【作者】 张健；

【导师】 罗军；

【作者基本信息】 南京理工大学 ， 化学工程与技术， 2019， 博士

【摘要】 有机笼状高能量密度化合物由于其分子结构对称,具有高能量、低感度等特性,同时热稳定性良好,一直受到人们的广泛关注。以金刚烷骨架为母体的含能化合物,包括多硝基金刚烷和多硝基氮杂金刚烷,同时具有高能和钝感的优点,深入对此类化合物的研究,有望在其中寻找到性能优良的高能量密度化合物。本文综述了高能量密度化合物的发展、多硝基金刚烷以及多硝基氮杂金刚烷的合成进展。在此基础上,针对多硝基金刚烷合成中遇到的高空间位阻的影响,一方面设计了位阻条件下硝基金刚烷合成偕二硝基金刚烷的方法,另一方面设计用位阻较小的氟原子取代硝基来合成含氟多硝基金刚烷;并且尝试用新路线来合成一种八硝基金刚烷,最后设计合成了一种二氮杂金刚烷及其衍生物。以2,2,4-三硝基金刚烷为底物研究了在位阻条件下制备其偕二硝基产物2,2,4,4-四硝基金刚烷的反应体系,确定了最佳的的反应条件,通过一个连续的亚硝化-氧化过程直接将硝肟酸钠转化为偕二硝基产物,并取得87%的收率。将该反应体系应用到几种多硝基金刚烷和芳基硝基烷烃的底物中,发现具有较好的底物适用性。最后研究了其反应机理,证实该反应是经历了自由基的反应历程。以4,4-二硝基金刚烷-2,6-二酮为原料,经肟化、氧化、亲电氟化3步反应合成出2,6-二氟-2,4,4,6-四硝基金刚烷,并利用单晶衍射技术获得了2,6-二氟-2,4,4,6-四硝基金刚烷的密度为1.787 g·cm^-3;以4,8-二羟基金刚烷-2,6-二酮为原料,经保护、氧化、肟化、氧化等8步反应合成出2,4,6,8-四氟-2,4,6,8-四硝基金刚烷。利用热重分析-差示扫描量热法技术研究了2,6-二氟-2,4,4,6-四硝基金刚烷、2,4,4,6-四硝基金刚烷、2,4,6,8-四氟-2,4,6,8-四硝基金刚烷和2,4,6,8-四硝基金刚烷的热稳定性;并利用Gaussian 09程序计算了它们的爆轰性能与密度,探讨了用氟原子取代金刚烷骨架上的氢原子或者硝基对于含能化合物性能的影响。以丙二酸二乙酯和多聚甲醛为原料,经环合、水解的步骤合成出具有四个甲酸的金刚烷骨架的化合物2,6-二氧代金刚烷-1,3,5,7-四甲酸,以此为原料设计了两条路线来合成1,3,5,7-四硝基金刚烷-2,6-二酮,并进行了合成探索。随后,尝试以四羧酸为原料一步合成四硝基金刚烷,详细研究了脂肪族羧酸在金属催化下合成硝基烷烃的方法。以1,5-环辛二烯为原料,经两条路线合成出关键的中间体9-叔丁氧羰基-9-氮杂[3.3.1]壬-2,6-二烯,随后经环氧化、环合等9步反应合成出一种新型含能材料2,4,4,6,8,8-六硝基-2,6-二氮杂金刚烷。利用单晶衍射技术获得了2,4,4,6,8,8-六硝基-2,6-二氮杂金刚烷的密度为1.959 g·cm^-3,利用TG-DSC技术研究了其热稳定性,该化合物具有较好的热稳定性（分解峰温为276℃）。利用Gaussian 09程序计算了2,4,4,6,8,8-六硝基-2,6-二氮杂金刚烷的爆轰性能,计算爆速为9310 m·s^-1,爆压为40.3GPa,与CL-20相当,是一种具有应用前景的高能量密度材料。本文开发了一种位阻条件下以硝基金刚烷作为底物合成偕二硝基金刚烷的方法,合成了两种含氟多硝基金刚烷,分别为2,6-二氟-2,4,4,6-四硝基金刚烷和2,4,6,8-四氟-2,4,6,8-四硝基金刚烷;并且探索了一种新的八硝基金刚烷的合成路线和以金刚烷羧酸直接脱羧硝化制备硝基金刚烷的方法,为合成含有更多硝基的金刚烷含能化合物奠定了基础。最后,开发了一种2,6-二氮杂金刚烷环的构建方法,以此为基础合成出了2,4,4,6,8,8-六硝基-2,6-二氮杂金刚烷,为此类化合物的合成提供了参考。更多还原

