Cobalt‐Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide

Cobalt‐mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO₂). CMRP of VAc is conducted using an alkyl‐cobalt(III) adduct that is soluble in scCO₂. Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass (M_n) are key parameters that affect the CMRP in scCO₂. It is noticed that CMRP is controlled for M_n up to 10 000 g mol^?1, but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO₂, is then successfully used to initiate the acrylonitrile polymerization. PVAc‐b‐PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO₂ without the utilization of fluorinated comonomers or organic solvents.