Product sample No. 13, Table 11, was 100% water soluble (AOAC method), Paper chromatography indicated the presence of ortho, pyro, and small amounts of higher polyphosphates in the product sample. Microscopic examination and X-ray diffraction revealed that the bulk of the orthophosphate consisted of the mixed salt (K, NH4)H2P04.All the solid products had low p H values. When the solid products are acidic, part or all of the polyphosphates readily hydrolyze to the ortho form in time. Conclusion
I n the determination of the kinetic rate expression for the reaction between phosphoric acid and potassium chloride, only the forward reaction portion was determined. The constants in the Arrhenius equation were determined experimentally, and the reaction rate was of the first order with respect to both chloride concentration and phosphoric acid concentration. The ammoniation of a KH2P04-H8P04melt can be successfully accomplished with the proper residence time, pressure, and temperature conditions. By use of a K : P mole ratio of 0.5 in the feed melt, the best operating conditions were 200-21OOC with a pressure in excess of 40 psi and a residence time above 4 min. Based on the experimental results, the degree of ammoniation of the final product increased with increased pressure, increased residence time, and decreased temperature. The degree of neutralization ranged from a mole ratio of (NH4 K) : P of 0.74-1.24. Since no preammoniation step was used in this process, this range was lower than t h a t of TVA for ammoniation of superphosphoric
+
acid into ammonium polyphosphate (up to 1.57 moles of N/ mole of P) . As a result of the work with the experimental ammoniatorreactor, the ammoniation portion of the process can be conducted in the same type of processing equipment as that used in the ammonium polyphosphate process. The most significant differences would be the need for higher temperatures and materials of construction that would be resistant to additional corrosiveness of the chloride ion. The results obtained with the experimental ammoniator-reactor could also be of value when considering that the potassium phosphates used in this process can be produced by methods other than the direct reaction of potassium chloride with phosphoric acid. References
Getsinger, J. G., U. S. Patent 3,382,059, May 7, 1968. Getsinger. J. G., Sieael, M. 11..Mann, H. C., J. Agr. Food Chem., 10 (J),341-4’(1962).‘ Hazen, W., Ross, W. H., U. S.Patent 1,456,850, May 29, 1923. Kelso, T. M., Stumpe, J. J., Williamson, P. C., Commer. Fert., 116 (3), 10-6 (1968). Mann, H. C., Chem. Eng. News,43 (39), 63 (September 27, 1965). Potts, J. hl., Elder, H. W., Scott, W. C., J . Agr. Food Chem., 9 (3), 178-80 (1961). Ross, W. H., Trans. Amer. Electrochem. SOC.,48, 299-310 (1925). Ross, W. H., Hazen, W., U. S. (Patent 1,456,831,May 29, 1923. Tennessee Valley Authority, 1968 Fertilizer Summary Data,” p 4, National Fertilizer Development Center, Muscle Shoals, Ala., 1969. RECEIVED for review March 15, 1971 ACCEPTED June 22, 1971 Presented at 160th Meeting, ACS, Chicago, Ill., September 1970. This work was financed by the Chemical Engineering Department and the Engineering Research Institute of Iowa State University.
Dibasic Acids from Ethylene and Dehydroabietic Acid Walter H. Schuller Southern Marketing and Nutrition Research Division, Agricultural Research Service, U S . Department of Agriculture, Olustee, Flu. Sd07.2
Ethylene, reacted with dehydroabietic acid in the presence of palladium(ll) acetate and silver acetate, gives a mixture of dimeric dibasic acids.
T h e reaction of ethylene with benzene in the presence of palladium(I1) acetate gave styrene and stilbene (Fujiwara et al., 1968, 1969). The application of this reaction to dehydroabietic acid was thus considered desirable with the goal of preparing rosin-based dimeric dibasic acids. Experimental
To a solution of 6 grams (0.02 mole) of dehydroabietic acid in 24 ml of glacial acetic acid and 100 ml of n-heptane were added 2.25 grams (0.01 mole) of palladium(I1) acetate and 16.63 grams (0.10 mole) of silver acetate. The mixture
was charged to a 500-ml round-bottomed, four-necked flask equipped with a thermometer, a gas inlet tube extending below the surface of the liquid, a mechanical stirrer, and a reflux condenser terminated with a drying tube filled with Drierite. Ethylene gas was bubbled through the dispersion with vigorous stirring under reflux (89OC) for 8 hr. The dispersion turned black, and the flask was heavily silvered by the end of the reaction. The solution was filtered, water washed, stripped, and the brown friable solid residue dried under reduced pressure over Drierite; yield, 6.86 grams; mp, 154-158OC dec; equiv tvt, 328. A portion was reacted with an excess of ether-diazomethane. Ind. Eng. Chem. Prod. Res. Develop., Vol. 10, No. 4, 1971
441
The esterified mixture was analyzed by gas-liquid chromatography (glc) and run isothermally a t 18OOC for a short period to determine monomer content and then linear temperature programmed to 360°C a t 30°C/min with a n airoxidized silicone column developed especially for the analysis of rosin-dimeric dibasic acids (Sinclair et al., 1970) (4.5-ft x a/lc-in., stainless steel, 3%, SE 52 on Gas-Chrom Q, cured in air a t 35OOC overnight). The yields based on dehydroabietic acid were dibasic acid dimers, 62%, methyl dehydroabietate, 38%, calculated from the glc volatile material. The total percent glc volatiles was 80%. The yield of dimer based on palladium(I1) acetate was about 100%. The ultraviolet spectrum on the crude ester mixture was, , ,A (95% ethanol) 298 mp (broad) (a 55), with peaks at 268 and 276 mg. The same experiment was repeated with cupric acetate in place of silver acetate. A 29% yield of dimer was obtained. A blaiik was run on dehydroabietic acid in the presence of palladium(I1) acetate and silver acetate without the addition of ethylene. No significant amount of dimer was formed. When palladium metal was substituted for palladium(I1) acetate, no reaction was observed, even in the presence of a large excess of silver acetate. The yields of dibasic dimeric acid based on palladium(I1) acetate were considerably lower when silver acetate was not present to presumably “recycle” (Fujimara et al., 1968, 1969) the palladium acetate. Yields were also much lower rvhen either acetic acid or n-heptane was used alone as a solvent for the reaction rather than a mixture of the two.
