A study combining magic-angle spinning NMR and small-angle X-ray scattering on the interaction in the mixture of poly(benzyl methacrylate) and ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide.

A mixture of poly(benzyl methacrylate) (PBnMA) and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2mim][NTf2]) exhibits lower-critical-solution-temperature (LCST)-type phase separation. An investigation combining magic-angle spinning NMR spectroscopy and small-angle scattering was performed to gain new insights into the interaction between PBnMA and the ionic liquid. The molecular mobility and the solute-solvent interaction in the system were investigated using 1H high-resolution magic-angle spinning NMR. Applying a magic-angle spinning frequency of 2 kHz allowed identifying the PBnMA peaks, which were not observed by conventional solution-state NMR. The peaks of [C2mim]+ almost coincided in the presence and absence of PBnMA, indicating the decoupling of the bulk solvent and polymer. The conformational state of PBnMA in [C2mim][NTf2] was investigated using small-angle X-ray scattering (SAXS). The pair distribution functions of PBnMA chains calculated from SAXS profiles suggest that PBnMA adopts a random coil conformation upon dissolution in [C2mim][NTf2]. The combined study clarifies the decoupled low mobility of polymers with a random coil conformation. It is considered that the specific decoupled low mobility is one of the origins of the decoupling conductivity of [C2mim][NTf2] in a matrix polymer. In addition, an increase in temperature induced a downfield shift and broadening of the [C2mim]+ peaks, suggesting that a larger amount of [C2mim]+ was bound to the PBnMA chains even at temperatures approaching the LCST.

Photo/thermoresponsive ABC triblock copolymer-based ion gels: photoinduced structural transitions.

A photo/thermoresponsive ABC triblock copolymer-based ion gel exhibiting photoinduced structural transitions accompanied by significant rheological changes is newly developed. The ABC triblock copolymer comprises an ionic liquid (IL)-phobic A block, an IL-philic B block, and a photo/thermoresponsive C block containing azobenzene moieties. The IL-phobic A block forms a rigid micellar core in an IL over a wide temperature range and the photo/thermoresponsive C block undergoes upper critical solution temperature (UCST)-type phase transition in ILs. In concentrated polymer solution, the ABC triblock copolymer can form a percolated micellar network at low temperatures through aggregation of A and C blocks as physical crosslinks, bridged by IL-philic B blocks. In contrast, the ion gel undergoes structural transition to jammed micelles at high temperatures due to the disassembly of the thermoresponsive C block, resulting in significant softening of the ion gel. Importantly, the temperature dependences of the viscoelastic properties of the ion gel differ drastically depending on photo-irradiation conditions as the photoinduced isomerization of azobenzene moieties in the C block modulates the affinity between the polymer chain and IL. Utilizing this feature, photoinduced softening/hardening of the ion gel is realized at constant temperature. This study provides a promising strategy to control the rheological properties of nonvolatile soft materials via contactless light irradiation that could be exploited in various applications such as photoresponsive soft actuators and photo-healable soft materials.

Neutron scattering studies on short- and long-range layer structures and related dynamics in imidazolium-based ionic liquids.

Alkyl-methyl-imidazolium ionic liquids CnmimX (n: alkyl-carbon number, X: anion) have short-range layer structures consisting of ionic and neutral (alkylchain) domains. To investigate the temperature dependences of the interlayer, interionic group, and inter-alkylchain correlations, we have measured the neutron diffraction (ND) of C16mimPF6, C9.5mimPF6, and C8mimPF6 in the temperature region from 4 K to 470 K. The quasielastic neutron scattering (QENS) of C16mimPF6 was also measured to study the dynamics of each correlation. C16mimPF6 shows a first-order transition between the liquid (L) and liquid crystalline (LC) phases at Tc = 394 K. C8mimPF6 exhibits a glass transition at Tg = 200 K. C9.5mimPF6, which is a 1:3 mixture between C8mimPF6 and C10mimPF6, has both transitions at Tc = 225 K and Tg = 203 K. In the ND experiments, all samples exhibit three peaks corresponding to the correlations mentioned above. The widths of the interlayer peak at ca. 0.2 Å-1 changed drastically at the L-LC transitions, while the interionic peaks at ca. 1 Å-1 exhibited a small jump at Tc. The peak position and area of the three peaks did not change much at the transition. The structural changes were minimal at Tg. The QENS experiments demonstrated that the relaxation time of the interlayer motion increased tenfold at Tc, while those of other motions were monotonous in the whole temperature region. The structural and dynamical changes mentioned above are characteristic of the L-LC transition in imidazolium-based ionic liquids.

Advanced Materials Based on Polymers and Ionic Liquids.

