MARCH, 1936
INDUSTRIAL AND ENGINEERlNG CHEMISTRY
Soap and silicate mixtures ( 1 , 14, 15) are good emulsifiers. Qualitative ob? servation of such 2 processes a s p: making asphalt I emulsions (8, 22, I S ) leads to the impression that 2k soluble silica 3GfI c o n t r i b u t e s to the r e s u l t s obCY tained. Here again is a field for further v, study. $ Under the conditions here reviewed the silica is in solution and can readily be CONCEIVTRATIOIV IN 56 NA=0 rinsed away after FIGURE 14. DEFLOCCULATION 9s SHOWN its work is done. BY CONCENTRATION OF SODIUM OXIDEvs. Laundries often SUSPENDING POWER ON MANGANESE DIfind it possible to OXIDE AT 40” AND 75” C. WHENSODIUM rinse less when AS SOAPS,SILICATE, OXIDEIs COMBINED using soap built AND CAUSTIC (RECALCULATED FROM FALL) with m e t a s i l i cate, and fabric shows no gain in ash after many cycles. Contrary results reported in certain older literature can only have come from the use of conditions which do not arise in modern American washing practice. Silicate solutions in washing practice, then, are alkaline compounds useful in some cases as such, but more often
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exhibiting distinctive properties as a function of the silica they contain. The freedom from stoichiometric boundaries within wide limits gives them a range of characteristics which further distinguish them from other alkalies used in cleansing processes. I n the interest of brevity, no attempt has been made to point out all the relationships to be derived from the graphs. They summarize extensive data and contain evidences worth careful study by those interested in detergent technic. Much additional work is needed to comprehend adequately the mechanism of cleaning in general, and in particular the advantages to be gained from the use of soluble silicates.
Literature Citations Baker, C. L., IND.ENQ.CHEM.,23, 1025-32 (1931) Ibid., 27, 1358-64 (1935). Carter, J. D., Ibid., 18, 248-52 (1926). I b i d . , 23, 1389-95 (1931). Fall, P. H., J. Phys. Chem., 31, 801-49 (1927). Grayson, F., Food Ind.,7, 231-2, 281-2 (1935). Hall, J. R., dissertation, Iowa State Coll., 1930; Iowa State Coll. J . Sci., 5,3 3 9 4 1 (1931). (8) Halvorsen, A. L., U. S.Patent 1,995,346 (1935). (9) McDowell, S. J., J. Am. Ceram. SOC.,10, 225-37 (1927). (10) Peterkin, A. J., and Smith, L., U. S. Patents 1,929,933 and (1) (2) (3) (4) (5) (6) (7)
1,929,934 (1933).
(11) Pinner, W. L., Philadelphia Quartz Co., Bull. 465 (1931). (12) Rouault, E., British Patent 421,269 (1933). (13) Smith, P. R . , U. S. Patent 1,989,775 (1935). (14) Stericker, W., IXD. ENQ.CHEM.,15, 244-8 (1923). (15) Vincent, G. P., J. Phys. Chem., 31, 1281-1315 (1927). (16) Weber, I. E., Melliand Tettile Monthly, 3 , 652-4, 753-4 (1931). (17) Banker and Schnabel,. “Die Beeinflussung der Waschwirkung von Seife und Seifenpulver durch Wasserglasfullung,” Berlin, Springer, 1917. RECEIVED November 21, 1935. Presented before the Division of Industrial and Engineering Chemistry a t the 13th Midwest Regional Meeting of the American Chemical Society, Louisville, K y , October 31 to November-2, 1935.
Influence of “STEARINE”on Heat Polymerization of Sardine Oil
QT
HIS paper deals primarily with the “stearines” (the higher melting mixed, saturated, and unsaturated, triglycerides) of sardine oil which separate by crystallization when the oil is chilled, and their eflect upon the heat polymerization of the oil. Much of the theory involved is applicable also to the vegetable drying oils because the paint oils, such as linseed, perilla, hempseed, etc., also contain saturated, unsaturated, and mixed triglycerides. For example, linseed oils contain from 6 to 11 per cent of saturated acids ( I ) , perilla about 12 per cent (chiefly palmitic), soy-bean oil about 10 per cent, and hempseed oil about per cent.
