BRIEFS Summary of papers published in this month's research quarterly, I&EG Product Research and Development
PHYSICAL, CHEMICAL, AND MECHANICAL CHARACTERISTICS OF A POLYPHENYL ETHER
The formulation, properties, characteristics, and pump loop behavior are reviewed for m-bis(m-phenoxyphenoxy)benzene,one of the more promising polyphenyl ethers for high temperature hydraulic fluid applications. Data are given for kinematic viscosity, thermal conductivity, specific heat, density, vapor pressure, pour point, flash point, fire point, bulk modulus, evaporation weight loss, stability (hydrolytic, thermal, radiation, and oxidative), fourball wear and transition temperature, effect of tricresyl phosphate as an antiwear additive, rolling contact fatigue, and pump loop behavior to 800' F. Excellent fluid performance was obtained in two closed pump loops at 400", 550°, and 700' F.; however, at 800' F. gel tended to form and small increases in viscosity and neutralization number occurred. D. R. Wilson, W. A. Marshall, R. E . Doh, and R. J. Benaing, Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio
IND.END.CHEM.PROD.RES. DEVELOP.6, 8-88 (1967)
l . O q trideca-5,11-diene(IV), the mono Diels-Alder adduct of hexachlorocyclopentadiene and cis, cis-cyclooctadiene. A polyester resin system based on this dibasic acid was compared with similar systems based on Chloran T M (trade-mark of Universal Oil Products Co.'s 2,3-dicarboxy-5,8-endo-methylene-5,6,7,8,9,9hexachloro-l,2,3,4,4a,5,8,8a-octahydronaphthalene anhydride) (11), chlorendic anhydride (I), and tetrachlorophthalic anhydride (TCPA, V). T h e physical properties of the resin system based on I11 were generally superior to those of the corresponding resins based on chlorendic anhydride and TCPA. The chief advantage of the new resin system over that based on Chloran T M is toughness or flexibility with retention of good strength properties, especially useful in some applications not requiring reinforced plastics, such as castings, pottings, coatings, and plasticizers.
R. C. Slagel, G. P. Shulman, and F. M. Young, T. L. Daniels Research Center, Archer Daniels Midland Go., Minneajolis, Minn. IND. ENC.CHEM.PROD.RES.DEVELOP. 6,100-104 (1967)
SYNTHESIS AND PROPERTIES OF SILOXANE-POLYETHER COPOLYMER SURFACTANTS
USE OF DIFFERENTIAL THERMAL ANALYSIS I N STUDYING GLASS TRANSITIONS AND THERMAL DEGRADATION OF POLYSTYRENE
Properties of a series of methylsiloxane-oxyalkylene copolymers are compared with typical hydrocarbon surface active agents. The siloxane surfactants were characterized by surface tensions as low as 20 to 21 dynes per cm. in aqueous solution and relati\.ely small micelles (aggregation numbers of 3.4 and 4.7). As a result of low aqueous surface tensions, certain of these copolymers were excellent wetting agents for low energy hydrophobic surfaces such as polyethylene. Unlike hydrocarbon derivatives, methylsiloxane-polyether copolymers were also surface active in nonaqueous polypropylene glycol systems, a contributing factor in the stabilization of polyurethane foam.
A series of commercial and standard polystyrene samples was studied using a differential thermal analyzer (DTA) designed for microsamples. Glass transition temperatures were measured and pretreatment of samples, reproducibility of observations, effect of heating rates, effect of sample size, effect of volatiles, and effect of molecular weight were studied in order to evaluate the utility of DTA as a laboratory tool for polymers. The range of samples used was such that the many unusual effects observed with commercial samples of varying history were easily discernible. DTA is also valuable for following thermal decomposition of polymers, as demonstrated by studies on a polystyrene sample.
Bernard Kanner, W.G. Reid, and I . H . Petersen, Union Carbide Corp., Tonawanda, A'. Y .
