This paper describes a new approach towards preparing self‐assembled hydrogen‐bonded complexes that have vesicle and patched spherical structures from two species of block copolymer in non‐selective solvents. The assembly of vesicles from the intermolecular complex formed after mixing polystyrene‐block‐poly(4‐vinyl phenol) (PS‐b‐PVPh) with poly(methyl methacrylate)‐block‐poly(4‐vinylpyridine) (PMMA‐b‐P4VP) in tetrahydrofuran (THF) is driven by strong hydrogen bonding between the complementary binding sites on the PVPh and P4VP blocks. In contrast, well‐defined patched spherical micelles form after blending PS‐b‐PVPh with PMMA‐b‐P4VP in N,N‐dimethylformamide (DMF): weaker hydrogen bonds form between the PVPh and P4VP blocks in DMF, relative to those in THF, which results in the formation of spherical micelles that have compartmentalized coronas that consist of PS and PMMA blocks.magnified image

A polystyrene melt, whose molecular weight (weight-average molecular weight ) 1050) is about that estimated for a Rouse segment, has been studied with depolarized photon-correlation and viscosity measurements. Theoretically the dynamic depolarized light scattering is shown to be affected by the reorientational motion of the whole polymer molecule in the long-time region and the local segmental motions in the short-time region. The elastic dumbbell model is used to describe the viscoelasticity and reorientational motion of the polymer molecule. Relaxation times 〈τ〉 and τv are extracted from the depolarized light scattering and viscosity measurement results, respectively. The ratio τv/〈τ〉, being independent of temperature as expected, is of the order of magnitude predicted from the theoretical analysis. We come to a similar conclusion supporting the above results by analyzing the depolarized photon-correlation results and the viscoelastic relaxation data in the glass-rubber transition zone of entangled polystyrene melts, which are available in literature.

Concentrated solutions of nearly monodisperse polystyrene samples in cyclohexane in the theta condition and in the entanglement-free region have been studied by means of the depolarized photon-correlation spectroscopy and viscosity measurements. It is shown that the viscoelastic behavior of the studied systems is described by the Rouse theory and that in agreement with the theoretical analysis the main polymer dynamic process probed by the depolarized Rayleigh scattering is basically the reorientational motion associated with a Rouse segment of the polymer chain, whose relaxation is independent of the scattering angle and the molecular weight. In addition to the main dynamic process, the tail region of a very fast process associated with the sub-Rouse-segmental motions can be observed, whose existence is expected from the theoretical analysis.