离子液体催化醇醛树脂的固化动力学及力学性能
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摘要
为了获得醇醛树脂固化的绿色催化剂,以离子液体1-磺酸丁基-3-甲基咪唑硫酸氢盐([HSO_3-pHim]HSO_4)为醇醛树脂的催化剂,用差示扫描量热法(DSC)对固化反应动力学进行研究,并用万能试验机测试了[HSO_3-pHim]HSO_4催化醇醛树脂基PBX的力学性能。结果表明,固化反应的平均表观活化能为2.59 kJ·mol~(-1),指前因子为994.61 s~(-1),反应级数为0.93,在[HSO_3-pHim]HSO_4含量为0.9%,固化温度为30℃时,PBX的拉伸和压缩强度分别为16 MPa和41 MPa,拉伸断裂延伸率为0.81%。与硫酸二乙酯(DES)催化PBX相比,采用[HSO_3-pHim]HSO_4为催化剂能将PBX的压缩模量降低35%。
To obtain a friendly green catalyst for aldol resin, the ionic liquid [HSO_3-pHim] HSO_4 was applied to cure aldol resin. The curing kinetics of aldol resin were studied by differential scanning calorimetry(DSC) method, and the mechanical properties of aldol resin based PBXs were studied by electronic universal testing machine. Results show that the average apparent activation energy,frequency factor and reaction order are 2.59 kJ · mol~(-1), 994.61 s~(-1) and 0.93, respectively. When the content of [HSO_3-pHim] HSO_4 is 0.9% and curing temperature is 30 ℃ the tensile strength, compression strength and elongation to fracture of PBX are 16 MPa,41 M Pa and 0.81%, respectively. Comparing to cured by diethyl sufate(DES), the compression modulus of the PBX cured by [HSO_3-pHim] HSO_4 decrease by 35%.
To obtain a friendly green catalyst for aldol resin, the ionic liquid [HSO_3-pHim] HSO_4 was applied to cure aldol resin. The curing kinetics of aldol resin were studied by differential scanning calorimetry(DSC) method, and the mechanical properties of aldol resin based PBXs were studied by electronic universal testing machine. Results show that the average apparent activation energy,frequency factor and reaction order are 2.59 kJ · mol~(-1), 994.61 s~(-1) and 0.93, respectively. When the content of [HSO_3-pHim] HSO_4 is 0.9% and curing temperature is 30 ℃ the tensile strength, compression strength and elongation to fracture of PBX are 16 MPa,41 M Pa and 0.81%, respectively. Comparing to cured by diethyl sufate(DES), the compression modulus of the PBX cured by [HSO_3-pHim] HSO_4 decrease by 35%.
引文
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[2]于剑昆.123树脂的合成、改性及在推进剂和炸药中的应用[J].化学推进剂与高分子材料,2011,9(1):31-39.YU Jian-kun.The synthesis,modifying and application in explosives and propellants of 123-resin[J].Propellants and Macromolecule Materials,2011,9(1):31-39.
[3]任务正,王泽山,杨红梅.火炸药理论和实践[M].北京:中国北方化学工业总公司,2001:594-595.REN Wu-zheng,WANG Ze-shan,YANG Hong-mei.Theory and Practice of Explosive[M].Beijing:China North Chemical Industries Corp.,2001:594-595.
[4]罗雪梅,左玉芬,黄黎明,等.硫酸二乙酯酸值对123树脂固化的影响研究[J].含能材料,2001,9(1):34-36.LUO Xue-mei,ZUO Yu-feng,HUANG Li-ming,et al.Influence of acid value in diethyl sulfate on the curing process of 123resin[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2001,9(1):34-36.
[5]郭嘉吻,刘玉存,柴涛,等.HTPB-异氰酸酯黏结剂体系的室温固化及性能研究[J].爆破器材,2015,44(3):7-8.GUO Jia-hu,LIU Yu-cun,CHAI Tao,et al.A Sutdy on the HT PB-isocyanate binder system curing at room temperature and related properties explosive materials[J].Explosive Materials,2015,44(3):7-8.
