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BARNACLE CEMENT: KEY TO 2ND GENERATION ANTIFOULING COATINGS
First generation antifouling coatings show depletion in time of toxic content by the slow leaching out into seawater. U p to three years effective fouling prevention on ships identifies such coatings. Second generation antifouling coatings will be characterized ultimately by a 10-year service life. This long period of antifouling effectiveness is feasible as a result of studies made on the attachment mechanism of barnacles, an important fouling type. .\t least four approaches will be made-namely, prevent initial mechanical attachment by utilizing specific chemicals, discourage attachment by using repellents, interfere with the hardening of the attachment cement, and develop surfaces of free energy values such that fouling cements cannot adhere.
John R. Saroyan, Elek Lindner, Carol A . Dooley, and Henry R . Bleile, Paint Laboratory, M a r e Island A’aual Shipyard, Vallejo, Calif.94592 IND.ENG.CHEM. PROD.RES.DEVELOP. 9, 122-133 (1970) OXIDATION AND AMMOXIDATION OF PROPYLENE OVER BISMUTH MOLYBDATE CATALYST
Research on the catalytic oxidation and ainmoxidation of propylene is described which led to the development of commercial processes for the production of acrolein and acrylonitrile. T h e initial research comprised a search for regenerable metal oxide “oxidants” of high activity and selectivity. This line of attack culminated in the discovery of a direct air oxidation catalyst based on bismuth molybdate, which gives high single pass conversion of propylene using near stoichiometric ratio of feeds. Conclusions are drawn from literature as well as from unpublished data in summarizing some of the important aspects of propylene oxidation and ammoxidation chemistry over bismuth molybdate catalysts.
James L. Callahan, Robert K . Grasselli, Ernest C . Milberger, and H . Arthur Strecker, T h e Standard Oil Company ( O h i o ) , Cleceland, Ohio 44128 IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 134-142 (1970) INFLUENCE OF STRUCTURE OF INITIAL COMPONENTS OF RADIATION CURING OF UNSATURATED OLIGOESTERS AND OLIGOESTERURETHANES
T h e radiation copolymerization of unsaturated oligoesters and oligoester-urethanes was investigated. T h e unsaturated oligoesters were synthesized from maleic anhydride, ethylene and diethylene glycol, phthalic anhydride, and endomethylenetetrahydrophthalic anhydride, adipic and sebacic acids being used as modifiers. Unsaturated oligoester urethanes of various free isocyanate group contents were produced by interaction of oligoethylene, oligodiethylene, and oligotriethylene maleates with tolylene, diphenylmethane, and hexamethylene diisocyanates. T h e relative rate of curing depends o n the structure of the oligomers, especially the monomers. I n the case of unsaturated oligoester-urethanes isocyanate groups participate in the curing reaction. I n radiation copolymerization both the yield of insoluble fraction and conversion of double bonds are higher than 68
INDUSTRIAL A N D ENGINEERING CHEMISTRY
in the presence of peroxide. Physical and mechanical characteristics, thermostability, and water and chemical resistance are, as a rule, higher for polymers obtained under the influence of high energy radiation.
S. I . Omel’chenko, :V. G. Videnina, V . G. M a b u s h o m , I . .V. Cheruefosoua, and G. A\’, Pyankob, Institute of High MoiPcular Chemistp, Kier?, USSR IND.ENG.CHEM. PROD.RES.DEVELOP. 9,143-146 (1970)
EFFECT OF ADDITIVE FUNCTIONALITY IN RADIATION CROSSLINKING OF POLYMERS. A SIMPLE MATHEMATICAL MODEL
.1 theoretical mathematical model of the effect of additive functionality on gel formation in a n irradiated polymer is presented. T h e simplified statistical approach is consistent with thc intuitive thought rhat there is a n optimum additive functionality. T h e model demonstrates this optimum to be 5 to 6 (analogous to 2l/1 or 3 vinyl groups). Similarly, an optimum concentration is found for initiation of gel formation. This simplified model may be further expanded to incorporate further constraints and more realistic assumptions.
