)相比于單取代聚炔具有顯著提高的穩(wěn)定性和特有的發(fā)光性能,這使PDSAs獲得成為一類特殊光電功能高分子的發(fā)展機(jī)遇,功能化也因此成為目前PDSAs的主導(dǎo)研究方向。但催化雙取代炔單體聚合的過渡金屬催化劑對水、氧和極性基團(tuán)相當(dāng)敏感,這極大地制約了新型功能化PDSAs的發(fā)展。聚合后修飾方法的引入很好地解決了這一難題。通過一個含有反應(yīng)性基團(tuán)的前驅(qū)體聚合物,可以衍生出多種具有特定功能的聚合物。目前,如鈀催化的偶聯(lián)反應(yīng),銅催化的疊氮-炔點擊反應(yīng),烯烴和巰基的點擊反應(yīng)等聚合后修飾方法已應(yīng)用到功能化雙取代聚炔的合成制備中。但受限于各種反應(yīng)的適用范圍,目前可以進(jìn)行功能化后修飾的聚炔種類還相當(dāng)有限,探索新型的雙取代聚炔前驅(qū)體進(jìn)行后修飾嘗試的工作依然具有很重要的意義�；诖�,本文以合成雙取代聚炔含醚前驅(qū)體為出發(fā)點,分別探索合成了含酚羥基官能團(tuán)和環(huán)氧基團(tuán)的雙取代聚炔,并對其進(jìn)行相應(yīng)的后修飾反應(yīng),以期進(jìn)一步豐富功能化雙取代聚炔的合成路線。本文首先合成了含不同保護(hù)基的雙取代炔單體,經(jīng)探索后發(fā)現(xiàn)含硅醚保護(hù)基的單體可以在WCl6-Ph4Sn催化體系中順利聚合。之后將所得聚合物進(jìn)行一步簡單的脫保護(hù)反應(yīng),即得含酚羥基的PDSA。酚羥基具有較高的反應(yīng)活性,可以進(jìn)行酯化、加成等多種反應(yīng)。本文首次應(yīng)用了酚-炔點擊反應(yīng)來進(jìn)行后修飾,在溫和條件下,聚合側(cè)鏈上的酚羥基與活性炔(羰基與端三鍵直接相連形成的化合物)在4小時內(nèi)發(fā)生近100%的點擊反應(yīng)。進(jìn)而用凝膠色譜、核磁、紅外等手段表征了聚合物結(jié)構(gòu),證明得到了預(yù)期產(chǎn)物,并研究了酚-炔點擊反應(yīng)產(chǎn)物的結(jié)構(gòu)。環(huán)氧基團(tuán)和巰基的點擊反應(yīng)條件溫和,效率高,在聚合物后修飾領(lǐng)域十分常見,同時含環(huán)氧基團(tuán)的雙取代聚炔還未被報道過。因此,第二個工作的目的是先合成側(cè)鏈為烯丙基醚基團(tuán)的雙取代聚炔,并探索控制其環(huán)氧化程度的條件,得到具有點擊修飾功能的雙取代聚炔。在經(jīng)過核磁紅外等手段表征后,證實成功得到了同時含環(huán)氧和雙鍵的雙取代聚炔。
[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.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O632.17
本文編號：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.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O632.17
【參考文獻(xiàn)】
相關(guān)期刊論文 前4條
1 Haiqiang Wu;Wenhui Dong;Zongtan Wang;Bicheng Yao;Ming Chen;Jingzhi Sun;Anjun Qin;Ben Zhong Tang;;An air-stable supported Cu(?) catalyst for azide-alkyne click polymerization[J];Science China(Chemistry);2015年11期
2 ;AZIDE-ALKYNE CLICK POLYMERIZATION:AN UPDATE[J];Chinese Journal of Polymer Science;2012年01期
3 ;Post-functionalization of disubstituted polyacetylenes via click chemistry[J];Science China(Chemistry);2011年12期
4 袁望章;趙輝;徐海鵬;孫景志;LAM J W Y;毛宇;金佳科;張雙;鄭強(qiáng);唐本忠;;用帶不同側(cè)鏈的雙取代聚乙炔衍生物增溶多壁碳納米管[J];高分子學(xué)報;2007年10期
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