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LIGHT SCATTERING BY PIGMENTARY RUTILE IN POLYMERICFILMS
Macroscopic scattering cross sections were calculated for polydisperse rutile suspended i n a polymeric film of refractive index 1.5 for wavelengths of 0.420, 0.560, and 0.590 micron, corresponding to blue, green, and red light, respectively. Maximum for green scattering (corresponding to the tinting strength of pigmentary rutile) occurred a t a mean diameter of 0.27 micron. Maximum for the difference between blue and red (corresponding to the undertone) occurred a t a diameter of 0.135 micron, and the minimum between 0.3 and 0.4 micron. Magnitudes of these extrema diminished with increasing widths of the particle size distribution.
R. A . SlejeQs and W . F. Sullivan, Titanium Pigment Division, National Lead Go., South Ambcy, A‘.J. 08879 I N D .ENG.CHEM.PROD.RES.DEVELOP. 9,266-271 (1970)
ACTIVITY AND SELECTIVITY OF HYDROTREATING CATALYSTS
Among the elementary reactions involved i n hydrotreatment of petroleum fractions and occurring without appreciable decrease i n mean molecular weight, most frequently encountered are hydrogenation of unsaturated compounds, and isomerization and hydrogeiiolyses of the small proportion of molecules containing heteroatoms such as sulfur, nitrogen, and oxygen. I n most cases, the catalysts involved are bifunctional-i.e., hydrogenatingdehydrogenating activity is produced by associating nickel Or cobalt sulfides with sulfurized molybdenum or tungsten compounds, and acidic activity is generally due to the carrier (silica, alumina, silica-alumina). For each type of hydrotreatment, both functions must be optimized. An initial approach to optimization was made by simultaneously bringing about hydrogenation of toluene and cyclohexene, hydroisomerization of cyclohexane, and hydrogenolysis of thiophene and pyridine. Changes in catalyst nature and composition involve considerable variations in the relative reactivities of these reactants. O n the basis of these results, it is possible to select the most suitable catalyst for a specific hydrotreatment. Some practical examples are given.
S.P. Ahuja, LM.L. Derrzen, and J. E. L e Page, Institut Frangats du Pitrole, 92 Rued-Malmaison, France IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 272-281 (1970)
POLYMER COATINGS. CONCEPTS OF SOLVENT EVAPORATION PHENOMENA
Advances i n phenomenological understanding have generally been a result of improvements i n the state of the a i t based on practical experience. In recent years more theoretical interest has been directed toward understanding solvent evaporation during polymer film formation and a clearer picture of this complex process has evolved. This is presented i n detail here, in the hope that the more theoretically minded reader will find satisfaction i n the reduction of theory to practice, and the coatings formulator will discover ustful simple tools and concepts to help solve daily problems.
Charles M . Hansen, P P G Industries, Inc., Sjringdale, Pa. 15144 IND. ENG.C H E MPROD. . RES.DEVELOP. 9,282-286 (1970) 62
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FLOW PROPERTIES OF PVC PLASTISOLS
Two PVC samples were studied i n plastisol form by determining viscosities on a cone-and-plate viscometer, over a wide range of concentrations, temperatures, and shear stresses. The particles were analyzed for shape and size distribution by electron microscopy, and found to represent bimodal spherical systems. The interaction between polymer and dispersant was studied by using two plasticizers-one reactive, one inert. The apparent viscosities of stable plastisols a t any shear stress may be described by known two-parameter equations, such as those of Mooney and Eilers. From the physical viewpoint, the empirical parameters, suitably corrected, represent intrinsic viscosity and packing volume. The corrections allow for increase of the kiscosity of the dispersing phase (measured by ultracentrifuge) due to partial polymer dissolution, and of the volume concentration due to swelling. The two parameters tend to their theoretical values a t high shear stress. Simplified relationships between viscosity and wcight concentration are included for practical use.
