2501-01-1Relevant articles and documents
Photolysis of perfluoroacyl fluorides
Tonelli, Claudio,Tortelli, Vito
, p. 117 - 123 (2000)
The photochemical decarbonylation and coupling of acyl fluorides containing perfluoroalkyl and perfluoro(oxa)alkyl chains have been re-examined. The reaction on either single acyl fluorides or on their binary mixtures has allowed the formation and isolation of macromolecular perfluoro(oxa)alkanes having interesting physical-chemical properties. These perfluoropolyethers are also useful as model compounds and standards to better characterize more complex mixtures of similar commercial products.
Viscosity effects on the thermal decomposition of bis(perfluoro-2-N-propoxypropionyl) peroxide in dense carbon dioxide and fluorinated solvents
Clayton Bunyard,Kadla,Desimone
, p. 7199 - 7206 (2007/10/03)
The thermal decomposition of the free-radical initiator bis(perfluoro-2-N-propoxyprionyl) peroxide (BPPP) was studied in dense carbon dioxide and a series of fluorinated solvents. For the fluorinated solvents, the observed first-order decomposition rate constants, kobs, increased with decreasing solvent viscosity, suggesting a single-bond decomposition mechanism. The kobs values are comparatively larger in dense carbon dioxide and similar to the zero-viscosity rate constants extrapolated from the decomposition kinetics in the fluorinated solvents. The decomposition activation parameters demonstrate a compensation behavior of the activation enthalpy with the activation entropy upon change in solvent viscosity. Comparison of the change in activation parameter values upon change in solvent viscosity for BPPP with two additional initiators, acetyl peroxide (AP) and trifluoroacetyl peroxide (TFAP), further suggests that carbon dioxide exerts a very minimal influence on the decomposition mechanism of these initiators through solvent-cage effects.