BRIEFS Summary of papers published in this month’s research quarterly, I@EC Product Research and Development
REACTIONS OF SODIUM SUCRATE I N SOLUTION. PREPARATION OF PURE LONG-CHAIN ETHERS OF SUCROSE.
STRESS-SOFTENING IN CROSSLINKED BLOCK COPOLYMER ELASTOMERS
Surface-active ethers of sucrose were prepared by the reaction of sodium sucrate and long-chain alkyl bromides in dimethyl sulfoxide. They were isolated from solution, and obtained in an analytically pure state, by a technique involving precipitation with barium hydroxide. Dodecylsucrose was produced in 87yo conversion and 73y0 yield, and 97Y0 of the unreacted sucrose was recovered. The product was a mixture of isomers. Octylsucrose, decylsucrose, hexadecylsucrose, and octadecylsucrose were also prepared, but in lower yields. Concentrated solutions of sodium sucrate in liquid ammonia were prepared in the presence of excess sucrose. The sodium sucrate in these solutions reacted readily with methyl iodide at reflux temperature, but not with long-chain alkylating agents. At higher temperatures under pressure, longchain alkylating agents reacted preferentially with the ammonia solvent.
Samples of styrene-butadiene-styrene (SBS) and poly(ester-urethane) block copolymer elastomers are crosslinked to determine the effect of cross-linking on stress-softening characteristics. Crosslinking agents studied are benzoyl peroxide, trimethylolpropane, and diphenylmethane diisocyanate. Stress-strain measurements on the uncrosslinked elastomers are made with increasing amounts of prestraining. The results show a pronounced Mullins effect, with the material appearing softer at extensions less than those previously applied. Chemical crosslinking has little influence on the stress-softening behavior unless the crosslinkage disrupts the aggregated glassy portions of the block copolymer. Reversible stress-strain curves are generated at higher levels of triol incorporation and to a lesser extent with crosslinking by benzoyl peroxide in the poly(ester-urethane). In each case the “modulus enhancement” observed in these block copolymer elastomers appears to lessen as the material exhibits less stress-softening.
J . A . Reeder, H. B. Rayner, G. Aitken, D . Bradley, and J . Atkinson, British Columbia Research Council, Vancouver 8, B.C., Canada IND.ENG.CHEM.PROD.RES.DEVELOP. 7, 230-234 (1968)
S. L. Cooper, D. S. Huh, and W. J . Morris, University of Wisconsin, Madison, Wis. 53706 IND.END.CHEM.PROD.RES. DEVELOP. 7, 248-251 (1968)
IMPROVEMENT OF PROPERTIES OF URETHANE ELASTOMERS BY REMOVAL OF TERMINAL UNSATURATION I N POLY(OXYPR0PYLENE)DIOLS
The production of soft urethane elastomers from commercially available high molecular weight poly(oxypropy1ene)diols has been limited because of the presence of terminal unsaturation. This work has demonstrated that these monohydroxyl-monounsaturated molecules were successfully converted into useful diol molecules by the platinum catalyzed addition of a silicon dihydride to the double bonds of two unsaturated molecules. Using a solution polymerization technique, the untreated poly(oxypropy1ene)diol of 4000 molecular weight produced carbon black filled elastomers that were tacky, low resilient materials with tensile strength, elongation, and tear strength of 32 psi, 275Y0, and 12 pli, respectively. The same diol treated with 1,1,1,3,5,7,7,7-octamethyltetrasiloxaneproduced tack-free, highly resilient elastomers with tensile strengths of 468 to 580 psi, elongations of 1740 to 180570, and tear strengths of 94 to 106 pli.
Harold R. Bylsma, Robert L. McKellar, and Martin C. Musoy, Dow Corning Gorp., Midland, Mzch. 48640
NEW METHOD OF PREPARING A NICKEL CATALYST
When a nickel plate was clad and welded with aluminum plates like a sandwich, a layer of Ni-A1 alloy was formed on the boundary of these metals. A nickel catalyst suitable for fixed-bed operations was prepared by treating this sandwich with an alkali. T h e activity of this catalyst was examined by vapor phase hydrogenation of acetone and its structure was studied by x-ray diffraction.
