Epoxy fatty acid ester plasticizers. Preparation and properties

Summary The preparation of epoxy fatty acid ester plasticizers has been reviewed. These plasticizers can be prepared by epoxidation reactions, utilizing a preformed peracid or anin-situ technique. A newin-situ epoxidation process, utilizing hydrogen peroxide and acetic acid in the presence of strong acid catalyst, has been described. Excellent conversions to epoxide have been achieved with a series of monounsaturated and polyunsaturated esters. Epoxy fatty acid esters are excellent plasticizers for vinyl resins. Their performance in a series of additional epoxy plasticizers of vegetable and marine origin is described. Novel epoxy plasticizers based upon mixed acetylated mono- and di-glyceride have been prepared and are found to have excellent plasticizer performance. Presented at the 28th fall meeting, American Oil Chemists’ Society, October 1954, Minneapolis, Minn.     

Recent studies of self-condensation and co-condensation of melamine-formaldehyde resins; cure at low temperatures

Self-condensation: recent research on the chemical pathways by which alcoholated melamine-formaldehyde (MF) resins react with themselves and on the product structures is summarized. Model compound studies suggest that bridges are less stable than widely thought unless they are in hexahydro-1,3,5-triazine ring structures. In acyclic structures they are probably less stable than bridges. Co-condensation: studies of how the composition of MF resins influences the rates of reaction with poly(ol) co-reactant show that MF resins that contain very low levels of and/or functionality are quite reactive. Reactivities of a variety of poly(ester) and acrylic coreactants were studied. By combining reactive MF resins with reactive co-reactants one can formulate high solids enamels that cure by co-condensation in 30 min at 50 to 65 °C with 0.5 parts per hundred (phr) of p-toluenesulfonic acid (p-TSA) catalyst. Cure at 25 °C appears feasible with higher catalyst levels.     

Iridoid glycoside metabolism and sequestration byPoladryas minuta (Lepidoptera: Nymphalidae) feeding onPenstemon virgatus (Scrophulariaceae)

A bivoltine checkerspot butterfly,Poladryas minuta, is aPenstemon specialist, not known to utilize any other plant genus for oviposition and larval feeding. At several intermontane plains sites of central Colorado, the butterfly utilizesPenstemon virgatus as its sole host plant. Analysis of the host plant showed it to contain three cinnamyl-type catalpol esters (scutellarioside-II, globularin, globularicisin) and catalpol. The host plant contained an average of 10% dry weight iridoids, but some variation among individual plants and leaves within plants was noted. Field-collected butterflies contained 2.1–8.7% dry weight catalpol, but no other iridoids. Adults from larvae fedP. virgatus in the lab contained 4.2–9.0% dry weight catalpol and excreted large amounts of catalpol in the meconium. No catalpol was found in the larval frass. Larvae did not consume three alternate iridoid-containing host-plant species, and most eventually died rather than feed on the alternate plants. Larvae did consume small amounts of artificial diets containing the alternate species andP. virgatus, but most went into diapause and some died. Survival was good on artificial diet containing 10% dry weight of the iridoid esters fromP. virgatus. Only catalpol was found in pupae and adults, but it was absent from the larval frass. The cinnamic-type acids expected from larval hydrolysis of the esters were not found in larval frass, pupae, or adults. These results are contrasted with those found for another checkerspot,Euphydryas anicia, which consumes a different host-plant species but was present at one of the same sites withPoladryas minuta.Paper 15 in the series Chemistry of the Scrophulariaceae. Paper 14 Boros, C.M., Stermitz, F.R., and Harris, G.H. 1990.J. Nat. Prod. 5372–80.     

