自修复环氧防腐涂层的研究进展

doi:10.16085/j.issn.1000-6613.2024-1363

摘要/Abstract

摘要：

环氧树脂涂料具有优异的附着力和防腐性能，但其在固化过程中容易产生空隙和裂纹，直接影响涂层的防腐性能和使用寿命。自修复环氧防腐涂层可以主动修复表面损伤，提高防腐性能。本文介绍了“外援型”和“内在触发型”两种自修复环氧防腐涂层。“外援型”的愈合是基于含有愈合剂的微胶囊、纳米纤维和纳米容器等添加成分，完成修复过程；“内在触发型”的愈合主要是基于聚合物链之间的可逆共价键或非共价键，在受损区域通过物理或化学反应实现主动愈合。通过对两种自修复环氧防腐涂层已有的研究进行分析，对比其优缺点，为未来开发新的自修复环氧防腐涂层提供了借鉴。

关键词: 环氧树脂, 涂层, 腐蚀, 修复, 聚合物

Abstract:

Epoxy resin coatings have excellent adhesion and anti-corrosion properties, but they are prone to voids and cracks during the curing process, which directly affect the anti-corrosion performance and service life of the coating. Self-healing epoxy anti-corrosion coatings can actively repair surface damage and improve corrosion protection. Two types of self-healing epoxy anticorrosive coatings were introduced: "external aid" and "internal trigger". "External" healing was based on additives such as microcapsules, nanofibers and nanocontainers containing healing agents to complete the repair process. "Intrinsically triggered" healing was based on reversible covalent or non-covalent bonds between polymer chains, which actively healed the damaged area through physical or chemical reactions. By analyzing the research progress of two kinds of self-healing epoxy anticorrosive coatings, the advantages and disadvantages of each were obtained, which provided a useful reference for the development of new self-healing epoxy anticorrosive coatings in the future.

Key words: epoxy resin, coating, corrosion, remediation, polymers

中图分类号:

TQ63

孙爱玲, 杨建军, 吴庆云, 吴明元, 张建安, 刘久逸. 自修复环氧防腐涂层的研究进展[J]. 化工进展, 2025, 44(10): 5881-5890.

SUN Ailing, YANG Jianjun, WU Qingyun, WU Mingyuan, ZHANG Jian’an, LIU Jiuyi. Research progress of self-healing epoxy anti-corrosion coatings[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5881-5890.

图/表 11

图1 使用不同种类微胶囊涂层的划痕区域的共聚焦显微镜图像[12]

图2 PVA/CS@Phen纳米纤维复合涂层和空白环氧涂层在海水中浸泡12h后的划痕区域的显微镜照片[24]

图3 S-EP、S-MK/EP、S-VK/EP和S-MK-VK/EP在质量分数3.5%的NaCl溶液中浸泡12h的光学图像（S表示划痕区域）[32]

图4 呋喃与马来酰亚胺之间的DA反应[37]

图5 FA-FGE-BMI的性能测试

表1 环氧树脂涂层样品的合成配方[41]

样品	环氧树脂 EP/g	3,3′-二硫代二丙酸 DTPA/g	三苯基膦 TPP/g	己二酸 ADA/g	二聚酸 DAA/g	DAA与DTPA的摩尔比
EP-ADA-DAA	4.00	0	0.13	0.74	1.12	—
EP-SS	4.00	1.47	0.13	0	0	0
EP-SS-DAA₁	4.00	1.26	0.13	0	0.56	0.17
EP-SS-DAA₂	4.00	1.05	0.13	0	1.12	0.40
EP-SS-DAA₃	4.00	0.82	0.13	0	1.74	0.80

表2 环氧树脂涂层样品的机械性能[41]

样品	抗拉强度/MPa	断裂伸长率/%	杨氏模量/GPa	韧性/MJ·m^-3
EP-SS	56.15±1.12	8.18±1.33	2.34±0.04	4.02±0.11
EP-SS-DAA₁	37.47±0.85	91.40±4.58	2.06±0.02	32.28±0.57
EP-SS-DAA₂	35.85±0.92	150.55±5.81	1.86±0.03	42.14±0.42
EP-SS-DAA₃	18.01±0.67	178.45±4.97	1.31±0.02	28.23±0.53

图6 在工业相机下EP-ADA-DAA和EP-SS-DAA2自修复前后的照片[41]

图7 含氢键和二硫键的自修复环氧树脂的合成示意图[44]

表3 制备各固化产物的反应物的摩尔比[46]

样品	SPE、CM-β-CD、CHCA、PEGBC摩尔比
SCCPB-0	1∶1∶1∶0
SCCPB-1	1∶1∶1∶1
SCCPB-2	1∶1∶1∶2
SCCPB-3	1∶1∶1∶3
SCCPB-4	1∶1∶1∶4

图8 SCCPB-4膜自修复前后的外观[46]

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