Page 64 - 《精细化工》2022年第3期

·486· 精细化工 FINE CHEMICALS 第 39 卷

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间，使得 PI 分子链链段可以在更低的温度“解冻”， 降低至 0.054 g/cm 。与 PI 气凝胶相比，随着 ANFs
导致复合气凝胶的 T g 降低。 添加量的增加（至 4%），复合气凝胶的杨氏模量由
1.8 MPa 提升至 6.9 MPa，压缩回弹率提升了 37%。
同时 ANFs/PI-4 复合气凝胶发生 70%应变后，微观
结构较 PI 气凝胶更加完整。ANFs/PI 复合气凝胶的
T 5 、T 10 和 T g 较 PI 气凝胶略微降低，ANFs 引入后复
合气凝胶的 T 5 和 T 10 约降低 10 ℃，T g 约降低 25 ℃。
参考文献：

[1] WANG D H, TAN L S. Origami-inspired fabrication: Self-folding or
self-unfolding of cross-linked-polyimide objects in extremely hot
ambience[J]. ACS Macro Letters, 2019, 8(5): 546-552.
[2] LIU J, ZHANG H B, XIE X, et al. Multifunctional, superelastic, and
lightweight MXene/polyimide aerogels[J]. Small, 2018, 14(45): 1802479.
[3] YU Z, DAI T W, YUAN S W, et al. Electromagnetic interference
shielding performance of anisotropic polyimide/graphene composite
aerogels[J]. ACS Appl Mater Interfaces, 2020, 12(27): 30990-31001.
[4] YANG F, ZHAO X Y, XUE T T, et al. Superhydrophobic polyvinylidene
fluoride/polyimide nanofiber composite aerogels for thermal insulation
under extremely humid and hot environment[J]. Science China
Materials, 2020, 64(5): 1267-1277.
[5] REN R P, WANG Z, REN J, et al. Highly compressible polyimide/
graphene aerogel for efficient oil/water separation[J]. Journal of
Materials Science, 2018, 54(7): 5918-5926.
[6] LUO Z S, FANG Y X, ZHOU M, et al. A borocarbonitride ceramic
aerogel for photoredox catalysis[J]. Angewandte Chemie International

图 6 PI 气凝胶和 ANFs/PI 复合气凝胶的 TGA（a）和 Edition, 2019, 58(18): 6033-6037.
[7] YAO H Y, ZHANG N, SHEN K Z, et al. From a flexible hyperbranched
DSC 曲线（b） polyimide to a microporous polyimide network: Microporous
Fig. 6 TGA (a) and DSC (b) curves of PI aerogel and architecture and carbon dioxide adsorption[J]. Polymer, 2017, 115:
ANFs/PI composites aerogel 176-183.
[8] SONG N N, MA T N, WANG T J, et al, Microporous polyimides
with high surface area and CO 2 selectivity fabricated from cross-
表 2 PI 气凝胶和 ANFs/PI 复合气凝胶的 T 5 ，T 10 和 T g linkable linear polyimides[J]. Journal of Colloid and Interface Science,
Table 2 T 5 , T 10 , T g of PI aerogel and ANFs/PI composite 2020, 573: 328-335.
aerogels
[9] QIU G R, MA W S, WU L. Low dielectric constant polyimide
样品 T 5/℃ T 10/℃ T g/℃ mixtures fabricated by polyimide matrix and polyimide microsphere
fillers[J]. Polymer International, 2020, 69(5): 485-491.
PI 558 591 288
[10] ZHAO X F, ZHANG J, WANG X J, et al. Polyimide aerogels
ANFs/PI-1 545 581 261
crosslinked with MWCNT for enhanced visible-light photocatalytic
ANFs/PI-2 543 584 266 activity[J]. Applied Surface Science, 2019, 478: 266-274.
ANFs/PI-3 545 580 260 [11] ZU G Q, KANAMORI K, MAENO A, et al. Superflexible
multifunctional polyvinyl polydimethylsiloxane-based aerogels as
ANFs/PI-4 548 584 264
efficient absorbents, thermal superinsulators, and strain sensors[J].
ANFs 468 517 — Angewandte Chemie International Edition, 2018, 130(31): 9870-9875.
注：“—”代表无明确的 T g。 [12] WANG N N, WANG H, WANG Y Y, et al. Robust, lightweight,
hydrophobic, and fire-retarded polyimide/MXene aerogels for effective
oil/water separation[J]. ACS Appl Mater Interfaces, 2019, 11(43):
3 结论 40512-40523.
[13] VANHERCK K, KOECKELBERGHS G, VANKELECOM I F J.
Crosslinking polyimides for membrane applications: A review[J].
本文通过化学劈裂法成功制备了 ANFs，采用物
Progress in Polymer Science, 2013, 38(6): 874-896.
理共混法将 ANFs 均匀分散在 PAA 溶液中，通过冷 [14] YI C H, LI W M, SHI S, et al. High-temperature-resistant and colorless
冻干燥法制得 ANFs/PAA 复合气凝胶，再经过热亚 polyimide: Preparations, properties, and applications[J]. Solar Energy,
2020, 195: 340-354.
胺化成功制备了 ANFs/PI 复合气凝胶。 [15] HE X Y, ZHANG L, MENG D P, et al. From hydrogel to aerogel: A
ANFs 可与 PAA 分子链形成氢键，使 ANFs 在 green fabrication of multifunctional polyimide absorbents[J]. European
Polymer Journal, 2017, 89: 461-467.
PI 基体中均匀分布，并以嵌入的形式被紧密地包裹
[16] CHAO M, LI Y M, WU G L, et al. Functionalized multiwalled
在 PI 基体中。ANFs 的加入使复合气凝胶的体积收 carbon nanotube-reinforced polyimide composite films with enhanced
缩率由 62.88%减少至 52.46%；密度由 0.070 g/cm 3 mechanical and thermal properties[J]. International Journal of Polymer