Novel waterborne fluorinated polyurethane (WFPU) based on hydroxyl-terminated poly(fluoroalkyl methacrylates) (HTPFMA) was prepared successfully. The microstructures and micro-phase separation of WFPU were evaluated through infrared spectroscopy (FT-IR), X-ray diffraction (XRD), dynamic mechanical analysis (DMA), and scanning electron microscope (SEM). FT-IR revealed that the H-bonded carbonyl in hard domains increased with the increasing of fluorine content, resulting in enhancing the extent of micro-phase separation between hard and soft segments. XRD results indicated that the crystallinity of hard segment was enhanced with the increasing of fluorine content. The direct visual microstructures by SEM showed that the micro-phase separation was more significant when the fluorine content increased. DMA also revealed strengthened micro-phase separation with increasing fluorine content. The studies of mechanical properties confirmed that WFPU based on HTPFMA had outstanding mechanical properties. The effects of fluorine content on the static contact angles, surface free energy, and surface composition were also studied. The static contact angles of the WFPU films against water and methylene iodide reached around 108° and 84°, respectively. X-ray photoelectron spectroscopy (XPS) confirmed that the fluorine surface enrichment factor in the outermost 10 nm depth was about 10–18 fold higher than its bulk level.

成功制备了基于羟基封端的聚甲基丙烯酸氟代烷基酯（HTPFMA）的新型水性氟化聚氨酯（WFPU）。通过红外光谱（FT-IR），X射线衍射（XRD），动态力学分析（DMA）和扫描电子显微镜（SEM）对WFPU的微观结构和微相分离进行了评估。傅立叶变换红外光谱（FT-IR）显示，硬结构域中的氢键羰基随着氟含量的增加而增加，从而导致硬链段和软链段之间的微相分离程度增强。XRD结果表明，随着氟含量的增加，硬链段的结晶度增强。SEM的直接目测显微结构表明，当氟含量增加时，微相分离更显着。DMA还显示随着氟含量的增加，微相分离增强。力学性能研究证实，基于HTPFMA的WFPU具有优异的力学性能。还研究了氟含量对静态接触角，表面自由能和表面组成的影响。WFPU膜对水和二碘甲烷的静态接触角分别达到108°和84°。X射线光电子能谱（XPS）证实，最外层10 nm深度的氟表面富集系数比其体积水平高约10–18倍。还研究了表面成分。WFPU膜对水和二碘甲烷的静态接触角分别达到108°和84°。X射线光电子能谱（XPS）证实，最外层10 nm深度的氟表面富集系数比其体积水平高约10–18倍。还研究了表面成分。WFPU膜对水和二碘甲烷的静态接触角分别达到108°和84°。X射线光电子能谱（XPS）证实，最外层10 nm深度的氟表面富集系数比其体积水平高约10–18倍。