May, 1945



Barnes, R. B., Liddel, U., and Williams, V. Z., IND. ENQ. CHEM., ANAL.ED.,15, 699 (1942). 38, 71 Baxter, G. P., and Wallace, C. C., J . Am. Chem. SOC.,

Chem. Industries, 54, 835-7 (1944). Davis, H. S., and Davis, M. D.: ~ N D .ENG. C H ~ M 15, . , 1075

Desgrez, A., Compt. rend., 152, 1707; 153, 895 (1911). Dickinson, H.C., Bur. of Standards, Bull. 11, 189 (1914). Dudley, H.C., and Neal, P. A,, J.Ind. Hug. Tozicol., 24, 27-36

Dudley, H. C., Sweeney, T. R., and Miller, J. W., Ibid.,
255-8 (1942).


Garner, J. B., Adams, L., and Stuchell, R. M., Petroleum Refiner, 21, 157 (1942).

(10) Henderson, B. W., Chem. Industries, 47, 50-1 (1940). (11) Jermstad, A.,Pharm. Acta Helv., 1, 202 (1926). (12) Jones, G. W., Kennedy, R. E., and Scott, G. S., U. S. Bur. Mines, Repts. Investigations 3597 (1941). (13) Koch, A,, IND. ENQ.CHEM., 32, 464-7 (1940). (14) Lawton, A. H., Sweeney, T. R., and Dudley, H. C., J. 2nd. Hug. T o x ~ c o25, ~ . ,13-19 (1943). (15) Mallette, F.S., Ind. Med., 12, 495-9 (1943). (16) Moureu, C., Bull. SOC. chim., [3]9,424-7 (1893). ' 4 1 27,904 (1920). (17) Moureu, C., and Brown, R. L., Ibid., 1 (18) Richards, T.W., and Barry, F., J . Am. Chem. SOC., 36, 1787-91 (1914). (19) Skau, E.L., J . Phus. Chem, 37, 609-14 (1933). ' ( 2 0 ) Timm, B.,and Meckg, R., Chem. Zentr., 1936, I, 2331. (21) Timmermans, J., Bull. eoc. chim. Belg., 31, 392 (1922).

Preparation and Thermal Decomposition
Western Reserve University Cleveland, Ohio
Castor oil is easily and quantitatively acetylated by acetic anhydride. Acetic acid, in the presence of p-toluenesulfonic acid as catalyst, leads to hydrolytic splitting of the glycerides unless the water of esterification is immediately removed. With continuous fractional distillation during esterification, castor oil can be acetylated with acetic acid. Acetylated castor oil slowly decomposes at 2 5 0 ' C. to form acetic acid and an oil of greater unsaturation than castor oil. The 9 5 ' , 300°, 306O, 3 1 2 ' , 320°, 330°, and 3 4 0 ' C. The rate of decomposition has been measured at 2 process is first order with an energy of activation of 44.5 kg.-cal. The thermal polymerization which occurs during the reaction can be minimized by high temperatures (320-340' C.) and short reaction times. The product is a light yellow oil having about 30% of molecules containing a pair of conjugated double bonds and suitable for use as a drying oil in protective coatings.

H E thermal decomposition of esters to form the corresponding acid and the olefin of the corresponding alcohol has been known since the work of Krafft (17) on cetyl palmitate: (1) Only recently, however, has this reaction found application in the preparation of certain unsaturated hydrocarbons and their derivatives. Among these applications may be noted the synthesis of various olefin hydrocarbons from acetate esters (39), butadiene from 2,3-butylene glycol diacetate ( I I ) , methyl acrylate from acetoxy methyl propionate (6, 7), and dehydrated castor oil from acetylated castor oil (5'). I n some instances the thermal decomposition of esters, especially the acetate esters, gives better yields of olefinic products with less likelihood of rearrangement of the carbon skeleton than the parallel dehydration of alcohols. The problem of converting castor oil to a drying oil is essentially one of dehydrating the secondary alcohol groups of the ricinoleic acid radicals, which castor oil contains to the extent of about S5Y0 ( I O ) , to double bonds a t either the 11,12 or 12,13 carbon atoms:




+ CisHaz

Various metho& have been developed to effect thjs dehydration, and their success is evidenced by the several commercial dehydrated castor oils now marketed and their wide acceptance in the protective coating industry (21). Briefly, these methods fall into three groups: (a) thermal dehydration of ricinoleic acid by distillation and esterification of the product with glycerol (32); (b) catalyzed thermal dehydration of castor oil by such catalysts as sulfuric and persulfuric acids (25, 29), phosphorus pentoxide (%), metallic oxides (ZZ), and alkali metal bisulfates (8); and (c) thermal decomposition of castor oil esters such as the acetate (S), phthalate (ST),and octadecadienoate ( 2 3 ) . The purpose of the present investigation was to study the preparation of acetylated castor oil, the kinetics of its thermal decomposition, and the properties of the resulting product.




Present address, Phillips Petroleum Company, Bartlesville, Okla.