Arie R a m and Z v i Schneider, Technzon-Israel Institute of Technology, Haifa, Israel
IND. ENG.CHEW.PROD. RES.DEVELOP.9,286-296 (1970)
PROPERTIES OF MONOCHLOROSTYRENEAS A VINYL MONOMER
The properties of monochlorostyrene (MCS) are compared with those of styrene, and advantages of using MCS i n certain applications are discussed. MCS homopolymerizes 1.34 to 13.0 times faster than styrene, depending on the method of initiation and the isomer used. T h e polymerization rate increases after p a r t i d conversion to polymer and the magnitude of this “gel” effect is a function of initiator concentration. Copolymerization rate data show that polymer formation is faster for MCS than styrene in mixtures with several selected comonomers. MCS monomercopolymer composition curves reveal more nearly ideal copolymer compositions with certain important comonomers such as 1,3butadiene. MCS can be substituted for styrene in fire-retardant polymer compositions. I t burns i n air but can be made fireretardant by addition of small amounts of Sbz03 or copolymerization with about 370 vinylidene chloride. Its use in fire-retardant high-impact thermoplastics and in unsaturated polyester resins is discussed. MCS exhibits interesting behavior in cellular plastics applications. Expandable poly-MCS beads retain volatile organic blowing agents better than polystyrene. Foams of poly-MCS resist collapse for prolonged periods a t temperatures as high as 225°C. A new concept for using these foams in expandable core molding is discussed.
R. J.Doltnski, R. M . .Vowak, and L . C. Rubens, The Dow Chemical Go., Midland, Mich. 48640 IND.END.CHEM.PROD.RES.DEVELOP. 9, 292-296 (1970)
CYCLOALIPHATIC EPOXY RESINS WITH IMPROVED STRENGTH AND IMPACT COUPLED WITH HIGH HEAT-DISTORTION TEMPERATURE
T h e toughness of cycloaliphatic epoxy resins, measured by the impact strength and area under the stress-strain curve, can be significantly improved through modification with several elastomeric materials containing functional groups. The toughness of these systems is proportional to the concentration of the elastomer.
BRIEFS Twofold to greater than tenfold improvements in impact have been obtained by the addition of 5 to 35y0 carboxyl-terminated butadiene-acrylonitrile copolymer, without significantly degrading the heat-distortion temperature. Simultaneous improvements were obtained in tensile strength and elongation. These systems have produced glass cloth-reinforced composites with high tensile strength, under both static and dynamic conditions. A. C. Soldatos and A: S . Burhans, Union Carbide Gorp:, Bound Brook, N . J . 08805
lent amount of sodium acetate shifts the equilibrium completely to the ?r-allylic complex. Specifically deuterated olefins can be obtained by dissolving the olefins in a solution of sodium chloropalladite in CHICOOD. Addition of sodium acetate after completion of the exchange affords the deuterated T-allyl complexes. The scope of the reaction and the mechanism are discussed.
H. C. Volger, KoninklijkelShell-Laboratorium,Amsterdam, Holland IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 311-317 (1970)
IND. ENG.CHEM.PROD.b s . DEVELOP: 9,296-300 (1970)
RADICAL POLYMERIZATIONOF ALLYL ISOCYANURATESWITH VINYL MONOMERS
NICKEL-ZEOLITECATALYST. INHIBITION OF SUSCEPTIBILITY TO SINTERING AND POISONING
The radical copolymerization of N,N'-bis- and N,N),N"-tris(2-hydroxy-3-allyloxypropyl) isocyanurates (DHAIC and THAIC) with methyl methacrylate (MMA) and styrene (S) was studied and the rate constants were evaluated. Increase in the functionality of allyl isocyanuric monomers was accompanied by growth of the rate constants for S and MMA. M M A copolymerizes with D H A I C and T H A I C a t a substantially higher rate than with S. The maximum completeness of copolymerization of S decreased at higher concentrations of T H A I C in the initial mixture, while that of MMA passed through a maximum.
