二十面體多硼氫陰離子化合物及其在火炸藥中的應(yīng)用研究進(jìn)展

2017-06-28 14:20:10單自興繩利麗楊榮杰

火炸藥學(xué)報 2017年3期

單自興，繩利麗，楊榮杰

(1. 北京理工大學(xué)材料學(xué)院，北京 100081;2. 武漢大學(xué)化學(xué)學(xué)院，湖北武漢 430072)

單自興1,2，繩利麗1，楊榮杰1

(1. 北京理工大學(xué)材料學(xué)院，北京 100081;2. 武漢大學(xué)化學(xué)學(xué)院，湖北武漢 430072)

引言

硼氫化合物作為高能材料，由于其熱值高，燃燒產(chǎn)物分子質(zhì)量低，在大推力火箭的研發(fā)中受到高度關(guān)注[1-2]。早在20世紀(jì)40年代，Leonard[3]和Sawyer[4]就指出，具有適度高體積密度的硼氫化合物是最有效的火箭液體燃料，它們?nèi)紵耆?，不發(fā)生爆燃，可產(chǎn)生最高的噴氣動力。1947年，Rundle[5]基于硼烷化學(xué)的結(jié)構(gòu)研究首次提出二電子三中心鍵新概念，大大促進(jìn)了硼氫化合物化學(xué)的發(fā)展。

本文主要依據(jù)文獻(xiàn)資料，系統(tǒng)介紹推進(jìn)劑及火炸藥研究中涉及的十二氫十二硼酸陰離子化合物的制備、熱行為、熱化學(xué)、能量性質(zhì)以及它們對推進(jìn)劑及火炸藥組分性質(zhì)的影響，展望此類化合物在推進(jìn)劑及火炸藥中的應(yīng)用前景，指出未來多硼氫化合物推進(jìn)劑研究的主要方向。

1 十二氫十二硼酸鹽研究概況

1955年，Longuet-Higgins[6]通過分子軌道理論計算，第一次預(yù)測到穩(wěn)定的硼氫化合物B12H12只能以陰離子形式存在。1960年，Hawthorne等[7]在2-碘代十硼烷與三乙胺反應(yīng)中首次低收率分離出十二氫十二硼酸雙三乙胺鹽[bis(triethylammonium) dodecahydrododeca-borate]，并通過X-射線分析確認(rèn)了這種硼氫陰離子的二十面體閉籠型結(jié)構(gòu)(見圖1)[8]。

最簡單的十二氫十二硼酸化合物是十二氫十二硼酸(H2B12H12)[33]，它通常由水溶性十二氫十二硼酸鹽通過氫離子柱上交換制備，并常以二水合物(H3O)2B12H12的形式存在。水合十二氫十二硼酸是一種強(qiáng)酸，可與金屬、金屬氧化物或金屬碳酸鹽以及氨、肼、鏈狀或雜環(huán)有機(jī)胺、有機(jī)膦、有機(jī)硫等Lewis堿反應(yīng)生成水溶性的或水難溶的、高度熱穩(wěn)定的十二氫十二硼酸鹽。十二氫十二硼酸的輕金屬鹽、氨鹽、低級胺鹽、雜環(huán)富氮鹽等具有良好的水溶性，使得通過復(fù)分解反應(yīng)可以方便實現(xiàn)陽離子轉(zhuǎn)換(見圖3)。

2 十二氫十二硼酸陰離子的制備

2.1 較低級硼烷在有機(jī)堿存在下熱解

2.2 較低級離子型硼氫合物熱解

2.3 MBH4與鹵化四烷基銨混合物熱解

2.4 MBH4與Lewis酸混合物熱反應(yīng)

2.5 較低級硼烷與硼烷絡(luò)合物的熱反應(yīng)

2.6 較低級硼烷與離子型硼氫合物熱反應(yīng)

2.7 甲硼烷絡(luò)合物與金屬硼氫化物熱加成反應(yīng)

2.8 硼合物的高溫還原偶聯(lián)反應(yīng)

