有机硅/酚醛杂化气凝胶的制备和性能研究

doi:10.11949/0438-1157.20230500

化工学报 ›› 2023, Vol. 74 ›› Issue (8): 3572-3583.DOI: 10.11949/0438-1157.20230500

• 材料化学工程与纳米技术 • 上一篇下一篇

有机硅/酚醛杂化气凝胶的制备和性能研究

徐文杰¹(), 贾献峰², 王际童¹, 乔文明¹(), 凌立成¹, 王任平³, 余子舰³, 张寅旭³

^1.华东理工大学化学工程联合国家重点实验室，上海 200237
^2.常州工学院碳纤维新材料产业学院，江苏常州 213032
^3.合盛硅业（鄯善）有限公司，新疆吐鲁番 838200

收稿日期:2023-05-23 修回日期:2023-07-23 出版日期:2023-08-25 发布日期:2023-10-18
通讯作者: 乔文明
作者简介:徐文杰（1997— ），男，硕士研究生，xwjecust@163.com
基金资助:
国家自然科学基金项目(22178107);新疆维吾尔自治区重点研发计划项目(2022B01031);上海浦江计划项目(21PJD019)

Preparation and properties of silicone/phenolic hybrid aerogel

Wenjie XU¹(), Xianfeng JIA², Jitong WANG¹, Wenming QIAO¹(), Licheng LING¹, Renping WANG³, Zijian YU³, Yinxu ZHANG³

^1.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^2.Industrial College of Carbon Fiber and New Materials, Changzhou Institute of Technology, Changzhou 213032, Jiangsu, China
^3.Hesheng Silicon Industry (Shanshan) Co. Ltd. , Tulufan 838200, Xinjiang, China

Received:2023-05-23 Revised:2023-07-23 Online:2023-08-25 Published:2023-10-18
Contact: Wenming QIAO

摘要/Abstract

摘要：

酚醛气凝胶的本征脆性限制了其在吸附、隔热等领域的应用。以3-氨丙基三乙氧基硅烷和对苯二甲醛配制有机硅溶液，将其与热塑型酚醛树脂-六亚甲基四胺溶液混合，利用化学键作用解决了两体系的相容性问题，再经溶胶-凝胶反应和常压干燥工艺制备有机硅/酚醛杂化气凝胶。由于韧性有机硅分子链的引入和较小凝胶颗粒尺寸的效应，改善了酚醛气凝胶的脆性。研究结果表明，杂化气凝胶具有纳米级凝胶网络结构，表现出较低的密度（0.187 g/cm³）和室温热导率[0.035 W/(m·K)]；在压缩应力作用下，杂化气凝胶能够更好地耗散应力而未发生脆性断裂，其压缩模量低至13.92 MPa，相较于纯酚醛气凝胶降低了46%。这种通过简易高效方法制备的杂化气凝胶具有广阔的应用前景。

关键词: 酚醛树脂, 有机硅, 气凝胶, 力学性能, 隔热性能

Abstract:

The inherent brittleness of phenolic aerogels limits its application in the fields of adsorption and heat insulation. In this study, silicone solution was prepared by using 3-aminopropyltriethoxysilane and terephthalaldehyde, which is mixed with the solution of thermoplastic phenolic resin and hexamethylene tetramine, solving the compatibility problem between the two systems through chemical bonding, and sol-gel reaction and ambient pressure drying were carried out to obtain the silicone/phenolic hybrid aerogel. Due to both the introduction of flexible silicone molecular chains and the effect of smaller gel particle size, the brittleness of phenolic aerogel is overcome. The results indicate that obtained hybrid aerogel possesses nanoscale gel network structure, and has a low density of 0.187 g/cm³ and a low room-temperature thermal conductivity of 0.035 W/(m·K). Besides, the hybrid aerogel can better dissipate the stress instead of experiencing brittle fractures under compressive stress. The modulus of the hybrid aerogel is as low as 13.92 MPa, 46% lower than that of phenolic aerogel. This hybrid aerogel prepared with a facile and efficient method is of promising application prospects.

Key words: phenolic, silicone, aerogel, mechanical, insulation

中图分类号:

TB 303

徐文杰, 贾献峰, 王际童, 乔文明, 凌立成, 王任平, 余子舰, 张寅旭. 有机硅/酚醛杂化气凝胶的制备和性能研究[J]. 化工学报, 2023, 74(8): 3572-3583.

Wenjie XU, Xianfeng JIA, Jitong WANG, Wenming QIAO, Licheng LING, Renping WANG, Zijian YU, Yinxu ZHANG. Preparation and properties of silicone/phenolic hybrid aerogel[J]. CIESC Journal, 2023, 74(8): 3572-3583.

