典型胍基化合物热稳定性研究
发布时间：2018-11-09 16:39
【摘要】：胍基化合物是指含有胍基基团的化合物或其衍生物。它们在许多行业具有广泛的应用前景,同时这类物质容易受热分解,具有不稳定性。本文选取四种典型的胍基化合物:硝基胍(NQ)、硝酸胍(GN)、甲基硝基胍(MNQ)和氨基胍硝酸盐(AGN)作为研究对象,探讨其稳定性。首先,利用快速扫描量热仪(RSC)对四种胍基化合物进行了初步筛选实验,结果表明四种胍基化合物在扫描范围内均存在较为剧烈的热分解反应,且反应都产生了大量不可凝性气体。四种胍基化合物的起始分解温度高低排序为:To(甲基硝基胍)To(硝基胍)To(氨基胍硝酸盐)To(硝酸胍),它们的产气量大小排序为V(甲基硝基胍)V(硝酸胍)V(氨基胍硝酸盐)V(硝基胍)。其次利用差示扫描量热仪(DSC)研究了它们在动态条件下的热分解特性,结果表明:硝基胍的热分析曲线存在"吸放热耦合现象",吸热峰和放热峰部分叠加,因此进一步探究了硝基胍水溶液的热分解特性;硝酸胍及氨基胍硝酸盐的分解放热峰均存在多个分解峰耦合的现象,表明其分解机理复杂。动态DSC得到了同RSC一样的起始分解温度排序,如果以此作为稳定性判据,可以得到甲基硝基胍的热稳定性最差。进一步对可能具有自催化性质的物质进行了等温实验,硝基胍、硝基胍水溶液及甲基硝基胍的热分解均呈现出自催化特性的钟型峰,而硝酸胍的分解峰则由三个峰叠加而成。两种模式下物质分解反应的Friedman方法活化能求解结果均表明四种胍基化合物的分解反应机理均不单一,但硝基胍水溶液的分解可用单步机理描述。进而基于模型拟合法计算得到了硝基胍水溶液分解反应的反应速率表达式。由于两种模式下硝酸胍分解峰均存在多峰叠加现象,利用AKTS对等温模式下的分解峰进行解耦,得到3个独立的分解放热峰:第一个峰为减速型的分解峰,放热速率随着反应进程呈下降趋势;第二个和第三个峰均为钟型放热峰,即反应模型为S型(即自催化模型)的分解峰。为此,第一步反应采用N级反应模型,第二、三步反应采用包含引发反应的自催化模型;应用非线性拟合得到了每步的动力学参数。得到各步反应的速率表达式。最后利用绝热量热仪(ARC)研究了四种物质的绝热热分解特性,测试结果显示,硝基胍、硝酸胍及甲基硝基胍在绝热条件下均只存在一个剧烈的分解放热阶段;氨基胍硝酸盐的分解则分为三个较弱的放热阶段。ARC实验得到了同RSC及DSC相同的起始分解温度排序。产气量计算表明物质的分解都产生了大量不可凝性气体,产气量大小排序同RSC实验一致。进一步进行了TMRad及 TD24的求解,四种物质的TD24高低排序为:TD24(甲基硝基胍)TD24(硝基胍TD24(氨基胍硝酸盐)TD24(硝酸胍),以TD24判据作为稳定性判据可以得到同To判据一样的结论,甲基硝基胍的稳定性最差。
[Abstract]:Guanidine compounds are compounds containing guanidine groups or their derivatives. They have wide application prospects in many industries, and these substances are easily decomposed by heat and unstable. Four typical guanidinyl compounds: nitroguanidine (NQ), guanidine nitrate (GN), methyl nitroguanidine (MNQ) and aminoguanidine nitrate (AGN), were selected to study their stability. First of all, four guanidin-based compounds were screened by a rapid scanning calorimeter (RSC). The results showed that the four guanidin-based compounds had severe thermal decomposition reactions in the scanning range. And the reaction produced a large number of non-coagulable gases. The initial decomposition temperature of four guanidinyl compounds was: To (methyl nitroguanidine) To (aminoguanidine nitrate) To (nitrate guanidine nitrate). The order of their gas production is V (methyl nitroguanidine) V (guanidine nitrate) V (aminoguanidine nitrate) V (nitroguanidine). Secondly, the thermal decomposition characteristics of nitroguanidine under dynamic conditions are studied by using differential scanning calorimeter (DSC). The results show that the thermal analysis curve of nitroguanidine is characterized by "heat absorption and exothermic coupling phenomenon" and the superposition of endothermic peak and exothermic peak. Therefore, the thermal decomposition characteristics of nitroguanidine aqueous solution were further investigated. There are several decomposition peaks coupling in the decomposition heat peaks of guanidine nitrate and aminoguanidine nitrate, which indicates that the decomposition mechanism is complex. The thermal stability of methylnitroguanidine can be obtained by using dynamic DSC as the same initial decomposition temperature order as RSC. Further isothermal experiments were carried out for substances with autocatalytic properties. The thermal decomposition of nitroguanidine in aqueous solution and methylnitroguanidine showed a bell peak of catalytic property, while the decomposition peak of guanidine nitrate was superposed by three peaks. The results of the activation energy solution of the Friedman method in both modes show that the decomposition mechanism of the four guanidinyl compounds is not single, but the decomposition of nitroguanidine aqueous solution can be