加成型酚醛改性双马树脂及其复合材料性能  

Properties of bismaleimide resin modified by addition-curing phenolic and their composites

作　　者：姜伟芳 王林祥 郑庆 袁荞龙[1] 黄发荣[1] JIANG Weifang;WANG Linxiang;ZHENG Qing;YUAN Qiaolong;HUANG Farong(Key Laboratory of Specially Functional Polymeric Materials and Related Technology of the Ministry of Education,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China;Shanghai Xinli Power Equipment Institute,Shanghai 200125,China)

机构地区：[1]华东理工大学材料科学与工程学院特种功能高分子材料及相关技术教育部重点实验室,上海200237 [2]上海新力动力设备研究所,上海200125

出　　处：《复合材料学报》2023年第2期741-752,共12页Acta Materiae Compositae Sinica

基　　金：上海航天科技创新基金(SAST2019-106);中央高校基本科研业务费专项资金(JKD01211701)。

摘　　要：双马来酰亚胺(BMI)树脂因其优异的性能已在航空航天、电子和其他工业领域获得应用,为满足其在高速飞行器结构件中需求,用加成型酚醛树脂改性BMI体系以改善其热-力学性能。通过Williamson醚化反应合成了炔丙基醚化酚醛树脂(PN)和烯丙基醚化酚醛树脂(AN),采用熔融共混法分别与N,N’-(4,4’-亚甲基二苯基)双马来酰亚胺(BDM)和2,2’-二烯丙基双酚A(DABPA)树脂体系(BD)共混,制备了三元热固性树脂:PN改性BD(BDPN)和AN改性BD(BDAN)。研究了两种加成型酚醛树脂改性的BD树脂体系的加工工艺性和固化行为的变化,并对改性前后固化树脂及其复合材料的热、力学性能进行了研究。结果表明:共混树脂体系都在极性溶剂中有好的溶解性,加工窗口都有50℃以上。BDPN和BDAN固化反应只有一个放热峰,最高放热峰值温度比BD树脂低。用FTIR跟踪验证了BD、BDPN和BDAN树脂体系发生的Ene、DielsAlder、Claisen重排和炔基与马来酰亚胺环的聚合反应。PN热氧稳定性好,改性的BDPN固化树脂空气中质量损失5wt%的温度(Td5)高于400℃,800℃残留率(Yr800℃)由3.7%提升至23.1%。BD、BDPN和BDAN固化物的极限氧指数(LOI)分别为30.2%、32.5%和31.0%,都属难燃材料。BDPN和BDAN树脂浇铸体冲击强度和弯曲模量分别提高了19%和30%,但弯曲强度都因交联密度的下降而有所下降。BDPN和BDAN固化物的吸水率都低于BD树脂,沸水中40 h时BDPN和BDAN分别比BD树脂降低了8.6%和14%。室温下T300碳纤维增强BDAN复合材料(T300CF/BDAN)弯曲强度、弯曲模量和层间剪切强度(ILSS)高于BD基复合材料;200℃下T300CF/BDPN的弯曲强度达575 MPa,保留率高达98.6%。炔丙基醚化酚醛树脂改性双马来酰亚胺树脂体系有望应用于耐200℃的复合材料结构件,为耐热双马来酰亚胺树脂的制备提供新的途径。Bismaleimide(BMI)resin has been widely used in aerospace,electronics and other industrial fields because of its excellent properties.In order to meet the needs of structural components for high-speed aircraft,the additional phenolic modifier is introduced to improve the thermo-mechanical properties of BMI resin.The propargyl etherified novolac(PN)and allyl etherified phenolic(AN)as an addition modifier were synthesized by Williamson etherification.The PN and AN were used to modify N,N’-(4,4’-diphenylmethylane)bismaleimide(BDM)/2,2’-diallyl bisphenol A(DABPA)resin system(BD)in melting mixing to obtain the ternary blended resins of BDPN and BDAN.The processability and cure reactions of the BDPN and BDAN were studied.The thermal property and mechanical property of the cured BD,BDPN and BDAN were further investigated.The results show that the ternary blended resins exhibit good solubility and meltability,and have an above 50℃of process window.There is only a single exothermal peak in DSC curves of BDPN and BDAN.The peak temperatures of BDPN and BDAN are lower than that of BD.The Fourier transform infrared(FTIR)was used to monitor the curing reactions of BD,BDPN and BDAN resins.The reactions of Ene,Diels-Alder,Claisen rearrangement and addition of alkyne and maleimido group were detected during curing.The cured PN resin has good thermo-oxidative stability.The residual yield at800℃(Y_(r800℃))of cured BD in air increases from 3.7%to 23.1%after the BD resin was modified with PN resin.The temperature of 5wt%mass loss(T_(d5))of the cured BDPN in air is higher than 400℃.The limited oxygen index(LOI)of the cured BD,BDPN and BDAN resins are 30.2%,32.5%and 31.0%,respectively.The cured resins are nonflammable.The impact strength and flexural modulus of the cured BD resin increase with addition of PN and AN resins.The impact strength and flexural modulus of the cured AN modified BD resin increase by 19%and 30%respectively.However,the flexural strength of the BDPN and BDAN resins decrease since the crosslinked densi

关 键 词：炔丙基醚化酚醛 烯丙基醚化酚醛 双马来酰亚胺树脂 改性共混 热-物理性能 

分 类 号：TB332[一般工业技术—材料科学与工程]