Fluoropolymers are attractive niche polymers used in high added value materials for high-tech applications in aerospace, electronics, coatings, membranes, cables, and the automotive industries. Among them, VDF- and TrFE-based copolymers exhibit remarkable electroactive properties allowing their incorporation into a wide range of devices such as printed memories, sensors, actuators, artificial muscles, and energy storage devices. In a first section, a detailed overview of semi-crystalline poly(VDF-co-TrFE) copolymers and of their ferroelectric (FE) properties from the point of view of polymer chemists is supplied. In addition to the polymer microstructure that may sometimes be controlled or influenced by the synthesis strategies, physical properties such as the phase transitions, and electroactivity are also affected by processing, such as annealing for example, and film thickness for example. Building on the conclusions and understanding obtained from the first section, the effect of the introduction of a termonomer (leading to poly(VDF-ter-TrFE-ter-M) terpolymers) is detailed in a second section of this review. Modifying the terpolymer chain microstructure has a major impact on the crystalline phase of the terpolymers that may result in a relaxor-ferroelectric behavior (RFE). The distribution of the termonomer along the polymer chain, the capacity of the termonomer units to enter the crystal lattice, as well as its dipole moment govern in large part the terpolymer electroactive properties. Poly(VDF-ter-TrFE-ter-CFE) and poly(VDF-ter-TrFE-ter-CTFE) terpolymers appeared to be the best candidates for RFE properties and were thus the most studied. In two following sections, the block or graft architectures of VDF- and TrFE- based copolymers, and the various crosslinking strategies used so far for such copolymers are described. Chemical modification is indeed a very powerful tool to tune electroactive properties of copolymers or to impart additional properties. Finally, in the last section, a few examples of emerging applications for these fluorinated electroactive polymers (EAPs) are briefly discussed. This review aims to provide a comprehensive report on the use of polymer chemistry as a tool to produce better electroactive fluorinated polymers, and highlights possible opportunities and perspectives for future progress in this field. Research in this interdisciplinary field requires different kinds of expertise, ranging from organic and polymer chemistries, polymer films engineering, physics of semi-crystalline polymers and electroactivity, to the design and fabrication of electronic devices.

含氟聚合物是有吸引力的利基聚合物，用于高附加值材料，用于航空航天，电子，涂料，膜，电缆和汽车行业的高科技应用。其中，基于VDF和TrFE的共聚物表现出显着的电活性，可将其结合到多种设备中，例如印刷存储器，传感器，致动器，人造肌肉和能量存储设备。在第一部分中，对半结晶聚（VDF- co提供了从聚合物化学家的角度出发的-TrFE）共聚物及其铁电（FE）性能。除了有时可以通过合成策略控制或影响的聚合物微观结构外，诸如相变和电活性之类的物理性质还受到诸如退火和例如膜厚度的处理的影响。在第一部分得出的结论和理解的基础上，引入三聚单体（产生聚（VDF- ter -TrFE- ter-M）三元共聚物）在本评论的第二部分中进行了详细介绍。改性三元共聚物链的微观结构对三元共聚物的结晶相具有重大影响，这可能会导致弛豫铁电行为（RFE）。三元单体沿着聚合物链的分布，三元单体单元进入晶格的能力及其偶极矩在很大程度上决定着三元共聚物的电活性。Poly（VDF- ter -TrFE- ter -CFE）和poly（VDF- ter -TrFE- ter-CTFE）三元共聚物似乎是RFE性能的最佳候选者，因此受到了最多的研究。在接下来的两个部分中，将介绍基于VDF和TrFE的共聚物的嵌段或接枝结构，以及迄今为止用于此类共聚物的各种交联策略。化学改性的确是调节共聚物的电活性或赋予附加性能的非常强大的工具。最后，在最后一节中，简要讨论了这些氟化电活性聚合物（EAP）新兴应用的一些示例。这篇综述旨在提供有关使用聚合物化学作为生产更好的电活性氟化聚合物的工具的综合报告，并重点介绍该领域未来发展的机会和前景。