高剪切速率下硼与HTPB、PBT和GAP端羟基的反应活性
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摘要
含硼富燃料推进剂具有较高的质量热值和体积热值,是固体火箭冲压发动机较理想的燃料之一,而无定形硼与黏合剂中的羟基可发生反应,导致推进剂药浆表观黏度增大快、药浆适用期缩短等问题。计算了分别以端羟基聚丁二烯(HTPB)、3,3?二叠氮甲基氧丁环?四氢呋喃共聚醚(PBT)和聚叠氮缩水甘油醚(GAP)为粘合剂的含硼推进剂的理论体积热值,并采用双螺杆转矩流变仪和红外光谱研究了B/HTPB、B/PBT和B/GAP体系在高剪切速率混合过程中的流变和红外特性,分析了硼粉表面酸性杂质与粘合剂端羟基的反应活性。结果表明,经过合理配方设计,B/PBT/AP和B/GAP/AP的质量比为50∶20∶30时的体积热值均超过64.00 MJ·~(-3),大于B/HTPB/AP体系的体积热值(61.08 MJ·dm~(-3))。在剪切速率为355.56 s~(-1)、55℃条件下,含25%硼的B/HTPB体系表观黏度快速增加到260 Pa·s,混合110 min发生凝胶现象;含40%硼的B/PBT体系混合7 h黏度仅从3.63 Pa·s上升到10 Pa·s;含55%硼的B/GAP体系混合7 h黏度由5.96 Pa·s下降到0.33 Pa·s。B/HTPB混合体系红外光谱B—O振动吸收峰随着混合时间的增加而逐渐增强,C—O(伯醇)振动吸收峰随着混合时间的增加而逐渐减弱,而B/PBT和B/GAP体系混合420 min后红外光谱B—O振动吸收峰和C—O(伯醇、仲醇)振动吸收峰几乎没有变化。PBT和GAP端羟基与硼粉酸性杂质的反应活性比HTPB的端羟基的活性低很多,这有利于改善含硼推进剂药浆的工艺性能。
The boron based fuel?rich propellant is considered as one of the ideal fuel for solid rocket ramjet owning to the high gravimetric and volumetric heating value of boron. However,the amorphous boron powder could react with the terminal hy?droxyl groups of the binder,causing increase of apparent viscosity and pot?life of the slurry shortening. The theoretical volumet?ric heating values of three boron?based propellants were calculated,in which hydroxyl?terminated polybutadiene(HTPB),3,3?bis(azidomethyl)oxetane and tetrahydrofuran copolyether(PBT)and gycidyl azide polymer(GAP)was used as the bind?er. The rheological properties and infrared characteristics of B/HTPB,B/PBT and B/GAP at high shear rate were studied by the co?rotating twin screw rheometer and Fourier transform infrared spectrometer,respectively. The reactivity of terminal hydroxyl groups for the three binders was analyzed. At a rational designed composition of 50∶20∶30,the volumetric heating values ex?ceeded 64.00 MJ·dm~(-3) for B/PBT/AP and B/GAP/AP,which was higher than B/HTPB/AP system(61.08 MJ·dm~(-3)). At shear rate of 355.56 ~(-1) and 55 ℃,the apparent viscosity for B/HTPB slurry with 25% boron rapidly increased to 260 Pa·s and reached gel state after 110 min mixing. After 7 h under same condition,the apparent viscosity increased from 3.63 Pa·s to 10.6 Pa·s for B/PBT with 40% boron,whereas reduced from 5.96 Pa·s to 0.33 Pa·s for B/GAP with 55% boron. For B/HTPB slurry,enhanced B—O vibration absorption and gradually weaken C—O vibration absorption were detected during mixing,which were un?changed for B/PBT and B/GAP slurries. Therefore,considering reacting with the acidic impurities on the surface of boron parti?cles,the reactivity of terminal hydroxyl groups of PBT and GAP were much lower than that of HTPB,which would facilitate pro?cessing of boron?based propellant.
