聚(乙烯基四唑-co-丙烯酸)的合成与表征

doi:10.11944/j.issn.1000-0518.2016.12.160116

摘要/Abstract

摘要：

以聚丙烯腈为原料,首先通过部分腈基的[3+2]合环反应转化为聚(乙烯基四唑-co-丙烯腈)[Poly(VT-co-AN)],再通过碱性水解反应将剩余的腈基转化为羧基,合成出聚(乙烯基四唑-co-丙烯酸)[Poly(VT-co-AA)]。采用傅里叶红外变换光谱仪(FT-IR)、核磁共振碳谱仪(¹³C NMR)、酸碱滴定等方法对Poly(VT-co-AN)和[Poly(VT-co-AA)的结构进行了表征,结果表明,Poly(VT-co-AN)的分子链中含有腈基、四唑基团和部分羧基,四唑基团的含量为68.6%,与酸碱滴定法测定的四唑基团的含量相近,[Poly(VT-co-AA)中含有四唑基团和羧基,不含有腈基,酸值高于Poly(VT-co-AN),四唑基团的含量为67.6%,与叠氮化钠与聚丙烯腈的摩尔比相近。热失重分析结果显示[Poly(VT-co-AA)的热分解速率加快,在270~285 ℃的温度区间内分解完全。

关键词: 聚(乙烯基四唑-co-丙烯酸), 聚丙烯腈, [3+2]合环反应, 碱性水解反应

Abstract:

Poly(vinlytetrazole-co-acrylonitrile)(Poly(VT-co-AN)) was synthesized via partial [3+2] cyclization of the cyano group of polyacrylonitrile, and then hydrolysis of the residual cyano group in basic condition leads to poly(vinyltetrazole-co-acrylic acid)( Poly(VT-co-AA)). The structures of Poly(VT-co-AA) and Poly(VT-co-AN) are characterized by FT-IR and ¹³C NMR. The results show that poly(VT-co-AN) contains tetrazole, cyano and carboxyl group, and the tetrazole content is 68.6%, which corresponds to the result of acid-base titration. The Poly(VT-co-AA) contains tetrazole and carboxyl group, and shows a higher acid value than Poly(VT-co-AN). The tetrazole content of Poly(VT-co-AA) is 67.6% and corresponds to the n(NaN₃)/n(PAN) ratio. Thermogravimetric analysis result shows that Poly(VT-co-AA) decomposes faster, and decomposes fully in 270~285 ℃.

Key words: poly(vinyltetrazole-co-acrylic acid), polyacrylonitrile, [3+2] cyclizaction, basic hydrolysis reaction

李栋梁, 国德旺, 康虎, 王娟, 马丽娥, 尹燕华. 聚(乙烯基四唑-co-丙烯酸)的合成与表征[J]. 应用化学, 2016, 33(12): 1396-1400.

LI Dongliang, GUO Dewang, KANG Hu, WANG Juan, MA Li'e, YIN Yanhua. Synthesis and Characterization of Poly(vinyltetrazole-co-acrylic acid)[J]. Chinese Journal of Applied Chemistry, 2016, 33(12): 1396-1400.

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