Hexafluoropropylene epoxide HFPO

Perfluoroepoxid.es were first prepared ia the late 1950s by Du Pont Co. Subsequent work on these compounds has taken place throughout the world and is the subject of a number of reviews (1 5). The main use of these epoxides is as intermediates in the preparation of other fluorinated monomers. Although the polymerisation of the epoxides has been described (6—12), the resulting homopolymers and their derivatives are not significant commercial products. Almost all the work on perfluoroepoxides has been with three compounds tetrafluoroethylene oxide (TFEO), hexafluoropropylene oxide (HFPO), and perfluoroisobutylene oxide (PIBO). Most of this work has dealt with HFPO, the most versatile and by far the most valuable of this class of materials (4). 

Preparation. The preparation of TFE has been described previously. Perfluorovinyl ethers (4-7) are prepared by the following steps. Hexafluoropropylene (HFP) [116-15-4] is oxidized to an epoxide HFPO [428-59-1] (5) which, on reaction with perfluorinated acyl fluorides, gives an alkoxyacyl fluoride. 

TEFLON" FEP was commercialized in 1959. At that time there appeared to be no hope of synthesis of a thermoplastic perfluorinated polymer of any structure other than FEP. Within two years the situation had changed as the result of a series of unexpected discoveries. For several years, research on the synthesis of perfluorocarbon epoxides had been underway in Du Pont, culminating in the discovery of a route to hexafluoropropylene epoxide (HFP0 )[5]. By 1960 sufficient HFPO had been made to permit exploration of its polymerization. This work shortly turned up an unusual polymerization system consisting of CsF initiator and polyethylene glycol ether solvent. Under the proper conditions this same system could be used to effect the condensation of HFPO with perfluorocarbon acid fluorides to produce perfluoroalkoxypropionyl fluorides [6]. These intermediates could be readily converted to perfluoroalkyl vinyl ethers by pyrolysis of their acid forms. 

Reaction of perfluoroaLkenes and hypochlorites has been shown to be a general synthesis of perfluoroepoxides (32) (eq. 7). This appears to be the method of choice for the preparation of epoxides from internal fluoroalkenes (38). Excellent yields of HFPO from hexafluoropropylene and sodium hypochlorite using phase-transfer conditions are claimed (34). 

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