Density-tuned polyolefin phase equilibria. 2. Multicomponent solutions of alternating poly(ethylene-propylene) in subcritical and supercritical olefins. Experiment and SAFT model

Shean Jer Chen, Ioannis Economou, Maciej Radosz

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Abstract

Different phase transitions (LCST, UCST, VL, and VLL) in binary, ternary, and, quaternary olefin-polyolefin systems are found to be easily tuned with density. Polyolefin is alternating poly(ethylenepropylene), PEP for short. The PEP phase transitions are quantitatively related to pressure, temperature, solvent composition, and its size. For example, supercritical ethylene drastically reduces the mutual solubilities of comonomers and PEP and hence increases the minimum pressure needed for complete miscibility. This ethylene antisolvent effect is modeled with statistical associating fluid theory (SAFT). SAFT also predicts that LCST and UCST curves can merge into a single U-LCST curve upon increasing the size difference between the polymer and solvent. Furthermore, one internally consistent set of SAFT parameters can correlate LCST, VL, and VLL equilibria simultaneously, which has not been demonstrated before. SAFT is verified experimentally with new phase equilibrium data obtained in an optical variable-volume cell for ternary PEP solutions in propylene + ethylene, 1-butene + ethylene, and 1-hexane + ethylene.

Original languageEnglish
Pages (from-to)4987-4995
Number of pages9
JournalMacromolecules
Volume25
Issue number19
Publication statusPublished - 1 Jan 1992
Externally publishedYes

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Polyolefins
Alkenes
Phase equilibria
Olefins
Propylene
Ethylene
Fluids
Experiments
Solubility
Phase transitions
Hexanes
Hexane
Butenes
Polymers
propylene
ethylene
PL 732
Chemical analysis
Temperature

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

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title = "Density-tuned polyolefin phase equilibria. 2. Multicomponent solutions of alternating poly(ethylene-propylene) in subcritical and supercritical olefins. Experiment and SAFT model",
abstract = "Different phase transitions (LCST, UCST, VL, and VLL) in binary, ternary, and, quaternary olefin-polyolefin systems are found to be easily tuned with density. Polyolefin is alternating poly(ethylenepropylene), PEP for short. The PEP phase transitions are quantitatively related to pressure, temperature, solvent composition, and its size. For example, supercritical ethylene drastically reduces the mutual solubilities of comonomers and PEP and hence increases the minimum pressure needed for complete miscibility. This ethylene antisolvent effect is modeled with statistical associating fluid theory (SAFT). SAFT also predicts that LCST and UCST curves can merge into a single U-LCST curve upon increasing the size difference between the polymer and solvent. Furthermore, one internally consistent set of SAFT parameters can correlate LCST, VL, and VLL equilibria simultaneously, which has not been demonstrated before. SAFT is verified experimentally with new phase equilibrium data obtained in an optical variable-volume cell for ternary PEP solutions in propylene + ethylene, 1-butene + ethylene, and 1-hexane + ethylene.",
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T1 - Density-tuned polyolefin phase equilibria. 2. Multicomponent solutions of alternating poly(ethylene-propylene) in subcritical and supercritical olefins. Experiment and SAFT model

AU - Chen, Shean Jer

AU - Economou, Ioannis

AU - Radosz, Maciej

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N2 - Different phase transitions (LCST, UCST, VL, and VLL) in binary, ternary, and, quaternary olefin-polyolefin systems are found to be easily tuned with density. Polyolefin is alternating poly(ethylenepropylene), PEP for short. The PEP phase transitions are quantitatively related to pressure, temperature, solvent composition, and its size. For example, supercritical ethylene drastically reduces the mutual solubilities of comonomers and PEP and hence increases the minimum pressure needed for complete miscibility. This ethylene antisolvent effect is modeled with statistical associating fluid theory (SAFT). SAFT also predicts that LCST and UCST curves can merge into a single U-LCST curve upon increasing the size difference between the polymer and solvent. Furthermore, one internally consistent set of SAFT parameters can correlate LCST, VL, and VLL equilibria simultaneously, which has not been demonstrated before. SAFT is verified experimentally with new phase equilibrium data obtained in an optical variable-volume cell for ternary PEP solutions in propylene + ethylene, 1-butene + ethylene, and 1-hexane + ethylene.

AB - Different phase transitions (LCST, UCST, VL, and VLL) in binary, ternary, and, quaternary olefin-polyolefin systems are found to be easily tuned with density. Polyolefin is alternating poly(ethylenepropylene), PEP for short. The PEP phase transitions are quantitatively related to pressure, temperature, solvent composition, and its size. For example, supercritical ethylene drastically reduces the mutual solubilities of comonomers and PEP and hence increases the minimum pressure needed for complete miscibility. This ethylene antisolvent effect is modeled with statistical associating fluid theory (SAFT). SAFT also predicts that LCST and UCST curves can merge into a single U-LCST curve upon increasing the size difference between the polymer and solvent. Furthermore, one internally consistent set of SAFT parameters can correlate LCST, VL, and VLL equilibria simultaneously, which has not been demonstrated before. SAFT is verified experimentally with new phase equilibrium data obtained in an optical variable-volume cell for ternary PEP solutions in propylene + ethylene, 1-butene + ethylene, and 1-hexane + ethylene.

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