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Pure Appl. Chem., 2009, Vol. 81, No. 10, pp. 1829-1841

Published online 2009-09-26

Thermodynamic study on phase transitions of poly(benzyl methacrylate) in ionic liquid solvents

Takeshi Ueki1, Asako Ayusawa Arai2, Koichi Kodama1, Sayaka Kaino1, Noriko Takada2, Takeshi Morita3, Keiko Nishikawa2* and Masayoshi Watanabe1*

1 Department of Chemistry and Biotechnology, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
2 Graduate School of Advanced Integration Science, Chiba University, 1-33 Yayoi, Inage-ku, Chiba 263-8522, Japan
3 Department of Chemistry, Faculty of Education, Aichi University of Education, Hirosawa 1, Igaya, Kariya 448-8542, Japan

Abstract: The lower critical solution temperature (LCST) phase behavior of poly(benzyl methacrylate) (PBnMA) in room-temperature ionic liquids (ILs) was studied by considering the effect of the chemical structure of ILs on the phase separation temperature (Tc). It was found that the LCST behavior of PBnMA was observed in ILs containing [NTf2] anions and PF6 anions. Tc changed significantly with a small change in the chemical structures of the cations. High-sensitivity differential scanning calorimetry (DSC) was successfully performed for studying the LCST phase separation of PBnMA in two different imidazolium-based ILs. Endothermic peaks corresponding to the phase separation of PBnMA from the ILs were clearly observed at ca. 100 °C in the DSC thermograms. It was experimentally verified for the first time that the negative enthalpy and entropy change of mixing of PBnMA in ILs caused the LCST phase separations. The absolute values of the thermodynamic parameters for the phase transition of PBnMA in ILs obtained in this study were much lower than those reported in previous studies for aqueous polymer solutions that exhibit LCST phase behavior, such as poly(N-isopropylarylamide) and poly(vinyl methyl ether). Small changes in the thermodynamic parameters resulted in a large change in the phase separation temperature even by small changes in the chemical structure of the ILs and polymers. The microscopic desolvation process detected from the DSC measurements was inferred to have occurred before the macroscopic phase separation detected from turbidity measurements. The dependence of the endothermic peak temperatures on the DSC scan rate was observed even at slow scan rates. These results indicate that the phase separation of PBnMA from ILs is characterized by extremely slow kinetics.