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我们报道利用叠氮基团与乙炔中间体(P2)的侧链端炔的1,3-偶极环加成反应实现双取代聚乙炔的后功能化(P3)的合成路线的设计和实验探索.其中聚乙炔前驱物(P2)由侧链带有三甲基硅乙炔的初级聚乙炔(P1)通过去硅化反应得到.P1由特殊设计的乙炔单体在WCl6-Ph4Sn催化作用下聚合得到.该单体有两个乙炔键,其中之一由三甲基硅封端.本文探索了两种合成路线,即“两步法”(目标聚合物P3从初级聚合物P1经由中间体P2得到)与“一锅法”(由P1一锅反应直接得到P3,中间体P2未经分离与纯化).实验结果表明“一锅法”更简便,且目标产物P3-1比两步法得到的产物P3-2具有更高的纯度与分子量.聚合反应与聚合物结构通过凝胶色谱(GPC)、傅里叶变换红外光谱(FTIR)与核磁共振氢谱(1HNMR)进行表征.
We report the design and experimental exploration of the post-functionalization (P3) of the disubstituted polyacetylene using the 1,3-dipolar cycloaddition of the side chain alkyne between the azide group and the acetylene intermediate (P2) , In which the polyacetylene precursor (P2) is obtained by the desilylation reaction of the primary polyacetylene (P1) with trimethylsilyl acetylene on the side chain, and the P1 is obtained by the polymerization of the specially designed acetylene monomer under the action of WCl6-Ph4Sn catalysis The monomer has two acetylene bonds, one of which is terminated by trimethylsilyl.This paper explores two synthetic routes, namely the “two-step method” (target polymer P3 is obtained from primary polymer P1 via intermediate P2 ) And “one-pot method” (one-pot reaction from P1 directly obtained P3, intermediate P2 without separation and purification) .Experimental results show that “one-pot method” is more convenient, and the target product P3-1 than two P3-2 obtained by the step method has higher purity and molecular weight.The polymerization reaction and polymer structure are characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance (1HNMR).