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摘要
分别以3,4′-二氨基二苯基醚(3,4′-ODA)和3,3′,4,4′-二苯甲酮四羧酸二酐(BTDA)作为二胺和二酐单体、5-降冰片烯-2,3-二甲酸酐(NA)作为封端剂,通过调节3种原料的化学计量比,在无水甲醇溶剂中合成了具有不同分子量的预聚体,并通过不同温度下的热处理获得了一系列聚酰亚胺(PI)树脂。结果表明:随着预聚体分子量的增加,固化后PI树脂的热稳定性得到提高,5%热失重温度(T5%)由460℃升至513℃,10%热失重温度(T10%)由513℃升至554℃;但是由于交联密度的降低,PI树脂的玻璃化转变温度(Tg)随预聚体分子量的增加从309℃降低至271℃。同时发现,合理的后固化可使PI树脂的耐高温性能得到提高。以该系列PI树脂为基体,采用手糊法制备了一系列碳纤维增强聚酰亚胺(CF/PI)复合材料,它们表现出优良的耐热性能(T5%:532～595℃,T10%:631～840℃,Tg:346～422℃)和机械性能(弯曲强度:559～811MPa,弯曲模量:46.3～59.9GPa,层间剪切强度:29.3～36.7MPa,冲击强度:88～104kJ/m2),可实现在航空航天领域的耐高温应用。
Abstract
Using 3,4′-oxydianiline (3,4′-ODA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) as diamine and dianhydride monomers,respectively,as well as 5-norbornene-2,3-dicarboxylic anhydride (NA) as end-capping agent,prepolymers with different molecular weights were synthesized in anhydrous methanol by adjusting the stoichiometric ratios of the three raw materials.Subsequently,a series of polyimide (PI) resins were obtained by thermal treatment at different temperatures.The results showed that the thermal stability of the cured PI resins was improved with the increase of molecular weights of prepolymers.For example,5% weight-loss temperature (T5%) increased from 460℃ to 513℃,and 10% weight-loss temperature (T10%) increased from 513℃ to 554℃.However,the glass transition temperature (Tg) of PI resins decreased from 309℃ to 271℃ with the increase of molecular weights of prepolymers due to lower crosslinking density.It was also found that the high temperature resistance of PI resins could be improved through reasonable post-curing.A series of carbon fiber-reinforced polyimide (CF/PI) composites were fabricated by hand lay-up using these PI resins as matrices.They exhibited excellent heat resistance (T5%:532～595℃,T10%:631～840℃,Tg:346～422℃) and mechanical properties (flexural strength:559～811MPa,flexural modulus:46.3～59.9GPa,interlaminar shear strength:29.3～36.7MPa,impact strength:88～104kJ/m2),which made them feasible for high-temperature applications in the aerospace and aeronautic industries.
关键词
碳纤维增强聚酰亚胺复合材料
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预聚体分子量
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后固化
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热性能
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机械性能
Key words
CF/PI composites
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molecular weight of prepolymer
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post-curing
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thermal properties
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mechanical properties
PMR型耐高温聚酰亚胺基体树脂及复合材料的制备与性能研究[J].
化工新型材料, 2023, 51(11): 111-117 DOI:10.19817/j.cnki.issn1006-3536.2023.11.049
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基金资助
湖南省科技创新团队项目(2021RC4072)
