Abstract Since the polymers containing long-chain perfluoroalkyl groups (–CnF2n+1, n ≥ 8) can cause harmful impacts on the environment, it is urgent to explore environmentally friendly fluorinated polymers as alternatives. In this study, a series of novel monomers, methacrylates bearing different spacers and short-chain perfluoroalkyl groups (–CnF2n+1, n ≤ 6), were designed and synthesized. First, photopolymerizations of the monomers were examined under UV-irradiation and the polymer coatings on polycarbonate substrates were obtained by spin-coating and photopolymerization using an environmentally friendly solvent. Then, surface properties of the polymer coatings were investigated by contact angles and the results show that the hydrophobicity and oleophobicity of the polymers are highly related to their structures. When –CONH- and 1,4-phenylene moieties were incorporated into the spacer between the main chain and the perfluoroalkyl group, the hydrophobicity and oleophobicity were significantly enhanced, which is attributed to hydrogen bond and π-π interaction between the side groups. Moreover, longer perfluoroalkyl groups can lead to higher hydrophobicity and oleophobicity of the polymer coatings. The polymer containing –CONH–, 1, 4-phenylene, and –(CF2)6F possesses excellent hydrophobicity and oleophobicity, which are comparable with poly (perfluoroctylethyl methacrylate). The polymer coatings were characterized by differential scanning calorimetry, X-ray photoelectron spectroscopy, X-ray diffraction, and polarizing optical microscopy. The results indicate that the combined effect of hydrogen bond and π-π interaction can effectively facilitate the orientation of the polymer chains to form a lamellar liquid crystalline structure, which can suppress the molecular mobility and significantly improve the surface properties of the polymers with short-chain perfluoroalkyl groups.

中文翻译：

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使用环保溶剂设计和合成具有短全氟烷基侧基的高性能聚合物

摘要 由于含有长链全氟烷基（–CnF2n+1，n≥8）的聚合物会对环境造成有害影响，因此迫切需要探索环保的含氟聚合物作为替代品。在本研究中，设计并合成了一系列新型单体，即带有不同间隔基和短链全氟烷基（–CnF2n+1，n ≤ 6）的甲基丙烯酸酯。首先，在紫外线照射下检查单体的光聚合，并使用环保溶剂通过旋涂和光聚合获得聚碳酸酯基板上的聚合物涂层。然后，通过接触角研究聚合物涂层的表面性质，结果表明聚合物的疏水性和疏油性与其结构高度相关。当 –CONH- 和 1 时，4-亚苯基部分被引入主链和全氟烷基之间的间隔基中，疏水性和疏油性显着增强，这归因于侧基之间的氢键和π-π相互作用。此外，更长的全氟烷基可导致聚合物涂层更高的疏水性和疏油性。含有–CONH–、1, 4-亚苯基和–(CF2)6F 的聚合物具有优异的疏水性和疏油性，可与聚（甲基丙烯酸全氟辛基乙酯）相媲美。通过差示扫描量热法、X 射线光电子能谱、X 射线衍射和偏光显微镜对聚合物涂层进行了表征。