聚天冬氨酸酯聚脲胺基组分分子结构对涂层微观结构及腐蚀介质扩散行为影响的分子动力学模拟研究

doi:10.11902/1005.4537.2024.326

中国腐蚀与防护学报

2025, Vol. 45

Issue (4): 975-982 CSTR: 32134.14.1005.4537.2024.326 DOI: 10.11902/1005.4537.2024.326

研究报告

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聚天冬氨酸酯聚脲胺基组分分子结构对涂层微观结构及腐蚀介质扩散行为影响的分子动力学模拟研究

夏渊¹, 廉兵杰¹, 程佳², 李文²(

)

1 中海油常州涂料化工研究院有限公司常州 213016
2 中国海洋大学材料科学与工程学院青岛 266100

Influence of Molecular Structure of Polyaspartic Ester Polyurea Amino Component on Microstructure of its Coating and Diffusion Behavior of Corrosive Media Within Coating: A Molecular Dynamics Simulation Study

XIA Yuan¹, LIAN Bingjie¹, CHENG Jia², LI Wen²(

)

1 CNOOC Changzhou Paint and Coatings Industry Research Institute Co., Ltd., Changzhou 213016, China
2 School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China

引用本文:

夏渊, 廉兵杰, 程佳, 李文. 聚天冬氨酸酯聚脲胺基组分分子结构对涂层微观结构及腐蚀介质扩散行为影响的分子动力学模拟研究[J]. 中国腐蚀与防护学报, 2025, 45(4): 975-982.
Yuan XIA, Bingjie LIAN, Jia CHENG, Wen LI. Influence of Molecular Structure of Polyaspartic Ester Polyurea Amino Component on Microstructure of its Coating and Diffusion Behavior of Corrosive Media Within Coating: A Molecular Dynamics Simulation Study[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(4): 975-982.

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摘要:

采用分子动力学模拟方法研究了聚天冬氨酸酯聚脲胺基组分的环状平面分子结构和线型分子结构对涂层微观结构及腐蚀介质扩散行为的影响。结果表明：相比于线型分子结构，环状平面分子结构具有较大的空间位阻，体系内自由体积较大，密度较小；分子结构支化程度的增加可进一步增加涂层的自由体积，导致体系致密性下降；分子链段长度的增大对体系致密性的影响较小；水分子可与聚脲分子形成氢键，并倾向于以聚集态的形式存在于涂层内部。从涂层耐蚀性的角度来说，线型分子结构更有利于形成致密的涂层结构，增强涂层耐蚀性。本文通过分子模拟方法开展的涂层结构与性能关联机制研究，为涂料配方设计提供了分子模拟筛选新手段。

关键词 ：聚天冬氨酸酯聚脲, 分子结构, 腐蚀介质, 分子动力学模拟

Abstract：

Herein, the influence of cyclic planar molecular structure and linear molecular structure of polyaspartic ester polyurea amino component on the microstructure of polyurea coatings and the diffusion behavior of corrosive media within the coating was studied by means of molecular dynamics simulation. The results indicate that compared with linear molecular structures, cyclic planar molecular structures have greater steric hindrance, resulting larger free volume and lower density of the polyurea system; The increase in molecular branching can further increase the free volume of the coating, leading to a decrease in the density of the system; The increase in molecular chain segment length has a relatively small impact on the compactness of the system; Water molecules can form hydrogen bonds with polyurea molecules and tend to exist in an aggregated state inside the coating. Regarding the corrosion resistance of the formed coating, linear molecular structures are more conducive to formation of dense coating structures and enhancement of coating corrosion resistance. Finally, this article conducts a study on the correlation mechanism between coating structure and performance through molecular simulation methods, providing a new means of molecular simulation screening for coating formulation design.

Key words： polyaspartic ester polyurea molecular structure corrosive media molecular dynamics simulation

收稿日期: 2024-10-09 32134.14.1005.4537.2024.326

ZTFLH:

TE58

基金资助:山东省高等学校青年创新团队发展计划(2023KJ033);青岛市海洋产业关键技术攻关项目(24-1-3-hygg-16-hy)

通讯作者: 李文，E-mail：liwen3710@ouc.edu.cn，研究方向为海洋功能防护材料

Corresponding author: LI Wen, E-mail: liwen3710@ouc.edu.cn

作者简介: 夏渊，男，1984年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2024.326 或 https://www.jcscp.org/CN/Y2025/V45/I4/975

图1 马来酸二乙酯与聚醚胺反应制备聚天冬氨酸酯树脂及该树脂与缩二脲异氰酸酯反应制备聚天冬氨酸酯聚脲反应原理图，3,3'-二甲基-4,4-二氨基二环己基甲烷，4,4'-二氨基二环己基甲烷分子结构及1,6-己二胺分子结构

图2 A1~A4树脂分子模拟模型，及A1树脂与缩二脲异氰酸酯反应生成聚脲分子模型和聚脲涂层体系模拟模型

图3 聚脲体系在不同聚合程度下的密度随模拟时间的演变

图4 A1聚脲6DT涂层自由体积(为了更清晰的观察自由体积形状，体系内的树脂分子以线的形式显示)

图5 4DT、6DT和8DT的四种树脂体系的FFV及其对比图

图6 水分子在6DT A1~A4聚脲体系内以及在不同分子链段长度A4聚脲体系内的MSD曲线

图7 A4聚脲分子结构中双键氧原子与水分子中氢原子间的径向分布函数，以及水分子分布及其与聚脲分子之间的氢键结构

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