Tetrafluoroethylene first synthesis

The first reactions of fluorinated olefins in C02 reported by DeSimone et al. involved the free-radical telomerization of 1,1 -difluoroethylene29 and tetrafluor-oethylene.30 This work demonstrated the feasibility of carrying out free-radical reactions of highly electrophilic species in solvents other than expensive fluorocarbons and environmentally detrimental chlorofluorocarbons. The work has since been more broadly applied to the synthesis of tetrafluoroethylene-based, nonaqueous grades of fluoropolymers,31,32 such as poly(tetrafluoroethylene-co-peduoropropylvinyl ether) (Scheme 2). These reactions were typically carried out at between 20 and 40% solids in C02 at initial pressures of between 100 and 150 bars, and 30-35°C (Table 10.1). 

The first part of the book deals with definitions and fundamental subjects surrounding the polymerization of fluoropol)miers. Basic subjects such as the identification of fluoropolymers, their key properties, and some of their everyday uses are addressed. The main monomer, tetrafluoroethylene, is extremely flammable and explosive. Consequently, safe polymerization of this monomer requires special equipment and technology. Molecular forces within these polymers are reviewed and coimected to macro properties. Monomer and polymer synthesis techniques and properties are described. Part One ends with a detailed list of advertised commercial grades of fluoroplastics. 

Tetrafluoroethylene (CF2=Cp2) is the main building block of all perfluorinated polymers, that is, polymers comprised of carbon, fluorine, and occasionally a small amount of oxygen. It is difficult to establish exactly the first successful synthesis. Publications in the 1890 s report a variety of attempts to synthesize TFE by direct reaction of fluorine with carbon, fluorine with chloromethanes, andtetrachloroethylene with silver fluoride.l hW The data presented are insufficient to determine that these efforts actually lead to TFE. Humistonl l reported the first documented preparation of TFE in 1919 which was disputed due to erroneous property data. 

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