By the use of excess acetic anhydride, castor oil is easily and quantitatively acetylated. Acetyl chloride cannot be used because the acetylated oil was found to contain combined chlorine, possibly as a result of the addition of hydrogen chloride to ethylenic linkages. Presumably ketene would be a suitable acetylating agent, since i t has been used successfully on other secondary alcohol esters (6, 34). From the economic standpoint, acetic acid would be the cheapest acetylating agent because its original cost is relatively low, and it is reformed on thermal decomposition of the acetylated oil. On the other hand, acetic anhydride forms one molecule of acetic acid during acetylation, and this

Acid No. The interaction of castor oil and acetic acid at reflux must lead to a complex group of equilibria involving. and this molecular weight is needed t o revise the value of 300 (saponification number of acetylated castor oil) which represents 100% acetylation. The acid value of the latter was 2.. with or without p-toluenesulfonic acid.107 mole or about 0. . but the rate of reaction was very slow. Saponification No.1% of p-toluenesulfonic acid (Table 11). Acid No. Hr. as shown by experiments 7 and 16 in which the reaction times were 60 and 11 hours.0. 0. The acid catalyst greatly accelerated the reactions. Acid NO. While this is readily calculated it is not useful since the actual molecular weight of the ester is not know.H10 135-145' C. To show that water is a requisite for the acid interchange. No. FOR 10 HOURS No. Assuming the distillate to be pure acetylated ricinoleic acid.. .(acid numher -Z. Saponification No.1 increasing amounts of water. No. 300. . O F CASTOR OIL (100 GRAMS) WITH ACETIC ACID (60 GRAMS) AT 130-145" C. Expt. the amount of free acids increased wit 1.0. AND 0. As Table I V shows. exactly. 202 206 248 202 1 9 20 21 56 20 TABLE 1 1 1 .. several model experiments were run with linseed oil. . It seemed likely that the water of esterification was a key factor in this process because the acetylated castor oil made with acetic anhydride as the acetylating reagent.75 .2 27. I n experiment 21 one gram of acetic anhydride was added to remove any traces of water. The presence of free higher acids in these esterification products showed that acid interchange or displacement was occurring.. and various glycerides based on all of these acids. The results parallel those of experiment 25 where acetic anhydride without acetic acid was used. but when small quantities of water were added in the following experiments. the yield should have been 16. Even in 12 hours (experiment 33) only 56% of the oil was esterified. 300 . Grams 21 1 25" 50 22 23 24 a No acetic acid used. would have to be converted to the anhydride.38 0. . acetylated ricinoleic acid.and 1% carbon-atom saturated and unsaturated acids. 37.. b 0. " TABLE 1 1 . b Calculated on the basis of 177 and 300 as t h e saponification numbers for castor and acetylated castor oil respectively. For acid numbers greater than 2. the acid along with any water formed was condensed and recycled. or by washing with water. The first consisted of passing acetic acid vapor through castor oil heated a t 160-240' C. if acetic acid were to be used successfully. and known amounts of water.0 1. due to hydrolysis t o form acids and possibly some esterification with acetic acid. 200 yo Acetylated. The discrepancy in these constants is probably due to the presence of other 18-carbonatom acids.0 4. HI. No.0 13. REACTION OF CASTOROIL (100 GRAMS) WITH ACETIC ACID (100 GRAMS PER HOUR)" T. Comparison with expt. had an acid number of 150 and saponification number of 311.0 189 189 196 206 214 saponification number . 16. A possible TABLE IV. Sapoiiification No. acetylation with little acid interchange was achieved in this way.075 0. Conditions are actually favorable for hydrolysis because the acetic acid serves as a coupling solvent for the oil and water and the p-toluenesulfonic acid acts as a hydrolysis catalyst.) for various periods of time. To determine if the reactions occurring between castor oil and acetic acid were susceptible to the usual esterification catalysts.3 43. contained practically no free acid. These values are not corrected for the free acid content. REMOVAL OF WATER These results clearly indicated that.. These considerations led to a study of the esterification of castor oil with acetic acid. Experiments 30-32 show that a temperature increase of 160 to 240' C.4 Saponification No. pressure..1% p-CH3CBHa803H.l" x 100 . weighed 14 grams. Therefore the acid interchange is not a direct process but rather an indirect one in which the intermediate reaction is hydrolysis of the glyceride. REACTION O F CASTOR OIL (100 GRAMS)" WITH ACETIC ACIDAT REFLUX (130-145" C.t h e per ccnt acetylated is: Saponification No. 70 grams of a product of acid number 47 and saponification number 313 was vacuum-distilled a t 1 mm. Expt. When the excess acid and water of esterification were removed by distillation. If t h e acid value of the sample is not greater than 2.H20 Time. If ketene were used. These are experimental values determined on the castor oii used in this work and on the acetylated oil made by acetic anh>dride acetylation. Reagent glacial acetic acid was used throughout this experiment. AczO.. A more accurate calculation would use the saponification number of the ester portion of the sample.2 2. several experiments were run in the presence of 0. REACTIONOF LINSEED OIL (50 GRAMS) WITH ACETICACID (25 GRAMS) AND 0..27 equivalent of hydroxyl. Hr. the partially acetylated oil was unexpectedly found to contain a considerable amount of free acids (Table I).O)--is used in place of t h e saponification number. axetic acid.0. respectively.1% p-CHtC&I4SOsH. 1. 2. 5 Expt. has little effect on the rate of acetylation.. These experiments indicate that an equilibrium is being approached a t which the acid number is about 50 at the end of a 60-hour reaction time.177 " . the by-product acetic acid would have to be cracked to reform ketene (6). Preliminary experiments were run by allowing castor oil and excess glacial acetic acid to react a t reflux (130-145' C. I n this anhydrous mixture practically no free acids were formed. b Calculated for completely acetylated castor oil. 31 shows that recycling the acid works as well. Grams Reaction Time.0 mole. along with that obtained from thermal decomposition. Water... which contains only traces of hydroxy acids. the ester number-Le. the water of esterification had to be removed immediately. ricinoleic acid.""dl" Time. Gram AT After passage through the oil. The distillate collected up to 215' C. 1.486 INDUSTRIAL AND ENGINEERING CHEMISTRY TABLE I.2 grams with acid number 165 and saponification number 330. 15 16 17 18 5 11 15 40 37 68 82 80 279 307 319 316 acid. No. REACTION Expt.8 3. Again acetylation was accompanied by the formation of large amounts of free acids. The free acids present must be of higher molecular weight than acetic since they were not removed by distillation up to 240' C. in addition to acetic acid and water. 160 Acid 30 31 32 33 340 200 240 200 200 3 3 3 12 3 No..2 2. T o make certain that the free acid content of these partially acetylated oils was due entirely to higher fatty acids.) Val. No water is formed in this reaction as long as a t least one mole of anhydride is taken for each equivalent of alcoholic hydroxyl. HOAc. TWO experimental approaches l o this condition were investigated.