Effect of Refrigeration on “Stearine” Content I n a bulletin (3)describing refrigeration of sardine oils and a simple specification for checking the degree of winterization, a curve (Figure 1) showed that it was necessary to specify a chill test of at least 12 hours to be assured of a n oil that was free of “stearine” from a practical standpoint. Fish-oil “stearine” i s not accurately defined. Pure stearin is the triglyceride of stearic acid, but in commercial parlance
OTHO M. BEHR Vegetable Oil Products Company, Inc., Wilmington, Calif.
the mono-, di-, and triglyceride combinations of mixed, saturated, and unsaturated triglycerides which solidify or crystallize from the oil a t various low temperatures are termed “stearines.” The saturated acids in these mixed glycerides of sardine oil are composed mostly of palmitic, myristic, and stearic acids. Weighed portions of “stearine” obtained from the filter press in the refrigeration plant were added to a thoroughly winterized oil which had a chill test of 41 hours. The curve shown in Figure 1 is the average of several determinations. This curve indicates that it is of little practical value to winterhe a n oil to stand up beyond a standard chill test of 12 hours, but that it is vitally important to clear the oil of “stearine” to this extent. Based on these data, this company
VOL. 28, NO. 3
INDUSTRIAL AND ENGINEERING CHEMlSTRY
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decided to have its winterized oils stand, on the average, 15 or 16 hours. However, a fully refined sardine oil, standing a chill test of 40 hours, with a n iodine value of 203.45, analyzed by the Twitchell (2) lead salt-alcohol precedure, was found still to contain 17.5 per cent saturated acids. (The experimental error in a single saturated acid determination ms,y be as high as 0.5 per cent.) It was decided, therefore, to determine the relation between the chill test and the actual percentage of saturated acids in the oil. Figure 2 represents the results. This curve is also asymptotic and, allowing for normal experimental errors in the saturated acid determinations, it substantiates the previous conclusion-namely, that an oil standing 15 or 16 hours is practically free of these glycerides containing saturated acids which will solidify a t 32" F. (0" C.) CHILLTNSTS.The chill tests referred to in this paper were made according to a tentative specification for a standard chill test for sardine oils which is a modification, by the writer, of the standard cold test of the National Cottonseed Products Association. This test is easily made with simple equipment,: Filter about 250 cc. of the oil to be tested into a suitable Pyrex beaker. Heat on the hot plate until the stirred oil registers 120' C. (248' F.). Transfer the oil, while still warm, into two standard 4-ounce (118.4-cc.) sample bottles. [This should be done at about 50" C. (122" F.).] Insert a cork stopper tightly and seal with paraffin. Attach a waterproof tag by wire to the neck of the bottle for sample identification. When the oil in the bottle is at room temperature (not to exceed 25" C.) note the date and time and bury the bottles completely in a bucket of finely cracked ice, and add sufficient cold water so that it rises in the bucket of ice to the top of the bottles. Replenish the ice when necessary to keep the bath a t 0' C. Examine the oil for clarity and brilliancy at hourly intervals, and as soon as a cloud is observed in the oil, note the date and time on the tag. The time, in hours, from immersion of the sample in the cracked ice to the appearance of a cloud is the reported chill test. Other chill tests which, for example, require a n oil that will remain clear for 2 hours a t 22" F. (-5.5" C.) are difficult to duplicate and require elaborate equipment. An oil which remained clear for 2 hours a t 22' F. had a saturated acid content of 16.77 per cent. It appears, therefore, that oils refrigerated to stand clear for 2 hours a t 22" F. will retain practically the same amount of saturated acids as those that pass the standard 20-hour chill test.
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Experiments were conducted where sardine oils were repeatedly refrigerated and filtered. In this case the clear oils would stand a chill test of 90 and 100 hours, but upon analysis the saturated acid content still remained 16.77 per cent. I n short, the difference in saturated acid content between an oil standing a 20-hour chill test and one standing 90 to 100 hours a t 32" F. or 2 hours a t 22" F. was, on the average, only 0.25 per cent. These tests show that a crude sardine oil will contain approximately 22 per cent saturated acid radicals. A thoroughly winterized oil will contain approximately 17 per cent saturated acid radicals. Such a n oil will remain clear, on an average, for 20 hours a t 0" C. While it is possible to lower the saturated acid content another 0.25 per cent, by continued refrigeration and repeated filtration, this procedure is impractical. It is estimated that the 5 per cent of saturated acid radicals removed constitute approximately 95 per cent of the "stearine" which may be removed by winterization. Removing this 5 per cent necessitates the loss of approximately 30 per cent of the original oil. A practical minimum guarantee of a 14-hour chill test a t 0" C. is recommended.
