Effect of Zinc Oxide Modified Silica Particles on the Molecular Dynamics of Carboxylated Acrylonitrile-Butadiene Rubber Composites.

This work examines the molecular dynamics of carboxylated acrylonitrile-butadiene rubber crosslinked with zinc oxide modified silica particles. ZnO/SiO2 with the wide range of ZnO concentrations were used as both a crosslinking agent and filler. A series of thermal measurements were applied to the characterization of the samples: differential scanning calorimetry, dynamical mechanical thermal analysis, and dielectric relaxation spectroscopy. A complementary experimental technique, which is equilibrium swelling in solvents, confirms the presence of ionic crosslinks, which are created between zinc ions and the functional carboxyl groups of the rubber, within the structure of the vulcanizates. These interactions influenced not only the affinity of the vulcanizates to solvents, but also their dynamic mechanical and dielectric properties. In these investigations, the influence of concentration of ZnO on the surface of the ZnO/SiO2 on the properties of the vulcanizates are described.

Evolution of high-temperature molecular relaxations in poly(2-(2-methoxyethoxy)ethyl methacrylate) upon network formation.

Copolymers of 2-(2-methoxyethoxy)ethyl methacrylate (poly(MEO2MA)) are regarded as bioinert replacements of poly(N-isopropylacrylamide) in some biomedical applications. Networks of poly(MEO2MA) of various architecture form thermo-responsive hydrogels. Here, we present dielectric and mechanical spectroscopy studies on segmental motions and network relaxation processes in linear poly(MEO2MA) and its networks - bare network and the network grafted with short poly(MEO2MA) chains. We show that the α process assigned to the segmental motions of poly(MEO2MA) is independent on the polymer topology and the glass transition temperature, Tg, associated with this process equals 235-236 K for all investigated systems. The α' relaxation observed above Tg by dynamical mechanical analysis is assigned to the sub-Rouse process. It strongly depends on the polymer network architecture and slows down by four orders of magnitude upon network formation.

Poly(vinyl methyl ether) hydrogels at temperatures below the freezing point of water-molecular interactions and states of water.

Water interacting with a polymer reveals a number of properties very different to bulk water. These interactions lead to the redistribution of hydrogen bonds in water. It results in modification of thermodynamic properties of water and the molecular dynamics of water. That kind of water is particularly well observable at temperatures below the freezing point of water, when the bulk water crystallizes. In this work, we determine the amount of water bound to the polymer and of the so-called pre-melting water in poly(vinyl methyl ether) hydrogels with the use of Raman spectroscopy, dielectric spectroscopy, and calorimetry. This analysis allows us to compare various physical properties of the bulk and the pre-melting water. We also postulate the molecular mechanism responsible for the pre-melting of part of water in poly(vinyl methyl ether) hydrogels. We suggest that above -60 °C, the first segmental motions of the polymer chain are activated, which trigger the process of the pre-melting.

Homologous series of dendronized polymethacrylates with a methyleneoxycarbonyl spacer between the backbone and dendritic side chain: synthesis, characterization, and some bulk properties.

First through fourth generation (G1-G4) dendronized macromonomers, 3, 5, 7, and 9, with a methyleneoxycarbonyl spacer between the polymerizable group and dendritic side chain (dendron) were synthesized, and their polymerization behavior to the corresponding dendronized polymers PG1s, PG2s, PG3s, and PG4s, respectively, was investigated by heating the monomers to 55 degrees C without intentional addition of initiator. This self-induced polymerization is referred to as thermally induced radical polymerization (TRP). The molar masses of PG1s-PG4s were determined by gel permeation chromatography in DMF calibrated to a recently developed G1 dendronized polymer standard (PG1). A comparison of this homologous series' polymerization results with those of an already existing one, which differed only by the lack of this spacer (referred to as PG1-PG4), was made to contribute to the issue of whether short spacers have an effect on polymerization. Several representatives of both series were also used in the first systematic and generation-dependent investigation of these unusual comb polymers' bulk properties. Both structure and dynamics were investigated by DSC, X-ray diffraction, and dynamic mechanical measurements.