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

doi:10.16085/j.issn.1000-6613.2019-0824

摘要/Abstract

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

中图分类号:

TQ 226.14

吴纯鑫,常雨淅,陈迪超,张建庭,金宁人,赵德明. 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[J]. 化工进展, 2020, 39(2): 696-701.

Chunxin WU,Yuxi CHANG,Dichao CEHN,Jianting ZHANG,Ningren JIN,Deming ZHAO. Synthesis of hydroxyl-modified PBO monomer 3,3′-diamino-4,4′-dihydroxybiphenyl hydrochloride[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 696-701.

图/表 10

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溶剂种类	纯度/%	收率/%
二氯甲烷	14.22	11.04
浓硫酸	18.36	19.65
甲苯和冰乙酸混合溶剂	92.43	81.39

溶剂种类	纯度/%	收率/%
二氯甲烷	14.22	11.04
浓硫酸	18.36	19.65
甲苯和冰乙酸混合溶剂	92.43	81.39

v(甲苯)∶v(冰乙酸)	纯度/%	收率/%
3∶2	69.22	55.04
1∶1	76.34	75.66
5∶7	92.43	81.39
3∶4	86.71	76.52

v(甲苯)∶v(冰乙酸)	纯度/%	收率/%
3∶2	69.22	55.04
1∶1	76.34	75.66
5∶7	92.43	81.39
3∶4	86.71	76.52

n(HNO₃)∶n(DHBP)	纯度/%	收率/%
1.8∶1	78.11	45.68
2.0∶1	92.43	81.39
2.2∶1	90.24	74.75
2.4∶1	86.76	73.50