SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

Hirosawa, Kazu; Fujii, Kenta; Ueki, Takeshi; Kitazawa, Yuzo; Littrell, Kenneth C.; Watanabe, Masayoshi; Shibayama, Mitsuhiro

doi:10.1039/C6CP02254E

Title: SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

Journal Article · Fri Jun 17 00:00:00 EDT 2016 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C6CP02254E· OSTI ID:1327601

Hirosawa, Kazu ^[1]; Fujii, Kenta ^[2]; Ueki, Takeshi ^[3]; Kitazawa, Yuzo ^[4]; Littrell, Kenneth C. ^[5]; Watanabe, Masayoshi ^[4]; Shibayama, Mitsuhiro ^[1]

Univ. of Tokyo (Japan). Inst. for Solid State Physics
Yamaguchi Univ., Ube (Japan)
National Inst. for Materials Science (NIMS), Tsukuba (Japan). Polymer Materials Unit
Yokohama National Univ., Hodogaya-ku (Japan)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Here, we utilized small-angle neutron scattering (SANS) to quantitatively characterize the LCST-type phase behavior of the poly(benzyl methacrylate) (PBnMA) derivative poly(2-phenylethyl methacrylate) (PPhEtMA) in the deuterated ionic liquid (IL) d₈-1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (d₈-[C₂mIm⁺][TFSA^-]). The SANS curves showed a discontinuous change from those characteristics of dispersed polymer chains to those of large aggregates of PPhEtMA chains suspended in the IL solution, indicating that phase separation occurs discontinuously at T_c. We also evaluated the enthalpic and entropic contributions to the effective interaction parameter χ_eff of PPhEtMA in [C₂mIm⁺][TFSA^-] and compared them with those of PBnMA. The absolute value of the enthalpic contribution observed for PPhEtMA was smaller than that for PBnMA. This difference in the enthalpic term can be attributed to the unfavorable interaction between the IL and the alkyl group in the side chain of PPhEtMA. In addition, the temperature dependence of χ_eff was smaller than the previously reported value for a thermo-responsive polymer in an aqueous system. Finally, it was found out that the strong dependence of T_c on the chemical structure in IL systems originated from the relatively smaller temperature dependence of χ_eff.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1327601

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 18, Issue 27; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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