Yushu Matsushita

Design and properties of supramolecular polymer gels

Supramolecular polymer gels are precisely designed physical gels brought together by reversible secondary interactions to form three dimensional networks of melt macromolecules. Generally, they differ from supramolecular gels because they are comprised of polymers instead of low molecular weight compounds. Recently, much effort has focused on designing supramolecular polymer gels and related materials with excellent properties; indeed, improvements have been made in their supramolecular interactions, complementarity in the non-covalent bonding units, the nature of the macromolecular building blocks, and strand elasticity of supramolecular polymer networks. Owing to the precise molecular design, they represent nanophase separation and characteristic viscoelasticity. Here, we review supramolecular polymer gels in terms of molecular design, morphology, and rheology. We also discuss future directions in practical application of supramolecular polymer gels.

Dimension of ring polymers in bulk studied by Monte-Carlo simulation and self-consistent theory.

We studied equilibrium conformations of ring polymers in melt over the wide range of segment number N of up to 4096 with Monte-Carlo simulation and obtained N dependence of radius of gyration of chains R(g). The simulation model used is bond fluctuation model (BFM), where polymer segments bear excluded volume; however, the excluded volume effect vanishes at N-->infinity, and linear polymer can be regarded as an ideal chain. Simulation for ring polymers in melt was performed, and the nu value in the relationship R(g) proportional to N(nu) is decreased gradually with increasing N, and finally it reaches the limiting value, 1/3, in the range of N>or=1536, i.e., R(g) proportional to N(1/3). We confirmed that the simulation result is consistent with that of the self-consistent theory including the topological effect and the osmotic pressure of ring polymers. Moreover, the averaged chain conformation of ring polymers in equilibrium state was given in the BFM. In small N region, the segment density of each molecule near the center of mass of the molecule is decreased with increasing N. In large N region the decrease is suppressed, and the density is found to be kept constant without showing N dependence. This means that ring polymer molecules do not segregate from the other molecules even if ring polymers in melt have the relationship nu=1/3. Considerably smaller dimensions of ring polymers at high molecular weight are due to their inherent nature of having no chain ends, and hence they have less-entangled conformations.

Analytical solutions describing the phase separation driven by a free energy functional containing a long-range interaction term

We are primarily concerned with the variational problem with long-range interaction. This functional represents the Gibbs free energy of the microphase separation of diblock copolymer melts. The critical points of this variational problem can be regarded as the thermodynamic equilibrium state of the phase separation phenomenon. Experimentally it is well-known in the diblock copolymer problem that the final equilibrium state prefers periodic structures such as lamellar, column, spherical, double-diamond geometries and so on. We are interested in the characterization of the periodic structure of the global minimizer of the functional (corresponding to the strong segregation limit). In this paper we completely determine the principal part of the asymptotic expansion of the period with respect to epsilon (interfacial thickness), namely, we estimate the higher order error term of the period with respect to epsilon in a mathematically rigorous way in one space dimension. Moreover, we decide clearly the dependency of the constant of proportion upon the ratio of the length of two homopolymers and upon the quench depth. In the last section, we study the time evolution of the system. We first study the linear stability of spatially homogeneous steady state and derive the most unstable wavelength, if it is unstable. This is related to spinodal decomposition. Then, we numerically investigate the time evolution equation (the gradient flow of the free energy), and see that the free energy has many local minimizers and the system have some kind of sensitivity about initial data. (c) 1999 American Institute of Physics.

The tricontinuous double-gyroid structure from a three-component polymer system

The tricontinuous structure of ABC-type triblock copolymer in bulk at equilibrium was studied by both transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS). Sample is an anionically polymerized isoprene-styrene-2-vinylpyridine triblock copolymer whose volume fraction is 0.22–0.59–0.19 and total molecular weight is 64 000. It was found that computer-simulated images based on tricontinuous structure with two parallel surfaces to the gyroid surface, which is one of the three-dimensionally infinite minimal surfaces agree well with the observed TEM images. Further, calculated diffraction patterns for the same tricontinuous structure well represent the observed SAXS intensity maps on imaging plates. These facts imply that the structure of the present triblock copolymer is the tricontinuous double gyroid structure, whose space group is I4132.

Jewelry Box of Morphologies with Mesoscopic Length Scales – ABC Star-shaped Terpolymers

Among several star molecules studied so far, the results for two similar but slightly different systems composed of all hydrophobic components, i.e. one low T(g) arm and two high T(g) arms were compared and discussed mainly. They are polyisoprene-arm-polystyrene-arm-poly(2-vinylpyridine) stars and polystyrene-arm-polybutadiene-arm-poly(2-vinylpyridine) ones, and are abbreviated as ISP and SBV, respectively, in the original literatures. Several periodic Archimedean tiling patterns can be naturally formed when the relative lengths of three chains are similar one another in both series. Core-shell type morphologies and actually three-phase four layer lamellar structures were also commonly observed for two series. A quasicrystalline tiling with dodecagonal symmetry can also be conformed at the targeted composition of ISP/homopolymer blend and a zinc-blende type structure was created at just a little outside of tiling region for the same blend. Furthermore, the several interesting structures from amphiphilic molecules, composed of a hydrophilic component, poly(ethylene oxide), a hydrophobic component, polymethylmethacrylate and a highly water-repellent polymer poly(perfluoropropyleneoxide) are described and introduced.

