Effect of halides on the solvation of poly(ethylene oxide) in the ionic liquid propylammonium nitrate
Ryan Stefanovic1, Zhengfei Chen2, Paul A FitzGerald3
1Priority Research Centre for Particle Processing and Transport, Newcastle Institute for Energy and Resources, The University of Australia, NSW 2308, Australia; School of Environmental & Life Sciences, The University of Newcastle, NSW 2308, Australia.
Hypothesis:
The solvation characteristics of poly(ethylene oxide) (PEO) in nanostructured protic ionic liquids (PILs) are driven by polymer-solvent interactions in the polar domains of the PIL. This work hypothesises that the nanostructure of a PIL can be altered via halide addition, directly affecting the solvation of PEO.
Experiments:
Small angle neutron scattering (SANS) is used to explore the conformation of 38 kDa PEO dissolved in the PIL propylammonium nitrate (PAN), a mol fraction of 10% propylammonium chloride (PACl) in PAN, and a mole fraction of 10% propylammonium bromide (PABr) in PAN.
Findings:
Each of these solutions are shown to behave as a good solvent for PEO, as determined by their Flory exponents and Zimm plot analysis. The quality of solvation is reduced by the addition of the halide salt, with the order of solvation as follows: PAN > Br- addition > Cl- addition. Our experimental observations are consistent with the recently reported solvation structure of PEO in these solutions (Stefanovic et al., 2018). The increased charge density from NO3- to Br- to Cl- results in greater net ionic interaction between the ionic charge centres. As PEO interacts with PAN primarily through the ammonium hydrogens of the cation, this increased ionic interaction effectively displaces the PEO, resulting in poorer solvation.
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