IND. EXG.CHEM. PROD.RES.DEVELOP. 6,88-92 (1967) CORRELATION OF SHRINKAGE PRESSURES DEVELOPED IN EPOXY, POLYURETHANE, AND SILICONE CASTING RESINS WITH INDUCTANCE MEASUREMENTS ON EMBEDDED ELECTRONIC COMPONENTS
The electrical properties of pressure-sensitive electronic components can be significantly altered as a result of embedment in casting resins. Inductance measurements have been obtained over a wide temperature range on a particularly pressure-sensitive ferrite-core transformer using 11 different potting compounds, including rigid, semirigid, and flexible epoxies, flexible and semirigid polyurethanes, silicone rubber, and wax. Pressure studies have been made on these compounds utilizing embedded pressurecalibrated thermometers. Inductance change is correlated with pressure buildup and with room temperature hardness, brittle point, and torsional modulus of the potting compounds. .41though thc addition of mineral filler reduces the thermal coefficient of expansion, the inductance loss and pressure buildup are greater for filled rigid and semirigid epoxy compounds than for the corresponding unfilled compounds. Increased stiffness and rigidity of the filled compounds are responsible for these effects.
C . t7. Lundberg, Bell Telephone Laboratories, Ine., ,Murray Hill, N . J .
IND.ENG.CHEM.PROD.RES.DEVELOP. 6, 92-100 (1967)
Alton Tex.
E.Martin and Howard F. Rase, The University of Texas, Austin,
IND.END.CHEM.PROD.RES.DEVELOP.6, 104-108 (1967)
SUBSTITUTED BIPHENYLS AND TERPHENYLS AS OXIDATIVELY AUTOINHIBITIVE COMPOUNDS
I n a study of oxidatively autoinhibitive biphenyls and terphenyls, set-butylbenzenes having phenyl, methoxyphenyl, sfc-butylphenyl, or fert-butylphenyl substituted in the ring, either singly or in combination, were prepared, and their autoxidation rates measured ae 100OC. Whereas sec-butylbenzenc oxidized in less than 24 hours, all of the substituted compounds, except 4-sec-butyl-4 '-tert-butylbiphenyl, were stable for a t least 100 hours. The latter compound, however, oxidized a t a much slower rate than see-butylbenzene. T h e stability of these compounds was attributed to autoinhibition. This is the resultant when the tendency to increase oxidation rate by electron-donating substituents is outweighed by the effectiveness of the inhibitor formed. The inhibitors are presumably hydroxybiphenyls or terphenyls and are a decomposition product of the hydroperoxide produced via autoxidation at the tertiary carbon. As confirming evidence that inhibitors are formed, it was found that 4-src-butylbiphenyl and 4-see-butyl-4'-methoxybiphenyl in mixtures with sec-butylbcnzene exerted a distinct oxidation-inhibiting effect on the latter. Most of the compounds were found to be nonspreading fluids.
NEW FLAME-RETARDANT POLYESTER SYSTEM BASED ON 2,3-BIS(ETHYLENE CARBOXY)-l,4,5,6,7,7,-HEXACHLOROBICYCLO[2.2.1]d-HEPTENE
Helen E. Mertuoy and Henry Gisser, Pitman-Dunn Research Laboratories, Frankford Arsenal, Philadelphia, Pa. 79737
A new chlorinated dibasic acid, 2,3-bis(ethylene carboxy)-1,4,5,6, 7,7 hexachlorobicyclo[2.2.1]-5-heptene (111), was synthesized by oxidative ozonolysis of 1,10,11,12,13,13-hexachlorotricyclo[8,2.
IND.ENG.CHEM.PROD.RES.DEVELOP. 6,108-112 (1967) (Continued on page 98) VOL. 5 9
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BRIEFS OXYPROPYLATION OF GLYCEROL.