3 十二氫十二硼酸鹽的熱行為

3.1 十二氫十二硼酸

3.2 十二氫十二硼酸金屬鹽

十二氫十二硼酸金屬鹽一般都具有高的熱穩(wěn)定性。輕的堿金屬(Li、Na)的十二氫十二硼酸鹽常與水、氨和作為溶劑的有機(jī)Lewis堿(如THF、diglyme、MeCN等)生成溶劑合物，而重的堿金屬(Cs、Rb)的十二氫十二硼酸鹽則易從水中得到純品。堿金屬十二氫十二硼酸鹽都具有非常高的分解溫度，如無水Cs2B12H12在真空管中加熱到810℃不發(fā)生任何變化；K2B12H12加熱到700℃未顯示出分解跡象；Na2B12H12·4H2O在140℃和195℃分別失去兩分子水得到無水物，直至505℃因發(fā)生氧化降解而呈現(xiàn)放熱效應(yīng)(可能生成B12H11OH，在830℃燃燒)。堿金屬(Li、Na、K)十二氫十二硼酸鹽的高溫?zé)岱纸庋芯勘砻?，分解過程中包含多個步驟，先生成含有二十面體B12骨架的失氫單體M2B12H12-x，接著生成(M2B12Hz)n聚合物[105]。堿土金屬及第三族金屬(包括稀土)的十二氫十二硼酸鹽通常在水中得到含不同數(shù)目水分子的溶劑合物；這些水合物在空氣中加熱時不同程度失水；有的在惰性氣氛中加熱時可得到無水物，但有的在高溫脫水時會發(fā)生分解。如，無水MgB12H12不能通過Mg(H2O)6B12H12·6H2O的簡單加熱脫水來制備[106]。研究表明，十二氫十二硼酸金屬鹽在惰性氣氛和真空狀態(tài)下的熱分解行為幾乎相同；而在空氣中加熱時分解溫度明顯降低，意味著氧化劑的存在會加速硼籠化合物的分解。

其他族金屬的十二氫十二硼酸鹽在較高溫度下的去溶劑化或去配體過程中也常常伴隨著分解。

3.3 十二氫十二硼酸銨鹽

十二氫十二硼酸銨鹽的熱穩(wěn)定性與銨陽離子的組成和結(jié)構(gòu)以及熱分解的氣氛密切相關(guān)。(NH4)2B12H12在200～400℃熱分解[107]得到H2和NH3的氣體混合物；而高于400℃只有H2放出；(NH4)2B12H12在惰性氣氛中熱解得到單質(zhì)硼，而在氨中得到六角形氮化硼[108]。質(zhì)子化的有機(jī)銨鹽熱穩(wěn)定性較低。質(zhì)子化富氮雜環(huán)銨鹽的熱分解溫度一般低于250℃，有的甚至在100℃以下就開始分解；如3,5-二氨基-1,2,4-三唑鹽的分解溫度為60～70℃[109]。然而，tran-丁烯-1,4-雙(3-甲基-1,3-咪唑)鹽[110]的分解溫度卻在300℃以上。加熱介質(zhì)也對富氮雜環(huán)銨鹽的熱穩(wěn)定性產(chǎn)生重大影響。Nedel′ko, V. V.等[111]研究了十二氫十二硼酸六次甲基四胺鹽的熱行為，指出在高于150℃時開始分解出NMe3等氣體產(chǎn)物，160～200℃時的熱分解不能用簡單的動力學(xué)方程描述，熱解殘余物是高孔隙難溶固體。Saldin等[112]研究了(C6O4H9NH3)2B12H12的熱轉(zhuǎn)變，發(fā)現(xiàn)它在約300℃ 時開始著火，加熱到1000℃ 時生成碳、無定型硼或(和)碳化硼的混合物。如果在空氣中加熱，則碳和氧化硼是主產(chǎn)物，且融化的氧化硼保護(hù)了硼或(和)碳化硼。一般說來，由正烷基構(gòu)成的季銨鹽熱穩(wěn)定性較高，分解溫度一般在250℃以上；隨著烷基碳鏈的增長，銨鹽的分解點或熔點迅速降低；如 (Me4N)2-B12H12約在342℃分解; (Et4N)2B12H12于306℃分解; (n-Bu4N)2B12H12熔點為240～242 ℃;(Hex4N)2B12H12熔點為83～84℃ (離子液體)。十二氫十二硼酸雙胍鹽在胍中引入一個氨基后，熔點和分解溫度明顯升高；但引入2個氨基或3個氨基后分解點反而有所降低。

4 十二氫十二硼酸鹽的熱化學(xué)

Shubina等[115]在低極性介質(zhì)中測定了(Bu4N)2B12H12與各種質(zhì)子給體作用的焓變和熵變，指出由[B12H12]2-到[B10H10]2-BH…HO的鍵強(qiáng)度增加，并且酸的給質(zhì)子能力的增加導(dǎo)致生成雙叉氫鍵(bifurcate H-bonds)。

