典型胍基化合物熱穩(wěn)定性研究
發(fā)布時間：2018-11-09 16:39
【摘要】：胍基化合物是指含有胍基基團的化合物或其衍生物。它們在許多行業(yè)具有廣泛的應(yīng)用前景,同時這類物質(zhì)容易受熱分解,具有不穩(wěn)定性。本文選取四種典型的胍基化合物:硝基胍(NQ)、硝酸胍(GN)、甲基硝基胍(MNQ)和氨基胍硝酸鹽(AGN)作為研究對象,探討其穩(wěn)定性。首先,利用快速掃描量熱儀(RSC)對四種胍基化合物進行了初步篩選實驗,結(jié)果表明四種胍基化合物在掃描范圍內(nèi)均存在較為劇烈的熱分解反應(yīng),且反應(yīng)都產(chǎn)生了大量不可凝性氣體。四種胍基化合物的起始分解溫度高低排序為:To(甲基硝基胍)To(硝基胍)To(氨基胍硝酸鹽)To(硝酸胍),它們的產(chǎn)氣量大小排序為V(甲基硝基胍)V(硝酸胍)V(氨基胍硝酸鹽)V(硝基胍)。其次利用差示掃描量熱儀(DSC)研究了它們在動態(tài)條件下的熱分解特性,結(jié)果表明:硝基胍的熱分析曲線存在"吸放熱耦合現(xiàn)象",吸熱峰和放熱峰部分疊加,因此進一步探究了硝基胍水溶液的熱分解特性;硝酸胍及氨基胍硝酸鹽的分解放熱峰均存在多個分解峰耦合的現(xiàn)象,表明其分解機理復雜。動態(tài)DSC得到了同RSC一樣的起始分解溫度排序,如果以此作為穩(wěn)定性判據(jù),可以得到甲基硝基胍的熱穩(wěn)定性最差。進一步對可能具有自催化性質(zhì)的物質(zhì)進行了等溫實驗,硝基胍、硝基胍水溶液及甲基硝基胍的熱分解均呈現(xiàn)出自催化特性的鐘型峰,而硝酸胍的分解峰則由三個峰疊加而成。兩種模式下物質(zhì)分解反應(yīng)的Friedman方法活化能求解結(jié)果均表明四種胍基化合物的分解反應(yīng)機理均不單一,但硝基胍水溶液的分解可用單步機理描述。進而基于模型擬合法計算得到了硝基胍水溶液分解反應(yīng)的反應(yīng)速率表達式。由于兩種模式下硝酸胍分解峰均存在多峰疊加現(xiàn)象,利用AKTS對等溫模式下的分解峰進行解耦,得到3個獨立的分解放熱峰:第一個峰為減速型的分解峰,放熱速率隨著反應(yīng)進程呈下降趨勢;第二個和第三個峰均為鐘型放熱峰,即反應(yīng)模型為S型(即自催化模型)的分解峰。為此,第一步反應(yīng)采用N級反應(yīng)模型,第二、三步反應(yīng)采用包含引發(fā)反應(yīng)的自催化模型;應(yīng)用非線性擬合得到了每步的動力學參數(shù)。得到各步反應(yīng)的速率表達式。最后利用絕熱量熱儀(ARC)研究了四種物質(zhì)的絕熱熱分解特性,測試結(jié)果顯示,硝基胍、硝酸胍及甲基硝基胍在絕熱條件下均只存在一個劇烈的分解放熱階段;氨基胍硝酸鹽的分解則分為三個較弱的放熱階段。ARC實驗得到了同RSC及DSC相同的起始分解溫度排序。產(chǎn)氣量計算表明物質(zhì)的分解都產(chǎn)生了大量不可凝性氣體,產(chǎn)氣量大小排序同RSC實驗一致。進一步進行了TMRad及 TD24的求解,四種物質(zhì)的TD24高低排序為:TD24(甲基硝基胍)TD24(硝基胍TD24(氨基胍硝酸鹽)TD24(硝酸胍),以TD24判據(jù)作為穩(wěn)定性判據(jù)可以得到同To判據(jù)一樣的結(jié)論,甲基硝基胍的穩(wěn)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.
【學位授予單位】：南京理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.2
本文編號：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.
【學位授予單位】：南京理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.2
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