0 120 0. After this preheater and before the ground-glass connection to the bubbler. When 170 grams of acid were used as in experiment 5 (Table I).Hz0AT 200" c. saponification number 177.6 120 10. and the off-vapor of acetic acid and water escaped through the side arm of the reaction flask into a water condenser. and with only 90 grams of acid the temperature was 138-160". Portionwise addition of the catalyst has the advantage of bringing the catalyst concentration to a maximum in the later stages of acetylation where the rate normally falls because of consumption of the acid and hydroxyl groups. Experiment 37 represents the most favorable conditions: 84y0 of the oil was acetylated in 6 hours. the partially acetylated oils were further treated with acetic anhydride and the saponification numbers measured. etherification would lead to a final product having somewhat less unsaturation and possibly slower drying power. it should not affect adversely the drying properties of the final dehydrated oil. of acetic acid-water (about 8 ml. The column used had a glass-helixfpacked section 152 cm.5 1.2 at start' 0:2 at 1hour' 0. and the packing consisted of singleturn glass helices about inch in diameter. the temperature ranged from 124' to 130" C.6gram of p-toluenesulfonic acid were allowed to react in the experiments summarized in Table VI. 234 289 296 302 299 303 301 306 291 lated AEexperiments 56-62 show.4 poises a t 23.2 at 2 hours: 0.'0. If these values are lower than 300. The acetylations with acetic acid vapor were carried out in a cylindrical reaction flask of about 35-mm. 1945 INDUSTRIAL AND ENGINEERING CHEMISTRY 487 explanation for this unusual result is that the amount of acid dissolved in the oil-Le. was water) if approximately 90% acetylation were obtained. Technical-grade acetic anhydride (Dow Chemical) was also distilled before using. and its acid number was only 9. in diameter.. The other substances tried were all much less effective. 39 42 45 46 43 44 ACETICACID (120 GRAMS)AND VARIOUSCATALYSTS (O. 3 Acid No. A silvered vacuum jacket and an automatic takeoff on a total condensing head completed the assembly. there has been a loss of hydroxyl groups (Table V).s-rf aphthalenedisulfonic acid 50 ACETYLATION PROCEDURE TABLE VI.7 170 a 0.25 120 6. sintered glass bubbler. No.. REACTION OF CASTOR OIL (200 GRAMS)WITH Expt.. The rate of distillation was adjusted so that the temperature at the head of the column was 100-101' C. measured a t total reflux on a %-heptane-methylcyclohexane mixture (18).1.. % Acetylated 66 84 82 6 9 245 284 286 Sap. but there was a simultaneous loss of hydroxyl groups to the extent of about 10%. a weight ratio of acid: oil of 1. No.0 1. The acetic acid was distilled from a distilling flask whose side arm was wrapped with wire gauze so that the vapor could be superheated with a wing-top flame. I n 62 (the oil was substantially completely acetylated in 3 hours a t 130-140" C.8 120 0. 70-170 grams of acetic acid.0 6. The fractionating column was a standard model purchased from the Ace Glass Company.8 0. in length and an efficiency of forty-two theoretical plates. Expt.4770. The efficiency was determined at total reflux with a mixture of . tion No. and viscosity 8.5. using the fractional distillation procedure (Table VII).220 is most suitable in terms of time. long and 14 mm.8 120 11. the reaction flask was heated to the desired temperature. Because of the possibility that a portion of the hydroxyl groups of castor oil might be destroyed either through etherification or dehydration. refluxing temperature.. and 0. On the other hand. 22 1 230 207 207 273 275 254 239 % A. One hundred grams of oil with the bubbler and thermometer immersed made a column about 12. and thermometer.9" C. A commercial grade of castor oil was furnished by the Sherwin-Williams Company. Hr. To substantiate the selection of p-toluenesulfonic acid as the best catalyst.1 at 2 hours b 0.16 0.3 0. the catalyst was added a t the start of the reaction (Table VI) TABLE VII. It would be expected that the greater concentration of acid would lead to more rapid acetylation. The second experimental technique designed to remove the water of esterification before it caused hydrolysis depended on continuous fractional distillation during the acetylation reaction. TABLE V.7 7.4 120 7. acid content of product.8 90 0. CHEMICALS.4 Saponification No. after Acetylation 296 288 289 the lower catalyst concentration a t the start does not produce water of esterification at such a high rate that it cannot be removed by distillation.lyo) Catalyst Trichloroaoetic acid Phosphoric acid (85%) Litharge Zinc oxide Acid No. Expt.0 3. that this is not the case must be due to a lower temperature of reaction-Le. 2.4 0. Time Acid Saponifica. If this were due entirely to dehydration.V 0. Benzene and p-toluenesulfonic acids have about the same activity but the former causes some discoloration of the oil.. Unless otherwise indicated.6 11. a T-tube held a thermometer to measure the vapor temperature. No.16 Time. Gram 0.. high.2 at 1 hour: . and degree of acetylation. REACTION OF CASTOR OIL (200 GRAMS) AND ACETIC ACIDWITH CONTINUOUS FRACTIONAL DISTILLATION HOAc. To increase the rate of acetylation under these conditions. its effective concentration-decreased with increasing temperature and thus offset the effect of temperature increase.6'~ 120 9. From these results it was concluded that castor oil could be satisfactorily acetylated with excess acetic acid in the presence of p-toluenesulfonic acid as catalyst by fractionally distilling water and some acetic acid continuously from the reaction mixtyre. It showed the following constants: acid number 1.3 at start 0 2 at 1hour 0. No. Two hundred grams of castor oil. also.6 3.0 3.0-0. the packed section was 152 cm. Hour. Experiments 54 and 51 of Table VI used smaller and larger relative quantities of acetic acid. I t s over-all length was 193 cm.4 8. several other substances were tried a t a reaction time of 2 hours. Obviously this process has a considerable economic advantage over the acetic anhydride acetylation. and the distillate consisted of 12-14 ml.70 AcetyGrams Gram 2. During an acetylation a slow current of dry nitrogen was passed through the acetic acid flask. 3 6 10 Saponification No. with 120 grams of acid the temperature was 130-140".1 13. 36 37 38 Catalyst.6" 0.May. ptoluenesulfonic acid was tried as a catalyst.3 at start.1 0. Catalyst. diameter fitted with a side arm. APPARATUS.5 cm. REACTION OF CASTOR OIL (100 GRAMS) WITH ACETIC ACID (100 GRAMSPER HOUR) AND p-CHaCeHJ30sH.cetylation 43 24 24 74 76 63 36 Toluenesulfonic acid 2 8enzenssulfonic acid Cam horsnlfonic soid 3. :'27 1. p-Toluenesulfonic acid monohydrate was Eastman Kodak's best grade. No. Technical-grade glacial acetic acid was distilled for use in the acetylations.

