Fluoropolymers are widely used as hydrophobic coatings on plastics, which have low stability and durability. Therefore, it has been a challenge to strengthen the bond force between plastics and fluoropolymers, to improve their chain entanglement, and to make the hydrophobicity of those materials more stable and durable. In this paper, fluorinated multiblock copolymers (PNANPF6-PCOE) with good hydrophobicity, processability and thermal stability were prepared by macromolecular cross metathesis (MCM) method. Notably, micro-nano structures were formed by simply controlling the reaction time of MCM due to the disparity of rigidity and flexibility and polarity in PCOE and PNANPF6 blocks. The micro-nano structures were also preserved in the blends of PNANPF6-PCOE/polypropylene (PP). The tensile mechanical properties and hydrophobicity of PNANPF6-PCOE/PP blends are affected by the length of PCOE and PNANPF6 blocks in multiblock copolymer. With the high temperature in melt-blending process, fluorinated segment groups could easily move and aggregate to the surface, and alkyl groups also would entangle and compatibly blend with polypropylene, which resulted in good thermal properties, well mechanical performance and great hydrophobicity. Most importantly, the antifouling durability to coffee, cola and ethanol was greatly enhanced by melt-blending process compared with solution coating method. This can provide a new strategy for the preparation of fluorinated multiblock copolymers with micro-nano structures, and would demonstrate a new way to achieve durable hydrophobicity and antifouling properties in general materials.

含氟聚合物广泛用作塑料上的疏水涂层，其稳定性和耐久性较低。因此，增强塑料和含氟聚合物之间的结合力，改善它们的链缠结，并使这些材料的疏水性更加稳定和持久，一直是一个挑战。本文采用高分子交叉复分解(MCM)方法制备了具有良好疏水性、加工性能和热稳定性的含氟多嵌段共聚物(PNANPF6-PCOE)。值得注意的是，由于PCOE和PNANPF6块的刚性、柔性和极性的差异，通过简单地控制MCM的反应时间就可以形成微纳米结构。PNANPF6-PCOE/聚丙烯（PP）共混物中也保留了微纳结构。PNANPF6-PCOE/PP 共混物的拉伸机械性能和疏水性受多嵌段共聚物中 PCOE 和 PNANPF6 嵌段长度的影响。在熔融共混过程中的高温下，氟化链段基团很容易移动并聚集到表面，烷基也能与聚丙烯缠结并相容共混，从而产生良好的热性能、机械性能和良好的疏水性。最重要的是，与溶液涂覆方法相比，熔融共混工艺大大提高了对咖啡、可乐和乙醇的防污耐久性。这可以为制备具有微纳结构的氟化多嵌段共聚物提供新策略，并为在通用材料中实现持久疏水性和防污性能提供新途径。