INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
486
TABLE V.
SWELLING
A B
54 63 66 58 34
C
D
.B
BATA FOR PULP SPECIMENS 20" c.
221 239 156 180 314
IN WATER AT
-2.5 -3.0 -3.5 -2.5 -1.5
-1.0 -1.0 -1.5 -1.0 0.0
ADSORPTION OF ALKALI TABLEVI. PREFERENTIAL
Specimen
NaOH Conen. of Original TemperaLiquor ture
% IS 16 18 16 1s 16 18 16 1s 16
c. 20 20 20 20 20
20 20 20 20 25
NaOH in S o h . within Drained Sheet
NaOH in Residual Ratio, NaOH Liquor Soln./Pulp
%
%
18.7 16.2 19.6 17.0 18.35 16.7 18.7 17.3 19.3 17.5
17.3 15.6 17.4 15.5 17.4 15.5 17.4 15.7 17.2 16.6
30/1 30/1 30/1 30/1 30/1 30/1 30/1 30/1 30/1 30/1
calculated according to the method of Jayme and Steinmann (6). These data lead to the same conclusions reached by these workers in that purification of base pulps by alkalies reduces the thickness-swelling volume, and a cold purification by alkali results in a higher value than a hot treatment. It is readily evident in Table I11that those pulps which show lesser swelling properties usually exhibit a relatively high weight increase, and with the lower alkali concentrations there is an additive advantage reflected both in the swelling and in the weight increase. For a given standard sheet, it is suggested that density differences in swelling properties of different types of cellulose reflect relations which are discerned under the microscope when individual fibers are treated in similar solutions, and that those differences relate in turn to chemical reactivity. On the other hand, differences in weight increase are more profobndly influenced by
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porosity of the standard density sheet, and free release of air is of great importance when complete availability and maximum adsorption of chemical by fiber is essential. Although the behavior of the felted sheet when immersed in water and in nonalkaline solution will be discussed more fully in a later article, a preliminary summary of results that were obtained when portions of specimens A to E were immersed in water a t 20" C. is given in Table V.
Preferential Adsorption of Alkali As was expected, the distribution of caustic in the drained sheet and in the drained liquor as determined by analysis shows that the cellulose sheet preferentially adsorbs alkali. I n all cases where analyses were made, sodium hydroxide concentration of the liquor in the drained sheet exceeded the alkaline strength of the original solution, whereas the drain liquor showed a reduced concentration. Table VI includes typical data. These results show that the specimens of high alphacellulose content, B and E , adsorb more sodium hydroxide from an 18 per cent sodium hydroxide solution than do the other samples of lower alpha-cellulose content which, with the exception of C, have had no unusual purification treatment. On the other hand, adsorption of sodium hydroxide from 16 per cent sodium hydroxide solution is as great for the hardwood sulfite specimen D as for B and E.
Literature Cited (1) Collins. G. E., J. Teztile Inst., 14, 264T (1924); Doree, C., "Methods of Cellulose Chemistry", p. 89, New York, D.Van Nostrand Co., 1933. (2) Faust, O.,Cellulosechem., 7,153-5 (1926); 7, 155-6 (1926). (3) Fugii, M., Cellulose Ind., 11, 21-5 (1925). (4) Hall, A. J., "Cotton Cellulose", Chap. 111,London, Ernest Benn, Ltd., 1924. ( 5 ) Jayme, G., Papier-Fabr., 35,305 (1937). (6) Jayme, G.,and Steinmann, R., Ibid., 35, 337-64T (1937). (7) Noll, A.,Ibid., 29, 114-16T (1931). (8) Rys, L., Ibid., 29, 325T (1931).
Detergents from Kerosene ALKYL AMINE HYDROCHLORIDES' A. R . PADGETT*WITH ED.,E. DEGERING P u r d u e University,
D
Lafayette, I n d .
