Polytetrafluoroethylene depolymerization

Bryant, W. M. D. Free energies of formation of fluorocarbons and their radicals. Thermodynamics of formation and depolymerization of polytetrafluoroethylene. J. Polymer Sci., in press. 

If a polymer is heated to the point where chemical bonds begin to break, radicals will normally be formed, rather than ions. Thus if chain scission takes place to produce free radicals at temperatures above T, rapid radical depolymerization, with production of monomer, is expected. This rapid depropagation is often termed unzipping. Table 1 shows some typical values for Tc for common polymers. They range widely from quite close to room temperature for polyacetal to close to 600°C for polytetrafluoroethylene. In reality, side reactions, which are discussed... 

Arkles, B. C. Bonnett, R. N. (Liquid Nitrogen Processing Corporation) Method for the Depolymerization of Polytetrafluoroethylene. US Patent 3,832,411, 1975. 

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