General Condition for Polymer Cononsolvency in Binary Mixed Solvents

被引:1
作者
Zhang, Xiangyu [2 ]
Zong, Jing [3 ]
Meng, Dong [1 ]
机构
[1] NYU, Dept Mol Pathobiol, Biomat Div, New York, NY 10010 USA
[2] Johns Hopkins Univ, Dept Chem & Biomol Engn, Baltimore, MD 21218 USA
[3] Mississippi State Univ, Dept Chem Engn, Mississippi State, MS 39762 USA
关键词
PREFERENTIAL ADSORPTION; PHASE-TRANSITION; CO-NONSOLVENCY; THERMORESPONSIVE POLYMERS; AQUEOUS-SOLUTIONS; WATER; POLY(N-ISOPROPYLACRYLAMIDE); POLY(N; N-DIETHYLACRYLAMIDE); SEPARATION; GELS;
D O I
10.1021/acs.macromol.4c00246
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Starting from a generic model based on the thermodynamics of mixing and abstracted from the chemistry and microscopic details of solution components, three consistent and complementary computational approaches are deployed to investigate the general condition for polymer cononsolvency in binary mixed solvents at the zeroth order. The study reveals chi(PS) - chi(PC) + chi(SC) as the underlying universal parameter that regulates cononsolvency, where chi(alpha beta) is the immiscibility parameter between the alpha- and beta-component. Two disparate cononsolvency regimes are identified for chi(PS) - chi(PC) + chi(SC) < 0 and chi(PS) - chi(PC) + chi(SC) > 2, respectively, based on the behavior of the second osmotic virial coefficient at varying solvent mixture composition x(C). The predicted condition is verified using self-consistent field calculations by directly examining the polymer conformational transition as a function of x(C). It is further shown that in the regime chi(PS) - chi(PC) + chi(SC) < 0, the reentrant polymer conformation transition is driven by maximizing the solvent-cosolvent contact, but in the regime chi(PS) - chi(PC) + chi(SC) > 2, it is driven by promoting polymer and cosolvent contact. In-between the two regimes when neither effect is dominant, a monotonic response of polymer conformation to x(C) is observed. Effects of the mean-field approximation on the predicted condition are evaluated by comparing the mean-field calculations with computer simulations. It shows that the fluctuation effects lead to a higher threshold value of chi(PS) - chi(PC) + chi(SC) in the second regime, where local enrichment of cosolvent in polymer proximity plays a critical role.
引用
收藏
页码:8632 / 8642
页数:11
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