Issue
Korean Journal of Chemical Engineering,
Vol.19, No.1, 126-131, 2002
Monomer Concentration Effect on the Phase Behavior of Poly(propyl acrylate) and Poly(propyl methacrylate) with Supercritical CO2 and C2H4
Experimental cloud-point data to temperature of 186 oC and pressure of ~2,500 bar are presented for ternary mixtures of poly(propyl acrylate)(PPA)-CO2-propyl acrylate (PA) PPA-C2H4-PA and poly(propyl methacrylate) (PPMA)-CO2-propyl methacrylate (PMA) systems. Cloud-point pressures of PPA-CO2-PA system were measured in the temperature range of 32 oC to 175 oC and to pressures as high as 2,070 bar with PA concentrations of 0.0, 5.0, 11.7 and 30.4 wt%. Adding 34.1 wt% PA to the PPA-CO2 mixture significantly changes the phase behavior. This system changes the pressure-temperature slope of the phase behavior curves from U-LCST region to LCST region as the PA concentration increases. Cloud-point data to 170 oC and 1,400 bar are presented for PPA-C2H4-PA mixtures and with PA concentration of 0.0, 5.7, 15.5 and 22.2 wt%. The cloud-point curve of PPA-C2H4 system shows relatively flat at 730 bar for temperatures between 41 and 150 oC. With 15.5 and 22.2 wt% PA the cloud-point curve exhibits a positive slope that extends to 35 oC and ~180 bar. Also, the ternary PPMA-CO2-PMA system was measured below 186 oC and 2,484 bar, and with cosolvent of 5.2-20.1 wt%. PPMA does not dissolve in pure CO2 to 233 oC and 2,500 bar. Also, when 41.5 wt% PMA is added to the PPMA-CO2 solution, the cloud-point curve shows the typical appearance of a lower critical solution temperature (LCST) boundary.
[References]
  1. Bardin JM, Patterson D, Polymer, 10, 247, 1969
  2. Byun HS, Hasch BM, McHugh MA, Mahling FO, Busch M, Buback M, Macromolecules, 29(5), 1625, 1996
  3. Byun HS, McHugh MA, Ind. Eng. Chem. Res., 39(12), 4658, 2000
  4. Kim K, Byun HS, HWAHAK KONGHAK, 38(4), 479, 2000
  5. Chen SJ, Radosz M, Macromolecules, 25, 3089, 1992
  6. Conway SE, Byun HS, McHugh MA, Wang JD, Mandel FS, J. Appl. Polym. Sci., 80(8), 1155, 2001
  7. Cowie JMG, McEwen IJ, J. Chem. Soc.-Faraday Trans., 70, 171, 1974
  8. DeSimone JM, Zihibin G, Elsebernd CS, Science, 257, 945, 1992
  9. Folie B, Gregg C, Luft G, Radosz M, Fluid Phase Equilib., 120(1-2), 11, 1996
  10. Lora M, Rindfleisch F, McHugh MA, J. Appl. Polym. Sci., 73(10), 1979, 1999
  11. LoStracco MA, Lee SH, McHugh MA, Polymer, 35(15), 3272, 1994
  12. McHugh MA, Krukonis VJ, "Supercritical Fluid Extraction: Principles and Practice," 2nd end., Butterworths Publishers, Stoneham, MA, 1993
  13. McHugh MA, Rindfleisch F, Kuntz PT, Schmaltz C, Buback M, Polymer, 39(24), 6049, 1998
  14. Prausnitz JM, Lichtenthaler RN, de Azevedo EG, "Molecular Thermodynamics of Fluid-Phase Equilibria," Englewood Cliffs, Prentice-Hall, NJ, 1986
  15. Rindfleisch F, DiNoia TP, McHugh MA, J. Phys. Chem., 100(38), 15581, 1996
  16. Wolf BA, Blaum G, J. Polym. Sci. B: Polym. Phys., 13, 1115, 1975
  17. Zeman L, Patterson D, J. Phys. Chem., 76, 1214, 1972