Jiro Yasumura and Tomio Yoshino, University of Tokushima, Tokushima, Japan, and Satoshi Abe, Nikki Chemical Co., Ltd., Ohtemachi, Tokyo, J a j a n IND.ENG.CHEM.PROD.RES.DEVELOP. 7, 252-254 (1968)
IND.ENG.CHEM.PROD.RES.DEVELOP. 7, 234-238 (1968) SOIL BURIAL RESISTANCE OF VINYL CHLORIDE PLASTICS
Soil burial resistance of 21 flexible, semirigid, and rigid poly(viny1 chloride) formulations used as electrical insulations or cable jackets was studied. Detailed descriptions of test procedures and evaluations are given. Burial (4 years) was in Georgia (soil pH 5.2) and New Mexico (soil pH 8.2). Performance was affected more by composition variables, particularly choice and concentration of plasticizers, than by burial location, depth, electrical potential, or metallic conductors used. Susceptibility of the various plasticizers to attack did not correlate well with previous determinations of their fungus resistances. Plasticizers-e.g., tricresyl phosphate, polyesters, natural rubber, and dipentaerythritol ester, that are nonmigratory and/or inherently microbial resistant-gave the best performance. Phthalate plasticizers were more susceptible to attack, branched-chain types showing somewhat better permanence than those prepared from normal alcohols.
T h e dehydrogenation of n-dodecane to linear dodecenes over molybdena-alumina catalysts was investigated. Selectivity to mono-olefin is about 6570 at a total paraffin conversion of 12 to 13% after the catalyst has been deactivated by substantial coking. Data on catalyst coking were obtained using thermogravimetric analytical techniques. The rate of coking depends on physical properties of the alumina, and on the type and concentration of hydrocarbon present. Initially the fresh molybdena-alumina catalysts studied display high acidity, but most of this acidity is not due to the intrinsic acidity of the alumina support.
J . B. DeCoste, Bell Telephone Laboratories, Inc., Murray Hill, N . J . 07974
J . F. Roth, J . B. Abell, and A . R. Schaefer, Central Research Department, Monsanto Go., St. Louis, Mo. 63166
IND.ENG.CHEM.PROD.RES.DEVELOP.7, 238-247 (1968)
IND.END.CHEM.PROD.RES.DEVELOP. 7, 254-258 (1968)
CATALYTIC DEHYDROGENATION OF HIGHER NORMAL PARAFFINS TO LINEAR OLEFINS OVER MOLYBDENA-ALUMINA CATALYSTS
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ACIDIC CATALYSTS FOR METHYLATION OF AROMATIC AMINES. ACTIVITY, SELECTIVITY, AND STABILITY OF ALUMINA AND SILICAALUMINA, SYNTHETIC OR NATURAL, I N THE PREPARATION OF DIMETHYLANILINE
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The activity, selectivity, and stability of solid acidic catalysts of the alumina and silica-alumina types were studied in the vapor-phase methylation of methylaniline with methanol. The best catalysts are the synthetic silica-aluminas for hydrocarbon cracking, which do not produce dimethyl ether during methylation (although they are good catalysts for the dehydration of pure methanol). Very pure aluminas are also good catalysts, but they give dimethyl ether as a by-product. This difference in selectivities is due to the protonic nature of silica-alumina, which forms stable compounds with methylaniline and inhibits the dehydration of methanol. Natural silica-aluminas are selective but less active than pure aluminas. Intermediate ether formation is not necessary for the alkylating activity of methanol, and in all cases the nitrogen was methylated. Fouling of the best catalysts is very slight, and the carbonaceous deposit can be eliminated by burning in air.
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Josk M . Parera, Aljredo Gonra‘ler, and ,tfiguel A . Barral, Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santa Fe, Argentina
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IND.ENG.CHEM.PROD.RES.DEVELOP. 7, 259-262 (1968)
COMPATIBILITY OF INORGANIC AZIDES WITH ORGANIC EXPLOSIVES
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Azide-explosive interaction at elevated temperatures was investigated using trinitrobenzene as a model high explosive. Both lead and sodium azide reacted with trinitrobenzene at 260’ C., as evidenced by the large volume of gas evolved and the formation of a black insoluble product which did not melt at 475’ C. The reaction was interpreted as an oxidation of the azide ion by the nitro groups, and must be considered as a limitation on the use of azides in intimate contact with typical organic explosives at elevated temperatures. Another example of explosive-azide interaction is shown by cyclotrimethylenetrinitramine in contact with commercial lead azides at 165” C.