URING recent years the chemist has been turning to the
utilization of some of the by-products of the gasoline industry as a source for comparatively cheap r.aw materials for organic syntheses. The preparation and utilization of the chlorination. products of kerosene, for example, appear to offer possibilities in this direction. Satisfactory yields of the chlorides of kerosene might be obtained, it was thought, by the application of the postulates developed a t Purdue University relative to the chlorination of the lower hydrocarbons (4). The alkyl chlorides from kerosene might be converted, in turn, into sodium alkyl sulfates ('7) as 1 The first paper in this aeries appeared in February (7). 9
Present address. Humble Oil and Refining Company, Baytown, Texas. .'
previously reported, or into the corresponding amines and amine hydrochlorides.
Chlorination of Kerosene The kerosene used in these experiments was obtained from the Standard Oil Company (Indiana) because of its high normal hydrocarbon content. This kerosene was carried through three complete fractionations in a batch column filled with glass helices, which was 1.5 inches (3.8 cm.) in diameter and 5 feet (1.52 meters) long. The column was operated a t the rate of about 2 ml. of distillate per minute a t 15 mm. pressure with a reflux ratio of 15 to 1, and a 5" cut
APRIL. 1940
INDUSTRIAL AND ENGINEERING CHEMISTRY
Kerosene fraction boiling at 95-100' C. (15 mm.) was chlorinated to yield about 85 per cent of the monochlorides, which were converted to N,N-diethanolkerosylamine by digesting with diethanolamine for about 18 hours at 185' C. Laurylamine, N,N-diethyllaurylamine, and K,AJ-diethanollaurylamine, and the corresponding chlorideswere prepared for use as reference compounds from lauryl bromide. The amine hydrochlorides were tested against sodium lauryl sulfate as a standard by use of the drop number test and the foam test. The results of the comparative tests indicate that the amine hydrochlorides of the composition tested here are less satisfactory than sodium lauryl sulfate as foaming agents. The primary amine hydrochlorides appear to compare more favorably with sodium alkyl sulfate than do the secondary amine hydrochlorides, and the amine hydrochlorides prepared from the kerosene fraction are the least satisfactory of those tested.
487
solution of hydrochloric acid to remove the kerosylamine as the hydrochloride. The acid solution of the kerosylamine was made strongly basic with sodium hydroxide to effect separation of the amine, which was separated, dried over sodium hydroxide flakes, and then subjected t o fractional distillation to give a 30 per cent yield. N,N-DIETHANOLKEROSYLAMINE HYDROCHLORIDE.The N,N-diethanolkerosylamine was dissolved in acetone and saturated with hydrogen chloride to give almost a theoretical yield of the hydrochloride, which was not obtained in a crystalline form but showed the normal chemical properties of the hydrochloride. REFERENCECOMPOUNDS.Laurylamine, N,N-diethyllaurylamine, N ,Ndiethanollaurylamine, and their hydrochlorides were prepared for reference compounds for use in the comparative tests. Laurylamine was prepared by the procedure of Davis and Elderfield (2) for n-heptylamine from n-heptyl bromide except that absolute methanol was replaced by absolute ethanol to increase the solubility of the lauryl bromide. The alcoholic solution of lauryl bromide was saturated with ammonia and allowed to stand a week, the alcohol recovered, the laurylamine hydrobromide decomposed with sodium hydroxide, and the laurylamine extracted with chloroform. The chloroform extract was fractionated in a modified Podbielniak column to give a 37 per cent yield of a product boiling a t 119-20" C. (9 mm.) and freezing a t 28" C., which was identified as laurylamine. The hydrochloride was obtained as a crystalline derivative by dissolving the amine in ether and saturating the solution with hydrogen chloride.
