【摘要】 针对反式构型的聚对苯撑苯并二?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。更多还原

【Abstract】 Transpoly(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-diaminohydroquinone hydrochloride(DAQH·2 HCl) 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 5 h,n(TCQ)∶n(NH3·H2 O)=1∶4,under which the yield of DADCQ was83.84% 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 6 h, pressure of hydrogen0.2―0.6 MPa, under which the yield of DAQH·2 HCl was 94.74% based on DADCQ and the purity was98.90% as determined by HPLC. The molecular structures of product and its intermediate were identified by FTIR、~1H NMR and EI-MS.更多还原