The metal-dispersion and related poison-resistance and size-selective characteristics of nickel can be destroyed by reduction in 1 weight yo nickel-loaded, Type Y zeolite to render it catalytically active. Electron microscope and x-ray studies show that the reduced nickel migrates to form larger crystallites with increasing severity of pretreatment. A significant portion of these crystallites appears on the outside surface, destroying possible size-selective characteristics. Mild pretreatment reduces the rate of crystal growth and produces a catalyst with slightly improved poison resistance. By incorporating Crz03 into the catalyst, a greatly improved poison-resistant catalyst is obtained.
Hristo Alaminov, Marin Michailov, and Tanja Michneva, Research Institute for the Chemical Industry, Soja, Bulgaria IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 301-304 (1970)
HYDROXYMETHYLATEDDERIVATIVES OF RESIN ACIDS. POLYURETHANEFILMS
J . D . Lawson and H. F. Rase, University of Texas, Austin, Tex. 78772 IND. ENC.CHEM.PROD.b s . DEVELOP. 9,317-324 (1970)
USE IN
New polyols derived from levopimaric acid involve the modification of polypropylene glycol ethers by reaction of propylene oxide and 12-hydroxymethyldihydroabietic acid and 12-hydroxymethyltetrahydroabietanol. Varying amounts of these glycols and the monopropylene glycol ester of the hydroxy acid were blended with trimethylolpropane, 1,4-butanediol, and polypropylene glycol and reacted with toluene diisocyanate. Ethylene glycol adipic acid polyester was modified by incorporating 12hydroxymethyltetrahydroabietanol in the polyester chain. The modified polyester was blended with a poly(ethy1ene adipate) glycol (molecular wt. 2000) and 1,4-butanediol, giving glycol mixtures which reacted also with T D I . Clear strong polyurethane films from both glycol systems containing 5, 10, 15, and 20% resinyl moiety were prepared and their polymer properties examined. Incorporation of the moiety gave strength, toughness, and stiffness to films which otherwise would have been soft and tacky. The formulations of some films with fairly low temperature and elastomeric properties were reported which contained (A) 20 to 25y0 of resinyl materials i n polyol mixtures having high average hydroxyl equivalent values, and (B) less T D I because of these high equivalent values. T h e work makes a significant contribution to urethane chemistry by describing some potentially inexpensive raw materials.
J . B. Lewis and G. W. Hedrick, Naval Stores Laboratory, US.Department of Agriculture, Olustee, Fla. 32072
OXIDATION OF PROPYLENE TO ACRYLIC ACID OVER A CATALYST CONTAlNlNG OXIDES OF ARSENIC, NIOBIUM, AND MOLYBDENUM
Propylene was oxidized by air to acrylic acid over catalysts containing oxides of arsenic, niobium or tantalum, and molybdenum, Acetic acid was a by-product, but only a trace of acrolein was in the product. Preferred catalysts contained 5 to 10% arsenic oxide, 10% niobium oxide, and 20% molybdenum oxide on a support such as silica. Conversions to acrylic acid of a t least 20 mole % were obtained in a single pass a t a yield of 50 mole yoand a production rate of 10 lb./cu. ft.-hr. Two reactors were connected in series, with product condensation and addition of make-up air between the reactors. A conversion to acrylic acid of 44% a t 53% yield and a rate of 3.4 lb./cu. ft.-hr. resulted. A preferred catalyst was made by preparing niobium and molybdenum oxides on silica, charging it to a reactor, and treating with arsenic trioxide. Although the catalysts lost arsenic trioxide slowly during use, stable activity was obtained by adding arsenic trioxide to the feed. A catalyst life in excess of 1100 hours in a 6-inch-diameter fluid-bed reactor was shown. Simple equations relating responses to experimental conditions are presented for this catalyst.