3.40
was selected which boiled between 95" and 100" C. at 15 mm. This fraction corresponds to the boiling range of dodecane, the derivatives of which were used as reference compounds in the comparative studies. The chlorination procedure was essentially that of Pelouze and Cahours (9) and of Mabery (6), except that no purification of the kerosene other than fractionation was attempted. The kerosene fraction selected (95-100" C. at 15 mm.) was placed in a flask immersed in a boiling water bath, and chlorine was introduced below the surface of the liquid a t a relatively slow rate during the induction period of half an hour and then more rapidly for one hour. The rate of flow of the chlorine was regulated so that about one third of the kerosene fraction was chlorinated. The removal of the hydrogen chloride formed in the reaction was then effected by blowing air through the reaction mixture for 15 minutes. The resulting product was subjected to careful rectification, and the fraction boiling a t 120-135" C. (15 mm.) was collected as the monochlorides. The yield was calculated to be about 85 per cent of the unrecovered kerosene fraction. The identity of the monochlorides was established by comparison with the monochlorides of Mabery (6) and of Pelouze and Cahours (7, 9).
Preparation of Compounds ~-,L~-DIETHANOLKEROSYLASIINE3. A 'solution Of kerosyl chloride was refluxed for 18 hours a t 185" C. with an excess of diethanolamine. The product was then dissolved in ether and extracted with water to remove the excess of diethanolamine. The ether layer was extracted with a 5 per cent 8 An adaptation by t h e a u t h o r t o conform t o t h e general amine nomenclature.
300 2.60 IL
0
A-
uqN-DIETHANOLKLROSYLAMINE RL
B * N,N- DIETHANOLLAURYLAMINE HCL C - N_,u-DIETHYLLAURYLAMINE HCL D-LAURYLAMINE HCL E- SODIUM LAURYL SULFATE
4 2.20
E
2
1.80
1.4 0 1.00
100 140 100 SECONDS PER 50 DROP5 60
I
CtO
FIGURE 1. DROPNUMBEROF AMINE HYDROCHLORIDES
N,N-Diethyllaurylamine was prepared according to the Somerville procedure (10) by dissolving lauryl bromide in a n excess of diethylamine and refluxing for 13 hours. The reaction product was filtered to remove diethylamine hydrobromide; the filtrate was dissolved in ether, washed with water to remove unreacted diethylamine, and then extracted with a slight excess of 5 per cent hydrochloric acid to remove the amine as the hydrochloride. The acid solution of the hydrochloride was made strongly basic with sodium hydroxide t o separate the amine, which was dried over sodium hydroxide flakes and fractionated to give a 56 per cent yield of a fraction boiling a t 101-104° C. (0.25 mm.) which was identified as N,N-diethyllaurylamine. The hydrochloride
INDUSTRI-41, AND ENGINEERING CHEMISTRY
488
*
was prepared in the same manner as laurylamine hydrochloride. N,N-Diethanollaurylamine was prepared by heating lauryl bromide with an excess of diethanolamine on a steam bath a t 100.' C. until a test drop dissolved completely in dilute hydrochloric acid. The reaction product was filtered to remove diethanolamine kydrobromide; the filtrate was disA-CJ.~-DILmnNOLKeRa5YLAMINE HCL B-~~-DIETHANOLLAURYLAMlNEHCL
-
190 C LAURYLAMINE HCL D- ~,,bl.DICTHYLLRURnAMINL HCL e- SODlUM LAURYL SULFATE I80
170 160
-z e
3
IS0
s -1 6 140
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height of the liquid level in milliliters. In all comparative tests the solutions were allowed.to stand the same length of time before the tests were run, the standard chosen for the series being sodium lauryl sulfate. The results are shown in Figure 2. A careful study of Figures 1 and 2 shows that laurylamine hydrochloride is comparable to sodium lauryl sulfate by the drop number test, but that all of the other amine salts are notably less satisfactory for foam-producing agents and general detergents as measured by these tests. This is in agreement with the results obtained on the corresponding sodium alkyl sulfates ( 7 ) if it be conceded that most of these derivatives are of the secondary type. Since there are twenty secondary hydrogen groupings to six primary hydrogen groupings in dodecane, secondary derivatives certainly represent the principal products. By the foam test, however, laurylamine hydrochloride as well as the other salts gave less satisfactory results than did sodium lauryl sulfate. The results are in agreement with those obtained by other investigators who concluded that the amine salts in general are not so satisfactory for foamproducing agents as sodium lauryl sulfate.