A STUDY OF VARIABLES
The oxypropylation of glycerol in the presence of alkaline catalyst has been studied in a semibatch operation. Initial catalyst concentration was varied from 0.22 to 2.3 weight yo KOH, temperature was varied from 220' to 270 O F., and agitation speed was varied from 50 to 200 r.p.m. The rate of reaction was shown to increase with increase in all three variables. The most significant variable was catalyst concentration, which gave a fourfold increase in reaction rate. Carl W. Yost, C . A . Plank, and E. R. Gerhard, University of Louisville, Louisuille, K y . IND. END.CHEM.PROD. RES.DEVELOP. 6, 113-115 (1967) QUATERNIZATIONS OF TRIETHYLAMINE AND TRIETHANOLAMINE WITH EPICHLOROHYDRIN
An investigation of cellulose-epoxide reactions, many of which are catalyzed by Lewis bases, necessitated a study of the reactions between epichlorohydrin and triethylamine or triethanolamine at room temperature. Preparation of the simple glycidyl quaternary chlorides has not been found feasible because triethylamine continues to react to form 2-hydroxytrimethylene-l,3-bis(triethylammonium chloride), which has been isolated for the first time in good yield. The triethanolamine, while initially quaternizing with epichlorohydrin, dimerizes to form [2,5-$-dioxanylenebismethylene] bis[tris( 2-hydroxyethy1)ammonium chloride], which was isolated in high yield. Physicochemical data have been used as the basis of mechanisms postulated for both reactions. John B. McKelvey, Ruth R. Benerito, and Truman L. W a r d , Southern Regional Research Laboratory, N e w Orleans, L a . IND.END.CHEM.PROD.RES.DEVELOP, 6, 115-120 (1967) BRASSYLIC ACID FROM OZONOLYSIS OF ERUCIC ACID
In bench-scale experiments, brassylic acid of 9890 purity was recovered in 70% of theoretical yield by ozonolyis of erucic acid. Alternatively, dimethyl brassylate of 95% purity was isolated in 88% yield. Brassylic acid of 95y0 purity was produced in a continuous 7-day pilot-plant process, but the achievable yield demonstrated in the laboratory was not realized in this preliminary scaleUP. H . J . Nieschlag and I. A . Wolff, Northern Regional Research Laboratory, U. S. Department of Agriculture, Peoria, Ill., and T . C . Manley and R. J . Holland, Welsbach Corp., Philadelphia, Pa. IND.ENG.CHEM.PROD.RES. DEVELOP. 6, 120-123 (1967) SPECIAL GRADE RDX FOR EXPLODING BRIDGE WIRE INITIATORS
Processing techniques have been developed which make it practical to manufacture exploding bridge wire (EBW) initiators with minimum firing voltages of about 1000 volts on a 0.6-microfarad capacitor and with standard deviations of less than 30 volts, using R D X (hexahydro-l,3,5-trinitro-s-triazine)recrystallized in a process which closely controls particle size and particle shape. Because of the nature of the particles, the sensitivity of the R D X charges is not affected by severe vibrations that simulate missile flight. Either R D X or PETN can be used in EBW initiators, but very little usage of R D X with exploding bridge wire ordnance has been described in the literature, although other workers have indicated its feasibility. R D X is somewhat more insensitive in the impact test than PETN and has a higher melting point and higher explosion temperature. Sensitivity of detonators loaded with PETN shifts approximately 40% when samples are conditioned a t 212' F., but no sensitivity shift is detected for RDX-loaded detonators conditionded at the same temperature. These facts indicate that R D X is a better explosive than PETN for use above 200" F. M . T . Hedges and W . B. Freeman, Ordnance Section, M a r t i n Marietta Corp., Orlando, H a . IND.ENG.CHEM.PROD.RES. DEVELOP.6, 124-126 (1967). AROMATIC STRUCTURES IN ASPHALT FRACTIONS
Solvent-derived fractions of a Venezuela residue were examined for elemental analysis, molecular weight, softening point, NMKj ESR, and x-ray diffraction. Observations agreed in general with previous reports on relation of composition to molecular weight; 98
INDUSTRIAL AND ENGINEERING CHEMISTRY
and to the layered structures of asphaltene pseudo-crystallites. The aromatic content was found to exist as condensed structures of three or four rings in oil and six to 16 rings in resins, while i n asphaltenes of up to 7500 molecular weight 32 to 105 rings are divided into islands of 16 to 20 condensed rings linked by saturated structures. Aromaticity of the asphaltenes (50 to 54%) was nearly constant over the molecular weight range 2500 to 7500. S. W . Ferris, E. P . Black, and J . B. Clelland, Sun Oil Co., Marcus Hook, Pa.