W . E. Campbell, E. L. McDaniel, W . H . Reece, J . E. Williams, and H. S. Young, Tennessee Eastman Co., Kingsport, Tenn. 37662 IND.ENC.CHEM.PROD.RES.DEVELOP.9, 325-334 (1970)
IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 304- 310 (1970)
SYNTHESIS OF ?r-ALLYLICPALLADIUM HALIDE COMPLEXES
r-Allylic palladium halide complexes, with a n alkyl or aryl group substituted a t the central carbon atom, can be obtained in high yields in a one-step synthesis by introducing the appropriate olefin into a sodium chloropalladite solution in glacial acetic acid in the presence of sodium acetate a t 85°C. The reaction proceeds via the ?r-olefinic palladium complex, which is in equilibrium with small amounts of the ?r-allylic complex. An equiva-
MORDENITE, ALUMINUM-DEFICIENT MORDENITE, AND FAUJASITE CATALYSTS IN CRACKING OF CUMENE
T h e adsorption and catalytic properties of H-mordenite with a conventional SiOz/A1203 ratio of 12 were compared to those of a highly aluminum-deficient mordenite with a ratio of 64. Cumene adsorption studies a t 200°F show that H-M(64) has a considerably larger adsorption capacity and a greatly decreased resistance to adsorptive diffusion, Cumene cracking was studied a t 400°, 450°, VOL. 6 2
NO. 9
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BRIEFS 500", and 550°F for extended periods of time to determine deactivation rates. The activity ( A ) of both catalysts decreases with time according to the relationship, A = atn, where n is approximately equal to -0.5 a t temperatures of 450" and above. The aluminum-deficient mordenite, H-M(64), is considerably more active than H-M(12), which is attributed to its lower diffusion resistance. The apparent activation energy of 11 kcal per mole is the same for both catalysts and is lower than that observed on other catalyst systems indicating diffusional limitations. Steaming of catalysts a t 1400'F greatly reduces activity. Comparable results with hydrogen-faujasite indicate unusually high deactivation a t 400 OF but relatively low deactivation a t 525 OF.
P. E. Eberly, Jr., and C. N . Kimberlin, Jr., Humble Oil and Rej%ing Go., Baton Rouge, La. 70821 IND.EKG.CHEM.PROD.RES DEVELOP.9, 335-340 (1970)
CHEMICALS FROM COAL
T h e history of chemicals from coal-primarily ammonia, the light aromatics (benzene, toluene, and xylene), tar acids, tar bases, tar or pitch, gas, and coke-is reviewed u p to 1962. Until about 1940 in the United States these were derived from coal through high-temperature by-product carbonization. When the 1940's brought increased demand, petroleum and natural gas were used as raw materials, and since that time have dominated.
CATALYTIC HYDROGENATION OF MULTlRlNG AROMATIC COAL TAR CONSTlTUENTS
I n a n attempt to increase the yields of benzene derivatives from coal hydrogenation, several parameters are investigated as they affect hydrogenation of anthracene : temperature, hydrogen pressure, catalyst, and reaction time. Below 250°C, yields of 9,lOdihydroanthracene may approach 807, weight. Continued hydrogenation yields 1,2,3,4-tetrahydroanthracene accompanied by a loss of hydrogen from the 9 and 10 positions. Further hydrotreating yields 1,2,3,4,5,6,7,8-octahydroanthracenewith cracking to naphthalene derivatives concurrent with or subsequent to the formation of the octahydroanthracene. Continued hydrogenation of the naphthalene derivatives yields benzene derivatives and gases. No evidence is observed of direct hydrocracking of the 9,lO-dihydro derivative. Hydrogenation of anthracene is firstorder with respect to anthracene concentration with an activation enthalpy of 3.8 kcal per mole and no activation entropy of -58 entropy units. T h e rate-controlling step appears to be orientation and adsorption of the reactants on the catalyst surface. Problems associated with attempts to hydrocrack the dihydro derivatives are discussed. W. H . Wiser, Surjit Singh, S. A . Qader, and G. R. Hill,Uniuersip of Utah, Salt Lake CiQ, Utah 841 12
IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 350-354 (1970)
H. R. Batchelder, Battelle Memorial Institute, Columbus, Ohio 43201 IND.ENG.CHEM.PROD.RES. DEVELOP.9, 341-343 (1970)
CONVERSION OF COAL TO ACETYLENE IN ARC HEATED HYDROGEN
The commercial potential of a process of converting coal to acetylene was demonstrated. Critical parameters such as acetylene yield, product stream concentration, and energy consumption were studied as functions of gas enthalpy and coal feed rates and their effect on the projected selling price of acetylene was evaluated. T h e plasma process is generally competitive with current commercial methods of producing acetylene and suggested modifications show promise of additional improvements.
