HNAB的制備及其熱分解動(dòng)力學(xué)文章編號(hào):1006-9941(2013)01000705HNAB的制備及其熱分解動(dòng)力學(xué)張靜,王娟,徐海鳳,周新利(南京理工大學(xué)化工學(xué)院,江蘇南京210094)摘要:以2,4,6-三硝基氯苯為原料,經(jīng)親核取代、九水合硝酸鐵研磨氧化制得2,2′,4,4′,6,6′-六硝基偶氮苯(HNAB)。利用MS,R和HNMR對(duì)中間體和最終產(chǎn)物的結(jié)構(gòu)進(jìn)行了表征,并對(duì)各反應(yīng)條件進(jìn)行了優(yōu)化。親核取代反應(yīng)較優(yōu)工藝為:硫酸肼2.0246·三硝基氯苯7.6g,甲醇15mL,三乙胺6mL,反應(yīng)溫度45℃,反應(yīng)時(shí)間24h;氧化反應(yīng)較優(yōu)工藝為:1,2-二(2,4,6-三硝基苯基)肼2.08,九水合硝酸鐵7.1g,累計(jì)研磨8h,總收率68.5%。利用DSC和TG研究了HNAB的熱行為。由 Ozawa法計(jì)算得熱分解機(jī)理為n=1的成核和核生長(zhǎng)機(jī)理,機(jī)理函數(shù)為f(a)=(1-a),其活化能和指前因子分別為123.48k,mol-1,3.965×10"s-'。關(guān)鍵詞:有機(jī)化學(xué);2,2’,4,4′,6,6′-六硝基偶氮苯(HNAB);九水合硝酸鐵;熱分解動(dòng)力學(xué)中圖分類號(hào):T55;O625.65文獻(xiàn)標(biāo)識(shí)碼:ADol:10.3969/j.issn.10069941.2013.01.002改進(jìn),以硫酸肼代替無(wú)水肼,避免了由于使用高純度肼1引言引起的危險(xiǎn),同時(shí)降低了反應(yīng)成本;以九水合硝酸鐵現(xiàn)代武器和工業(yè)爆破技術(shù)的發(fā)展對(duì)含能材料的做氧化劑研磨制得HNAB,反應(yīng)條件簡(jiǎn)單,能耗低,無(wú)安全性能要求越來(lái)越高。常規(guī)的TNT、RDX等單質(zhì)炸污5染;考察了親核取代以及氧化反應(yīng)的影響因素,確藥曾多次發(fā)生意外爆炸事故,因此,鈍感含能材料定了較優(yōu)的工藝條件;利用DSC和TG熱分析方法研是重要的研究方向。究了HNAB的熱分解機(jī)理,為HNAB的生產(chǎn)、儲(chǔ)存和據(jù)文獻(xiàn)[2-3]報(bào)道,與六硝基芪(HNS)和太安運(yùn)輸安全提供參考。(PETN)相比,2,2,4,4’6,6′-六硝基偶氮苯(HNAB)2實(shí)驗(yàn)部分是一種相對(duì)鈍感的含能材料。HNAB的H327cm14、PETN的H=13cm51、HNS的H0=2.1試劑及儀器54cm。就性能上看,HNAB的密度為2,4,6-三硝基氯苯,自制;硫酸肼,化學(xué)純,國(guó)藥1.77g·cm,爆速高達(dá)7250m·s',特勞茨爾試驗(yàn)集團(tuán)化學(xué)試劑有限公司;甲醇,分析純,國(guó)藥集團(tuán)化學(xué)表明,其威力為TNT的1.23倍;HNS的密度為試劑有限公司;九水合硝酸鐵,分析純,西隴化工股份1.70g·cm-3,爆速為7000m·s-1,其威力為TNT的有限公司;三乙胺,分析純,國(guó)藥集團(tuán)化學(xué)試劑有限公1.2倍;PEN的密度為1.45g·cm-3,爆速為司;吡啶、碳酸鉀和丙酮均為分析純,國(guó)藥集團(tuán)化學(xué)試7275m·s-,其威力為TNT的1.2倍。因此,HNAB劑有限公司具有一定的應(yīng)用前景,國(guó)外也開展了對(duì)其性能、合成工Finnigan Tsq Quantum Ultra Am液質(zhì)聯(lián)用光譜藝的研究?jī)x,美國(guó) Thermo Finnigan公司;紅外光譜儀,日本現(xiàn)有的HNAB的合成方法以2,4,6-三硝基氯 SHIMADZU公司;500MHz核磁共振波譜儀,瑞士苯為原料,經(jīng)無(wú)水肼親核取代后由發(fā)煙硝酸或以冰醋 Bruker公司;DsC823e差示掃描量熱儀,酸為溶劑,氮氧化物氧化制得。實(shí)驗(yàn)使用高純度肼,不瑞士 METTLER TOLED公司;TCA/SDTA851e熱分僅成本高,而且具有一定的危險(xiǎn)性,同時(shí)氧化條件比較析儀,瑞士 METTLER TOLED公司?？量獭１疚氖窃谖墨I(xiàn)[10]基礎(chǔ)上對(duì)合成工藝進(jìn)行了2.2合成路線收稿日期:201203407;修回日期:20120605以2,4,中國(guó)煤化工酸肼發(fā)生親核取作者簡(jiǎn)介:張靜(1987-),女,研究生,主要從事含能材料相關(guān)研究代反應(yīng),生成CNMHG)肼,然后經(jīng)九水emailzj_freefly@126.com合硝酸鐵固相化刷mND,言線見(jiàn) Scheme1。