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Thermodynamics of Phase Behavior in PEO/P(EO‐b‐DMS) Homopolymer and Block Co‐Oligomer Mixtures under Pressure
Authors:Shichun Jiang  Lijia An  Bingzheng Jiang  Bernhard A. Wolf
Abstract:The cloud‐point temperatures (Tcl's) of poly(ethylene oxide) (PEO) and poly(ethylene oxide)‐block‐polydimethylsiloxane (P(EO‐b‐DMS)) homopolymer and block‐oligomer mixtures were determined by turbidity measurements over a range of temperatures (105 to 130 °C), pressures (1 to 800 bar), and compositions (10–40 wt.‐% PEO). The system phase separates upon cooling and Tcl was found to decrease with an increase in pressure for a constant composition. In the absence of special effects, this finding indicates negative excess volumes. Special attention was paid to the demixing temperatures as a function of the pressure for the different polymer mixtures and the plots in the T? plane (where ? signifies volume fractions). The cloud‐point curves of the polymer mixture under pressures were observed for different compositions. The Sanchez‐Lacombe (SL) lattice fluid theory was used to calculate the spinodals, the binodals, the Flory‐Huggins (FH) interaction parameter, the enthalpy of mixing, and the volume changes of mixing. The calculated results show that modified P(EO‐b‐DMS) scaling parameters with the new combining rules can describe the thermodynamics of the PEO/P(EO‐b‐DMS) system well with the SL theory.
image

Cloud point curves for various PEO/P(EO‐b‐DMS) polymer mixtures at various pressures on the T?PEO plane.

Keywords:phase behavior  poly(ethylene oxide)/poly(ethylene oxide)‐block‐polydimethylsiloxane mixture  pressure effects  Sanchez‐Lacombe lattice fluid theory  thermodynamics
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