Richard E. Gannon, Val J . Krukonis, and Theodore Schoenberg, AVCO Corp., Lowell, Mass. 01851 IND.ENG.CHEM.PROD.RES.DEVELOP, 9, 343-347 (1970)
HYDRODESULFURIZATION OF BITUMINOUS COAL CHARS
Illinois No. 6 char was desulfurized by hydrotreatment at about 1600°F. The char initially contained about 27, organic sulfur and 1% inorganic sulfur (FeS) from pyrolysis of pyrite. Removal of the organic sulfur is rapid and limited primarily by a n equilibrium between H2S in the gas and sulfur in the char. The reaction of the FeS with Hz proceeds more slowly than would be expected from equilibrium. The rate-limiting step appears to be either the inherent solid-gas kinetics, or the diffusion of H2S through the reacted shell of iron surrounding the FeS. About log', of the sulfur content of the char was not removed even by prolonged hydrotreatment; however, it is possible to remove over 80% i n 20 minutes. Because of the high equilibrium ratio of H2 to HeS, a n H2S acceptor material would have to be admixed with the char bed to have a commercially viable process.
C. A . Gray,
IM.E. Sacks, and R. T . Eddinger, FIMC Corp., Princeton,
A'. J . 08540
1x11. ENG.CHEM. PROD.RES.DEVELOP. 9, 354-361 (1970) PARTIAL DECARBOXYLATION OF COAL AROMATIC ACIDS BY TRANSITIONMETAL COMPLEXES
I n the presence of carbon monoxide and hydrogen, dicobalt octacarbonyl, C O ~ ( C O )catalyzes ~, the selective partial decarboxylation of phthalic acid or anhydride and substituted phthalic acids or anhydrides to yield the corresponding benzoic acids. I n the case of pyromellitic acid, the CoZ(C0)s is consumed in the decarboxylation, becoming a reactant instead of a catalyst. By using derivatives of C O ~ ( C Oin ) ~which one or two carbonyl groups are replaced by trialkylphosphine ligands, it is possible to preserve the catalytic activity of the complex. Such a catalyst will selectively decarboxylate benzenepolycarboxylic acids containing carboxyl groups on adjacent carbons to mixtures of isophthalic and terephthalic acids. By applying this reaction to a mixture of acids obtained by alkaline oxidation of coal, char, or other coal derivatives, it is possible to obtain a product rich in isophthalic and terephthalic acids.
Increasing U.S. sulfur needs will probably be met largely by desulfurization of fuels. Twenty per cent of U.S. coals contain over 3YG sulfur. I n the manufacture of pipeline gas from 1.5 and 4.4c0 sulfur coals, during pretreatment 15 to 25y0 of the sulfur is converted to sulfur dioxide; most of the rest is converted to H2S during hydrogasification. The economics of sulfur recovery from H2S only and from joint H2S and SO2 by the Claus reaction are presented. Over-all sulfur recoveries are 91 and 81c0 for low- and high-sulfur coals. I n the $20 to $40 per ton sulfur price range, the pipeline gas price is lowered from 0 to 1 and from 1.5 to 5.5 cents per million B.t.u., for the 1.5 and 4.470 sulfur coals, respectively.