CHINESE JOURNAL OF ENERGETIC MATERIALS含能材料2013年第21卷第1期(7-11)張靜,王娟,徐海鳳,周新利應(yīng)是以肼作為親核試劑,需要在堿性條件下進(jìn)行。而三乙胺不僅可以調(diào)節(jié)混合液的pH至堿性,同時(shí)還能保證反應(yīng)在均相條件下進(jìn)行,若三乙胺加入量過(guò)少,體系中的肼沒(méi)有完全釋放出來(lái),親核取代不完全,但加入e(NO3)3·9H2O量過(guò)多時(shí),產(chǎn)物會(huì)有部分溶于其中,難提純,從而影響收率。由此可知,本實(shí)驗(yàn)硫酸肼和三乙胺的比例選用Scheme 11:2.8,收率較高。2.3實(shí)驗(yàn)過(guò)程表1硫酸肼與三乙胺的物料比對(duì)反應(yīng)收率的影響2.311,2二(2,4,6·三硝基苯基)肼的合成與表征 Table1 Effect of mole ratio of hydrazine sulfate(n,)to以15mL甲醇為溶劑,稱取硫酸肼2.0 g triethylamine(n2) on the yield(0.015mol)和2,4,6-三硝基氯苯7.6g(0.03mol)于n1:n21:2.02.51:2.81:3.01:3.250mL三口燒瓶中,水浴緩慢升溫至45℃,分6次加入干yied/%70.175.380.278.3梁的三乙胺6mL(0.042mol),反應(yīng)24h,抽濾,甲醇洗滌,甲醇重結(jié)晶,干燥后得黑色固體11.2g,收率80.2%,3.1.2反應(yīng)時(shí)間對(duì)反應(yīng)收率的影響m.p.233~236℃(文獻(xiàn)值:235~237℃)。硫酸肼2.0g(0.015mol),2,4,6-三硝基氯苯7.6gS(m/z):453(M'),407(M'-NO2),361(0.03mol),甲醇15mL,分批加入三乙胺6mL,45℃條(M'-2NO,): H NMR( DMSO, 500 MHz),8件下反應(yīng),反應(yīng)時(shí)間對(duì)收率影響的試驗(yàn)結(jié)果見(jiàn)表28.5883(d,2H,N—H),9.1717(s,4H,Ar-H)。2.3.2HNAB的合成與表征表2反應(yīng)時(shí)間對(duì)反應(yīng)收率的影響稱取1,2-二(2,4,6三硝基苯基)肼2.0 g Table2 Effect of reaction time on the yield(0.004mol)和九水合硝酸鐵7.1g(0.02mol)于研 ction t/h18缽中,累計(jì)研磨8h至混合物呈黃色(采用間歇式研yield/%75.578.480.280.480.7磨,過(guò)程緩慢并且跟蹤體系溫度,跟蹤表明研磨過(guò)程無(wú)明顯放熱),用丙酮洗出產(chǎn)物,將混合液倒入碎冰中,由表2可知,隨著反應(yīng)時(shí)間的延長(zhǎng)反應(yīng)收率呈增抽濾冰水洗滌,千燥,冰醋酸重結(jié)品,千燥得橙黃色固長(zhǎng)趨勢(shì)。當(dāng)反應(yīng)時(shí)間為24h時(shí),收率為80,2%,繼續(xù)體1.78,收率為854%,m,P.20.0222℃(文延長(zhǎng)反應(yīng)時(shí)間,增長(zhǎng)趨于平緩,說(shuō)明親核取代已進(jìn)行得獻(xiàn)值:221~223℃)較為完全。該反應(yīng)為雙分子親核取代反應(yīng),2,4,6-三IR(KBr, cm"),v:3091.89(C=CH),1600.96硝基氯苯上的三個(gè)硝基的位阻比較大,給親核試劑的(C=C),15392,1348.24(-NO2),1409.96(N=N進(jìn)攻帶來(lái)一定的困難,所以,反應(yīng)收率可以通過(guò)延長(zhǎng)反MS(m/z):452(M);'HNMR(DMSO,500MH),6:應(yīng)時(shí)間提高。當(dāng)反應(yīng)時(shí)間為24h時(shí),薄層色譜(TLC)9.3370(5,4H,Ar-H)。分析產(chǎn)物轉(zhuǎn)化已基本完全,繼續(xù)延長(zhǎng)反應(yīng)時(shí)間對(duì)增大3結(jié)果與討論收率收效甚微。綜合考慮,反應(yīng)時(shí)間選擇24h為宜。3.1.3反應(yīng)溫度對(duì)反應(yīng)收率的影響3.11,2-二(2,4,6-三硝基苯基)肼的合成條件優(yōu)化硫酸肼2.0g(0.015mo),2,4,6-三硝基氯苯7.6g3.1.1三乙胺與硫酸肼的物料比對(duì)反應(yīng)收率的影響(0.03mol),甲醇15mL,分批加入三乙胺6m,反應(yīng)硫酸肼2.0g(0.015mo1),2,4,5-三硝基氯苯7.6g24h,反應(yīng)溫度對(duì)收率影響的試驗(yàn)結(jié)果見(jiàn)表3。