Solvents, swelling properties

The catalytic application of clays is related closely to their swelling properties. Appropriate swelling enables the reactant to enter the interlamellar region. The ion exchange is usually performed in aquatic media because the swelling of clays in organic solvents, and thus the expansion of the interlayer space, is limited and it makes it difficult for a bulky metal complex to penetrate between the layers. Nonaqueous intercalation of montmorillonite with a water-sensitive multinuclear manganese complex was achieved, however, with the use of nitromethane as solvent.139 The complex cation is intercalated parallel to the sheets. 

Other functionalized supports that are able to serve in the asymmetric dihydroxylation of alkenes were reported by the groups of Sharpless (catalyst 25) [88], Sal-vadori (catalyst 26) [89-91] and Cmdden (catalyst 27) (Scheme 4.13) [92]. Commonly, the oxidations were carried out using K3Fe(CN)g as secondary oxidant in acetone/water or tert-butyl alcohol/water as solvents. For reasons of comparison, the dihydroxylation of trons-stilbene is depicted in Scheme 4.13. The polymeric catalysts could be reused but had to be regenerated after each experiment by treatment with small amounts of osmium tetroxide. A systematic study on the role of the polymeric support and the influence of the alkoxy or aryloxy group in the C-9 position of the immobilized cinchona alkaloids was conducted by Salvadori and coworkers [89-91]. Co-polymerization of a dihydroquinidine phthalazine derivative with hydroxyethylmethacrylate and ethylene glycol dimethacrylate afforded a functionalized polymer (26) with better swelling properties in polar solvents and hence improved performance in the dihydroxylation process [90]. 

Finally, first attempts were made to extend the concept of soluble hyperbranched polymers to dendronized sohd-phase materials. Recently, the first dendronized sohd phase, accessible in only one reaction step was reported (Fig. 7.4) [36]. The coupling of hyperbranched polyglycerol to Merrifield resin yields a new type of high-loading sohd-phase hybrid material with loading capacities of ca. 3 mmol g and good swelling properties even in protic solvents (see also Section 3.4). 

Strong evidence of the dominant Influence of molecular conformation on the properties of coals Is Implicit In the several data sets which show an extremum In the measured property when plotted against carbon rank. Examples are the extrema which occur In the solid state properties of mass density (22,23) and proton spin-lattice relaxation rate (24) as well as In solvent swelling and extractablllty ( ). 

Another important consideration was the choice of resin. The use of Hmb was developed using resins composed of polydimethylacrylamide polymerized within the pores of a solid, macroporous support, either Pepsyn or polyhipe, both are exemplified below. The use of Hmb involves the switching of solvents from DMF to dichloromethane the resins mentioned have excellent swelling properties in both solvents. However, some commercial polystyrene supports have given poor results because of the need to switch solvents, which can cause problems due to resin shrinkage. 1 ... 

The effect of polymer-filler interaction on solvent swelling and dynamic mechanical properties of the sol-gel-derived acrylic rubber (ACM)/silica, epoxi-dized natural rubber (ENR)/silica, and polyvinyl alcohol (PVA)/silica hybrid nanocomposites was described by Bandyopadhyay et al. [27]. Theoretical delineation of the reinforcing mechanism of polymer-layered silicate nanocomposites has been attempted by some authors while studying the micromechanics of the intercalated or exfoliated PNCs [28-31]. Wu et al. [32] verified the modulus reinforcement of rubber/clay nanocomposites using composite theories based on Guth, Halpin-Tsai, and the modified Halpin-Tsai equations. On introduction of a modulus reduction factor (MRF) for the platelet-like fillers, the predicted moduli were found to be closer to the experimental measurements. 

The kinetic theory of rubber elasticity is so well known and exhaustively discussed (17, 27, 256-257, 267) that the remarks here will be confined to questions which relate only to its application in determining the concentration of elastically effective strands. In principle, both network swelling properties and elasticity measurements can provide information on network characteristics. However, swelling measurements require the evaluation of an additional parameter, the polymer-solvent interaction coefficient. They also involve examining the network in two states, one of which differs from its as-formed state. This raises some theoretical difficulties which will be discussed later. Questions on local non-uniformity in swelling (17) also complicate the interpretation. The results described here will therefore concern elasticity measurements alone. 

The description of the physical properties of fluoroelastomers is necessarily less precise than that of fluoroplastics because of the major effect of adding curatives and fillers to achieve useful cross-linked materials of a given hardness and specific mechanical properties Generally, two parameters are varied increasing cross-link density increases modulus and decreases elongation, and raising filler levels increases hardness and decreases solvent swell because of the decreased volume fraction of the elastomer In addition to these two major vanables, the major determinants of vulcanizate behavior are the chemical and thermal stabilities of its cross-links The selection of elastomer, of course, places limits on the overall resistance to fluids and chemicals and on its service temperature range... 

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