claim: 1. A prodtigt' obtgined as di&tillation residue upon distilling to 600' P ' a condensation prodttct ovf a;ketorie having an@aromatic group and'an alkyl radical of at least six carbon atoms with a dihalo 15 aliphatic hydrocarbgn compound having not more than 5 carbon atoms. 2. Product according to claim 1 in which the dihalo c . ompound is an !aliphgtic chlorine compound containing from I to 5 carbon atoms. 20 3. Product according to claim 1 in which the dihalo @aliphatic hydrocarbon is ethylene dichloride. 4. Product according to claim 1 in which the aiomatic group of the ketone is a carbo-cyclic 2,3 radical. 5. Product according to claim 1 in which the aromatic radical of the ketone is an aromatic radical. 6. Product according to claim 1 in which the 30 aromatic radical is a naphthyl group' 7. An oil-soluble viscous residue obtained by distilling to 600' F. a condensation product, substantially non-volatile at temperatures up to about 600' P., of a ketone having the general 35 formula RCOR', in which R is an aryl group and RI is an alkyl group having more than 5 carbon atoms, with a halogenated hydrocarboii having the general formula (CH2) nX2, in which X is a halogen and n is 1-5. 40 8. A viscous residue obtained by the steam distillation to 600' F. of a Friedel-Crafts condensation product of phenyl heptadecyl ketone with ethylene dichloride, said residue being soluble in mineral oil, substantially non-volatile at tem45 peratures up tD about 600' F. and having the property of lowering the pour point of waxy mineral lubricating oils when added thereto in small amounts. 9. A product obtained as distillation residue 50 upon distilling to 6001 P. a condensation product of a ketone having the general formula RCOR', in which R is a phenolic radical and R' is an alkyl group having at least 5 carbon atoms, with a dichlor aliphatic hydrocarbon having 1-5 carbon 55 atoms. 10. The process which comprmes condensing a ketone containing an -aromatic radical and an aliphatic radical of at least 6 carbon atoms with a dihalo hydrocarbon compound of 1-5 carbon 60 atoms, by means of a Friedel-crafts catalyst, and distilling the product to 600' F. 11. The process which comprises condensing an aryl alkyl ketone having an alkyl group of at least 6 carbon atoms with a dichlor -aliphatic hy05 drocarbon of 1-5 carbon atoms, by nieans of aluminum chloride at a temperature between about room temperature and about 150' F., hy&olyzing the aluminum chloride catalyst and subjecting the condensation product to distilla7o tion to obtain as distillation residue a high molecular weight condensation product soluble in.nunerai oil. 12. The process of preparing wax-modifying compounds which comprises condensing about 70 equal weights of a ketone having the general

4 21341,454 formula RCOR" in which-R is an aromatic radical and R' is an alkyl radical of at least 6 carbon atoms, and of a dichlor allphatic hydrocarbon of 1-5 carbon atoins in the presence of aluminum chloride as catalyst at a temperature between the approximate hmits of room temperature and about 1501 F., hydrolyzing and remgving the catalyst and distilling the reaction product under reduced pressure to obtain as distillation residue a high molecular weight condensation product soluble in mineral oil and having wax-modifying pr.operties. 13. The process which comprises condensing phenyl heptadecyl- ketone with ethylene dieworide In the presence of aluminum chloride at a temperature between the approximate limits of room temperature about 1501 P., hydrolyzing and removing the, aluminum chloride and subjedting the conden@ation products to flre and steam.dist,illation to a.temperature of about 600' P. to obtbiri as distillatidn residue a high molecular weight condensation product soluble in,min10 eral oil and having pour-depressing properties wherl added to waxy mineral lubricating oils in small amounts. EUGENE LTEBER.