(0.03mol),甲醇15m,45℃條件下反應(yīng)24h,三乙胺與硫酸肼的物料比對(duì)收率影響的試驗(yàn)結(jié)果見(jiàn)表1。表3反應(yīng)溫度對(duì)反應(yīng)收率的影響由表1可知,三乙胺的用量對(duì)反應(yīng)收率影響顯著,Table 3 Effect of reaction temperature on the yield收率隨著三乙胺用量的增加顯著增大。當(dāng)硫酸肼和三reaction te中國(guó)煤化工乙胺的比例為1:2.8時(shí),反應(yīng)收率高達(dá)80.2%,繼續(xù)0.274.570.4CNMHG添加三乙胺,收率呈下降趨勢(shì)。從反應(yīng)機(jī)理上看,該反Chinese Joumal of Energetic Materials, Vol 21, No. 1, 2013(7-11)含能材料wW.energetic-materials. org.cnHNAB的制備及其熱分解動(dòng)力學(xué)由表3可知,反應(yīng)溫度對(duì)收率的影響較為明顯,反收率為82.9%;繼續(xù)提高九水合硝酸鐵用量,反應(yīng)收率應(yīng)溫度由35℃升至45℃,產(chǎn)率由71.3%增至80.2%,增加不明顯,說(shuō)明1,2-二(2,4,6-三硝基苯基)肼已基本達(dá)到了最大值。取代反應(yīng)的反應(yīng)速率隨著反應(yīng)溫度的被氧化完全。從反應(yīng)成本方面考慮,1,2-二(2,4,6-三硝升高而增大,但當(dāng)溫度過(guò)高時(shí),肼受熱分解生成有毒的基苯基)肼和九水合硝酸鐵的最佳摩爾比為1:5。氧化氮煙氣,不僅給實(shí)驗(yàn)帶來(lái)危險(xiǎn)性,而且參加反應(yīng)的3.2.2研磨時(shí)間對(duì)反應(yīng)收率的影響親核試劑的量減少,收率也隨之降低,所以該反應(yīng)的最1,2-二(2,4,6-三硝基苯基)肼2.0g(0.004mol)佳反應(yīng)溫度應(yīng)控制在45℃左右。和九水合硝酸鐵7.1g(0.020mo)于研缽中研磨,研3.1.4堿對(duì)反應(yīng)收率的影響磨時(shí)間對(duì)收率影響的試驗(yàn)結(jié)果見(jiàn)表6硫酸肼2.0g(0.015mo|),2,4.6·三硝基氯苯7.6g0.03mo),甲醇15mL,反應(yīng)24h,不同堿對(duì)收率影響的表6研磨時(shí)間對(duì)反應(yīng)收率的影響試驗(yàn)結(jié)果見(jiàn)表4ble 6 Effect of grinding time on the yield表4堿對(duì)反應(yīng)收率的影響yieid/%78.280.482.982.982.9Table 4 Effect of different alkali on the vieldpyridinepotassium carbonatetriethylamine由表6可知,研磨時(shí)間是影響反應(yīng)收率的重要因yied/%78.678.980.2素之一,反應(yīng)收率隨著反應(yīng)時(shí)間的延長(zhǎng)先增大后趨于平緩,當(dāng)研磨時(shí)間為8h時(shí),收率達(dá)到82.9%,繼續(xù)延由表4可以看出,以三乙胺調(diào)節(jié)反應(yīng)體系的酸堿長(zhǎng)時(shí)間對(duì)增大收率收效甚微。該反應(yīng)為固相與固相之性效果最佳,反應(yīng)收率最高,為80.2%。碳酸鉀加入間的反應(yīng),由于固體質(zhì)點(diǎn)間鍵力大,所以,反應(yīng)速度較體系,反應(yīng)過(guò)程為非均相體系,不僅給反應(yīng)帶來(lái)一定的慢,延長(zhǎng)反應(yīng)時(shí)間有益于原料的氧化,研磨8h后,原困難,而且不利于后處理;以吡啶為堿釋放肼發(fā)生親料已基本反應(yīng)完全,繼續(xù)延長(zhǎng)反應(yīng)時(shí)間對(duì)提高收率無(wú)核取代反應(yīng),雖然反應(yīng)可在均相條件下進(jìn)行,但是,吡益。綜上所述,最佳累計(jì)研磨時(shí)間為8h。啶的堿性較弱,加人量不足則無(wú)法產(chǎn)生足量的肼,加入3.3HNAB的熱分解動(dòng)力學(xué)量過(guò)多會(huì)溶解一定量的產(chǎn)物,在后處理過(guò)程中增加產(chǎn)3.3.1DSC分析物的損失,而三乙胺的堿性比吡啶大,調(diào)節(jié)酸堿性效果樣品質(zhì)量為0.5200mg,升溫區(qū)間為50~500℃好,降低了產(chǎn)物的損失。