Acknowledgment
'r kL5 .
This project was sponsored by The Matheson Alkali Works, Inc., under the general supervision of H. B. Hass.
Z I30 1
I PO
Literature Cited 110
I
2
4
6
8
IO
I2
14
MINUTES
FIGVRE 2. FOAM TESTox AMINEHYDROCHLORIDES
solved in ether, washed with water to remove unreacteti diethanolamine, and then extracted with 5 per cent hydrochloric acid to remove the amine as the hydrochloride. The acid solution of the hydrochloride was made strongly alkaline to liberate the free amine which was then extracted with petroleum ether and crystallized, to give a 77 per cent yield of a product which melted slightly above room temperature. % .
Comparative Interfacial Tension and Foam Values The drop number test used is a modification of the Pantyukhov method ( 1 . 8). A water solution of the amine hydrochlorides (0.2 per cent by weight) was run slowly from a ground-tip buret into benzene, and the number of milliliters of the solution required to produce 50 drops was determined. The rate of dropping was varied and the number of milliliters per 50 drops plotted against the rate of dropping. The procedure was described in some detail by Harkins and Brown ( 3 ) . Sodium lauryl sulfate was used as the standard, and the results are shown in Figure 1. The foam test was made by a modification of the Hetzer method ( 5 ) . A tube, 93 inches (2.36 meters) long and 3.6 inches (9.14 cm.) inside diameter, was equipped at one end with a sintered glass plate through which compressed air was forced with the consequent formation of small bubbles. A 200-ml. portion of a 0.2 per cent by weight solution of the compound to be tested mas introduced into this tube, and foam was produced by compressed air a t a rate to fill the tube in 5 minutes. The air was then turned off, and fifteen consecutive readings at I-minute intervals were taken of the
Boxser, H., Xelliand Teztile Nonthly, 4, 380-4 (1932); Evans, J. G., J . Sac. Dyers Colorists, 51, 233-40 (1935); Gotte, E., Kolloid-Z., 64, 327-31, 331-5 (1933); Gotte, E., and Kling, IT., Ibid., 64, 222-7 (1933). Davis, T. L., and Elderfield, R. C.. J . Am. Chem. Sac., 54, 14991503 (1932). Harkins and Brown, Ibid., 41, 499 (1919). Hass, H. B., McBee, E. T., and Weber, P., IND. ENG.CHEM., 27, 1190-5 (1935); 28, 333-9 (1936); Hass, H. B., McBee, E. T., Hinds, G. E., and Gluesenkamp, E. W., Ibid., 28, 1178 (1936); Hass, H. B., McBee, E. T., and Hatch, L. F., Ibid., 29, 1355-8 (1937). Hetzer, Seifensieder-Ztg., 59, 637-9, 653-5, 669-71 (1932) ; Chem.-Ztg., 57, 715-16, 735-6 (1933). Mabery, Proc. Am. Acad. Arts Sei., 32, 121-76 (1897); Am. Chem. J., 19, 419 (1897). Padgett. A. R., and Degering, E. F., IKD. ENG. CHEM.,32, 204 (1940). Pantyukhov, K.,Xasloboino Zhirovoe Delo, 1929. No. 2, 20-5. Peloure and Cahows, Compt. rend., 54, 1241 (1862); 56, 505 (1863); 57, 62 (1863); J . prakt. Chem., 88, 314 (1863); 89, 359 (1863); 91, 98 (1864); Ann. cham. phys., 141 1, 1 (1864). Somerville, I. C., U. S. Patents 1,836,047-8 (Dec. 15, 1931). PRESENTED before t h e Division of Industrial and Engineering Chemistry a t the 98th Meeting of the American Chemical Society, Boston, Mass. This paper is a n abstract of a portion of a thesis submitted by A . R. Padsett to the faculty of Purdue University in partial fulfillment of the requirements for the degree of doctor of philosophy in chemistry.
