April, 1945
INDUSTRIAL AND ENGINEERING CHEMISTRY
The difficulty lies in the determination of volatile and the subsequent translation of the phthalic anhydride values to a nonvolatile basis. Various methods of test for percentage of volatile were tried, but they were not sufficiently accurate to use as the basis for determination of the phthalic anhydride content of the extracted vehicle solids. On a straight alkyd resin varnish, which had not been made into a paint and to which no drier had been added, two different operators, working some 5 months apart, obtained the same value for the phthalic anhydride content. With the methods of analysis now available, no definite conclusion can be drawn from the change in the phthalic anhydride content of the extracted vehicle. In other words, a change of a few tenths per cent in the phthalate content of the extracted vehicle cannot be determined, and therefore a study of the vehicle does not show the possible formation of lead phthalate or other phthalate reaction products. CONCLUSIONS
1. No reaction takes place between true red lead (PbsOJ and
alkyd resin. Reaction takes place only between the free litharge (PbO) and the alkyd resin vehicle. Red lead pigments containing 92% or more PbaO*do not react with alkyd resin vehicles to form lead phthalate. The evidence of formation of lead phthalate in the case of red lead of 85% true red lead content is not conclusive. 2. The phthalate found in the extracted red lead pigments was present as unextracted alkyd resin retained on the pigment. 3. After long storage, red lead-alkyd resin paints, in which the pigment is 97% true red lead, show no change in'paint film flexibility.
403
4. The phthalate content of the vehicle extracted from red lead paints cannot be determined accurately with present methods of analysis. 5. The method established for determining the phthalate content of the extracted pigment, as set forth, is quantitative and reliable. ACKNOWLEDGMENT
The authors desire to acknowledge the assistance of the staff of the National Lead Company Research Laboratories for many suggestions which materially contributed to the work reported in this paper. LITERATURE CITED
(1) Am. Soc. for Testing Materials, Standards, Part 11, D154-38, p890 (1942). (2) Ibid., Part 11,D522-41, p, 938 (1942). (3) Ibid., Part 11,D563-40T, p. 1362 (1942).
(4) Federal Specification, TT-P-141A. (5) Fonrobert and Munchmeyer, FarbenZtg., 41,747 (1936). (6) Goldberg, A. I., IND. ENO.CHIIM.,ANAL.ED.,16, 198 (1944). (7) Iowa State Highway Comm., Specification 41-59-7, Shop Coat (July 15,1941). (8) Naval Aircraft Specification ST-15c (July, 1938). (9) Sanderson, J. M., A.S.T.M. Bull., 107, 15 (1940). (10) Sheiton,J. G., Metal Finishing, 39, 703 (1941). (11) Taylor, J. J., Paint, Oil Chem. Rev., 105, No. 10, 10 (1943). (12) Toeldte, W., Farben Ztg., 45, 67 (1940). (13) U. 5. Maritime Comm. Specification 52-MC-23 (Aug. 28, 1943). (14) Ibid., M C 52-A-1, Class XXII (June 6,1939). (15) U.S. Treasury Dept. Specification 358 (July 8, 1939). PRESENTED before the Division of Paint, Varnish, and Plastics Chemistry at t h e 108th meeting of the AMERICANCHmirrcAL SOCIETY, New York, N. Y.
Compatibility of DDT with Insecticides, Fungicides, and Fertilizers ELMER E. FLECK AND H. L. HALLER Bureau of Entomology and Plant Quarantine, U . S . Department of Agriculture, Beltsuilb, M d .
T
HE indicated widespread use of DDT as an insecticide ( I , 4)
and its known instability in the presence of certain catalysts ( 2 ) make it desirable to have information as to the possible cata-
lytic effect of other insecticides, fungicides, fertilizer materials, and accessories with which it may be applied. DDT is a rather stable compound by itself. Long periods of exposure to the air have caused no appreciable change. Irradiation of the solid material, spread in a thin layer, for 35 hours with a 100-watt General Electric mercury vapor lamp, type AH-4, caused the melting point of DDT to be lowered by only 2' C. Similarly, an alcoholic solution of pure D D T showed no change after exposure to sunlight for over a year.