Patented Feb. 8, 1944 21341@454 UNITED STATES PATENT OFFI@CE 2 341,454 ART OF MANUFACTURING LUBRICATING OILS Eugene Lieber, West Nevv Brighton, N. Y. assignor to Standard Oil DeveloPment Company a 1porporation of Delaware No Drawing. Application N I ovember 8,,1941, Serial No. 418,32@ 13 Claims. (Cl. 260-592) The preserit invention relates to the art of heterocyclic radicals such as fWf@irSrl, ftiryl, pArmanufacturing lubricating oils, and more specifically to addition agents capable of reducing the pour Points of waxy lubricating oils, and to waxy lubricating oils containing such addition agents. .5 The invention will be fully understood from the fonowing description. Addition agents for lubricating oils have been made by condensation of chlorides of long chain fatty acids with aromatic hydrocarbons in the 10 presence of relatively liarge amounts of aluminum chloride. These materials wwch are described as aryl alkyl ketones have been proposed as agents for increasing the oihness and adherence of oils to bearing surfaces. Examination of a large 15 number of these compounds shgws that many of them have little or no wax.-modifying qualities and in consequence are of small effect in reducing the pour point of waxy lubricating oils. The present invention relates to a method for 20 greatly increasing the pour-depressing pdtency of these aryl alkyl ketones and comprises a process in wwch the said ketones are recondensed with short chain dihalo compounds. The short chain compounds which are used in this connection are 25 preferably halogenated hydrocarbons contain-mg from 1 to 5 carbon atoms, such as dichlor methane, ethylene dichloride, propylene dichloride and the like, as weE as the corresponding bromine, fluorine and iodirie compounds. Among the var- 30 ious compounds that can be 'used, the chlorine derivatives are the cheapest, the most readily available and give the most satisfactory products, and among these ethylene dicworide is to be preferred. 35 The aryl alkyl ketones employed as the other reactant in the present Drocess are characterized ,by the following structural formula, R-C-R' 11 0 40 where R is a cyclic r@adicgl and R' is an aliphatic radical containing six or moro carbon atoms either open chain or cyclic. Among the various cyclic radicals that can be employed may be 45 mentioned, first, the aromatic radicals of the simple ring type such as phenyl, diphenyl, and -alkylated phenyl radicals such as tolyl and xylyl. Condensed ring aromatic radicals may also be employed such as naphthyl or anthryl, or the alkyl- 50 ated compounds of such radicals, for example, methyl or ethyl naphthyl. Hydroaromatic. radicals may be employed as well, such as tetra-hydro naphthyl. Other carbocyclic @and heterocyclic bazyl and the like, as well.as thti riidic:@ls of futdn. pyrrole, thiophene, pyridine,,etc. It will b6 under@tood that any of thi@si@ radicals may b4@ 4@mployed in the ketone in which the other radical is a hydrocarbon gkoup of at least six corboii atoins. Substituted aromaties or other cycle coiii pounds may be used containin-g oxygen, nitroge"n, or other inorganic el@inent in the substituent group, as for exainple, liy4roxy aromatic compounds, e. g., phenol, alpha- or beta-naphthol, cresols, petroleum phenols, especially the fraction theredf having an average composition corresponding to tertiary butyl benzene, or @amino aroMatic compounds, e. g., aniline, toluidine naphthylamine etc The aliphatic radicals are preferably sai@rat'ed such as hexyl, heptyl, oetyl, nonyl and higher such as - heptadecyl, but unsatu@ rated open ch-ain aliphatic radicals may also be employed as well as aliphatic cyclic radicelis su.ch as found in the naphthenic aci d and alcohols. In the condensation, the two reactants are ordinarily used in about equal weight,and are mixed with or without a solvent such as naphtha, kerosene or an inert halogenated solvent such as tri or tetrachlor ethane, carbon disulfide or the like. The cotidensation is effected by the use of batalysts such as alumitiitm chloride, boron, fluorlide and their known equivalents. The catalyst is preferably added to the mixture oi the two re@ actants and while the proporti6n may vary, it,is found that As little as .16 mol catalyst p I er mol of the dihalo compound is satisfactory. The temperatu re may vary over a con for exam ple, from about room to about 150' F., but@it is prefer erature from about room temperature to 1260 'or 1301 P. T-he ingredients should be stirred during the ieactio,n during which largei volumes of hy@ drogen chloride gas are evolved. Ordinarfly gn hour or two is -satisfz@ctory for tho@ reaction @ but the various factors of time,,temperature, catalyst and the amount thereof are@ riot totally'indep6ndent so that one or more- mety be @varied over a rather wide ralage if cqmpensation @is iii@(ie in bther factots. The product@fs tecoveied from reaction mixture by first diluting With a@l@rde-volume of solvent such as kerosene or naphtha and hydrolyzing the cgtalyst with water or alcohol, but preferably with a mixture of water and ,alcohol I@Thich settles a@ a I,OYer from tho oil and con tains the.hydrolyz i2d,.prodifet's of the c@4talyst. The oily materiol is,. withdrawn land 50133!@pted. t6 d'IStille@tion iio to -a t'e-m' "p'ex"At.'Ui@e arqiirid' 6 AO' P radicals which rnay be lised are the variou5 55 WWdh offei@tsth,6.rtW.OV'gl of t]@6 s'olv@ent and low-

