The radical copolymerization of VDF with M monomer, their properties and applications are presented. First, after listing a non-exhaustive series of comonomers and macromonomers, and their reactivity towards VDF deduced from the kinetics of copolymerizations to suggest a reactivity order. This review proposes non-exhaustive examples of conventional and controlled (RDRP) radical copolymerization. Other parameters to control these reactions were exposed, such as initiators including specific radicals (e.g.,°CF₃, °OCF₃ and borane radicals), as well as various reaction media (aqueous, solution and supercritical CO₂). Crosslinking of these VDF-based copolymers bearing peculiar functions is also useful to enhance the properties of such fluorinated materials. In addition, environmental concerns on such copolymers regarding their persistency are established but more recent studies claim that these macromolecules are polymers of low concern because of the high molar masses and thermal, chemical, photochemical, hydrolytic, inertness and biological stability to satisfy the regulatory assessment criteria. In that way, more recent studies on the mineralization of poly(VDF-co-M) copolymers under subcritical water led to fluoride anions which could react onto Calcium to yield CaF₂ to close the loop of these fluorinated copolymers. Finally, several applications are supplied showing that these copolymers are key actors in our daily life (functional coatings, elastomers, thermoplastic elastomers, distillation membranes, and materials for Energy such as electrolytes for Lithium ion batteries, fuel cell membranes, sensors, actuators, dye sensitized solar cells and photovoltaics).

介绍了VDF与M单体的自由基共聚及其性能和应用。首先，在列出了一系列非详尽的共聚单体和大分子单体之后，它们对 VDF 的反应性是从共聚动力学推导出来的，以表明反应性顺序。本综述提出了常规和受控 (RDRP) 自由基共聚的非详尽示例。暴露了控制这些反应的其他参数，例如包括特定自由基（例如，°CF ₃、°OCF ₃和硼烷自由基）的引发剂，以及各种反应介质（水溶液、溶液和超临界 CO ₂）。这些具有特殊功能的基于 VDF 的共聚物的交联也可用于增强此类氟化材料的性能。此外，对此类共聚物的持久性方面的环境问题已经确立，但最近的研究声称这些大分子是低关注的聚合物，因为它们具有高摩尔质量和热、化学、光化学、水解、惰性和生物稳定性以满足监管评估标准。以这种方式，最近关于聚（VDF- co - M）共聚物在亚临界水中矿化的研究导致氟阴离子可以与钙反应生成CaF ₂关闭这些氟化共聚物的环。最后，提供的几个应用表明这些共聚物是我们日常生活中的关键角色（功能性涂料、弹性体、热塑性弹性体、蒸馏膜和能源材料，例如锂离子电池的电解质、燃料电池膜、传感器、致动器、染料敏化太阳能电池和光伏）。