Thermal stability of “living” polymer–lithium systems

The thermal stabilities of polybutadienyllithium, polyisoprenyllithium, and polystyryllithium solutions have been determined in hydrocarbon solvents. Kinetic analysis indicated that a complex mechanism was involved in the thermolysis of polybutadienyllithium. The thermal stability was observed to increase with increasing lithium concentration, suggesting the presence of competitive reactions in addition to the expected elimination of lithium hydride. The thermal stability of the three systems studied was consistent with their reported degrees of association: dimeric polystyryllithium was less stable than tetrameric polyisoprenyllithium or hexameric polybutadienyllithium.     

Theory of “Cohesive” vs “Adhesive” Separation in an Adhering System

It is shown that there is limited validitity to the doctrine that true interfacial separation, in an adhering system, is highly improbable. An analysis employing the Griffith-Irwin crack theory yields these results: The important parameters are, difference in elastic moduli, ΔE; differences in g, the energy dissipation per unit crack extension; thickness, Δ₁ or δ₂, of the region where dissipation occurs; and the presence or absence of strong interfacial bonds. If the forces across the interface are appreciably weaker than the cohesive forces in either phase, there is a strong minimum in g at the interface. For flaws of equal size, an interfacial flaw will be the site of initiation of failure. If strong interfacial bonds are present, then if Δg and ΔE have the same sign, failure is most probable, deep within one phase. If Δg and ΔE have opposite signs, failure may be initiated, and may propagate, at a distance δ from the interface, in the phase with lower g. This may be mistaken for weak-boundary layer failure.     

“HETEROGENIZING” HOMOGENEOUS CATALYSTS

For many years, it has been customary to classify catalysts as “homogeneous” or “heterogeneous.” The former commonly operate through the formation of “intermediate compounds,” and the latter, by adsorption of the reactants on the catalyst surface. The line between the two is a fine one, for the distinction between adsorption and compound formation is not at all clear, and seems to be becoming less and less clear as we learn more about adsorption. In recent years, several writers [l-7] have stressed the point that there is a good deal of overlap between homogeneous and heterogeneous catalysis. Experimental evidence supporting this point of view is accumulating, and while we are not prepared to say that there is no distinction, we can say with certainty that many homogeneous catalysts can be converted into heterogeneous ones, retaining the advantages of great activity and selectivity inherent in homogeneity and, at the same time, assuming the ready recovery which is the great advantage of heterogenity. In practice, of course, the matter is not quite that simple, for other factors must be considered. On the whole, however, many advantages have been found in the use of heterogenized homogeneous catalysts.     

On the so-called “semi-ionic” C–F bond character in fluorine–GIC

The short-range structures of fluorine–graphite intercalation compounds with stage-1 structures, C_xF (x = 2.47, 2.84, 3.61), were analyzed by means of neutron diffraction. It has been shown that the so-called “semi-ionic” C–F bond character in C_xF is essentially covalent with the bond length of 0.140 nm, and the original planar graphene sheets are buckled at the sp³-hybridized carbon atoms bound to fluorine atoms. Conjugated C–C double bonds with the bond length of 0.142 nm are preserved between the carbon atoms unbound to fluorine atoms in C_xF, while other C–C bonds are single bonds with the bond lengths of 0.153 nm. The C–F bond order in C_xF is slightly lower than those in poly(carbon monofluoride) ((CF)_n) and poly(dicarbon monofluoride) ((C₂F)_n), which is explained by the hyperconjugation involving the C–C bonds on the carbon sheets and C–F bond.     

The role of pore structure in the catalytic behavior of “unaged” and “aged” silica-alumina catalysts

This is a review of research concerning the role played by the porous structure of silica-alumina catalysts on the evolution of organic catalytic processes. A strong effect of the geometrical shape of the pores on catalytic activity and selectivity has been evidenced. The experimental results have also been interpreted by means of a simplified mathematical model, able to relate selectivity for a reaction of the type A → B → C to the geometrical features of macro-microporous catalyst pellets, or granules. The theoretical results are in qualitatively satisfactory agreement with the experimental data.     

Interpretation of the “melt strength” test

The “melt strength” test for molten polymers is shown to be a function of several rheological parameters. Interpretation of results in terms of extensional viscosity differences is consequently not straightforward, if possible at all.