Jerome LM.Rosen and Herbert T . Simmons,Sr., U . S. Naval Ordnance Laboratory, White Oak, Silver Spring, M d . , 20510
IND. ENG.CHEWPROD.RES.DEVELOP. 7,262-264 (1968)
NUCLEAR RADIATION DAMAGE VS. THERMAL DECOMPOSITION OF 1,3-DIAMINO-2,4,6-TRlNlTROBENZENE AND 2,2‘,4,4‘,6,6’HEXANITROSTILBENE
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Two explosive compounds, 1,3-diamino-2,4,6-trinitrobenzeneand 2,2‘,4,4’,6,6’-hexanitrostilbene, were subjected to neutron and gamma radiation from a power reactor at flux levels of about n/sq cm/scc fast 3.85 X 108 R per hour and 7.5 X neutron flux. Unchanged compound remaining after irradiation was determined by thin-layer chromatography. Similarly, samples heated at 280’ C were analyzed for residual compound. Ratios of unchanged sample to solid products proved nearly the same for irradiated and heated samples at each of three levels of degradation for corresponding equivalent weight losses. The over-all changes in 1,3-diamino-2,4,6-trinitrobenzeneand 2,2’,4,4’,6,6’-hexanitrostilbenewere much greater than indicated by gaseous products.
J . C. Hofsommer, J . M . Rosen, and J . S. Feifer, U . S. Naval Ordnance Laboratory, White Oak, Stlver Sprzng, M d . 20510 IND.ENG.CHEM.PROD.RES.DEVELOP. 7, 265-266 (1968)
developed a dimensionless group lately? SYNTHESIS OF ACIDS BY THE LIQUID-PHASE OXIDATION OF n-HEXANE
I n the liquid-phase oxidation of n-hexane at 160' C under 25 atm and catalyzed by manganese naphthenate, a high yield of acetic acid was obtained. T h e mechanism of acid formation was deduced from the analysis of the products formed in the oxidation of pure n-hexane, and those formed in the oxidation of n-hexane disturbed by inorganic basic salts or by initial amounts of butyric acid. T h e kinetics of the accumulation of the acids shows that the distribution of acids results simultaneously from the oxidation of the hydrocarbon and its alcoholic and ketonic degradation derivatives, and from the decarboxylative oxidation of the acids.
Jean Rouchaud and Bernard Lutete, Department of Physical Organic Chemistry, University of Lovanium, Kinshasa X I , Congo IND.ENG.CHEM. PROD.RES.DEVELOP. 7, 266-270 (1968)
DELAYED COKING OF LOW-TEMPERATURE LIGNITE PITCH
A Texas lignite pitch was subjected to delayed coking a t 800' to 1200°F, yields of coke, gas, and oil were determined, and the effect of coking temperature was established. As expected, a n increase in coking temperature increased the coke and gas yields and decreased the oil yield. Yields at 800' and 1200°F,respectively, were coke, 25 and 45, oil, 43 and 17, and gas, 17 and 39 weight yo. The coke appears suitable as an aggregate for metallurgical electrode manufacture or low-sulfur fuel for power generation, the oil as a source of electrode binder and phthalic and maleic anhydrides, and the gas as a substitute for natural gas or source of hydrogen via steam reforming.
John S. Berber, Richard L. Rice, and Robert L. Lynch, Morgantown Coal Research Center, Bureau of Mines, U. S. Department of the Interior, Morgantown, W. V a . 26505
IND.END.CHEWPROD.RES.DEVELOP. 7, 270-274 (1368)
REFINING OF PYROLYTIC SHALE OIL
A pyrolytic shale oil was refined into marketable products to determine the severity of hydrodenitrogenation needed for sustained refining and the yields and qualities of the refined products. T h e refining steps were: delayed coking, with recycle of heavy coker distillate; hydrodenitrogenation of coker distillate, followed by fractionation ; further hydrodenitrogenation of naphtha; reforming of nitrogen-free naphtha; catalytic cracking of gas oil from the hydrodenitrogenated coker distillate. Temperature and pressure maximums of 950'F and 1500 psig were well within the scope of current refinery practice. Nitrogen content of the reformer feedstock was 1.5 ppm, and that of the cracking stock was 100 ppm (basic); thus, both were adequately free of nitrogen to ensure long catalyst life. Reformates and catalytic gasolines of 98 octane number were produced. The hydrodenitrogenated coker distillate yielded a large volume of specification grade diesel fuel. Yields and product distributions for each refining step were determined, along with properties of the finished liquids.
If you have, and you're just about to call it the Humperdinck Number, hold on a minute. Someone else may have used and named the group already. To find out who, you need a couple of I&EC reprints: Dimensionless Groups Part I (I&EC 58131, 46-60, March 1966) Dimensionless Groups Part I1 (I&EC 60(3), 71-78, March 1968) In these two articles, G. D. Fulford and J. P. Catchpole alphabetically list 285 dimen sionle s s groups with their symbols, definitions, fields of significance and use, and original references. Special tables also list the groups under their constituent variables and the exponents to which they are . raised. Order from: Reprints ACS Publications, Dept. G 1155 16th St. N.W. Washington, D.C. 20036
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IND.END.CHEM. PROD.RES.DEVELOP. 7, 274-282 (1968)
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