2,341,454 er boiiing products which are not Very effective from the wax modifying standpoint and the desired product is collected as the distillation residue. The product is a viscous, green to brown oil; 5 the color is good and while it may darken light oils to soine extent, it is a satisfactory, shade, characteristic of high grade petroleum oils. When this material is added to a waxy lubricating oil in proportion of 1/2 to 5 %, a marked depression in 10 the material to be added depends on the particular ketone and dihalo aliphatic compound employed in the manufacture, and likewise on the particular oil in which the material is used, as 15 well as the degree of pour depression desired. The product may also be employed as a dewaxing aid in about the same amounts disclosed above and as an ingredient in various compositions containing wax where it is desired to modify 20 t,he crystal. structure. Although the products of this invention are b,pparently complex and composed of a mixture of compounds at least hav'mg sorne difference in molecuiar weight, if not in actual type of struc- 25 ture, it is believed that the niajority of the components of this product are linear condensation products having a general formula R-E" R-R")-R 1 30 c o c 0 n RI I 0 . in wh I ich R represents an aromatic or other cyclic ;radical, RI is a monovalent aliphatic radical such .6s an alkyl group contaihing at least 6 carbcn 35 atoms, R" is a bivalent hydrocarbon interlinking gr6up hav'ulg from I to 5 carbon atoms and n : is an inte.aer indicating the number of mono,meric units combined linearly. between the ter.minal units shown. :If a phen6lic ketone is used 4o As raw material, then the linear conden@ation product will contain hydroxy groups, which might be represented in the above general formula as being attached directly above each R. Such phenolic condensation products can be 45 converted to corresponding metal derivatives, e. g., ,of calcium, barium, magnesium, aluminum or sodium, in the same way in which simple phenols ;are converted into corresponding metal phenates and such metal phenolic condensation prodiicts tio may be used as addition agents in lubricating oils .6r other petroleum fractions. The phenolic condensation products can also be used as interme.iiiates for conversion into other types of products useful in the industrial arts; for instance, the@, 55 May be reacted with sulfur halides to form high phorus acid layer. 'Me acid chioride was then added to a solution containing 1 molecular proportion of an aromatic hydrocarbon dissolved in several volumes of kerosene, the particular aromatic hydrocarbon dissolved in several volumes of kerosene, the, particular aromatip hydrocarbon clepending pn the particu'lar k6tone, desired. Aluminum chloride was ihen added in slightly more than 1 molecular proportion and temperature raised while stirring to 200' P., which tem@'reaction mixture was cooled, diluted with an equal volume of, kerosene and neutralized with alcohol and wat6@. The sludge was settled and the kerosene layer I distilled to 600' F. with fire and steam. These three ketones were then added to. a waxy oil and the pour point determined. P o u r p o i n t S a m p l e 1 % k e t o n e 5 . 0 % k e t o n e the pour point is obtained. The exact amount of @ 'perature was maintained for about 5 hours. The Oil+Phenyl-heptadecyl ketone ----------- 30 15 Oil+Naphthyl-heptadecyI ketone --------- 30 20 30 20 011+Xylyl-heptadecyl ketone ---------- --- From the above it wiR be seen that the ketones were very weak pour point depressants. Exampl'c 11 The three ketones prep6,red in Exarhple I were then recondensed with ethylene dichloride using equal weights and, 14 grams of AIC13 per 100 grams of the ketone. Condensation was@ effected by refluxing for 3 hours then diluting with kerbsene, neutralizing with alcohol and water, decanting th6 kerosene layer and distilling to 600 to secure the desired product as a distillation residue. The yield of product varied from 77% to 88% based on the weight of ketone used and the product was a dark green, viscous oil. These three products were then added t6 a waxy oil of 30' F. pour point with the following results: Pour point Sample 1% ketone 5.0% ketona Oil+recondensed phenyl-hoptadecyl ke- -F. F tone -------- ---------------------------- -25 ------------- Oil+recondensed naphthyl-heptadecyl ketone -------------------------------------- 0 --- I --------- Oil+recondensed xylyl-hoptadecyl ketone - ------------ -20 molecular weight phenolic sulfur-containing co,@idensation products useful as anti-oxida;nts, in Phenyl heptadecyi ketone wE@s recond6rised mineral lubricating. oils and other pet@oleum hy- with ethylene dichloride as in the previous exdrocarbon fractions. , Also, if desired, the hy60 ample except that the proportion of catalyst was 'aroxy groups of the phenolic conden@ation prodvaried. The,pour depressor was ,ucts may be esterified tG form a new type of high in the 30' P. pour point oil. molecular weight polyesters, useful as 'addition agents in lubricating oils as well as in fatty oil -pompositions to be used in making paints, var- 65 Exampie III again tested Pour point Gr@ catalyst/100 gr. keto I ne Yield/loo, )aishes, and other coating or impregnating coni- gr. ketone 5.0% positions. Example I 7 --------- ----------------- -------------- 87 -15 -15 A series of heptadecyl aryl, ketones were - made 70 21 ---------------------------------- ----- 88 -20 -20 up according to the following procedure. One 35 ----------------------------------------- 78 -25 +15 'molec@lar proportion' of stearic acid was converted to the acid chloride b@ reacting with phos- it will be seen that if more than 7 grams of phorus trichl6ride on a water bath and the stearyl , catalyst is used the pour. point d e p r e s s o r i s . ' I n chloride wgs'decaxited from the aqueous phos- 7s dependent of the amount used.

