Abstract: Based on the current worldwide trend of using 1,2,4,5-tetraaminobenzene (TAB)and its hydrochloride (TAB·4HCl)in new materials and absence of relevant study in China, a new method of synthesizing polymer grade monomer TAB·4HCl was studied, systematic analysis and optimization was made for the synthesis process, and the relationship of the ammonolysis selectivity with pressure and temperature were clarified. The results showed that 4,6-dinitro-1,3-phenylenediamine (DADNB)was prepared by double ammonolysis reaction at 1.0 MPa pressure in 1,4-dioxane solvent from 1,3-dichloro-4,6-dinitrobenzene (DCDNB)ammonia as ammonolysis agent, and then hydrogenated in methanol solvent, the solution containing TAB was obtained after the hydrogenation liquid was decolored with active carbon, then TAB·4HCl was obtained by adding hydrochloric acid and concentrating under reduced pressure and filtering, with 99.3% purity and 79.7% total yield. Finally, with synthesis reliability of 99% and good practical value, a plan for solvent recovery and recycling was proposed for commercialization of TAB·4HCl production.

Key words: 1,2,4,5-tetraaminobenzene tetrahydrochloride, ammonolysis selectivity, 4,6-dinitro-1,3-phenylenediamine;1,3-dichloro-4,6-dinitrobenzene

摘要： 基于目前1,2,4,5-四氨基苯（TAB）及其盐酸盐（TAB·4HCl）在国外被开发应用于新材料的发展趋势和国内尚未涉及的现状，研究了聚合级单体TAB·4HCl的合成新方法，并对其合成工艺进行了系统的分析和优化，明确了氨解选择性与压力、温度的关系。结果表明：以4,6-二硝基间二氯苯（DCDNB）为原料，氨水为氨解剂在1.0 MPa的压力下，于1,4-二氧六环溶剂中进行双氨解反应，先制得4,6-二硝基间苯二胺（DADNB），然后在甲醇溶剂中进行催化加氢还原，最后经活性炭吸附脱色制得TAB的溶液后加入盐酸进行成盐，再减压浓缩制得99.3%纯度的TAB·4HCl，总收率79.7%。并在99%的合成可信度和良好实用价值的前提下，最后提出了TAB·4HCl制备过程中溶剂回收和循环使用的产业化方案。

关键词: 1,2,4,5-四氨基苯盐酸盐, 氨解选择性, 4,6-二硝基间苯二胺, 4,6-二硝基间二氯苯