L . D . iVichoL and G. R. Beibeco, Moleculon Research Cor$., Cambridge, Mass. 02142 IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 147-149 (1970)
EFFECT OF COMPOSITION POLYESTER COATINGS
IN RADIATION CURING OF UNSATURATED
Unsaturated polyester resins can be cured satisfactorily with high energy electrons. Styrene is a more efficient crosslinking monomer for unsaturated polyester molecules than ring-substituted styrenes, methacrylate, or dimethacrylates. T h e degree of unsaturation in the polyester chain, as well as the ratio of monomer to polyester unsaturation, is critical in obtaining a satisfactory cure at low dose. A styrenated 1,2-propylene glycol-maleic anhydride alkyd with a n alkyd unsaturation to monomer ratio of 1 to 0.6 gave satisfactory cure at 5 megarads. Dose rates above 2 megarads per second resulted in a lower conversion, at a given total dose, than lower dose rates. Dose fractionation (administering the total dose in two steps instead of one) gave a higher degree of conversion. These effects are explained in terms of competition among recombination, termination, and “chain” propagation mechanisms.
Gerhard J . Piefsch, American Cyanamid Co., Stamford, Conn. 06904 I N D . E N D . CHEM.
PROD.RES.DEVELOP. 9, 149-154 (1970)
ACRYLIC COPOLYMERS FOR RADIATION-CURED COATINGS
Acrylic copolymers containing pendant epoxy groups react with unsaturated acids to produce polymers which crosslink when exposed t o electron irradiation. T h e properties of coatings, prepared by exposing solutions of the polymers in vinyl monomers to 275-kilovolt electrons, depend upon the unsaturation content and
BRIEFS the chemical composition of the polymers. The hardness and solvent resistance increase and flexibility decreases when unsaturation increases. Compositional changes in the polymer influence these to a lesser degree but affect solution properties and longer term performance properties.
J . D . A'ordstrom and J . E. Hinsch, Industrial and Chemical Products DiuiJion, Ford Motor Co., Dearborn, Mich. 48121
IND.END.CHEM.PROD.RES.DEVELOP. 9, 155-158 (1970)
PETROLEUM COKE HANDLING PROBLEMS
Calcined petroleum coke is a n industrial carbon used as a raw material in the aluminum and graphite industries. From the time it is first formed as a by-product of petroleum refining until it is processed into elemental carbon it is handled many times. Extreme care must be exercised a t each point of handling to preserve the desired physical structure and required degree of purity. Recommended procedures are discussed in detail.
H . W . Nelson, Great Lakes Carbon Corp., N e w York, N . Y., 1 0 0 1 7 IND.END.CHEM.PROD.RES.DEVELOP. 9, 176-178 (1970) ELECTRON RADIATION CURING OF STYRENE-POLYESTER MIXTURES. EFFECT OF BACKBONE REACTIVITY AND DOSE RATE
Mixtures of styrene monomers with unsaturated polyesters of varying composition and molecular weight were irradiated with a 500-kv electron accelerator. The extent of cure was evaluated as a function of styrene content, polyester composition, and molecular weight by measuring volatile monomer and sol and gel content of the irradiated mixtures. Density of crosslinking in the cured material was qualitatively estimated from swollen gel measurements. T h e effect of dose rate on curing efficiency was also studied. All results were used to infer the mechanism of gel formation in the different solutions and under the various irradiation conditions. T h e applicability of the results to the design of coatings mixtures for high speed radiation curing is discussed.
