SOLUBILITY OF POLY(TETRAFLUOROETHYLENE-CO-19 MOL-PERCENT HEXAFLUOROPROPYLENE) IN SUPERCRITICAL CO2 AND HALOGENATED SUPERCRITICAL SOLVENTS

Citation
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
Citations number
34
Categorie Soggetti
Polymer Sciences
Journal title
ISSN journal
00249297
Volume
29
Issue
20
Year of publication
1996
Pages
6548 - 6555
Database
ISI
SICI code
0024-9297(1996)29:20<6548:SOPMH>2.0.ZU;2-U
Abstract
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.