The boron based fuel?rich propellant is considered as one of the ideal fuel for solid rocket ramjet owning to the high gravimetric and volumetric heating value of boron. However,the amorphous boron powder could react with the terminal hy?droxyl groups of the binder,causing increase of apparent viscosity and pot?life of the slurry shortening. The theoretical volumet?ric heating values of three boron?based propellants were calculated,in which hydroxyl?terminated polybutadiene(HTPB),3,3?bis(azidomethyl)oxetane and tetrahydrofuran copolyether(PBT)and gycidyl azide polymer(GAP)was used as the bind?er. The rheological properties and infrared characteristics of B/HTPB,B/PBT and B/GAP at high shear rate were studied by the co?rotating twin screw rheometer and Fourier transform infrared spectrometer,respectively. The reactivity of terminal hydroxyl groups for the three binders was analyzed. At a rational designed composition of 50∶20∶30,the volumetric heating values ex?ceeded 64.00 MJ·dm~(-3) for B/PBT/AP and B/GAP/AP,which was higher than B/HTPB/AP system(61.08 MJ·dm~(-3)). At shear rate of 355.56 ~(-1) and 55 ℃,the apparent viscosity for B/HTPB slurry with 25% boron rapidly increased to 260 Pa·s and reached gel state after 110 min mixing. After 7 h under same condition,the apparent viscosity increased from 3.63 Pa·s to 10.6 Pa·s for B/PBT with 40% boron,whereas reduced from 5.96 Pa·s to 0.33 Pa·s for B/GAP with 55% boron. For B/HTPB slurry,enhanced B—O vibration absorption and gradually weaken C—O vibration absorption were detected during mixing,which were un?changed for B/PBT and B/GAP slurries. Therefore,considering reacting with the acidic impurities on the surface of boron parti?cles,the reactivity of terminal hydroxyl groups of PBT and GAP were much lower than that of HTPB,which would facilitate pro?cessing of boron?based propellant.
引文
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[8]唐汉祥,陈江,吴倩,等.硼粉改性对推进剂工艺性能的影响[J].含能材料,2005,13(2):69-73.TANG Han-xiang,CHEN Jiang,WU Qiang,et al.Effect of modified boron powder on propellant processing characteristics[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2005,13(2):69-73.
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[10]Hui-xiang Xu,Wei-qiang Pang,Hong-wei Guo,et al.Combustion characteristics and mechanism of boron-based,fuel-rich propellants with agglomerated boron powder[J].Central European Journal of Energetic Materials,2014,11(4),575-587.
[11]庞爱民.固体火箭推进剂理论与工程[M].北京:中航宇航出版社,2014:202-372.PANG Ai-Ming.The theory and engineering of solid rocket propellant[M]. Beijing:China Aerospace Publishing House,China,2014; pp:202-372.
[12]张琼方,张教强,国际英,等.超细硼粉的3,3-双(叠氮甲基)环氧丁烷-四氢呋喃共聚醚包覆研究[J].含能材料,2005,13(3):185-188.ZHANG Qiong-fang,ZHANG Jiao-qiang,GUO Ji-ying,et al.Research on the surface coating of superfine boron particles with PBT[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2005,13(3):185-188.
[13]R Pein,S Anders.Investigation of fuel-rich boron combustion in a pressurized combustion bomb[J].Analytica Chimica Acta,2002,5(1-6):427-437.
[14]Ing-Ming SHYU,Tai-Kang Liu.Combustion characteristics of GAP-coated boron particles and the fuel-rich solid propellant[J].Combustion and Flam,1995,100(4):634-644.
[15]Glenn H Fredrickson,Ludwik Leibler.Theory of diffusion-controlled reactions in polymers under flow[J].Macromolecules,1996,29:2674-2685.
[16]Hong Zheng,Wei Yu,Chixing Zhang.Numerical sim ulation of morphology of polymer chain coils in complex flows[J].Chinese Journal of Polymer Science,2005,23(5):453-462.
[17]石海信.机械力化学效应及应用[J].化学教学,2008,5:50-55.SHI Hai-xin.Chemical effect of mechanical fore and its application[J].Education in Chemistry,2008,5:50-55.
[18]姜爱民,于胜春,邹长青.立式捏合机混合釜内推进剂药浆混合过程数值仿真[J].海军航空工程学院学报,201 1,26(24):381-386.JIANG Ai-ming,YU Sheng-Chun,ZOU Chang-qing.KNumerical simulation of the m ixing of composite solid propellant slurry in a kneading mixer[J].Journal of Naval Aeronautical and Astronautical University,2011,26(24):381-386.
[19]R L Werner,K G O'Brien.The infra-red spectra of the borate esters[J].Australian Journal of Chem istry,1 955,8(3):355.
[20]高鸿宾.有机化学(第四版)[M].北京:高等教育出版社,2005:296-301.GAO Hong-bin.Organic chemistry(the fourth edition)[M].Beijing:Higher Education Press,China,2005:296-301.
[2]Brain Van Devener,Jesus Paulo L Perez,Scott Anderson.Air-stable,unoxidized,hydrocarbon-dispersible boron nanoparticles[J].Materials Research Society,2009 24(P11):3462-3464.
[3]胡秀丽,周伟良,肖乐勤,等.硼及其团聚颗粒在HTPB中流变性能的研究[J].固体火箭技术,2014,37(3):369-375.HU Xiu-li,ZHOU Wei-liang,XIAO le-qin,et al.Effect of boron powder and agglomerated boron particles on the rheogical property of HTPB[J].Journal of Solid Rocket Technology,2014,37(3):369-375.
