Crystalline polar additives associations

Modification of Ionic Associations by Crystalline Polar Additives... 

This paper attempts to further explore the modification of ionic associations by a crystalline ionic plasticizer, such as zinc stearate, at the solid state. Mechanical properties, swelling behavior, and morphological aspects were studied in order to better understand the role of such crystalline polar additives. 

Duvdevani(40) have been directed at modification of ionomer properties by employing polar additives to specifically interact or plasticize the ionic interactions. This plasticization process is necessary to achieve the processability of thermoplastic elastomers based on S-EPDM. Crystalline polar plasticizers such as zinc stearate can markedly affect ionic associations in S-EPDM. For example, low levels of metal stearate can enhance the melt flow of S-EPDM at elevated temperatures and yet improve the tensile properties of this ionomer at ambient temperatures. Above its crystalline melting point, ca. 120°C, zinc stearate is effective at solvating the ionic groups, thus lowering the melt viscosity of the ionomer. At ambient temperatures the crystalline additive acts as a reinforcing filler. 

The process yields a random, completely soluble polymer that shows no evidence of crystallinity of the polyethylene type down to —60°C. The polymer backbone is fully saturated, making it highly resistant to ozone attack even in the absence of antiozonant additives. The fluid resistance and low temperature properties of ethylene—acryUc elastomers are largely a function of the methyl acrylate to ethylene ratio. At higher methyl acrylate levels, the increased polarity augments resistance to hydrocarbon oils. However, the decreased chain mobiUty associated with this change results in less fiexibihty at low temperatures. 

Practical problems associated with infrared dichroism measurements include the requirement of a band absorbance lower than 0.7 in the general case, in order to use the Beer-Lambert law in addition infrared bands should be sufficently well assigned and free of overlap with other bands. The specificity of infrared absorption bands to particular chemical functional groups makes infrared dichroism especially attractive for a detailed study of submolecular orientations of materials such as polymers. For instance, information on the orientation of both crystalline and amorphous phases in semicrystalline polymers may be obtained if absorption bands specific of each phase can be found. Polarized infrared spectroscopy can also yield detailed information on the orientational behavior of each component of a pol3mier blend or of the different chemical sequences of a copoljnner. Infrar dichroism studies do not require any chain labelling but owing to the mass dependence of the vibrational frequency, pronounced shifts result upon isotopic substitution. It is therefore possible to study binary mixtures of deuterated and normal polymers as well as isotopically-labelled block copolymers and thus obtain information simultaneously on the two t3q>es of units. 

Membranes and model membranes exhibit liquid crystalline behavior and this has been exploited in a number of studies to obtain valuable information on the structure and dynamics of membrane associated peptides and proteins as well as on the interaction of the peptides with the membranes themselves. NMR spectroscopy of nuclei such as proton, carbon, deuterium, nitrogen and phosphorus has been utilized for such purposes. Structure elucidation of membrane-associated peptides and proteins in oriented bilayers by solid-state NMR spectroscopy has been reviewed. A survey on the use of static uniaxially oriented samples for structural and topological analysis of membrane-associated polypeptides is available. The theoretical background has been dealt with and a number of examples of applications provided. In addition, ongoing developments combining this method with information from solution NMR spectroscopy and molecular modelling as well as exploratory studies using dynamic nuclear polarization solid-state NMR have been presented. The use of N chemical shift anisotropy, dipolar interactions and the deuterium quadrupolar split-... 

Figure 8). The enthalpy and entropy changes associated with these transitions are summarized in Table 4. Presently we do not know the degree of crystallinity of these polyethers. However, the fact that the enthalpy and entropy changes of all transitions are larger than those of melting seems to indicate that the polyethers exhibit multiple smectic mesophases. Additional support for smectic type mesophases are provided by their high viscosity and by the optical polarizing micrographs which exhibit mosaic textures, typical of higher ordered smectic phases, or batonnets textures,...

The formation of bilayer vesicles was also observed for dialkyldimethylammonium bromide 33 in ether-containing ionic liquids 26, 27 (Figure 24) [124]. Ionic amphiphiles intrinsically possess solvophilic (or ionophilic) groups and electrostatic repulsions between them are highly screened in ionic liquids. In addition, the presence of ether-linkages in ionic liquids increases their net polarity. These factors contribute to enhance the association force of ammonium amphiphiles in ionic liquids and concurrently increase the thermal stability of gel(crystalline) state bilayers [124]. 

The interfacial tension can undergo significant changes if the polarity of the medium is altered, such as in the stability/coagulation transition caused by the addition of water to hydrophobic silica dispersions in propanol or ethanol [44,52,53]. Also, the addition of small additives of various surface-active substances can have a dramatic effect on the structure and properties of disperse systems and the conditions of transitions [14,16,17,26]. The formation and structure of stable micellar systems and various surfactant association colloids, such as microemulsion systems and liquid crystalline phases formed in various multicomponent water/hydrocarbon/surfactant/alcohol systems with varying compositions and temperatures, have been described in numerous publications [14-22,78,79,84-88]. These studies provide a detailed analysis of the phase equilibria under various conditions and cover all kinds of systems with all levels of disperse phase concentration. Special attention is devoted to the role of low and ultralow values of the surface energy at the interfaces. The author s first observations of areas of stable microheterogeneity in two-, three-, and four-component systems were documented in [66-68],... 

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