Rate measurements were made a t 293".6 of 1. Two experimental procedures appeared to be practicable: I n the first the evolved acid was collected in excess standard alkali.167 2 4 TtME <MINUTES) 6 Figure 1. CONSTANTS. Saponification. and hydroxyl numbers.5 kg. the literature contains relatively little kinetic data on this process. and viscwities were determined in the usual way. After refluxing 2 hours the product was transferred to a 5-liter. This must be done cautiously because of the exothermic reaction. and a typical set of data is given in Table VIII. The product had an acid number of 2.1. k equals 0. 5 I 3 IO ' 6 b\\ 1 ' ' ' ' ' I5 9 . x Figure 2. ACETYLATION WITH k ? E T I C ANHYDRIDE. Alternatively. until no more dis- -0.4680. and 340" C.488 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol.00049.z)= 2.9 moles) of acetic anhydride were carefully brought to reflux in a 3-liter round-bottom flask. thermometer. 306".467 1621 1651 1681 1741 1771 $. The straight-line curves obtained show that the thermal decomposition of acetylated castor oil is a first-order reaction in the temperature range 295-340' C. which means that about 0. From the slopes of these lines the specific reaction rate constants k were calculated: -log (a ..100 t 040oL&. Rudy and Fugaasi (SO) and Warrick and Fugassi (38) investigated the vapor-phase . 99-100% based on the hydroxyl number of the castor oil (159). By measuring the rate of acetic acid formation at varibus times. and viscosity at 23. three-neck flask fitted with a nitrogen inlet tube. 312O.05% of a sample of acetylated castor oil will decompose per minute a t 250" C. The yield was 1130 grams. Although ZL number of acetate esters have been thermally decomposed for purposes of synthesis. n2. From the foregoing data constant IC can be evaluated : log k = -44.07 moles) of castor oil and 500 grams (4.0. 5 tillate came over. 37. efficient mercury-seal stirrer. 1000 grams (1. 1 part of pure n-heptane and 2 parts of pure methylcyclohexane (18). acid. No. With B stream of nitrogen passing beneath the surface of the oil and with vigorous stirring the mixture was heated to 240" C.-cal. the rate of thermal decomposition could be determined. The second procedure was found to give more reproducible results. 330% 340% c 340. 300°.500 1 2.767 1. Rate Measurements a t 295" t o 340" C.367 "i 1 1 I : / t /i d d 1 7 1 1 1 0 6 / O/ \I 2 0 I 2 -1. KINETICS O F THERMAL DECOMPOSITION Preliminary experiments showed that acetylated castor oil slowly decomposed with the formation of acetic acid a t about 250" C. The average of several determinations was forty-two theoretical plates. refractive index. the distillate could be collected and weighed. of 3. by plotting log k against l / T in Figure 2 and determining the slope from this graph. and aliquot portions of this solution were titrated at various time intervals. and glass delivery tube connected to a water condenser set for distillation.303 -t + constant (3) The energy of activation was calculated to be 44. saponification number of 300. Reciprocal of Temperature From this equation the rate of decomposition can be estimated at any temper8ture. if fairly large samples of oil (500 grams) were taken. 320°. a t 250' C.567 -1.9" C.2 poises. I n Figure 1 log (a-2) is plotted against time for each of the rate experiments. Log k v s .403 R ___ + 15. For example. 330°.286 -1.