Hanumantha Rao等[109]測定了多種十二氫十二硼酸富氮鹽的熱化學(xué)數(shù)據(jù)。指出除十二氫十二硼酸羥胺鹽(離子液體，具有最低的摩爾生成焓和最高的爆熱，800℃燃燒后的殘留質(zhì)量分?jǐn)?shù)近20%)外，其他多氮鹽燃燒時殘留質(zhì)量分?jǐn)?shù)均在60%以上；十二氫十二硼酸雙三氨基胍鹽燃燒后的殘留質(zhì)量分?jǐn)?shù)竟高達(dá)78.5%。另一方面，十二氫十二硼酸富氮鹽的爆熱隨著氮含量的增加而降低。但是，這些十二氫十二硼酸富氮鹽在純化、干燥及應(yīng)用過程中可安全處理而不發(fā)生爆炸。

Hanumantha Rao等[119]也測定了一些烷基咪唑鹽[1,4-2(3-甲基亞胺-唑)-2-丁炔、2(3-甲基-n-丁基咪唑)、2(3-甲基-n-己基咪唑)、2(3-甲基- n-辛基咪唑)、2(3-甲基-n-十一烷基咪唑)]的標(biāo)準(zhǔn)摩爾燃燒熱(-15000～ -28000kJ/mol)、標(biāo)準(zhǔn)摩爾生成焓(-700～ -3300kJ/mol)和爆熱(-43300～ -45300kJ/mol)，其中，丁炔-2-撐-3-甲基咪唑鹽和雙3-甲基-丁基咪唑鹽的標(biāo)準(zhǔn)摩爾生成焓分別為-811和-745kJ/mol。

5 十二氫十二硼酸鹽在推進(jìn)劑及火炸藥中的應(yīng)用

在火炸藥和推進(jìn)劑研究中涉及的十二氫十二硼酸鹽主要是堿金屬鹽、氮基陽離子鹽和少數(shù)過渡金屬鹽(包括Ti、Cu、Fe、Pb等)，如表1 所示。

表1 火炸藥研究中主要涉及的十二氫十二硼酸鹽Table 1 Major salts involved in the study of propellant and explosive

5.1 與推進(jìn)劑組分的作用及催化硝胺分解的機(jī)制

龐維強(qiáng)等[120-121]研究了十二氫十二硼酸四乙銨鹽與固體推進(jìn)劑中一些常見組分的相容性，指出，十二氫十二硼酸四乙銨鹽與3-硝基-1，2，4-三唑-5-酮鉛(NTO-Pb)、六硝基六氮雜異伍茲烷(CL-20)、環(huán)氧乙烷-四氫呋喃共聚醚(PET)、聚乙二醇(PEG)、N-100、端羥基聚丁二烯(HTPB)、CB、A1、Mg、Al2O3, C2、二酸二異辛酯(DOS)和KP組成的二元體系是相容的，對端羥基疊氮聚醚(GAP)和奧克托今(HMX)稍敏感，對己二酸酮(AD-Cu)、β-Cu和φ-Pb敏感，對RDX、3，4-二硝基呋咱基氧化呋咱(DNTF)和GUDN不相容。他們觀察發(fā)現(xiàn)除2,4-甲苯二異氰酸酯(TDI)外，CL-20、HMX、GAP、RDX、AP、NTO-Pb、HTPB、DOS、IPDI、AD-Cu、Al 粉和 Mg粉對十二氫十二硼酸四乙銨鹽的熱分解(305.8℃)不產(chǎn)生明顯影響。

另一方面，大量的研究[122-126,132-134,137]表明，十二氫十二硼酸鹽能改善固體推進(jìn)劑的燃燒性能，特別是催化硝胺推進(jìn)劑的分解。當(dāng)十二氫十二硼酸鉀應(yīng)用于含三氨基胍的推進(jìn)劑配方中時，推進(jìn)劑的燃速大幅度提高。20世紀(jì)90年代初，Schroeder[122]報道了硼氫化合物加速硝胺推進(jìn)劑的分解，指出堿金屬硼氫化合物可使黑索金(RDX)在其熔點附近開始分解。之后Schroeder[123]又對硼氫酸鹽對硝胺推進(jìn)劑燃燒的促進(jìn)作用進(jìn)行了評述。后來Schroeder等[124]研究了K2B12H12對RDX熱分解行為時指出K2B12H12能夠加速RDX分解，并改變分解產(chǎn)物的分布，證明1,3,5-三嗪、單亞硝基-RDX (MRDX)和相關(guān)硝胺是這種熱分解的產(chǎn)物，這對于闡明K2B12H12加速RDX熱分解的機(jī)制非常有意義。關(guān)于多硼氫化合物催化硝胺分解的機(jī)制，Schroeder[123]認(rèn)為是硼氫化合物中的B-H鍵進(jìn)攻硝胺官能團(tuán)所致(見圖 4)。