E@tample. IV Phen-yl' heotadecyl ketone was@ recoiiclensgd with an equal quantity of ethylene dichloride as before using 7 grams of catalyst per 100 grams of ketone but providing time of 8 hours refluxihg instead of 3 hours as before. The pour del@ressing power was somewhat inereas6d by the. lesser time. Exaniple V Heptadecyl naphthyl ketone@ was ptepared as in Example I and was recondensed with an equal amount of ethylene dichloride wing AIC13 and a reaction period of 8 hours. The prbduct was recovered as before and 1% of the product in the 30' F. pour point oil reduced the same to -201 P. Example VI A phenyl-aliphatic ketone was made up. by condensation of benzol with acid chlorides of niixed acids prepared by the low temperature oxidation of paraffin wax, the waxy acids being a cut having an average of 16 to 18 carbon atoms. 1% of this ketone when added to a waxy oil of 30' P. pour point reduced the same to +5o F. while 3% produced the same reduction. This ketone was then recondensed with an equal quantity of ethylene dichloride to 150 of the ketone at refluxing temperature for 3 hours, using 10 gr. AIC13 and the product separated as before. 1 % of this product reduced the pour point of the oil to -20' F. and 5% to below -30' F. In another series of experiments the recondensation was repeated with different amounts of catalyst. When 30 and 50 grams of catalyst were u ed 1% of the product reduced the pour points of the oil from +30 to below -30' F. Example VII 100 grams of naplithenyl ketone of naphthalene were prepared by the procedure sholwm in Example I using naphthenic oils (acid No. 215) instead of stearic acid. This ketone was then recondensed with an equal quantity of ethylene dichloride using 10 grams of AIC13 at a reaction period of 3 hours. The product was separated as indicated in Example II and 82 grams were obtained. It was deep green and viscous. 1 % of this product in the oil having an original pour point of 30' F. produced a depression to -51 P., whereas 1% of the original naphthen'Yl ketone produced no reduction whatever. 5% of the recondensed product showed a pour point of -200 F. whereas 5% of the original showed none whatever. The experiment was repeated using 20 grams of AlCI3 under the same conditions. 1% and 5% respectively in the waxy oil gave Pour points of O' F. and -15' F. respectively. Example VIII A naphthenyl ketone of benzene was produced and 100 grams were recondensed with 100 grams of ethylene dichloride using 7 grams of AIC13 for 3 hours. The product was finished as before and 5 % in the waxy oil showed a depression in pour point from 30' P. to -15' F., whereas the ketone in 5% concentration showed a depression from +30- F. tD +15'F. in the appended claims the word "aromatic" is intended to include simple carbocyclic and heterocyclic radicals as well as partially, but notcompletely, saturated hy&oaromatic derivatives thereof, -T@hi's applicati6n 9,, continiiation-in-part of applioation Serial No. 248,234, fll6d I)ecernber 29, 1998. The present invention, i's @ not@ to be litnited to any theory ofthe mec]3:anism.,Df the@ proces8l nor to any particular reagents, catalyst and the like, but only to the following claims in- *Mch it is desired to claim all novelty inherent ift the invention. 10 :I