硅基乳液凝胶的制备及应用

doi:10.11949/0438-1157.20250419

摘要/Abstract

摘要：

设计了一种半油性液体凝胶（HOLH）。HOLH中的硅油分子可从乳液微滴中逸出，并在光固化聚合凝胶后，自由渗入含有两亲性可交联有机聚硅氧烷的水凝胶基质中。这种乳液凝胶通过均匀分布的不混溶且可移动的硅油分子，实现了类油脂分泌功能及表面润滑层，与传统水凝胶相比，HOLH表现出更低的水分蒸发率（空气中暴露7 d，相对质量从45%提升至75%左右）和优异的液体排斥性（滑动角<10°），可有效阻隔水、油类及血液等复杂液体。此外，乳液凝胶骨架中分散的聚苯胺纳米粒子赋予HOLH优异的压敏性，使其兼具抗污性能与传感功能。该策略为调控水凝胶组分与硅油分子相互作用、设计界面功能及仿生材料提供了新思路。

关键词: 水凝胶, 乳液, 光固化, 防污表面, 界面, 传感水凝胶

Abstract:

This study designed a half-oily liquid hydrogel (HOLH). The silicone oil molecules in HOLH can escape from the emulsion droplets and, after photocuring polymerization and gelation, freely infiltrate into the hydrogel with composed of amphiphilic cross-linkable organic polysiloxanes. This emulsion gel achieves achieved a sebum-like secretion function and a lubricating surface layer through uniformly distributed immiscible and mobile silicone oil molecules. Compared with traditional hydrogels, HOLH exhibits a lower water evaporation rate (the relative weight increases from 45% to around 75% when exposed to air for 7 d) and excellent liquid repellency (sliding angle <10°), effectively blocking complex liquids such as water, oils, and blood. In addition, the polyaniline nanoparticles dispersed in the emulsion gel skeleton give HOLH excellent pressure sensitivity, making it have both antifouling properties and sensing functions. This strategy provides new ideas for regulating the interactions between hydrogel components and silicone oil molecules, and for designing interfacial functions and biomimetic materials.

Key words: hydrogel, emulsion, photocuring, anti-fouling surface, interface, sensing hydrogel

中图分类号:

TQ 322.4

蒋子冰, 徐秀彬, 肖创洪, 刘健伟, 韦林洁, 吴旭. 硅基乳液凝胶的制备及应用[J]. 化工学报, 2025, 76(12): 6527-6535.

Zibing JIANG, Xiubin XU, Chuanghong XIAO, Jianwei LIU, Linjie WEI, Xu WU. Research and application of silicone-based emulsion hydrogel[J]. CIESC Journal, 2025, 76(12): 6527-6535.

图/表 5

图1 两亲性可交联有机硅氧烷的设计与合成（a）；凝胶形成过程的明场图像（b）和共聚焦激光扫描显微镜（CLSM）图像（c）；CLSM图像显示乳液[（d）、（e）]和HOLH[（f）、（g）]的结构

Fig.1 Design and synthesis of amphiphilic cross-linkable organic polysiloxanes (a)；Bright-field images of the gel formation process (b) and confocal laser scanning microscopy (CLSM) images (c)；CLSM images show the structures of the emulsion [(d),(e)] and HOLH [(f),(g)]

图2 HOLH制备及结构示意图（a）；HOLH截面的 EDX 元素分布（b）；HOLH截面结构的CLSM 图像（c）

Fig.2 Schematic illustration of the preparation and structure of HOLH (a)； EDX elemental mapping of cross-sections of HOLH (b)； CLSM images showing the cross-section structures of HOLH (c)

图3 固相水凝胶（a）和HOLH（b）在空气中、水中和硅油中放置7 d后的照片；固相水凝胶和HOLH的透光率（c）；固相水凝胶和HOLH在空气中、水中和硅油中暴露不同时间后的质量变化（d）

Fig.3 Photographs of solid hydrogel (a) and HOLH (b) stayed in air, water, and silicon oil for 7 d； The transmittance of solid hydrogel and HOLH (c)；Time profile of change in mass of the solid hydrogel and HOLH after exposure in air, water, and silicon oil for various periods (d)

图4 水、十六烷、食用油、泵油、原油、氢氧化钠溶液、盐酸溶液、大肠杆菌悬浮液、指纹液体、牛血清白蛋白溶液、血液和酱油在HOLH表面上的接触角（体积为2 µl）和滑动角（体积为20 µl）（a）；液体（20 µl）从表面滑落的视频截图（b）

Fig.4 Contact angles(2 μl in volume) and sliding angles (20 μl) of water, hexadecane, cooking oil, pump oil, crude oil, NaOH, HCl, E. coli, FP liquid, BSA solution, blood and soy sauce on the HOLH surfaces(a); Video Screenshot of 20 μl liquids sliding off the surfaces(b)

图5 按下传感HOLH时灯泡亮度的变化（a）；传感HOLH的力学性能（b）；传感HOLH的加载 - 卸载压缩测试（c）；在 50% 压缩率下进行超过 100 次循环的传感HOLH循环压缩曲线（d）；在 50% 压缩率下进行超过 100 次循环的传感HOLH相对电阻变化（e）；传感HOLH在压缩下的相对电阻变化（f）；应力-应变曲线以及测量最小弯曲半径时拍摄的照片（g）；在弯曲下的相对电阻变化（h）

Fig.5 The change in brightness of the bulb when pressing the sensor HOLH (a); The mechanical properties of the sensor HOLH (b); The loading-unloading compression test of the sensor HOLH (c); The cyclic compression curve of the sensor HOLH for more than 100 cycles at a compression rate of 50% (d); The relative resistance change of the sensor HOLH for more than 100 cycles at a compression rate of 50% (e); The relative resistance change of the sensor HOLH under compression (f); The stress-strain curve and the photo taken when measuring the minimum bending radius (g); The relative resistance change under bending (h)

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