双马来酰亚胺-聚醚砜复相树脂固化与相行为
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摘要
采用非等温DSC研究了双马来酰亚胺-聚醚砜(BMI-PES)复相树脂体系的固化行为和固化动力学,根据Kissinger方程计算BMI-PES复相树脂固化的表观活化能和指前因子,利用Crane方程计算反应级数,得到反应动力学方程,进行了实验固化度与理论固化度对比验证,通过SEM研究BMI-PES复相树脂微观相结构随固化温度和时间的演化规律。树脂固化行为显示:BMI-PES复相树脂固化反应存在自催化现象,PES参与了BMI固化;随着升温速率增大,BMI-PES复相树脂固化特征温度均向高温移动,但固化热焓基本不变;随着PES添加量增多,反应速率增大,BMI-PES复相树脂固化热焓降低,而峰值固化温度无变化。固化动力学研究表明:随着PES添加量增多,BMI-PES复相树脂固化表观活化能增大,但指前因子和反应级数无变化,固化为一级反应;BMI-PES树脂在200℃固化时,反应前期固化度实验数据与理论值吻合度很高。SEM结果表明,BMI-PES树脂经180℃固化处理后产生了相反转结构。
The curing process and curing kinetics of bismaleimide-polyethersulfone(BMI-PES)multi-phase systems were investigated by DSC using the non-isothermal method at different heating rates.The apparent activation energy and the pre-exponential factor of the curing BMI-PES resin systems were calculated by Kissinger method,and the reaction series were computed by means of Crane formula,and the kinetic equation was concluded.The curing reaction kinetics formula of BMI-PES resin was presented and validated with the homologous experiment.The microphase structure evolution of the curing BMI-PES resin systems with the curing temperature as well as curing time was investigated by SEM.The results indicate that autocatalytic phenomenon exists in the curing reaction process of BMI-PES system and PES resin participates in the curing process of BMI resin.With the increasing of the heating rate of BMI-PES,the curing characteristic temperatures of BMI-PES systems shift toward higher temperature values while the curing enthalpy values are almost constant.With the increasing of the PES content,the curing rate increases accordingly,while the enthalpy decreases,and the curing peak temperature is almost constant.Based on the curing kinetics study,the apparent activation energy of BMI-PES curing reaction increases while the pre-exponential factor and the reaction series are not changed.The curing process of the curing reactions follows the first order reaction.The experimental cure degree is fitted highly well with the theoretical one in the initiation of curing reaction at200℃.The SEM results suggest that phase inversion structure exists in BMI-PES resin system after 180℃.
The curing process and curing kinetics of bismaleimide-polyethersulfone(BMI-PES)multi-phase systems were investigated by DSC using the non-isothermal method at different heating rates.The apparent activation energy and the pre-exponential factor of the curing BMI-PES resin systems were calculated by Kissinger method,and the reaction series were computed by means of Crane formula,and the kinetic equation was concluded.The curing reaction kinetics formula of BMI-PES resin was presented and validated with the homologous experiment.The microphase structure evolution of the curing BMI-PES resin systems with the curing temperature as well as curing time was investigated by SEM.The results indicate that autocatalytic phenomenon exists in the curing reaction process of BMI-PES system and PES resin participates in the curing process of BMI resin.With the increasing of the heating rate of BMI-PES,the curing characteristic temperatures of BMI-PES systems shift toward higher temperature values while the curing enthalpy values are almost constant.With the increasing of the PES content,the curing rate increases accordingly,while the enthalpy decreases,and the curing peak temperature is almost constant.Based on the curing kinetics study,the apparent activation energy of BMI-PES curing reaction increases while the pre-exponential factor and the reaction series are not changed.The curing process of the curing reactions follows the first order reaction.The experimental cure degree is fitted highly well with the theoretical one in the initiation of curing reaction at200℃.The SEM results suggest that phase inversion structure exists in BMI-PES resin system after 180℃.
