tion of sucrose monostearate and distearate have also been applied withour substantial modifications to the preparation of other fatty acid esters of sucrose. By increasing the ratio of methyl ester to sucrose in the reaction mixture, x o r e highly substituted derivatives of SLICI ose are obtained. T h e sucrose esters are new and coniplex chemical compounds. Further improvements will undoubtedly be made in the manufacturing process. For csample. it can be expected that a n increase in the reaction temperature \vi11 reduce both solvent requirements and the reaction time.
( J d y 11, 1933); Ibid., 1,917,257 (July 11, 1933). Hess, Kurt, Chem. Ber. 54B, 499-523 (1921 ). Lorand, E. J., U. S. Patent 1,959,590
Acknowledgment T h e investigation described herein \\.as supported by the Sugar Research Foundation? Inc., New York? N. Y.
Literature Cited (1) Bailey, Alton E., "Industrial Oil and Fat Products," 2nd ed.. p. 40. Interscience, N e w York, 1951. ( 2 ) Berthelot, M., Ann. chim. et phys. 3. 60. 93 11860'). ( 3 ) Clayton, 3. 6., Lindstrom, E. G.. Stewart, F. A , . U. S. Patent 2,700,022 (Jan. 18: 1955). (4) Hass, H . B., Snell, F. D., York. W. C., Osipow, L. O., U. S. Patent applied ,
(May 22, 1934). Snell, F. D., Snell, C. T.. .'Coloiimetric Methods of Analysis." 3rd ed., vol. 3, p. 45, Van Nostrand. New York, 1953. York, W. C., Finchler, Arthur, Osipow. Lloyd, Snell, F. D., XI1 International Congress of Pure and Applied Chemistry, Zurich, Switzerland, J u l y 21-27, 1955.
>
for. ( 5 ) Harris, B. R.: U. S. Patent 1,917,250
for review October 28, 1955 ACCEPTED March 21, 19.56 Prcsented at the 46th meeting of the .her-ican Oil Chemists' Society, Philadelphia. Pa.. October 10-12, 1955. EIVI:D
LLOYD OSIPOW, FOSTER DEE SNELL, DOROTHEA MARRA,
AND
WILLIAM C. YORK
Foster D. Snell, Inc., 29 West 15th St., New York 11, N. Y.
Surface Activity of Monoesters
...
Fatty Acid Esters of Sucrose Evaluation studies indicate that these esters are emulsifying agents and good detergents. They are sufficiently stable to hydrolysis for use in cotton detergency applications. Low toxicity also points to particular usefulness in cosmetic, pharmaceutical, and food applications.
T H E monoesters \\.ere prepared by the first procedure described in the preceding paper. They were purified by repeated crystallization from acetone.
saponification of each of the sucrose esters employed in this study are given in Table I. Comparison of the experimental saponification value with the theoretical value for the monoester indicates that all of the sucrose esters are essentially pure tnonoesters. Equilibrium solubility values Mere not determined. .A11 these sucrose esters ap-
Physical Properties T h e specific rotation, softening point. and per cent acyl radical determined by
Table I.
Physical Properties of Sucrose Esters .lCyl &dLcal
(Ethyl Alcohol)
Poznt.