[4]Liu Yunfei.Chen Yu,Shi Liang,et al.Preparation of BAP composite particals and their effects on rheological properties of HTPB/B/AP slurries[J].Journal of Energetic Materials,2014,32:2.
[5]魏青,李葆萱,邰红勤.功能组分对含硼富燃料固体推进剂药浆流变特性的影响[J].西北工业大学学报,2004,22(1):100-103.WEI Qing,LI Bao-xuan,TAI Hong-qin.On adjusting function components for optimizing rheological properties of slurry of boron-based fuel-rich solid propellaint[J].Journal of North western Polytechnical University,2004,22(1):1 00-1 03.
[6]魏青,李葆萱,邰红勤.AP包覆硼对富燃推进剂药浆流变特性的影响[J].推进技术,2003,24(5):467-469.WEI Qing,LI Bao-xuan,TAI Hong-qin.Effect of boron coated with AP on the rheological properties of slurry of fuel-rich propellant[J].Juornal of Propulsion Technology,2003,24(5):467-469.
[7]胥会祥,赵凤起,李勇宏.硼粉中和改性对B/HTPB混合物流变性能影响研究[J].含能材料,2007,15(4):341-344.XU Hui-xiang,ZHAO Feng-qi,LI Yong-hong.Effecct of neutralised boron powder on rheological characteristic of B/HTPB[J].Chinese Journal of Energetic Materia ls(Hanneng Ca iliao),2007,15(4):341-344.
[8]唐汉祥,陈江,吴倩,等.硼粉改性对推进剂工艺性能的影响[J].含能材料,2005,13(2):69-73.TANG Han-xiang,CHEN Jiang,WU Qiang,et al.Effect of modified boron powder on propellant processing characteristics[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2005,13(2):69-73.
[9]Weiqiang Pang,Xuezhong Fan,Wei Zhang,et al.Application of amorphous boron granulated with hydroxyl-terminated polybutadiene in fuel-rich solid propellant[J].Propellans,Ex-plosives,Pyrotechnics,201 1,36,360-366.
[10]Hui-xiang Xu,Wei-qiang Pang,Hong-wei Guo,et al.Combustion characteristics and mechanism of boron-based,fuel-rich propellants with agglomerated boron powder[J].Central European Journal of Energetic Materials,2014,11(4),575-587.
[11]庞爱民.固体火箭推进剂理论与工程[M].北京:中航宇航出版社,2014:202-372.PANG Ai-Ming.The theory and engineering of solid rocket propellant[M]. Beijing:China Aerospace Publishing House,China,2014; pp:202-372.
[12]张琼方,张教强,国际英,等.超细硼粉的3,3-双(叠氮甲基)环氧丁烷-四氢呋喃共聚醚包覆研究[J].含能材料,2005,13(3):185-188.ZHANG Qiong-fang,ZHANG Jiao-qiang,GUO Ji-ying,et al.Research on the surface coating of superfine boron particles with PBT[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2005,13(3):185-188.
[13]R Pein,S Anders.Investigation of fuel-rich boron combustion in a pressurized combustion bomb[J].Analytica Chimica Acta,2002,5(1-6):427-437.
[14]Ing-Ming SHYU,Tai-Kang Liu.Combustion characteristics of GAP-coated boron particles and the fuel-rich solid propellant[J].Combustion and Flam,1995,100(4):634-644.
[15]Glenn H Fredrickson,Ludwik Leibler.Theory of diffusion-controlled reactions in polymers under flow[J].Macromolecules,1996,29:2674-2685.
[16]Hong Zheng,Wei Yu,Chixing Zhang.Numerical sim ulation of morphology of polymer chain coils in complex flows[J].Chinese Journal of Polymer Science,2005,23(5):453-462.
[17]石海信.机械力化学效应及应用[J].化学教学,2008,5:50-55.SHI Hai-xin.Chemical effect of mechanical fore and its application[J].Education in Chemistry,2008,5:50-55.
[18]姜爱民,于胜春,邹长青.立式捏合机混合釜内推进剂药浆混合过程数值仿真[J].海军航空工程学院学报,201 1,26(24):381-386.JIANG Ai-ming,YU Sheng-Chun,ZOU Chang-qing.KNumerical simulation of the m ixing of composite solid propellant slurry in a kneading mixer[J].Journal of Naval Aeronautical and Astronautical University,2011,26(24):381-386.
[19]R L Werner,K G O'Brien.The infra-red spectra of the borate esters[J].Australian Journal of Chem istry,1 955,8(3):355.
[20]高鸿宾.有机化学(第四版)[M].北京:高等教育出版社,2005:296-301.GAO Hong-bin.Organic chemistry(the fourth edition)[M].Beijing:Higher Education Press,China,2005:296-301.
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