[6]刘磊,陈京,郑元锁,等.环氧化端羟基聚丁二烯室温固化及性能研究[J].固体火箭技术,2012,35(6):807-811.LIU Lei,CHEN Jing,ZHENG Yuan-suo,et al.Study on properties of epoxidized hydroxyl terminated polybutadiene cured at room temperature[J].Journal of Solid Rocket Technology,2012,35(6):807-811.
[7]Lee S,Choi C H,Hong I K,Lee J W.Polyurethane curing kinetics for polymer bonded explosives:HTPB/IPDI binder.Korean Journal of Chemical Engineering,2015,32(8)1701-1706.
[8]蔡贾林,史远通,罗观,等.离子液体[BMIM][PF6]对季戊四醇丙烯醛树脂的增塑性能研究[J].含能材料,2016,24(11):1084-1088.CAI Jia-lin,SHI Yuan-tong,LUO Guan,et al.Study on the plasticizing properties of ionic liquid[BMIM][PF6]for acroleinpentaerythritol resin[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2016,24(11):1084-1088.
[9]Rogers R D,Voth G A.Ionic Liquids[J].Accounts of Chemical Research,2007,40:1077-1078.
[10]Plechkova N V,Seddon K R.Application of ionic liquids in the chemical industry[J].Chemical Society Reviews,2008,37(1):123-150.
[11]Dyson P J,Geldbach T J.Application of ionic liquids in synthesis and catalysis[J].Electrochemisty Srociety Interface,2007,16(1):50-53.
[12]徐庆兰.高聚物粘结炸药包覆过程及粘结机理的初步探讨[J].含能材料,1993,1(2):1-5.XU Qing-lan.Preliminary study on the coating process and bonding mechanism of polymer bonded explosive[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),1993,1(2):1-5.
[13]CUI Xian-bao,CAI Jia-lin,ZHANG Yin,et al.Kinetics of transesterification of methyl acetate and n-butanol catalyzed by ionic liquid[J].Industrial&Engineering Chemistry Research,2011,50(20):11521-11527.
[14]刘晶如,罗运军.非等温DSC研究Al/HTPB/TDI体系的固化反应动力学[J].含能材料,2009,17(1):83-86.LIU Jing-ru,LUO Yun-jun.Curing kinetics of HTPB/TDI/Al system by non-iso thermal DSC[J].Chinese Journal of Energetic M aterials(Hanneng Cailiao),2009,17(1):83-86.
[15]胡荣祖,赵凤起,高红旭,等.关于从不同恒速降温条件下的DSC曲线峰温计算结晶/凝固反应动力学参数的一点注释[J].含能材料,2008,16(4):362-363.HU Rong-zu,ZHAO Feng-qi,GAO Hong-xu,et al.On a note of calculating the kinetic parameters of crystallization/solidification reaction from peak temperatures of DSC curves under different constant cooling rate conditions[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2008,16(4):362-363.
[16]蔡贾林,高登攀,郑申声,等.季戊四醇丙烯醛树脂体系固化动力学及流变特性[J].含能材料,2015,23(6):558-562.CAI Jia4in,GAO Deng-pan,ZHEN Shen-sheng,et al.Curing kinetics and rheological properties of pentaerythritol acrylic resin system[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2015,23(6):558-562.
[17]Kissinger H E.Reaction kinetics in different thermo analysis[J].Analytical Chemistry,1957,29:1702-1706.
[18]Ozawa T.A new method of analyzing thermo-gravimetric data[J].Bulletin of the Chemical Society of Japan,1965,3(11):1881-1886.
[19]Crane L W.Analys is of curing kinetics in polymer composites[J].Polymer Science,Polymer Letter Edition 1973,11:533-543.
[20]陈春燕,王晓峰,李巍,等.热固性浇注PBX力学行为的影响因素探讨[J].爆破器材,2014,43(5):6-10.CHEN Chun-yan,WANG Xiao-feng,LI Wei,et al.Influence factors of the mechanical behavior of thermoset casting plastic bonded explosive[J].Explosive Materials,2014,43(5):6-10.