Organically modified aluminosilicate mesostructures were synthesized from two metal alkoxides with the use of poly(isoprene-b-ethyleneoxide) block copolymers (PI-b-PEO) as the structure-directing molecules. By increasing the fraction of the inorganic precursors with respect to the polymer, morphologies expected from the phase diagrams of diblock copolymers were obtained. The length scale of the microstructures and the state of alignment were varied using concepts known from the study of block copolymers. These results suggest that the use of higher molecular weight block copolymer mesophases instead of conventional low-molecular weight surfactants may provide a simple, easily controlled pathway for the preparation of various silica-type mesostructures that extends the accessible length scale of these structures by about an order of magnitude.

The electrosteric stabilization of model colloidal dispersions is quantified through high-frequency rheometry and complementary techniques. Model aqueous dispersions with a poly(butyl acrylate)polystyrene core and a layer of poly(methacrylic acid) grafted onto the surface are prepared and characterized. The influence of pH, electrolyte concentration, and amount of polymer in the stabilizing layer on dispersion stability and rheology is investigated. Dynamic light scattering, electrophoretic mobility, and rheology are used to quantify thickness, hydrodynamic permeability, and charge density of the stabilizing shell. A collapsed layer at low pH leads to aggregation after addition of salt, while a swollen layer at high pH induces stability. The colloidal interaction potential is deduced from measurements of the high-frequency elastic modulus using torsional resonators. The complex electrosteric forces are shown to be dominated by the excess osmotic pressure created by overlap of the electrosteric layer for particles in contact. The measured moduli G′ ∞ can be predicted quantitatively based on a simple model for the osmotic repulsion introduced by Vincent et al. [J.

Double electron-electron resonance (DEER) spectroscopy is introduced as a new tool for the characterization of mesoscopic structures in polymers. This method can characterize distance distributions between spin probes in a range between 1.5 and 8 nm and can be applied to the measurement of ion cluster sizes and intercluster distances in ionically end-capped polymers by using ionic spin probes that attach themselves to the surface of the ion clusters. The results on intercluster distances for systems based on homopolymers are in agreement with earlier results from small-angle X-ray scattering (SAXS), while the cluster sizes can be rationalized by comparison with a force field molecular model of an ion cluster. The DEER experiment could also be applied to an ionically end-capped diblock copolymer for which a SAXS measurement of the intercluster distance failed.

The urethane polyaddition reaction was discovered about 80 years ago. Since then this chemistry has further developed into many industrial applications and grown into a multibillion dollar business. The versatility of polyurethanes is founded in a broad spectrum of properties which can be achieved ranging from flexible to rigid and from compact to foamed by choosing suitable combinations of starting materials, the key raw materials being polyol and isocyanate. While on the industrial megaton scale the number of isocyanate building blocks is quite limited, there is a huge choice of polyols and additives available to achieve tailor‐made polymer properties for various applications. For the future development of polyurethanes, the two major trends, i) the further improvement of all sustainability characteristics and ii) digitalization in product and process development, are discussed. The former is reflected in four main areas: the production of improved insulation materials to reduce energy consumption; production of raw materials with an improved carbon footprint; odor and emission reduction in indoor applications; and recycling of production and consumer waste. The present review concludes with a few examples as to how digitalization can change and accelerate research and development work in the future.

Endfunctionalized polyisoprenes (PI) and polystyrenes (PS) with either one sulfonate or ammonium end group and α,ω-macrozwitterionic PI and PS have been synthesized and investigated by CW-EPR using the spin probe technique. From the extrema separation of the temperature dependent spectra a characteristic temperature, T‘50G, is introduced which can be employed as a measure for the temperature dependence of the chain end association in these telechelic ionomers. In this way it is shown that the mobility of an ionic 2,2,6,6-tetramethylpiperidine-N-oxyl derivative is dramatically restricted when compared to the corresponding nonionic probe. For PI the reduction in probe mobility corresponds to temperature shifts as high as 140 K relative to the dynamics of the polymer, indicating the presence of highly immobilized ion multiplets. As shown by the temperature dependent data, the method is sensitive to additional immobilization of the ionic domains induced by bulky substituents adjacent to the ionic chain ends. Comparison of the EPR results with structural data from SAXS measurements reveals that the main factors governing the dynamics of multiplets are the chemical type of ionic end group and the nature of the polymer backbone. Analysis of the EPR data for telechelic PS shows that in high-T g polymers the dynamics of the ionic aggregates occurs at comparable time scales as the dynamics of the polymer backbone.