Allan S. Hoffman, J o h n T . Jameson, Warren A . Salmon, Donald E. Smith, and David A. Tragejer, MassachusettJ Institute of Technology, Cambridge, M a s s . 02139 IND.ENG.CHEWPROD. RES.DEVELOP. 9, 158-167 (1970)
COKING OF COAL SOLUTIONS IN A LABORATORY COKE OVEN
The aluminum industry requires a large amount of high purity coke for the anodes used i n the reduction of alumina. Potential shortages of high quality petroleum coke have led to studies of methods of producing satisfactory coke from coal. The coking and calcining of centrifuged solutions of high volatile bituminous coal were studied by heating in the slot of a laboratory coke oven. The coke was produced in large strong lumps with properties that compared favorably with those of a calcined petroleum coke now used in alumina reduction cell anodes. T h e yield of coke in a 20-ton run of a coal in the laboratory coke oven agreed with the yield in retort studies conducted on the same coal a t 1000° by the Bureau of Mines. The coke oven provides a satisfactory method of producing calcined coke from coal solutions.
V . L , Bullough, L. 0 . Daley, and W. R. Johnson, Reynold? Metals Co., Shejield, Ala. 3 5 6 6 1
IND.ENG.CHEM.PROD.RES.DEVELOP.9, 179-182 (1970) PILOT PLANT PREPARATION OF POLYSTYRENE OF VERY NARROW MOLECULAR WEIGHT DISTRIBUTION
T h e availability of polymers of very narrow molecular weight distribution offers the potential of the detailed correlation of polymer properties with molecular weight. A series of polystyrenes, virtually monodisperse, covering the molecular weight range from 600 to 1,800,000, has been prepared in 30 pound batches. T h e preparative techniques, based on laboratory work performed a t Mellon Institute, are described. These polymers are of considerable utility to calibrate instruments and study molecular weight effects in fundamental and applied polymer research.
Timothy Altares, Jr., and E. L. Clark, Pressure Chemical Go., Pittsburgh, Pa. 1 5 2 0 1
IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 168-171 (1970)
EFFECT OF FILLERS O N WET COMPRESSIVE CREEP OF CELLULOSE ACETATE
Cellulose acetate desalination membranes undergo irreversible creep Wet compressive creep of films was used to study this phenomenon and to develop creep-resistant plastic compounds. A test unit was built to measure creep under the 1500-psi pressure used in sea water desalination of stacked films immersed in water. Wet compressive creep of cellulose acetate was reduced markedly by reinforcing with solid fillers. Highest efficiency was shown by carbon black and several coarse particle size fillers. Chemical nature of the filler surface was also important. Increasing filler content helped somewhat, but much less than proportionally. Use of high molecular weight, or mild crosslinking, was much less effective than use of solid fillers.
R. D . Deanin, Lowell Technological Institute, Lowell, M a s s , 0 1 8 5 2 , and Bernard B a u m , S. A . Margosiak, and W. H . Holley, Jr., DeBell @ Richardson, Inc., Hazarduille, Conn. 06036 IND.ENG.CHEM.PROD.Res. DEVELOP. 9, 172-175 (1970)
CHARACTERIZATION OF ASPHALT FOR USE AS BINDER TO MAKE COKE BRIQUETS FROM LOW RANK COAL CHAR
Certain asphalts make excellent briquetting binders for use in the manufacture of metallurgical coke briquets from low rank coal char. T o characterize asphalts for this use, a wide variety of asphalt products were used as binder in test briquets, and the principal dependent variables of briquet crushing strength and losses associated with curing and coking correlated with the composition (asphaltenes, resins, and oils) as determined by solvent analysis. Average briquet strength, coke residue, and net curing losses all greatly increased with increasing asphaltene content of the binder. T h e scatter of the data was greater when correlations were attempted with other properties of the binder such as resin plus asphaltene content, and C / H ratio. The effects of curing the green briquets in air compared with curing in a n inert nitrogen atmosphere are also reported. T h e strength of briquets cured in air was more than double that of briquets cured in nitrogen alone.