Influence of "Stearines' ' o n Oil Polymerization Theoretically, the presence in a n oil of saturated acid radicals would hinder the polymerization of the oil. A varnish plant in the East, which uses a recording thermometer during the kettle-bodying of sardine oils, reported that a thoroughly winterized oil with a 12-hour chill test (F. F. acid, 0.25 per cent) polymerized several hours sooner, to the same degree of polymerization as measured b y the viscosity, than winterized varnish-grade oil previously used. The only reasonable explanation was that the former oil was lightly winterized, in which case it would have a chill test of 0.5 to 0.75 hour. No sample remained for test purposes; therefore to prove this point, the following experiment was conducted: Two 20,000-pound (9000-kg.) batches of sardine oil were taken from the same tank and were alkali-refined, bleached, and filtered in the same manner. One batch (VM06) was lightly winterized to stand a chill test of 0.5 hour. The other batch (VM08) was "zerolized" and turned out with a chill test of 20 hours. In order, for comparison, to have a sample abnormally high in "stearine," a third sample (VMOO) was made up with "stearine" collected from the filter press during the fist filtration. This sample had a saturated acid content of 27.7 per cent. These three oils were then heat-bodied at the same time, in the same oil bath, under identical heat input conditions, and for the same length of time. Roughly, the heating was carried to 500" F. (260" C.) in one hour, then to 565" F. (296' C.) in 0.5 hour, and finally held a t 565" F. for 0.5 hour. During the reaction the zerolized oil liberated the most heat during the exothermic reaction of polymerization, but, since this was allowed to escape, the temperatures of the oils remained within 5" F. (2.8" C.) of one another. The results are as follows : Oil
a
Viscosity Deoipoises
Polymerization Iodine Value
%
VM08 VM06 VMOO Letters in parentheses are Gardner-Holt viscosities.
125.6 116 103
The zerolized VM08 oil acquired a body 133 per cent greater than the lightly winterized VM06, but the actual percentage of oil polymerized, as measured by the insolubility of polymerized oil in acetone, was 140 per cent greater. The difference in the saturated acid content of the two winterized oils was only 2.5 per cent but this difference, measured as solid saturated acids, was 50 per cent.
MARCH, 1936
INDUSTRIAL AND ENGINEERING CHEMISTRY
It may be concluded, therefore, that highly refrigerated oils will polymerize more rapidly under the same heat input than lightly winterized oils. The presence of glycerides, solid a t freezing temperatures, are detrimental to polymerization.
Influence of “Stearine” o n Reactivity of Sardine Oil with Synthetic Resins In view of the fact that the “stearines” have an influence on the polymerization of the oil itself, it was decided to determine their influence on the reactivity of the sardine oils with some of the synthetic resins : EXPERIMENT 1. One hundred grams of a 100 per cent phenolic resin were heated with 200 grams each of three alkali-refined sardine oils used in the previous polymerization experiments. The oil-gum mixtures were heated in the same size flasks in the same oil bath and for the same length of time to insure e uivalent heating conditions. The heating was carried to 565’ F. 9296’ C.) in one hour, then held a t 565” F. for one hour. The results are given in Table I. OF “STEARINE,’ ON REACTIVITY OF OILSWITH TABLE I. EFFECT SYNTHETIC RESINS
Oil
-Viscosity in Decipoises at 25‘ C . 7 Bakelite Rauzene Eater gum BR 254 X150 No. 1 Experimknt 1
VM08 VM06 VMOO
Solution only, V M 0 8 WS03 a
Experiment 2 40 (P) Experiment 3 362 ( Z 2 )
.. 88 (V)
Experiment 4 VM linseed oil 55 (T) 11 (D-E) The letters in parentheses are Gardner-Holdt viscosities.