IND.ENG.CHEM.PROD.RES.DEVELOP. 6, 127-132 (1967) PERFORMANCE OF ODD- AND EVEN-CHAIN PURE ALCOHOL MONOLAYERS IN WATER EVAPORATION RETARDATION
Specially purified samples of odd and even saturated fatty alcohols, CIZ-C~O, were prepared and analyzed. Evaporation rate tests were performed systematically on water surfaces protected with monomolecular films of the purified alcohols, using a precision, specially designed, laboratory apparatus on which modifications and improvements had been made. This apparatus and method, used over the past 9 years, give reproducible results in laboratory studies, and indicate performance expected in mono-molecular film application on outdoor reservoirs. Detailed results are given for nine alcohols. A search of the technical literature disclosed no appreciable studies of odd carbon chain alcohols as reservoir evaporation retardants. When the evaporation retardation properties of the alcohols tested are expressed in terms of per cent water savings, a linear relationship with increasing carbon chain length is observed, from 18% for C12 to 65% for CZO. A correlation between evaporation rates expressed in terms of specific evaporation resistance, r, from the present study and those of others, shows agreement, even though the methods were widely different.
Edward R. Noe and Russell G. Dressler, Trinity University, San Antonio, T e x. IND. ENG.CHEM.PROD.RES.DEVELOP. 6,132-137 (1967) PREPARATION OF PURE CHLORINE DIOXIDE. REACTIONS OF CHLORINE OR SODIUM HYPOCHLORITE WITH SODIUM CHLORITE IN THE PRESENCE OF ACETIC ANHYDRIDE
Pure chlorine dioxide is generated when 1 mole of acetic anhydride is allowed to react with 1 mole of sodium chlorite in aqueous solution. When the initial concentration of sodium chlorite is maintained between 0.6 and 1.4 grams per liter, the yield of chlorine dioxide is about 52%. The stoichiometry of the reactions corresponding to the process is discussed. When 1.1 to 1.2 moles of acetic anhydride are introduced into an aqueous solution containing 1 mole of sodium chlorite in the concentration range of 0.6 to 1.4 grams per liter and 0.45 to 0.5 mole of active chlorine (either chlorine or sodium hypochlorite), pure chlorine dioxide is produced in about 95y0 yield. The reaction is suited for continuous operation. The scope and limitations of the process are discussed.
W i l l y Masschelein, Service Laboratories de la Compagnie Intercomrnunale Bruxelloise des E a u x , Brussels, Belgium IND.END.CHEM.PRODUCT RES.DEVELOP. 6, 137-142 (1967) CATALYTIC HYDROGENATION OF BUTYRONITRILE
Nickel, cobalt, platinum, palladium, rhodium, and ruthenium catalysts were tested for the hydrogenation of butyronitrile to amines (butylamine, dibutylamine, and tributylamine). The relative amounts of primary, secondary, and tertiary amines formed, catalyst activities, and resistance to inhibition were of particular interest. Methanol and water were compared as solvents, and the effect of alkaline additives was determined. Nickel and cobalt appear to be the best catalysts for the preparation of a primary amine, rhodium best for secondary amine preparation, and platinum and palladium best for tertiary amine preparation. The mechanism of the reaction and the effect of added bases on the product distribution are discussed.
Harold Greenjeld, Uniroyal Chemical Division, Uniroyal, Inc., Naugatuck, Conn. IND.ENG.CHEM.PROD.RES.DEVELOP, 6,142-144 (1967)