Ionic liquids (ILs) are ambient temperature molten salts, which have attracted considerable attention owing to their unique properties. In this contribution, we review advanced materials composed of ILs and polymers for the basis of a new design protocol to fabricate novel materials. As electrolytes for electrochemical devices, cross-linked polymers containing ILs (ion gels) are endowed with functional properties inherited from ILs and mechanical consistency derived from polymers. To create such materials, micro-phase separation of block copolymers and colloidal arrays in the ILs are utilized. Based on the molecular design of task-specific ILs, the resultant ion gels are applicable as electrolytes for actuator, fuel cell, and secondary battery applications. Thermo- and photo-responsive polymers in ILs are also highlighted, whereby such stimuli elicit changes in the solubility of the self-assembly of block copolymers and colloidal arrays in the ILs. Further, thermo- and photo-reversible changes in the self-assembled structure can be exploited to demonstrate sol-gel transitions and fabricate photo-healable materials.

Thermosensitive Phase Separation Behavior of Poly(benzyl methacrylate)/Solvate Ionic Liquid Solutions.

We report a lower critical solution temperature (LCST) behavior of binary systems consisting of poly(benzyl methacrylate) (PBnMA) and solvate ionic liquids: equimolar mixtures of triglyme (G3) or tetraglyme (G4) and lithium bis(trifluoromethanesulfonyl)amide. We evaluated the critical temperatures (Tcs) using transmittance measurements. The stability of the glyme-Li+ complex ([Li(G3 or G4)]+) in the presence of PBnMA was confirmed using Raman spectroscopy, pulsed-field gradient spin-echo NMR (PGSE-NMR), and thermogravimetric analysis to demonstrate that the complex was not disrupted. The interaction between glyme-Li+ complex and PBnMA was investigated via 7Li NMR chemical shifts. Upfield shifts originating from the ring-current effect of the aromatic ring within PBnMA were observed with the addition of PBnMA, indicating localization of the glyme-Li+ complex above and below the benzyl group of PBnMA, which may be a reason for negative mixing entropy, a key requirement of the LCST.

From Macromolecular to Small-Molecular Triggers: Facile Method toward Photoinduced LCST Phase Behavior of Thermoresponsive Polymers in Mixed Ionic Liquids Containing an Azobenzene Moiety.

Instead of the reported photoinduced lower critical solution temperature (LCST) phase transition behavior in ionic liquids (ILs) achieved by photofunctional polymers, this study reports the facile photoinduced LCST phase behavior of nonfunctionalized polymers (poly(benzyl methacrylate) (PBnMA) and poly(2-phenylethyl methacrylate) (PPhEtMA)) in mixed ILs (1,3-dimethylimidazolium bis(trifluoromethanesulfonyl)amide; [C1 mim][NTf2 ] and a newly designed functionalized IL containing an azobenzene moiety (1-butyl-3-(4-phenylazobenzyl)imidazolium bis(trifluoromethanesulfonyl)amide; [Azo][NTf2 ])) as a small-molecular photo trigger. Interestingly, the length of the alkyl spacer between the ester and aryl groups, which is the only structural difference between the two polymers, leads to two different photoresponsive LCST phase transition behaviors. On the basis of spectroscopic studies, the different phase transition behaviors of PBnMA and PPhEtMA may attribute to the different cooperative interactions between the polymers and [C1 mim][NTf2 ].

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

We have 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 Tc. Furthermore, we evaluated the enthalpic and entropic contributions to the effective interaction parameter χeff 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 χeff was smaller than the previously reported value for a thermo-responsive polymer in an aqueous system. It was found out that the strong dependence of Tc on the chemical structure in IL systems originated from the relatively smaller temperature dependence of χeff.

Self-Assembly of Polyether Diblock Copolymers in Water and Ionic Liquids.

Here the thermoresponsive self-assembly of diblock copolymers comprising poly(ethyl glycidyl ether) (PEGE) and poly(ethylene oxide) (PEO) in water and ionic liquids (ILs) is investigated. PEGE undergoes lower critical solution temperature (LCST) phase separation in both water and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2 mim][NTf2 ]), while PEO is a compatible segment for these solvents. The diblock copolymers, PEGE-b-PEO, undergo thermosensitive unimer-micelle transitions at temperatures close to the LCST point (TLCST ) of the PEGE homopolymer in water but not in [C2 mim][NTf2 ], even at temperatures much higher than TLCST . The difference in the thermoresponsivity of these solutions is explored using differential scanning calorimetry results from rather small magnitudes of the thermodynamic parameters for the phase transition of the PEGE segment in [C2 mim][NTf2 ], compared with those in water. Due to such small magnitudes, TLCST of the PEGE segment for the block copolymers in the IL is greatly affected by the elongation of soluble PEO segments.

Photoreversible gelation of a triblock copolymer in an ionic liquid.