F. P. McCandless and J . M . Blake, Departmrnt University of Colorado, Boulder, Colo. 80302
of
Chemical Engineering,
IND.END.CHEM.PROD.RES. DEVELOP. 9, 183-186 (1970)
STRUCTURAL CHANGES ACCOMPANYING COKE CALCINATION
The effect of temperature upon structural changes which occur during the calcination of raw petroleum coke has been investigated utilizing conventional and high temperature microscopy techniques, x-ray diffraction, and porosirnetry. The maximum rate of contraction of a coke, which is accompanied by a sharp increase in apparent density, crystallite growth and porosity, occurs in the temperature range of 700" to 800OC.
M a c k P . Whittaker, Fred C. Miller, and Harlan C. Fritz, Great Lakes Research Corporation, Eltzabethton, Tenn. 37643 IND.ENG.CIIEM.PROD.RES.DEVELOP. 9, 187-190 (1970) VOL. 6 2
NO. 6
JUNE 1970
69
BRIEFS WETTABILITY OF PETROLEUM COKES BY PITCH
Four petroleum cokes having widely differing microstructures were tested for wettability by a standard coke-oven pitch. Baked laboratory Soderberg anodes containing substantial amounts of these cokes had apparent densities and resistivities related to the wettability. For good wettability the binder must be absorbed into the pore structure of the coke.
tential is developed for the by-products propane-I ,2-diol, ethylene glycol, and a mixture of higher polyhydric alcohols containing tetritol, pentitol, methyl fructoside, and hexitol.
G. oan Line. A . J . Driessen. A . C. Piet. and J . C. Vlueter. - , Technoloeical UniuersiQ ' Twente," Enschbde, Netherlands IND. ENG.CHEM. PROD. R E S .D E V E L O 9 P ,. 210-212 (1970)
114.B . Dell and R . W . Peterson, Aluminum Go. 0', America, 'Vew Kenstngton, Pa. 15068
IND. ENG.CHEM.PROD.RES.DEVELOP. 9, 190-194 (1970) DEHYDROGENATION OF DICYCLOHEXYL OVER A PLATINUM-ALUMINA CATALYST WITHOUT ADDED HYDROGEN
THERMAL CRACKING OF TARS AND VOLATILE MATTER FROM COAL CARBONIZATION
Two tars (from vertical-retort and fluidized-bed carbonization) as well as volatile matter from 500OC. static-bed carbonization of coal were cracked i n static-bed reactors between 500' and 1000°C. and at residence times of 1 to 440 seconds. T h e effects of process variables-temperature, residence time, and composition of raw tar-on the yields and properties of products were investigated. Conclusions were drawn regarding the nature of chemical reactions involved and the mechanism of tar cracking. T h e main products were gas and carbon. T h e gas could be useful industrially as fuel gas or as a source of olefins for chemical syntheses; the carbon could be used as raw material for electrodes for the metallurgical industries.
T h e dehydrogenation of dicyclohexyl (DCH) is a n endothermic reaction proceeding stepwise first to phenylcyclohexene (PCH) and then to diphenyl (DP). Complete conversion to D P has a heat of reaction of about 1100 Btu per pound. Studies are being made on the utility of this reaction for cooling the engines and other high-temperature sections of hypersonic aircraft. The effect of pressure, temperature, and space velocity o n the rates of the reaction over platinum-alumina was determined i n the range 10 to 30 atm, 700' to 1200°F, and 30 to 100 liquid hourly space velocity (LIISV). High selectiviry for diphenyl was favored by high temperature, high conversion, and low pressure. Apparent activation encrgies of 8 and 43 kcal per mole were observed for the first and second reaction steps, respectively. Compared to methylcyclohexane ( M C H ) , relatively less heat sink was available at low conversions, but more a t high conversions and higher temperatures. Thermally, DCH is somewhat more reactive than
MCH.