5.2 在推進(jìn)劑及火炸藥中的應(yīng)用

十二氫十二硼酸鹽在推進(jìn)劑中主要用作高能、高密度燃料、燃料添加劑和氣體發(fā)生劑以及燃速調(diào)節(jié)劑[125-126]。

早在1963年，Du Pont公司[127]就合成了通式為M(2-n)(B12H12-n-yXy·nSRR′)b(n-2)的十二氫十二硼酸鹽，用作彩色火焰的燃料添加劑。

Trofimenko[130]指出，將硫、氟、疊氮基、氰酸基、硫氰酸基等在光照條件下引入全鹵代的二十面體硼酸鹽(NH4)2B12Br12或H2B12Cl12中，再用四甲基氯化銨水溶液處理得到的四甲基銨鹽，如(Me4N)2B12Br11N3，可以用作高能燃料的組分。

Shibata等[132]將K2B12H12用于含三氨基胍的推進(jìn)劑配方中，當(dāng)壓強(qiáng)為49.02MPa時，燃速為54000mm/s，而在98.04MPa時燃速高達(dá)92000mm/s，是M30推進(jìn)劑燃速的1000倍。Johnson等[133]將K2B12H12用于含硝基胍的推進(jìn)劑配方中，結(jié)果顯示組分反應(yīng)速率加快，且短時間內(nèi)產(chǎn)生大量氣體。

Mangum[134]最近公開了一種無氯的可燃固體推進(jìn)劑配方，其中，K2B12H12、CS2B12H12和(Bu4N)2B12H12被用作固體氧化劑KIO4、燃料和黏合劑組成的火箭推進(jìn)劑燃燒的催化劑。實驗表明，十二氫十二硼酸鹽的加入(質(zhì)量分?jǐn)?shù)0.5%～5.0%)使推進(jìn)劑的密度提高0.15～0.51g/cm3, 體積比沖可提高3511～10646N·s/kg，比沖可提高10～50s (見表2)。有趣的是, 當(dāng)硼氫鹽的質(zhì)量分?jǐn)?shù)為2%、與KIO4的質(zhì)量比為10∶90時，引入上述3種硼氫鹽后推進(jìn)劑的燃速分別為4089.4、787.4和736.6mm/s；而當(dāng)CS2B12H12的用量增加時，燃速迅速增加；當(dāng)CS2B12H12與KIO4的質(zhì)量比為30∶70時，推進(jìn)劑的燃速高達(dá)25400mm/s。即使以廉價的硝酸鉀代替高碘酸鉀，在類似情況下，推進(jìn)劑燃速也能達(dá)到17881.6mm/s (見表 3)。基于表3數(shù)據(jù)不難推想，用廉價的K2B12H12代替CS2B12H12可能效果更佳。

表2 十二氫十二硼酸鹽對固體復(fù)合推進(jìn)劑性能的影響[134]Table 2 Effect of dodecahydrododeca-borate salts on the properties of solid composite propellants

注：黏合劑為多元醇+異氰酸酯+穩(wěn)定劑+添加劑；十二氫十二硼酸鹽的質(zhì)量分?jǐn)?shù)是固體復(fù)合推進(jìn)劑的2%。

表3 十二氫十二硼酸鹽與不同氧化劑混合物的燃速[134]Table 3 Burning rate of the mixture of dodecahydrododeca- borate salts with different oxidizers

