Ca. Mertdogan et al., SOLUBILITY OF POLY(TETRAFLUOROETHYLENE-CO-19 MOL-PERCENT HEXAFLUOROPROPYLENE) IN SUPERCRITICAL CO2 AND HALOGENATED SUPERCRITICAL SOLVENTS, Macromolecules, 29(20), 1996, pp. 6548-6555
High-pressure cloud-point data are presented for poly(tetrafluoroethyl
ene-co-19.3 mol % hexafluoropropylene) (FEP(19)) in CF4, C2F6, C3F8, C
3F6, CClF3, CO2, and SF6 at 118-250 degrees C and pressures as high as
2700 bar. Cloud-point curves for a given solvent virtually superpose
for FEP(19) concentrations between 2 and 10 wt %. It is not possible t
o dissolve FEP(19) in CO2 at temperatures less than 185 degrees C due
to strong quadrupolar self-interactions relative to cross-interactions
between FEP(19) and CO2. The location of the cloud-point curves in pr
essure-temperature space are directly related to the product of the po
larizability and molar density, rho(i) alpha(i) of the solvent as dete
rmined at the cloud-point pressure at a given temperature. The average
of rho(i) alpha(i) is 5.14 x 10(-24) mol +/-7% for the SCF solvents c
onsidered in this study calculated at 200 degrees C and it is 5.41 x 1
0(-24) mol +/-7% for all of the solvents except CF4 and CO2 at 170 deg
rees C. This simple correlation provides a means for estimating cloud-
point pressures for nonpolar polymers with nonpolar solvents, or for p
olar solvents at very high temperatures where polar interactions are d
iminished. Using this correlation, it is not possible to predict when
crystallization may occur or when polar interactions will dictate the
phase behavior as observed for CO2 at temperatures below 185 degrees C
. With one temperature-independent and one temperature-dependent mixtu
re parameter the Sanchez-Lacombe equation of state (SLEOS) is capable
of modeling the phase behavior of FEP(19) in the solvents considered i
n this study except for CO2 which required two temperature-dependent p
arameters. It is not possible to even qualitatively model the cloud-po
int behavior if the two mixture parameters are set to zero. Hence, the
utility of the SLEOS is limited since cloud-point data are needed to
fix the values and the temperature dependence of the mixture parameter
s.