三嵌段烯基聚NIMMO含能黏合剂的合成与固化
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摘要
以1,4-丁二醇为引发剂,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)为第一单体,烯丙基缩水甘油醚(AGE)为第二单体,采用阳离子开环聚合的方法合成了三嵌段烯基聚NIMMO含能黏合剂,采用红外光谱和核磁共振对产物进行了表征,并以合成的含能黏合剂和四甲基对苯二腈氧化物(TTNO)为原料制备了聚异噁唑啉弹性体,研究了弹性体的力学性能和热性能。结果表明,该含能黏合剂具有较低的黏度(25℃时黏度为4. 76 Pa·s),在室温下即可被TTNO固化; R值为2. 0时,得到的弹性体室温下拉伸强度为0. 60 MPa,升温速率10 K/min时的DSC曲线峰温为216. 0℃,有望应用于复合固体推进剂。
Energetic binder triblock alkenyl poly3-nitratomethyl-3-methyloxetane(NIMMO) was synthesized by cationic ring-opening polymerization method using 1,4-butylene glycol as initiator,BF3·OEt2 complex as catalyst,NIMMO as the first monomer and allyl glycidyl ether(AGE) as the second monomer. The product was characterized by infrared spectrum and nuclear magnetic resonance(NMR). The poly(oxazoline) elastomer was prepared using synthesized energetic binder and tetramethyl-terephthalobisnitrile oxide(TTNO) as raw materials. Mechanical properties and thermal properties of the elastomer were investigated. Results show that the energetic binder has lower viscosity(the viscosity at 25℃ is 4. 76 Pa·s) and can be cured by TTNO at room temperature. When R value is 2. 0,the tensile strength of obtained elastomer is 0.60 MPa and the peak temperature of DSC curve at a heating rate of 10 K/min is 216. 0℃. The elastomer is expected to be used in the composite solid propellant.
Energetic binder triblock alkenyl poly3-nitratomethyl-3-methyloxetane(NIMMO) was synthesized by cationic ring-opening polymerization method using 1,4-butylene glycol as initiator,BF3·OEt2 complex as catalyst,NIMMO as the first monomer and allyl glycidyl ether(AGE) as the second monomer. The product was characterized by infrared spectrum and nuclear magnetic resonance(NMR). The poly(oxazoline) elastomer was prepared using synthesized energetic binder and tetramethyl-terephthalobisnitrile oxide(TTNO) as raw materials. Mechanical properties and thermal properties of the elastomer were investigated. Results show that the energetic binder has lower viscosity(the viscosity at 25℃ is 4. 76 Pa·s) and can be cured by TTNO at room temperature. When R value is 2. 0,the tensile strength of obtained elastomer is 0.60 MPa and the peak temperature of DSC curve at a heating rate of 10 K/min is 216. 0℃. The elastomer is expected to be used in the composite solid propellant.
引文
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[4]Henry Feuer.Nitrile Oxides,Nitrones and Nitronates in Organic Synthesis[M].Hoboken:A John Wiley&Sons,Inc,2008.
[5]Huffman B,Schultz R,Schlom P.Novel reagents for heat-activated polymer crosslinking[J].Polymer Bulletin,2001,47(2):159-160.
[6]Kotelnikov S A,Sukhinin V S,Ermilov A S.Kinetics of formation and curing of oligoether urethane allyl ester[J].Russian Journal of Appllied Chemistry,2002,75(3):477-479.
[7]樊亚勤,向尧,雷永林,等.对苯二腈氧化物的合成及其室温固化性能[J].精细化工,2017,34(9):1063-1069.FAN Ya-qin,XIANG Yao,LEI Yong-lin,et al.Synthesis of terephthalonnitrile oxide and its curing properties at room temperature[J].Fine Chemicals,2017,34(9):1063-1069.
[8]Grundmann C,Grünanger P.The Nitrile Oxides[M].Heidelberg:Springer-Verlag Berlin,1971.
[9]莫洪昌,卢先明,李娜,等.3-硝酸酯甲基-3-甲基氧杂环丁烷与四氢呋喃共聚醚的合成与表征[J].含能材料,2011,20(2):172-175.MO Hong-chang,LU Xian-ming,LI Na,et al.Synthesis and characterization of copolyether of 3-nitratomethyl-3-methyloxetane and tetrahydrofuran[J].Chinese Journal of Energetic Materials,2011,20(2):172-175.
[10]莫洪昌,甘孝贤,邢颖,等.含能黏合剂PNIMMO的合成与性能[J].火炸药学报,2008,31(5):24-27.MO Hong-chang,GAN Xiao-xian,XING Ying,et al.Synthesis and properties of energetic binder PNIMMO[J].Chinese Journal of Explosives&Propellants,(Huozhayao Xuebao),2008,31(5):24-27.
[11]Grundmann C,Dean J M,Nitrile oxides V.Stable aromatic nitrile oxides[J].Journal of Organic Chemistry,1965,30(8):2809-2812.
[12]王晓川,舒远杰,雷永林,等.腈氧化物固化端羟基聚丁二烯[J].精细化工,2018,35(4):695-699.WANG Xiao-chuan,SHU Yuan-jie,LEI Yong-lin,et al.Curing of hydroxyl-terminated polybutadiene(HTPB)with nitrile oxide[J].Fine Chemicals,2018,35(4):695-699.