W. R. Hesp and P . L. Waters, Division of Mineral Chemistry, C S I R O , Sydnty, Australia
A . W . Ritchie and A . C. :Vixen, Shell Deuelopment Co., E m e i y i l l e , CUI$. 9 4 6 0 8
IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 194-202 (1970)
IND.ENG.CHEM.P R O DRES. . D E V E L O 9, P . 213-219 (1970)
CATALYTIC CRACKING OVER CRYSTALLINE ALUMINOSILICATES. MICRBREACTOR STUDY OF GAS OIL CRACKING
Instantaneous rate data are obtained in a microreactor for the cracking of a 500" to G O O O F gas oil fraction over a crystalline aluminosilicate catalyst a t on-stream times ranging from 10 seconds to 2 minutes. Aromatic and nonaromatic extracts from this gas oil are separately cracked and their contributions to catalyst activity decay, coke formation, and product distribution evaluated. From a comparison of rate data for a series of fused ring naphthenes, evidence of molecular size limitation on cracking rate is given. Abundance of five-member ring products is indicative of scission and recyclization reactions of the naphthenes.
D. M .
iVace,
Mobil Research and Development Gorp., Paulsboro, :\'. J .
08066
IND.ENG.CHEM.PROD.RES.D E V E L O P 9,. 203-209 (1970)
LIGAND FACTORS IN THE ISOMERIZATION OF OLEFINS BY PALLADIUM COMPLEXES
T h e double bond isomerization of 1-hexene in methylene chloride catalyzed by a series of 1,3-dichloro-2-hex-l-ene-4 (p-Z-pyridine S-oxide)-palladium(I1) complexes has been studied. The reaction is very sensitive to the electronic nature of the trans A'-oxidc ligand, and olefin isomerization results only when the X'-oxide ligand dissociates from the original palladium-olefin complex. When the complex conrains a strongly electron-withdrawing nitro group on the ,V-oxide, the dissociative equilibrium is favored in the direction of free ligand and produces a very effective catalyst system. If the complex is structured with $-mcthylpyridine :\'-oxide, dissociation is negligible and minimal isomerization occurs. T h e experimental results support either the metalhydridc or a pseudo-T-allyl mechanism for the isomerization.
W m . H. Clement and Thomas Spcidel, Ithaca College, Ithaca, 14850
)\'. Y .
IND. ENG.CHEM. PROD. RES.DEVELOP. 9 , 220-223 (1970)
CONTINUOUS PRODUCTION OF GLYCEROL BY CATALYTIC HIGH PRESSURE HYDROGENOLYSIS OF SUCROSE
St.vt.ral continuous reactor systems are discussed for the caralgtic high prcijurc hydrogrnol}sis of sucrose to glycerol. 'Thcoreiically and acriia!ly. continuous reactors lead ro lo\\.er slycerol yizlds than in a hitch process. 'l'\%.ocontiiiuous stirred tank rcilctori i i i c.scdd(' c o n s t i t u t c ;t reasonal>!c compromise. . \ n economic ev'iluaiion of rhe suerosc roiite ro glycerol in c3mparisoii \\ irh orher synrhrric glycerol procrsrs bascd on al:yi chloridc anti acrolriii sa!cs posuqqejts that the sucrosc p I O c C 5 s can bc competiri\e i f .% 70
INDUSTRIAL AND ENGINEERING CHEMISTRY
KINETIC STUDY OF HYDROGENATION OF DINITROTOLUENE AND OF m-DINITROBENZENE
h kinetic study has been made to determine the optimum conditions for the palladium-catalyzed hydrogenations of dinitrotoluene to toluenediamine and of m-dinitrobenzene to m-phenylenediamine. The rate-determining step under the recommended conditions is the diffusion of hydrogen. The reaction rate is zeroorder with respect to the nitro compound and first-order with respect to the pressure of hydrogen. I t increases, but not linearly,
BRIEFS with increasing catalyst concentration, has a low temperature coefficient, and is markedly dependent on the efficiency of agitation. Suitable solvents are alcohols and aromatic hydrocarbons.
di(2-hydroxyethyl)morpholinium, and droxyethy1)piperazinium.