Saldin等[94-99]發(fā)明了十二氫十二硼酸甲殼素鹽[(C6O4H9NH3)2B12H12]的制備方法，觀察到這種鹽能快速點火并完全燃燒，是一種防爆、無毒和無毒氣排放、耐熱、耐濕、具有優(yōu)良力學(xué)性能和鍵合作用的高能物質(zhì)，適于用作槍粉、煙火、炸藥、推進(jìn)劑的點火劑、起爆藥的組分[98-99, 137-141]。如十二氫十二硼酸甲殼素鹽本身[140]以及與過渡金屬，特別是Cu2+、Co2+、Ni2+、Zn2+或Mn2+[138]以及鎂或鋁[138]的硝酸鹽(或高氯酸鹽)組成的復(fù)合物，用作煙火藥等的能量增強(qiáng)型點火添加劑(energy-intensive igniting additives)。含有有效量鉻酸甲殼素鹽(氧化劑)的十二氫十二硼酸甲殼素鹽用作煙火的點火添加劑，使得煙火藥燃燒時不產(chǎn)生有害氣體[140]。十二氫十二硼酸甲殼素鹽與高氯酸或高氯酸銨或高氯酸甲殼素鹽的加合物被用作耐熱的和具有良好力學(xué)性能的煙火配方中的無毒貯藏穩(wěn)定劑[141]。

Saldin等也將十二氫十二硼酸烏洛托品鹽[142]和超細(xì)聚四氟乙烯-氧化石墨水溶膠與十二氫十二硼酸生成的勻膠[143]分別用作煙火的高能點火劑和燃燒穩(wěn)定劑以及集能系統(tǒng)(condensed energy systems)的高能組分。

Saldin等[144]還將多乙撐亞胺的水溶液與十二氫十二硼酸作用制得的十二氫十二硼酸乙撐亞胺鹽[(C2H4NH·0.4H2B12H12]用作煙火藥點火添加劑。Saldin等[145]指出，由H2B12H12水溶液和超細(xì)PTFE加到含氧化石墨的水溶膠中，制得的均相水溶液可用作火藥、煙火藥和炸藥中的高能組分。

將十二氫十二硼酸富氮鹽及雜環(huán)銨鹽應(yīng)用于固體火箭推進(jìn)劑中近年受到較多關(guān)注，已有多項專利和研究報告。Hanumantha Rao和Muralidharan[109,119]以及Shackelford[146]等認(rèn)為，十二氫十二硼酸氮雜環(huán)銨鹽，包括咪唑鹽、1,2,4-三唑鹽、1,2,3-三唑鹽、四唑鹽、吡唑鹽、噁唑鹽、異噁唑鹽、呋咱鹽、氧化呋咱鹽等高的體積密度以及燃燒產(chǎn)物的低分子量，適于在固體火箭推進(jìn)劑中用作鈍感含能材料和燃燒加速劑。它們有利于提供高密度比沖，增強(qiáng)推進(jìn)劑的能量，增加導(dǎo)彈有效負(fù)荷，改善燃燒性能，進(jìn)而提高火箭推進(jìn)劑的比沖。另一方面，這些鹽的極低蒸汽壓為推進(jìn)劑的生產(chǎn)、使用以及突發(fā)事件的處理提供了方便和健康保證。

6 多氫多硼酸鹽離子液體在推進(jìn)劑中的應(yīng)用

硼氫離子液體具有蒸汽壓低、熔點低、密度高、穩(wěn)定性高和反應(yīng)性低的特性，對推進(jìn)劑及火炸藥工作者具有極大吸引力。非取代的十二氫十二硼酸銨鹽離子液體，迄今僅有數(shù)種[十二氫十二硼酸雙四正己銨鹽、十二氫十二硼酸雙羥胺鹽、十二氫十二硼酸雙5-(3,5-二硝基甲苯)-1H-四唑-4-銨鹽、十二氫十二硼酸雙3,5-二氨基-1H-1,2,4-三唑-4-銨鹽等]。Gabel和Justus[147-149]以及Kopytin[150]等報道了合成含B12H11- (NR1R2R3)-陰離子的高能離子液體的方法，制備出一系列胺取代的二十面體硼氫陰離子的高能離子液體(優(yōu)選的陽離子是Li+、R4N、咪唑和吡啶)。2015年，Jenne和Kirsch[151]制備出另一類烷氧基取代的[B12X11OR]2-(X=Cl、Br、R = Pr、octyl、dodecyl)的二十面體硼鹵酸鹽，其中，十一氯正丙氧基十二硼酸-1-己基-3-甲基咪唑鹽熔點為96℃。

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SHAN Zi-xing1,2, SHENG Li-li1, YANG Rong-jie1

(1. School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081，China；2. College of Chemistry and Molecular Sciences,Wuhan University, Wuhan 430072，China)