Discussion
The reaction of ethylene with dehydroabietic acid in the presence of palladium(I1) acetate and silver acetate in a hydrocarbon-acetic acid solvent system was successfully carried out. A good yield of mixed dimeric dibasic acids was obtained. The glc curve of the reaction product of ethylene and dehydroabietic acid was similar t o that obtained from the sulfuric acid dimerization of abietic acid (Sinclair et al., 1970). A total monomer peak, identified in the present case as being mainly unreacted methyl dehydrobietate, came off the glc column isothermally a t 1 8 O O C in both cases. The dimeric dibasic acid esters came off on linear temperature programming to 360°C. The appearance of the peaks in the dimer region of the glc curves was similar in both cases. The ultraviolet spectrum of the reaction product of ethylene and dehydroabietic acid confirmed the presence of stilbenetype compounds ,,A,[ stilbene 295 mp ( a 150)]. The absence of peaks in the 240-250 mp region indicated the probable absence of any significant amount of single-step arylation reaction product ,,A,[ styrene 244 mp ( a 121)]. literature Cited
Fujiwara, Y., Moritani, I., Afatsuda, AI., Teranishi, S., Tetrahedron Lett., 35, 3863 (1968). Fujiwara, Y., Moritani, I., Danno, S.,Asano, R., Teranishi, S., J. Amer. Chem. SOC.,91, 7166 (1969). Sinclair, R . G., Berry, D. A,, Schuller, W. H., Lawrence, R. V., Ind. Evg.Chem. Prod. Res. Develop., 9, 60 (1970). RECEIVED for review April 29, 1971 ACCEPTEDJune 26, 1971
Nylon-9 Via 9-Aminononanoic Acid from Soybean Oil’ William R. Miller, Everett H. Pryde, Richard A. Awl, William 1. Kohlhase, and D. Joe Moore2 Northern Regional Research Laboratory, C S D A , Peoria, Ill. 61604
9-Aminononanoic acid was prepared from soybean oil by a four-step process. Alcoholysis of the oil gave alkyl esters of the component fatty acids. Reductive ozonolysis of these esters gave an alkyl azelaaldehydate used for reductive alkylation of ammonia. The alkyl 9-aminononanoate was not isolated but hydrolyzed directly to 9-aminononanoic acid. Yields in the reductive alkylation-hydrolysis were better than 90% of crude amino acid purified by precipitation from water with an organic nonsolvent. Polymerization by heating at atmospheric pressure gave nylon-9 of high molecular weight. Nylon-9 fibers prepared by melt spinning had strengths comparable to those of commercial nylons.
H i g h e r nylons developed commercially-nylons-8, -10, -11, and -12-have some valuable properties for plastics applications (Pryde and Cowan, 1967; Horn et al., 1963). These properties include low moisture absorption, good dimensional stability, and favorable melting points and densities. As a result markets for these new nylons are expanding. Correspondence should be addressed to Dr. J. C. Cowan, Oilseed Crops Laboratorv, ARS, USDA, 1815 North University Street, Peoria, Ill. 61604. Present address, Hewlett Packard Co., 2459 University Avenue, St. Paul, hfinn. 442
Ind. Eng. Chem. Prod. Res. Develop., Vol. 10, No. 4, 1971
Iiylon-9 has some properties equivalent or superior t o those of other new nylons (Pryde and Cowan, 1967). An economic process for preparation of nylon-9 may make it an attractive candidate for commercial applications. One potential route to nylon-9 iiivolves reductive alkylation (Emerson, 1948) of ammonia with an alkyl azelaaldehydate, ROCO(CH&CHO, to form the primary amino ester (Anders et ai., 1965b) of 9-aminoiionanoic acid, the monomer for nylon-9 (Otsuki and Funahashi, 1958). iZlkyl azelaaldehydates are bifunctional products readily obtained by reductive ozonolysis of unsaturated fatty esters derived from vegetable