綜上所述,該調(diào)節(jié)反應(yīng)體系的升溫速率為10K·min,氣氛為流動(dòng)N2,流速為酸堿性選用三乙胺效果最佳。20.0mt·min。DSC曲線如圖1所示。3.2HNAB的合成條件優(yōu)化3.2.11,2-二(2,4,6-三硝基苯基)肼和九水合硝酸1099891m鐵的物料比對(duì)反應(yīng)收率的影響34817℃1,2-二(2,4,6-三硝基苯基)肼和九水合硝酸鐵于研2 63402mJlized-6542Jg'peak37206℃缽中研磨,反應(yīng)物料比對(duì)收率影響的試驗(yàn)結(jié)果見(jiàn)表5。219.71℃2peak22150℃表51,2-二(2,4,6·三硝基苯基)肼和九水合硝酸鐵的物料比對(duì)反應(yīng)收率的影響Table 5 Effect of mole ratio of 1, 2-bis(2, 4, 6-trinitrophenyl)hydrazine( n, ) to Fe(NO, ),9H, o(n,)on the yieldT/℃1:31:41:51:6圖1HNAB的DSC曲線yield/%75.677.882.982.983.0Fig 1 DSC cruve of HNAB由表5可知,九水合硝酸鐵作為氧化劑參加反應(yīng),反THE由圖1B先吸熱熔化后分解放熱應(yīng)收率隨氧化劑用量的增加而增大,當(dāng)1,2-二(2,4,6-三其熔點(diǎn)為21中國(guó)煤化工獻(xiàn)值(221.95~硝基苯基)肼和九水合硝酸鐵的摩爾比為1:5時(shí),反應(yīng)22295℃CNMHG始放熱分解,峰CHINESE JOURNAL OF ENERGETIC MATERIALS含能材料2013年第21卷第1期(7-11)張靜,王娟,徐海鳳,周新利溫為372.06℃,分解熱焓為1920.98」·g。這表對(duì)于炸藥的熱分解,通過(guò)不同升溫速率的TG曲明,HNAB具有較高的熔點(diǎn)和分解溫度,耐熱性能良線進(jìn)行非等溫動(dòng)力學(xué)分析時(shí),常用 Ozawa公式:好。分析原因認(rèn)為,HNAB分子中具有大共軛體系(1對(duì)稱結(jié)構(gòu),而且基團(tuán)配置均勻,這對(duì)分子的熱穩(wěn)定性和l9=gkx()-2315-04767耐熱性能非常有利13式中,B為升溫速率K·mn;A為指前因子,s;a為3.3.2HNAB的熱分解動(dòng)力學(xué)炸藥反應(yīng)深度;R為理想氣體常數(shù),·mo·K';E為樣品質(zhì)量為(0.5000±0.02)mg,升溫區(qū)間為表觀活化能mo;T為溫度,k;F(a)為機(jī)理函數(shù)的50~500℃,升溫速率為1015、20、25K·min,氣氛為積分形式流動(dòng)N2,流速為30.0mL·mn,TG曲線如圖2所示。本實(shí)驗(yàn)的升溫速率分別為10、15、20、25K·min1根據(jù)HNAB的熱重分析曲線求出反應(yīng)深度a分別為30.40.50.6、0.7、0.8時(shí)所對(duì)應(yīng)的分解溫度T。根據(jù)公式(1)和試驗(yàn)數(shù)據(jù)對(duì)B與1/T進(jìn)行線性擬合,由20 Kmin直線斜率獲得表觀活化能E,計(jì)算結(jié)果見(jiàn)表7。根據(jù)Doye法5,公式(1)可變換成lg F(a)AERBRT0對(duì)于任何熱分解反應(yīng)機(jī)理函數(shù)5,1gF(a)與1/T均呈線性關(guān)系,線性擬合分析表明,當(dāng)n=1時(shí),通過(guò)r℃圖2HNAB在不同升溫速率的熱重曲線Doye法與 Ozawa法求得的表觀活化能接近,且線性Fig 2 TG curves of HNAB at different heating rates擬合所得的相關(guān)系數(shù)好,計(jì)算結(jié)果見(jiàn)表8。表7 Ozawa法計(jì)算的HNAB的熱分解活化能Table 7 Thermal decomposition activation energy for HNAB by Ozawa's methodtemperature/KE/k·molB=10K·minB=15K·minB=20K·minB=25K·min-1Ozawa's method593.8910.26617.66113.97602.92616.5620,31627.74112.10611.45628.39119.89617.4630.02634.44642.00119.47623.49635639.84647.04126.61629.03644.12644.5110.90.8635.99651.92662.37mean表81gF(a)-1/T線性擬合的結(jié)果Table 