Reactions of polyunsaturated fatty alcohols. IX. Molecular-weight distribution of some conjugated soybean vinyl ether homopolymers

The molecular-weight distributions of several conjugated soybean vinyl ether homopolymers were studied by means of the integral fractionation technique. Polymers having number average molecular weights of 2,200, 4,800 and 10,000 prepared with stannic chloride as catalyst as well as a polymer having a molecular weight of 3,400 prepared with boron trifluoride as catalyst were included in the study. The observed distributions for all the polymers were found to approximate the socalled “most probable” distributions expected theoretically for polymers obtained by simple difunctional polymerization. Presented at annual meeting. American Oil Chemists' Society, New Orleans, La., April 20–22, 1959. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Gaseous ammonia as a refining agent for cottonseed oils

In this investigation the application of gaseous ammonia to cottonseed oil refining was explored. The ammonia reacted quantitatively with the free fatty acids in the oil; its solubility in coftonseed oil was determined as a function of pressure. In “degumming” it was more efficient in removing phosphatides than other agents. A reduction in refining loss resulted for oils refined with gaseous ammonia as outlined and compared with the standard AOCS cup loss analysis. However, the oil colors were substantially higher even though the ammonia treated oils were re-refined with caustic solution. Results using cottonseed oil-hexane “miscellas” containing less than 70% oil showed low refining losses, but the colors were estremely high. Above 70% oil content the losses were higher, but the colors were lower. The colors never equalled “standard cup” results. This study was sponsored by the Texas Engineering Experiment Station and the Cotton Research Committee of Texas.     

Removal of fatty soil from glass by surfactants and surfactant-builder compositions

Previous papers have reported radiotagged fatty soil removal from glass either by solvents or by aqueous solutions of sodium tripolyphosphate and other builders. This paper provies soil-removal data for aqueous systems of both pure and built surfactant compositions of the nonionic and alkylbenzene sulfonate types. In general, nonionics are the most effective detergents for the system fatty soil/glass; the 10-mole ethylene oxide adduct products show peak soil-removal. Nonionic surfactants appear most effective for soil removal when used in baths closely approaching their cloud-points. Though modification of hydrophobe by EO addition can affect cloud point, peak soil-removal effectiveness seems to be controlled by hydrophobe selection. Highest soil removal for the alkylbenzene series occurred with the longer alkyl chain (pentadecyl). Admixture of surfactant and sodium tripolyphosphate provided synergistic compositions with certain 10-EO surfactants. Building of anionics markedly improved soil removal over the pure material but seldom exceeded the removal by STP alone. Presented at 34th fall meeting, American Oil Chemists' Society, New York, October 17–19, 1960.     

Water as a Promoter of the Complete Oxidation of Volatile Organic Compounds over Uranium Oxide Catalysts

The effect of water addition on the complete oxidation of benzene and propane VOCs by uranium oxide catalysts has been investigated. Benzene oxidation was studied using a silica supported U₃O₈ catalyst. Complete oxidation is promoted by the addition of 2.6% water compared with the reactivity when no water is added to the reactant feed. Increasing the water concentration to 12.1% resulted in a suppression of oxidation activity. Investigation of propane oxidation using U₃O₈ shows a dramatic promotion of activity. Propane conversion was ca. 50% at 600 °C without added water, whilst it increased to 100% at 400 °C with the addition of 2.6% water. A comparison of oxidation activity has been made with Mn₂O₃, an oxide recognised for complete oxidation. In contrast to the U₃O₈ catalysts the addition of 2.6% water suppresses the activity of Mn₂O₃. In situ powder X-ray diffraction studies showed that the bulk U₃O₈ structure was stable under all the reaction conditions. The origin of the increased activity is not clear but may be due to modification of the catalyst surface and the contribution from new reaction pathways such as steam reforming.     

