本文選題：五氧化二氮　切入點(diǎn)：機(jī)理　出處：《武漢科技大學(xué)》2016年碩士論文

【摘要】：采用五氧化二氮作為硝化劑的新工藝是當(dāng)前具代表性的新型硝化技術(shù)。五氧化二氮/硝酸體系在含能材料方面應(yīng)用廣泛,如硝解3,7-二硝基-1,3,5,7-四氮雜雙環(huán)[3,3,1]壬烷(DPT)制備1,3,5,7-四硝基-1,3,5,7-四氮雜環(huán)辛烷(HMX)。隨著五氧化二氮電解制備的成熟化,五氧化二氮/硝酸體系有望將來在工業(yè)上得到大規(guī)模的應(yīng)用,相關(guān)硝化機(jī)理的研究顯得越來越重要。本文主要研究了五氧化二氮/硝酸體系硝解DPT制備HMX的機(jī)理,主要分兩個(gè)方面進(jìn)行研究:一是底物DPT的斷鍵方式,二是五氧化二氮以什么形式進(jìn)攻DPT。通過利用液相色譜-質(zhì)譜聯(lián)用儀來監(jiān)測反應(yīng)過程中產(chǎn)生的中間產(chǎn)物,推斷出了DPT可能的斷鍵路線,同時(shí)也得出,在低溫和低酸度且體系的硝化能力不能過強(qiáng)的條件才有利于HMX的生成。通過幾組實(shí)驗(yàn)直接和間接地確定了五氧化二氮在硝酸中是以硝酰陽離子的形式進(jìn)攻DPT:五氧化二氮/硝酸硝化對氯硝基苯為一級反應(yīng),反應(yīng)速率與共價(jià)五氧化二氮分子沒有關(guān)系,排除了共價(jià)五氧化二氮分子硝化機(jī)理;五氧化二氮/硝酸硝化萘,沒有1,3-二硝基萘和2,3-二硝基萘生成,排除了自由基硝化機(jī)理;五氧化二氮/硝酸拉曼光譜有硝酰陽離子的特征吸收峰,并且隨著五氧化二氮濃度增加,硝酰陽離子特征峰面積增大,五氧化二氮/硝酸硝化對氯硝基苯的產(chǎn)物的量會(huì)隨著硝酸銨的加入,而逐漸減少,當(dāng)對氯硝基苯和對硝基甲苯同時(shí)加入體系中,會(huì)先硝化對硝基甲苯,然后再硝化對氯硝基苯,這幾組實(shí)驗(yàn)都證明了硝酰陽離子硝化機(jī)理。根據(jù)五氧化二氮/硝酸體系硝解DPT制備HMX的機(jī)理的研究結(jié)果,提出了五氧化二氮/硝酸/有機(jī)溶劑體系。在已研究的四種有機(jī)溶劑中,同比例條件下,五氧化二氮/硝酸/乙酸酐體系符合硝化能力適中、低酸度條件,制備HMX的收率最好,其中當(dāng)乙酸酐和硝酸體積比為2:3,時(shí),五氧化二氮/硝酸/乙酸酐硝解DPT制備HMX的收率為87.9%。
[Abstract]:The new process of nitrification using nitrogen pentoxide as nitrifying agent is a representative new nitrification technology. Nitrogen pentoxide / nitric acid system is widely used in energetic materials. For example, the synthesis of HMXX by nitriolysis from 3HN 7- DPTs (3 DPTs). With the maturation of electrolysis of nitro pentoxide, the system of nitrogen pentoxide / nitric acid is expected to be applied on a large scale in the future, and the system is expected to be widely used in industry with the development of the electrolysis of nitro 2 pentabicylic acid (HMXX), and the synthesis of HMXX is expected to be carried out in a large scale in the future, and the results show that the HMXX system is suitable for the production of HMXX in the future. The study of nitrification mechanism is becoming more and more important. In this paper, the mechanism of nitration of DPT in nitrite / nitric acid system has been studied in two aspects: first, the bond breaking method of DPT substrate. The second is the form in which nitrogen pentoxide attacks. By using liquid chromatography-mass spectrometry to monitor the intermediate products produced in the reaction process, the possible bond breaking route of DPT is inferred, and the possible bond breaking route is also obtained. The formation of HMX was facilitated by low temperature and low acidity, and the nitrification ability of the system could not be too strong. It was determined directly and indirectly by several experiments that nitrogen pentoxide attacks HMX in nitric acid as nitroyl cationic acid: pentoxide. Nitration of p-chloronitrobenzene by nitration of diazo / nitric acid was a first-order reaction. The reaction rate was not related to the covalent dinitrogen pentoxide molecule, and the nitration mechanism of the covalent nitrogen pentoxide molecule was excluded, while nitration naphthalene pentoxide / nitration of naphthalene nitrate did not produce 1o 3-dinitronaphthalene and 2o 3-dinitronaphthalene, which excluded the mechanism of free radical nitration. The characteristic absorption peaks of nitrate cations were found in the Raman spectra of nitrogen pentoxide / nitric acid, and the area of the characteristic peaks increased with the increase of nitrogen pentoxide concentration. When p-chloronitrobenzene and p-nitrotoluene were added into the system, p-nitrotoluene and p-chloronitrobenzene were first nitrated and then nitration of p-chloronitrobenzene. These experiments have proved the nitration mechanism of nitrate cationic acid. According to the mechanism of nitration of DPT in nitration of nitrogen pentoxide / nitric acid system, In this paper, the nitrogen pentoxide / nitric acid / organic solvent system was proposed. In the four organic solvents studied, under the same proportion, the nitrification ability of the nitrogen pentoxide / nitric acid / acetic anhydride system was moderate, and the yield of HMX was the best under the condition of low acidity. When the volume ratio of acetic anhydride to nitric acid was 2: 3, the yield of HMX was 87.9% when the ratio of acetic anhydride to nitric acid was 2: 3, and the yield of HMX was 87.9% when the ratio of acetic anhydride to nitric acid was 2: 3.
【學(xué)位授予單位】：武漢科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：TQ126.23

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