F. S. Dovell, W . E. Ferguson, and Harold Greenjeld, Uniroyal Chemical Division, Uniroyal, Inc., Naugatuck, Conn. 06770
Pa. 19078
N,N,N’,N’-tetra(2-hy-
H. H. Weldes, Philadelphia Quartz Co. Research Laboratories, Primos, IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 243-248 (1970)
IND.END.CHEM.PROD.REF.DEVELOP. 9,224-229 (1970)
AMINE AND AMMONIUM SILICATE SOLUTIONS
NEW REACTION FOR CONVERTING ALCOHOLS TO UNSATURATESTHE BBT PROCEDURE
The reaction of alcohol xanthates with compounds containing hetero-atom unsaturation-Le., chloroacetic acid, chloroacetonitrile, etc.-produces derivatives that can subsequently react with dilute aqueous acid or Lewis acids in nonaqueous media to form cyclic intermediates with the thiocarbonyl sulfide to produce a n olefin subsequently. This is a n entirely new method for producing olefins from alcohols. This relatively simple procedure has been used to introduce unsaturation into moriorneric as well as polymeric alcohols. As typical examples, it has been possible to introduce significant unsaturation into cellitlose, starch, poly(viny1 alcohol), and cholesterol as well as simpler alcohols and polyols. I t is proposed that the general method be called “the BBT procedure.”
N . I. RiriXe, JJ. J . Bridiefnrd, and A . 1,’. Tirrbah, Tee-Pak, Inc., Danuzlle, Ill. 61832 IND. ENG.CHLhf.
PROD.
RES.DEVELOP. 9, 230-233 (1970)
NEW SYNTHESIS OF ISOPRENE BASED ON FORMALDEHYDE AND ISOBUTYLENE
A new synthesis of isoprene from formaldehyde and isobutylene has been developed. The yield of isoprene obtained has been improved compared with other processes which utilize these raw materials, by first converting the formaldehyde to chloromethyl methyl ether by reaction with anhydrous hydrogen chloride and methanol. Chloromethyl methyl ether is added to isobutylene to produce 3-chloro-3-methylbutyl methyl ether. This intermediate is decomposed by a highly efficient pyrolysis reaction to isoprene, methanol, and hydrogen chloride. The latter two materials are recycled. Isoprene yield based on formaldehyde IS in excess of 80% when pure isobutylene is used. An ultimate yield over 90Yc should be possible upon recycle of the various intermediates. When a refinery stream containing dilute isobutylene is used as the isobutylene source, the yield is somewhat lower.
D. W . H a l l , F. L. Dormzsh, and E. Hurley, Jr., DenLer Research Center, Marathon Oil Go., Littleton, Colo. 80720 IND.ENG.CHEM.PROD.RES.DEVELOP. 9,234-242 (1970)
NEW CLASS OF CRYSTALLINE SOLUBLE SILICATES
Crystalline, water-soluble double silicates containing alkali metal and quaternary ammonium ions have been prepared and characterized. These silicates can contain sodium, potassium, or lithium ions as well as mixtures of these alkali metal cations in combination with a number of quaternary ammonium ions, such as tetramethylammonium, tetra(2-hydroxyethyl )ammonium, N , A’-
The preparation and properties of stable aqueous amine and ammonium silicate solutions by simple ion exchange methods are described. T h e mole ratio range of amine silicates is between 2 and 10 SiOz/amine, and of the ammonium silicates between 2 and 6 Si02/(NH4)20. These solutions are stable for long periods of time at moderate concentrations.
H. H. Weldes, Phaladelphia Quartz Go. Research Laboratorzes, Primos, Pa. 19018 IND.ENG.CHEM.PROD.Rcs. DEVELOP. 9, 249-253 (1970)
ION EXCHANGE SORPTION OF TITANIUM(1V) AND TITANIUM(1II) FROM SULFATE SOLUTIONS
In developing ion exchange techniques for purifying industrial titanium sulfate solution
