Fluoroolefin Polymerization in Carbon Dioxide

The first reported polymerization of fluoroolefins in carbon dioxide was by Fukui and coworkers [39,40]. Tetrafluoroethylene, chlorotrifluoroethylene,and other fluoroolefins were polymerized in the presence of CO2 using ionizing radiation [39, 40] and free-radical initiators [40]. DeSimone and coworkers reported the homogeneous telomerization of tetrafluoroethylene [41] and vinylidene fluoride [42] in CO2 using AIBN as an initiator. The kinetics of AIBN decomposition in CO2 is well understood [4]. However, peroxide initiators are preferred over azo initiators for producing stable endgroups in fluoroolefins... 

Heterogeneous Polymerization of Fluoroolefins in Supercritical Carbon Dioxide... 

Heterogeneous Polymerization of Fluoroolefins in Supercritical Carbon Dioxide 331 Table 1 Critical temperatures and pressures of substances useful as supercritical fluids [9]... 

Romack TJ (1997) Polymerization of fluoroolefins in liquid and supercritical carbon dioxide (free radical). PhD Thesis, University of North Carolina at Chapel HUl, Chapel Hill,NC... 

Polymerization of fluoroolefins in liquid and supercritical carbon dioxide eliminates the use of water and C-8 surfactant that has been identified as a persistent organic pollutant (R. Carbonell) ... 

Some examples will illustrate the polymerization of fluoroolefins in supercritical carbon dioxide medium. 

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