【Abstract】 High energy-density cage-like compounds have attracted extensive attention for their high energy and low sensitivity owing to their symmetrical structures,particularly in combination with good thermal stability.The energetic compounds based on adamantane skeleton,including polynitroadamantanes and polynitroazaadamantanes,have the advantages of high energy and insensitivity.It is expected that high energy-density materials with excellent properties will be developed by futher study on these compounds.Herein,recent progress of the development of high energy-density compounds,the synthesis of polynitroadamantanes and polynitroazaadamantanes were reviewed.Then,in view of the influence of high steric hindrance in the synthesis of polynitroadamantanes,the method of synthesizing adamantane with gem-dinitro group from nitroadamantane under steric hindrance condition was designed;on the other hand,the fluorine atom,with smaller steric hindrance,was used to replace nitro group to synthesize fluorine-containing polynitroadamantanes.In addition,a new route was attempted to synthesize1,2,2,3,5,6,6,7-octanitroadamantane,and finally one of diazaadamantane and its derivative were prepared.The reaction system of preparing 2,2,4,4-tetranitroadamantane from2,2,4-trinitroadamantane was studied.The optimal reaction conditions were determined and the highest yield was achieved as high as 87%.Sodium nitronates was directly converted into gem-dinitro products through a new nitrosation and oxidation tandem process.The reaction system has been applied to several polynitroadamantanes and arylnitroalkanes with good applicability of substrates.Finally,the reaction mechanism was studied,and it was confirmed that the reaction was a free radical reaction process.2,6-Difluoro-2,4,4,6-tetranitroadamantanewassynthesizedfrom4,4-dinitroadamantane-2,6-dione via oximation,oxidation and electrophilic fluorination.The crystal density of 2,6-difluoro-2,4,4,6-tetranitroadamantane was 1.787 g·cm^-3.2,4,6,8-Tetrafluoro-2,4,6,8-tetranitroadamantane was prepared in eight steps from4,8-dihydroxyadamantane-2,6-dione.Subsequently,the thermal stability of2,6-difluoro-2,4,4,6-tetranitroadamantane,2,4,4,6-tetranitroadamantane,2,4,6,8-tetrafluoro-2,4,6,8-tetranitroadamantane and 2,4,6,8-tetranitroadamantane were studied by thermogravimetric analysis and differential scanning calorimetry（TG-DSC）,and their detonation properties and densities were calculated by using the Gaussian 09program.Finally,the influence of substituting groups of fluorine,hydrogen and nitro group in the framework of adamantane on the properties was discussed.2,6-Dioxane-1,3,5,7-tetracarboxylic acid was synthesized from diethyl malonate and polyformaldehyde via cyclization and hydrolysis.Two routes were designed to synthesize1,3,5,7-tetranitroadamantane-2,6-dione based on this tetracarboxylic acid,but both routes failed.Subsequently,the synthesis of nitroalkanes from aliphatic carboxylic acids catalyzed by metal was studied in detail for one-step synthesis of tetranitroadamantane from tetracarboxylic acid.The key intermediate of 9-（tert-butoxycarbonyl）-9-azabicyclo[3.3.1]nona-2,6-diene was synthesized from 1,5-cyclooctadiene via two routes.Subsequently,2,4,4,6,8,8-hexanitro-2,6-diazaadamantane was synthesized in nine steps.The crystal density of 2,4,4,6,8,8-hexanitro-2,6-diazaadamantane was 1.959 g·cm^-3 and the thermal stabilityofthecompoundwasstudiedbyTG-DSC.2,4,4,6,8,8-hexanitro-2,6-diazoadamantane has a decomposition peak temperature of276℃,calculated detonation pressure of 40.3 GPa and detonation velocity of 9310 m·s^-1,which makes it possible to be used as high energetic materials.In this paper,a method for the synthesis of adamantane bearing gem-dinitro groups from nitroadamantane was developed.Two fluorine-containing polynitroadamantanes,2,6-difluoro-2,4,4,6-tetranitroadamantane and 2,4,6,8-tetrafluoro-2,4,6,8-tetranitro-adamantane,weresynthesized.Anewsynthesisrouteof1,2,2,3,5,6,6,7-octanitroadamantane and a method of preparing nitroadamantane from alkyl carboxylic acid were explored,which established the foundation of the synthesis of the adamantanes containing more nitro groups.Finally,a method of constructing the skeleton of2,6-diazzadamantanewasdeveloped.Thereafter,2,4,4,6,8,8-hexanitro-2,6-diazaadamantane was synthesized,which provided a template for the synthesis of other energetic cage-like compounds.更多还原