Abstract
The critical degree of polymerization (Jcrit) at which polymer chains become insoluble in the continuous medium and particle formation commences has been estimated under a variety of experimental conditions for the nitroxide-mediated precipitation polymerizations of styrene (St) at 110 °C and tert-butyl acrylate (t-BA) at 118 °C in supercritical carbon dioxide (scCO2) mediated by N-tert-butyl-N-[1-diethylphosphono(2,2-dimethylpropyl)]oxy (SG1). The value of Jcrit increases with increasing target molecular weight, initial monomer loading, and pressure. Under the conditions investigated, Jcrit for t-BA is higher than that for St, which is consistent with greater solubility of poly(acrylates) in neat scCO2. A simple graphical approach has been developed and successfully employed, whereby Jcrit can be predicted as a function of both target molecular weight and initial monomer loading on the basis of a data set of Jcrit versus initial monomer loading.
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