高等学校化学学报

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (3): 556.

• 研究论文 • 上一篇    下一篇

一种新的4,6-二氨基间苯二酚盐酸盐的制备方法及与对苯二甲酸的缩合聚合

张春燕, 史子兴, 朱子康, 徐纪平   

  1. 上海交通大学化学化工学院, 复合材料国家重点实验室, 上海 200240
  • 收稿日期:2003-01-21 出版日期:2004-03-24 发布日期:2004-03-24
  • 通讯作者: 史子兴(1972年出生),男,博士,副教授,主要从事杂环聚合物材料的研究.E-mail;zxshi@sjtu.edu.cn E-mail:zxshi@sjtu.edu.cn

A New Method for Synthesis of DAR·2HCl and Its Polymerization with Terephthalic Acid

ZHANG Chun-Yan, SHI Zi-Xing, ZHU Zi-Kang, XU Ji-Ping   

  1. National Key Laboratory of Composite Materials, School of Chemistry and Chemical Technology, Shanghai Jiaotong University, Shanghai 200240, China
  • Received:2003-01-21 Online:2004-03-24 Published:2004-03-24

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被引次数

25

摘要： 以间苯二酚为原料,通过乙酰化、肟化、Beckmann重排、水解反应制备4,6-二胺基间苯二酚盐酸盐(DAR·2HCl),并用FTIR,MS,元素分析,1HNMR和13CNMR等对DAR·2HCl及中间体进行了表征.同时,将DAR·2HCl和对苯二酸(TPA)成盐,然后进行缩聚得到具有较高分子量的PBO.通过FTIR和固体13CNMR表征了PBO的结构,并研究了PBO的热性能.

关键词: 4, 6-二乙酰基间苯二酚, 二肟, 4, 6-二氨基间苯二酚盐酸盐(DAR·, 2HCl), TPA盐, 聚苯并唑(PBO)

Abstract: A new method for synthesizing 4,6-diaminoresorcinol dihydrochloride(DAR·2HCl) was adopted by three steps, which will give DAR·2HCl without involving any nitro or halo compound but in high yields and high regioselectivity. In the first step, the resorcinol was reacted with acetic anhydride to give the 4,6-diacylresorcinol, then followed by the oximation of 4,6-diacylresorcinol to form the dioxime with the addition of hydroxylamine hydrochloride, finally, the dioxime was subject to producing DAR·2HCl by Beckmann rearrangement in the presence of polyphosphoric acid . The structures of these two intermediates and the final product(DAR·2HCl) were characterized and confirmed by FTIR, MS, elemental analysis, 1H NMR and 13C NMR etc ., the results show that all the products are very pure. Meanwhile, the salt of 4,6 diaminoresorcinol/terephthlate(TPA) was prepared with DAR·2HCl and terepthalic acid. By using TPA salt as the starting monomer, polybenzoxazole(PBO) with a high molecular weight was obtained in the polyphosphoric acid. The structure and thermal property of PBO were characterized by means of FTIR, solid state 13C NMR and TGA.

Key words: 4,6-Diacetylresorcinol, Dioxime, 4,6-Diaminoresorcinol dihydrochloride(DAR·2HCl), TPA salt, Polybenzoxazole(PBO)

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