the initial step is chelation through an intramolecular hydrogen bond. Tzmu.. . which must be formed by cracking because all uacombined acetic acid is distilled.560 55 41.9 40 33.843 69.8 25 22. Acid No..2 3.-cal. a property which depends on the extent of thermal polymerization or "bodying". .6 IX 320 35 88 7 8 6. which is 99% of the theoretical yield of 422 grams. The theoretical yield'of acetic Acid from 500 grams of acetylated castor oil is 78. ..0 11. secondary.. The fact that these are esters of a tertiary alcohol may account for the lower energies of activation compared to the acetylated castor oil.322 -1.7 3 1 XI11 340 21 100 8. from the kinetic standpoint the decomposition of one molecule of acetylated ricinolein should not differ materially from the decomposition of three molecules of acetylated methyl ricinoleate. No.9 X 320 45 90 9. and tertbutyl propionate a t 240-296" C. log IC -1. 1945 INDUSTRIAL AND ENGINEERING CHEMISTRY 489 decomposition of tert-butyl acetate a t 242302" C.839 -1.6 29.x) 0 CH. but the complexity of the system prevents a complete analysis of all the simultaneous reactions which may take place. 78.8 1.3 1. .77 7.6 IV 70 82 8..747 55. Poises I 295 145 79 9. 295' 300 306 312 320 330 340 x t . Expt. These data show that the products vary considerably in viscosity. 1 J. Hurd ( I d ) . Then the proton from the beta-carbon atom with respect to the oxygen atom is transferred to the carbonyl oxygen.45 2.5) grama of acetic acid remaining at time t.90 4.6 VI1 312 55 82 11.. The least polymerization (as measured by viscosity) is obtained by the use of a high temperature and a short reaction time.Q°C.1 1.470 70 48. as the energy of activation (33).5 1. Recent measurements on this substance a t 290-320" C..1 grams of acetic acid.3 and 39. have given 42." Grams H Therefore two reactions have occurred simultaneously which may not be kinetically identical.3 6 0 V 306 80 306 79 8.386 85 53 8 24. II I -C-.. .6 kg.821 -0. 5 ( a . and rearrangement of the resulting fragments gives acetic acid and a molecule with a new double bond: H- TABLE VIII. .3 ' 1.13 0: 1 -C- I 78. Some cracking t o form other volatile products probably occurs in all of the experiments and certainly in those whose loss of weight exceeds 78.893 1.. .-C\/?-H. for example. but no new evidence either for or against it has been found. . the viscosity and acid number of the oil can be controlled to some extent.9 il. and here again the reactions leading to these isomers may not be identical in rate or energy of activation.1 grams. I n a glyceride containing one or more acetylated ricinoleic acid radicals. the product from experiment 12 had a vis- TABLB X. Examination of the products has shown the presence of both conjugated and nonconjugated double bonds: These products form because the atom of hydrogen which pairs with the acetate group may come from either carbon atom 11 or 13: Table X summarizes several decompositions run on 500gram samples of acetylated castor oil a t various temperatures and reaction times. 0 DECOMPOSITION OF ACETYLATED CASTOR OIL" AT 295" * 1" C.. The observed energies of activation were 40.2 16 7 XI1 340 6 81 12.3 7 8 VI 306 90 86 7. There is evidence that the ease of thermal decomposition of esters varies with the parent alcohol and increases in the order: primary. I n most cases the yield was about 415 grams. Min. . I n all owes the product contains some free acid. the presence of two double bonds in each chain theoretically permits the formation of four geometrical isomeric forms.652 44.9 51.0 6.538 -1. 19). the other carbonoxygen bond is split.11 + .7 10 8 4 1. tertiary (14.7 VI11 312 65 80 12 1 9. . From a practical standpoint the kinetic measure- Viscosity at23..111 -0. it thus resembles the dehydration of alcohols.. it seems likely ments reported here are useful.08 2. The reaction mechanism for the decomposition of esters and of similar compounds has been discussed by Ingold ( I S ) .lo * . RATECONSTANTS AT VARIOUS TEMPERATURES k 102 1. I n the case of tert-butyl propionate no change in velocity constant with pressure was observed a t pressures down to 17 mm. This assumption is not unreasonable if one notes the many atoms which separate the acetate ester groups in the glyceride molecule.667 I I This proposed mechanism has been carefully considered. +I OH CH8-L =0 + I t I cI1 C1 I C-H A H TABLE IX.16 kg. According to their view.1 27. Furthermore.0 I11 300 56 306 71 12.3 a 5 represents grams of acetic acid collected in time t' ( a . This polymerization is favored by longer reaction times a t % given temperature (compare experiments IIIVI) and by higher reaction temperatures (experiments I11 and VII). OILS FROM THERMAL DECOMPOSITION that the splitting out of the units to form acetic acid from each carbon chain would proceed independently.2 36.1 grams.1 -C- Temp. Time.12 /H :0: CHs-&f\- J:C-H C- I I C-H I I I .-cal.5 I1 125 78 9.74 15. A more exact definition of the reaction in terms of the structurally isomeric and stereoisomeric products formed cannot be formulated. O C. Closely related to the decomposition of acetylated castor oil is the decomposition of acetylated methyl ricinoleate..x) Log ( a . THERMAL DECOMPOSITION UNDER VARIOUS 13 12 H H 11 10 9 CONDITIONS Wt. - :d 'A-H. which has secondary alcohol groups.8 11. Loss. respectively. Min.0 Theoretioally.May. On the basis of this assumption the observed reaction rates and energy of activation correspond to the elimination of a single molecule of acetic acid and formation of a new double bond. and Stevens (36).882 -1. By the proper choice of temperature and time. Le.5 7. Time.

