The phase behavior of several commercially available poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) block copolymers (PEO−PPO−PEO or Pluronics L) in compressed carbon dioxide has been investigated within the framework of dry nuclear decontamination. For this purpose, cloud points have been measured in the pressure and temperature range from P = (10 to 40) MPa and from T = (293 to 338) K, respectively. To find a reliable method for surfactant selection, the perturbed-chain statistical association fluid theory (PC-SAFT) equation of state (EoS) has been applied to model the experimental data. The pure-component and the respective homopolymer + CO2 binary interaction parameters have been fitted to liquid densities and to homopolymer + CO2 binary equilibrium data. The phase behavior of Pluronics L copolymers as a function of concentration, molar mass, and copolymer composition has been predicted very accurately using a constant PEO−PPO binary interaction parameter k
PEO-PPO = 0.007. The PC-SAFT model was also successfully applied to Pluronics R copolymers (PPOPEOPPO), although a different k
PEO-PPO = −0.018 was required to match the experimental data. The model predictions have shown that Pluronics L copolymers with molar mass M < 2750 g·mol−1 and a PEO mass fraction in the copolymer of less than 30 % have sufficiently low cloud-point pressures and are therefore the most suitable for the decontamination process.
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