Solubility Study of Fluorinated Polymer and Block-Copolymer in Compressed CO2

Nitroxide-mediated radical polymerization was used to synthesize poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) homopolymer, PFDA, and totailor the synthesis of semifluorinated polystyrene-b-PFDA block copolymer, PS-b-PFDA. The solubility of the polymers was investigated in thesolvent carbon dioxide (CO2) using cloud point and light scattering techniques. The solvent quality of CO2 for PFDA homopolymer was shownto increase with CO2 pressure and this information coupled with the size of the block copolymer species indicated the formation of PS-b-PFDAmicelles. Residual PS homopolymer remained soluble in PS-b-PFDA micelles at low pressure and induced the formation of a second populationof larger aggregates when the solvent quality was tuned.© 2005 Elsevier B.V. All rights reserved.