of maleic anhydride solution are added by a pipet. for 2 hours and then filtering. No. then with 10 ml.0 200 11. The temperature reached 305" C. This is readily done by treating the crude ester with 1% of Magnesol clay with vigorous stirring at 100' C.0 203 6.7 32 9. Phenolphthalein indicator ie used.490 I N D U S T R I A L AND E N G I N E E R I N G CHEMISTRY Vol. Poises n'D" nz6 No. FJ7ith no catalyst.0 ml.9347 127 IV 9.32 gram. At the end of the refluxing the mixture is allonTed to cool. the condenser is rinsed with 5 ml. and the nitrogen flow was adjusted to 120 bubbles per minute at a small bubble counter. CONSTANTS O F DEHYDRATED CASTOR OILS % Conjugation UltraMaleic violet anhy. of water. No. CONSTANTS.-cal. After vigorous shaking the aqueous layer is drawn into a 250-ml. This temperature was maintained manually to * 1' C..5 85 10. alkali.V. the oil film rapidly absorbs oxygen in the absence of driers. The high saponification number in experiment XI1 is probably due to some undecomposed acetate groups. if the p-toluenesulfonic acid catalyst is first removed. Increase. and refluxing is continued for 15 minutes.0 grams of acetic acid were formed in 20 minutes. NaOH for sample CATALYZED THERMAL DECOMPOSITIONS - X normality X 12.6 130 20. by direct heating with a Mekker flame. a n efficient mercury seal stirrer..1 gram. diluted to 1 liter with additional toluene.0 60 7. separatory funnel.. RATE Time. and (c) the effect of catalysts on the distribution of conjugated and nonconjugated products. one would predict that the conjugated isomer would predominate. weighed to the nearest milligram.9' C. The flask was fitted with a nitrogen inlet tube reaching to the surface of the oil.absorpdridem tion(d0) 23 34 25 33 23 29 (4).0 1.b Viscosity a t 23. after 75 minutes.68 weight of sample RATE MEASUREMENTS.0 22.13 double bonds and. XI1 1 2 . of warm reagent-grade toluene. From the fact that systems of conjugated double bonds are stabresult of ilized by 5-8 kg. for a triglyceride based on 18-carbon-atom taining a pair of conjugated double bonds. 5. and its rate of thermal polymerization at 305" C.1 1. No. Other significant properties of three of these oils are given in Table XI.6 95 16. 3.4865 0.9467 121 Based on maleic anhydride values of Ellis and Jones lated M. OF THERMAL POLYMERIZATION AT 305" C. The combined aqueous extracts are titrated with standard base: Maleic anhydride value = (A where .. The following modified Ellis and Jones procedure gave reproducible results: Sixty grams of redistilled maleic anhydride are dissolved in 500 ml. and filtered after standing overnight. a calibrated thermometer. The per is (M. 37. As Tables XI1 and XI11 show. DECOMPOSITION PROCEDURE Although maleic anhydride values for conjugation (4) are considered less reliable than the ultraviolet absorption measurements (do). therefore.6 1. Other investigators have also observed that dehydrated castor oil made by various methods contains only about 30% of conjugated double bonds (28).Iodine numbers were found by the Wijs 60minute procedure (12). in the same way as the rate measurements were made.0 The initial film weights were about 0.V.5 109 15.6 125 One liter of oil was heated and mechanically stirred in an open stainlesssteel kettle. and the maleic acid acts as a dibasic acid. Poises 0 3. The content of conjugated molecules is of particular interest because the relatively low values show that the major product probably has 9.A. These properties were also apparent when the oil was formulated into varnishes and paints.lO and 12. that. and a condenser set for distillation. the rate of decomposition was TABLE XII. Tung oil 2. Fiftygram samples of acetylated castor oil and 2% by weight of catalyst were heated to 300' C. There is no apparent explanation for the distribution of products observed.8 60 2.0 N aqueous sodium hydroxide is standardized against 1. is high. and then brought to the desired reaction temperature as rapidly as possible.2 19. .0 105 41.0 85 9.4 5. NaOH A average ml. This heat-up time t o the desired temperature varied from 5 to 9 minutes.9417 125 VI 9. As Table XI shows.0 grams of acid in this time.4838 0. Acid fication 23. 0 210 3. The acetylated castor oil used in these experiments was made by the acetic anhydride method. Five hundred grams of acetylated oil were placed in the flask.B ) ml.4 15. The acetic acid was collected in tared flasks and weighed t o the nearest 0. each concent conjugation ViscosSaponi./87) X 100. is weighed in a 250-ml.OO3-INCH FILMS ON 3 X 5 INCH TINPANELS Wt. The apparatus for the rate measurements consisted of a 2-liter three-neck round-bottom flask. 5 cosity of only 3.0 15. These values probably do not measure total unsaturation because of the conjugated double bonds present (9). per mole of resonance energy as a4 contributing structures which are not possible for isolated double bonds ( U ) .A. Duplicate samples and duplicate blanks are run. The product prepared by acetic acid esterification with fractional distillation can also be used. After cooling.6 0 .ity a t Iodino Expt. Approximately 3.0 ml. Approximately 1. and soap resistance.0 grams of oil. the absorption measurements give results which are somewhat higher than those obtained with maleic anhydride (24). NaOH for blank B = ml. of water. the hydrogen atom of carbon atom 13 was preferentially removed as acetic acid (compare Equation 5).0-gram samples of pure maleic acid dissolved in 100 ml. and the mixture is refluxed for 5 hours. round-bottom flask with a ground-glass joint. TABLE XI. and the toluene solution extracted again with 25 ml. No. As is generally true of polymerized oils. the upper two thirds was insulated with a l / d inch layer of asbestos cement. If a catalyst caused the formation of 4. of ether. Erlenmeyer flask.TABLE XIII. The sample was brought t o 240' C. those of higher viscosity have higher indices and densities and lower iodine values. Examination of the film-forming properties of this product showed that it dried rapidly to a hard. Min. A variety of substances was tried as catalysts for the thermal decomposition of acetylated castor oil to determine (a) the general nature of the active catalysts for this reaction. of water are added. Mg.9' C. The acetic acid formed in that interval was discarded and "zero time" taken when the reaction temperature was reached. 25. and the solution is transferred to a 100-ml.5 32. portions of water for rinsing. RATE O F OXYGEN ABSORPTION FOR O.1 poises. nontacky film of good water.2 115 56. they were determined here for the sake of comparison. using three 10-ml. solution is cooled. ( b ) the possibility of operating the process a t lower temperatures and/or shorter reaction times.0 22.4860 0.1 27. is 87.* Time Dehydrated Alkali-refined castor oil linseed oil Hour: 0 0 0 3. The calcuaoids.

