烯基聚醚含能黏合剂的合成与固化
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摘要
以三羟甲基丙烷为引发剂、三氟化硼·乙醚络合物为催化剂、3-硝酸酯甲基-3-甲基氧杂环丁烷(NIMMO)为单体,制备了三官能度的聚NIMMO(T-PNIMMO),随后在其端基共聚烯丙基缩水甘油醚(AGE),合成了烯基聚醚含能黏合剂(AGE-T-PNIMMO)。采用FTIR和NMR对产物进行了表征,并以四甲基对苯二腈氧化物(TTNO)为固化剂固化合成的烯基聚醚含能黏合剂制备出弹性体,考察了弹性体的力学和热性能。结果表明:该黏合剂具有低黏度(20℃黏度为8.93 Pa·s)、较低的玻璃化转变温度(-57.4℃)及可室温固化的特点;R(固化剂TTNO的腈氧基团与AGE-T-PNIMMO双键的物质的量之比,下同)=1.0时,得到的弹性体拉伸强度最高可达0.80 MPa,分解峰峰温为202℃。
The tri-functional poly(3-nitratomethyl-3-methyloxetane)(T-PNIMMO) was synthesized using trimethylolpropane as initiator, boron trifluoride ether complex as catalyst, and 3-nitric ester methyl-3-methoxycyclobutane(NIMMO) as monomer. Then, the copolymerization of T-PNIMMO and allyl glycidyl ether(AGE) led to alkenyl polyether energetic binder(AGE-T-PNIMMO). The product was characterized by FTIR and NMR. Subsequently, the mechanical properties and thermal properties of elastomer prepared after curing with tetramethyl-terephthalobisnitrile oxide(TTNO) were investigated. The results show that the energetic binder has low viscosity(20 ℃, 8.93 Pa·s), low glass transition temperature(Tg)(-57.4 ℃), and can be cured at room temperature. When R value(molar ratio of nitrile oxygen group of TTNO to double bond of AGE-T-PNIMMO) was 1.0, the tensile strength and thermal decomposition peak temperature of the elastomer were 0.80 MPa and 202 ℃.
The tri-functional poly(3-nitratomethyl-3-methyloxetane)(T-PNIMMO) was synthesized using trimethylolpropane as initiator, boron trifluoride ether complex as catalyst, and 3-nitric ester methyl-3-methoxycyclobutane(NIMMO) as monomer. Then, the copolymerization of T-PNIMMO and allyl glycidyl ether(AGE) led to alkenyl polyether energetic binder(AGE-T-PNIMMO). The product was characterized by FTIR and NMR. Subsequently, the mechanical properties and thermal properties of elastomer prepared after curing with tetramethyl-terephthalobisnitrile oxide(TTNO) were investigated. The results show that the energetic binder has low viscosity(20 ℃, 8.93 Pa·s), low glass transition temperature(Tg)(-57.4 ℃), and can be cured at room temperature. When R value(molar ratio of nitrile oxygen group of TTNO to double bond of AGE-T-PNIMMO) was 1.0, the tensile strength and thermal decomposition peak temperature of the elastomer were 0.80 MPa and 202 ℃.
引文
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[15]MoHongchang(莫洪昌),GanXiaoxian(甘孝贤),XingYing(邢颖), et al. Synthesis and properties of energetic binder PNIMMO[J].ChineseJournalofExplosives&Propellants(火炸药学报),2008,31(5):24-27.
[16]Wang Xiaochuan(王晓川), Shu Yuanjie(舒远杰), Lei Yonglin(雷永林), et al. Curing of hydroxyl-terminated polybutadiene(HTPB)with nitrile oxide[J]. Fine Chemicals(精细化工), 2018, 35(4):695-699.
[17]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).GB/T 528—2009[S].Beijing:Standards Press of China(中国标准出版社), 2009.
