Hierarchically Mesostructured Polyisobutylene‐Based Ionic Liquids

Appiah, Clement; Akbarzadeh, Johanna; Marinow, Anja; Peterlik, Herwig; Binder, Wolfgang H.

doi:10.1002/marc.201600020

Cited by 4 publications

(4 citation statements)

References 42 publications

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“…There are some examples of poly(2-oxazoline)s bearing IL cation end groups such as trialkylammonium , or pyridinium. , Moreover, ionic poly(2-phenyl-2-oxazoline) macromonomers and corresponding comblike polyelectrolytes have been prepared . Concerning PIB, end-functionalized polymers having IL-type termini − and imidazolium salts bearing two pendant PIB chains , have been reported. However, to the best of our knowledge, ionic PIB–poly(2-oxazoline) copolymer structures have not been described yet.…”

Section: Introductionmentioning

confidence: 99%

Thermoresponsive Polymer Ionic Liquids and Nanostructured Hydrogels Based upon Amphiphilic Polyisobutylene-b-poly(2-ethyl-2-oxazoline) Diblock Copolymers

et al. 2019

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The precise molecular engineering of amphiphilic diblock copolymers as thermoresponsive polymer ionic liquids (PILs) couples polyisobutylene (PIB) and poly(2ethyl-2-oxazoline) (PEtOx) blocks via an imidazolium cation. It enables thermal switching of micellar self-assembly and yields nanostructured hydrogels. Just one ionic liquid (IL)type imidazolium cation is readily incorporated into the backbone of the PIB−IL−PEtOx block copolymers by terminating the cationic 2-ethyl-2-oxazoline (EtOx) ringopening polymerization by alkylation of an imidazoleterminated PIB. The PEtOx block length varies as a function of the PIB-imidazole/EtOx molar ratio and governs solubility, hydrophilic/hydrophobic balance, and nanophase separation. In spite of the presence of highly hydrophobic PIB segments, PIB−IL−PEtOx are rendered water soluble with increasing PEtOx block length and form spherical and elongated micelles as well as hydrogels exhibiting wormlike nanostructures. Furthermore, the lower critical solution temperature of PEtOx segments is the key to thermoresponsive behavior of both water-soluble copolymers and copolymer hydrogels. Owing to low glass temperature and high stability of PIB, these PIB−PILs represent attractive macromolecular nanosystems enabling thermal switching of solubilization, dispersion, transport, and shuttling of molecules and nanoparticles.

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Section: Introductionmentioning

confidence: 99%

Thermoresponsive Polymer Ionic Liquids and Nanostructured Hydrogels Based upon Amphiphilic Polyisobutylene-b-poly(2-ethyl-2-oxazoline) Diblock Copolymers

et al. 2019

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“…Based on the mesoscale organization of ionic “multiplets”, the formation of nanostructures consisting of ionic clusters within the obtained POILs in solution is expected. Therefore, the morphologies of P(APMIN(Tf) 2 - co -TFEA) 7 and POIL triblock 4 were first investigated via TEM (Figure A,D): nanoparticles with diameter ( d ) of 10–20 nm are formed from P(APMIN(Tf) 2 - co -TFEA) 7 (Figure A), while POIL triblock 4 demonstrates larger and crowded globular nanoparticles ( d = 40–70 nm) under the same experimental conditions (Figure D).…”

Section: Resultsmentioning

confidence: 99%

“…Although there is an accepted repertoire for the synthesis of POILs by conventional free radical polymerization and living/controlled polymerization techniques (such as atom transfer radical polymerization (ATRP), , RAFT, , nitroxide-mediated polymerization (NMP), TERP, and CMRP) or living carbocationic polymerization, − there still is the need to more precisely introduce comonomers into POILs and also allow a more detailed characterization of the final POILs. ,− …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Morphology of Semifluorinated Polymeric Ionic Liquids