+42.5" +42.2' +39.8' +37.6" 4-39.35'
90-91 67-69 60-62 50-54 52-53
SClIjllat t U I l t
Sucrose laurate Sucrose myristate Sucrose palmitate Sucrose oleate Sucrose stearate Tall oil-polyoxyethylene condensate
O
C
pear to be soluble in warm water, ethanol. methanol, and acetone. Solutions of sucrose palmitate and sucrose stearate, 2073 in hot water. formed viscous solutions and gels on cooling to room temperature. Aqueous solutions of sucrose laurate are low-viscosity fluids ai room temperature, even a t 30% concentration. T h e solubility of the sucrosc
Theoret-
zcaP
Fouid
35.0 38.2 41.25 42.0 42.3
35.0 39.0 40.0 39.2 44.1
Intcvfacuzl Tenswn, D y n e s C m '
-Surface Tenszon DyneslCm
___
~~
Concn
%
~
__
1.0
02
01
0 05
10
02
01
007
33.4 33.1 33.7 31.8 33.5
33.4 33.1 33.7 30.8 33.1
33.7 34.8 33.7 31.5 34.0
35.6 34.8 35.0 32.7 33.7
7.6 7.3 6.3 5.4 6.2
7.1 6.3 5.9 5.0 6.6
7.9 7.0 6.2 5.0 7.7
8.4 7.4 6.2 6.2 7.2
40.4
41.0
41.0
42.0
6.7
7.0
7.2
7.7
43.0
47.0
48.0
48.0
13.0
15.2
16.1
16.5
31.0
30.9
29.4
29.3
2.3
2.3
2.0
2.6
Polyoxyethylene-polyoxypropyl-
ene condensate Sodium dodecylbenzene sulfonate " Based on monoester. Aqueous solutions at room temperature. e Against Nujol.
1462
INDUSTRIAL AND ENGINEERING CHEMISTRY
monoesters in cottonseed oil and methyl stearate is well under 1% a t 25' and 7 5 O c. Surface and interfacial tension measurements using the d u Nouy interfacial tensiometer are also recorded in Table I. along with values for other surfactants she\\ n for comparison.
Table
HI.
Launder-Ometer Test Results on Cotton with Built Detergents at 60"
Table II. Draves Test at 0.2% Detergent Concentration and 50" C.
Active detergent Sodium tripolyphosphate Tetrasodium pyrophosphate Sodium metasilicate (pentahydrate Sodium sulfate Sodium bisulfate
Sucrose laurate Sucrose myristate Sucrose palmitate Sucrose oleate Sucrose stearate Sodium dodecylbenzene sulfonate Tall oil-polyoxyethylene condensate
" 5-gram unscoured 3-gram hook.
33 52 41 25 97
37 46 48 48 112
1
1
62
33
cotton skein with
20 40 10 10
IO 10
pH of 1.0% solution, 9.8 S o d Redeposztzori on Clean Cloth I ( tth 0 025% A d d d Carbon Blach" 2-Grazii E ater 15-Gram Kate! _ .?-Gram a t_ o 15-Gram E'ater _ _ F_ D e t e r a d Concii pr . (1.35 0 . 2 0.35 0.2 0.35 0.35 0.2
____h o d Remoial"
~~~~
~~~
~
Sztrfactaizt
Sucrose laurate 11.1 Sucrose myristate 11.3 Sucrose palmitate 12.9 Sucrose oleate 12.5 Sucrose stearate 12.1 Sodium dodecylbenzene sulfonate 12.9 Tall oil-polyoxyethylene condensate 12.5 Water 3.0
11.1
-30.1 -29.1 -26.1 -27.1 -28.1
-28.6 -27.2 -25.5 -26.0 -21.6
-31 .O -38.9 -32.7 -35.4 -29.0
-33.3 -31.0 -31.6 -31.6 -29.3
10.5
-35.3
-28.3
-36.7
-31.8
-18.7 -44.3
-15.0 -42.6
-29.9 -40.8
12.0 12.3 13.4 12.8 12.9
12.3 13.8 15.5 16.3 14.1
9.6 14.9 15.3 12.1
13.3
14.2
10.9 2.9
11.0 4.0
8.9 3.1
-12.9 -44.7
Results expressed as brightness units regained, based on magnesium oxide are averages of four replicates.
Table IV.
= 100 ;
values
Launder-Ometer Test Results on Cotton with Mixtures of Sucrose Palmitate and Sodium Dodecylbenzene Sulfonate
Sinking Time. Seconds" 2-grazn 15-grain zcattr ?cat