Topological effect in ring polymers investigated with Monte Carlo simulation

We studied equilibrium conformations of ring polymers in the melt over the wide range of segment number up to 1000 by the Monte Carlo simulations and the bond fluctuation model, and estimated Florys scaling exponent nu. The radial distribution function of segments for the ring polymers in the melt is obtained. We have found that nu for ring polymers is decreased with increasing segment number N, and nu goes down to 0.365 when N reaches 1000, whose value is apparently smaller than the theoretically predicted one, i.e., 25. Those values are in contrast to the well established nu value of 0.5 for linear polymers in the melt. This is because ring polymer chains in the melt are squeezed both by their own topological effect and the compression effect by the neighboring ring polymer coils which are also squeezed at bulk state. The difference in our result and the theory may be due to the fact that the estimation of topological entropy loss was ignored in the theoretical prediction, while it has been taken into consideration in the present study. If polymer coils repel each other in melt at N --> infinity, we have the limiting nu value of 13, so we conclude that nu is in the range of 13 < or = nu << 0.365 when the molecular weight of a ring polymer is high enough.

Simple preparation of supramolecular polymer gels viahydrogen bonding by blending two liquid polymers

Preparation of supramolecular polymer gels based on simple molecular design was demonstrated by blending carboxyl-terminated telechelic polymers and poly(ethyleneimine), where balance of an attractive force due to hydrogen bonding and a repulsive force induced by phase separation between polymers has been found as a key factor of supramolecular gelation.

Kaleidoscopic morphologies from ABC star-shaped terpolymers

Star-shaped terpolymers of the ABC type composed of incompatible polymer components give a variety of ordered structures with mesoscopic length scales depending on their composition ratio. Their peculiar features are summarized in this report. Polymer components adopted are polyisoprene (I), polystyrene (S) and poly(2-vinylpyridine) (P), and many monodisperse samples of the I(X)S(Y)P(Z) type were anionically prepared. Firstly our focus is on molecules of the I(1.0)S(1.0)P(x(1)) type, where x(1) is only a variable. The complex but systematic morphology change was displayed within the range 0.2 ≤ x(1) ≤ 10, that is, their structures change from spherical plus lamellae structure for I(1.0)S(1.0)P(0.2) to periodic tilings (0.4 ≤ x(1) ≤ 1.9), then to lamellae-in-lamella (3.0 ≤ x(1) ≤ 4.9) and lamellae-in-cylinder (7.9 ≤ x(1) ≤ 10) structures with increasing x(1). Here if we pay attention to the structural variation of the P domain inclusively, it transforms from sphere to cylinder, lamella and then to matrix, which is the same as that for linear polymers. Among them, several periodic Archimedean tiling patterns can be naturally formed when the relative lengths of the three chains are close to one another. Moreover, it has been found that the tiling zone is spread out widely. For example, the series I(1.0)S(1.8)P(x(2)) (with 0.8 ≤ x(2) ≤ 2.9) and the other series I(1.0)S(y)P(2.0) (with 1.1 ≤ y ≤ 2.7) show mostly Archimedean tilings. Additionally, block copolymer/homopolymer blends with a composition of I(1.0)S(2.7)P(2.5) reveal a quasicrystalline tiling with dodecagonal symmetry. Furthermore, a zinc-blende-type four-branched network structure was created just a little outside of the tiling region for a block copolymer/homopolymer blend of I(1.0)S(2.3)P(0.8). When some more asymmetry in chain length is introduced, hyperbolic tiling on a gyroid membrane has successfully been constructed for the sample I(1.0)S(1.8)P(3.2) and it transforms into a hierarchical cylinders-in-lamella structure with further increase in P content to I(1.0)S(1.8)P(6.4). Thus, kaleidoscopic morphologies have been generated from ABC star-shaped terpolymers and their structural change has turned out to be very sensitive to relative compositions.

Preparation and morphology of multiblock copolymers of the (AB)n type

Abstract Styrene(S)-isoprene(I) multiblock copolymers of the (SI)n type (n = 1, 2, 3, 4) were prepared by a multistep monomer addition technique of anionic polymerization. Molecular weights of SI diblock units are almost the same and the total polystyrene volume fractions are about 0.5. All the film specimens cast from toluene solutions were found to have alternating lamellar structures. The lamellar domain spacing monotonically decreases and approaches an asymptotic value with increasing the number of blocks.

Chain elongation suppression of cyclic block copolymers in lamellar microphase-separated bulk

Chain elongation suppression of cyclic block copolymers in microphase-separated bulk was determined quantitatively. Solvent-cast and annealed films are confirmed to show alternating lamellar structure and their microdomain spacing D increases with increasing total molecular weight M according to the relationship D proportional, variant M0.59, which agrees quite consistently with the theoretically predicted power law, i.e., D proportional, variant M3/5. This result is in contrast to the well-established issue for linear block copolymers, where the relationship D proportional, variant M2/3 has been confirmed to hold both experimentally and theoretically. This means that chain elongation of each component block is suppressed considerably, owing to their looped conformation in strongly segregated bulk.