Sidnq Friedman, S. R. Harris, and lroing Wender, Pittsburgh Coal Research Center, Bureau of Mines, Pittsburgh, Fa. 15273
C. L. Tsaros, J . L. Arora, and W. Bodle, Institute of Gas Technology, Chicago, Ill. 60616
IND.END.CHEM.PROD.RES.DEVELOP. 9, 343-350 (1970)
IND.ENC.CHEM.PROD.RES.DEVELOP.9, 362-368 (1970)
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INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
SULFUR RECOVERY IN THE MANUFACTUREOF PIPELINE GAS FROM COAL
BRIEFS
ETHYLENE-STEAM REACTION INDUCED BY OZONIZER DISCHARGE
In the presence of a Siemens ozonizer discharge, ethylene and steam react exothermally to produce a large number of gaseous and liquid products. The effect of molar ratio, space velocity, pressure, temperature, and reactor power on ethylene conversion was determined. T h e gaseous products consist of hydrogen, carbon dioxide, carbon monoxide, and traces of hydrocarbons. The liquid fraction is more complex. I t contains at least 75 components, mostly paraffins, olefins, and oxygenates. T h e oxygenates are largely alcohols. T h e total product consists of C1 through ~ with Cg through Ca hydrocarbons approximately C I molecules, and n-butanol predominating. T h e experimental data indicate that ethylene conversion increases with steam-ethylene molar ratio, electrical power, and temperature, and decreases with increasing flow rate. There is no reaction at any condition in the absence of a discharge.
T . C. Rugfiel, P. F . Mossbauer, M . F. Ferrer, and Daniel Bienstock, Bureau of Mines, Pittsburgh, Pa. 15213 IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 369-376 (1970)
CARBON BLACK FEEDSTOCK FROM LOW TEMPERATURE CARBONIZATION TAR
Low temperature carbonization tar provides a high-volume source of aromatic feedstock for carbon black production. The yield from a typical 10,000-ton-per-day coal processing unit is estimated to be 4000 barrels per day of residual oil, enough to supply a 200,000,000-pounds per year carbon black plant. Selective hydrotreating purifies the raw tar by removing oxygen, nitrogen, and sulfur to yield a full range highly aromatic product from which carbon black feedstock can be recovered by fractionation. The heteroatom conversion produces a feedstock comparable to that currently available from petroleum. Hydrocarbon saturation is held to a minimum to achieve low hydrogen costs and produce more valuable aromatic distillate by-products. Pilot scale production of good quality intermediate surface area furnace type carbon black has been attained starting with raw tar. A preliminary evaluation, based on pilot data, indicates a reasonable profit on the over-all process, when competitive values are placed on the carbon black feedstock and by-products.
D . C. Berkebile, H . N. Hicks, and W . S. Green, Ashland Oil, lnc., Ashland, Ky. 41101 IND.ENG.CHEM.PROD.RES.DEVELOP. 9,376-381 (1970)
mercial blacks. A patent has been granted to the U.S. Government. Cost studies indicate that carbon black could economically be produced from coal.
G. E. Johnson, W . A . Decker, A . J . Forney, and J . H. Field, Bureau of Mines, U S . Department of the Interior, Pittsburgh, Pa. 15213 IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 382-387 (1970)
KINETICSOF FORMATION OF HYDROGENCYANIDE FROM METHANE AND AMMONIA IN A MICROWAVE FLAME
T h e reaction of CH4 with NHa to produce HCN was studied a t pressures of 10 and 25 torr in a microwave plasma. Operating conditions covered a range of flow rates from 60 to 1050 cc. per minute. N T P and microwave power from 70 to 500 watts, over which range the conversion to HCN varied from 9 to 78%. The theory of diffusion-controlled operation was applied to this discharge, leading to the conclusion that E , / p and the average electron energy remained constant for operation a t a given pressure, Furthermore, specific power was unchanged despite changes in the total power and thus the electron density did not vary. These results justified replacing reaction time with specific energy as a correlating variable in the rate equations. Production of H C N appeared to be a first-order series reaction mechanism in which the rate constants a t both pressures were equal to 0.035 liter per watt hour.
