Well-Defined Fluorinated Copolymers: Current Status and Future Perspectives

Abstract

Well-defined fluoropolymers exhibit unique properties such as excellent oil and water repellency, satisfactory thermal stability, low refractive index, and low surface energy.The origin of these properties is attributed to the presence of strong electronegative and low polarizable Fluorine atom in the backbone of such polymers which leads to a strong C F bond (with a high bond dissociation energy of 485 kJ mol −1 ). Due to these features, these polymers have found applications as functional coatings, thermoplastics, biomedical items, separators and binders for Li-ion batteries, fuel cell membranes, piezoelectric devices, high quality wires and cables, etc. Usually, fluoropolymers are synthesized by conventional radical (co)polymerization of fluoroalkenes which leads to the production of (co)polymers with ill-defined end group, uncontrolled molar mass, and high dispersity values. In the last two decades, significant developments of various reversible deactivation radical polymerization (RDRP) techniques have helped the design of macromolecular architectures (including block, graft, star, dendrimers) on demand. However, for relevant new applications, well-defined fluoropolymers with well-defined macromolecular architectures (e.g. block copolymers as thermoplastic elastomers and electroactive polymers or graft copolymers for fuel cell membranes) are required.Several RDRP methods developed in the last couple of decades have paved the way for the synthesis of (co)polymers with well-defined molar mass, dispersity, chain end-functionality and

Triphenylene containing blue-light emitting semi-fluorinated aryl ether polymers with excellent thermal and photostability

“…Fluorine imparts enhanced properties to polymeric materials targeted for high performance or extreme conditions such as those needed for protective coatings, optoelectronic thin films, biomedical devices, aerospace materials, gas-separation membranes, and fuel cell applications. [1][2][3] The growing organic electronics industry has long sought extremely durable, lightweight, and cheap optoelectronic devices (e.g., OLEDs, organic photovoltaics (OPVs), and organic field-effect transistors (OFETs)) with high luminance at low voltage, and high color purity. 4,5 Translating the organic light-emitting diode (OLED) performance of fragile organometallics (such as Alq3 by Kodak in 1987 6 ) into robust polymers with real macromolecular properties continues to be a ''holy grail'' for organic electronics.…”

Renewable isosorbide‐enchained semi‐fluorinated aromatic ether polymers

“…Polymers containing fluorine are desired as high‐performance materials for extreme (mean) environments due to their high‐thermal stability, low‐dielectric constant, good chemical resistance, and low‐surface energy 1–3 . Such high‐performance materials play important roles in coatings, elastomers, optoelectronics, proton‐exchange membrane, and biomedical applications 4–6 . Unlike traditional/fully‐fluorinated polymers, semi‐fluorinated polymers are more solution and melt‐processable and can maintain certain desired properties of perfluoropolymers 7 …”

Visible‐Light‐Enabled Organocatalyzed Controlled Alternating Terpolymerization of Perfluorinated Vinyl Ethers

“…[9] Thec ontrolled polymerization of fluoroalkenes remains am ajor challenge. [13] In particular,t he controlled co-and terpolymerization of perfluorinated vinyl ethers (PFVEs), which represent an important category of industrially relevant fluoroalkenes (e.g., Viton, [6] Kalrez [7] ), have been rarely achieved. Conventional methods not only typically require elevated temperature and pressure,b ut also suffer from uncontrolled molecular weight, broad dispersity,p oor chainend fidelity and incomplete conversion, [14] restricting the broader accessibility of well-defined fluoropolymers and applications that are facilitated by mild operation conditions.…”