Synthesis and (co)polymerization of monofluoro, difluoro, trifluorostyrene and ((trifluorovinyl)oxy)benzene

Abstract

The synthesis of aromatic fluoromonomer compounds functionalized by halogen atoms, organic functions or acid groups prepared and characterized by different methods, are described in this review. This review deals with the synthesis and the polymerization of fluorostyrene bearing the fluorine atom(s) in α and/or β position, mainly. These syntheses involve different reactants such as α,α-difluoroethylbenzene, or aryl iodides and vinylidene fluoride, or styrene and fluorination agents for α-fluorostyrene and sodium 1,2-difluoroacetate, or triphenylphosphine, fluorotrichloromethane, zinc dust and a ketone for the β-fluorostyrene. Their homopolymerizations using different systems (mainly radical and cationic polymerization) and various processes (suspension, emulsion, bulk, or in solution) are also described. The second part reported several synthetic routes to obtain α,β- or β,β-difluorostyrene bearing different reactants such as vinyl zincic reagent (F2C=C(CF3)ZnX (X=Br or I)) and palladium catalysts. This review also describes the synthesis of α,β,β-trifluorostyrene functionalized by a halogen or an acid group, using mainly a cross-coupling reaction between perfluoroalkenylzinc reagent and aryl iodides in the presence of a palladium catalyst. The thermocyclodimerization of α,β,β-trifluorostyrene and the emulsion copolymerization of dimethylphosphonate-4-substitued-α,β,β-trifluorostyrene with α,β,β-trifluorostyrene are studied. Finally, the state of the art of synthesis and (co)polymerization of [(α,β,β-trifluorovinyl)oxy] benzene functionalized or not is described. The main method to obtain such monomer is based on a coupling reaction between functionalized phenate and 1,2-dibromo-tetrafluoroethane (BrCF2CF2Br) followed by a dehalogenation step. The homopolymerization realized by thermocyclodimerization involves fluoropolymers incorporating perfluorocyclobutane groups. These fluoropolymers lead to innovative applications such as membranes for fuel cells, microlithography, and optics. In each part of the review, the specific chemical, physical and thermal properties of all fluoropolymers incorporating aromatic fluoromonomers are reported and discussed. © 2003 Elsevier Ltd. All rights reserved.