目的 为兼顾聚氨酯（PU）涂层在红外低发射率、光学透过率与环境耐候性能间的协同平衡,本文创新性地提出一种含氟结构可控的分子设计策略,构建兼具低红外发射率、高透光性和优异耐候性的多功能聚氨酯涂层体系。方法 基于聚氨酯软硬段可调的结构特性,以端羟基聚丁二烯（HTPB）为软段、异佛尔酮二异氰酸酯（IPDI）为硬段,采用1H,1H,2H,2H-全氟辛醇改性IPDI三聚体（IPDIT）制备有机氟接枝单元（FIPDIT）,并协同自制交联剂共聚,合成系列氟改性聚氨酯涂层（FPU）。并采用红外发射率、透光率、水接触角、耐溶剂性、紫外老化及拉伸等测试系统评估涂层的性能,重点分析氟含量对涂层在8~14 μm波段红外发射率及其他关键性能的影响规律。结果 FT-IR与XPS分析表明,氟元素以有机氟链段形式成功接入聚氨酯分子主链。当氟含量为7%时,所制备涂层综合性能最佳,其红外发射率为0.57,透光率达90.9%,雾度为1.08%,吸水率为0.5%,水接触角为121.36°,良好的拉伸强度为2.43 MPa,断裂伸长率为580.7%,紫外老化耐受时间达800 h,表现出优异的功能特性与环境适应性能。结论 在聚氨酯分子中引入氟链段可在不明显提高红外发射率的前提下,显著增强涂层的耐环境性能,为新一代适用于复杂海洋环境的多功能聚氨酯涂层材料的设计提供了新的材料设计思路与实验依据。
Abstract
In modern optoelectronic detection and target protection systems, infrared (IR) stealth, optical transparency, and environmental durability are often mutually constrained. Achieving low IR emissivity typically requires the incorporation of metallic or high-refractive-index components, which inevitably reduces optical transmittance. Conversely, enhancing transparency often compromises mechanical strength and environmental stability. Although low-emissivity coatings characterized by low cost, facile processing, and favorable optical properties have attracted increasing attention, conventional metal-based systems, while effective in suppressing IR radiation, generally exhibit high reflectivity or opacity, limiting visible-light transmission. Transparent polymers, such as PMMA and PC, frequently display high IR emissivity (ε > 0.8) due to strong absorption from C—H, N—H, and O—H bonds in the 8-14 μm range, making it challenging to simultaneously achieve optical transparency and low emissivity. Consequently, designing a single material system that integrates IR stealth with optical compatibility and environmental robustness has become a critical scientific and engineering challenge. Polyurethane (PU), with its excellent mechanical properties, strong film-forming ability, and tunable molecular architecture, provides an ideal platform for addressing this challenge, as its IR absorption is closely linked to the chemical composition of its soft and hard segments, offering a route to tailor spectral response through molecular design. Although prior studies have advanced material modification and performance optimization, reducing IR emissivity via fillers or enhancing transparency and weathering resistance through copolymerization and crosslinking-most efforts has focused on single-property enhancement, lacking systematic multi-performance design strategies. Comprehensive solutions that achieve low IR emissivity while maintaining high optical transparency, mechanical integrity, interfacial stability, and environmental durability remain scarce, directly limiting the practical application of IR stealth coatings in complex operational environments. Therefore, exploring polymer systems that simultaneously fulfill these multifunctional requirements and elucidating the relationships among molecular structure, interfacial characteristics, and macroscopic performance constitute both a fundamental scientific problem and a key technological bottleneck in protective coating design. The work aims to propose a controllable molecular design strategy based on PU to achieve synergistic optimization of low IR emissivity, high optical transmittance, and robust environmental stability. Hydroxyl-terminated polybutadiene (HTPB) was employed as a flexible soft segment, and isophorone diisocyanate (IPDI) as a rigid hard segment. A fluorinated grafting unit (FIPDIT) was synthesized by modifying the IPDI trimer (IPDIT) with 1H,1H,2H,2H-perfluorooctanol and copolymerized with HTPB and a custom-designed crosslinker to form a series of fluorine-modified PU (FPU) resins. Introducing fluorine at the molecular scale reduced polymer polarity, regulated surface energy, and optimized interfacial structure, simultaneously modulating IR emissivity, optical transparency, and environmental durability. FT-IR and XPS analyses confirmed successful incorporation of —CF3 groups into the PU backbone, achieving ordered molecular structures and intrinsic low-emissivity characteristics. Systematic test results indicated that with the increasing fluorine content, the infrared emissivity and optical transparency of the FPU coating showed no significant changes, while the environmental resistance was remarkably enhanced. The optimized coating with 7% fluoride content achieved an IR emissivity of 0.57, transmittance of 90.9%, haze of 1.08%, water contact angle of 121.36°, tensile strength of 2.43 MPa, elongation at break of 580.7%, and UV-aging resistance up to 800 h. Moderate fluorine incorporation effectively mitigated dipole-dipole interactions, refined microphase separation, and enhanced interfacial hydrophobicity and oxidative stability, enabling synergistic regulation of emissivity, transparency, and durability. Overall, this work demonstrates that precise molecular design and interface engineering via fluorine incorporation can overcome traditional trade-offs in PU coatings, achieving a balanced integration of IR stealth and optical transparency. The findings provide both theoretical guidance and experimental validation for developing next-generation fluorinated PU coatings for harsh marine and atmospheric environments and establish a versatile framework for multispectral protective and smart optical defense materials.
关键词
氟改性 /
红外低发射率 /
聚氨酯涂层 /
光学性能 /
耐环境性
Key words
fluorine modification /
low infrared emissivity /
polyurethane coating /
optical properties /
environmental resistance
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基金
厦门市自然科学基金（35022202571083）; 725所青年基金项目（LW246908）
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