(709h) The Role of Chlorine Substituent in Gas Transport Properties of Polychlorotrifluoroethene (PCTFE)

Yavari, M., University at Buffalo, The State University of New York
Lin, H., University at Buffalo, The State University of New York
Okamoto, Y., New York University


Polymeric membranes have been widely used for
industrial gas separation due to their inherent advantages such as high energy-efficiency.
There is a great interest in understanding the polymer structure/property
relationship to design high performance membranes with high gas permeability
and selectivity. Halogenated polymers have emerged as interesting membrane
materials for gas separation. For example, perfluoropolymers govern the upper
bounds for He/H2, He/N2, and He/CH4 separation
in the Robeson’s plots, which is ascribed to the more favorable interactions
for He than other gases with fluoropolymers, as shown in the Figures above.
Herein, we demonstrate that chlorine groups exhibit unique separation
properties for the removal of noble gas from mixtures, as exemplified in
polychlorotrifluoroethylene (PCTFE, -CF2-CFCl-). At 35 oC,
PCTFE exhibits a He permeability of 26 Barrers and pure gas selectivity of He/H2,
He/CO2 and He/CH4 of 6.2, 53 and 1,100, respectively.
These selectivity values are among the highest reported, and the performance is
near or above the upper bounds for these separations. Interestingly, PCTFE also
shows a H2/CO2 selectivity of 8.5 at 35 oC,
an attractive performance for H2 purification and CO2
capture. The effect of Cl substituents on CO2 solubility can be
interpreted using the regular solution theory. Similar behavior for CO2/CH4
solubility selectivity is also observed in halogenated organic liquids. This
presentation will also discuss potential applications of halogenated polymers for
the separation of other noble gases (such as Argon) from their mixtures.