INDUSTRIAL AND ENGINEERING CHEMISTRY
2468
(7) Collings, W. R., Chem. E n g . S t r i a , 23, 1616 (1945). (8) Daudt, W.H., U. S. Patent 2,444,555 (July 6, 1948). (9) Dow Corning Corp., hlidland. hfich., “Silicones--Sew Engineering Materials” (1945-48). (10) E’itzsimmons,V. G., Pickett, D. I,., hlilitz, R. O., and Zismati. W. A . , T ~ a n sA . m . Soc. M c c l i . Ennrs.. 68, 361 (1946). (11) Fox, H. W., Taylor, P. W.,arid %isman, IT’. A , , IIVD.E s o . CHEM.,39, 1401 (1947). (12) Hunter, M. J., Hyde, J. F., Wairick, P2. L., arid Fletcher, If. .J J . Am. C l m . SOC.,68, 667 (1946). (13) Hyde, J. F., U. S. Patent 2,371,050 (March 6, 1945). (14) Ibid., 2,410,346 (Oct. 29, 1946). (15) Ibid., 2,432,665 (Dec. 16, 1947). (16) Ibid., 2,441,320 (May 11, 1948). (17) Ibid., 2,457,677 (Dec. 28, 1948). (18) Hyde, J. F., and De Long, R. C.,J . .4m. Chem. So( 63, 1194 (1941). (19) Kauppi, T. A . , and Pedciwii, W . W.,Lubricatioii Eng., 3, 17 (1947). (20) Kauppi, T. A . , and I’edrrsen, U’. IV., h’trtl. Pcfroleum ’ V e u Y , Tech. Sect., 37, 944 (1945). (21) Kauppi, T. A . , and Pedersen, LY. IV.,S.A.E. J o w n u l , 54, 121 (1946). ( 2 2 ) hlurphy, C. M., Ronians. J: B., and Zisrnan. If’. .4., Trans. A m . SOC.Mech. Engrs.. 71, 561 (1949).
(23) Xeilsoii, J. Rudd, Crawford, 1.’. JV., arid Srnith, D. C.. J , Optical Soc. A m . , 37, 296 (1947). (24) Patnode, IT.,and n’ilcock. 1). I.‘., J . d r n . Chem. Sor.. 68, 358 (1946). (”5) Post, Howard \V., “Silicones and Other Organic Silicon C‘om-
pounds,” Sew York. Keinhold Publishing Corp., 1949. Richards, R. E., and Thompson, H . W . , J . Chem. Soc., 1949, p. 124.
.
Itochow, E. G . , Clteni. Eng. S e w s , 23, 612 (1945). Rochow, E. G . , “Introduction to Chemistry of Silicones.” New York, John Wiley & Sons, 1946. Sauer, R. O., J . Am. Chem. Soc.. 6 8 , 954 (1946). Smith. D. C . , French, J. I I . , and O’Neil, J. J., Naval Research Lab., n’ashington. D. C.. R p p t . P-2746 (January 1946). Sullivan, hl. V.,Wolfe, J. K., and Zisnian, W. A , , IND.ENhat62.SY0 heavy component corresponds to a value of 41.5 cs. Thus, the estimated viscosity of the I)ltLiid is 41.5 cs. at 140" F. u-1iic.h is a satisfactory approximation
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
December 1950
of the experimental value, 38.2 cs. The remaining properties may he determined from Figures 1 and 3: niolecular weight, 810; density, 1.904 grams per ml.; and vapor pressure, 14 microns of mercury. The effect of temperature changes on these propert,ies may be determined between 100” and 210” F.
.4dditional work on lubrication properties is impossible a t the preaent time. However, as dctcrmined hy usage these oils compare fdvorably with hydrocarhoii oils.
2471
( 5 ) Ibid., I(-328 (AECU-34) (Doc. 31, 1948).
(6) Ibid., IC-400(AECLJ-300) (hlay 20, 1949). (7) Ibid., I C 4 1 (AECU-241). ( 8 ) Gucker, F. T., Jr., Gagc, F. \V., and Moshcr, C. E., J . A ~ LChem. .
Soc., 60, 2582 (1938). (9) Hanson, W. E., Rept. on Usc of Modified Menaica-Wright Molecular Weight Apparatus, Mellon Institute of Industrial
Research, Pittsburgh, Pa. (September 1945). (10) Hickman, K. C. D., Chem. Rev.,34, 52 (1944). (11) Hickman, K. C. D., el d., IND. ENG.CHEM.,ANAL.En., 9, 364-7 (1937).