Some of the more common insecticides, fungicides, and fertilizers have been tested for catalytic action in the dehydrochlorination of DDT. Materials used for diluents have been shown to vary in their activity as catalysts for the decomposition of DDT. The anhydrous chlorides of iron, aluminum, and chromium are active dehydrohalo-
In contrast to this stability in the neutral state, it has been shown that DDT in alcoholic solution readily reacts with alkalies in accordance with the following reaction (3):
c1 I Cl-c-cl 1
+ KaOH
C-H
60 Cl
c1
-
c1 c1-
t:II 4-NaCl f H2O
C
$0 c1
c1
genation catalysts for DDT. The catalytic action of anhydrous ferric chloride has been shown to be promoted by solution in naphthalene, chloronaphthalene, chlorobenzene, 0- and p-dichlorobenzenes, and nitrobenzene, and inhibited by various hydrocarbon and fatty oils, alcohols, ketones, acids, and anhydrides.
INDUSTRIAL AND ENGINEERING CHEMISTRY
404
TABLEI. CATALYTIC AcrIvIm
OF PRESEXCE OF
ACCESSORY XATERIALS IN DDT
Material Alumina Aluminum chloride Aluminum powder Kaolin Bentonite Calcium oxide Hydrated lime Chromic chloiide, CrCla.GHz0 Chromic chloride, anhydrous (0.01%) Chromic oxide Chromium Stainless steel (18-8) Copper powder Cupric chloride Frianite Fuller's earth Iron powder (U.S.P.,, hydrogen reduced) Iron powder (alcoholized) Iron filings Iron oxide (red) Iron oxide, magnetic (black) Iron rust
Lead Lead chloride Lead sulfate Magnesium oxide Nickel powder Pyrax ABB (sample 1) Pyrax ABB (aample 2) Sariri tr
a
Noles HC1 Evolved per hfole D D T None 1.00 None 1.03 0.32 None'" None" 0.05 0.98 None" 1,02 0.98 None 0.12 0.04 1.00 None 1.00 0.9s
0.32 0.79
0.73 None 0 86 0 34 1 02 Sone None 0 09 0 09 0 070 0.07 0.04 0 91 Xone None 1.03 None 1.05 None None None None
D D T was isolated unchanged from the melt.
It, has been shown ( 2 ) that certain catalysts also will decompose DDT, with the formation of hydrochloric acid and 2,2-bis(p-chloropheny1)-1,l-dichloroethylene. The latter compound, formed either by catalytic action or by reaction of DDT with an alkali, is markedly inferior to D D T as an insecticide. Procedure. The apparatus used to test for catalytic activity was t,he same as t,hat described previously ( 2 ) . Into a 6-inch Pyrex U-tube were placed 2 grams of recrystallized DDT (melting at 104-106" C.) and 2 grams of the material to be tested. The C-tube was connected to a gas-Fvashing bottle which contained 50 ml. of water to absorb any hydrochloric acid that might be liberated. A gentle current of dry air was drawn through the apparatus. The U-tube was placed in an oil bath at 115-1203 C. to a depth of about 3 inches. After heating for 1 hour, the absorption bottle was disconnected, and the contents were titrated with 0.1 h' sodium hydroxide, using phenolphthalein as an indicator. The liberation of 1 mole of hydrochloric acid requires 56 ml. of 0.1 N sodium hydroxide for neutralization. I n cases where a basic substance such as lime was used, the D D T was extracted from the cooled melt with ether, and after removal of the ether, the melt,ing point of the residue was checked for possible lowering. The melting point of 2,2-bis(p-chlorophenyl)-1,l-dichloroethyleneis 88-89' C. Insecticides. Commercial grades of sodium fluoride, sodium fluosilicate, cryolite, Paris green, calcium arsenate, and lead arsenate showed no catalytic activity in decomposing DDT. Likewise, pure rotenone and pyrethrum were found to be inactive. When pure nicotine was used, the DDT decomposed and the product WEB isolated by means of ether extraction, mashing with dilute acid and then with water, and evaporation of the ether. The decomposition product melted a t 70-79" C. By recrystallization from alcohol the melting point wae raised, and the prod-
Vol. 37, No. 4
uct was identified as 2,2-bis( p-chlorophenyl) -1,1-dichloroethylene by a mixed melting point determination. Since basic nitrogencontaining compounds react with DDT, this action with nicotine should be regarded as the t'ype obtained with alcoholic caustics rather than as a catalytic decomposition. Tests to determine xhether this reaction occurs under field conditions would seem to be in order. Fungicides. Commercial lime-sulfur and 2,3-dichloro-1,4napht,hoquinone shollyed no catalytic action. With mixtures of D D T and ferric dimethyl dithiocarbamate 0.05 mole of hydrochloric acid was evolved. With Bordeaux mixture 0.04 mole, and with sulfur 0.07 mole, were obtained. Fertilizers. The following f d l i a e r s shon7ed no catalytic activity: ammonium sulfate, monoammonium phosphate, ammoniated superphosphate, ammonium nitrate, Cyanamid, inanure salts, potassium sulfate, Uramon, dicalcium phosphate, double superphosphate, sulfate of potash-magnesia, potassium chloride, sodium nitrate, steamed bonemeal, Milorganite, and mixed fertilizers No. 1 (8-84, No. 2 (8-12-16), KO. 3 (5-10-5), S o . 4 (4-12-4), No. 5 (4-10-6), and KO.6 (3-9-6). Dolomitic limestone was the only fertilizer tested which showed catalytic activity. One-hour heating of the mixture produced 0.89 mole of hydrochloric acid. The catalytic action persisted after the limestone had been slurried with water and then dried at 110" C. This treatment would destroy the catalytic action if it were due to small traces of anhydrous ferric, aluminum, or chromic chlorides.
