五唑阴离子盐前驱体2,6-二甲基-4-氨基苯酚盐酸盐晶体的制备及特性  

Synthesis and Characterization of the Pentazolate Anion Precursor of 2,6-Dimethyl-4-aminophenol Hydrochloride Crystals

作　　者：王鹏飞 孙志营 詹淼 郑金刚 孙呈郭 WANG Peng-fei;SUN Zhi-ying;ZHAN Miao;ZHENG Jin-gang;SUN Cheng-guo(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan 114051,China;Scientific research,Liaoning Qingyang Special Chemical Co.,Lid,Liaoyang 111000,China;School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

机构地区：[1]辽宁科技大学化学工程学院,辽宁鞍山114051 [2]辽宁庆阳特种化工有限公司科研中心,辽宁辽阳111000 [3]南京理工大学化学与化工学院,江苏南京210094

出　　处：《含能材料》2022年第5期475-482,共8页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(11972178)。

摘　　要：为改善2,6-二甲基-4-羟基苯基五唑的产率和纯度问题,实验探讨了以2,6-二甲基苯酚为原料,经亚硝化、还原、成盐三步反应制备芳基五唑的母体原料2,6-二甲基-4-氨基苯酚盐酸盐(DMAPH)晶体的方法。采用红外光谱(IR)、X-射线单晶衍射(SCXRD)、扫描电镜(SEM)、X-射线粉末衍射(PXRD)、差示扫描量热分析(DSC)和理论计算对其化学结构、晶体结构、晶体形貌和稳定性能进行表征。结果表明:以亚硝酸钠和冰乙酸作为亚硝化试剂,亚硝化产率可达90%以上。通过改变析晶溶剂,可获得片状、针状、块状和板状形貌的盐酸盐晶体,而温度只会影响析出晶体的粒径大小。甲醇溶剂析出的DMAPH晶体主要占比晶面是(400)晶面,其他溶剂析出的主要占比晶面为(214)晶面。DMAPH的分解峰温在220~240℃,具有良好的热稳定性,相比无定型的DMAPH粉末,晶体对空气的稳定性较好,比较适合长期储存。To improve the yield and purity of 2,6-dimethyl-4-hydroxyphenylpentazole,the preparation method of 2,6-dimethyl-4-hydroxyphenylpentazole(DMAPH)crystal,the raw material of arylpentazole,was investigated through three steps including nitrification,reduction and salification from 2,6-dimethylphenol(DMP).The structure,crystal morphology and stability were characterized with infrared spectroscopy(IR),single crystal X-ray diffraction(SCXRD),scanning electron microscopy(SEM),powder X-ray diffraction(PXRD),differential scanning calorimetry(DSC)and theoretical calculation.The results reveal that the yield of 2,6-dimethyl-4-nitrosophenol is up to 90%in the presence of glacial acetic acid and sodium nitrite.The different shapes of DMAPH crystal including sheet,needle,block and plate morphology can be obtained by changing the solvent,while the temperature only affect the particle size of precipitated crystals.The(400)face is the main crystal face of DMAPH crystal from methanol,while in other solvents it is the(214)face.The DMAPH crystals exhibit good thermal stability with decomposition peak temperature ranging from 220-240℃.In contrast to amorphous DMAPH powders,the crystalline DMAPH solids have better stability in air,and are more suitable for long-term storage.

关 键 词：亚硝化 2 6-二甲基-4-氨基苯酚盐酸盐 五唑阴离子盐前驱体 晶形调控 芳基五唑前驱体 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]