Aromatic ethers, biphenyl π-conjugation and dynamically imine-bond enhanced waterborne polyurethanes: synergistic molecular design for high-performance carbon fiber sizing coatings

IF 7.3 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings Pub Date : 2025-09-20 DOI:10.1016/j.porgcoat.2025.109680

Xin Song, Chunfeng Li, Lei Le, Zhihao Zhang, Mingli Liu

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引用次数: 0

Abstract

Waterborne polyurethanes (WPUs) have emerged as the preferred option for researchers aiming to replace solvent/emulsion-based resins in carbon fibers (CFs) coatings, owing to their superior adhesion, eco-friendliness, and cost-effectiveness. However, conventional polyether/polyester-based WPU coatings often exhibit insufficient mechanical properties, thermal stability, and weathering resistance. To address these limitations, a diol (PHBA-D1000) containing dynamically reversible imine bonds was synthesized via Schiff base formation between 4-hydroxybenzaldehyde (PHBA) and Jeffamine D1000. Ethoxylated bisphenol A (BPE) and 1,4-bis(2-hydroxyethoxy) benzene (HQEE) were copolymerized proportionally as co-monomers, using PHBA-D1000 as the soft-segment backbone to produce BPE/HQEE-modified WPUs (EWPUs). These EWPUs incorporate π-π conjugated benzene stacking, aromatic ether, biphenyl, carbamate, polyurea, imide, carboxylic acid, and carbonyl groups within their molecular structure. The synergistic effects of these co-monomers improved the overall properties of EWPUs, yielding coatings with better thermal stability (T5% at 269.5 °C), higher tensile strength (46.1 MPa), and greater adhesion (18.7 kPa), showcasing improvements of 26.7 %, 95.3 %, and 21.9 %, respectively. Utilizing EWPUs as sizing coatings significantly enhanced the reactivity, wettability, and mechanical properties of CFs. These coatings introduced functional groups and rigid chains onto the fiber surface, effectively repairing CF surface defects and increasing surface roughness. The surface energy and monofilament tensile strength of EWPU-coated CF reached 59.3 mN/m and 6.216 GPa, respectively, corresponding to improvements of 66.1 % and 24.5 % compared to unsized CF. EWPUs demonstrate outstanding overall performance and notable functional characteristics, highlighting their significant potential for diverse applications and further development.

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芳香醚，联苯π共轭和动态亚胺键增强水性聚氨酯：高性能碳纤维上浆涂料的协同分子设计

水性聚氨酯（wpu）由于其优异的附着力、环保性和成本效益，已成为研究人员在碳纤维涂层中取代溶剂/乳基树脂的首选。然而，传统的聚醚/聚酯基WPU涂料往往表现出不足的机械性能、热稳定性和耐候性。为了解决这些问题，在4-羟基苯甲醛（PHBA）和Jeffamine D1000之间通过席夫碱形成合成了含有动态可逆亚胺键的二醇（PHBA-D1000）。以乙氧基化双酚A （BPE）和1,4-双（2-羟基乙氧基）苯（HQEE）为共聚单体，以PHBA-D1000为软段骨架，按比例共聚制得BPE/HQEE改性wpu （ewpu）。这些ewpu在其分子结构中包含π-π共轭苯堆叠、芳香醚、联苯、氨基甲酸酯、聚脲、亚胺、羧酸和羰基。这些共单体的协同作用改善了ewpu的整体性能，获得了更好的热稳定性（269.5°C时T5%），更高的抗拉强度（46.1 MPa）和更大的附着力（18.7 kPa），分别提高了26.7%，95.3%和21.9%。利用ewpu作为施胶涂层，显著提高了碳纤维的反应性、润湿性和机械性能。这些涂层在纤维表面引入了官能团和刚性链，有效地修复了碳纤维表面缺陷，增加了表面粗糙度。ewpu包覆CF的表面能和单丝抗拉强度分别达到59.3 mN/m和6.216 GPa，与未包覆CF相比，分别提高了66.1%和24.5%。ewpu具有出色的综合性能和显著的功能特征，具有广阔的应用前景和进一步开发潜力。

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来源期刊

Progress in Organic Coatings 工程技术-材料科学：膜

CiteScore

11.40

自引率

15.20%

发文量

577

审稿时长

48 days

期刊介绍： The aim of this international journal is to analyse and publicise the progress and current state of knowledge in the field of organic coatings and related materials. The Editors and the Editorial Board members will solicit both review and research papers from academic and industrial scientists who are actively engaged in research and development or, in the case of review papers, have extensive experience in the subject to be reviewed. Unsolicited manuscripts will be accepted if they meet the journal''s requirements. The journal publishes papers dealing with such subjects as: • Chemical, physical and technological properties of organic coatings and related materials • Problems and methods of preparation, manufacture and application of these materials • Performance, testing and analysis.