29 (1941)..812 (1936). Y. of Paint. The catalyst became black. IND.. French Patent 831. F. H.. Sulfuric (96 ) Decompn. P. 1942. but the nickel catalyst yielded a product having 40% of two double-bond conjugation.. Patent 2. 1945 INDUSTRIAL AND ENGINEERING CHEMISTRY 49 1 TABLE XIV. lowered t o 270° C. Ingold. Paint J. V.. E.. (11) Hill. R. heated. (38) Warrick.72 (1940). Patent2. after recovery of the acetic acid.D. Buffalo.555 (1940). 20 ( 5 ) . p. temp. A. Since metallic hydrogenation catalysts are capable of catalyzing t h e partial isomerization of the double bonds in linseed and soybean oils to conjugated positions (1. lowered t o 280° p-Toluenesu$onic Decompn. 24. (25) N. J. Operation of the column under reduced pressure would permit the acid number of the oil to be held to low values.CHUM. D. R. and Fisher. IND. 8. and the catalyst was again active for a short time. in air. an increase of 6% over an oil prepared without nickel. H. 8. Div.. and Neville. J . 36.. W. U. (26) Organic Syntheses.. New York. F.1938).. S. T. Chem. 229 (1944). W. R. Reinhold Publishing Corp. Patent 3'16. and Mamano..1237. IND. P. and Claborn. 1. 12. Harold Fleming was Sherwin-Williams Fellow in Organic Chemistry at Western Reserve University in 1940-42. I f the use of high temperatures and short reaction times t o make oils of low viscosity led t o appreciable quantities of volatile decomposition products. 96 (1936). The results of the catalyzed experiments are summarized in Table XIV. ACS. J. C. ANAL. (37) Ubben. and Kraybill. H . J. 61.ED. H. G. (4) Ellis. 18.. IND. (36) Stevens. Soo. 5. 2727 (1939). (10) Hilditch.. 2. lowered t o 230' Metallic oxides Alumina (Alcora) None Litharge None Titania (pigment grade) None Slight increase Titania gel (from TiClr).. F. 739. 16). 1940). C. 15. CATALYTIC THERMAL DECOMPOSITIONS AT 300" C. 1943. Ibid.. (33) Smith.36. Chem. ED. 31. E. The titania gel was tested in several experiments because of its reported activity for the decomposition of ethyl acetate (31). 20 (1940). J . . h. 1314 (1940).. R. could undoubtedly be best done by means of a vertical. Ber.May. D. B. C. After regenerating by heating to 400' C.. I P B I D S ~ Nbefore T ~ D the Division o f Organic Chemistry at t h e 108th Meeting of the AMIDRICLN CEIBMICAL SOCI~TY. 16.... 20. lowered t o 270° Merouric chloride None Zinc chloride Decompn. K.. A. D. (16) Klosky..CHEM. Patent 2. N.and Richmond. E. 4.. S. (26) Metals None Aluminum None Iron None Nickel None Raney nickel ($8) Miscellaneous Pumice None E-Tolueneaulfonyl chloride Decompn. 60. E. 7. ANAL.. 1942. J. and Jones.O. R. CLTALYBT" EFFECT ON RATID OF HOAc FORMATION Phosphoric (66%) Decompn. temp. An exception was p-toluenesulfonyl chloride which gave an oil of very light color and with no appreciably greater viscosity than a similar sample made with no catalyst. Am. Phys. packed column through which the acetylated castor oil would flow.. Be?. Ph. chin. L. lowered t o 250' Trichloroacetic None Anhydrous metallic acetates Lead acetate None Zina acetate Inoreased r a t e 80% Anhydrous metallic chlorides Ferric chloride Decompn. June.G. 1941). Kass.. Brit. Patterson and W. ED. and Neville. C.494 (Aug.136 (1941). Div.. .. By controlling the rate of flow in the column an4 its temperature. R. E.. the esterification with acetic acid using continuous fractional distillation and the purification of the recovered acetic acid should offer no difficulty. pp. U. V. and was found to have some activity a t the start of the reaction but this activity was quickly lost. P. J. T. and Raney nickel. L. J . 55 (1941). (8) Forbes. the original light brown color appeared.... probably because of the deposition of carbon. 