化工进展 ›› 2020, Vol. 39 ›› Issue (2): 696-701.DOI: 10.16085/j.issn.1000-6613.2019-0824

• 精细化工 • 上一篇    下一篇

羟基改性聚对亚苯基苯并二唑单体3,3′-二氨基-4,4′-二羟基联苯盐酸盐的合成

吴纯鑫(),常雨淅,陈迪超,张建庭,金宁人,赵德明()   

  1. 浙江工业大学化学工程学院,浙江 杭州 310014
  • 收稿日期:2019-05-20 出版日期:2020-02-05 发布日期:2020-03-12
  • 通讯作者: 赵德明
  • 作者简介:吴纯鑫(1972—),女,博士,副教授,研究方向有机合成。E-mail:annewu@zjut.edu.cn
  • 基金资助:
    江苏省重大科技计划支撑项目(BE2011129);浙江省教育厅项目(Y201121211)

Synthesis of hydroxyl-modified PBO monomer 3,3′-diamino-4,4′-dihydroxybiphenyl hydrochloride

Chunxin WU(),Yuxi CHANG,Dichao CEHN,Jianting ZHANG,Ningren JIN,Deming ZHAO()   

  1. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhengjiang, China
  • Received:2019-05-20 Online:2020-02-05 Published:2020-03-12
  • Contact: Deming ZHAO

摘要:

为改进聚对亚苯基苯并二唑(PBO)纤维复合黏结性能差等缺点,在苯环上引入极性基团羟基进行化学分子结构改性,3,3′-二氨基-4,4′-二羟基联苯盐酸盐(DADHBP·2HCl)是羟基改性PBO的关键单体。以4,4′-二羟基联苯(DHBP)为原料经硝化、还原反应合成得到中间体3,3′-二硝基-4,4′-二羟基联苯(DNDHBP)和羟基改性PBO的单体DADHBP·2HCl,并对其反应条件进行了优化。结果表明:对于硝化反应,以甲苯、冰乙酸的混合液为反应溶剂,n(DHBP)∶n(HNO3)=1∶2,反应温度5℃,反应时间2.5h,收率81.39%,高效液相色谱(HPLC)纯度(质量分数)92.43%;还原反应,n(DNDHBP)∶n(FeSO4·7H2O)=1∶9,乙醇为溶剂,七水合硫酸亚铁为助剂,n(DNDHBP)∶n(N2H4·H2O)=1∶5.5,反应温度78℃,反应时间9h,热过滤,滤饼盐酸精制后得到DADHBP·2HCl,收率67.16%,HPLC纯度(质量分数)98.20%。中间体和产物结构经红外光谱、核磁氢谱和电喷雾质谱表征确认。

关键词: 4,4′-二羟基联苯, 3,3′-二氨基-4,4′-二羟基联苯盐酸盐, 硝化反应, 还原反应

Abstract:

In order to improve the poor performance of PBO composite bonding, a polar group hydroxyl group is introduced into the benzene ring for structural modification, and 3,3′-diamino-4,4′-dihydroxybiphenyl hydrochloride(DADHBP·2HCl) is a key monomer for modification. The intermediate 3,3′-dinitro-4,4′-dihydroxybiphenyl (DNDHBP) and the hydroxyl-modified PBO monomer DADHBP·2HCl were synthesized by the nitration and reduction reaction of 4,4′-dihydroxybiphenyl, and the reaction conditions were optimized. The results showed that for the nitration reaction, the yield of 65% of DNDHBP with a HPLC purity 98.65% could be achieved under the conditions of reaction temperature 5℃, reaction time 2.5h and n(DHBP)∶n(HNO3)=1∶2 in the mixed solvent of toluene and glacial acetic acid. The catalytic reduction reaction was conducted in ethanol as solvent under the conditions of n(DNDHBP): n(N2H4·H2O)=1∶5.5, reaction temperature 78℃ and reaction time 9h using ferrous sulfateheptahydrate as auxiliary [n(DNDHBP):n(FeSO4·7H2O)=1∶9]. After the hot filtration of the reaction mixture, DADHBP·2HCl could be obtained with a yield of 67.16% and a HPLC purity of 98.20% through refined by hydrochloric acid. The intermediate and product structures were confirmed by FT-IR, 1H-NMR and EI-MS.

Key words: 4,4′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, nitrification reaction, reduction reaction

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