[2]Ahmad N, Khan M, Ma X, et al. The influence of cross-linking/chain extensionstructuresonmechanicalpropertiesofHTPB-based polyurethaneelastomers[J].ArabianJournalforScienceand Engineering, 2014, 39(1):43-51.
[3]Gaur B, Lochab B, Choudhary V, et al. Azido polymers—energetic bindersforsolidrocketpropellants[J].JournalofMacromolecular Science-Polymer Reviews, 2003, 43(4):505-545.
[4]Abrishami F, Zohari N, Zeynali V. Synthesis and characterization of poly(glycidyl nitrate-block-caprolactone-block-glycidyl nitrate)(PGN-PCL-PGN)tri-blockcopolymerasanovelenergeticbinder[J].Propellants Explosives Pyrotechnics, 2017, 42(9):1032-1036.
[5]Dong Q, Li H, Liu X, et al. Thermal and rheological properties of PGN,PNIMMOandP(GN/NIMMO)synthesizedviamesylate precursors[J].PropellantsExplosivesPyrotechnics,2018,43(3):294-299.
[6]Ma S, Li Y, Li Y, et al. Research on the mechanical properties and curing networks of energetic GAP/TDI binders[J]. Central European Journal of Energetic Materials, 2017, 14(3):708-725.
[7]BarbieriU, PolaccoG, PaesanoE,etal.Lowrisksynthesisof energeticpoly(3-azidomethyl-3-methyloxetane)fromtosylated precursors[J].PropellantsExplosivesPyrotechnics,2006,31(5):369-375.
[8]Badgujar D, Talawar M, Asthana S, et al. Advances in science and technology of modern energetic materials:An overview[J]. Journal of Hazardous Materials, 2008, 151(2/3):289-305.
[9]Desail H, Cunliffe A, Hamid J, et al.Synthesis and characterization ofα,ω-hydroxy and nitrato telechelic oligomers of 3,3-(nitratomethyl)methyl oxetane(NIMMO)and glycidyl nitrate(GLYN)[J]. Polymer,1996, 37(15):3461-3469.
[10]GolofitT,Zy?kK.Thermaldecompositionpropertiesand compatibilityofCL-20withbindersHTPB,PBAN,GAPand polyNIMMO[J]. Journal of Thermal Analysis and Calorimetry, 2015,119(3):1931-1939.
[11]Keicher T, Kuglstatter W, Eisele S, et al. Isocyanate-free curing of glycidylazidepolymer(GAP)withbis-propargyl-succinate(II)[J].Propellants Explosives Pyrotechnics, 2009, 34(3):210-217.
[12]Fan Yaqin(樊亚勤), Xiang Yao(向尧), Lei Yonglin(雷永林), et al.Synthesisofterephthalonnitrileoxideanditscuringpropertiesat roomtemperature[J].FineChemicals(精细化工),2017,34(9):1063-1069.
[13]Huffman S, Schultz A, Schlom J. Novel reagents for heat-activated polymer crosslinking[J]. Polymer Bulletin, 2001, 47(2):159-166.
[14]RaoM,ScariahK,VargheseA,etal.Evaluationofcriteriafor blending hydroxy terminated polybutadiene(HTPB)polymers based onviscositybuild-upandmechanicalpropertiesofgumstock[J].European Polymer Journal, 2000, 36(8):1645-1651.
[15]MoHongchang(莫洪昌),GanXiaoxian(甘孝贤),XingYing(邢颖), et al. Synthesis and properties of energetic binder PNIMMO[J].ChineseJournalofExplosives&Propellants(火炸药学报),2008,31(5):24-27.
[16]Wang Xiaochuan(王晓川), Shu Yuanjie(舒远杰), Lei Yonglin(雷永林), et al. Curing of hydroxyl-terminated polybutadiene(HTPB)with nitrile oxide[J]. Fine Chemicals(精细化工), 2018, 35(4):695-699.
[17]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).GB/T 528—2009[S].Beijing:Standards Press of China(中国标准出版社), 2009.