309..246.CHEM.. D.570 (Sept. . The first two substances did not alter the amount of conjugated molecules. S. Soc. Oil & Soap. I. (28) Priest.. (31) Sabatier. U. Patent 2.. 1. 800. CHEM. . ENQ... Phys.. C. H. J .. S. W. E. Brode of Ohio State University. LARGE SCALE OPERATION If the preparation . E. New York. might serve to suppress the cracking reactions if they were recycled in the column with the acetylated oil.. 135.. P. The ultraviolet absorption measurements were made by J.. Memphis.. acti vated alumina. H.336. Am. The financial support of the Sherwin-Williams Company and the advice and suggestions of Robert F. V.. J.830 (Dec. van. (18) Lecky. (3) Brod.. 1943. A. . (12) Ho. 'and Pelt... Patent2. 60.212. Reo. L. Aluminum.385 (Aug. "Catalysis". C. (20) Mitchell. 765 (1941). W. 57. "Catalysis in Organic Chemiatry".230. J. (32) Scheiber. Ink Maker. and Ewell.1940).8. Chem. U.226. F. Patent 2. 21. J. E.. H. iron. L. Tenn. however. 63. 61.. G. (39) Wibaut..538 (May 13. H. ANAL.. and Egloff. and Blunck. 1940. F. 8. S. and Reed. 'The activity of the strong acids and the metallic chlorides in this reaction resembles the catalytic dehydration of alcohols (9). thesis. Noury & van der Lande. ENQ.15 (1941). 1%some instances a very active catalyst accelerated the decomposition so that all of the acetic acid (7. B.295..3018 (1883).. dehydrated oils of any desired viscosity could be made. H. Mikusch. H. T. U. M. ENQ. A... U. (6) Fein. G.. Morrell. (35) Sorenson. (27) Pauling.. and Burr.. Ratchford. (21) Morgan. 11.. K. LITERATURE CITED considered to be increased 33%. Van Nostrand Co. 1937. 12.G. was reached.Jr. (29) Priester. 7.186 (Dec. J. New York. IND. R. 679 (1933). Am.. (15) Kass.. S.. and Fugassi.C H ~ M32. (34) Smith. 1940. J.224. Div. New York.. J. P. H. H.. p. P... 32. 1922. ACKNOWLEDGMENT . ENQ. N.. 29. 8. "Chemical Constitution of Natural Fats". CHEM.. IND. those products. (22) Munzel. Chem. (2) Berkman. D.. . (24) Norris. A. .8 grams) was collected before 300' C.. (7) Fisher. and Sherman. and Isaacs.. Chem. and Fugassi. J..1938). Varnish.912 (Dec. D. Am. 2132 (1941). Most of the catalysts which appreciably accelerated the decomposition rate also caused discoloration of the oil and were therefore of no practical value. and Plastics Chem. J . John Wiley & Sons. temp. Am.. and niokel were approximately 100-mesh powders. C. lowered t o 280' inc sulfate None 5 The acids and salts used were reagent grade. .. 1055 (1938).Patent. and Mikusch.549 (Feb.the action of nickel in t h i s case is probably on the dehydrated castor oil itself rather than on the acetylated oil by way of a directive effect during decomposition. (13) Hughes.. P. 13. and Inorg. (14) Hurd. C. (30) Rudy. and Smith.2512 (1882). ED. Ibid. 544 (1940). J. ENQ. (5) Fallows. 66. 1942).. P.644 (Sept. and Scott.. R. 17.. S. Western Reserve Univ. (9) Forbes. (17) Krafft.(19) Menschutkin. Paint Manuf.768 (June 24.. and Wen. L. temp..1125 (1925).1941). von. Analyst... of Phys. temp. trav. 15.. 2419 (1938). of Phys. rtnd Inorg. C.and thermal decomposition of acetylated castor oil were carried out on a large scale.. temp. and Price.. 1930). Detroit. although presumably (1) Anonymous. J . ACS... .. J. SOC. Ultraviolet absorption measurements were made on samples prepared in the presence of 2% of p-toluenesulfonic acid. 41 (1942). 236 (1944). 5. C. D. Ruthruff are gratefully acknowledged. 1943). 1940). (23) Nessler. A. Chem. Wan.. Industrieele Maatschappij v. Frenah Patent 830... A. Chem. ENQ. Chem. and Mellers. The thermal decomposition step. T. ANAL. von. W. L. U.. B. AClds this would not affect the rate of decomposition (888).. A. ACS.

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