The reversible micellization and sol-gel transition of block copolymer solutions in an ionic liquid (IL) triggered by a photostimulus is described. The ABA triblock copolymer employed, denoted P(AzoMA-r-NIPAm)-b-PEO-b-P(AzoMA-r-NIPAm)), has a B block composed of an IL-soluble poly(ethylene oxide) (PEO). The A block consists of a random copolymer including thermosensitive N-isopropylacrylamide (NIPAm) units and a methacrylate with an azobenzene chromophore in the side chain (AzoMA). A phototriggered reversible unimer-to-micelle transition of a dilute ABA triblock copolymer (1 wt%) was observed in an IL, 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim]PF6), at an intermediate "bistable" temperature (50 °C). The system underwent a reversible sol-gel transition cycle at the bistable temperature (53 °C), with reversible association/fragmentation of the polymer network resulting from the phototriggered self-assembly of the ABA triblock copolymer (20 wt%) in [C4 mim]PF6.

Thermoreversible nanogel shuttle between ionic liquid and aqueous phases.

We describe a nanogel that can reversibly shuttle between a hydrophobic ionic liquid (IL) phase and an aqueous phase in response to temperature changes. A thermosensitive diblock copolymer, consisting of poly(ethylene oxide) (PEO) as the first segment and a random copolymer of N-isopropylacrylamide (NIPAm) and N-acryloyloxysuccinimide (NAS) as the second segment, was prepared as a nanogel precursor using anionic ring-opening polymerization of EO followed by reversible addition-fragmentation chain-transfer (RAFT) polymerization of NIPAm and NAS. After the micellization of the diblock copolymer in an aqueous solution upon heating to temperatures higher than the lower critical solution temperature (LCST) of the second segment, a coupling reaction of the NAS group of the P(NIPAm-r-NAS) core with ethylenediamine gave a nanogel with a well-solvated PEO corona. The nanogel exhibited contrasting thermosensitivities in the aqueous and IL phases. Dynamic light scattering measurements revealed that the nanogel exhibited LCST phase behavior (low-temperature-swollen/high-temperature-shrunken) in the aqueous phase and the opposite upper critical solution temperature (UCST) phase behavior (high-temperature-swollen/low-temperature-shrunken) in hydrophobic ILs. The nanogel favored the aqueous phase at low temperatures and the IL phase at high temperatures because of the solubility changes in the PEO corona. Upon increasing the temperature, the nanogel underwent a swollen-to-shrunken phase change in the aqueous phase, a transfer from the aqueous phase to the IL phase, and a shrunken-to-swollen phase change in the IL phase. These processes were thermally reversible, which made the round-trip shuttling of the nanogel between the aqueous and IL phases possible.

Specific solvation of benzyl methacrylate in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ionic liquid.

It has been established that poly(benzyl methacrylate) in a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2mIm(+)][TFSA(-)]), exhibits lower critical solution temperature (LCST)-type phase separation. In this work we investigated the solvation structure of benzyl methacrylate monomer in the ionic liquid by using high-energy X-ray diffraction with the aid of a molecular dynamics simulation. It was found that the C2mIm cation orderly distributes above and below a benzyl group within benzil methacrylate (BnMA), while the TFSA anion distributes around the equatorial position of the benzyl group where no cation distribution is found, with a weak interaction between TFSA and BnMA. The relationship between specific solvation and the LCST phase separation mechanism was considered at the molecular level.

Heterogeneous slow dynamics of imidazolium-based ionic liquids studied by neutron spin echo.

We have investigated structure and relaxation phenomena for ionic liquids 1-octyl-3-methylimidazolium hexafluorophosphate (C8mimPF6) and bis(trifluoromethylsulfonyl)imide (C8mimTFSI) by means of neutron diffraction and neutron spin echo (NSE) techniques. The diffraction patterns show two distinct peaks appeared at scattering vectors Q of 0.3 and 1.0 Å(-1). The former originates from the nanoscale structure characteristic to ionic liquids and the latter due to the interionic correlations. Interestingly, the intensity of the low-Q peak drastically grows upon cooling and keeps growing even below the glass transition temperature. The NSE measurements have been performed at these two Q positions, to explore the time evolution of each correlation. The relaxation related to the ionic correlation (ionic diffusion) is of Arrhenius-type and exhibits nonexponential behavior. The activation energy (Ea) of the ionic diffusion, which is linked to viscosity, depends on the type of anion; the larger is the anion size, the smaller Ea becomes for most of anions. On the other hand, two kinds of relaxation processes, slower and faster ones, are found at the low-Q peak position. The most significant finding is that the fraction of the slower relaxation increases and that of the faster one decreases upon cooling. Combining the NSE data with the diffraction data, we conclude that there exist two parts in ILs: one with the ordered nanostructure exhibiting the slow relaxation, and the other with disordered structure showing faster relaxation. The structure and dynamics of ILs are heterogeneous in nature, and the fraction of each part changes with temperature.