Advertisement

Korean Journal of Chemical Engineering

, Volume 19, Issue 1, pp 114–119 | Cite as

The effect of hydrogen bonding on the phase behavior of poly(ethylene-co-acrylic acid)-ethylene-cosolvent mixtures at high pressures

  • Sang-Ho Lee
  • Mark A. McHugh
Article

Abstract

Experimental cloud-point data to 260 °C and 2,500 bar are reported to demonstrate the impact of two cosolvents, acetone and methanol, on the phase behavior of polyethylene, poly(ethylene-co-2.4 mol% acrylic acid) (EAA2.4), poly(ethylene-co-3.9 mol% acrylic acid) (EAA3.9), poly(ethylene-co-6.9 mol% acrylic acid) (EAA6.9), and poly(ethylene-co-9.2 mol% acrylic acid) (EAA9.2) in ethylene. In pressure-temperature (P-T) space, the miscibility of EAA copolymers in ethylene decreases significantly with temperature and with increasing acrylic acid content of EAA due to self-association of the acrylic acid segments. Acetone and methanol, both dramatically enlarge the solubility of EAA copolymers due to the hydrogen bonding with acrylic acids in the EAA. At low concentrations, methanol is a better cosolvent than acetone. However, the impact of methanol diminishes rapidly with increasing methanol concentration once all the acrylic acids in the EAA are hydrogen bond with methanol molecules.

