反式PBO的AA型单体2,5-二氨基对苯二酚盐酸盐的合成

doi:10.16085/j.issn.1000-6613.2018-2128

摘要/Abstract

摘要：

针对反式构型的聚对苯撑苯并二噁唑（PBO）纤维杂环分子直线性更好、相比顺式PBO来说反式PBO的力学性能和光电性能更加优异等特点，提出了以四氯苯醌（TCQ）为原料经氨解和加氢还原等反应合成得到中间体2,5-二氨基-3,6-二氯苯醌（DADCQ）和反式PBO的AA型单体2,5-二氨基对苯二酚盐酸盐（DAQH?2HCl），并对其反应条件进行了优化。结果表明：对于氨解反应，以乙腈和乙醇混合液为溶剂，反应温度74℃，n(TCQ)∶n(NH₃·H₂O)=1∶4，反应时间5h，DADCQ收率83.84%，HPLC纯度96.37%；加氢还原反应，5% Pd/C为催化剂，m(5% Pd/C)∶m(DADCQ)=1∶20，水为溶剂，反应温度50℃，氢压0.2～0.6MPa下反应6h后，经浓盐酸析出得到DAQH?2HCl，收率94.74%，HPLC纯度98.90%。中间体和产物结构经FTIR、¹H NMR和EI-MS表征确认。

关键词: 四氯苯醌, 2,5-二氨基对苯二酚盐酸盐, 氨解, 加氢还原

Abstract:

Trans poly(p-phenylene benzobisoxazole) (PBO) fiber has better linearity than cis-PBO fiber, and the mechanical properties and photoelectric performance of trans-PBO fiber are better than that of cis-PBO fiber. In view of the above characteristics, trans-PBO AA type monomer 2,5-diamino-hydroquinone hydrochloride (DAQH·2HCl) and the intermediate 2,5-diamino-3,6-dichlorobenzoquinone (DADCQ) were synthesized through aminolysis and catalytic hydrogenation reduction reaction by using tetrachlorobenzoquinone(TCQ) as raw material, and the experimental conditions were investigated. Proper experimental conditions for aminolysis were found as: acetonitrile and ethanol mixture as solvent，reaction temperature 74℃ and reaction time 5h，n(TCQ)∶n(NH₃·H₂O)=1∶4，under which the yield of DADCQ was 83.84% based on TCQ and the purity was 96.37% as determined by HPLC; proper catalytic hydrogenation reduction reaction conditions were found as: 5% Pd/C as catalyst, m(5% Pd/C)∶m(DADCQ)=1∶20, water as solvent, reaction temperature 50℃, reaction time 6h, pressure of hydrogen 0.2―0.6MPa, under which the yield of DAQH?2HCl was 94.74% based on DADCQ and the purity was 98.90% as determined by HPLC. The molecular structures of product and its intermediate were identified by FTIR、¹H NMR and EI-MS.

Key words: tetrachlorobenzoquinone, 2,5-diamino-hydroquinone hydrochloride, aminolysis, catalytic hydrogenation reduction

中图分类号:

TQ226.14

董斌, 吴杰, 张建庭, 吴纯鑫, 金宁人, 赵德明. 反式PBO的AA型单体2,5-二氨基对苯二酚盐酸盐的合成[J]. 化工进展, 2019, 38(06): 2947-2952.

Bin DONG, Jie WU, Jianting ZHANG, Chunxin WU, Ningren JIN, Deming ZHAO. Synthesis of trans-PBO AA type monomer 2,5-diamino-hydroquinone hydrochloride[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2947-2952.

图/表 10

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溶剂种类	纯度/%	收率/%
乙腈	94.91	83.25
乙醇	87.71	77.56
甲醇	73.38	60.00

溶剂种类	纯度/%	收率/%
乙腈	94.91	83.25
乙醇	87.71	77.56
甲醇	73.38	60.00

混合溶剂V _乙腈:V _乙醇	纯度/%	收率/%
5∶5	90.40	69.90
6∶4	89.41	73.32
7∶3	90.14	82.49

混合溶剂V _乙腈:V _乙醇	纯度/%	收率/%
5∶5	90.40	69.90
6∶4	89.41	73.32
7∶3	90.14	82.49

溶剂	n(TCQ):n(NH₃·H₂O)	纯度/%	收率/%
30%乙醇	1∶2	95.85	59.01
30%乙醇	1∶4	96.37	83.84
30%乙醇	1∶6	93.88	83.68
30%乙醇	1∶8	90.14	82.49
乙腈	1∶2	92.17	62.22
乙腈	1∶4	94.59	81.39
乙腈	1∶6	93.81	83.71
乙腈	1∶8	94.91	83.25