Abstract
Despite the great interest in nanoconfined materials nowadays, nanocompartmentalized poly(ionic liquid)s (PILs) have been rarely investigated so far. Herein, we report on the successful alkylation of poly(1-vinylimidazole) with methyl iodide in bicontinuous nanophasic poly(1-vinylimidazole)-l-poly(tetrahydrofuran) (PVIm-l-PTHF) amphiphilic conetworks (APCNs) to obtain nanoconfined methylated PVImMe-l-PTHF poly(ionic liquid) conetworks (PIL-CNs). A high extent of alkylation (~95%) was achieved via a simple alkylation process with MeI at room temperature. This does not destroy the bicontinuous nanophasic morphology as proved by SAXS and AFM, and PIL-CNs with 15–20 nm d-spacing and poly(3-methyl-1-vinylimidazolium iodide) PIL nanophases with average domain sizes of 8.2–8.4 nm are formed. Unexpectedly, while the swelling capacity of the PIL-CN dramatically increases in aprotic polar solvents, such as DMF, NMP, and DMSO, reaching higher than 1000% superabsorbent swelling degrees, the equilibrium swelling degrees decrease in even highly polar protic (hydrophilic) solvents, like water and methanol. An unprecedented Gaussian-type relationship was found between the ratios of the swelling degrees versus the polarity index, indicating increased swelling for the nanoconfined PVImMe-l-PTHF PIL-CNs in solvents with a polarity index between ~6 and 9.5. In addition to the nanoconfined structural features, the unique selective superabsorbent swelling behavior of the PIL-CNs can also be utilized in various application fields.
Highlights
Nanoconfined material structures, including polymers as well, due to the wide range of unique structural features, properties, and effects arising under nanocompartmentalized conditions, have created significant worldwide interest over the last couple of years
With the poly(3-methyl-1-vinylimidazolium iodide) (PVImMe)-l-PTHF poly(ionic liquid)s (PILs)-CN, 0.64, 0.71, and 0.63 n values are obtained for DMF, DMSO, and NMP, respectively
Gravimetric and solid-state NMR measurements indicate that the yields of the alkylation reaction in the conetworks were over 95%, and poly(3-methyl-1-vinylimidazolium iodide) (PVImMe) poly(ionic liquid) phases, crosslinked with PTHF chains, are formed
Summary
Nanoconfined material structures, including polymers as well, due to the wide range of unique structural features, properties, and effects arising under nanocompartmentalized conditions, have created significant worldwide interest over the last couple of years In addition to revealing the basic features of the synthesis and swelling behavior of these conetworks, it was found by us that the PVIm-l-PTHF conetworks possess nanophase-separated morphology with ~7–20 nm average domain sizes and bicontinuous (cocontinuous), i.e., a mutually nanoconfined domain structure in an unprecedented broad range of composition (~25–60% weight fraction of PVIm) [39]. This unique cocontinuous nanoconfined phase structure and the imidazole rings in the PVIm-l-PTHF conetworks provide various possibilities to create several novel materials which have not existed before. We report on the synthesis, structural investigations, and the unexpected swelling behavior of PIL conetworks obtained by converting the imidazole rings to imidazolium ionic liquid moieties inside the nanostructured PVIm-l-PTHF conetworks
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