Thorkild Juul-Dam and N . F. Brockmeier, University of Texas, Austin, Tex. 78712 IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 388-397 (1970)
TITANIUM DIOXIDE PIGMENT. EXTRACTION OF CHROMIUM
LIQUID-LIQUID
Chromium, a trace impurity that degrades the whiteness of titanium dioxide pigments, was removed from concentrated, highly acidic, industrial titanium sulfate solutions by liquid-liquid extraction. The chromium(II1) in sulfuric acid solutions of ilmenite ore was oxidized with sodium chlorate to extractable anionic chromium(V1) species. More than 99% of the chromium was removed by multiple batch extractions with 5 vol. yo Alamine 336 in xylene; titanium losses were less than 1yo. The chromium content of extracted solutions containing 110 grams of T i 0 2 per liter was decreased to less than 1 ppm on the T i 0 2 basis. This is below the level where the whiteness of titanium dioxide pigments is adversely affected. Commercially available secondary, tertiary, and quaternary amines were investigated as chronium extractants. Pretreatment of extractants was necessary for complete removal of chromium.
J . P. Bonsack, Glidden-Durkee Division, S C M Corg., Baltimore, M d . 2 1226 IND.END. CHEM.PROD.RES. DEVELOP. 9, 398-403 (1970) CARBON BLACK PRODUCED BY THE PYROLYSIS OF COAL
Carbon black equivalent to commercial grade has been produced by the pyrolysis of coal a t 1250' to 1350°C at the U.S. Bureau of Mines, Pittsburgh, Pa. The maximum yield of black obtained from Pittsburgh seam coal (hvab rank) is about 20% by weight based on the raw coal fed. The work has been done on a benchscale electrically heated unit with a maximum coal feed rate (70y0 - 200 mesh) of 3 pounds per hour. By-products are a coal char which could be burned for power generation and by-product gas (8 to 9 cu. feet per pound of coal) containing 80% hydrogen. The carbon black product has been evaluated in chemical and rubber compounding tests by industrial companies and found to be equivalent in quality to the fine thermal (FT) grade of com-
4-ESTERS OF TRIMELLITIC ANHYDRIDE
Three methods were evaluated for the selective 4-esterification of trimellitic anhydride : transacidolysis with acetates, acylation of a hydroxy compound with trimellitic anhydride acid chloride in the presence of a tertiary base, and thermal reactions with alcohols. T h e second method is most general for the selective esterification; yields were particularly high with phenols. I n the thermal esterifications, free trimellitic anhydride and its triester were always by-products, suggesting a series of equilibria involving transacidolysis as the key step. Twenty-four 4-esters of trimellitic anhydride are described. Selective hydrolysis of the anhydride VOL. 6 2
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BRIEFS
groups gives 4-esters of trimellitic acid; the long-chain esters formed strong monomolecular film on water.
COMMUNICATION
Imre Puskas and E. K . Fields, Amoco Chemicals Gorp., Whiting, Ind. 46394
IDENTIFICATION OF CRUDE OILS BY THEIR GAMMA SPECTRA FOLLOWING NEUTRON IRRADIATION
IND. ENC.CHEhf. PROD. RES.DEVELOP. 9,403-407 (1970)
HEAVY METAL TEREPHTHALATES
Simple terephthalates of divalent iron, cobalt, nickel, copper, and manganese and of silver and lanthanum were prepared by metathesis from sodium terephthalate and the corresponding metal ion solutions. F e ( I I I ) , C r ( I I I ) , and Ni formed insoluble basic salts. The basic ferric terephthalate gave iron oxide and free terephthalic acid on extensive hydrolysis. Fe(I1) and Co(I1) terephthalates split off terephthalic acid and became dimetallic basic terephthalates a t 270°C in water. The water solubilities, stabilities toward acetic acid, and compositions were investigated. The infrared spectra and x-ray diffraction patterns are presented. The probable forms of iron impurities formed during the manufacture and purification of terephthalic acid are discussed.
Fawzy G. Sherif, Eastern Laboratory, E.I. du Pant de hTemours @ Co., Inc., Gibbstown, N.J . 08027 IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 408-412 (1970)
High resolution gamma-ray spectrometry in the range of 0 to 4 Mev, following neutron irradiation of crude oil, was investigated as a means of identifying the oil’s origin. Traces of heavy metals (which have large thermal neutron activation cross sections) would in general vary according to reservoir location, yielding a different gamma spectrum for different oils. T h e method is applied to identifying the reservoir responsible for the oil spill into the Santa Barbara Channel. The conclusions compare favorably with those using conventional chemical techniques, and the time and effort devoted to the analysis are reduced considerably.
