The hydrophobic and oleophobic surface properties of polystyrene can be improved by using specific perfluorinated polystyrene copolymers as additives. In this work, an efficient synthetic route consisting in chemical modification via nucleophile substitution of chlorinated copolymers precursors was optimized. FTIR, ¹H NMR, ¹³C NMR and ¹⁹F NMR spectroscopic techniques were used to verify the overall conversion of reactions, characterize the chemical structures and quantify the composition of fluorinated part in the synthetized copolymers. Additionally, the thermal characterizations performed by Differential Scanning Calorimetry and the microstructure revealed by Optical Microscopy and X-ray diffraction, evidenced that the copolymer based on 19 mol.% of fluorinated monomer exhibits a singular properties and seems closer to a periodic copolymer conformation. These singular properties would originate from an interpenetrating conformation and explain the homogeneous morphology for all formulations based on this copolymer in comparison with copolymers based on 4 and 37 mol.% of fluorinated monomer. Finally, the functionality of the synthetized copolymers was evaluated, by measurement of water/oil static contact angles, and also in blend with a commercial polystyrene matrix at various wt.% of additives ranging from 100 ppm to 100 %. The effects of nature and content of copolymers on the hydrophobic and oleophobic surface properties were investigated. For all copolymers, the more the additive content increases, the more the surface properties are improved, obeying a threshold behavior for 4 and 37 mol.% and a quasi-linear behavior for 19 mol.%. Finally, it was evidenced that the surface properties improvement results both from the presence of a critical percentage of fluorine in the polymers blends and its consequence on the morphological properties. The additive based on 19 mol.% of fluorinated monomer allowing the achievement of higher static contact angles even with very low percentages of additive was identified as an optimal additive for improvement of polystyrene surface properties.

通过使用特定的全氟化聚苯乙烯共聚物作为添加剂，可以改善聚苯乙烯的疏水和疏油表面特性。在这项工作中，优化了一种有效的合成路线，包括通过氯化共聚物前体的亲核取代进行化学改性。FTIR、¹ H NMR、¹³ C NMR 和¹⁹F NMR光谱技术用于验证反应的整体转化率，表征化学结构并量化合成共聚物中氟化部分的组成。此外，差示扫描量热法进行的热表征以及光学显微镜和 X 射线衍射显示的微观结构证明，基于 19 mol.% 氟化单体的共聚物表现出奇异的性质，似乎更接近于周期性共聚物构象。这些独特的特性源于互穿构象，并解释了基于该共聚物的所有配方与基于 4 和 37 mol.% 氟化单体的共聚物相比的均匀形态。最后，评估合成共聚物的功能，通过测量水/油静态接触角，以及与商业聚苯乙烯基质以不同重量百分比的添加剂混合，范围从 100 ppm 到 100 %。研究了共聚物的性质和含量对疏水和疏油表面性质的影响。对于所有共聚物，添加剂含量增加得越多，表面性能改善得越多，在 4 和 37 mol.% 时遵循阈值行为，在 19 mol.% 时遵循准线性行为。最后，有证据表明，表面性能的改善源于聚合物共混物中氟的临界百分比的存在及其对形态性能的影响。该添加剂基于 19 mol。