SANS Studies on Spatial Inhomogeneities of Slide-Ring Gels

Slide-ring gels (SR gel) [previously termed as topological or polyrotaxane gels:  Okumura, Y.; Ito, K. Adv. Mater. 2001, 13, 485] have remarkable physical properties, such as large extensibility and mechanical strength. The SR gels are cross-linked polyrotaxane (PR) consisting of poly(ethylene glycol) (PEG) chains and α-cyclodextrin (CD), in which the cross-linkers are made of CD dimers and capable of sliding along the PEG chains. To elucidate the physical picture and properties, the scattering functions, I(q)s, of SR gel in NaOD aqueous solutions (NaODaq) and in deuterated dimethyl sulfoxide (d-DMSO) were investigated by small-angle neutron scattering (SANS) and were compared with those of pregel solutions, where q is the magnitude of the scattering vector. The following facts were disclosed: (1) The polyrotaxane chains take a rodlike conformation in d-DMSO, whereas a Gaussian chain in NaODaq. (2) The degree of inhomogeneities of SR gel in NaODaq has a minimum around the sol−gel transition, whereas that in d-DMSO increases monotonically with increasing cross-linker concentration. (3) I(q) of SR gel in NaODaq can be described by a Lorentz function, while that in d-DMSO is given by the sum of a squared Lorentz function and a scattering function for a rod. These differences in I(q) are ascribed to the difference in the stacking behavior of CD molecules on PEG chains in PR

Difference in Lower Critical Solution Temperature Behavior between Random Copolymers and a Homopolymer Having Solvatophilic and Solvatophobic Structures in an Ionic Liquid^†

The solubility and phase behavior of poly(benzyl methacrylate) (PBzMA) and poly(styrene-co-methyl methacrylate) (P(St-co-MMA)) in a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfone)imide ([C2mim][NTf2]), have been explored as a function of temperature. Although both polymers have solvatophobic phenyl groups and solvatophilic methacrylate groups in the structure, their distribution on the polymer chains is quite different. In PBzMA, both structures are incorporated in each monomer unit, whereas in P(St-co-MMA)s the distribution is statistically determined by the monomer reactivity ratio of St and MMA. Both polymer solutions in [C2mim][NTf2] become turbid with an increase in temperature (lower critical solution temperature (LCST) behavior). The turbidity change occurs sharply at 100 °C for PBzMA, whereas it is sluggish for P(St-co-MMA)s. The LCST-type phase-separation temperature for P(St-co-MMA)s decreases with an increase of the St composition. The sluggish phase separation for P(St-co-MMA)s has been explained in terms of the presence of the MMA sequences along the polymer chain, which inhibits the St aggregation to a certain extent. The dynamic light scattering (DLS) measurements for PBzMA reveal that the hydrodynamic radius of PBzMA suddenly changes at 100 °C; below this temperature, no aggregation is observed. This result strongly implies that the coil-to-collapse transition is of the first-order type. It has been demonstrated that the LCST-type phase separation of the polymers in an ionic liquid is greatly affected by the distribution of the solvatophilic and solvatophobic groups on the polymer chains

SANS Studies on Deformation Mechanism of Slide-Ring Gel

The deformation mechanism of “slide-ring” (SR) gels was investigated with small-angle neutron scattering (SANS). The SR gels were prepared by coupling α-cyclodextrin (CD) molecules on polyrotaxane chains consisting of poly(ethylene glycol) and CD. Because of a hollow structure of CD molecules, the cross-links made of CD molecules in a figure-of-eight shape can slide along the polymer chain. A normal butterfly pattern was observed for the first time in two-dimensional SANS isointensity profiles for the SR gels under uniaxial deformation, where the normal butterfly pattern means a prolate isointensity pattern in the direction perpendicular to the stretching direction. However, by either increasing the cross-link density or increasing the stretching ratio, the normal butterfly patterns changed to abnormal butterfly patterns as are commonly observed in conventional covalent-bonded chemical gels. The difference in the deformation mechanism as well as the cross-linking inhomogeneities between the SR gels and the covalent-bonded chemical gels is discussed by focusing on the unique architecture of the SR gels

SANS Studies on Deformation Mechanism of Slide-Ring Gel

The deformation mechanism of “slide-ring” (SR) gels was investigated with small-angle neutron scattering (SANS). The SR gels were prepared by coupling α-cyclodextrin (CD) molecules on polyrotaxane chains consisting of poly(ethylene glycol) and CD. Because of a hollow structure of CD molecules, the cross-links made of CD molecules in a figure-of-eight shape can slide along the polymer chain. A normal butterfly pattern was observed for the first time in two-dimensional SANS isointensity profiles for the SR gels under uniaxial deformation, where the normal butterfly pattern means a prolate isointensity pattern in the direction perpendicular to the stretching direction. However, by either increasing the cross-link density or increasing the stretching ratio, the normal butterfly patterns changed to abnormal butterfly patterns as are commonly observed in conventional covalent-bonded chemical gels. The difference in the deformation mechanism as well as the cross-linking inhomogeneities between the SR gels and the covalent-bonded chemical gels is discussed by focusing on the unique architecture of the SR gels