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The dynamics of designed short polyisoprene (PI) chains in the melt is investigated on a wide temperature window using dielectric relaxation spectroscopy and pulsed field gradient nuclear magnetic resonance (NMR). At high temperatures, molecular dynamics (MD) simulations performed using two different models (an explicit atom model and a united atom one) capture very well the dynamic properties documented experimentally. Structures pre-equilibrated with end-bridging Monte Carlo are used as initial configurations for MD runs at different temperatures, providing predictions for the temperature dependence of the dynamics of this bulk PI. Local dynamics is unique, independently of the probe (dielectric relaxation, dynamic light scattering, nuclear magnetic resonance, neutron scattering), although mean correlation times are significantly affected, to different extents, by librations. Chain dynamics over the molecular weight and temperature range studied can be described well by the Rouse model, as shown by both...

We report on the structure and dynamics of model mono-, di-, and tri-ω-functionalized three-arm star polybutadiene melts. By using x-ray scattering and dynamic rheological measurements, we find that functionalization of the arm ends can lead to distinctly different supramolecular structures and material behavior. The monofunctionalized samples behave like multiarm nonionic star-like dendrimers, whereas the difunctional stars resemble a transient network consisting of highly branched structures with a very broad relaxation spectrum. On the other hand, the trifunctional stars seem to develop an unusually regular structure of dominant intramolecularly aggregated functional groups leading to collapsed star conformations, resembling soft spheres, and a well-defined terminal relaxation. These results suggest that by tailoring the telechelic functionalization of regular star polymers, a route to design and obtain a wealth of controlled supramolecular structures exhibiting a rich and variable dynamics could open.

The morphologies formed by block copolymers with a double‐graft, H or S2IS2 architecture were investigated using transmission electron microscopy (TEM) and small angle neutron scattering (SANS). Here S and I represent blocks of polystyrene and polyisoprene, respectively. These materials were synthesized using anionic polymerization and chlorosilane linking, and they were characterized using size exclusion chromatography, membrane osmometry, and low‐angle laser light scattering. This characterization work confirmed the desired molecular architectures and narrow molecular weight distributions. The results of morphological characterization indicate that one can understand complex grafting architectures by decomposing them into fundamental building blocks, which are taken as the component single graft structures out of which the larger structure is constructed. We propose rules for dividing structures into these components, which we call constituting block copolymers. The morphological behavior of the more co...

Dielectric spectroscopy has been employed to study selectively the local and global dynamics of polyisoprene (PI) in three microphase separated star diblock copolymers (SI)4, where PI and polystyrene (PS) form the core and corona, respectively. The thermally induced order-to-disorder transition (ODT) has been identified by rheology and small-angle x-ray scattering (SAXS). All dielectric measurements were made at temperatures well below the ODT and the polystyrene glass transition temperatures, where the four PI chain ends are tethered by the glassy polystyrene domains. The ordered state morphology, studied by SAXS, revealed the formation of PS spheres (fPS=0.25, where fPS is the polystyrene volume fraction), polyisoprene cylinders (fPS=0.68), and a lamellar structure (fPS=0.41) in the three copolymers. In contrast to the local segmental motions, the chain orientational dynamics associated with the amplitude and the characteristic relaxation time are strongly influenced by the spatial confinement. The main...

The morphologies of several styrene–isoprene miktoarm star copolymers have been examined by small angle x‐ray scattering and electron microscopy. Three of these polymers were of the three‐armed A2B type, and six were four‐armed A3B miktoarms. The ordered microphase‐separated morphologies displayed by these polymers were seen to be highly dependent on the architecture of the chains, and were quite different from those that occur in the corresponding linear block copolymers. These results can be quite well explained by a theory of Milner which is based on the bending energy of the microphase interface and the ability of the chains to stretch away from the interface between the microphases. We speculate that the small differences between the observations and theoretical predictions are due to the effects of the compression of chains in small gaps between adjacent domains.

Data on hydrodynamic and thermodynamic properties of several well‐defined, linear flexible polymer chains in thermodynamically good solvents and theta solvents are tabulated and critically evaluated. The polymers considered are 1,4‐polybutadiene, 1,4‐polyisoprene, polyisobutylene, polystyrene, and poly(α‐methylstyrene). Extensive data, obtained as a function of molecular weight, are evaluated for the intrinsic viscosity, radius of gyration, hydrodynamic radius, and second virial coefficient. The resulting power law relationships between the measured properties and polymer molecular weight are reported.