described by one-step mechanism. The reaction rate expression of nitroguanidine solution decomposition reaction was obtained based on the model fitting method. Due to the phenomenon of multi-peak superposition of the decomposition peak of guanidine nitrate in both modes, the decomposition peak in isothermal mode is decoupled by AKTS, and three separate liberation heat peaks are obtained: the first peak is the decomposition peak of deceleration type. The exothermic rate decreased with the reaction process. The second and third peaks are both clock type exothermic peaks, that is, the decomposition peak of the reaction model is S-type (that is, the autocatalytic model). For this reason, the first step reaction adopts the N-order reaction model, the second, the three-step reaction adopts the autocatalytic model including the initiation reaction, and the kinetic parameters of each step are obtained by nonlinear fitting. The rate expression of each step reaction is obtained. Finally, the adiabatic decomposition characteristics of four substances were studied by adiabatic calorimeter (ARC). The results showed that nitroguanidine, guanidine nitrate and methylnitroguanidine had only one severe phase of liberation fever under adiabatic condition. The decomposition of aminoguanidine nitrate can be divided into three weaker exothermic stages. ARC experiments have obtained the same initial decomposition temperature order as RSC and DSC. The calculation of gas production shows that the decomposition of matter produces a large amount of non-condensable gases, and the order of gas production is consistent with that of RSC experiment. The TD24 order of the four substances is TD24 (methyl nitroguanidine) TD24 (nitroguanidine TD24 (aminoguanidine nitrate) TD24 (guanidine nitrate). Using TD24 criterion as stability criterion, we can get the same conclusion as To criterion, the stability of methyl nitroguanidine is the worst.
【学位授予单位】：南京理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.2
本文编号：2320978
[Abstract]:Guanidine compounds are compounds containing guanidine groups or their derivatives. They have wide application prospects in many industries, and these substances are easily decomposed by heat and unstable. Four typical guanidinyl compounds: nitroguanidine (NQ), guanidine nitrate (GN), methyl nitroguanidine (MNQ) and aminoguanidine nitrate (AGN), were selected to study their stability. First of all, four guanidin-based compounds were screened by a rapid scanning calorimeter (RSC). The results showed that the four guanidin-based compounds had severe thermal decomposition reactions in the scanning range. And the reaction produced a large number of non-coagulable gases. The initial decomposition temperature of four guanidinyl compounds was: To (methyl nitroguanidine) To (aminoguanidine nitrate) To (nitrate guanidine nitrate). The order of their gas production is V (methyl nitroguanidine) V (guanidine nitrate) V (aminoguanidine nitrate) V (nitroguanidine). Secondly, the thermal decomposition characteristics of nitroguanidine under dynamic conditions are studied by using differential scanning calorimeter (DSC). The results show that the thermal analysis curve of nitroguanidine is characterized by "heat absorption and exothermic coupling phenomenon" and the superposition of endothermic peak and exothermic peak. Therefore, the thermal decomposition characteristics of nitroguanidine aqueous solution were further investigated. There are several decomposition peaks