Accessory Materials. Accessory material that may be used in the preparation of DDT dusts, as well as other compounds encountered in the manufacture and use of DDT, were tested. The results are recorded in Table I. The wide difference in the catalytic activity of various samples of the same mineral indicates the presence of small amount's of active catalysts unevenly distributed in the mineral. Of these catalysts known at present, iron and iron oxides, chromium, and anhydrous ferric, aluminum, and chromic chlorides are indicated. Of this group the anhydrous chlorides are most active. Ferric and chromic chlorides may be formed by the action of D D T on the metals themselves. It is therefore indicated that t'he catalytic action of the various accessory mat,erials of mineral origin is due to small amounts of cntalytic impurities apt to be found in minerals. Hence the content of catalytic substance may vary with the source of the mineral. I n diluted dusts the action of these catalysts is not rapid until temperatures are reached that are above the melting point of
O F SOLVENTS I N PRESENCE TABLE11. CATALYTIC ACTIVITY OF DDT AND ANHYDROUS FERRIC CHLORIDE
Moles HC1 Evolved per Mole D D T None' Acetic anhydride 1 07 Chlorobenzene 1.07 e-Chloronaphthalene 0.1s Cyclohexanone 1.00 p-Dichlorobenzene 1 05 o-Dichlorobenzene 0 .80 o-Lhcl;lorLi8enzene , b a t h temp. 50-55' C.) 0 11 ,,-Di,,l.!oritenzeiie ::3qih m i h temp. 27-30' C. for 4 hr.) Sonen Dioxane 1.10 Ethl-lene chloride (SOe (80' C.) 0.02 Fuel oil (No. 2) 0.02 Kerosene None Motor oil (S.A.E. 30) 1.05 Naphthalene 1.13 Kitrobenzene 0.02 Octadecyl alcohol 0 0% Oleyl alcohol 0.43 Refrigeration oil (unsaturation-free) Kone Soybean oil 0 05 Stearic acid 0.02 Tetrahydronaphthalene 0 02 p-Toluenesulfonic acid None Velsicol AR-60 0.16 Xylene Solvent
4
D D T was isolated unchanged from the melt.
April, 1945
INDUSTRIAL AND ENGINEERING CHEMISTRY
405
benzenes. With o-dichlorobenzenethe catalytic action was shown to occur even at room temperature.
DDT. Since this temperature is above that ordinarily encountered under normal outdoor conditions, decomposition effected by an accessory material under the accelerated test should be viewed &s indicating storage tests at working temperatures.
ACKNOWLEDGMENT
The fertilizer materials were supplied by the Bureau of Plant Industry, Soils, and Agricultural Engineering, through the courtesy of J. 0. Hardesty.
Solutions of DDT. For this series of tests 2 grams of recrystallized D D T and 2 grams of the solvent were placed in the U-tube. After the temperature of the tube and its contents had come up to that of the oil bath, 2-3 mg. of anhydrous ferric chloride were dropped down the inlet arm of the U-tube. The tube was then shaken gently to ensure good mixing with the catalyst. The results (Table 11) show that most of the solvents used with DDT have a marked inhibiting action toward the catalytic decomposition reaction. The notable exceptions are the nitro- and chloro-
LITERATURE CITED
(1) Annand, J . Econ. Entomol., 37, 125 (1944). (2) Fleck and Haller, J . Am. Chem. Soc., 66,2095 (1944). (3) Roark and McIndoo, I?. S. Dept. Agr., Bur. Entomol. Plant Quarantine. E-631.Dee.. 1944. (4) Zeker, Ber.,' 7, 1180 (1874); Brand and Busse-Sundermann. Ibid., 75,1819 (1942).