IMAGING OF PARTICLE MOTION IN FLUID-SOLID SYSTEMS USING A GAMMA CAMERA

A new approach is presented for the characterization of particle motion in fluid-solid systems based on dynamic imaging with a gamma scintillation camera. A two-dimensional spouted bed of 200-500 micron diameter anion exchange resin beads was used as a test system. One or several beads were radiolabeled with the 140 keV gamma emitting radionuclide 99m-Tc pertechnetate, and particle velocity, panicle path, the spatial distribution of particle residence times, and local bed density were determined from the measured temporal and spatial distributions of particle activity. While care must be exercised in the interpretation of data when the scale for changes in the spatial distribution of activity approaches the limits of camera resolution, the method is quantitative, non-invasive, and well suited to the study of systems having symmetry in one spatial dimension.     

Phase Stability of Fine-Grained (Mg,Y)-PSZ

A fine-grained zirconia, which has been costabilized with yttria and magnesia, has been prepared. Its stability during subeutectoid annealing at 1100^deg;C, and its hydrothermal stability during hydrothermal treatment at 180^deg;C, have been determined and they are compared to those of Y-TZP and Mg-PSZ materials .     

Nitrate Radicals in Tropospheric Chemistry

Nitrate radicals are being recognized as key intermediates in a growing list of important chemical processes in the atmosphere. Here, the role of nitrate radicals (NO₃) in tropospheric chemistry is discussed, with special emphasis on results from field measurements, most of which have been made by differential optical absorption spectroscopy (DOAS), with matrix-isolation electron spin resonance being an alternative technique. Nitrate radicals were observed in the atmosphere at peak mixing ratios of 350 ppt. Long-term observation of NO₃ shows that 24-h averages in rural air masses are closer to a few ppt. Nevertheless, the NO₃ radical plays an important role in the non-photochemical conversion of NO_x to HNO₃. Also, NO₃ is a strong oxidizing agent and initiates the night-time removal of atmospheric trace species such as olefins, aromatic hydrocarbons, and organic sulfur compounds. Finally, night-time peroxy radical production and release of reactive halogen species from sea salt aerosol might be initiated by NO₃ reactions.     

Bubble nucleation and growth in fluids

The nucleation and growth of CO₂ bubbles in non-Newtonian and Newtonian fluids that were initially supersaturated under different pressures are investigated in the present work. Quantitative information by means of two cameras reveals that at an immobile nucleation site the bubble grows rapidly followed by a linear increase in bubble diameter with time. After reaching a critical size, the bubble detaches from the stagnant site to rise in liquids with an exponential temporary increase for both the diameter and distance. A simple physical reasoning was proposed to qualitatively explain these observed phenomena. Recently, the growth rate and flow fields around a CO₂ micro-bubble were measured in a microdevice by a micro-Particle Image Velocimetry in water. This information at microscale gives new insight into the complex mechanism of bubble nucleation and growth in fluids and could help to develop a rigorous theoretical modelling and numerical simulation such as the Lattice Boltzmann approach.     

Mode I Fracture Resistance of a Laminated Fiber-Reinforced Ceramic

The mode I fracture resistance of a ceramic matrix composite has been measured. Simultaneous observations have revealed that the resistance is dominated by frictional dissipation upon the pullout of fibers that fracture in the crack wake off the crack plane. Numerical and analytical crack growth simulations have been compared with the experimental results. One important feature in this comparison concerns the occurrence of large-scale bridging. With these effects taken into account, the simulations and the experiments are found to be in good correspondence for acceptable magnitudes of the interface sliding stress.     

Mechanical Behavior of Several Hybrid Ceramic-Matrix-Composite Laminates

Several different hybrid laminated composites comprised of alternating layers of dense ceramic sheets (either SiC or Si₃N₄) and fiber-reinforced ceramic-matrix-composite (CMC) layers (Nicalon fibers with either glass or glass-ceramic matrices) have been fabricated and characterized. The effects of the reinforcement architecture (unidirectional vs cross-ply) and the relative volume fractions of the phases on the tensile and flexural properties have been examined. Comparisons have been made with the properties of the constituent layers. Rudimentary models have been developed to describe the onset of cracking and for the minimum volume fraction of CMC required to develop multiple cracks and thus obtain a high failure strain.