coupling in the decomposition heat peaks of guanidine nitrate and aminoguanidine nitrate, which indicates that the decomposition mechanism is complex. The thermal stability of methylnitroguanidine can be obtained by using dynamic DSC as the same initial decomposition temperature order as RSC. Further isothermal experiments were carried out for substances with autocatalytic properties. The thermal decomposition of nitroguanidine in aqueous solution and methylnitroguanidine showed a bell peak of catalytic property, while the decomposition peak of guanidine nitrate was superposed by three peaks. The results of the activation energy solution of the Friedman method in both modes show that the decomposition mechanism of the four guanidinyl compounds is not single, but the decomposition of nitroguanidine aqueous solution can be described by one-step mechanism. The reaction rate expression of nitroguanidine solution decomposition reaction was obtained based on the model fitting method. Due to the phenomenon of multi-peak superposition of the decomposition peak of guanidine nitrate in both modes, the decomposition peak in isothermal mode is decoupled by AKTS, and three separate liberation heat peaks are obtained: the first peak is the decomposition peak of deceleration type. The exothermic rate decreased with the reaction process. The second and third peaks are both clock type exothermic peaks, that is, the decomposition peak of the reaction model is S-type (that is, the autocatalytic model). For this reason, the first step reaction adopts the N-order reaction model, the second, the three-step reaction adopts the autocatalytic model including the initiation reaction, and the kinetic parameters of each step are obtained by nonlinear fitting. The rate expression of each step reaction is obtained. Finally, the adiabatic decomposition characteristics of four substances were studied by adiabatic calorimeter (ARC). The results showed that nitroguanidine, guanidine nitrate and methylnitroguanidine had only one severe phase of liberation fever under adiabatic condition. The decomposition of aminoguanidine nitrate can be divided into three weaker exothermic stages. ARC experiments have obtained the same initial decomposition temperature order as RSC and DSC. The calculation of gas production shows that the decomposition of matter produces a large amount of non-condensable gases, and the order of gas production is consistent with that of RSC experiment. The TD24 order of the four substances is TD24 (methyl nitroguanidine) TD24 (nitroguanidine TD24 (aminoguanidine nitrate) TD24 (guanidine nitrate). Using TD24 criterion as stability criterion, we can get the same conclusion as To criterion, the stability of methyl nitroguanidine is the worst.
【学位授予单位】：南京理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.2
【参考文献】
相关期刊论文 前9条
1 尹瑞丽;陈利平;陈网桦;吴珂;张彩星;李焓;于诚;;两种量热模式下物质热分解的动力学补偿效应[J];物理化学学报;2016年02期
2 许诚;毕福强;张敏;葛忠学;刘庆;;3,3'-二硝胺基-4,4'-偶氮呋咱二胍盐的合成、晶体结构及性能[J];含能材料;2015年02期
3 杨庭;陈利平;陈网桦;张彩星;高海素;路贵斌;周奕杉;;分解反应自催化性质快速鉴别的实验方法[J];物理化学学报;2014年07期
4 彭敏君;路贵斌;陈网桦;陈利平;吕家育;;苯胺溶剂中偶氮二异丁腈热分解特性及动力学[J];物理化学学报;2013年10期
5 胡荣祖;赵凤起;高红旭;马海霞;张海;徐抗震;赵宏安;姚二岗;;2,2,2-三硝基乙基-N-硝基甲胺的热安全性（英文）[J];物理化学学报;2013年10期
6 鲍士龙;陈网桦;陈利平;高海素;吕家育;;2,4-二硝基甲苯热解自催化特性鉴别及其热解动力学[J];物理化学学报;2013年03期
7 柏薇薇;姚旭明;苏建国;;硝酸胍生产方法与用途[J];辽宁化工;2012年12期
8 江治,李疏芬,赵凤起,陈沛,阴翠梅,李上文;纳米金属粉对HMX热分解特性的影响[J];推进技术;2002年03期
9 洪三国,傅孝愿;硝基胍热解反应途径的量子化学研究[J];物理化学学报;1991年01期
，本文编号：2320978
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2320978.html
教材专著