.. 44 (Q)
10 ( D )
The degree of reaction was to be judged by the resulting viscosities of the oil-resin mass. The body of the oil-resin reaction was so heavy, however, that it was found necessary to add 200 cc. of pure turpentine to each flask in order to obtain satisfactory viscosity readings. After the addition of 172 grams (200 cc.) of turpentine, the zerolized oil (VM08) produced a viscosity 120 per cent greater than the lightly winterized oil (VM06) and 200 per cent greater than the oil abnormally high in “stearine” (VMOO). EXPERIMENT 2. To determine how much of this body was due to pure gum solution in the bodied oil, the zerolized oil was heatbodied under the same temperature condition- to 200 grams of this oil, 100 grams of Bakelite BR 254 were d d e d . The mixture was warmed sufficient1 to dissolve the resin without reand reduced with 200 cc. of turaction (300’ F., or 148.9’ pentine. The viscosity was 40 decipoises. Consequently, where the oil and resin were allowed to react a t 565” F. (296’ C.), the resulting body of the thinned varnish was practically 400 per cent greater than the body of the bodied oil with the resin dissolved therein. The conclusion is that the zerolized oil (VM08) reacts de-
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301
cidedly bet,ter with the 100 per cent phenolic resin than the lightly winterized oil (VM06). EXPERIMENT 3. To compare the reaction of phenolic resins, modified phenolic resins, and ester gum with sardine oil, experiment 1 was repeated. However, in this case the oil, a nonbreak zerolized sardine oil (WS03) wit>han acid number of 1.5, was the same in the three beakers but the resins were changed’ that is, 100 grams of ester gum No. 1, Rauzene X150, and Bakelite 254 were used with 200 grams of oil and subsequently reduced with 172 grams of turpentine. The results are given in Table I. The body of the ester gum-sardine oil reaction was about the same as the body of the purely dissolved resin (Bakelite 254) in the heat-bodied sardine oil, which would indicate that the ester gum-sardine oil mixture was merely one of solution. The Rauzene X150, after being reduced with thinner, was twice as heavy, and the Bakelite 254 about eight times as heavy in body as the ester gum-sardine oil mixture. Another intereating observation is that the neutral Varnish Makers sardine oil (VM08), bodied in combination with Bakelite 254, had less than half the viscosity of the nonbreak sardine oil (WS03) which had an acid number of 1.5. EXPERIMENT 4. Ex eriment 3 was duplicated as nearly as possible, using a Varnist Makers linseed oil in place of the sardine oil. The nonbreak Rardine oil (WS03) produced with Bakelite 254 a varnish with a body nearly seven times as heavy as the Varnish Makers linseed oil; and the Varnish Makers eardine oil produced a body nearly three times as heavy as the Varnish Makers linseed oii. I n these experiments the heating curve of the oil bath did not vary over 10” F. (5.6’ C . ) during the 2 hours when the temperature of oil was above 450” F. (232.2’ C . ) . The conclusion is that more reaction takes place between phenolic resins and sardine oil than with linseed oil (probably because of the highly unsaturated clupanodonic acid radicals in the sardine oil) and that a maximum of reactivity takes place with thoroughly winterized oils. It would appear well worth while for the varnish maker t o investigate the possibilities of varnishes made with synthetic resins in which the sardine oil would replace the linseed oil completely and part of the China wood oil.
Acknowledgment The writer wishes to acknowledge with appreciation the work of Potter Holmes, who made the saturated acid determinations, and Thayer Pattison, who assisted with the laboratory work. The writer is also indebted to B. M. Pattison for permission to present this paper.
Literature Cited (1) Jamieson, G. S., “Vegetable Fats and Oils,” p. 238, A. C. S. Monograph No. 58, New York, Chemical Catalog Co., 1932. (2) Twitohell,J. IND.ENQ.CHEM.,13,806 (1921) ; modified by Boughman and Jamieson, Oil & Fa8 Ind., 7, 331 (1930). (3) Vegetable Oil Products Co., Tech. Bull. 2 (1935). HECBIVEDSeptember 12, 1935. Presented before the Division of Paint and Varniah Chemistry at the 90th Meeting of the Ameriaan Chemical Society, San Francisco, Calif., August 19 to 23. 1936
BESSEMBR STEELPLANT, PITTSBURGH, PA.
From a painting reproduced by courtesy of School o j Mineral Industries Gallery, The Pennsylnanca State College