8 Result of linear fitting g F(a)-1/TOzawa's methodB/K. min-bnterceptE/kJ·molf/k」·mol10.21196411.22720.99156.778x101010.36206651.70980.9906121.091.104×1012.89336794.00240.9908123.681.112×1012mean123.483.965×101線性擬合分析結(jié)果表明,HNAB的熱分解屬于a=kf(a)n=1的成核和核生長(zhǎng)機(jī)理,反應(yīng)機(jī)理函數(shù)的微分形式中國(guó)煤化工為:f(a)=(1-a),熱分解動(dòng)力學(xué)方程為:=3.965CNMHGChinese Joumal of Energetic Matenials, Vol 21, No. 1, 2013(7-11)含能材料www.energetic-materials.orgenHNAB的制備及其熱分解動(dòng)力學(xué)diaminoazofurazan and diaminoazoxyfurazan[ 1]. 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Chinese Journal of Explosives& Pro-LI Hong-zhen, HUANG Ming, HUANG Yi-gang, et al. Progress inlants( Huo Hayao Xuebao), 2009, 32(2): 32-35Synthesis and Thermal Decomposition Kinetics of HexanitroazobenzeneZHANG Jing, WANG Juan, XU Hai-feng, ZHOU Xin-liSchool of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094,ChinaAbstract: Hexanitroazobenzene( HNAB ) was prepared via nucleophilic substitution reaand oxidation reaction using picrylchloride as raw materials. The intermediate and final product were characterized by MS, IR and H NMR. The reaction conditionswere optimized. The nucleophilic substitution reaction conditions are determined as: hydrazine sulfate 2.0 g, 2,4, 6-trinitrochlorobenzene 7.6 g, methyl alcohol 15 mL, triethylamine 6 mL, reaction time 24 h under 45 C. The oxidation reaction conditions aredetermined as: 1, 2-bis(2, 4, 6-trinitrophenyl)hydrazine 2.0 g, iron( m)nitrate nonahydrate 7. 1 g, cumulative grinding 8 h. Thetotal yield is 68.5%. Thermal behaviors of HNAB were studied by DSC and TG. The thermal decomposition mechanism of HNABthe thermal decomposition process of HNAB obtained by the Ozawa's method are 123. 48 k). mol-, 3. 965x 101,on ofis classified as random nucleation and growth with n=1. The activation energy, pre-exponential factor and mechanism fura), respectively中國(guó)煤化工Key words: organic chemistry: hexanitroazobenzene( HNAB ) iron( l)nitrate-osition kineticsCLC number: T 55: O625 65Document code: ATHCNMHG941.2013.01.002CHINESE JOURNAL OF ENERGETIC MATERIALS含能材料2013年第21卷第1期(7-11)