RIRLIOGRAFHY
( I ) Am. Scc. Testing Materials, Standards, Part 111-A, p. 325
(1946). ( 2 ) Fawcett, W. M., J . SOC. Chem. Ird. (London). 58, 43 (1939). (3) Gabbard, J. L., e t al., Union Carbide and Carbon Corp., Oak Ridge, Tenn., Rcpt. A-3655 (hIDDC-1456) (May 23. 1947). ( 4 ) Ibid.. K-124 ( M D D C - l i 2 4 ) (Jail. 1.5, 1848).
(12) Howat, D. I>., Chem. Age (London),45, 309 (1941). (13) John, K. T.. ./. Rrwcwch Notl. Bur, Standards, 37, 173 (194fi). (14) Vorhoek, F. H . , and Marshall. A . I,., .1. Am, Chem. Soc., 61, 2737
(1939). RECEIVED April
12, lD50. This paper is based on work performed for the At,ornic Energy Cornmiasion h y Carbide & Carbon Chemicals Division. l.nioii C a r h i d e & C’arhon Corporation. Ouk Ridge, T e n n .
Lubricants Produced by Reactions in Glow Discharge R . S. WHITELEY, C. N. KIMBERLIN, G. L. RIATHESON’,
AND R . W.
RICHARDSON
Esso Laboratories, Baton Rouge, La.
B
EFORE World War 11, motor lubricating oils, particularly aviation oils produced by the Volt01 or Electrionprocess, were widelyused in Europe. These oils were in productioll as late as 1940 (gw),and one o f the twoprincipa] lubricants used by the Germ&n Luftwaffe waB a blend of 15y0Voltol concentrate with 85% Edeleanu relined
T h i s report presents studies undertaken to determiric. the type produots which could be made by treating in the glow discharge various raw materials such as fatty oils, acidR and alcohols, esters, lubricating oil fractions, petrolatum, parfin wax, and biphenyl. Polymerization o r condensation was the basic reaction although some hydrogenation and dehydrogenation ~ ~ ~ u r r eLimited d. data are offered to show that positively charged Particles SUPaviation plied most Of the energy Of reaction. oils were produced from blends of selected mineral oils with “voltolized” rapeseed,, sperm, and other fatty oils. Lubricating oil additives such as pour inhibitors and viscosity index improvers resulted from voltolizing petrolatum and wax. Other interesting products were polyweight alcohols, esters and hasic acids, high ketones, and drying oils. Labratory for conducting liquid-phase reactions under the influence of discharges from either direct or alternating cllrrent is described.
( 4 ). Since the war, Electrion oil is again on the European market and is used for blending with mineral oil base s t o c l i ~ to produce high quality aviation and automotive lubricants. The process of thickening or polymerizing lubricants by the use of a glow discharge has been known for about 40 years. The process was patented by Alexander de Hemptinne (8) in 1909 and commercial operation was started before 1910 (6). The fact that this process is in use today even on a limited scale is remarkable considering the many advances in petroleum and Iubricarit technology. The de Hemptinne patents (8) were first exploited by the “SociBt6 Anonyme Elektrion.” The product was called “elektrion” and the manufacturing process “elektrionization” (6). These terms are not as familjar as are the German substitutes, “voltol” and “voltolization,” possibly because of the preponderance of German over Dutch or French publications on the subject. Consequently, the more familiar German names are used in this article. Evtensive exploratory research has been carried out to extend de Hemptinne’s early work and to lind other reactions which can be promoted by the electrical glow discharge. Several hundred literature references pertaining tu the effect of the glow disPresent address, Standard Oil Development Company, Elizabeth, N. J.
c*harg:e011 both Ilclulds and gases were found. Interesting descriptions of the foreign commercial installations are available ( 7 , 10, 16, 19, 16), arid adequate bibliographies of the more comprehensive articles are given in several literature surveys (16, 17, 89,
141. This paper is primarily a description of laboratory investigatiom for tho production of lubricating oil additionagents byvoLto1isation. A number Of interesting products Were also formed from high boiling organic materials such as fatty acids, alcohols, esters; aromatic compounds, and p a r a f i i waxes. A liinited amount of information on the mechanism of the reaction was obtained, and the influence of a number of process and electrical variables on the efficiency of the operation and on the quality of the products was determined. The electrical power required to effect a given degree of reaction was measured, and a method of measuring the power consumed is described. REACTIONS LNVOLVED
I n voltolization, as applied commercially to liquid-phase reactions, the apparatus is constructed so t h a t the liquid flows between vertical electrodes which carry opposite charges. In addition to the liquid within the area surrounding the electrodes, a rarefied atmosphere of some gws is maintained. When a suitable voltage is applied to the electrodes, a glow discharge is established. T h e liquid is recycled between the electrodea until the desired product is obtained. The most obvious effect produced by voltolization is a marked increase in Viscosity; however, the over-all reactions are much