引文
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[14]张晨乾,安学锋,董慧民,等.反应性聚醚砜对RTM用6421BMI树脂性能的影响[J].热固性树脂,2012,21(6):33-36.ZHANG C Q,AN X F,DONG H M,et al.Effect of reactive polyethersulphone on the properties of 6421bismaleimide resin for RTM[J].Thermosetting Resin,2012,21(6):33-36(in Chinese).
[15]董慧民,闫丽,安学锋,等.双马来酰亚胺/聚醚砜复相树脂固化中相形貌与化学流变性能[J].航空材料学报,2018,38(6):64-70.DONG H M,YAN L,AN X F,et al.Phase morphology and chemorheology during curing of polyethersulfone/bismaleimide multi-phase system[J].Journal of Aeronautical Materials,2018,38(6):64-70(in Chinese).
[16]QIAN J Y,PEARSON R A,DIMONIE V L,et al.Synthesis and application of core-shell particles as toughening agents for epoxies[J].Journal of Applied Polymer Science,1995,58(2):439-448.
[17]KISSINGER H E.Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
[18]CRANE L W,DYNES P J,KAELBLE D H.Analysis of curing kinetics in polymer composites[J].Journal of Polymer Science:Polymer Letter Edition,1973,11(8):533-540.
[19]何平笙.新编高聚物的结构与性能[M].北京:科学出版社,2009.HE P S.Structure and properties of polymers,updated edition[M].Beijing:Science Press,2009(in Chinese).
[20]张明,安学锋,唐邦铭,等.高性能双组份环氧树脂固化动力学研究和TTT图绘制[J].复合材料学报,2006,23(1):17-25.ZHANG M,AN X F,TANG B M,et al.Cure kinetics and TTT-diagram of a bicomponent high performance epoxy resin for advanced composites[J].Acta Materiae Compositae Sinica,2006,23(1):17-25(in Chinese).
[2]李伟东,张金栋,刘刚,等.高韧性双马来酰亚胺树脂的固化反应动力学和TTT图[J].复合材料学报,2016,33(7):1475-1483.LI W D,ZHANG J D,LIU G,et al.Curing reaction kinetics and TTT diagram of high toughness bismaleimide resin[J].Acta Materiae Compositae Sinica,2016,33(7):1475-1483(in Chinese).
[3]董慧民.离位点阵增韧RTM复合材料的制备、结构与性能[D].北京:中国航空研究院,2015.DONG H M.Preparation,structure and properties of ex-situ toughened composites based on lattice-distributed ESTMfabrics using RTM method[D].Beijing:Chinese Aeronautical Establishment,2015(in Chinese).
[4]董慧民,安学锋,益小苏,等.纤维增强聚合物基复合材料低速冲击研究进展[J].材料工程,2015,43(5):89-100.DONG H M,AN X F,YI X S,et al.Progress in research on low velocity impact properties of fibre reinforced polymer matrix composite[J].Journal of Materials Engineering,2015,43(5):89-100(in Chinese).
[5]刘润山.双马来酰亚胺树脂增韧及用作先进复合材料基体的发展[J].复合材料学报,1990,7(4):79-84.LIU R S.The development of new tough bismaleimide resins as matrix for advanced composite materials[J].Acta Materiae Compositae Sinica,1990,7(4):79-84(in Chinese).
[6]孙占红,赵渠森.热塑性树脂增韧双马来酰亚胺树脂的研究[J].复合材料学报,1993,10(2):47-52.SUN Z H,ZHAO Q S.Research on toughening bismaleimide resin with thermoplastic resin[J].Acta Materiae Compositae Sinica,1993,10(2):47-52(in Chinese).
[7]董慧民,益小苏,安学锋,等.纤维增强热固性聚合物基复合材料层间增韧研究进展[J].复合材料学报,2014,31(2):273-285.DONG H M,YI X S,AN X F,et al.Development of interleaved fibre-reinforced thermoset polymer matrix composites[J].Acta Materiae Compositae Sinica,2014,31(2):273-285(in Chinese).