Key words

Poly(ethylene-co-acrylic acid) Hydrogen Bond Cosolvent Phase Behavior High Pressures 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Baker, G., “Modem Plastics,” Chemical Week Associates, NY, Mid October (1991).Google Scholar
  2. Boysen, R. L. “Olefin Polymers (High Pressure Polyethylene),” In M. Grayson (Ed.), Kirk-Othmer Encyclopedia of Chemical Technology, New York, John Wiley & Sons (1981).Google Scholar
  3. Brentin, R. P., “Modem Plastics Encyclopedia,” Chemical Week Associates, NY (1988).Google Scholar
  4. Earnest, T. R. Jr. and MacKnight, W. J., “Infrared Studies of Hydrogen Bonding in Ethylenemethacrylic Acid Copolymers and Ionomers”Macromolecules,13, 844 (1980).CrossRefGoogle Scholar
  5. Gregg, C. J., Stein, F. P. and Radosz, M., “Phase Behavior of Telechelic Polyisobutylene (PIB) in Subcritical and Supercritical Fluids. 1. Interand Intra-association Effects for Blank, Monohydroxy, and Dihydroxy PIB (1K) in Ethane, Propane, Dimethyl Ether, Carbon Dioxide, and Chlorodifluoromethane,”Macromolecules,27,4972 (1994a).CrossRefGoogle Scholar
  6. Gregg, C. J., Stein, F. P. and Radosz, M., “Phase Behavior of Telechelic Polyisobutylene (PIB) in Subcritical and Supercritical Fluids. 2. PIB Size, Solvent Polarity, Inter- and Intra-association Effects for Blank, Monohydroxy, and Dihydroxy PIB (1K) in Ethane, Propane, Carbon Dioxide, and Dimethyl Ether,”Macromolecules,27,4981 (1994b).CrossRefGoogle Scholar
  7. Hasch, B. M., Meilchen, M. A., Lee, S.-H. and McHugh, M. A., “Cosolvency Effects on Copolymer Solutions at High Pressures,”J. Polym. Sci., Polym. Phys. Ed.,31, 429 (1993a).CrossRefGoogle Scholar
  8. Hasch, B. M., Lee, S.-H. and McHugh, M. A., “The Effect of Copolymer Architecture on Solution Behavior,”Fluid Phase Equilibria,83, 341 (1993b).CrossRefGoogle Scholar
  9. Hasch, B. M., Meilchen, M. A., Lee, S.-H. and McHugh, M. A., “High Pressure Phase Behavior of Poly(ethylene-co-methyl acrylate) with Low Molecular Weight Hydrocarbons,”J. Polym. Sci., Polym. Phys. Ed.,30,1365 (1992).CrossRefGoogle Scholar
  10. Irani, C. A. and Cozewith, C., “Lower Critical Solution Temperature Behavior of Ethylene — Propylene Copolymers in Multicomponent Solvents,”J. Appl. Poly. Sci.,31, 1879 (1986).CrossRefGoogle Scholar
  11. Kaus, M. J., “Modern Plastics Encyclopedia,” Chemical Week Associates, NY, Mid October (1988).Google Scholar
  12. Lee, S.-H. and McHugh, M. A., “Phase Behavior Studies with Poly(ethylene-co-methacrylic acid) at High Pressures,”Polymer,38, 1317 (1997).CrossRefGoogle Scholar
  13. Lee, S.-H., LoStracco, M. A. and McHugh, M. A., “Cosolvent Effect on the Phase Behavior of Poly(ethylene-co-acrylic acid) Butane Mixtures,”Macromolecules,29,1349 (1996).CrossRefGoogle Scholar
  14. Lee, S.-H., LoStracco, M. A. and McHugh, M. A., “High-pressure, Molecular Weight-dependent Behavior of (co)polymer Solvent Mixtures: Experiments and Modeling,”Macromolecules,27,4652 (1994a).CrossRefGoogle Scholar
  15. Lee, S.-H., LoStracco, M. A, Hasch, B. M. and McHugh, M. A., “Solubility of Poly(ethylene-co-acrylic acid) in Low Molecular Weight Hydrocarbons: Effect of Copolymer Concentration, Solvent Quality, and Copolymer Molecular Weight,”J. Phys. Chem.,98, 4055 (1994b).CrossRefGoogle Scholar
  16. 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).CrossRefGoogle Scholar
  17. Luft, G. and Wind, R. W., “Phasenverhalten von Mischungen aus Ethylene und Ethylene Acrylsaure Copolymeren Unter Hohem Druck,”Chem. Ing. Tech.,64,1114 (1992).CrossRefGoogle Scholar
  18. Meilchen, M. A., Hasch, B. M., Lee, S.-H. and McHugh, M. A., “Poly (ethylene-co-methyl acrylate) Solvent Cosolvent Phase Behavior at High Pressures,”Polymer,33,1922 (1992).CrossRefGoogle Scholar
  19. Meilchen, M. A., Hasch, B. M. and McHugh, M. A., “Effect of Copolymer Composition on the Phase Behavior of Mixtures of Poly(ethylene-co-methyl acrylate) with Propane and Chlorodifluoromethane,”Macromolecule,24,4874 (1991).CrossRefGoogle Scholar
  20. Mergenhagen, Sr. L. K., “Modern Plastics,” Chemical Week Associates, NY, Mid October (1991).Google Scholar
  21. Otocka, E. P. and Kwei, T. K., “Properties of Ethylene Acrylic Acid Copolymers,”Macromolecules,1, 244 (1968).CrossRefGoogle Scholar
  22. Pratt, J. A., Lee, S.-H. and McHugh, M. A., “Supercritical Fluid Fractionation of Copolymers Based on Chemical Composition and Molecular Weight,”J. Appl. Polym. Sci.,49,953 (1993).CrossRefGoogle Scholar
  23. Prausnitz, J. M., Lichtenthaler, R. N. and de Azevedo, E. G., “Molecular Thermodynamics of Fluid-Phase Equilibria,” 2nd ed., PrenticeHall, Englewood Cliffs, NJ (1986).Google Scholar
  24. Rätzsch, M. T., Wagner, P., Wohlfarth, C. and Heise, D., “Studies on the High-pressure Equilibrium in Mixtures of Ethylene and Ethylenevinyl Acetate Copolymers,”Acta Polymerica,33, 463 (1982).CrossRefGoogle Scholar
  25. Rätzsch, M. T., Wagner, P., Wohlfarth, C. and Gleditzsch, S., “Studies of Phase Equilibria in Mixtures of Ethylene and (ethylenevinyl acetate) Copolymers at high Pressures. Part III. Effect of the Molecular Weight Distribution,”Acta Polymerica,34, 340 (1983).CrossRefGoogle Scholar
  26. Reid, R. C., Prausnitz, J. M. and Pouling, B. E., “The Properties of Gases and Liquids,” 4th ed., McGraw-Hill, New-York (1987).Google Scholar

Copyright information

© Korean Institute of Chemical Engineering 2002

Authors and Affiliations

  1. 1.Department of Chemical EngineeringDong-A UniversityBusanRepublic of Korea
  2. 2.Department of Chemical EngineeringVirginia Commonwealth UniversityRichmondUSA

Personalised recommendations