Organic/inorganic hybrid polyimide matrix resins with high temperature resistance
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摘要: 热固性聚酰亚胺树脂基复合材料已在航空航天领域得到了广泛的应用，然而随着航空航天技术的发展，传统有机聚酰亚胺基体树脂的耐温等级逐渐不足以达到飞行器的设计和应用需求，发展新型耐高温有机/无机杂化聚酰亚胺树脂成为国内外研究重点。本文总结了近年来国内外有机/无机杂化聚酰亚胺基体树脂的发展现状，重点从合成方法、结构设计与性能调控、固化过程和高温降解行为等方面对含笼状倍半硅氧烷聚酰亚胺、含碳硼烷聚酰亚胺和含硅氧烷聚酰亚胺的特点和耐热机制进行了介绍，并对有机/无机杂化聚酰亚胺树脂未来发展面临的挑战与机遇进行了讨论分析。Abstract: Thermosetting polyimide resin matrix composites have been widely used in aerospace industry, but the heat resistance of traditional organic polyimide matrix resins is gradually insufficient to satisfy the design and application requirement of the aircrafts, with the development of aerospace technology. Therefore, novel organic/inorganic hybrid polyimides resistant to higher temperature have become the focus of research. In this paper, the recent progress of organic/inorganic hybrid polyimide matrix resins was summarized. The synthetic pathway, structure design, performance control, curing process and degradation behavior of polyhedral oligomeric silsesquioxane-containing polyimide, carborane-containing polyimide and siloxane-containing polyimide were reviewed, providing a detailed description of the characteristics and thermo-resistant mechanism of the organic/inorganic hybrid polyimide resins. The challenges and opportunities for the future development of organic/inorganic hybrid polyimide resins were also discussed and analyzed.
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Key words:
- polyimide /
- organic/inorganic hybrid /
- matrix resin /
- composite /
- thermo-resistant mechanism
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图 4 含碳硼烷反应性改性剂与有机聚酰亚胺树脂共混体系[26, 28-29]
Figure 4. Blend systems of carborane-containing reactive modifiers and organic polyimides[26, 28-29]
Carb-PEPA—Carborane-containing phenylethynyl terminated imide compound; CB-PEPA—Carborane-containing imide monomer; APCB—Acetylenic monomer containing carborane; AFR-PEPA—Fluorinated phenylethynyl terminated imide oligomer; PI-mPDA—Phenylethynyl-terminated imide oligomer; m-EFDA—Acetylene-terminated imide monomer
表 1 经288℃/1024 h热氧老化后T650-35碳纤维增强含POSS聚酰亚胺复合材料失重和288℃的弯曲性能数据[20]
Table 1. Weight loss and flexural property at 288℃ of the T650-35 carbon fiber reinforced POSS-containing polyimide composites after aging at 288℃ for 1024 h[20]
Matrix Mass loss/wt% Flexural strength/MPa Flexural modulus/GPa HFPE-II-52 0.90 654±41 54±1 HFPE-II-52+7.5wt%POSS-PETI 0.84 694±21 57±1 HFPE-II-52+15wt%POSS-PETI 0.60 746±34 59±1 Notes: PETI—Phenyl-ethynyl terminated oligoimide; HFPE-II-52—A kind of high temperature fluorinated thermosetting polyimide resin. 
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表 2 T700碳纤维增强含碳硼烷聚酰亚胺复合材料力学性能数据[28]
Table 2. Mechanical property of T700 carbon fiber reinforced carborane-containing polyimide composites[28]
Matirx Flexural strength/MPa Flexural modulus/GPa Interlaminar shear strength/MPa PI-mPDA 1270 93 56 PI-mPDA +5wt%CB-PEPA 1592 117 62 PI-mPDA +10wt%CB-PEPA 1612 116 63 PI-mPDA +15wt%CB-PEPA 1524 107 66 PI-mPDA +20wt%CB-PEPA 1406 115 54 PI-mPDA +25wt%CB-PEPA 1591 113 52
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表 3 500℃/1 h热氧老化前后含碳硼烷聚酰亚胺树脂力学性能数据[30]
Table 3. Mechanical property of carborane-containing polyimide resins before and after thermo-oxidative aging at 500℃ for 1 h[30]
Matrix Tensile strength/MPa Tensile modulus/GPa Elongation at break/% CBA-BPDA-1 11.53±1.08 1.32±0.15 0.88±0.12 Aged CBA-BPDA-1 8.42±2.28 1.55±0.14 0.55±0.16 CBA-BTDA-1 10.84±2.12 1.88±0.15 0.57±0.08 Aged CBA-BTDA-1 6.05±1.20 2.12±0.12 0.30±0.06 Notes: CBA-BPDA-1—Oligomer based on CBA and 2,3′,3,4′-biphenyltetracarboxylic acid dianhydride (α-BPDA) with an average degree of polymerization of 1; CBA-BTDA-1—Oligomer based on CBA and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) with an average degree of polymerization of 1.
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