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Competition between CO₂-philicity and Mixing Entropy Leads to CO₂ Solubility Maximum in Polyether Polyols

Ylitalo, Andrew S. and Chao, Huikuan and Walker, Pierre J. and Crosthwaite, Jacob and Fitzgibbons, Thomas C. and Ginzburg, Valeriy G. and Zhou, Weijun and Wang, Zhen-Gang and Di Maio, Ernesto and Kornfield, Julia A. (2022) Competition between CO₂-philicity and Mixing Entropy Leads to CO₂ Solubility Maximum in Polyether Polyols. Industrial & Engineering Chemistry Research, 61 (34). pp. 12835-12844. ISSN 0888-5885. doi:10.1021/acs.iecr.2c02396.

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In carbon dioxide-blown polymer foams, the solubility of carbon dioxide (CO2) in the polymer profoundly shapes the structure and, consequently, the physical properties of the foam. One such foam is polyurethane-commonly used for thermal insulation, acoustic insulation, and cushioning which increasingly relies on CO2 to replace environmentally harmful blowing agents. Polyurethane is produced through the reaction of isocyanate and polyol, of which the polyol has the higher capacity for dissolving CO2. While previous studies have suggested the importance of the effect of hydroxyl end groups on CO2 solubility in short polyols (<1000 g/mol), their effect in polyols with higher molecular weight (≥1000 g/mol) and higher functionality (>2 hydroxyls per chain)-as are commonly used in polyurethane foams-has not been reported. Here, we show that the solubility of CO2 in polyether polyols decreases with molecular weight above 1000 g/mol and decreases with functionality using measurements performed by gravimetry-axisymmetric drop-shape analysis. The nonmonotonic effect of molecular weight on CO2 solubility results from the competition between effects that reduce CO2 solubility (lower mixing entropy) and effects that increase CO2 solubility (lower ratio of hydroxyl end groups to ether backbone groups). To generalize our measurements, we modeled the CO2 solubility using a perturbed chain-statistical associating fluid theory (PC-SAFT) model, which we validated by showing that a density functional theory model based on the PC-SAFT free energy accurately predicted the interfacial tension.

Item Type:Article
Related URLs:
URLURL TypeDescription
Ylitalo, Andrew S.0000-0003-4086-3508
Chao, Huikuan0000-0001-9930-3586
Walker, Pierre J.0000-0001-8628-6561
Wang, Zhen-Gang0000-0002-3361-6114
Kornfield, Julia A.0000-0001-6746-8634
Alternate Title:Competition between CO2-philicity and Mixing Entropy Leads to CO2 Solubility Maximum in Polyether Polyols
Additional Information:The authors express their gratitude to Prof. Richard C. Flagan of Caltech for helpful discussions while planning, performing, and writing up this work and to Dr. Sriteja Mantha of Caltech for help with the group contribution method. The authors would also like to thank Dr. Maria Rosaria Di Caprio for help training A.S.Y. to use G-ADSA at the University of Naples. A.S.Y. acknowledges support by the Dow University Partnership Initiative and the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1745301.
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1745301
Issue or Number:34
Record Number:CaltechAUTHORS:20220906-252603000
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:116722
Deposited By: Olivia Warschaw
Deposited On:09 Sep 2022 18:04
Last Modified:09 Sep 2022 18:04

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