图/表 10

图1 Si/PR杂化气凝胶的制备过程、反应机理及宏观照片

Fig.1 Preparation process, reaction mechanism and digital photographs of Si/PR hybrid aerogel

表1 Si/PR杂化气凝胶样品的体积收缩率和密度

Table 1 Volume shrinkage and density of representative Si/PR hybrid aerogel samples

Samples	Volume shrinkage/%	Density/(g/cm³)
Si/PR-0	3.7	0.170
Si/PR-25	4.2	0.187
Si/PR-50	7.9	0.242
Si/PR-75	8.6	0.293
Si/PR-100	9.6	0.327

图2 Si/PR杂化气凝胶的X射线光电子能谱及傅里叶红外光谱图

Fig.2 XPS spectrum and FT-IR spectra of Si/PR hybrid aerogel

图3 Si/PR杂化气凝胶的微观形貌、粒径分布及氮气吸附-脱附等温线

Fig.3 SEM photographs, particle size distribution and N2 adsorption-desorption isotherms of Si/PR hybrid aerogel

表2 Si/PR杂化气凝胶样品的孔结构特征

Table 2 Textural characteristics of Si/PR hybrid aerogel sample

Samples	S_BET/ (m²/g)	S_meso/(m²/g)	V_total/(cm³/g)	V_mic/(cm³/g)	V_meso/(cm³/g)	Porosity/%
Si/PR-0	12.56	10.28	0.03	0	0.03	99.49
Si/PR-25	48.63	27.93	0.10	0	0.10	98.13
Si/PR-50	69.72	49.43	0.19	0	0.18	95.40
Si/PR-75	94.34	75.44	0.27	0	0.26	92.09
Si/PR-100	127.47	81.20	0.30	0.01	0.29	90.19

图4 典型的 Si/PR杂化气凝胶的面扫元素分布图

Fig.4 Elemental mapping images of the representative Si/PR hybrid aerogel sample

图5 Si/PR杂化气凝胶样品的热失重曲线和失重速率曲线

Fig.5 TG curves and DTG curves of Si/PR hybrid aerogel samples

图6 Si/PR杂化气凝胶的压缩力学性能表征

Fig.6 Characterization of compressive mechanical properties of Si/PR hybrid aerogel

图7 增韧机理示意图

Fig.7 Schematic diagram of the toughening mechanism

图8 Si/PR杂化气凝胶的隔热机理示意图及室温热导率

Fig.8 Schematic diagram of the heat insulation mechanism and room-temperature thermal conductivities of Si/PR hybrid aerogels

