Abstract
Experimental cloud-point data to temperature of 186 °C 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 °C to 175 dgC 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 °C 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 °C. With 15.5 and 22.2 wt% PA the cloud-point curve exhibits a positive slope that extends to 35 °C and ~180 bar. Also, the ternary PPMA-CO2-PMA system was measured below 186 °C and 2,484 bar, and with cosolvent of 5.2-20.1 wt%. PPMA does not dissolve in pure CO2 to 233 °C 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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Bardin, J. M. and Patterson, D., “Lower Critical Solution Temperature of Polyisobutylene Plus Isomeric Alkanes,”Polymer,10,247 (1969).
Byun, H. S., Hasch, B. M., McHugh, M. A., Mähling, G. O. and Buback, M., “Poly(ethylene-co-butyl acrylate). Phase Behavior in Ethylene Compared to the Poly(ethylene-co-methyl acrylate)-Ethylene System and Aspects of Copolymerization Kinetics at High Pressure,”Macromolecules,29,1625 (1996).
Byun, H. S. and McHugh, M. A., “Phase Behavior and Modeling of Supercritical Carbon Dioxide-Organic Acid Mixtures,”Ind. Eng. Chem. Res.,39,4658 (2000).
Byun, H. S. and Kim, K., “Cosolvent Effect on the Phase Behavior of Poly(butyl methacrylate)-CO2-Butyl Methacrylate System at High Pressure,”HWAHAK KONGHAK,38, 479 (2000).
Chen, S. J. and Radosz, M., “Density-Tuned Polyolefin Phase Equilibria. 1. Binary Solutions of Alternating Poly(ethylene-propylene) in Subcritical and Supercritical Propylene, 1-Butene, and 1-Hexene. Experiment and Flory-Patterson Model,”Macromolecules,25, 3089 (1992).
Conway, S. E., Byun, H. S., McHugh, M. A., Mandel, F. S. and Wang, J. D., “Poly(lactide-co-glycolide) Copolymer Solution Behavior in Supercritical CO2, CHF3, and CHC1E2,”J. Appl. Polym. Sci.,80,1155 (2001).
Cowie, J. M. G. and McEwen, I. J., “Upper and Lower Critical Solution Temperatures in the Cosolvent System Acetone(1)+Diethyl Ether(2)+Polystyrene(3),”J. Chem. Soc., Faraday Trans.,70, 171 (1974).
DeSimone, J. M., Zihibin, G. and Elsebernd, C. S., “Synthesis of Fluoropolymers in Supercritical Carbon Dioxide,”Science,257, 945 (1992).
Folie, B., Gregg, C., Luft, G. and Radosz, M., “Phase Equilibria of Poly (ethylene-co-vinyl acetate) Copolymers in Subcritical and Supercritical Ethylene and Ethylene-Acetate Mixtures,”Fluid Phase Equilibria,120, 11 (1996).
Lora, M., Rindfleisch, F. and McHugh, M. A., “Influence of the Alkyl Tail on the Solubility of Poly(alkyl acrylates) in Ethylene and CO2 at High Pressure: Experiment and Modeling,”J. Appl. Polym. Sci.,73, 1979 (1999).
LoStracco, M. A., Lee, S.-H. and McHugh, M. A., “Comparison of the Effect of Density and Hydrogen Bonding on the Cloud-point Behavior of Poly(ethylene-co-methyl acrylate)-Propane-Cosolvent Mixtures,”Polymer,35, 3272 (1994).
McHugh, M. A. and Krukonis, V. J., “Supercritical Fluid Extraction: Principles and Practice,” 2nd edn, Butterworths Publishers, Stoneham, MA (1993).
McHugh, M. A., Rindfleisch, F., Kuntz, P. T., Schmaltz, C. and Buback, M., “Cosolvent Effect of Alkyl Acrylates on the Phase Behaviour of Poly(alkyl acrylates)-Supercritical CO2 Mixtures,”Polymer,39, 6049 (1998).
Prausnitz, J. M., Lichtenthaler, R. N. and de Azevedo, E. G., “Molecular Thermodynamics of Fluid-Phase Equilibria,” Englewood Cliffs, Prentice-Hall, NJ (1986).
Rindfleisch, F., DiNoia, T. P. and McHugh, M. A., “Solubility of Polymers and Copolymers in Supercritical CO2,”J. Phys. Chem.,100, 15581 (1996).
Wolf, B. A. and Blaum, G., “Measured and Calculated Solubility of Polymers in Mixed Solvents: Monotony and Cosolvency,”J. Polym. Sci.: Part B: Polym. Phys.,13, 1115 (1975).
Zeman, L. and Patterson, D., “Pressure Effects in Polymer Solution Phase Equilibria. II. System Showing Upper and Lower Critical Solution Temperatures,”J. Phys. Chem.,76,1214 (1972).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Byun, HS., Park, C. Monomer concentration effect on the phase behavior of poly(propyl acrylate) and poly(propyl methacrylate) with supercritical CO2 and C2H4 . Korean J. Chem. Eng. 19, 126–131 (2002). https://doi.org/10.1007/BF02706885
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF02706885