H . B. Eldridge and J . P . Flaherty, University of Wyoming, Laramie, Wy0,82070 IXD. EKG.CHEY.PROD.RES.DEVELOP. 9,422-423 (1970)
CORRESPONDENCE
Comments on an article on oxidation of aromatic hydrocarbons with H B r / H 2 0 promoters.
3-METHYL- AND 3-ETHYL-m-TERPHENYL AND RELATED CYCLOHEXANE DERIVATIVES OF m- AND p-TERPHENYL
c‘. M . Selwitz, Gulf Research t Y Deuelofiment Go., Pittsburgh, Pa. 75230 Ephraim Kehat, Technion-Israel Institute of Technology, Haifa, Israel
The syntheses of 3-methyl- and 3-ethyl-m-terphenyl and intermediates i n the preparation of these compounds and 4-methyl-pterphenyl are described. Dehydrogenation of l-phenyl-3-(mtolyl)-1,3-cyclohexadiene, yielded disproportionated products, 3-methyl-m-terphenyl and l-phenyl-3-(m-tolyl)cyclohexanein the expected stoichiometric ratio of 2 to 1. l-Phenyl-3-(m-tolyl)cyclohexane was assigned a cis-ee conformation based on NMK data. afDehydrogenation of l-(4-biphenylyl)-4-methyl-l-cyclohexene forded disproportionated products, 4-methyl-fi-terphenyl and 1-(4biphenylyl)-4-methylcyclohexane i n a ratio of 2 to 1, indicating that disproportionation was the minor reaction, while dehydrogenation was the major reaction. The latter product, 1-(4-biphenylyl)-4-methylcyclohexane,was assigned a trans-ee conformation on the basis of the N M R data.
IND.ENG.CHEM.PROD.RES.DEVELOP.9, 424 (1970).
D. A . Scala, J . S.Adams, Jr., and A . E. Bekebrede, Monsanto Research Gorp., Everett, Mass. 0 2 1 4 9 IND.ENG.CHEM.PROD,RES.DEVELOP. 9,413-419 (1970)
COMMUNICATION ANHYDROUS ALUMINUM BROMIDE I N ORGANIC SOLVENTS
Aluminum bromide, a Lewis acid catalyst, is used in isomerization. Its functional usefulness could be increased if it were in solution. I t is soluble in many solvents. Under ambient conditions, molten aluminum bromide was added to cyclohexane to form concentrated anhydrous aluminum bromide solutions for convenience in handling and metering. Disproportionation was retarded for 15 to 30 days by addition of 0.5 to 1 volume yo of an aromatic compound such as benzene or 0.5 weight yo of 1,1,3-tris(3-hydroxyphenyl)propane. Stability is affected by storage temperature, amount of moisture in the chemicals and exposure to air, light, or ambient moisture. Corrosiveness was investigated with several materials of construction.
P. M . Triuedi, Michigan Chemical Gorp., St. Louis,Mich. 48880 IKD.ENG.CHEM.PROD.RES. DEVELOP. 9,419-422 (1970) 66
INDUSTRIAL AND ENGINEERING CHEMISTRY
INTERACTION OF LIQUIDS AT SOLID SUBSTRATES ADVANCES IN CHEMISTRY SERIES NO. 87 Papers f r o m t w o symposia by the Division of Organic Coatings and Plastics Chemistry of the American Chemical Society. This volume includes twelve papers comprising t h e symposium on “The Interaction of Liquids a t Solid Substrates,” chaired by Allen L. Alexander. These papers include work on “coupling agents,” adhesion of polymers, organic/inorganic interfaces, and ultrasonic impedometry. Also included are four papers concerned with heparinized surfaces a t the blood/material interface which were part of the symposium on “The Medical Applications of Plastics,” chaired by R. I. Leininger.
212 pages with index
Clothbound
(1968)
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