参考文献 32

1	Lee J H, Park S J. Recent advances in preparations and applications of carbon aerogels: a review[J]. Carbon, 2020, 163: 1-18.
2	Yu Z L, Yang N, Apostolopoulou-Kalkavoura V, et al. Fire-retardant and thermally insulating phenolic-silica aerogels[J]. Angewandte Chemie, 2018, 57(17): 4538-4542.
3	Wu K D, Dong W, Pan Y K, et al. Lightweight and flexible phenolic aerogels with three-dimensional foam reinforcement for acoustic and thermal insulation[J]. Industrial & Engineering Chemistry Research, 2021, 60(3): 1241-1249.
4	Wu K D, Zhou Q, Cao J X, et al. Ultrahigh-strength carbon aerogels for high temperature thermal insulation[J]. Journal of Colloid and Interface Science, 2022, 609: 667-675.
5	Wilson S M W, Al-Enzi F, Gabriel V A, et al. Effect of pore size and heterogeneous surface on the adsorption of CO₂, N₂, O₂, and Ar on carbon aerogel, RF aerogel, and activated carbons[J]. Microporous and Mesoporous Materials, 2021, 322: 111089.
6	Hasegawa G, Kanamori K, Kiyomura T, et al. Hierarchically porous carbon monoliths comprising ordered mesoporous nanorod assemblies for high-voltage aqueous supercapacitors[J]. Chemistry of Materials, 2016, 28(11): 3944-3950.
7	Song W D, Jia X F, Ma C, et al. Facile fabrication of lightweight carbon fiber/phenolic ablator with improved flexibility via natural rubber modification[J]. Composites Communications, 2022, 31: 101119.
8	Jia X F, Song W D, Chen W, et al. Facile fabrication of lightweight mullite fiber/phenolic ablator with low thermal conductivity via ambient pressure impregnation[J]. Ceramics International, 2021, 47(19): 28032-28036.
9	Cheng H M, Fan Z H, Hong C Q, et al. Lightweight multiscale hybrid carbon-quartz fiber fabric reinforced phenolic-silica aerogel nanocomposite for high temperature thermal protection[J]. Composites Part A Applied Science and Manufacturing, 2021, 143: 106313.
10	Jia X F, Dai B W, Zhu Z X, et al. Strong and machinable carbon aerogel monoliths with low thermal conductivity prepared via ambient pressure drying[J]. Carbon, 2016, 108: 551-560.
11	Seraji M M, Sameri G, Davarpanah J, et al. The effect of high temperature sol-gel polymerization parameters on the microstructure and properties of hydrophobic phenol-formaldehyde/silica hybrid aerogels[J]. Journal of Colloid and Interface Science, 2017, 493: 103-110.
12	Li F J, Xie L, Sun G H, et al. Regulating pore structure of carbon aerogels by graphene oxide as ‘shape-directing’ agent[J]. Microporous and Mesoporous Materials, 2017, 240: 145-148.
13	Tannert R, Schwan M, Ratke L. Reduction of shrinkage and brittleness for resorcinol-formaldehyde aerogels by means of a pH-controlled sol-gel process[J]. The Journal of Supercritical Fluids, 2015, 106: 57-61.
14	Schwan M, Ratke L. Flexibilisation of resorcinol-formaldehyde aerogels[J]. Journal of Materials Chemistry A, 2013, 1(43): 13462-13468.
15	Wu C, Huang H, Jin X Y, et al. Water-assisted synthesis of phenolic aerogel with superior compression and thermal insulation performance enabled by thick-united nano-structure[J]. Chemical Engineering Journal, 2023, 464: 142805.
16	Huang H, Hong C Q, Jin X Y, et al. Facile fabrication of superflexible and thermal insulating phenolic aerogels backboned by silicone networks[J]. Composites Part A: Applied Science and Manufacturing, 2023, 164: 107270.
17	Yu Z L, Wu Z Y, Xin S, et al. General and straightforward synthetic route to phenolic resin gels templated by chitosan networks[J]. Chemistry of Materials, 2014, 26(24): 6915-6918.
18	Hasegawa G, Shimizu T, Kanamori K, et al. Highly flexible hybrid polymer aerogels and xerogels based on resorcinol-formaldehyde with enhanced elastic stiffness and recoverability: insights into the origin of their mechanical properties[J]. Chemistry of Materials, 2017, 29(5): 2122-2134.
19	Wang L, Wang J L, Zheng L H, et al. Superelastic, anticorrosive, and flame-resistant nitrogen-containing resorcinol formaldehyde/graphene oxide composite aerogels[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(12): 10873-10879.
20	Hayase G. Fabrication of boehmite nanofiber internally-reinforced resorcinol-formaldehyde macroporous monoliths for heat/flame protection[J]. ACS Applied Nano Materials, 2018, 1(11): 5989-5993.
21	Shahzamani M, Bagheri R, Bahramian A R, et al. Preparation and characterization of hybrid aerogels from novolac and hydroxyl-terminated polybutadiene[J]. Journal of Materials Science, 2016, 51(17): 7861-7873.
22	师建军, 孔磊, 左小彪, 等. 酚醛/SiO₂双体系凝胶网络结构杂化气凝胶的制备与性能[J]. 高分子学报, 2018(10): 1307-1314.
	Shi J J, Kong L, Zuo X B, et al. Preparation of PR/SiO₂ hybrid phenolic aerogel with bi-component gel networks[J]. Acta Polymerica Sinica, 2018 (10): 1307-1314.
23	Wang C H, Cheng H M, Hong C Q, et al. Lightweight chopped carbon fibre reinforced silica-phenolic resin aerogel nanocomposite: facile preparation, properties and application to thermal protection[J]. Composites Part A: Applied Science and Manufacturing, 2018, 112: 81-90.
24	Li S, Han Y, Chen F H, et al. The effect of structure on thermal stability and anti-oxidation mechanism of silicone modified phenolic resin[J]. Polymer Degradation and Stability, 2016, 124: 68-76.
25	Li S, Li H, Li Z, et al. Polysiloxane modified phenolic resin with co-continuous structure[J]. Polymer, 2017, 120: 217-222.
26	Chen D J, Gao H Y, Jin Z K, et al. Vacuum-dried synthesis of low-density hydrophobic monolithic bridged silsesquioxane aerogels for oil/water separation: effects of acid catalyst and its excellent flexibility[J]. ACS Applied Nano Materials, 2018, 1(2): 933-939.
27	Chen D J, Gao H Y, Liu P P, et al. Directly ambient pressure dried robust bridged silsesquioxane and methylsiloxane aerogels: effects of precursors and solvents[J]. RSC Advances, 2019, 9(15): 8664-8671.
28	He H, Geng L Y, Liu F, et al. Facile preparation of a phenolic aerogel with excellent flexibility for thermal insulation[J]. European Polymer Journal, 2022, 163: 110905.
29	Yin R Y, Cheng H M, Hong C Q, et al. Synthesis and characterization of novel phenolic resin/silicone hybrid aerogel composites with enhanced thermal, mechanical and ablative properties[J]. Composites Part A: Applied Science and Manufacturing, 2017, 101: 500-510.
30	Zhan H J, Wu K J, Hu Y L, et al. Biomimetic carbon tube aerogel enables super-elasticity and thermal insulation[J]. Chem, 2019, 5(7): 1871-1882.
31	Yun S, Luo H J, Gao Y F. Ambient-pressure drying synthesis of large resorcinol-formaldehyde-reinforced silica aerogels with enhanced mechanical strength and superhydrophobicity[J]. Journal of Materials Chemistry A, 2014, 2(35): 14542-14549.
32	Zhao S Y, Zhang Z, Sèbe G, et al. Multiscale assembly of superinsulating silica aerogels within silylated nanocellulosic scaffolds: improved mechanical properties promoted by nanoscale chemical compatibilization[J]. Advanced Functional Materials, 2015, 25(15): 2326-2334.

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有机硅/酚醛杂化气凝胶的制备和性能研究

Preparation and properties of silicone/phenolic hybrid aerogel

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