[8]安学锋,张晨乾.PES颗粒层间增韧碳纤维/双马树脂RTM复合材料[J].复合材料学报,2013,30(s1):65-69.AN X F,ZHANG C Q.CF/BMI RTM composite materials toughened by interlayers of PES particles[J].Acta Materiae Compositae Sinica,2013,30(s1):65-69(in Chinese).
[9]陈宇飞,郭红缘,李志超,等.聚醚砜/双马来酰亚胺-环氧树脂复合材料的微观结构与性能[J].复合材料学报,2017,34(5):939-944.CHEN Y F,GUO H Y,LI Z C,et al.Micro-structure and properties of polyether sulfone/bismaleimide-epoxy composite[J].Acta Materiae Compositae Sinica,2017,34(5):939-944(in Chinese).
[10]丁妍羽,贾玉玺,姚形龙,等.聚醚砜-环氧树脂共混体系相分离过程的数值模拟[J].复合材料学报,2018,35(1):81-88.DING Y Y,JIA Y X,YAO X L,et al.Numerical simulation of phase separation processes of polyethersulfone-epoxy resin blend systems[J].Acta Materiae Compositae Sinica,2018,35(1):81-88(in Chinese).
[11]YU Y F,ZHANG Z C,GAN W J,et al.Effect of polyethersulfone on the mechanical and rheological properties of polyetherimide-modified epoxy systems[J].Industrial&Engineering Chemistry Research,2003,42(14):3250-3256.
[12]陈凤华,郭颖,孙同臣,等.EP-PI及BMI-PES的反应诱导相分离[J].宇航材料工艺,2016,46(3):37-42.CHEN F H,GUO Y,SUN T C,et al.Reaction-induced phase separation of the epoxy/polyimide and bismaleimide/polyethersulfone blends[J].Aerospace Materials&Technology,2016,46(3):37-42(in Chinese).
[13]刘小云.双马来酰亚胺改性体系相分离的几个物理和化学问题[D].上海:复旦大学,2006.LIU X Y.Study on some chemical and physical issues in the phase separation process of modified bismaleimide systems[D].Shanghai:Fudan University,2006(in Chinese).
[14]张晨乾,安学锋,董慧民,等.反应性聚醚砜对RTM用6421BMI树脂性能的影响[J].热固性树脂,2012,21(6):33-36.ZHANG C Q,AN X F,DONG H M,et al.Effect of reactive polyethersulphone on the properties of 6421bismaleimide resin for RTM[J].Thermosetting Resin,2012,21(6):33-36(in Chinese).
[15]董慧民,闫丽,安学锋,等.双马来酰亚胺/聚醚砜复相树脂固化中相形貌与化学流变性能[J].航空材料学报,2018,38(6):64-70.DONG H M,YAN L,AN X F,et al.Phase morphology and chemorheology during curing of polyethersulfone/bismaleimide multi-phase system[J].Journal of Aeronautical Materials,2018,38(6):64-70(in Chinese).
[16]QIAN J Y,PEARSON R A,DIMONIE V L,et al.Synthesis and application of core-shell particles as toughening agents for epoxies[J].Journal of Applied Polymer Science,1995,58(2):439-448.
[17]KISSINGER H E.Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
[18]CRANE L W,DYNES P J,KAELBLE D H.Analysis of curing kinetics in polymer composites[J].Journal of Polymer Science:Polymer Letter Edition,1973,11(8):533-540.
[19]何平笙.新编高聚物的结构与性能[M].北京:科学出版社,2009.HE P S.Structure and properties of polymers,updated edition[M].Beijing:Science Press,2009(in Chinese).
[20]张明,安学锋,唐邦铭,等.高性能双组份环氧树脂固化动力学研究和TTT图绘制[J].复合材料学报,2006,23(1):17-25.ZHANG M,AN X F,TANG B M,et al.Cure kinetics and TTT-diagram of a bicomponent high performance epoxy resin for advanced composites[J].Acta Materiae Compositae Sinica,2006,23(1):17-25(in Chinese).