溶剂挥发和相分离法制备环氧树脂基疏水涂层

解国庆; 张衍; 刘育建; 方俊

doi:10.14135/j.cnki.1006-3080.20210531001

溶剂挥发和相分离法制备环氧树脂基疏水涂层

doi: 10.14135/j.cnki.1006-3080.20210531001

华东理工大学材料科学与工程学院，特种功能高分子材料及相关技术教育部重点实验室，上海 200237

基金项目: 中央高校基本科研业务费专项资金资助（JKD01211701）

详细信息

作者简介:
解国庆（1995-），女，安徽宿州人，硕士生，主要研究方向为疏水涂层的制备。E-mail：gqocto@outlook.com

通讯作者:
张衍，E-mail：yzhang@ecust.edu.cn

中图分类号: TQ638
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- 文章访问数: 161
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- PDF下载量: 30
- 被引次数: 0
出版历程
- 收稿日期: 2021-05-31
- 网络出版日期: 2021-09-03

Preparation of Epoxy Resin-Based Hydrophobic Coating by Solvent Volatilization and Phase Separation

Key Laboratory of Specially Functional Polymeric Materials and Related Technology of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 以氟硅改性的环氧树脂为基体，采用二甲苯/乙酸乙酯混合溶剂制备疏水涂层，研究氟硅含量、溶剂种类对涂层疏水性能和微观形貌的影响。结果表明，随着氟硅含量的增加，涂层的接触角逐渐变大。仅以二甲苯为溶剂时，制备的涂层表面较为光滑，接触角最高为105.0°；在二甲苯/乙酸乙酯体系中，由于溶剂挥发速率的差异，涂层表面形成了5~15 µm微孔。同时，氟硅与环氧链段的相分离遵循成核-增长机制，微孔中产生0.1~0.6 µm突起。涂层成膜过程中氟、硅自发向外表面迁移以降低其表面能。当氟硅的含量（质量分数）增加到30%时，涂层表面微孔和孔内凸起可以截留更多的空气，涂层的最大接触角提高到115.5°，疏水性明显提高。并且涂层具有强附着力（5B）和高硬度（6H），表明其应用性能优良。
- 环氧树脂 /
- 氟硅含量 /
- 溶剂挥发 /
- 相分离 /
- 疏水涂层
Abstract: Hydrophobic coatings were prepared in xylene or xylene/ethyl acetate solvent by using 10% and 30% (mass fraction) fluorosilicate modified epoxy resin as the matrix. The influence of fluorosilicon content and solvent type on hydrophobicity as well as micromorphology of the coatings were investigated. The results show that with the increase of fluorosilicon content, the contact angle of the coating enhances. When only using xylene as the solvent, the surface of the coating is relatively smooth, and the maximum contact angle is 105.0°. In xylene/ethyl acetate system, 5~15 µm micropores are formed attributing to the difference of solvent volatilization rate. Meanwhile, 0.1~0.6 µm bumps are generated in those micropores along with phase separation of fluorosilicon and epoxy segments according to nucleation-growth mechanism. The surface energy of coatings reduces with the spontaneous migration of F and Si to the outer surface in the process of film formation. When the content of fluorosilicon segments increases to 30%, much more air could be trapped in the micropores and protrusions. The highest contact angle of the coating rises to 115.5° and the hydrophobicity is improved obviously. The coating also exhibits high adhesion of 5B and hardness of 6H, suggesting its excellent application performance.
- epoxy resin /
- fluorosilicon content /
- solvent volatilization /
- phase separation /
- hydrophobic coating

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图 1 不同质量分数氟硅改性环氧树脂以二甲苯、二甲苯/乙酸乙酯为溶剂所获涂层的SEM图

Figure 1. SEM images of coatings prepared fluorosilicon modified epoxy with different mass fractions in xylene and xylene/ethyl acetate solvents, respectively

(a1), (a2)— 10%, Xylene; (b1), (b2) — 30%, Xylene; (c1), (c2) — 10%, Xylene/Ethyl acetate; (d1), (d2) — 30%, Xylene/Ethyl acetate

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图 2 二甲苯/乙酸乙酯混合溶剂制备的氟硅改性环氧涂层成膜过程示意图

Figure 2. Processing schematic of fluorosilicon modified epoxy coating prepared in xylene/ethyl acetate solvent

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图 3 30%氟硅改性环氧涂层不同位置的EDS谱图

Figure 3. EDS spectra of 30% fluorosilicate modified epoxy coating at different positions

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图 4 溶剂体系对不同质量分数的氟硅改性环氧树脂涂层接触角的影响

Figure 4. Effect of solvent type on the contact angle for fluorosilicon modified epoxy coating with different mass fractions

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图 5 不同溶剂体系制备的氟硅改性环氧涂层的接触角照片

Figure 5. Contact angles of fluorosilicon modified epoxy coatings prepared in different solvents

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表 1 二甲苯和乙酸乙酯的Hansen溶解度组合参数与比挥发速度

Table 1. Hansen solubility parameters and specific volatilization rates of xylene and ethyl acetate

Solvent	δ_d/（J·cm⁻³）^1/2	δ_p/（J·cm⁻³）^1/2	δ_h/（J·cm⁻³）^1/2	δ^a)/（J·cm⁻³）^1/2	Specific volatilization rate^b)
Xylene	17.8	1.0	3.1	18.2	75
Ethyl acetate	15.8	5.3	7.2	18.1	430
a) Hansen solubility parameter is composed of dispersion force (δ_d), polarity force (δ_p) and hydrogen bonding force (δ_h), and satisfies ${{\rm{\delta }}^{\rm{2}}}{\rm{ = \delta }}_{\rm{d}}^{\rm{2}}{\rm{ + \delta }}_{\rm{p}}^{\rm{2}}{\rm{ + \delta }}_{\rm{h}}^{\rm{2}}$;b) Specific volatilization rate = Mass/(Area × Time), generally, the volatilization rate of butyl acetate is taken as the standard, which is recorded as 100; and the ratio of the volatilization rate of other solvents to that of butyl acetate is the specific volatilization rate of the solvent

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表 2 w=30%氟硅改性环氧涂层不同位置的表面元素相对含量（EDS）分析

Table 2. Surface element relative content of 30% fluorosilicate modified epoxy coating at different positions

Surface of the hole	w/%
Surface of the hole	C	O	Si	Si_Theory	F	F_Theory
Inner surface	56.44	17.04	23.98	10.44	2.54	1.63
Outer surface	68.71	16.86	11.93	10.44	2.50	1.63

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