Reactions of glycerol with poly(ethylene ether carbonate) polyols

Poly(ethylene ether carbonate) polyols can be modified by chemical reactions with polyglycol modifiers under conditions of elevated temperatures and reduced pressures. The modifier becomes chemically incorporated into the modified polyol and is used to control properties such as moisture sensitivity, CO₂ content, T_g, density, etc. in the resultant polyol. However, glycerol cannot be used as a modifier for poly(ethylene ether carbonate) polyols under the same conditions since it reacts with poly(ethylene ether carbonate) polyols by a transesterification reaction sequence to form glyceryl carbonate. As the temperature is increased, the glyceryl carbonate decomposes to yield glycidol and carbon dioxide. These reactions are conveniently followed by ¹³C-NMR. The preparation of glyceryl carbonate by this process has not been previously reported.     

Thermal and flammability properties of a silica–poly(methylmethacrylate) nanocomposite

PMMA, poly(metheylmethacrylate), nanocomposites were made by in situ radical polymerization of MMA, methylmethacrylate, with colloidal silica (ca. 12 nm) to study the effects of nanoscale silica particles on the physical properties and flammability properties of PMMA. Transparent samples resulted and the dispersity of the particles was examined by transmission electron microscopy and atomic force microscopy. The addition of nanosilica particles (13% by mass) did not significantly change the thermal stability, but it made a small improvement in modulus, and it reduced the peak heat release rate roughly 50%. Last, the flame‐retardant mechanism provided by the addition of nanosilica particles in PMMA is discussed. Published 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2072–2078, 2003     

Synthesis and photo-induced solution properties of new rigid-rod polyimides

A series of new, substituted pyromellitic dianhydrides were synthesized from 1,2,4,5-tetramethylbenzene. New soluble rigid-rod polyimides were obtained from the dianhydrides and 2,2′-bis(trifluoromethyl)-4,4′-biphenyl (PFMB) in phenolic solvents in the presence of isoquinoline as a catalyst. The polyimides are soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), m-cresol and other solvents, in spite of having no bending in their rigid structures.

UV irradiation changed color of the polyimide solutions and also their viscosity. We observed new absorbance in the 700-nm region and an ESR signal by UV irradiation. The new visible absorbance and the ESR signal are derived from the same origin. They are attributed to the anion radical of the diimide moiety in the polyimide as deduced from the hyper fine structure of the ESR signal. In addition, UV irradiation diminishes the solution viscosity.     

Transparent,methacrylate-based polymer networks with controlled crosslinker ductility

A series of transparent methacrylate-based crosslinked polymer networks are prepared in which the crosslinker length is controlled as a means to investigate the effects of network ductility on mechanical and ballistic properties. In each network the optical clarity of pure poly(methyl methacrylate) (PMMA) is retained, as well as a low value of haze. Both the glass transition temperature (T_g) and the tensile modulus of the networks are highly tunable, with network values both above and well below that of pure PMMA or the pure crosslinker network. The ballistic performance is likewise affected, with performance values of up to 400% greater than neat PMMA. We examine the effects of the crosslinker molecular weight on the impact performance, finding that, in these systems, the molecular weight between crosslinks is not a driving factor for the impact performance, and this may broadly translate to polymer networks in general. We find that improvements in ballistic performance can be realized at low molecular weight between crosslinks, provided the crosslinking agent is of sufficient ductility.     

The Oxidation of NdFeB Magnets

The oxidation kinetics in air of a commercial NdFeB magnet have been investigated over the temperature range 335–500°C. The oxide microstructure has been characterized by SEM, XRD and cross-sectional TEM. The results show that the external scale formed consists of an outer layer of Fe₂O₃ and an inner layer of Fe₃O₄ but that the principal degradation process is the formation of an extensive zone of internal oxidation. HREM has been used to show that this zone contains NdO particles embedded in an -Fe matrix. These particles are discrete and very small, approximately 2 nm in diameter, and have an amorphous structure. The -Fe matrix has a columnar grain structure with a grain width of approximately 100 nm. It is argued that the high rates of internal oxidation arise because the external-oxide layers are not protective at the oxidation temperature, and oxygen penetrates to the zone front by fast diffusion along the columnar -Fe grain boundaries.