FERMENTATION PROCESS FOR ITACONIC ACID LEWIS B. LOCKWOOD AND GEORGE E. WARD Northern Regional Research Laboratory,
U. S . Department of Agriculture, Peoria, Ill.
A fermentation process for the production of itaconic acid, based on the cultivation of a superior strain of Aspergillus terreus (NRRL 1960) on the surface of glucose nutrient media, has been developed and operated on a semipilot plant scale. Itaconic acid yields in excess of 30 grams per 100 grams of glucose supplied are obtained in 12 days. The major portion of itaconic acid produced can be recovered by crystallization after concentrating and cooling the filtered liquors. The fermentation is resistant to contamination, since the nutrient medium is maintained at a low pH level throughout the culture period.
R
ESEARCH on the production of itaconic acid (methylene succinic acid), a potential raw material for resins of the methacrylate type, was undertaken as a means of increasing the industrial utilization of agricultural products. Itaconic acid was first reported as a product of mold metabolism by Kinoshita (3) who obtained it from cultures of Aspergillus itaconicus. Calam, Oxford, and Raistrick (1) reported obtaining small quantities of this acid from one strain of Aspergillus terreus, and preliminary investigations conducted by Moyer and Coghill (6) confirmed the suitability of Aspergillus terreus for bringing about this reaction, The present paper describes the production of itaconic acid from glucose on a semipilot plant scale, using the organism and conditions found best in this Laboratory. The organism was a strain of Aspergillus terreus isolated by Kenneth B. Raper from a soil sample obtained from San Antonio, Texas. It was one of the best itaconic acid-producing strains found in preliminary investigations. The organism is carried in this Laboratory's culture collection as Aspergillus terreus (NRRL 1960) and is maintained in stock culture on Czapek-Dox solution agar as cited by Thom and Church ( 7 ) . To obtain frangible spore-bearing material from Aspergillus terreus to be used for the inoculation of production cultures, a medium of the following composition was employed: Glucose monohydrate (commercial), grams 275 NaNOa, g r a m 5 MgSOc7Hz0, gram 0.024 KC1, gram 0.005 H I P O I , gram 0.003 Concd. corn steep liquora, ml. 0.5 a A commercial by-producc of the corn wet-milling industries. I t contains approximately 50% total solida, and is a rich source of mineral nutrients and protein degradation products. ~~
Distilled water was added to bring the medium to 1000 ml. Sterile 50-ml. portions in 200-ml. Erlenmeyer flasks were heavily seeded with spores obtained from a IO-day-old slant culture. On the liquid medium, a good crop of spores was obtained after 5-day incubation a t 30" C. One flask culture is sufficient to inoculate 100 liters of nutrient solution; appropriate portions were used to inoculate the 12-liter quantities of medium used in each of the seven fermentation pans. The fermentation was conducted in shallow aluminum pans, 22 X 36 x 2 inches, in a cabinet described by Ward, Lockwood, May, and Herrick (8) for the cultivation of molds on the surface of solutions. The pans were sterilized with flowing steam for 3 hours, then cooled under a slight pressure of sterile air. The inoculated solutions then were blown into the pans through sterile glass tubes inserted through the front of the cabinet. Twelve liters of medium were placed in each pan. The fermentation solution had the following composition: Glucose monohydrate (commercial), grams MgS04.7H~0,g r a m NHdi01, gram NaC1, gram ZnS04.7H90, gram Nitric acid (sp. gr. 1.42), ml. Concd. corn steep liquor, ml.
165 4.4 2.5 0.4 0.0044
1.60
4.0
and distilled water was added to bring the volume to 1000 ml. The initial pH was approximately 2.0. Throughout the 12-day fermentation period the tier of cultures was aerated a t the rate of 5 liters of humidified air per minute. The entering air was sterilized by passage through a cotton filter. The considerable heat evolved during the course of the fermentation was dissipated by the circulation of cold water through coils installed in the cabinet. The temperature was maintained a t 30' to 32' C. by a thermostatically operated solenoid valve controlling the flow of water to the coils. At harvest the solutions were drained from the pans, and the pans and mycelia were washed with small quantities of cold water. Main filtrates and washings from each panwere combined, and appropriate samples were taken for analysis. Glucose determinations were made by the method of Shaffer and Hartmann (6). Itaconic acid was deterrdined by the bromination method of Koppeschaar ( 4 ) , as modified in this Laboratory by Friedkin ( 2 ) . /
