Effect of halogen substituents on polymer membrane hydrophobicity, swelling and transport mechanism: chlorine versus fluorine

While the role of fluorine on mass transport in polymers has been subject extensive research efforts, less attention paid to played by other halogens, such as chlorine. These efforts favored synthesis a plethora perfluoropolymers which, although exhibiting enhanced physical aging resistance relative conventional hydrocarbon-based polymers, suffer from swelling and plasticization presence hydrocarbons. In this study, we show that chlorine alters their hydrophobicity while enhancing size-sieving ability. Model polar vapors, methanol water, non-polar hydrocarbon vapors were selected for fundamental study series co-polymers perfluoro(2-methylene-4-methyl-1,3-dioxolane (PFMMD) chlorotrifluoroethylene (CTFE), namely poly(PFMMD-co-CTFE), systematically varied molar amount CTFE (i.e., chlorine). Fundamental structure-property correlations developed possible applications field membrane separations outlined. Finally, solubility data chlorinated fluids liquids was discussed support our conclusions. • Chlorine hydrophobicity. Poly(PFMMD-co-CTFE)'s interaction with hydrocarbons is more unfavorable than perfluoropolymers. Poly(PFMMD-co-CTFE) exhibits better