et al. 2018

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Polymeric ionic liquids (POILs) are important materials in the field of ionic liquid gating, requiring the precise synthesis of new POILs with tailored structural variability and defined nanoscaled structure. In the current contribution, using reversible addition–fragmentation chain-transfer polymerization (RAFT) technique, the homopolymerization of three imidazolium-based acrylates with different counterions is reported, namely 1-[2-acryloylethyl]-3-methylimidazolium bis(trifluoromethane)sulfonamide (APMIN(Tf)2), 1-[2-acryloylethyl]-3-methylimidazolium hexafluorophosphate (APMIPF6), and 1-[2-acryloylethyl]-3-methylimidazolium tetrafluoroborate (APMIBF4), to afford the respective poly(ionic liquid)s (POILs). All polymerizations display pseudo-first-order kinetics and a rapid growth of P(APMIN(Tf)2), P(APMIPF6), and P(APMIBF4), yielding homopolymers with controlled molar mass, revealing a strong influence of the counterions on the polymerization rate, increasing in the order of BF4 Θ < PF6 Θ < N(Tf)2 Θ. As a direct determination of molecular weights via size exclusion chromatography (SEC) of the POIL homopolymers from RI and UV detectors was not successful, we developed an alternative strategy to generate accurate, “normal” SEC peaks of POILs using RAFT copolymerization technique: APMIN(Tf)2 was copolymerized with a semifluorinated monomer 2,2,2-trifluoroethyl acrylate (TFEA), allowing to study the influence of the comonomer feeding ratio on the resulting SEC signals of P(APMIN(Tf)2-co-TFEA) copolymers. We found that when the feeding molar ratio of TFEA is adjusted to 0.77, symmetric SEC peaks from the resulting P(APMIN(Tf)2-co-TFEA) copolymers are obtained. Furthermore, copolymerizations of TFEA with the other two IL monomers, APMIPF6 and APMIBF4, are also performed to afford P(APMIPF6-co-TFEA) and P(APMIBF4-co-TFEA) copolymers. Moreover, the propensity of the so-obtained POIL random copolymers P(APMIN(Tf)2-co-TFEA), P(APMIPF6-co-TFEA), and P(APMIBF4-co-TFEA) to grow a new block (polypentafluorostyrene, PPFS) is explored, intending to generate the fluorinated POIL triblock copolymers P(APMIN(Tf)2-co-TFEA)-b-PPFS-b-P(APMIN(Tf)2-co-TFEA), P(APMIPF6-co-TFEA)-b-PPFS-b-P(APMIPF6-co-TFEA), and P(APMIBF4-co-TFEA)-b-PPFS-b-P(APMIBF4-co-TFEA), respectively. The morphology and size of such semifluorinated POILs are investigated using transition electron microscopy (TEM), atomic force microscopy (AFM), and dynamic light scattering (DLS), revealing the aggregated nanoparticles from P(APMIN(Tf)2-co-TFEA) due to the mesoscale organization of the ionic “multiplets”. Significantly larger and crowded globular objects/aggregates are formed from the chain-extended POIL triblock P(APMIN(Tf)2-co-TFEA)-b-PPFS-b-P(APMIN(Tf)2-co-TFEA) copolymers under the same conditions.

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“…Another class of imidazole-based polymers belongs to poly(ionic liquid)s (PILs), that is macromolecules with ionic liquid (IL) moieties. Due to the challenging tasks of the synthesis, revealing the structure–property relationships, and the broad range of special application possibilities, PILs have been intensively investigated in recent years (see e.g., references [ 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 77 , 78 , 79 ] and references therein). PILs may find applications in energy production as proton [ 57 ], electron [ 58 , 59 ], or Li-ion [ 60 , 73 ] conducting materials; as metal free [ 61 ] and metal containing [ 62 ] catalysts; gas separation membranes [ 63 , 64 ]; DNA isolation microspheres [ 65 ] etc.…”

Section: Introductionmentioning

confidence: 99%

Nanoconfined Crosslinked Poly(ionic liquid)s with Unprecedented Selective Swelling Properties Obtained by Alkylation in Nanophase-Separated Poly(1-vinylimidazole)-l-poly(tetrahydrofuran) Conetworks

et al. 2020

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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.

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Hierarchically Mesostructured Polyisobutylene‐Based Ionic Liquids

Cited by 4 publications

References 42 publications

Thermoresponsive Polymer Ionic Liquids and Nanostructured Hydrogels Based upon Amphiphilic Polyisobutylene-b-poly(2-ethyl-2-oxazoline) Diblock Copolymers

Thermoresponsive Polymer Ionic Liquids and Nanostructured Hydrogels Based upon Amphiphilic Polyisobutylene-b-poly(2-ethyl-2-oxazoline) Diblock Copolymers

Synthesis and Morphology of Semifluorinated Polymeric Ionic Liquids

Nanoconfined Crosslinked Poly(ionic liquid)s with Unprecedented Selective Swelling Properties Obtained by Alkylation in Nanophase-Separated Poly(1-vinylimidazole)-l-poly(tetrahydrofuran) Conetworks

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